# What an Engineer Finds Amazing About the Claims of Arctic and Antarctic Melting

Guest opinion by Ronald D Voisin

It’s just amazing how we as a society can let global group-think ideas have fantastically large continued public traction when direct scientific observation utterly refutes the very basis of the ideas.  Can not the alarmist scientific folks (I’m thinking here of Mann, Alley, Schmidt, Hansen, etc.) be just a little bit honest about what is actually going on?

Sea level rise is widely reported every single day as an imminent man-made climatic disaster.  Portions of Greenland melt, and portions of Antarctica melt. are presented as proof-positive that human burning of fossil fuels is causing the Earth to overly warm and therefore causing these melts…which will lead to coastal inundation…and we must therefore change our ways at any cost.

However, it just so happens that these same portions of Greenland and Antarctica melt are now known to be situated over highly active geothermal sites…and that 100% of the observed melt is easily and readily attributable to current enhanced geothermal heat release.

91 UNDERWATER VOLCANOES ANTARCTICA

Now, exactly why it is that that enhanced geothermal heat release is happening just now, is unknown.  But it surely has nothing to do with human consumption of fossil fuels. Can it actually be argued that this misrepresentation of cause-and-effect is somehow, nonetheless, in the public interest?

An intellectually honest, potentially wrong and disprovable, but likely meritful answer, as to why geothermal heat release might be currently enhanced, can be found here:

https://wattsupwiththat.com/2017/04/09/an-engineers-explanation-of-climate-change

Ronald D Voisin is a retired engineer.  He spent 27 years in the Semiconductor Lithography Equipment industry mostly in California’s Silicon Valley.  Since retiring in 2007, he has made a hobby of studying climate change.  Ron received a SEE degree from the Univ. of Michigan – Ann Arbor in 1978 and has held various management positions at both established semiconductor equipment companies and start-ups he helped initiate.  Ron has authored/co-authored 31 patent applications, 27 of which have issued.

UPDATE: This graph from David Middleton really tells the story about Greenland:

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## 777 thoughts on “What an Engineer Finds Amazing About the Claims of Arctic and Antarctic Melting”

1. Tom Halla says:

Geothermal influences just don’t fit the narrrative.

• I’m waiting for a report to prove that
global warming CAUSES underseas volcanoes!

• jorgekafkazar says:

That paper will be out any day now. It will be worse than we thought and will involve the word ‘robust.’ Hint: models and shonky statistical methods will be involved.

• Gil says:

Yes, and it will claim to generate additional tantalizing questions that will require more grant money for further study.

• John Harmsworth says:

And when you ask for the data they will tell you they dropped it in the volcano!

• Mike says:

Yes and the words impact and transition. Don’t forget those!

• noaaprogrammer says:

You left out “sustainable.”

• Alan Tomalty says:

Any time I hear the word “sustainable” I ask the speaker what his/her defintion is. When they say the usual idea that we will run out of the resource, I tell them that the supply and demand price curves will always work their magic. You cannot run out of a commodity because the price will soar and people will have to stop using it because of the high cost. New alternatives are always found . If they say population will become too large, I point to the World Bank projections of a maximum number of 11.2 billion based on the downward trend of the % increase since 1960. Advanced societies with family planning dont have many babies. Most developed nations are far below the replacement rate of 2.1 So in the end the only valid meaning that sustainable has is in the area of pollution. There are 5 trillion pieces of plastic in our oceans and nano technology threatens our garbage dumps and eventually our water systems. Non air pollution is what we should be concerned about; not CO2.

• Ben Vorlich says:

Anyone who has researched their family tree becomes aware of how quickly family size reduces once infant mortality rates fall to modern Western levels. Once 90+% of children survive then the next generation have 4 to 6 children compared with the 10+ of their parents generation. This reduction in family size continues to fall to 0,1,2 or 3 for subsequent generations. Even in countries were religion would make you think otherwise.

• Felix says:

“Demographic transition” has been recognized for at least a decade.

Culture can however short circuit the process, as has happened in much of the Islamic world, due to lack of freedom for women.

• That is becoming the real tragedy of climate change alarm-ism. Money and effort wasted on a non-problem while the real problems get pushed to a back burner.

• TruthSeeker says:

Don’t forget that favorite big word, ‘Anthropogenic’!

• son of mulder says:

Or the removal of oil, gas and coal has caused a subtle perturbation of the earth’s crust thus unleashing Vulcan’s terror….I think not.

• Joe Wagner says:

I remember seeing a “CO2 causes volcanoes” paper posted on here some time ago. I admit the title was such Compost Fodder I didn’t bother reading it or even remembering when it was posted.

• MarkW says:

Didn’t Al Gore once claim that global warming is making the rocks softer?

• ozspeaksup says:

• It’s possible to link temperature changes to sea level changes. And it’s possible to link sea level change and isostatic movements to the pressure field surrounding a magma chamber. This means it’s possible that as a continental ice mass causes a continent to drop, and sea level drops over 100 meters, subsea. volcanism will increase. On the other hand, a warmer climate melts ice caps, raises sea level, and this ought to suppress magma reaching the surface until the chamber pressure rises. I believe the effect will be short lived.

• mellyrn says:

https://www.rt.com/usa/429588-volcano-study-mass-extinction/

The article begins, “Devastating volcanic eruptions, caused by excess carbon in the atmosphere. . . .”

To be fair, the study described by the article does not appear to make that claim, and it’s even possible that the article meant to begin the other way round, as something like “Excess carbon dioxide, caused by devastating volcanic eruptions . . . ” would go better with the actual text. If so, one can only hope they are embarrassed.

• Peppykiwi says:

Hard to tax volcanoes!

• I agree they don’t fit the mantra.

However, more importantly using incorrect images of Antarctica is not good.

As a New Zealander I must object to the top image that shows a huge Antarctica with a miniscule NZ below it. In fact NZ is about the same size as the West Antarctic Peninsula.

I was polite and didn’t object when it was used in an earlier post… but we all have our limits!

Was the map maybe produced/posted by an Australian? Or is that just another conspiracy theory?

• whiten says:

No conspiracy, Alastair .
This error will immediately be corrected, once NZ joins EU as a member state.
After Aus and Canada, of course. 🙂

cheers

• donb says:

Agree. Heat flow data were recently reported for some areas under West Antarctica where melting glaciers are located. The values were only several times average crustal het flow, which is mostly less than 0.1 watt per square-meter. That is not capable of melting much ice.

• steven mosher says:

yup

• Alan Tomalty says:

Well the surface temperatures in 97% of the land base of Antarctica are not capable of melting any ice any of the time

• Robert B says:

Maybe a bit late but a strong current is more important than a fraction of a degree warming.

• steven mosher says:

The real problem is that the lawyers cannot tell the difference between or the similarity of technical education of a scientist and an engineer. To them the ‘scientists’ are ‘experts in the field of ‘science’ and engineers are just some sort of peasant who gets their hands dirty helping to make money for their (lawyer’s) clients/political supporters.

That is not just a rhetorical potshot at lawyers and political ‘scientists’ who dominate the political class but an accurate reflection on their state of technical ignorance such that they simply do not even comprehend the technical aspect of engineering education and the great overlap with that required for the physical sciences. They actually have no objective basis by which they can seek out genuinely expert advice.

• jimB says:

As an old guy with a BSChE degree (as well as a JD), I agree totally. Most people do not know that scientists often come up with off-the-chart theories just to explore unknown territory. Engineers are much more circumspect, lest boilers explode and bridges fall down.

• jorgekafkazar says:

Exactly. Publish or perish requires a greater stream of new stuff than can be generated, so academics have to deny the reality of some of the old stuff in order to publish something.

OTOH, a novel way to construct a bridge was recently utilized by a bridge design company and selected for its aesthetics by Florida Intl. University as “a gleaming testament to FIU’s lofty institutional aspirations.” A second bidder’s more conventional design was rejected as “banal” by the university.

Give me banal every time.

• Richard of NZ says:

I’m sure the second bidder would be beaming with delight except for the minor problem of dead people and destroyed reputations.

p.s. beam theory is (was?) used for bridge engineering.

• rocketscientist says:

I an am MIT educated engineer, with some gifted children. My daughter is an architect (USC) but has advanced math skills. When she was studying beam theory she was having some difficulty remembering the formulas for shear moment and bending, until I pointed out they are differentials/integrals of each other and this is where her calculus would be handy. She finished her assignments well ahead of schedule, and when her architecture professor asked at the next session if any students were having difficulty with the assignments as several had complained. She said they were easy if you understood the calculus behind them, to which her professors replied there’s no calculus involved in architecture.

• Phaedrus says:

How many times have I heard that rhetoric from the knowledgeable!

• steven mosher says:

• Pop Piasa says:

You really are the Homer Simpson of English scholars, Mosh. Gotta hand it to ya mate!

Youv’e reached your very own stage of enlightenment Mosh. Well done. How old are you?

• steven mosher says:

talk to us about saftey factors.

• DonM says:

Be more specific … what do you want to know?

There’s benefit and there’s cost. Experience and analysis are used for balance of each, but the true benefit and true cost can never be known.

For example, your uncle, doubling up on condoms may have saved him some heartache, but then world may have then been bereft of your witticisms.

Well Mosh, there are safety factors and there are general load factors, there are dynamic load factors and service load factors as well as return periods for environmentral loads which in reality are a statistical load factors and over the top of that there are a range of quality assurance considerations such as material strength and quality certifications, similar for joining technologies (welding, bolting and other fasteningsetc etc etc) not to miention fire risk, corrosion risk, vibration considerations and so on all of which is about risk management so people don’t die.

Where are the equivalents in ‘science’?

Pal review??

LOL

• Kalifornia Kook says:

As a retired engineer (with a physics degree), I’m biased. But I still gave that a +1. Engineers make it real. Scientists never have to explain to a customer why a bridge failed, a plane crashed, or why a Tesla ran into the rear end of a semi. When scientists screw up, a few other scientists ask why. When an engineer screws up, people are likely to get hurt or die. Engineers get sued.

• Enginer says:

My wife has chidded the AIChE for the in-activity of its memebership on many technical issues. Rightly so.
Like “scientists,” Engineers are trained to seperate out often-conflicting explanations for natural phenomenon and act accordingly. However, for most engineers, peer acceptance is not as significant as actually solving problems and saving or making money.
My money is on the cost-benefit siding with adaptation instead of betting on the likelyhood that solar variation trumps CO2 increase.

• Engineer:
I think engineers are just not that interested
in the climate change fiction, and fairy tales,
that are so exciting for most leftists,
for the same reason that they don’t read comic books!

• rocketscientist says:

We tend not to tolerate fools gladly.

In our game fools kill people en masse. We don’t tolerate them at all.

• I don’t think climate change is fiction. Nor do I think the greenhouse effect is fiction. I’m more focused on the actual physics, how it works within the atmosphere, the feedbacks, and the flaws I see in the IPCC structure, the way they work, and their models. There’s a lot that’s wrong even if one thinks the basic theory is more or less right.

• TruthSeeker says:

The driving force is not climate. That’s just a smokescreen.
The real driving force is overarching government control of people via taxation, wealth redistribution, and controlling their energy use. The true goal is destroying free enterprise and replacing it with socialism. Every now and then the UN-IPCC bureaucrats slip up and admit this.

• Robertvd says:

1984 Big Government

• Graemethecat says:

Indeed. Engineers know full well that there is a real, tangible physical world out there which is utterly indifferent to Man’s words and desires. Lawyers believe that words and desires dictate reality.

• michael hart says:

Actually, I have a bit more faith in lawyers, or competent ones at least.
In a court of law, under oath, a good lawyer should be able to get even the bestest of scientists to admit just how much of science actually boils down to subjective interpretation. As in “Justify to the court, if you please, just why you think surface temperature measurements are more to be regarded than satellite temperature measurements. (Or vice versa).”

A lot of lay persons might be unpleasantly surprised by the replies where honesty is required under sanction of law.

• michael hart says:

To qualify, I don’t necessarily have more faith in lawyers than Engineers (far from it), but I do have faith in good ones to drag out some admissions from scientists which they would not be so honest about when they think they are just leading some media folks or politicians along like the Pied-piper.

• Kalifornia Kook says:

Most engineers have to prove their designs will work. They have to build prototypes. They have to show they’ve gotten it right in the past. I tend to trust those who have prototypes that IO can examine, collect data that I can review, run my own analysis against.
in a court of law, you’re only allowed to take into account testimony. If it goes against your training or common sense, you’re supposed to ignore that, do no more analysis.
How can one determine proper conclusions when facts are so carefully metered?

• I have an engineering degree from a good university and a science degree from a word class university, but I chose to earn living in engineering. Having experienced both I found in the field of science you can make string of errors, no matter you keep rewriting till it looks right. On the other hand in the engineering business if you are lucky one of two errors may be tolerated depending on the damage done, else you are out with a ruined reputation.

• EW3 says:

Had an electricity teacher at Brooklyn Tech in 1968 who would drop your grade for a lab report from an A to a B for a spelling error. B to C for a 2nd spelling error.

Will let you imagine what he did to your grade for math errors.

He simply explained, if you build a bridge or build a dam, errors can be costly even deadly.

• MarkW says:

How do you teach electricity?

• Joe Born says:

As a lawyer who worked with a great many engineers over the years, I hold them in high regard as a group; some of the smartest people I’ve known were engineers. And I agree that the public in general has only a vague idea of what disciplines engineers master. (From what little I’ve seen, most “rocket science” is really engineering.)

Just like us lawyers, though, engineers don’t always stay in their lanes. I was recently reminded of a WUWT post about climate feedback by an electrical engineer. Although electrical engineers tended in my experience to be the group most knowledgeable about feedback, the one who wrote that piece completely blew it in trying to apply feedback to climate. And he proved completely impervious to correction.

Conclusion: for the information consumer, credentials are of limited value. That’s just as true of engineers as it is of scientists—or lawyers.

Actually have to agree with you there having done quite a bit of ‘expert’ witness work over the years and seen what I call ‘rent an expert’ dribble utter crap for ‘the other side’. Its the zealots and whores who are the problem. Those who come to the matter with an agenda other than just their professional duty.

In my eqperience good lawyers faced with robust expert evidence contrary to their client’s position will try and mitigate their client’s loss and settle (while putting up a robust defence etc)

• bahamamike says:

jhborn..
Lawyers deal with man made laws which can be repealed and/or replaced. We hapless engineers are obliged to work with the Laws of physics, Thermodynamics, Young’s Modulus, Avagadro etc. which are immutable alas!
Imagine the possibilities if we could repeal the 2nd. Law of Thermodynamics… perpetual motion.. for a start.. we could all have everything we wanted and for FREE.
Regards

• Phil. says:

My first experience with feedback was with Chemical engineers particularly with regard to reactor engineering (part of my PhD thesis) Great book was by Rutherford Aris.

• Ian Macdonald says:

Not quite. Science involves two aspects; theoretical predictions, usually based on mathematics, and empirical observation or experiment. Both are necessary to do valid science.

Engineering is the application of science to commercial projects, and it too involves both theory and practice. The difference is that the engineer has a more direct objective, whereas the scientist is concerned with knowledge itself.

The problem you mention arises when scientists simply start parroting textbooks without having any understanding. In fact what they are doing then is not science, it is something more akin to religion. This is less of a problem in the engineering sector, because an engineer who did that would be faced with a string of embarrassing and costly failures. The scientist, not so much.

• I have been a member of committees which had oversight over research and development budgets, what I saw being proposed for research programs involved acquiring knowledge we could use to make more money. I think what we did in engineering research was similar to what biomedical labs do to find better drugs.

3. Doug S says:

Excellent point Ronald. My question is, where and how is this geothermal activity expressed in the various computer models? I’d like Dr. Mann or Dr. Schmidt to at least give us a thumb nail sketch as to how they included this into their projections of ice loss and SLR.

• Sara says:

They didn’t include geothermal because it is not a steady state occurrence. Breathing, which produces CO2, is a steady state occurrence, and therefore, they find it useful for their models.

• John Shotsky says:

The IPCC’s charter is to categorize HUMAN CAUSED climate change. Natural climate change is not part of their charter, thus the focus on CO2 that is human generated. You can read their charter, if you search hard enough for it. It is laughable…if CO2 does NOT cause climate change, the IPCC has absolutely no charter left.

• As far as I know detailed mapping of geothermal heat flow isn’t included in reanalysis programs which are used to estimate ocean energy content. I would love to see this changed to see if it introduces changes in local ocean circulation, mixing and heat flow.

4. Latitude says:

The data is always hiding somewhere that it can only be modeled…

First they say the ice will melt at the bottom..and it will all slide off
..then they say it’s losing mass because of global warming..when the temp is below 0

5. Felix says:

“Imminent”.

The spelling Nazi.

• HotScot says:

British US

centre center
fibre fiber
litre liter
tyre tire
colour color

The spelling Fuhrer.

🙂

• HotScot says:

Pity I know nothing about HTML!

• Smart Rock says:

you mean führer?

Google “extended ascii codes” to find out how to do exotic characters (must have numeric keypad with numlock on)

It has symbols and superscripts so we can write ±273°K and 1341W/m² but it won’t do subscripts so we still have to write CO2 and H2O

Alternatively, write in Word and copy and paste into WordPress – seems to work most of the time – but still won’t do subscripts

former Scot

• “it won’t do subscripts so we still have to write CO2 and H2O”
CO₂, H₂O?
Unicode.

• steven mosher says:

thanks nick. none of these engineers could figure it out.

• Monna M says:

Unnecessary and snotty, Steve.

• Clyde Spencer says:

Those twos look to me like smaller font, not actual subscripts.

• Ed Zuiderwijk says:

Ach so!

6. Javier says:

Heat doesn’t have a tag of origin, so it is subject to interpretation.

7. Jeff Alberts says:

Again, failure to study history. Sea level is always a give and take. If Greenland loses all its ice, a whole new continent would be open for habitation, while existing continents might lose a little around the edges.

Then, in the distant future (hundreds or thousands of years), when all the skyscrapers on Greenland and northern Canadia are being crushed by advancing glaciers, it will be blamed on humans, by people with short attention spans. It’s the same situation we’re now in with SLR. Used to be a lot higher during the Holocene Climate optimum, then gradually dropped, and we kept building along the shorelines, cuz it’s purdy.

Now SLR is slowly rising, again, as is its wont, and its being blamed on humans by people with short attention spans. The beat goes on.

• HotScot says:

Jeff

Knocking on an open door here.

Modern society grasped the wrong end of the King Canute stick.

8. Alley says:

“Lastly, let me make an obvious prediction predicated on the prediction that the Earth has recently begun to cool and assuming that some appreciable level of cooling (0.1-0.3 degree C) takes place over the next several years.

Atmospheric CO2 is going to spike hard in the coming years. And before it stops spiking it will likely attain an annual contribution level appreciably larger than the then-current anthropogenic emission.”

That was four years ago. Where is the obvious cooling?

• goldminor says:

You linked the same graph which is posted just above. So what is your point? Over the course of that sat record the atmosphere has gained around 74 ppm of CO2, a bit over half of the 122 ppm gain over the last 160+ years. Now some portion of that 0.5 C temp gain over the last 40 years is natural.

That doesn’t say much for the warming ability of CO2 when record amounts of CO2 have been entering into the system every year over the last 40 years. So no obvious warming caused by CO2, or it would be reflected in the above graph.

• Alley says:

“You linked the same graph which is posted just above.”

Exactly. My point is that it shows a warming planet. Why someone would use it to show otherwise is hilarious.

• fonzie says:

YOU gave a time frame of the last “four years” which is why someone would use it to show otherwise (hilarious)…

• Alley says:

No, that was Ronald D Voisin that I quoted.

HE have a timeframe of four years, which is why people re laughing at him.

• MarkW says:

You have to remember, to a troll, only those time frames that give the results he wants to see are legitimate.

• Alley says:

One must remember that a denier’s explanation is always based on a cherry pick that gives the results they wanted. The author used a few years, and lost the bet.

• Jeff Alberts says:

“One must remember that a denier’s explanation is always based on a cherry pick that gives the results they wanted. The author used a few years, and lost the bet.”

And Mann didn’t cherry pick his bristlecone pines, then grossly overweight them in order to obtain a hockey stick. No sirreee!

And Briffa didn’t cherry pick Yad06, no sirree!

• Alley says:

No matter the proxy leading to the ground station record, there is a hockey stick.

YESSIREE!

• MarkW says:

Not surprising since the algorithm was designed to create hockey sticks, even from random data.

• MarkW says:

Fascinating how only the other side cherry picks.
For example, you are only interested in the small fraction of the temperature record that shows what you want to believe.

• Steven Fraser says:

Hmmm, lessee… The May, 2014 Global lower troposphere anomaly was .24. May, 2018 value was .18 for the same metric.

Question: Where is the C02 warming over those 4 years?

• Alley says:

Signed, other people who think cherry picking is the way to go.

• Richard M says:

Alley, I’ve noticed a lot of denial in your comments. Better get used to it.

• Richard M says:

It’s even worse that that.

May 2001 .20 C
May 2002 .25 C
May 2003 .21 C

Arguably no warming this century.

• DW Rice says:

Richard M

“May 2001 .20 C
May 2002 .25 C
May 2003 .21 C

Arguably no warming this century.”
___________________________

Here are ALL the global May temperatures published by UAH TLT v6.0 since 2001, with trend:-

https://s33.postimg.cc/af9x8jk5b/UAH_May_from_2001.png

The trend shows a warming rate for May of +0.114 C/dec; a total warming of of +0.2C this century.

• Richard M says:

DW Rice, trends are not that indicative of reality when they are influenced by outliers such as the recent El Nino. Sorry if you failed freshman math.

• Gary Pearse says:

Rice .144/ decade is 1.44 C per Century! Hey this is just pre progressive post normal arithmetic.

• Alley says:

Exactly! This is what we see from deniers. A listing of a few years, and sometimes something so stupid as a single month in one year to the same month in another.

When will they realize two things: use the entire earth (not a single location) and compare at least decades.

• Jeff Alberts says:

Alley, do you know what intensive properties are? Do you know why a representation of a global temperature is a complete fantasy?

• Alley says:

I see that you don’t believe in a human body temperature either. It is impossible to have an “average” body temp, and more to the point, impossible to know if the body is increasing in temp.

It’s why 1 out of 100 doctors tell you you don’t have a fever when you take your temp at two locations, because the body is so complex. Best to wait until you have 10,000 locations to see if that infection is the cause.

• syccomputing says:

“I see that you don’t believe in a human body temperature either.”

Alley, you’ve made another logical error, i.e., the False Equivalence fallacy.

https://en.wikipedia.org/wiki/False_equivalence

The human body is a non-chaotic (i.e., “closed”?) system, therefore, it has characteristics that are common to all humans and generally measurable.

The climate system is not the same type of system, as the IPCC documentation says:

“In sum, a strategy must recognise what is possible. In climate research and modelling, we should recognise that we are dealing with a coupled non-linear chaotic system, and therefore that the long-term prediction of future climate states is not possible. ”

http://ipcc.ch/ipccreports/tar/wg1/505.htm

The two systems cannot be considered comparable.

• MarkW says:

Fascinating how the troll demands that anyone who looks at any portion of the temperature record that doesn’t show what it wants to believe is guilty of cherry picking. Even though he is doing just that.
It’s also fascinating how any method of looking at the data that doesn’t show what it wants to believe is by definition not legitimate.

• Ed Zuiderwijk says:

• Alan Tomalty says:

Can we at least agree that since UAH has learned their lesson of correcting for satellite drift, from now on we can all trust the UAH figures? It is certainly the only temperature record that we skeptics trust and since you alarmists are using it to bolster your global warming trends, I would expect that within the next 5 years when the UAH temperature trend goes down , that you alarmists won’t turn around and start calling the UAH results garbage.

• Alley says:

“Can we at least agree that since UAH has learned their lesson of correcting for satellite drift, from now on we can all trust the UAH figures?”

YES!! That is why the number of people who said the earth isn’t warming has dropped off. UAH agrees with ground stations, and that’s what science does.

It is certainly not the only record we scientists trust. Deniers took a long while to come to their senses. Now most finally (finally) agree that adjustments are necessary.

A decade ago we heard about how scientists would be eating crow when the temps went down. Record warm years should have put a stop to that nonsense.

They are probably the very same people who today say that temps will go down next decade. See you in 10!

• Latitude says:

Alley..since you are a “we scientists”…
..can you please explain how using the best science…the models so spectacularly failed?

• Alley says:

The models from IPCC, including the first, and pretty much spot on.

Did you miss these simple facts? The models did a GREAT job. How else do you explain that the two of the past three years are ABOVE the center line of the model projections?

Answer: You can’t. Someone told you they failed, you believed them without any simple research. Will take you 5 minutes.

• Latitude says:

Post a link to the graph that shows that……

• Latitude says:

AMS Journals online…
January 2017
Comparing Tropospheric Warming in Climate Models and Satellite Data

when the most recent versions of satellite datasets are used, the previously claimed ratio of three between simulated and observed near-global TMT trends is reduced to approximately 1.7.

https://journals.ametsoc.org/doi/abs/10.1175/JCLI-D-16-0333.1

• Alley sez:

“The models from IPCC, including the first, and pretty much spot on.”

You should wear a climate T-shirt that says:
“I Am Clueless”.

• Alley says:

Richard needs a shirt that says “I mock people who know more than me.”

• MarkW says:

Alley needs a tee-shirt that says “Everything I know is wrong”.

• fonzie says:
• Two of the past three years were impacted by the very strong 2016 El. Niño event. The temperature anomaly has dropped 0.7 deg C since the 2016 peak. A proper model comparison would involve rerunning the models with actual atmospheric CO2 and CH4 concentrations, and by painting the grid in the Tropical pacific with the ENSO values from 2007 to 2017. But it seems nobody wants to check to see if the models even project well for 10 years.

• “rerunning the models with actual atmospheric CO2 and CH4 concentrations”
People have very strange ideas on how GCMs work. You can’t do that. You can prescribe initial values and boundary fluxes, and even distributed sources, but a GCM is about fluid transport with mass conservation. And you can’t “paint the grid”. AOGCMs model both air and ocean, with various fluxes at the surface which depend on the evolution in both domains. You can’t just “paint” stuff in.

It’s true that there are projects to develop decadal prediction, using recent initialization, rather than winding back, as GCMs usually do. It’s hard, and I don’t think progress is yet that good.

• fonzie says:

And yet, UAH shows no net warming in the last fifteen years…

• No. Trend since 2003 is about 1.2°C/Century, about the same as trend since 1979.

• Latitude says:

Which was about the same as the previous trend…that no one can explain

• Previous trend? In the lower troposphere? Tell us more.

• Latitude says:

wasn’t there a same trend from around 1900 to 1940? yeah, I know there were no satellites…..but warmest claim that same temp history too

• fonzie says:

Nick, i said NET warming. Besides, trend lines are worthless when dealing with transient events. Temps could dip below the anomaly of the pause and yet trend lines would indicate warming. (skeptics were making the same dopey argument that you’re making back in ’08 with the la nina cooling)…

• “Besides, trend lines are worthless when dealing with transient events.”
So how can you say that net warming is zero?

• Jeff Alberts says:

“So how can you say that net warming is zero?”

Net warming since when? Using 30 years is a cop out. Let’s go back 1000, 2000, 7000…

• fonzie says:

i can say it because the earth is no warmer than it was fifteen years ago…

• Richard M says:

Come on, Nick. Using ENSO to create a trend is anti-science nonsense. Is that all you’ve got?

• I didn’t choose the interval. The claim was zero warming in the last fifteen years. No, the warming (UAH V6) was 1.2 °C/century. If you don’t like the presence of El Nino, cherry-pick a different interval.

• Alley says:

And yet, UAH shows the same warming in the past 15 years, the same as ground stations.

• Latitude says:

I thought you were only concerned about the last 2-3 years?
UAH does show the same…flat for a decade…the a minute warming on the tag end
Did you miss the part where the models missed that decade?
…models astronomical failure

• Alley says:

“I thought you were only concerned about the last 2-3 years?”

• Latitude says:

obviously….because you keep quoting it
…and accusing other people of cherry picking

• Alley says:

YES! The author quotes three years. Why can’t I quote the author?

• Richard M says:

Alley, UAH shows no trend if you remove the effects of ENSO. I do get a chuckle out of people who claim to be scientists and who clearly doesn’t understand basic math.

May 2018 .18 C

May 2001 .20 C
May 2002 .25 C
May 2003 .21 C

• steven mosher says:

UAH does not have a great track record.
you cant even get the current code for their modelling of temperature. and they dont report structural uncertainty. bad.

• MarkW says:

Funny how this is only bad when other people do it.

• Funny how this is only bad when other people do it.

• Sunsettommy says:

The one where they project a .30C / decade warming rate, while the chart YOU linked to shows about half that. That means it is mostly a natural warming rate with very little CO2 effect to brag about.

You need to do some homework if you want to stop being ignorant of something the IPCC first published this temperature rate in 1990, TWENTY EIGHT years ago!

• Alley says:

Natural warming? What is causing the warming? It’s certainly not natural. If only natural, we would be slightly cooling.

Hold on to the word natural.

• fonzie says:

https://i.imgur.com/yvrMXFy.png

High solar activity correlates with warming, low solar activity correlates with cooling. Solar activity has been high in recent decades hence (natural) warming…

(alley kat, whate’er it is that yer smokin’ there, pass it o’er to me… ☺️)

• Alley says:

“Solar activity has been high in recent decades hence (natural) warming…”

Oh my. Since when did low solar activity (pretty low in the past few decades) suddenly become high? Up is down.

• fonzie says:

Folks, this guy is a LIAR. We had high solar activity all the way up to THIS decade. (either that or he’s too stoned to read a graph)…

• Sunsettommy says:

it is clear you have no argument, just noise.

You completely ignored the Per Decade warming rate projection from the IPCC.

You are indeed ignorant, and you CHOSE to be that way.

• Jeff Alberts says:

“Natural warming? What is causing the warming? It’s certainly not natural. If only natural, we would be slightly cooling.”

It was naturally warmer in the past during this interglacial, therefore we have no reason to believe the modest warming of the lat 150 years isn’t natural. You need to prove otherwise.

• MarkW says:

Alley, What caused the warming of 1000, 2000, 3000, 5000, and 20000 years ago.
The temperatures during those times were all warmer than today, Sometimes much warmer?

If you can’t specifiy a cause, how can you be so certain that it is impossible for the same factors to be acting now?

• “The one where they project a .30C / decade warming rate”
OK, show that please, and show what they actually do say. I suspect you, like many, are stuck on the 1990 FAR, where they projected an average of 0.30°C/decade over the next century, at the surface. Not for the next two decades in the troposphere. And, of course, that was in the early days of GCMs. The IPCC has a lot more up-to-date analysis, but you would never think of referring to that.

• Latitude says:

ok…I got it…..they didn’t know what they were talking about then
…but they do now

• In fact, in 1990, they said 0.3°C/decade, range 0.2 to 0.5, in their then scenario A. 0.2°C/decade with Scenario B, 0.1 with scenarios C and D (all with ranges). It’s true that as GCMs developed, that was able to be improved. That’s why people work on this stuff.

• Latitude says:

well, if they would quit claiming accuracy every time…only for it to change dramatically in the future….they wouldn’t have this credibility problem

It’s at the point, only some idiot would believe them now……..

• “only for it to change dramatically in the future”
It hasn’t changed dramatically in the future. People just don’t seem interested in what they actually said. There were scenarios, time intervals (a century), and a range of expected values. And nothing since is outside the range they quoted.

• Alley says:

I see that no cherry-picker would touch the IPCC projections vs where were are today.

There is a reason for that. The past few years actually exceeded the center line.

• Sunsettommy says:

Again you offer NOTHING , but noise.

Try posting something with actual evidence/numbers…..

• John F Pittman says:

In fact Nick, AR4 stated that 0.3 C/decade was expected for the next two decades. They also stated that a 0.2C minimum was already in the pipe. With BAU, approximately 0.3 C /decade would be expected for the past decade. Since the AR4 was specifically stating 2030 in terms of natural variation limits, the correct answer is yes, that the projection of 0.3C/decade has been invalidated at present. At 2030, if still invalidated, it will mean that natural variation was incorrectly minimized, or that the models’ sensitivities were to high. More importantly, it calls into question the attribution of natural versus anthropogenic and reduces the efficacy of the multiple lines of evidence.

• “In fact Nick, AR4 stated that 0.3 C/decade was expected for the next two decades.”

Why is it so hard to give a quote. Or at least a specific reference. The AR4 SPM (p 12) was quite explicit:

“For the next two decades a warming of about 0.2°C per decade is projected for a range of SRES emission scenarios.”

• Sunsettommy says:

You left out the REST of the projection

“…Even if the concentrations of all greenhouse gases and aerosols had been kept constant at year 2000 levels, a further warming of about 0.1°C per decade would be expected. ”

You are pathetic.

• You can’t read. They aren’t saying that it will be 0.2°C per decade, but if we do everything right, it will be 0.3°C per decade. They are saying that if we do everything right, it will be 0.1°C per decade. That is the committed warming.

In fact, of course, we did not keep all GHGs constant at year 2000 levels. So that bit doesn’t apply anyway.

• Alley says:

“You are pathetic.”

You can always spot the non-scientist. Insults are key.

• MarkW says:

Says the troll who has nothing but insults.

• John F Pittman says:

It is in the AR4 chapters and supplemental material; not in SPM. In the AR4 it is in 2 chapters and if you include attribution 3 or more chapters.

If Sunsettommy is correct, then depending on the wording and attribution in SPM, the estimate stands at 0.3C/decade. That “about” has a bit of play to it. Why not quote what the actual chapters state?

I agree about the calendar decades, as far as the chapters go. They gave a summary of this for 2030 in a supplemental graph and discussion pdf version.

• “It is in the AR4 chapters and supplemental material; not in SPM. In the AR4 it is in 2 chapters and if you include attribution 3 or more chapters.”
Well, for heavens sake, give a proper cite. Where?

The part in the SPM references Chap 10.3. They don’t give anything much more explicit in words, but they do show a graph (10.4). Here it is; I’ve added trend and marker lines:

https://s3-us-west-1.amazonaws.com/www.moyhu.org/2018/06/ar4.png

The brown line is 2°C/century, and is tangent to the scenario curves at 2000.The red line is 1 °/century and is tangent to the orange constant composition curve.

• steven mosher says:

no john. ar4… 0.2c

• John Pittman says:

Yes. I do remember, Thanks for the reminder.

• Sunsettommy says:

Typical Nick, who keeps getting behind the curve, try this from 2007 IPCC report:

“For the next two decades, a warming of about 0.2°C per decade is projected for a range of SRES emission scenarios. Even if the concentrations of all greenhouse gases and aerosols had been kept constant at year 2000 levels, a further warming of about 0.1°C per decade would be expected. ”

https://www.ipcc.ch/publications_and_data/ar4/wg1/en/spmsspm-projections-of.html

That was ELEVEN years ago!

• “For the next two decades, a warming of about 0.2°C per decade is projected for a range of SRES emission scenarios.”
They actually meant calendar decades, if you check with the section they refer to. But OK, for that period Jan 2008 to now, Hadcrut warmed at 0.285°C/decade.

• Alley
A tenth of a degree C., or two tenths,
of warming since 1980,
is just as likely to be measurement error,
as the alternative — a small, harmless variation
of temperatures that no one would notice
unless smarmy loud leftists (like you?)
kept bellowing that the world was coming
to an end from “climate change” !

• Alley says:

0.63°C since 1980, straight line. Definite warming.

• The UAH satellite data, which has far less infilling (wild guessing) than any compilation of surface data, shows the peak warm temperature in the year 1980 is less than two tenths of a degree C. cooler than the May 2018 average.

The UAH chart is above in these comments.

You cherry-picked a low point in 1979 to come to a different conclusion.

The 1998 El Nino peak was just 0.1 degree C.
cooler than the 2015/2016 El Nino peak.

Note that EL Nino (ENSO)
heat releases
are INCLUDED
in temperature charts,
even though they are
local events, not global,
and natural events, not man made,
and of course they have nothing
to do with CO2.

I’m really surprised you didn’t
use the 2015/2016 El Nino heat peak
as the end point of your own measurement,
because then you could have said +1.3 degrees C. !

• Alley says:

“cooler than the May 2018 average.”

CHERRY PICK!!!!!

• HotScot says:

Alley

Excellent!

Now the northern and southern hemispheres will warm a little at night and the equatorial regions will stay largely the same.

The vast areas of Canada and Russia currently under perma frost might be released to productive agricultural land to feed a growing global population.

Well, growing in the developing world because they have limited access to electricity, just burning wood and dung which will kill 120,000,000 inhabitants (WHO*) prematurely by 2050 (32 years away) from conditions caused by burning wood and dung to cook and heat with. BTW ‘prematurely’ frequently = kids.

But that’s OK, your comfortable existence will be maintained the more you shout and wave your arms about CO2 being the enemy, restricting these countries from receiving international funds to build the very fossil fuelled power stations you and your ancestors built your prosperity on.

The world id doomed, as long as you’re doomed last.

How very effing scientific of you.

*World Health Organisation

• jorgekafkazar says:

Can we hold you to that “See you in 10?” That will be plenty soon.

• Alley says:

1980s: I bet the next decade will be warmer than the current.
Winner
1990s: I bet the next decade will be warmer than the current.
Winner.
2000s: I bet the next decade will be warmer than the current.
Winner. We don’t even need to complete the next few years.
2010s: I bet the next decade will be warmer than the current.

• DonM says:

During any past or present decade: There has not been any reasonable correlation between CO2 concentration and temp.

2020’s: There will not be any reasonable correlation between CO2 and temp.

• Alley says:

Rise in CO2, rise in temps.

Se, not so hard, is it?

• MarkW says:

Over the last 100 years temperatures have gone up, temperatures have gone down and temperatures have held constant for decades. All while CO2 levels have risen.

Reality is a lot more complex than your mind appears to be able to handle.

• MarkW says:

Alley is another troll that believes that absent man, nothing would ever change.
Therefor if it’s warming, that alone is proof that man has caused it.

• MarkW says:

If it’s warming, it must be caused by CO2.

Yea, you’ve repeated that whopper quite a few times. I’m almost convinced that you actually believe it.

• steven mosher says:

except thats not the sat record. thats one data product with no reported uncertainties

• Ozonebust says:

Alley
Ocean heat removal leaves a trend in the temperature records.

Ocean heat release alters atmospheric mass and density. It is those trends that are not being recognised and recorded currently.

When only one metric is used, (temperature) you only get one dimension. Earths systems are multi dimensional, that is my area of interest.

The trends that I am recording are all declining having peaked around 2006. Yes some little upward spikes occur, cbut understanding the cause of those spikes is important.

Ocean heat release by water vapour is volumetric.
Regards

• Ian Macdonald says:
9. Bruce Cobb says:

“Can not the alarmist scientific folks (I’m thinking here of Mann, Alley, Schmidt, Hansen, etc.) be just a little bit honest about what is actually going on?”

Why start now?

• Alley says:

Why are you assuming that the super majority of climate scientists AND scientists in other disciplines who have all come to the same basic conclusions are wrong, and that the few remaining scientists who keep cherry picking to show otherwise are right?

• Latitude says:

Mostly because it no longer makes any sense………

• Alley says:

So where is the additional warming coming from?

• Latitude says:

I really don’t care….the only thing that would be scary..is the warmest idea that that temperature is supposed to be constant
Besides that…..no one has one single clue…our science is not there yet
….the rest of it is all lying hysterical hyperbole

• Alley says:

“is the warmest idea that that temperature is supposed to be constant”

OK, then. That is what no scientists ever has said, but I hear it all the time on sites like these.

• Latitude says:

That’s because we don’t believe anyone…..that has predicted nothing accurately so far……
Balls not in our court….balls in your court….prove it’s not natural

• Alley says:

So you believe the IPCC, who have consistently done a great job!

• Chris says:

False, the ball is not in our court. It’s in yours. You need to convince the world’s scientific organizations of your position. You don’t have to, of course, but then you’ll just be crowing about your position here on WUWT.

• fonzie says:

(the sun)…

• Alley says:

HA HA HA!!! The sun?

How does less solar irradiance mean more warming?

• fonzie says:

(there hasn’t been less solar irradiance)…

• fonzie says:

(ha ha ha)…

• Bruce Cobb says:

Why do you assume some “super majority” of scientists have come to “basic conclusions” honestly and scientifically? Oh wait, I know why – because you have guzzled the Klimate Koolade, and because you find the ideolgy to your liking.

• Alley says:

Sorry to hear about your Koolade habit. Makes you think the super majority of scientists are all in on an elaborate hoax. You know the odds of tat happening are about 1:1,000,000,000, right?

• fonzie says:

No, not necessarily an elaborate hoax, rather spectacular groupthink/bias/greed. (much like yourself)…

BTW, are you actually the Alley referred to in this post? (and i thought you were some lightweight troll)…

• Sweet Old Bob says:

Bingo !

• Alley says:

No, I wish I was that Alley.

• Sara says:

Why? Because, Alley, they get grant money for toeing the line of “manmade CO2 is the cause of it all”.

They fail to admit or recognize that the planet has gone through many, many climate changes when humans did NOT exist, but they blaming EVERYTHING on a gas that is generated ONLY PARTLY by humans. When they stick to the line that “it’s all the fault of H. Sapiens”, they are refusing to recognize any other influences of any kind that are natural, NOT man-made, and NOT something they can control.

• Alley says:

Is getting money from oil interests part of that equation?

• HotScot says:

Alley

You benefit from it, but we don’t see you throwing your plastic computer out the window.

Does that make you an oil harlot?

• Alley says:

I see. So the BEST program which was paid for by the Koch brothers is OK with you?

It was OK with me.

• MarkW says:

When reality doesn’t support your lies, just make up more lies.

• Sara says:

Can you read, Alley? I said GRANT money. I did not designate the source.

Furthermore, how would the oil industry benefit by funding research that wants to shut it down and put you and the rest of us OUT in the cold weather with no source of fuel for cooking or heating?

Don’t change the subject. I said GRANT money. In the USA science grants are funded by the NSF, a government agency, just as art grants are funded by the National Endowment for the Arts.

• Latitude says:

“Furthermore, how would the oil industry benefit by funding research that wants to shut it down and put you and the rest of us OUT in the cold weather with no source of fuel for cooking or heating?”

……….THIS

• Alley says:

They benefit because Heartland gives you people like Watts and Curry.

• MarkW says:

Once again, the troll has run out of ideas and has to instead make up lies to attack those who refuse to worship as it does.

• Jeff Alberts says:

“They benefit because Heartland gives you people like Watts and Curry.”

I assume you left a word or two out there. Anyway, do you have any evidence of your claim?

• fonzie says:

(no question, alley, money talks)…

• PiperPaul says:

Who pays *you*?

• Alley says:

*I* pay me. Well, technically my company pays me.

• Milocrabtree says:

You mean your Mom pays you. It’s called an allowance.

• Chris says:

Impressive, Milo, an insult that a high school kid would be embarrassed to trot out.

• milocrabtree says:

Your knowledge of high school thinking is awesome. We don’t get many high schoolers commenting here so your adolescent insight is quite welcome. Thanks for a different point of view.

• Chris says:

You’re right, Milo, it’s mainly geriatrics.

• milocrabtree says:

You sticking up for Alley is touching. Ineffective, but touching.

• Chris says:

Better than yours, which are light on substance AND light on creativity.

• milocrabtree says:

I’m clearly casting pearls before swine…

• MarkW says:

Chris, we’re just dealing at a level you capable of understanding.

• Chris says:

That is true, Mark, you are. One sentence posts with no supporting links – ever. That’s Mark’s level!

• Gary Pearse says:

Because it is profitable “to come this conclusion, Mr Alley and hazardous to your career if you dont buy in.

• Alley says:

Profitable would be the one who came to an opposite conclusion and proves it.

Still waiting.

• Pop Piasa says:

Funny, the proof is in front of you in the form of miserably failed models. You can’t see that, or are you waiting for that “delayed acceleration” that the trolls here touted several years back?

• Alley says:

Models have doen EXTREMEMLY well. How else do you get all IPCC models to be on target the last few years?

Impressive, if you’ve been paying attention.

• Alan Tomalty says:

ha ha ha ha ha Show me 1 model that has predicted anything correctly. The only one that comes close is the Russian one.

• Pop Piasa says:

May I also respectfully add that “conclusions” are not yet possible on this subject, which tends to get the alarmist camp much less traction among those of the general populace who are well informed on the subject. You are not helping your cause here, with all due respect.

• Alley says:

Conclusion: Earth is warming, CO2 is the primary forcing.

• Alley
Why would you care about what
government bureaucrat “scientists”
predict for the climate in 100 years,
when their predictions in the past
30 years were for triple the warming
that actually happened … and no one
predicted the flat trend from 2003
to 2015 … and no one predicted no change
in the average temperature of Antarctica
since the 1970s ?

of wrong predictions do you require
before you stop parroting the predictions

When you grow up, and gain more (some) wisdom,
you will find out that “experts” are worse at
predicting the future than laymen …
and laymen are really bad !

• Alley says:

“when their predictions in the past
30 years were for triple the warming
that actually happened”

Um, OK. SO since their projections were very accurate, and two of the past three years were ABOVE the projections at those points, then you’re going to have to change your gut feelings.

Welcome to the science!

• Sara says:

Wow, Alley, you ARE illiterate. You completely lack comprehension of what you just quoted.

Their predictions were wildly inaccurate, so tell me WHERE in that phrase you quoted did you get ‘VERY accurate’????

I am concerned that you quote things with no understanding. When something is quoted at 300% of the actual results, that is a vast FAILURE on the part of the forecaster.

• Alley says:

“Their predictions were wildly inaccurate,”

You really are aliterate. All you need to do is read. I gave a link above, shows that the models did extremely well.

Read something. Stop waving your hands around telling people that they are not accurate. I proved they were, you never showed otherwise.

• Sara says:

Alliterate? Not a bit, and certainly not in what I said, since ALLITERATE does not mean the same thing as ILLITERATE/

Alley is so busy finding ways to poke people purposelessly that there is no need to notice niggling nonsense.

That’s a little alliteration with a lot of information.

• “Alliterate?”
No. Illiterate that from your memory. He said aliterate.

• Alley says:

“ALLITERATE does not mean the same thing as ILLITERATE/”

Did you have to look that up?

No one has any idea what you just said …
including you !

MY CLIMATE BLOG FOR
people who don’t believe
a climate catastrophe is in progress,
because they have common sense:
Over 18,000 page views so far —
http://www.elOnionBloggle.Blogspot.com

• Alley says:

I will type slower next time. Not sure what you are having a problem with.

• MarkW says:

18K views? And you are proud of that?

• Latitude says:

” and two of the past three years”

LOL……they totally missed the bump
and the entire precious decade they blew it!

• Alley says:

Still warming, still at the projected rate. Only a cherry picker would be concerned about specific years.

Gee, what could be warming the earth?

• fonzie says:

(we were, but we aren’t warming)…

• Latitude says:

Alley> “Only a cherry picker would be concerned about specific years.”

Alley again> ” and two of the past three years were ABOVE the projections”

…and what happened in the decade before El Nino….
no model predicted that…not even close
If the models can’t predict something that obvious, they are worthless

• Alley says:

” and two of the past three years were ABOVE the projections”

I know. I wish the author would stop making predictions about the next few years, but since he failed, he should own up to it.

• HotScot says:

Richard Greene

Oi!

As a layman, I resent that remark. My predictions over the last 40 years have been pretty accurate i.e. eff all out the ordinary is happening climate wise.

• fonzie says:

(because scientists have been wrong before and will be wrong again)…

• commieBob says:

Why are you assuming that the super majority of climate scientists AND scientists in other disciplines who have all come to the same basic conclusions are wrong, …

First, we have to demonstrate that such a thing can happen. Exhibit A would be forty years of disastrously bad nutrition science. link In particular, good science was harshly suppressed.

Second, if climate science were completely solid, they wouldn’t have to resort to junk like Dr. Mann’s hockey stick to bolster it.

We find in climate science exactly the same mechanisms that beset nutrition science. For that reason I find a super majority of scientists utterly unconvincing.

10. Steven Mosher says:

“are presented as proof-positive that human burning of fossil fuels is causing the Earth to overly warm and therefore causing these melts…which will lead to coastal inundation…and we must therefore change our ways at any cost.”

Err no they are not presented as proof positive. Science is about evidence supporting a contingent conclusion. Physics tells us that more c02 will warm the planet. Physics also tells us that a warmer planet is likely to have less ice. Evidence. As for changing our way of life at any cost? Nope, nobody argues that.
Cutting back on c02 is not “any cost”. It is one cost. Expensive for sure.

You do better as an engineer if you dont use hyperbole.

• Richard Brimage says:

Steven, I have seen this assertion over and over. As one with a degree in physics I can understand the roots of the assertion. However I have a question for you since I trust your expertise in the field. Does this assertion make the assumption that nothing else changes? My experience in working with a single variable and making strong conclusions is you must consider all the variables in concert.

• Tom Dayton says:

Richard, climatologists have carefully considered the effects of many factors. A good and recent summary is an article written six months ago by Zeke Hausfather. An excellent animated graph was published by Bloomberg. A few years older is a post at SkepticalScience (read the Basic tabbed pane and then the Intermediate one). Michael Tobis explained how to properly interpret the IPCC reports’ statements on attribution. A good, brief explanation of the topic of attribution from 2010 is a post at RealClimate.

• Sunsettommy says:

This B.S. NEEDS to stop since you over educated fellas miss the simple evidence that utterly destroys the AGW conjecture.

Why persist in the lie?

• Pop Piasa says:

That stuff reads like the worship folder at the Model Fellowship of Mann, Church of Omnipotent Greenhouse In Carbon.You offer us circular thinking based on conjecture by folks supporting their own agendas.

• HotScot says:

Tom Dayton

Meantime, in the real world, the only empirical manifestation of increased atmospheric CO2 is that the planet has greened by 14%.

Anything else is conjecture, or what you would call computer models.

• HAS says:

Tom, thought this looks interesting, must read it through. Started with Hausfather and the first thing he does is produce a graph of Haustein’s global warming index against Berkeley Earth’s temp series and says:

“The combination of all radiative forcings generally matches longer-term changes in observed temperatures quite well. ….. There are also periods from 1900-1920 and 1930-1950 where some larger disagreements are evident between projected and observed warming, ….”

Since the index is created by regressing temp against forcings over the same period, I decided to give up at this point. An author that either didn’t know how the index was constructed (or worse still, did and was out to deceive), and knew so little about statistics didn’t know what a projection is.

• Tom Dayton says:

HAS, you completely missed the point of that graph, which is to decompose the temperature trend into components explained by (correlated with) several factors known from basic physics to influence temperature. Perhaps you should take an actual statistics class instead of pretending you know statistics.

• HAS says:

Tom, I’ve taken a few statistics classes in my time, and I sorry to say had you been one of my students you mightn’t have passed.

• Tom Dayton says:

HAS, I’ve taught several statistics classes in my time, including graduate ones.

• Teaching people how to lie with statistics is not something to be proud of.

• HAS says:

So you’ll understand about circularity and projections being inferences out of sample then. Why defend the indefensible? Regardless of what one might say about the construction of the index (and perhaps set a critique of that as an assignment for your class), Hausfather misrepresents it in his first comment. Polemic not science.

I am sorry my little attempt to defuse your abuse passed you by. I was making a pun on the fact that ‘take’ could mean ‘teach’, and the later was the meaning I was using it in, when you were rudely implying that even attending would be outside my competence. Do you get that now?

• Jeff Alberts says:

The fact that we’re presented with a single line purporting to be “global temperature” or “anomaly” makes it bogus from the start. You can’t average temperature readings from all over the place and expect a meaningful result. Intensive properties dude.

• Joel O’Bryan says:

that animated graph has model derived CO2 levels based on GHG theory, not the MLO measured CO2.
They had the computer program back calculate a CO2 based on temps. The way you can know that is subsequent years in their plot have lower CO2 levels than previous years average.

A total joke. Penultimate Fake science.

Wrong. Physics tell us CO2 is a GHG. Common sense tells us that will lead to warming. But it is alarmist models that tell us the planet will overheat, leading to massive ice loss, stronger, more frequent storms, crop losses, disease migration, polar bear extinction, etc. Models are not evidence. They are, as their creators honestly state, simply scenarios of what might happen if their thousand variable model of a non-linear, chaotic system are correct. There. Fixed it for ya.

• LOL@Klimate Katastrophe Kooks says:

Physics tells us no such thing. Remember, an efficient IR absorber is also an efficient IR emitter.

The warmists have constructed a very complex fantasy about how CO2 causes global warming… so complex that they probably never thought anyone would catch on to the very-well-hidden violation of 2Lot (2nd Law of Thermodynamics).
————————————————————
Let’s do a gedanken experiment:
—————
CO2’s ~15 micron absorption spectrum corresponds to a blackbody temperature of ~-80 C, which makes that an extremely low-energy (long wavelength) regime. It also happens to be a relatively energy-sparse region of the blackbody curve, given that there’s not a lot of matter radiating at ~-80 C.

So which do you think is more likely:

1} That CO2 is absorbing extremely low-energy photons, increasing its vibrational quantum state (and thus its collisional radiationless transition probability… because remember, for collisional radiationless transition to have a very high probability, the molecule must be highly excited… as you can see from the UMLT monoatomic oxygen in this study…
https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/2006JA011736
…such that it’s transferring its vibrational quantum state energy to the translational kinetic energy of other molecules…

or…

2} Other molecules with a much higher-energy (shorter wavelength) absorption spectrum absorbing photons of a higher energy level than that which CO2 can absorb, becoming vibrationally excited then transferring that energy to and via collision with CO2, which then undergoes emission relaxation by emitting a 15 micron photon (as outlined in the study I cited prior:
https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/2006JA011736

{HINT: #2 is the correct answer.}

In arguing for their position, the warmists are essentially arguing that energy is flowing from a lower-energy to a higher-energy regime… I think you can see the problem in that, yes? It’s a very sneaky and round-about way of violating 2Lot. Energy cannot flow from a lower-energy regime to a higher-energy regime.
————————————————————

There are four forms of molecular energy:
1} Electron quantum state (quantized potential energy)
2} Vibrational state (quantized kinetic energy)
3} Rotational state (quantized kinetic energy)
4} Translational energy (unquantized kinetic energy, the only energy which we can measure as temperature)

The time-independent Schrodinger equation treats translational kinetic energy separately from electron quantum state, vibrational quantum state and rotational quantum state because translational energy is the only energy which is not quantized.

The warmists have it exactly backward.

Remember back when they claimed that CO2 would cause stratospheric warming? That was because they were claiming that CO2 was absorbing a photon, increasing its vibrational quantum state, then transferring that vibrational (kinetic) energy to other molecular constituents of the atmosphere in the form of translational energy (the only form of molecular energy which we can measure as temperature). Since that sort of energy transfer has a probability distribution which depends upon molecular abundance, pressure and excitation level, it generally only happens at certain altitudes.

The warmists were claiming it happened in the stratosphere, but empirical observation proved them wrong.

When no stratospheric warming was empirically observed (indeed, the stratosphere cooled), they then switched to claiming that CO2 would cause the stratosphere to cool (to come into line with empirical observation), but it would cause the troposphere to warm… by the very same collisional radiationless transition mechanism… but they forgot that the wide absorption spectrum of water in the troposphere precludes there being many sufficiently energetic photons in the troposphere to sufficiently excite CO2’s vibrational quantum state to make the collisional radiationless transition probability very high. And they forgot that energy cannot flow from a lower-energy to a higher-energy regime… that violates 2LoT.

In reality, the reverse happens throughout the atmosphere (the process shown in the UMLT (upper mesosphere, lower thermosphere) in the above-cited study)… other molecular constituents absorb higher-energy photons, become vibrationally excited and transfer that energy to CO2 via collisional radiationless transition, whereupon CO2 undergoes emission relaxation by emitting a 15 micron photon.

We know that CO2 is not undergoing collisional radiationless transition and thereby increasing the translational kinetic energy of other molecules because the emission spectrum for CO2 is sharply defined, not a quasi-continua:

https://en.wikipedia.org/wiki/Collision-induced_absorption_and_emission
“Molecular fly-by collisions take little time, something like 10^-13 s. Optical transition of collisional complexes of molecules generate spectral “lines” that are very broad – roughly five orders of magnitude broader than the most familiar “ordinary” spectral lines. The resulting spectral “lines” usually strongly overlap so that collision-induced spectral bands typically appear as continua (as opposed to the bands of often discernible lines of ordinary molecules).”

So in fact, other molecular constituents of the atmosphere absorb radiation at a region of the blackbody curve which is higher-energy and less-sparse, become vibrationally excited, collide with CO2, the CO2 becomes excited and emits a low-energy ~15-micron photon.

Given that the mean free path length for the IR emitted by CO2 increases with increasing altitude, the net vector for that emitted IR is upward.

That’s why CO2 has been shown to cause cooling throughout the atmosphere, except for a very slight amount of warming at the tropopause:

https://co2islife.files.wordpress.com/2017/01/spectralcoolingrates_zps27867ef4.png

You’ll further hear warmists talking about increasing CO2 atmospheric concentration causing a widening of the ‘shoulders’ of the purported absorption band of CO2… but take a look at the image above.

You are looking downward on those ‘shoulders’, and you can see that CO2 causes cooling… so a widening of those ‘shoulders’ as CO2 atmospheric concentration increases means it’ll cause cooling at a wider band of frequencies. And as CO2 atmospheric concentration increases, you’ll see the center of that rainbow of colors labeled ‘CO2’ go toward even more extreme cooling.

This utterly destroys the entire underlying basis for CAGW. It cannot continue to exist as a reasonable hypothesis. It has been nullified.

Thus dies CAGW… in reality, CO2 causes global cooling (as has been empirically observed in several studies which you can Google for yourself if you’re so inclined… they’re all publicly available), and more of it will cause more global cooling.

So CO2 acts as a negative feedback to the completely natural warming the planet had recently experienced. That forcing has ended, the planet is now cooling, and as CO2 atmospheric concentration continues to increase, it will exacerbate the cooling.

That’s why the planet never went into runaway warming back when CO2 levels were as much as 20 times higher than today, and in fact when CO2 was that high, an ice age started. That ice age lasted until the CO2 had sufficiently rock-weathered out of the atmosphere to allow warming.

• Clyde Spencer says:

You said, ““Molecular fly-by collisions take little time, something like 10^-13 s. ” This sounds like a description of Mosher’s activity here.

• Steve Keohane says:

Yes, the mosher molecule, and brownian motion. The latter could be taken as a double entendre.

• WBWilson says:

Excellent synopsis, LOL@Klimate Katastrophe Kooks.

It is refreshing to see some actual physics based reasoning. This should help make it clear that the condensing GHG (H2O) is preeminent in the formation of the self-organizing dissipative structures (which we call weather). It is these structures that disseminate the energy from the sun over the whole earth. CO2 is only ever a bit player, of little relevance and opposite sign.

http://rammb.cira.colostate.edu/ramsdis/online/images/latest/goes-west_goes-east/goes-west_full_disk_water_vapor.gif

• WBWilson says:

P.S.- LOL, I don’t think you will see any replies from Mosher, Stokes, Alley, Silber or any of the common trolls here.

• Phil. says:

A synopsis which opens with:

“CO2’s ~15 micron absorption spectrum corresponds to a blackbody temperature of ~-80 C, which makes that an extremely low-energy (long wavelength) regime. It also happens to be a relatively energy-sparse region of the blackbody curve, given that there’s not a lot of matter radiating at ~-80 C.”

shows anything but ‘actual physics based reasoning’.
CO2’s ~15 micron absorption spectrum corresponds to a region near the maximum radiance of the blackbody curve at a temperature of 288K.

• Jim Masterson says:

>>
CO2’s ~15 micron absorption spectrum corresponds to a region near the maximum radiance of the blackbody curve at a temperature of 288K
<<

According to Wien’s displacement law, the maximum of a BB curve at 288K is 10.06 microns.

• teerhuis says:

The maximum of a BB curve at 288 K in the frequency spectrum, inversed to wavelength, is at 17.7 µm. Energy has an even distribution in that spectrum.

• teerhuis says:

Last sentence should be: ‘Energy is linearly distributed in that spectrum.’
In a spectrum with uniform energy distribution the maximum of 288 K radiation is at 13.1 µm.

So the maximum depends on which distribution you choose.
For 288 K the distributions according to wavelength, energy, frequency give maxima (expressed as wavelength) at resp. 10.1, 13.1 and 17.7 µm.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“A synopsis which opens with:

‘CO2’s ~15 micron absorption spectrum corresponds to a blackbody temperature of ~-80 C, which makes that an extremely low-energy (long wavelength) regime. It also happens to be a relatively energy-sparse region of the blackbody curve, given that there’s not a lot of matter radiating at ~-80 C.’
shows anything but ‘actual physics based reasoning’.
CO2’s ~15 micron absorption spectrum corresponds to a region near the maximum radiance of the blackbody curve at a temperature of 288K.”

You were saying?

• Phil. says:

Phil wrote:
“A synopsis which opens with:

‘CO2’s ~15 micron absorption spectrum corresponds to a blackbody temperature of ~-80 C, which makes that an extremely low-energy (long wavelength) regime. It also happens to be a relatively energy-sparse region of the blackbody curve, given that there’s not a lot of matter radiating at ~-80 C.’
shows anything but ‘actual physics based reasoning’.
CO2’s ~15 micron absorption spectrum corresponds to a region near the maximum radiance of the blackbody curve at a temperature of 288K.”

You were saying?

Yes, I was saying that the absorption spectrum of CO2 has nothing to do with the temperature of a black body emitter!
To put you straight the CO2 absorption spectrum is centered on the energy separation between the ground state vibrational energy level and the excited vibrational level (v=1). It corresponds to an energy separation of 7.98 kJ/mole (667 cm^-1). The BB radiation being emitted by the surface at a temperature of ~288K peaks at 565cm^-1 with a spectral radiance of 0.136 W/m^2/sr/cm^-1, the spectral radiance at the center of the CO2 absorption band is 0.131 W/m^2/sr/cm^-1.
You’re right about there being not much radiance at -80ºC, the spectral radiance in that case is 0.041 W/m^2/sr/cm^-1.

• LOL@Klimate Katastrophe Kooks says:

Now let’s flip the argument on its head, Phil… what is the absorption spectrum of CO2? Is it not the same as the emission spectrum?

So therefore, per quantum physics, CO2 cannot absorb any radiation except on those CO2 spectrum brightlines, and as you stated, the spectral radiance in that case is extremely low.

So the method by which you warmists are claiming CO2 causes atmospheric heating cannot take place, except for a mere 0.041 W/m^2/sr/cm^-1.

In other words, Phil, you’ve just proven my point that the warmists have the process exactly backward. Is that what you wanted to do? LOL

• Phil. says:

Now let’s flip the argument on its head, Phil… what is the absorption spectrum of CO2? Is it not the same as the emission spectrum?

So therefore, per quantum physics, CO2 cannot absorb any radiation except on those CO2 spectrum brightlines, and as you stated, the spectral radiance in that case is extremely low.

Actually I said no such thing, I said that the CO2 spectrum absorbs at ~96% of the peak of a 288K blackbody (131/136)

So the method by which you warmists are claiming CO2 causes atmospheric heating cannot take place, except for a mere 0.041 W/m^2/sr/cm^-1.

So you’re still trying to spout the nonsense that the earth’s surface is emitting at a temperature of -80ºC

In other words, Phil, you’ve just proven my point that the warmists have the process exactly backward. Is that what you wanted to do? LOL

Actually I’ve just proved you don’t have a clue about the subject!

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“You’re right about there being not much radiance at -80ºC, the spectral radiance in that case is 0.041 W/m^2/sr/cm^-1.”

LOL@Klimate Katastrophe Kooks wrote:
“So therefore, per quantum physics, CO2 cannot absorb any radiation except on those CO2 spectrum brightlines, and as you stated, the spectral radiance in that case is extremely low.”

Phil trips over himself:
“Actually I said no such thing…”

Phil… you do yourself a great disservice in proffering a dishonest stance. You’re better than that, Phil. Don’t resort to outright lies so early after having lost the argument. LOL

• Phil. says:

Phil wrote:
“You’re right about there being not much radiance at -80ºC, the spectral radiance in that case is 0.041 W/m^2/sr/cm^-1.”

LOL@Klimate Katastrophe Kooks wrote:
“So therefore, per quantum physics, CO2 cannot absorb any radiation except on those CO2 spectrum brightlines, and as you stated, the spectral radiance in that case is extremely low.”

Phil trips over himself:
“Actually I said no such thing…”

Exactly as I keep telling you your idiotic stance that CO2 can only absorb radiation emitted by an object at -80ºC is total nonsense. Such an object doesn’t emit much radiance but it’s irrelevant because everywhere on the planet except the S Pole in winter is emitting far more 15µm photons. In fact as I said above at the average temperature of 288K the radiance is ~95% of the peak value.

• LOL@Klimate Katastrophe Kooks says:

Now, Phil. We all know I said no such thing, so your attempt at FUD’ing things up just isn’t going to work.

I specifically stated that CO2 absorbs at 15 um. I also specifically stated that 15 um photon flux is negligible in comparison to the flux of shorter-wavelength photons. I also specifically stated that the molecules absorbing those shorter-wavelength photons are already more vibrationally excited than CO2 could ever hope to make them, therefore your arguing for the warmist CAGW mantra (that CO2 absorbs a 15 um photon, becomes vibrationally excited, collides with other molecular constituents of the atmosphere and thereby increases their translational kinetic energy (temperature)) means you’re arguing against the 2nd Law of Thermodynamics… namely that energy cannot flow from a lower-energy regime to a higher-energy regime.

Why do you persist in your science denialism, Phil? Is it because you’re trying to defend liberalism’s title of “The Party For Dummies”? LOL

• “I also specifically stated that 15 um photon flux is negligible in comparison to the flux of shorter-wavelength photons.”
And that is just totally wrong. Here again is that observed Barrow Alaska spectrum. It shows downwelling IR at the surface. Since it doesn’t seem to be getting through to you, I have marked 15 μm with a red line and the intensity at 15 μm with a green arrow. It is not negligible. It is close to peak.

https://s3-us-west-1.amazonaws.com/www.moyhu.org/2018/06/PettyFig8-2.jpg

• LOL@Klimate Katastrophe Kooks says:

Now superpose the two, Nick. Did you forget the effects of water vapor in your desperate attempt to attribute the spectral curve to CO2? LOL

• Water vapor has nothing to do with it. Here is your statement again:
“I also specifically stated that 15 um photon flux is negligible in comparison to the flux of shorter-wavelength photons.”
Just stupidly, provably wrong.

• LOL@Klimate Katastrophe Kooks says:

Nick Stokes denies that water vapor absorbs in the same frequency bands as CO2! How’s that science-denialism working for you, Nick? LOL

Do try to think tangentially, Nick. [SNIP] LOL

Now Nick, do you deny that the spectral curve expands upward and leftward upon a temperature increase?
You’ll note that photon energy increases going leftward.

So while the low-energy long-wavelength photon absolute count does indeed increase, the proportion of low-energy to high-energy photons falls with increasing temperature.

[SNIP]

If temperature is increasing, and higher-energy photon flux is proportionally increasing, do you suppose the other molecular constituents of the atmosphere are already more vibrationally excited due to vibronic coupling than CO2 could ever hope to make them?

What’s this say, Nick?
“Since electronic transitions are very fast compared with nuclear motions, vibrational levels are favored when they correspond to a minimal change in the nuclear coordinates. The intensity of a vibronic transition is proportional to the square of the overlap integral between the vibrational wavefunctions of the two states that are involved in the transition.”

Didn’t you know that homonuclear diatomic molecules are only approximated as rigid rotors with a fixed bond length because that makes solving the time-independent Schrodinger equation simpler, Nick? That’s what leads simpletons to state that homonuclear diatomic molecules cannot absorb photons because those simpletons think the homonuclear diatomic molecule’s dipole moment never changes. So they think the molecule can never become vibrationally excited.

Didn’t you know that molecular vibrational quantum state energy can only be approximated as a harmonic oscillator near the ground state, but for excited molecules in the real world, they have anharmonic potentials (the restoring force is no longer proportional to the square of the displacement from the equilibrium position)?

So in your simplistic world, nitrogen (being a homonuclear diatomic molecule) cannot under any circumstances absorb photons and therefore can never become excited except by collision! Isn’t that what Phil stated? Isn’t that what every warmist believes, Nick?

Now Nick… you’ve agreed with Phil (and you obviously agree with the warmist position), so you’re now forced to defend both your and his position.. the warmist position.

What’s this say, Nick?
“In the case of nitrogen, the 1 s electrons are screened and localized, so their orbitals do not overlap effectively. In turn, the remaining 10 valence electrons occupy molecular orbitals resulting from mixing the atomic orbitals 2s and 2p, including s–p interactions due to their proximity. The discrete electron energy structure of the molecule is furthermore split into the superimposed fine spectrum of vibrational states. Because each electronic state is characterized by a different bond length and strength due to the various electron distributions, the molecular oscillator will have a variety of potential energy curves associated with distinctive vibrational states, each with a range of differently spaced vibrational levels. The molecule also has quantized rotational degrees of freedom complicating even more the energy level diagram. However, these levels are much closer than the vibrational levels, such that they form only a band spectrum.”

[SNIP]

[No mocking is necessary in polite conversation. Please make your technical points without resorting to insults. -mod]

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“So you’re still trying to spout the nonsense that the earth’s surface is emitting at a temperature of -80ºC”

That’s kind of the point, Phil. I’m arguing that it’s *not* emitting much at that temperature, therefore there aren’t many 15 um photons for CO2 to absorb, therefore the entire premise for how you warmists claim CO2 to cause atmospheric heating cannot take place as you claim.

But as you said, it is “nonsense that the earth’s surface is emitting at a temperature of -80ºC”.

So you’ve been backed into yet another corner, from which you’re forced to agree with me.

If you’re trying to defend warmism, you’re utterly incompetent at it, Phil. LOL

• Phil. says:

Phil wrote:
“So you’re still trying to spout the nonsense that the earth’s surface is emitting at a temperature of -80ºC”

That’s kind of the point, Phil. I’m arguing that it’s *not* emitting much at that temperature,

You’re right it isn’t, but since the earth’s surface isn’t at -80ºC it is irrelevant!

• LOL@Klimate Katastrophe Kooks says:

Do you deny that 15 um photon flux is negligible in comparison to shorter-wavelength photon flux, Phil?

Do you deny that atmospheric molecules which absorb those shorter-wavelength photons are already more vibrationally excited than CO2 could ever hope to make them, Phil?

You’re still arguing against 2LoT, Phil. I’ve presented heaps of evidence that you’re wrong (including discussing the physics of how a CO2 laser works… by the same principle which applies in the free atmosphere), yet you persist in trying to squirm away from reality.

You’ve already argued from the perspective that water vapor causes cooling, what makes it so difficult for you to admit that CO2 does the same?

Do the warmists have a metaphorical gun to your head, Phil? [Snip] LOL

• Phil. says:

Do you deny that 15 um photon flux is negligible in comparison to shorter-wavelength photon flux, Phil?

Under what circumstances?

Do you deny that atmospheric molecules which absorb those shorter-wavelength photons are already more vibrationally excited than CO2 could ever hope to make them, Phil?

Which molecules and which photons?
The three major species in the atmosphere can’t be vibrationally excited (N2, O2, Ar).

You’re still arguing against 2LoT, Phil. I’ve presented heaps of evidence that you’re wrong (including discussing the physics of how a CO2 laser works… by the same principle which applies in the free atmosphere), yet you persist in trying to squirm away from reality.

You made a garbled attempt at copying how a CO2 laser works from a book and made mistakes and the same principle does not apply in the free atmosphere.

You’ve already argued from the perspective that water vapor causes cooling, what makes it so difficult for you to admit that CO2 does the same?

It certainly does, in the stratosphere; the reasons for the strong cooling effect shown by water vapor in the troposphere as shown in the figure you presented from Clough and Iacono were clearly explained in their paper. You couldn’t be bothered to read them, a bit careless on your part.

Do the warmists have a metaphorical gun to your head, Phil? Be a man, stand up for the truth, for once in your rotten life. LOL

Mods: Is the above consistent with site policy?
“Respect is given to those with manners, those without manners that insult others or begin starting flame wars may find their posts deleted.”

[The above is absolutely not consistent with site policy. The unacceptable portions of this conversation are being snipped, and warnings are being issued. Please rest assured that continued behavior by the offending party will result, first in moderation, and then banning (if politeness and respectability cannot be maintained). We apologize for the delay in addressing this conversation…just saw these posts this morning. -mod]

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“The three major species in the atmosphere can’t be vibrationally excited (N2, O2, Ar).”

What’s this say, Phil?
“In the case of nitrogen, the 1 s electrons are screened and localized, so their orbitals do not overlap effectively. In turn, the remaining 10 valence electrons occupy molecular orbitals resulting from mixing the atomic orbitals 2s and 2p, including s–p interactions due to their proximity. The discrete electron energy structure of the molecule is furthermore split into the superimposed fine spectrum of vibrational states. Because each electronic state is characterized by a different bond length and strength due to the various electron distributions, the molecular oscillator will have a variety of potential energy curves associated with distinctive vibrational states, each with a range of differently spaced vibrational levels. The molecule also has quantized rotational degrees of freedom complicating even more the energy level diagram. However, these levels are much closer than the vibrational levels, such that they form only a band spectrum.”

It says your [Snip] view of how the world works is wrong, Phil. LOL

[Snip]

[If you’re incapable of making your point without resorting to insults, then don’t post. -mod]

• Phil. says:

[The above is absolutely not consistent with site policy. The unacceptable portions of this conversation are being snipped, and warnings are being issued. Please rest assured that continued behavior by the offending party will result, first in moderation, and then banning (if politeness and respectability cannot be maintained). We apologize for the delay in addressing this conversation…just saw these posts this morning. -mod]

Thanks

• Phil. says:

Mod: This is the most offensive but you have to know British english to know that!
Phil, you pedantic twat.

• LOL@Klimate Katastrophe Kooks says:

Now you’ll have to explain how a 15 micron photon (corresponding to a blackbody temperature of ~-80 C) is warming an atmosphere at 288 K (~14.85 C).

Or do you believe the Laws of Thermodynamics can be nullified to further your religious belief in CAGW?

• LOL@Klimate Katastrophe Kooks says:

LOL@Klimate Katastrophe Kooks wrote:
“Now you’ll have to explain how a 15 micron photon (corresponding to a blackbody temperature of ~-80 C) is warming an atmosphere at 288 K (~14.85 C).

Or do you believe the Laws of Thermodynamics can be nullified to further your religious belief in CAGW?”

Phil, can you get your crickets to pipe down a bit? I’m trying to sleep. LOL

• “Now you’ll have to explain how a 15 micron photon (corresponding to a blackbody temperature of ~-80 C) is warming an atmosphere at 288 K (~14.85 C).”
This is a silly argument. A 15 μm photon does not “correspond” to a BB temperature of -80°C. That is simply the maximum of the BB spectrum if the units are spectral radiance per unit wavelength. But the spectrum is quite broad. With those units, the Wien formulation is indeed
T = b/λ, where b = 2.898e-3 m K
and as your calculator says, with λ=15 μm, that is 193.2 K.

But if it is expressed as flux per unit frequency, the Wien maximum is
T = bf/λ, where bf = 5.099e-3 m K
giving a temperature of 340 K. This is what Phil. and teerhuis are using.

Both are valid, and as teerhuis says, the frequency version has the virtue that it corresponds to energy. All it means is that the max of the spectrum has no special significance. It doesn’t mean that photons can’t heat air at normal temperature. In fact, CO₂ lasers at 10 μm are used for thermally cutting steel, even though the corresponding peak is at b/1e-5=290K.

Just to check the calculation there, as teerhuis says, for 17.7 μm the peak is at 288K.

• Jim Masterson says:

>>
Just to check the calculation there, as teerhuis says, for 17.7 μm the peak is at 288K.
<<

If you are getting different answers from the same law, then the math isn’t correct.

Wien’s displacement law for frequency is:
$\displaystyle {{\nu }_{\max }}=T\times 1.04\times {{10}^{11}}Hz/K$

Plugging in 288K gives us:
$\displaystyle {{\nu }_{\max }}=2.9952\times {{10}^{13}}Hz$

Converting to seconds:
$\displaystyle \frac{1}{{{\nu }_{\max }}}=3.3387\times {{10}^{-14}}sec$

And converting to wavelength:
$\displaystyle {{\lambda }_{\max }}=(3.3387\times {{10}^{-14}}sec)\centerdot (299,792,458\ m/\sec )=10.01microns$

That’s pretty close to my previous calculation.

Jim

• “If you are getting different answers from the same law, then the math isn’t correct.”
No. It’s very well known that in spectral matters, you can use frequency or wavelength on the x-axis. And it makes a difference to the maximum, which is why claiming that there is a unique temperature related to a wavelength makes no sense. The difference is spelt out here, with a calculator. For 288K it shows:

https://s3-us-west-1.amazonaws.com/www.moyhu.org/2018/06/wien.png

• LOL@Klimate Katastrophe Kooks says:

It’s only a “silly argument”, Nick, because you don’t understand enough to understand that you’re wrong. You’ve obviously never studied quantum physics… if you had, you’d understand how wrong you are.

Was Niels Bohr just blowing smoke up everyone’s butt when he introduced quantization, Nick?
https://i.imgur.com/JSmRism.png

No. You’re just misapplying the Wien formula because you lack the knowledge necessary to properly use the tools available. Somewhat akin to you warmists attempting to hammer the CAGW nail with a red herring. LOL

Is CO2 a blackbody emitter, Nick? You appear to believe that it is (as do Phil and teerhuis), which highlights your lack of knowledge of quanta, the underlying premise of quantum mechanics.

Why do we speak of the 15 um brightline for CO2, Nick, if CO2 is a blackbody emitter with a wide emission spectrum? Oh, that’s right… because it’s not a blackbody emitter… so you can’t use the Wien formula to calculate a blackbody curve for maximum energy flux… the energy flux is all centered around that brightline. That’s how quantum mechanics works, Nick.

Here’s CO2, Nick:
https://i.imgur.com/iozZLeB.png
https://i.imgur.com/fy8JWZw.png

Is that a “spectrum” for CO2, Nick? No? No. Quantum mechanics dictates that atoms and molecules, when excited, emit very specific wavelength photons.

Why, you even (unwittingly) had the answer in your own question above, Nick! Do you even understand where?

Of course, you knew already that what you were spouting was utter BS, Nick… why would you speak of brightlines in the CO2 spectrum (such as at 15 um, right, Nick?), then turn around and claim that using the Wien formula to calculate a blackbody curve for maximum energy flux is perfectly acceptable, when you know full well that CO2 emits in brightlines?

Or are you merely confused, Nick?

Educate yourself, Nick. You’re making a fool of yourself.

• Phil. says:

No. You’re just misapplying the Wien formula because you lack the knowledge necessary to properly use the tools available. Somewhat akin to you warmists attempting to hammer the CAGW nail with a red herring. LOL

Actually it was your original post which misapplied the Wien equation and you got all bent out of shape when I corrected your mistake.

Is CO2 a blackbody emitter, Nick? You appear to believe that it is (as do Phil and teerhuis).

I certainly do not as is clear from my earlier post. I guess you realized that you misapplied the Wien equation and are trying to wriggle out of it.

This is what you said: “CO2’s ~15 micron absorption spectrum corresponds to a blackbody temperature of ~-80 C, which makes that an extremely low-energy (long wavelength) regime”

• LOL@Klimate Katastrophe Kooks says:

[Snip] matter other than CO2 will emit at 15 um when it’s temperature is at ~-80 C.

But as you said in your being forced to agree with my original post, the spectral radiance in that region is extremely sparse.

Now, Phil… if the spectral radiance in that region is extremely sparse, just how is the warmist claim (that CO2 is absorbing photons, becoming vibrationally excited, colliding with other molecular constituents of the atmosphere, and transferring its vibrational quantum state kinetic energy to the translational energy (which we measure as temperature) of those other molecular constituents via radiationless collisional transfer) going to work?

Stop dodging the question, Phil.

• Phil. says:

Matter other than CO2 emits at 15µm at a whole range of temperatures and at the surface temperature of 288K it emits much more than at -80ºC. That’s the stupid idea you need to get out of your head. Look here for example:

http://hyperphysics.phy-astr.gsu.edu/hbase/imgmod/bbrc4b.gif

You’ll see that 15000nm (15µm) is emitted as an increasing function of temperature.

• LOL@Klimate Katastrophe Kooks says:

Only when viewed in terms of total photon flux at 15 um, Phil.

When viewed in relation to total photon flux of all photons, the 15 um photon flux proportionally falls with increasing temperature.

Do you deny that 15 um photon flux is negligible in comparison to shorter-wavelength photon flux, Phil?

Do you deny that atmospheric molecules which absorb those shorter-wavelength photons are already more vibrationally excited than CO2 could ever hope to make them, Phil, therefore the mechanism by which you warmists claim CO2 causes warming cannot occur?

Stop evading those hard questions, Phil. The fate of your religious belief in CAGW hangs in the balance. LOL

• LOL@Klimate Katastrophe Kooks says:

Further, Nick, your lack of knowledge of how laser cutting works is on full display, as is your desperate attempt at diverting the conversation from atmospheric CO2 quantum physics via non sequitur.

A laser cutter cannot cut steel without using a laser gas, which is usually pure oxygen. Now Nick… what happens to steel when thermally excited in a pure oxygen environment? It burns, Nick. It literally burns.

The laser isn’t “cutting” the steel, it’s merely facilitating an exothermic chemical reaction which causes the steel to burn.

The reason they use CO2 lasers, rather than shorter-wavelength lasers, is because CO2 lasers have a higher gain and thus allow a higher energy input than other lasers (pump:output can be as high as 20%)… we simply couldn’t make a more powerful UV laser until recently. The CO2 laser was developed in 1964, giving it a development head start. And it’s not pure CO2… it’s a mixture of CO2, N2, H2 or Xe, and He.

But take a look at this, Nick:
https://en.wikipedia.org/wiki/Carbon_dioxide_laser
“The population inversion in the laser is achieved by the following sequence: electron impact excites vibrational motion of the nitrogen. Because nitrogen is a homonuclear molecule, it cannot lose this energy by photon emission, and its excited vibrational levels are therefore metastable and relatively long-lived. Collisional energy transfer between the nitrogen and the carbon dioxide molecule causes vibrational excitation of the carbon dioxide, with sufficient efficiency to lead to the desired population inversion necessary for laser operation.”

Just as I described happens in the atmosphere, happens in a CO2 laser, Nick! You’ve just demonstrated my point. Thanks, Nick. You’re a real pal. LOL

• Phil. says:

But take a look at this, Nick:
https://en.wikipedia.org/wiki/Carbon_dioxide_laser
“The population inversion in the laser is achieved by the following sequence: electron impact excites vibrational motion of the nitrogen. Because nitrogen is a homonuclear molecule, it cannot lose this energy by photon emission, and its excited vibrational levels are therefore metastable and relatively long-lived. Collisional energy transfer between the nitrogen and the carbon dioxide molecule causes vibrational excitation of the carbon dioxide, with sufficient efficiency to lead to the desired population inversion necessary for laser operation.”

Just as I described happens in the atmosphere, happens in a CO2 laser, Nick! You’ve just demonstrated my point. Thanks, Nick. You’re a real pal. LOL

Except the N2 absorption line required is a forbidden transition and so the N2 level can’t be optically excited that’s why in a CO2 laser an electronic discharge is used to excite that level. Can’t happen in the atmosphere (except perhaps in a lightning strike).

• LOL@Klimate Katastrophe Kooks says:

Now Phil is claiming that the N2 molecule can determine how it was vibrationally excited, and only undergo certain types of relaxation for certain types of excitation!

[Snip]

• Phil. says:

Now Phil is claiming that the N2 molecule can determine how it was vibrationally excited, and only undergo certain types of relaxation for certain types of excitation!

My, your fantasy world is certainly a rich one, Phil.

It’s not a fantasy world, it’s called quantum mechanics, you appear to be unfamiliar with it. Homonuclear diatomics such as N2 don’t have a dipole and can’t be vibrationally excited by radiation. They can be excited by an electronic discharge which is how the N2 in the CO2 laser is excited.

• LOL@Klimate Katastrophe Kooks says:

The Principles of Lasers, 5th Edition says you’re wrong, Phil. I suggest you review what I’d written prior:

Now Phil, what does this say:
http://www.kinetics.nsc.ru/chichinin/books/Chem_Phys/Svelt09.pdf#page=458

“Finally the higher vibrational levels of N2 are also closely resonant with the corresponding CO2 levels, and transitions between the excited levels and the 001 level of the CO2 molecule occur rapidly.”

Why, that says the vibrational quantum states of N2 are closely resonant with the corresponding CO2 levels! Do you think that relationship somehow magically changes in the free atmosphere, Phil?

So while the lowest N2 transition is indeed electric-dipole forbidden, that transition isn’t purposely used in a CO2 laser!

Again quoting the Principles of Lasers, 5th Edition:
“Note that, since the 01 – 00 transition is the least energetic transition in any of the molecules in the discharge, relaxation from the 01 level can only occur by transferring this vibrational energy to translational energy of the colliding partners (VT relaxation). From the theory of elastic collisions we then know that energy is most likely to be transferred to the lighter atoms, i.e., to helium in this case.”

The higher vibrational levels of N2 *are* used (see the first quote above)… and they’re optically allowed.

Don’t you feel silly now, Phil? LOL

• LOL@Klimate Katastrophe Kooks says:

[Snip]

Phil wrote:
“It’s not a fantasy world, it’s called quantum mechanics, you appear to be unfamiliar with it. Homonuclear diatomics such as N2 don’t have a dipole and can’t be vibrationally excited by radiation.”

https://journals.aps.org/pra/abstract/10.1103/PhysRevA.96.043422
“Combining with theoretical calculation, our results demonstrate that both vibrational and electronic excitation occurs for ionized nitrogen molecules in 800-nm femtosecond laser fields.”

That’s 0.8 um photons, Phil, just on the infrared side of the visible spectrum. It is also the strongest output range of the Sun’s total irradiance spectrum. That reaches all the way down through the entire atmosphere, Phil.

https://i.imgur.com/guLIdlR.png

https://i.imgur.com/Z5PnG9F.png

But… but… but Phil, you said N2 cannot be vibrationally excited by photons under any circumstances! [Snip]

• Phil. says:

My reply to this trolling appears to have gone astray, so I’ll try again.
Phil, you said N2 cannot be vibrationally excited by photons under any circumstances! How, oh how, Phil, are you going to recovery from this, your greatest loss of credibility to date? LOL

It’s quite apparent that you haven’t the faintest clue about quantum mechanics, Phil. LOL
Oh I know a lot about QM, you on the other hand just post any paper you find which you think might fit and don’t read past the title. It’s not my credibility that’s at stake.
A minor detail to you I’m sure but this isn’t about vibrationally excited N2 it’s about Nitrogen ions (N2+) created by an intense laser beam.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Oh I know a lot about QM”

Says the guy who claims that N2 cannot, under any circumstances, become vibrationally excited.

Don’t you know about vibronic coupling of the electronic quantum state to the vibrational quantum state, Phil?

What’s this say, Phil?
“In the case of nitrogen, the 1 s electrons are screened and localized, so their orbitals do not overlap effectively. In turn, the remaining 10 valence electrons occupy molecular orbitals resulting from mixing the atomic orbitals 2s and 2p, including s–p interactions due to their proximity. The discrete electron energy structure of the molecule is furthermore split into the superimposed fine spectrum of vibrational states. Because each electronic state is characterized by a different bond length and strength due to the various electron distributions, the molecular oscillator will have a variety of potential energy curves associated with distinctive vibrational states, each with a range of differently spaced vibrational levels. The molecule also has quantized rotational degrees of freedom complicating even more the energy level diagram. However, these levels are much closer than the vibrational levels, such that they form only a band spectrum.”

It says your [snip] view of how the world works is wrong, Phil. LOL

[Snip]

• Phil. says:

Phil wrote:
“Oh I know a lot about QM”

Says the guy who claims that N2 cannot, under any circumstances, become vibrationally excited.

Didn’t say that, it can’t be excited by absorbing a photon corresponding to the vibrational energy level. I clearly stated that it can be excited by an electronic collision such as in the CO2 laser.

Don’t you know about vibronic coupling of the electronic quantum state to the vibrational quantum state, Phil?

Yes.

What’s this say, Phil?

It says that the N2 molecule has discrete electronic, vibrational and rotational energy levels, what it does not say is how transitions between those levels can be achieved which is the point.

It also says that your [Snip] view of how the world works which you acquired from Wikipedia and googling is wrong, Kook.

• LOL@Klimate Katastrophe Kooks says:

LOL@Klimate Katastrophe Kooks wrote:
“Says the guy who claims that N2 cannot, under any circumstances, become vibrationally excited.”

Phil wrote:
“Didn’t say that…”

Phil previously wrote:
“The three major species in the atmosphere can’t be vibrationally excited (N2, O2, Ar).”

I’ll leave it up to the reader to draw their own conclusions about Phil.

• Phil. says:

The readers will no doubt note that the “under any circumstances” was added by you. They will no doubt then draw their own conclusions about you.

• LOL@Klimate Katastrophe Kooks says:

You’re being pedantic, Phil. You didn’t state any exceptions to your wholly manufactured “rule”. “Can’t be vibrationally excited” isn’t really open to interpretation, wouldn’t you say?

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Didn’t say that, it can’t be excited by absorbing a photon corresponding to the vibrational energy level.”

So Phil denies that N2 can undergo nonresonant Raman scattering in his stating that N2 has a net electric dipole and thus cannot be excited by radiation, and he specifically denies above that N2 can undergo resonant Raman scattering (a subset of Raman scattering where the incident photon just so happens to correspond to the difference between two vibrational energy levels).

Unbelievable… this is the same guy who’s stated emphatically that he knows a lot about Raman scattering… but who couldn’t accurately describe the process, and simultaneously admitted and denied that it occurred for N2. LOL

Of course, we all know that N2 can undergo Raman scattering… including Phil. He’s just confused, is all. LOL

• LOL@Klimate Katastrophe Kooks says:

Seriously, Phil. Think about what you write before you write it.

It matters not how the N2 molecule becomes vibrationally excited, it’ll transfer its vibrational quantum state kinetic energy to the other molecular constituents of the atmosphere (whether that atmosphere is in the… erm… atmosphere, or in a CO2 laser) via collisional radiationless transition.

Now Phil… can you think of any ways a N2 molecule may become vibrationally excited in the free atmosphere? Perhaps by impinging upon a warmer surface?

• LOL@Klimate Katastrophe Kooks says:

Eh, the forum mangled my last reply, so let’s try that again:

Finally, Phil, stop being so literal. A ‘forbidden transition’ is as ‘forbidden’ as you lead people to believe. It merely violates the selection rules.

Now Phil, what does this say:
http://www.kinetics.nsc.ru/chichinin/books/Chem_Phys/Svelt09.pdf#page=458

“Finally the higher vibrational levels of N2 are also closely resonant with the corresponding CO2 levels, and transitions between the excited levels and the 001 level of the CO2 molecule occur rapidly.”

Why, that says the vibrational quantum states of N2 are closely resonant with the corresponding CO2 levels! Do you think that relationship somehow magically changes in the free atmosphere, Phil?

So while the lowest N2 transition is indeed electric-dipole forbidden, that transition isn’t purposely used in a CO2 laser!

Again quoting the Principles of Lasers, 5th Edition:
“Note that, since the 01 – 00 transition is the least energetic transition in any of the molecules in the discharge, relaxation from the 01 level can only occur by transferring this vibrational energy to translational energy of the colliding partners (VT relaxation). From the theory of elastic collisions we then know that energy is most likely to be transferred to the lighter atoms, i.e., to helium in this case.”

The higher vibrational levels of N2 *are* used (see the first quote above)… and they’re optically allowed.

[Snip]

• LOL@Klimate Katastrophe Kooks says:

Should be “A ‘forbidden transition’ isn’t as ‘forbidden’ as you lead people to believe.”

• Phil. says:

Finally, Phil, stop being so literal. A ‘forbidden transition’ is as ‘forbidden’ as you lead people to believe. It merely violates the selection rules.

This makes no sense.

Now Phil, what does this say:
http://www.kinetics.nsc.ru/chichinin/books/Chem_Phys/Svelt09.pdf#page=458

“Finally the higher vibrational levels of N2 are also closely resonant with the corresponding CO2 levels, and transitions between the excited levels and the 001 level of the CO2 molecule occur rapidly.”

Why, that says the vibrational quantum states of N2 are closely resonant with the corresponding CO2 levels! Do you think that relationship somehow magically changes in the free atmosphere, Phil?

It certainly does since in our atmosphere we lack the necessary electrical discharges to excite the N2 to its first vibrational level.

So while the lowest N2 transition is indeed electric-dipole forbidden, that transition isn’t purposely used in a CO2 laser!

It certainly is, it’s responsible for the collisional excitation to the CO2 001 state. In order for the CO2 to lase there needs to be a population inversion so the 100 and 020 lower levels need to be deactivated and this is enhanced by the collisional deactivation with helium. The 010 level is the excited state that occurs as a result of FIR excitation in the atmosphere.

You’ll see the energy diagram below:
https://image.slidesharecdn.com/laser-150713091919-lva1-app6892/95/laser-16-638.jpg?cb=1436779386

Again quoting the Principles of Lasers, 5th Edition:
“Note that, since the 01 – 00 transition is the least energetic transition in any of the molecules in the discharge, relaxation from the 01 level can only occur by transferring this vibrational energy to translational energy of the colliding partners (VT relaxation). From the theory of elastic collisions we then know that energy is most likely to be transferred to the lighter atoms, i.e., to helium in this case.”

The higher vibrational levels of N2 *are* used (see the first quote above)… and they’re optically allowed.

The transitions referred to here are the CO2 transitions to the ground state referred to above. (020-010)

[Snip]

• LOL@Klimate Katastrophe Kooks says:

[Snip]

https://www.rp-photonics.com/forbidden_transitions.html
“Dipole-forbidden transitions between energy levels may nevertheless occur based on other mechanisms such as quadrupole transitions.”
You’ll note that “such as quadrupole transitions” doesn’t denote solely quadrupole transitions, Phil, you pedantic twat. LOL

“forbidden transitions of isolated atoms or ions can have upper-state lifetimes of milliseconds or even many seconds”

According to Phil, once those atoms are in an upper-state, they just have to stay there… forever. LOL

Further, the lowest N2 transition in a CO2 laser is used to fully de-excite the N2 molecule via collision with He, after it’s collided with CO2. This is why the He must be cooled for population inversion to be a continuous process. It is not “responsible for the collisional excitation to the CO2 001 state”, Phil.

That’s why I wrote:
‘Again quoting the Principles of Lasers, 5th Edition:
“Note that, since the 01 – 00 transition is the least energetic transition in any of the molecules in the discharge, relaxation from the 01 level can only occur by transferring this vibrational energy to translational energy of the colliding partners (VT relaxation). From the theory of elastic collisions we then know that energy is most likely to be transferred to the lighter atoms, i.e., to helium in this case.”’

[Snip]

• Phil. says:

“forbidden transitions of isolated atoms or ions can have upper-state lifetimes of milliseconds or even many seconds”

According to Phil, once those atoms are in an upper-state, they just have to stay there… forever. LOL

Yeah they just sit there waiting for a collision. 🙂

Further, the lowest N2 transition in a CO2 laser is used to fully de-excite the N2 molecule via collision with He, after it’s collided with CO2. This is why the He must be cooled for population inversion to be a continuous process. It is not “responsible for the collisional excitation to the CO2 001 state”, Phil.

You have it completely backwards, the N2 molecule is excited to its first vibrationally excited state by an electronic discharge. That excited N2 collides with a CO2 molecule exciting it to its 001 vibrational state and deactivating the N2. The CO2 then emits photons (lases) and falls to either the 100 or 020 vibrational states which are collision ally deactivated to the ground state.

That’s why I wrote:
‘Again quoting the Principles of Lasers, 5th Edition:
“Note that, since the 01 – 00 transition is the least energetic transition in any of the molecules in the discharge, relaxation from the 01 level can only occur by transferring this vibrational energy to translational energy of the colliding partners (VT relaxation). From the theory of elastic collisions we then know that energy is most likely to be transferred to the lighter atoms, i.e., to helium in this case.”’

Yes you copied that but not for the first time you misunderstood what you read and thought it was the N2 states that were being deactivated!

You keep making a fool of yourself, Phil. Are all warmists gluttons for punishment, or are you speshul? LOL

Clearly it’s not me who’s being foolish. (except perhaps for wasting my time with someone who clearly doesn’t have a clue about the subject and is probably boring everyone to tears.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Yeah they just sit there waiting for a collision.”

They could (but don’t). That doesn’t explain the fact that homonuclear diatomics have an upper state lifetime… even isolated molecules. Didn’t you read what I wrote, Phil? How do you explain the upper state lifetime of an isolated homonuclear diatomic, Phil?

Here’s a question, Phil: Why is the sky blue?

Could it be Rayleigh scattering of molecular nitrogen and oxygen (which includes elastic scattering as well as the inelastic contribution from rotational Raman scattering ), Phil?

For homonuclear diatomics under an IR photon flux, vibrational quantum state-Raman coupling is enhanced significantly due to vibrational resonance, Phil.

[Snip]

Phil claims the sky isn’t blue, because he doesn’t know about inelastic scattering! How’s that science denialism working for you, Phil? LOL

[Um, I’m pretty sure you literally just made up this claim “out of blue” right now. -mod]

As regards a CO2 laser, helium provides elastic collisions, not inelastic ones, Phil. Thus the increased elastic collision rate provides a greater randomization rate. It does not “deactivate to the ground state” CO2… that’s what laymen are lead to believe [Snip]. It increases the translational kinetic energy per inelastic mean free path. This *raises* the effective vibrational excitation cross-section (the ‘electron temperature’) to the optimum 1.8 eV necessary for population inversion to occur in a CO2 laser. In other words, Phil, it *depopulates* the lower energy level and thus supports the population inversion. It also cools the lasing medium, which is why the helium must be cooled for population inversion to be a continuous process.

See:
Roles of Helium and Nitrogen in CO2 Laser Excitation
Offenberger, Rose
Journal of Applied Physics 41, 3908 (1970)

Hey, Phil, I thought you said N2 cannot absorb photons under any circumstances because it’s a homonuclear diatomic with no net electric dipole, and therefore is optically forbidden. How, then, do you explain a microwave-excited CO2 laser, Phil? Are you claiming microwave radiation is not mediated by photons, Phil? LOL

Optimization of Microwave-Excited CO2 Laser System and Generation of Pulsed Optical Discharges in Strong Magnetic Fields
https://docserv.uni-duesseldorf.de/servlets/DerivateServlet/Derivate-2178/178.pdf

[Snip]

• Phil. says:

Still flailing around with more and more ridiculous rants I see.

Here’s a question, Phil: Why is the sky blue?

Could it be Rayleigh scattering of molecular nitrogen and oxygen (which includes elastic scattering as well as the inelastic contribution from rotational Raman scattering ), Phil?
Exactly, absolutely nothing to do with the absorption of photons and relies on the polarizability of the molecule. Raman is extremely weak, its signal about 1000 times weaker than Rayleigh and depends on 1/wavelength^4 which is why blue is scattered more effectively than red.

Phil claims the sky isn’t blue, because he doesn’t know about inelastic scattering! How’s that science denialism working for you, Phil? LOL

More nonsense from the ‘proud troll’.

As regards a CO2 laser, helium provides elastic collisions, not inelastic ones, Phil. Thus the increased elastic collision rate provides a greater randomization rate. It does not “deactivate to the ground state” CO2…

Certainly does, that’s how the population inversion is maintained, populate the upper level by collisional excitation by N2 and depopulate the lower level.
Notable that the ‘proud troll’ references the first link that a Google search finds for ‘the role of He in CO2 lasers’, which is a letter to the editor dating back to 1969! You’d think he could find something more substantial given the almost 50 years of development and use of CO2 lasers. His previous error in stating that the helium deactivated the lower excited state on N2 originates with an error in the Wikipedia page on CO2 lasers!
Notice in the energy diagram of the laser process how it states that He deactivates the 020 and 010 levels exactly as I described. Also see that the N2 excited state is at almost the exact energy as the 001 CO2 level (that’s why the energy transfer process is termed ‘resonant’). In order to excite the CO2 molecule the N2 molecule has to transfer all its energy and to return to its ground state, there is no energy in a ‘lower excited N2 state’ to be transferred to the He.
https://image.slidesharecdn.com/laser-150713091919-lva1-app6892/95/laser-16-638.jpg?cb=1436779386

Last but not least:

Hey, Phil, I thought you said N2 cannot absorb photons under any circumstances because it’s a homonuclear diatomic with no net electric dipole, and therefore is optically forbidden. How, then, do you explain a microwave-excited CO2 laser, Phil? Are you claiming microwave radiation is not mediated by photons, Phil? LOL

CO2 is not N2, nor is it a homonuclear diatomic!

What we have in the ‘proud troll’ is a troll who googles the topics, posts the first one he finds and posts it without reading it (doesn’t much matter because he doesn’t understand it any way). Not a good source for reliable science.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Exactly, absolutely nothing to do with the absorption of photons and relies on the polarizability of the molecule. Raman is extremely weak, its signal about 1000 times weaker than Rayleigh and depends on 1/wavelength^4 which is why blue is scattered more effectively than red.”

Raman scattering, according to Phil, has “absolutely nothing to do with the absorption of photons”! Unbelievable.

Did you forget that for homonuclear diatomics under an IR photon flux, vibrational quantum state-Raman coupling is enhanced significantly due to vibrational resonance, Phil?

LOL@Klimate Katastrophe Kooks wrote:
“Hey, Phil, I thought you said N2 cannot absorb photons under any circumstances because it’s a homonuclear diatomic with no net electric dipole, and therefore is optically forbidden. How, then, do you explain a microwave-excited CO2 laser, Phil? Are you claiming microwave radiation is not mediated by photons, Phil? LOL”

Phil wrote:
“CO2 is not N2, nor is it a homonuclear diatomic!”

Now, Phil, just who are you trying to fool here? What gasses are used in a CO2 laser, Phil?

I thought you said N2 cannot absorb photons under any circumstances because it’s a homonuclear diatomic with no net electric dipole, and therefore is optically forbidden. How, then, do you explain a microwave-excited CO2 laser, Phil?

Phil wrote:
“there is no energy in a ‘lower excited N2 state’ to be transferred to the He.”

Vibrational spectra of N2: An advanced undergraduate laboratory in atomic and molecular spectroscopy
http://users.df.uba.ar/dmitnik/estructura3/articulostrabajo/vibrationalN2.pdf
“In the case of nitrogen, the 1 s electrons are screened and localized, so their orbitals do not overlap effectively. In turn, the remaining 10 valence electrons occupy molecular orbitals resulting from mixing the atomic orbitals 2s and 2p, including s–p interactions due to their proximity. The discrete electron energy structure of the molecule is furthermore split into the superimposed fine spectrum of vibrational states. Because each electronic state is characterized by a different bond length and strength due to the various electron distributions, the molecular oscillator will have a variety of potential energy curves associated with distinctive vibrational states, each with a range of differently spaced vibrational levels. The molecule also has quantized rotational degrees of freedom complicating even more the energy level diagram. However, these levels are much closer than the vibrational levels, such that they form only a band spectrum.”

You’ll especially note the text: “Because each electronic state is characterized by a different bond length and strength due to the various electron distributions, the molecular oscillator will have a variety of potential energy curves associated with distinctive vibrational states, each with a range of differently spaced vibrational levels.”

Did you forget about vibronic coupling again, Phil?

• Phil. says:

LOL@Klimate Katastrophe Kooks wrote:
“Hey, Phil, I thought you said N2 cannot absorb photons under any circumstances because it’s a homonuclear diatomic with no net electric dipole, and therefore is optically forbidden. How, then, do you explain a microwave-excited CO2 laser, Phil? Are you claiming microwave radiation is not mediated by photons, Phil? LOL”

Phil wrote:
“CO2 is not N2, nor is it a homonuclear diatomic!”

Now, Phil, just who are you trying to fool here? What gasses are used in a CO2 laser, Phil?

I thought you said N2 cannot absorb photons under any circumstances because it’s a homonuclear diatomic with no net electric dipole, and therefore is optically forbidden. How, then, do you explain a microwave-excited CO2 laser, Phil?

If you actually read the thesis you linked to you’d find that the laser was not microwave-excited rather it was a microwave amplifier.
“The beamline system consists of a Q-switched CO2 laser oscillator, a beam expander, and a microwave-excited CO2 laser amplifier. ”

Phil wrote:
“there is no energy in a ‘lower excited N2 state’ to be transferred to the He.”

Vibrational spectra of N2: An advanced undergraduate laboratory in atomic and molecular spectroscopy
http://users.df.uba.ar/dmitnik/estructura3/articulostrabajo/vibrationalN2.pdf

You’ll especially note the text: “Because each electronic state is characterized by a different bond length and strength due to the various electron distributions, the molecular oscillator will have a variety of potential energy curves associated with distinctive vibrational states, each with a range of differently spaced vibrational levels.”

Did you forget about vibronic coupling again, Phil?

No, but we’re not talking about electronically excited N2 so it’s not relevant. As I have pointed out a few times the vibrationally excited N2 (by electronic discharge) gives up its energy to the CO2 and falls back to its ground state, hence no energy left to give up to the He.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“If you actually read the thesis you linked to you’d find that the laser was not microwave-excited rather it was a microwave amplifier.”

A microwave amplifier is a laser, Phil, it just has its feedback suppressed (or doesn’t have an optical cavity), and its output is fed into the Q factor-modulated CO2 laser.

You’ll note both the amplifier and the laser were, by definition, CO2 lasers.

“microwave-excited CO2 laser amplifier”
“Q-switched CO2 laser oscillator”

• LOL@Klimate Katastrophe Kooks says:

mod wrote:
“[Um, I’m pretty sure you literally just made up this claim “out of blue” right now. -mod]”

Phil wrote:
“Homonuclear diatomics such as N2 don’t have a dipole and can’t be vibrationally excited by radiation.”

Without Raman scattering (which results in vibrational excitation of homonuclear diatomics, and which also exhibits a substantially increased vibrational quantum state-Raman cross-section under IR photon flux) in the atmosphere, the sky would be more purplish. So no, I didn’t make it up “out of the blue”.

That’s why astrophysicists using differential optical absorption spectroscopy must account for Vibrational Raman Scattering (VRS) via a corrective spectra in determining the molecular constituents of the atmospheres of exoplanets.

While O2 (also a homonuclear diatomic) and water vapor causes much more in-filling of Fraunhofer lines than N2, the warmists are arguing that the process simply doesn’t exist for homonuclear diatomics. While scientists first thought VRS was inconsequential, it was found that satellite limitations prevented retrieval of accurate data at wavelengths beyond 0.431 um for strong Fraunhofer in-filling.

• Phil. says:

As pointed out above a 15 micron photon has nothing to do with -80ºC. Any 15 micron photon carries the same amount of energy, 7.98 kJ/mole, regardless of the temperature of its emitter. Whether it is absorbed has nothing to do with the Laws of Thermodynamics, if the energy exactly matches the separation between the currently occupied energy level and another higher level then the photon will be absorbed.
In most cases the atmosphere will be cooler than the surface so your appeal to the LoT is moot.

Hopefully some scientific facts will help to nullify your religious belief in ‘fake’ science and get you to actually read the papers you link to.

• LOL@Klimate Katastrophe Kooks says:

Yes, Phil… the Wien formula is just a fairy tale made up to confuse warmists. LOL

A 15 um photon isn’t going to be emitted by any matter on this planet unless it’s extremely cold. You yourself have said the spectral radiance in that region is extremely sparse. So you’ve been forced into a corner and now you’re in agreement with me on that point, at least.

Now, Phil… if the spectral radiance in that region is extremely sparse, just how is the warmist claim (that CO2 is absorbing photons, becoming vibrationally excited, colliding with other molecular constituents of the atmosphere, and transferring its vibrational quantum state kinetic energy to the translational energy (which we measure as temperature) of those other molecular constituents via radiationless collisional transfer) going to work?

Once again, you’ve proven my point. You’re really not very good at this, Phil. LOL

• Phil. says:

Yes, Phil… the Wien formula is just a fairy tale made up to confuse warmists. LOL

It appears to confuse you, it just relates the shape of the bb emission curve to temperature.

A 15 um photon isn’t going to be emitted by any matter on this planet unless it’s extremely cold. You yourself have said the spectral radiance in that region is extremely sparse.

On the contrary 15 µm photons will be emitted everywhere on this planet even at the S Pole! There will be more emitted in the hotter regions.

300……………………0.150
288……………………0.131
273……………………0.108
250……………………0.077
200……………………0.029

So you’ve been forced into a corner and now you’re in agreement with me on that point, at least.

Not in a corner at all, just astounded how little you understand about the subject and continue to pontificate about it!

Now, Phil… if the spectral radiance in that region is extremely sparse, just how is the warmist claim (that CO2 is absorbing photons, becoming vibrationally excited, colliding with other molecular constituents of the atmosphere, and transferring its vibrational quantum state kinetic energy to the translational energy (which we measure as temperature) of those other molecular constituents via radiationless collisional transfer) going to work?

Again your myth that 15µm photons can only occur at -80ºC is the origin of your complete misunderstanding of the physics. As I’ve pointed, out such photons are emitted from the whole earth’s surface, the hotter it is the more there are.

Once again I’ve proved your ideas to be false

• LOL@Klimate Katastrophe Kooks says:

Phil states:
It is “nonsense that the earth’s surface is emitting at a temperature of -80ºC”.

Phil trips over himself again:
“On the contrary 15 µm photons will be emitted everywhere on this planet even at the S Pole! There will be more emitted in the hotter regions.”

You seem confused, Phil. That’s four times you’ve tripped over yourself. LOL

Phil wrote:
“Again your myth that 15µm photons can only occur at -80ºC”

Phil… resorting to dishonesty is no way to win an argument. Where have I ever stated that?

Now as to your statement that 15 um photons are being emitted everywhere… of course they are, for the simple reason that more photons of all wavelengths are being emitted for a given increase in temperature… for a blackbody emitter.

Is soil a blackbody emitter, Phil? Soil exhibits increasing reflectance with increasing wavelength from the visible through the mid-IR ranges.

Is water a blackbody emitter, Phil? LWIR penetration is measured in nanometers, and water is SW selective.

Is snow a blackbody emitter, Phil? It is highly reflective to radiation centered around 0.5μm, yet highly absorbing to radiation centered around 10μm. Dry snow is highly reflective, whereas wet snow is a strong absorber/emitter.

You know… the stuff that makes up the great majority of the surface of the planet. Not exactly a blackbody… which is why all the models which attempt to apply the Stefan-Boltzmann Law to the planet fail miserably.

“You’re right about there being not much radiance at -80ºC, the spectral radiance in that case is 0.041 W/m^2/sr/cm^-1.”

Even at 288 K, the 15 um photon flux is tiny in comparison to the shorter-wavelength photons being emitted.

And that still doesn’t account for the fact that the same relationship between N2’s vibrational quantum states and CO2’s vibrational quantum states (a close resonance such that N2 tends to transfer its vibrational kinetic energy to CO2 via collisional radiationless transition) which occurs in a CO2 laser also takes place in the free atmosphere.

In your arguing for the opposite process taking place, you warmists are arguing that a lower-energy photon is being absorbed by CO2, that CO2 becomes vibrationally excited, it collides with other molecules and increases their translational kinetic energy, causing heating of molecules which are already absorbing much higher-energy photons (and are thus much more vibrationally excited than CO2). That violates 2LoT, Phil, no matter how much you try to obfuscate the issue with straw men, sidelines and outright lies.

In reality, CO2 doesn’t cause atmospheric warming, but instead causes cooling (just as it does in a CO2 laser, Phil), just as you now admit water vapor does… in fact, CO2 accounts for ~48 W/m^2 worth of OLR.

https://i.imgur.com/RJ7bHgm.png

• Phil. says:

Phil wrote:
“Again your myth that 15µm photons can only occur at -80ºC”

Phil… resorting to dishonesty is no way to win an argument. Where have I ever stated that?

Here are three times:

“You moron, matter other than CO2 will emit at 15 um when it’s temperature is at ~-80 C.”

“A 15 um photon isn’t going to be emitted by any matter on this planet unless it’s extremely cold. ”

“CO2’s ~15 micron absorption spectrum corresponds to a blackbody temperature of ~-80 C, which makes that an extremely low-energy (long wavelength) regime. It also happens to be a relatively energy-sparse region of the blackbody curve, given that there’s not a lot of matter radiating at ~-80 C.”

• “The laser isn’t “cutting” the steel, it’s merely facilitating an exothermic chemical reaction which causes the steel to burn.”
Red hot steel doesn’t burst into flame. The laser had to get it very hot before cutting could happen. And as your link says, it is also used for welding, which doesn’t involve combustion. If CO2 emission can do that, I think it can warm the atmosphere.

“A 15 um photon isn’t going to be emitted by any matter on this planet unless it’s extremely cold. You yourself have said the spectral radiance in that region is extremely sparse”

Absolute nonsense. Here are two real, measured spectra, from Barrow Alaska. They are taken over a thawing ice-field at about 268K. They are in wave number, so 15 μm is 667 cm⁻¹. You can see looking up from ground that that is a region of peak emission from the air. And looking down from 20 km, it is part of the bite that CO₂ takes out, so that it shows as if emitted from about 225K (TOA, rather than in the atmospheric window region (8-14 μm) which comes at the intensity appropriate for ground emission (268K).

https://s3-us-west-1.amazonaws.com/www.moyhu.org/2010/05/PettyFig8-2.jpg

• LOL@Klimate Katastrophe Kooks says:

Still attempting to non sequitur your way out of this, Nick? LOL

I didn’t say it “burst into flames”, Nick. I stated that the steel burns, as in “it’s an exothermic chemical reaction”. I explicitly stated same in my prior post.

https://www.acsys.de/en/laser-cutting/laser-burn-cutting.html
“Oxygen is used as the cutting gas for laser burn cutting. The laser penetrates into the metal and heats the material up. The oxygen is blown into the cutting joint at pressures of up to 6 bar. Then the heated metal reacts with the oxygen, thereby releasing more energy. The energy input is significantly increased by the exothermic reaction. This way, laser burn cutting allows high cutting speeds and the processing of thick metal sheets.”

What would you call an exothermic oxidative reaction involving oxygen, Nick, other than ‘burning’? I’m sure you’ve seen metal burn before, Nick… think along the lines of lighting a steel-wool pot scrubber. It *burns*.

Now as to your “CO2 lasers are hot, so CO2 can heat the atmosphere”… do you not realize that in the ‘atmosphere’ of the lasing chamber, it is CO2 which is acting as a ‘coolant’ by emitting radiation? The same thing happens in the free atmosphere, regardless of the method by which N2 originally becomes vibrationally excited.

Do you not realize that N2’s vibrational quantum states are closely resonant to CO2’s vibrational quantum states such that N2 tends to transfer its vibrational kinetic energy to CO2 (which then undergoes emission relaxation by emitting a photon), just as the Principles of Lasers, 5th Edition states?

“The laser penetrates into the metal and heats the material up.”
“Now you’ll have to explain how a 15 micron photon (corresponding to a blackbody temperature of ~-80 C) is warming an atmosphere at 288 K”
Now we have 10 μm photons (corresponding on your Wien formula to 17°C) heating steel to ignition temperature. Or melting in the case of welding.

And you still haven’t backed up your claim that “A 15 um photon isn’t going to be emitted by any matter on this planet “ in the face of measured spectra that show that it certainly is.

• LOL@Klimate Katastrophe Kooks says:

Nick Stokes demonstrates his inability to grok energy density. LOL

[Snip…although you do get a couple points for using “grok”, your tone and insulting approach to this conversation are not acceptable for this site. -mod]

• LOL@Klimate Katastrophe Kooks says:

And yet the warmist trolls can come onto the site daily and trash the science which proves that CO2 does not and cannot cause atmospheric warming, simply because they’ve bought a simplistic scientific viewpoint (and scads of manipulated data) pushed by ‘scientist’ activists with an agenda?

I say it’s time to take the kid gloves off and start treating them like the science-denying enemies of reality that they are.

Reality has so mauled the warmists that CAGW is already mortally wounded and writhing as it bleeds out. Let’s put CAGW out of its misery once and for all. It’s the humane thing to do.

• Phil. says:

The same thing happens in the free atmosphere, regardless of the method by which N2 originally becomes vibrationally excited.

Do you not realize that N2’s vibrational quantum states are closely resonant to CO2’s vibrational quantum states such that N2 tends to transfer its vibrational kinetic energy to CO2 (which then undergoes emission relaxation by emitting a photon), just as the Principles of Lasers, 5th Edition states?
So if you pass an electric discharge through the air to pump up the N2 to its excited state you could get some 10.6 micron emissions. However, that’s the only way you could excite the nitrogen since it’s not accessible by absorbing radiation. So no the same thing does not happen in the free atmosphere.

• LOL@Klimate Katastrophe Kooks says:

I’ve already proven you wrong on this point, Phil. N2 can indeed be vibrationally excited by photon absorption.

———-
Ooopsie, Phil. Seems you’re doing what you do best again… pulling “facts” straight from your sun-don’t-shine. LOL

Phil wrote:
“It’s not a fantasy world, it’s called quantum mechanics, you appear to be unfamiliar with it. Homonuclear diatomics such as N2 don’t have a dipole and can’t be vibrationally excited by radiation.”

https://journals.aps.org/pra/abstract/10.1103/PhysRevA.96.043422
“Combining with theoretical calculation, our results demonstrate that both vibrational and electronic excitation occurs for ionized nitrogen molecules in 800-nm femtosecond laser fields.”

That’s 0.8 um photons, Phil, just on the infrared side of the visible spectrum. It is also the strongest output range of the Sun’s total irradiance spectrum. That reaches all the way down through the entire atmosphere, Phil.

https://i.imgur.com/guLIdlR.png

https://i.imgur.com/Z5PnG9F.png

But… but… but Phil, you said N2 cannot be vibrationally excited by photons under any circumstances! How, oh how, Phil, are you going to recovery from this, your greatest loss of credibility to date? LOL

It’s quite apparent that you haven’t the faintest clue about quantum mechanics, Phil. LOL
———-

• LOL@Klimate Katastrophe Kooks says:

https://courses.lumenlearning.com/introchem/chapter/homonuclear-diatomic-molecules/
“Diatomic molecules have quantized energy levels for rotation and vibration.”

If a molecule’s got a quantized energy level for its vibration and a fluctuation in dipole moment, there’s going to be a photon of a sufficient energy to match the transition energy gap and thus vibrationally excite the molecule, Phil.

N2 has a single vibrational mode and no net permanent dipole, and only has a weak induced dipole, so it’s absorption in the IR is very small, but you said it could not happen at all.

Do you suppose all the collisions N2 undergoes might have an effect upon its induced dipole moment such that its stretching mode can absorb a photon, Phil?

Do you suppose an electronic excitation might induce a dipole fluctuation such that a photon could be absorbed, Phil?

Do you suppose thermal excitation of the N2 molecule has an effect upon its vibrational state, Phil?

Do you think electrons don’t impinge upon N2 in the free atmosphere, Phil, that it only happens in a CO2 laser?

Role of electronic excited N2 in vibrational excitation of the N2
ground state at high latitudes
https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/2005JA011292

This is how it works, Phil, in all circumstances… in a CO2 laser, in Picosecond Coherent Anti-Stokes Raman Scattering tests, and in the free atmosphere:
“Carbon dioxide injection, which results in significant reduction of nitrogen vibrational temperature, even at low CO2 mole fractions in the flow, illustrates the other extreme.”

Why, oh why, so you keep embarrassing yourself, Phil? LOL

• Phil. says:

Role of electronic excited N2 in vibrational excitation of the N2
ground state at high latitudes
https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/2005JA011292

More irrelevant trolling, referring to the thermosphere, guess what it’s rather hotter up there than down here!

This is how it works, Phil, in all circumstances… in a CO2 laser, in Picosecond Coherent Anti-Stokes Raman Scattering tests, and in the free atmosphere:
“Carbon dioxide injection, which results in significant reduction of nitrogen vibrational temperature, even at low CO2 mole fractions in the flow, illustrates the other extreme.”

Thank you for that one I worked with his PhD advisor back in the day, even showed him my CARS setup as I recall. Trust me the conditions for CARS don’t exist in our atmosphere.

Why, oh why, so you keep embarrassing yourself, Phil? LOL

I’m not, I’m just having a good laugh at the nonsense you’re posting.

• LOL@Klimate Katastrophe Kooks says:

But Phil, I’ve already cited a study which shows that N2 can be vibrationally excited by 0.8 um photons. That’s just outside the visible spectrum on the infrared side. That also happens to be the strongest output range of the Sun’s total irradiance spectrum. That reaches all the way down through the entire atmosphere, Phil.

Or are you now denying that infrared light can reach the surface of the planet, Phil?

Define “hotter”, Phil. While the molecules in the upper atmosphere do indeed have a higher translational kinetic energy, if you were to go up there without thermal protection, you’d freeze to death.

You seem to be confused as to everyday definitions, Phil. LOL

Now, Phil… why would we use Coherent Anti-Stokes Raman Scattering tests to probe how N2 behaves if we thought its behavior somehow magically changed in the free atmosphere?

Now Phil is claiming that N2 knows whether it’s undergoing CARS testing or is in the free atmosphere, and magically changes its Raman frequencies!

Wow, Phil… does your fantasy world include a pink sky? LOL

• Phil. says:

But Phil, I’ve already cited a study which shows that N2 can be vibrationally excited by 0.8 um photons.

You haven’t, try reading the paper!

• LOL@Klimate Katastrophe Kooks says:

I’ve provided graphics showing the wide absorption spectrum of N2, based upon several studies. I’ve shown that the N2 vibrational quantum state-Raman coupling is significantly increased under IR photon flux due to vibrational resonance.

It’s you, Phil, who’s claiming that N2 cannot absorb photons under any circumstances (denying that Raman scattering occurs for N2 molecules… you do know how Raman scattering works, yes, Phil?), that it cannot become vibrationally excited except by collision (thereby implying that vibronic coupling doesn’t exist for N2)… that’s the warmist line, and after you deviated to agree with the Clough and Iacono study that water vapor (what you warmists call a GHG) actually causes *cooling*, you remembered your warmist indoctrination and began toeing the warmist line again.

Except I’ve shown that it works the opposite of what you warmists claim… in CO2 lasers, in Coherent Anti-Stokes Raman Scattering tests, and in the free atmosphere.

Why would we use Coherent Anti-Stokes Raman Scattering tests to probe how N2 behaves if we thought its behavior somehow magically changed in the free atmosphere?

Now, Phil… if, as you claim, N2 can only become vibrationally excited by collision… what’s to stop N2 from becoming vibrationally excited by collision with the much more prevalent in our atmosphere water vapor and oxygen?

Why do you warmists claim that the only collision which can vibrationally excite N2 is that with CO2, which comprises only 0.041% of the atmosphere by volume, especially in light of the fact that I’ve shown that it’s energetically favorable for the energy transfer in that situation to go the other direction (in CO2 lasers, in CARS testing and in the free atmosphere)?

Remember, Phil… N2 has only one prevalent vibrational quantum state (with several vibronic coupling ranges of lesser importance)… one prevalent vibrational quantum *energy* *level*, Phil. So once N2 is vibrationally excited, the process will work the same in CO2 lasers, in CARS testing and in the free atmosphere because that N2 vibrational quantum state energy is highly resonant to CO2’s quantum state such that it’s energetically favorable for N2 to give up its vibrational quantum state energy to CO2 upon collision.

If you wish to disprove this, you’ll have to explain how it is that the vibrational quantum state of N2 somehow magically changes in the free atmosphere.

• LOL@Klimate Katastrophe Kooks says:

Let’s get technical, Phil.

Let’s examine the characteristic vibrational temperature of the two molecules in question.

Theta_vib = hv/k
where:
h = Planck constant
v = oscillator frequency
k = Boltzmann’s constant

What’s the vibrational temperature of N2?
http://www.scs.illinois.edu/~makri/New-Web-Site/444-web-page/sol3.pdf#page=3
N2: 3374 K

Now, Phil… what’s the rotational and vibrational temperature of CO2?
http://iopscience.iop.org/article/10.1088/1361-6595/aa902e/pdf
T_rotation: 500 K
T_assymetric_stretch: 1050 K

You’ll note that the N2 was calculated for its ground state, and the CO2 for its most excited state such that *if* CO2 were ever going to transfer its vibrational and rotational quantum state energy to N2, it’d be bound to happen under those circumstances.

*What* *does* *this* *mean*, Phil?

It means that the maximum vibrational temperature of CO2 doesn’t come anywhere close to enough energy to excite N2 from its vibrational ground state upon collision.

And that means it is energetically favorable for N2 to transfer its vibrational quantum state energy to CO2 upon collision under all circumstances… in a CO2 laser, in CARS testing and in the free atmosphere.

So just as I said in my original post, the warmists have it exactly backward, and their claim that CO2 causes warming violates 2LoT.

[Hey Mod… I’m doing a victory dance, but can I at least poke a pointy stick at the anti-science warmists? Just this once? LOL}

• LOL@Klimate Katastrophe Kooks says:

You’ll further note that the ground-state vibrational temperature of N2 corresponds to a Wien formula peak emission wavelength of 0.84885 micron radiation.

And you’ll remember my prior post:
———-
https://journals.aps.org/pra/abstract/10.1103/PhysRevA.96.043422
“Combining with theoretical calculation, our results demonstrate that both vibrational and electronic excitation occurs for ionized nitrogen molecules in 800-nm femtosecond laser fields.”

That’s 0.8 um photons, Phil, just on the infrared side of the visible spectrum. It is also the strongest output range of the Sun’s total irradiance spectrum. That reaches all the way down through the entire atmosphere, Phil.
———-

And you’re further remember my stating that for homonuclear diatomics under an IR photon flux, vibrational quantum state-Raman coupling is enhanced significantly due to vibrational resonance, Phil.

• LOL@Klimate Katastrophe Kooks says:

Although this guy is a warmist, he does dance around the truth:

http://www.barrettbellamyclimate.com/page15.htm
———————————
The existence of the ν3(1) level is highly important with regard to its collisional excitation by nitrogen molecules in their first excited vibrational mode that has a transition wavenumber of 2359.6 cm-1, almost a perfect match for the excitation of the anti-symmetric stretching vibration of CO2:

N2 [ν1(1)] + CO2 [ν20(0)] → N2 [ν1(0)] + CO2 [ν3(1)]

The CO2 [ν3(1)] state can then emit radiation or be degraded to the lower energy levels from which radiation may be emitted.
———————————

You’ll note that’s N2’s first excited vibrational mode, and CO2’s *highest* excitation mode.

But more importantly, his last sentence states exactly what I’ve been stating.

And given that the mean free path length of that radiation increases with increasing altitude (as I stated in my original post)…
https://i.imgur.com/xz3nzgH.png
…the net vector for that radiation is upward.

Thus CO2 causes cooling, not warming.

• Phil. says:

You’ll note that that graph refers to the thermosphere not the troposphere!

• LOL@Klimate Katastrophe Kooks says:

That graph above starts at 0 km, Phil. If one were to zoom in, one would see a similar exponential increase in the mean free path length for radiation at all altitudes, but at a smaller magnitude compared to higher altitudes.

Just where do you suppose the troposphere starts, Phil? Below 0 km? LOL

• Phil. says:

You’ll further note that the ground-state vibrational temperature of N2 corresponds to a Wien formula peak emission wavelength of 0.84885 micron radiation.

And you’ll remember my prior post:
———-
https://journals.aps.org/pra/abstract/10.1103/PhysRevA.96.043422
“Combining with theoretical calculation, our results demonstrate that both vibrational and electronic excitation occurs for ionized nitrogen molecules in 800-nm femtosecond laser fields.”

That’s 0.8 um photons, Phil, just on the infrared side of the visible spectrum. It is also the strongest output range of the Sun’s total irradiance spectrum. That reaches all the way down through the entire atmosphere, Phil.

And it’s about N2+ ions not N2 molecules, a totally different animal and irrelevant to what happens in the troposphere!

• LOL@Klimate Katastrophe Kooks says:

Vibrational quantum state excitation in N2. Not ionized, at approximately ambient temperature and atmospheric density. Using visible range photons which are right at the peak of the sun’s spectral output.

It’s so much fun, always being right. LOL

• Phil. says:

Garbage, it’s V-T transfer not V-V transfer!
The excited CO2 has more vibrational energy than 95% of the surrounding N2 molecules have translational energy so no 2LOT violation.
“I’m doing a victory dance”

• LOL@Klimate Katastrophe Kooks says:

Nor for N2 molecules under IR flux, they don’t. Did you forget about the significant increase in vibrational quantum state-Raman coupling for homonuclear diatomics under IR photon flux, Phil?

Are you claiming that translational energy somehow trumps vibrational energy, Phil? If one molecule (N2) has a higher vibrational energy than the other (CO2), it’ll transfer that vibrational energy to the second molecule regardless of the translational energy. And as I’ve shown, N2 in its first vibrational excitation mode has more than enough to vibrationally excite CO2.

You’ve got your energy flows all mixed up, Phil.

• Phil. says:

But N2 in the troposphere isn’t vibrationally excited and CO2 is!
To excite N2 vibrationally to its first vibrational level would require 4.3𝜇m radiation which is singularly scarce however it’s a forbidden transition anyway.

• LOL@Klimate Katastrophe Kooks says:

A “forbidden transition”, you say? So you’re saying that N2 can not, under any circumstances, absorb photons to become vibrationally excited, Phil? Isn’t that what you’ve repeatedly claimed?

What’s this say, Phil?
https://netl.engineering.osu.edu/raman-pumping-measurements-vibration-vibration-v-v-rates-nitrogen-oxygen-and-hydrogen
“The figure above shows typical results of these measurements. 150 ns after Raman excitation of the v=1 state of nitrogen, the lowest three N2 states are populated; 5 microseconds later, the lowest five states have become populated. Vibrational levels v>1 become populated by the V-V energy transfer in collisions of two vibrationally excited molecules.”

Oh, it says that they used *photons* in the visible range (0.607 and .707 micron) to vibrationally excite N2 (in fact, approximately 1/3 of all N2 molecules were driven to their first vibrational excitation level within 5 microseconds) then monitored the Stokes shift with a second laser; and that vibrational quantum state energy levels v>1 were populated by molecular collision (remember, Phil, this experiment was done in a pure N2 environment, so it was collision between N2 molecules only that drove the molecules to higher vibrational energy levels… do you suppose something like that takes place in the free atmosphere, Phil?).

You’ll note the N2 was not ionized. You’ll further note this experiment was done at near atmospheric density (760 Torr) and near ambient temperature (300 K). You’ll further note the pump photons were in the visible range, right at the peak of the sun’s spectral output.

That’s about as close to the free atmosphere as you can get in a laboratory environment, wouldn’t you say, Phil?

Further, it says I’m correct about what I’ve been saying about homonuclear diatomic vibrational quantum state-Raman cross-section increasing significantly under photon flux. The effect is strongest under IR photon flux, but also occurs for photons in the visible range.

So I’ve shown you Coherent Stokes and Anti-Stokes Raman Scattering tests (the energy of the scattered radiation being less than the pump radiation for the Stokes line, and more than the pump radiation for the anti-Stokes line); I’ve shown you Stimulated Raman Scattering tests; I’ve shown you that N2 can indeed become vibrationally excited (while not ionized, at approximately atmospheric density and temperature, by both IR and visible range photons) by vibrational quantum state-Raman coupling; I’ve shown you that under an IR (and visible range) photon flux, vibrational quantum state-Raman cross-section increases substantially; I’ve shown you that it is energetically favorable for N2’s vibrational quantum state energy in its predominant vibrationally excited mode to be imparted to CO2 and not the other way around (independent of translational kinetic energy, given that it’s much lower than vibrational quantum state kinetic energy… remember, they’re both kinetic energy, described in units of temperature).

Just admit you’re wrong, Phil. There’s no need to continue flogging the dead horse of CAGW… it’s dead. Bury it already. It’s stinking up the joint. LOL

• Phil. says:

A “forbidden transition”, you say? So you’re saying that N2 can not, under any circumstances, absorb photons to become vibrationally excited, Phil? Isn’t that what you’ve repeatedly claimed?

What’s this say, Phil?
https://netl.engineering.osu.edu/raman-pumping-measurements-vibration-vibration-v-v-rates-nitrogen-oxygen-and-hydrogen

They agree with me:
“Since N2 does not have a dipole moment, the absorption of infrared radiation and accompanying direct vibrational excitation is prohibited due to basic optical selection rules.”

Oh, it says that they used *photons* in the visible range (0.607 and .707 micron) to vibrationally excite N2

No it does not, it says they perturbed the ground state N2 molecules by focussing a 532nm laser beam (pump) into a 100µm diameter region and simultaneously also illuminating them with a 607nm laser pulse (Stokes beam).

and that vibrational quantum state energy levels v>1 were populated by molecular collision (remember, Phil, this experiment was done in a pure N2 environment, so it was collision between N2 molecules only that drove the molecules to higher vibrational energy levels… do you suppose something like that takes place in the free atmosphere, Phil?).

No because the probability of a N2 molecule in the free atmosphere being simultaneously (within 10^-16 sec) hit by two photons of frequencies separated by exactly the frequency necessary to excite the first vibrational state is extremely small. Actually the chance of being hit simultaneously by two photons of any frequency is very small. So no, something like that doesn’t take place in the free atmosphere.

You’ll note the N2 was not ionized. You’ll further note this experiment was done at near atmospheric density (760 Torr) and near ambient temperature (300 K). You’ll further note the pump photons were in the visible range, right at the peak of the sun’s spectral output.

That’s about as close to the free atmosphere as you can get in a laboratory environment, wouldn’t you say, Phil?

But not very representative of the illumination in the free atmosphere which is why your concept does not work. In their experiment the illumination was 50% 532nm and 40% 607 nm.

Further, it says I’m correct about what I’ve been saying about homonuclear diatomic vibrational quantum state-Raman cross-section increasing significantly under photon flux. The effect is strongest under IR photon flux, but also occurs for photons in the visible range.

Hardly, the Raman cross section depends on 1/𝜆^4.
As I’ve repeatedly showed you Raman is a very weak effect and contributes negligibly to the vibrational state of N2 in the troposphere. Consequently the N2 in the troposphere is overwhelmingly in its vibrational ground state.
Consequently in collisions between an IR excited CO2 molecules and neighboring N2 molecules the CO2 vibrational energy will be transferred via multiple collisions to the translational energy of the N2 molecules. If N2 (v=1) were a significant contributor in the atmosphere we would expect to see 10.6µm emissions which we do not.

So it’s time for you to admit you’re wrong about your theory of the role of vibrationally excited N2 in the troposphere and give it a rest.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“They agree with me:
“Since N2 does not have a dipole moment, the absorption of infrared radiation and accompanying direct vibrational excitation is prohibited due to basic optical selection rules.””

They most certainly do not agree with you, Phil. You’ll note the word *direct* in the text above, Phil. What have we been talking about, Phil? Raman scattering, not direct vibrational excitation.
https://i.imgur.com/msXQTo1.png
Raman scattering means a single photon is absorbed, and two photons are emitted, Phil.

I thought you said that homonuclear diatomics couldn’t be vibrationally excited by radiation, Phil. Remember?

Phil wrote:
“Homonuclear diatomics such as N2 don’t have a dipole and can’t be vibrationally excited by radiation.”

Yeah… yeah you *did* emphatically state that under no circumstances could homonuclear diatomics be vibrationally excited by radiation!

Now you’re arguing about Raman scattering, which *is* photon absorption and emission, Phil. The Stokes shift is a result of vibrational relaxation. Get that, Phil? That means you’re wrong yet again.

Now Phil… where does the increase in vibrational quantum state energy come from when a photon is Raman scattered from a homonuclear diatomic? Does it just pop into existence from nowhere? Or does it come *from* *the* *incident* *photon*, Phil? In other words, Phil, it’s an inelastic collision.

So you’re being pedantic again, Phil, as you squirm mightily in trying to prove yourself “not wrong”. LOL

Phil wrote:
“No it does not, it says they perturbed the ground state N2 molecules by focussing a 532nm laser beam (pump) into a 100µm diameter region and simultaneously also illuminating them with a 607nm laser pulse (Stokes beam).”

The 0.532 um first laser was focused in the Raman shifting cell, Phil, which had a 1:1 mixture of N2 and He. That was needed to generate the 0.607 um and 0.707 um Stokes pump photons. The 0.532 um photon flux played no part in vibrationally exciting the N2 in the Nitrogen Cell.

“As described in [12], the helium buffer serves primarily to increase the thermal conductivity of the mixture, which is important for dissipation of the excess translational energy associated with the conversion of a pump photon (532 nm) to a Stokes photon (607 nm). Approximately 25% of the incident pump photons are converted to either the first or second Stokes frequencies (607 and 707 nm, respectively) by the SRS process.”

“The SRS pump, consisting of the collinear residual second harmonic and first and second Stokes frequency beams, is collimated and refocused with a 300 mm focal length lens into a second cell containing pure N2 at room temperature and variable pressure between 300 and 760 Torr.”

So the first-laser second harmonic 0.532 um photon flux going into the Nitrogen Cell was residual (“the collinear residual second harmonic”). The only reason the first-laser 0.532 photons were pumped into the Nitrogen Cell is because they couldn’t be easily removed from the Stokes pump photon flux coming out of the Raman Cell. It didn’t participate in the vibrational excitation of the N2 in the Nitrogen Cell.

The second 0.532 um laser beam was the probe beam. It didn’t participate in the process of vibrationally exciting the N2 in the Nitrogen Cell (you’ll note there was a time delay between each 0.607 um and 0.707 um pump pulse and 0.532 um probe pulse).

Thus the rest of your argument is rendered moot. I’ll still respond, just to ensure that the point is driven home that *you* *are* *wrong*. Again.

Phil wrote:
“No because the probability of a N2 molecule in the free atmosphere being simultaneously (within 10^-16 sec) hit by two photons of frequencies separated by exactly the frequency necessary to excite the first vibrational state is extremely small. ”

Two photons are not required to vibrationally excite the N2, Phil. Don’t you know how Raman scattering works? That there were two frequencies of pump photons (0.607 um and 0.707 um) in the referenced test was a result of the two Stokes frequencies produced in the Raman Cell.

The 0.532 um photon flux didn’t participate in the vibrational excitation of N2 in the test referenced. The 0.607 um and 0.707 um photons are the first and second Stokes frequencies produced in the Raman Cell. Each Stokes frequency gives a different quantum transition of the N2 in the Nitrogen Cell.

The Stokes shift is a result of vibrational relaxation. So you’ve unwittingly argued for my point, Phil. LOL

Phil wrote:
“Hardly, the Raman cross section depends on 1/𝜆^4.”

Yes, Phil. That’s why the Raman cross-section increases under shorter-wavelength photon fluxes… such as in the visible range, as the referenced study showed, which used photons near the spectral peak of the sun’s output to vibrationally excite N2.

The probability of photon scattering for a given frequency is directly proportional to the density of electromagnetic modes (photon density of states), even if the medium possesses a finite dielectric permittivity.

The Raman signal depends upon more than merely the frequency. It also depends upon the number of molecules involved in the process, the spectral intensity, the *effective* Raman cross-section of the molecules and *enhancement* *factors*, Phil.

Phil wrote:
“As I’ve repeatedly showed you Raman is a very weak effect”

https://i.imgur.com/MzSqcet.png
The measured Raman spectra of air (atmospheric pressure) with integration times of 1s and 100s

“and contributes negligibly to the vibrational state of N2 in the troposphere. Consequently the N2 in the troposphere is overwhelmingly in its vibrational ground state.”

Well, Phil, I’ve already shown that N2 can become vibrationally excited via collision with other N2 (as well as via Raman scattering)… and as the vibrational quantum number increases, the vibrational quanta become smaller and therefore transitions occur more frequently. Further, the coupling between vibrational levels increases substantially under photon flux (microwave, IR and visible range, as I’ve shown), meaning that multiquanta transitions become nearly as probable as single quantum transitions (see: Schuler, Zwanzig; J. Chem. Phys., 33, 1778 (1960)).

This is why the vibrational quantum state-Raman coupling increases significantly under IR photon flux due to vibrational resonance, Phil.

Vibrationally excited N2 is produced at a flux of ~10^10 cm^-2 sec^-1 via collisional processes in the atmosphere, Phil (see: Dalgarno, Vibrationally Excited Molecules In Atmospheric Reactions). Photon flux increases both the quantum state and the vibrationally-excited flux (due to vibrational quantum state-Raman couping) of N2, Phil.

So yet again you’re wrong, Phil.

• Phil. says:

Phil wrote:
“They agree with me:
“Since N2 does not have a dipole moment, the absorption of infrared radiation and accompanying direct vibrational excitation is prohibited due to basic optical selection rules.””

They most certainly do not agree with you, Phil. You’ll note the word *direct* in the text above, Phil. What have we been talking about, Phil? Raman scattering, not direct vibrational excitation.

No we started off talking about direct vibrational excitation which is what you are quoting when you refer to my remarks about ‘forbidden transitions’ etc., clearly they agree with me in that area. Having been rebutted on that topic you ran off to change the subject to Raman.

The 0.532 um first laser was focused in the Raman shifting cell, Phil, which had a 1:1 mixture of N2 and He. That was needed to generate the 0.607 um and 0.707 um Stokes pump photons. The 0.532 um photon flux played no part in vibrationally exciting the N2 in the Nitrogen Cell.
Again you need to read the paper just not copy and paste it, the title is ‘Stimulated Raman pumping’, that requires two frequencies, a pump frequency, 532 cm-1, and a Stokes frequency, 607 cm-1. They needed those two simultaneous frequencies to create that vibrationally excited state which is why they designed the illumination system the way they did. As they say:
“we present new experimental results in which N2 molecules are laser excited to the v=1 vibrational by a process known as stimulated Raman scattering (SRS), where ωp is the laser “pump”frequency and ωs is the Stokes beam frequency.

𝒉ωp + 𝒉ωs + N2(0) ➝ 2𝒉ωs + N2(1) ”

Since you’ve completely misunderstood the paper you linked to (yet again!) the rest of your post is meaningless. You’re totally wrong, yet again.
Phil wrote:
“No because the probability of a N2 molecule in the free atmosphere being simultaneously (within 10^-16 sec) hit by two photons of frequencies separated by exactly the frequency necessary to excite the first vibrational state is extremely small. ”

Two photons are not required to vibrationally excite the N2, Phil. Don’t you know how Raman scattering works?
As clearly stated above two such photons are required for stimulated Raman which is what is being discussed here, and yes I do know how it works, you do not.
By the way the Dalgarno paper you refer to is about the thermosphere , the same error you keep making!

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“No we started off talking about direct vibrational excitation which is what you are quoting when you refer to my remarks about ‘forbidden transitions’ etc., clearly they agree with me in that area.”

We’ve been discussing Raman scattering for days, Phil. You said just last night that N2 in the troposphere isn’t vibrationally excited! Remember, Phil?

Phil wrote:
“Consequently the N2 in the troposphere is overwhelmingly in its vibrational ground state.”

You’re waffling and squirming. Again.

Phil wrote:
“Again you need to read the paper just not copy and paste it, the title is ‘Stimulated Raman pumping’, that requires two frequencies, a pump frequency, 532 cm-1, and a Stokes frequency, 607 cm-1.”

Yes, Phil… in the *Raman* *Cell*. The two Stokes beam frequencies are the pump frequencies for the *Nitrogen* *Cell*. Did you read the report, Phil?

Phil wrote:
“They needed those two simultaneous frequencies to create that vibrationally excited state which is why they designed the illumination system the way they did. As they say:
“we present new experimental results in which N2 molecules are laser excited to the v=1 vibrational by a process known as stimulated Raman scattering (SRS), where ωp is the laser “pump”frequency and ωs is the Stokes beam frequency.””

*You* need to read and understand the paper (and the SRS process), Phil. Again, they used the 0.532 um and 0.607 um photons in the Raman Cell to generate the 0.607 and 0.707 um Stokes frequencies, which became the pump frequencies for the Nitrogen Cell, with the 0.532 um frequency as *residual*. As the report states, the 0.532 um photon flux pumped from the Raman Cell into the Nitrogen Cell was *residual*, Phil.

The two pump frequencies for the Raman Cell were 0.532 um (90%) and 0.607 um (10%, generated by diverting some of the 0.532 um photon flux through Rhodamine 610 and 640 laser dyes). Did you read the report, Phil?

And the second *Stokes* beam is what is creating the enhanced Raman scattering cross-section in the Nitrogen Cell, Phil.

As a consequence of the amplified energy transition rate, the intensity of the Stokes beam experiences a stimulated Raman gain, and the intensity of the pump beam experiences a stimulated Raman loss in the Raman Cell.

Spontaneous Q-branch Raman scattering is used to determine the vibrational distribution function as a function of time with respect to the Nitrogen Cell’s pump pulse (0.607 um and 0.707 um photon flux, which includes the residual 0.532 um photon flux from the Raman Cell).

“Also note that 150 ns is selected for the minimum delay time in order to avoid interferences due to stray room scattering from the first and second Stokes pump beams”

So the 0.532 um beam in the Nitrogen Cell didn’t play a part in the Stimulated Raman Scattering taking place in the Nitrogen Cell. It had a time delay of at least 150 ns. It was merely a probe beam.

The 0.532 um beam from the Raman Cell to the Nitrogen Cell had experienced a stimulated Raman loss in the Raman Cell and was thus merely residual when it was pumped along with the 0.607 um and 0.707 um Stokes beams into the Nitrogen Cell.

In the Nitrogen Cell, the first and second Stokes beams were used to stimulate Raman scattering, and the second 0.532 um beam was diverted into a monochromator to measure the Stokes vibrational bands. That’s why they called them “the first and second Stokes pump beams”, Phil. That’s why Fig. 3 is described as “Each peak corresponds to a single Stokes vibrational band”, Phil.

Since you’ve completely misunderstood the paper you linked to (yet again!) the rest of your post is meaningless. You’re totally wrong, yet again.

Phil wrote:
“By the way the Dalgarno paper you refer to is about the thermosphere , the same error you keep making!”

Doesn’t matter the altitude, Phil. I’ve shown that visible range photons and infrared photons can vibrationally excite N2, and those photons reach the surface of the planet from the sun. If you were arguing about microwave, you might have a point, but you don’t… because yet again you’re wrong.

And that’s not even taking into account that N2 has a higher vibrational temperature than CO2, so it will, in all circumstances, transfer its vibrational quantum state kinetic energy to the lower-energy CO2, which then undergoes emission relaxation.

—————
Absorption of solar radiation by CO2 in the 2.7‐ and 2.77‐μm bands (000 -> 101 and 000 -> 021) results in fluorescent emissions at 4.3 μm due to the decay of these levels via 101 -> 100 and 021 -> 020. They are an order of magnitude greater than the radiance due to the resonance transition 001 -> 000 centered at 4.26 μm.

N2 is 2359.6 cm-1, which is 4.23801 um.

This is *why* N2 will *always* transfer its vibrational quantum state kinetic energy to CO2, Phil. The Laws of Thermodynamics dictates it does so.

Exactly as the website I linked to above says:
“N2 [ν1(1)] + CO2 [ν20(0)] → N2 [ν1(0)] + CO2 [ν3(1)]”

So as I said in my original post, the warmists have it exactly backward.

And as I said in my original post, thus dies CAGW.
—————

• Phil. says:

Phil wrote:
“No we started off talking about direct vibrational excitation which is what you are quoting when you refer to my remarks about ‘forbidden transitions’ etc., clearly they agree with me in that area.”

We’ve been discussing Raman scattering for days, Phil. You said just last night that N2 in the troposphere isn’t vibrationally excited! Remember, Phil?

Phil wrote:
“Consequently the N2 in the troposphere is overwhelmingly in its vibrational ground state.”

You’re waffling and squirming. Again.

My statement is correct, the N2 in the troposphere is overwhelmingly in its vibrational ground state. The very weak Raman effect does not excite a significant number of N2 molecules in the troposphere.

Phil wrote:
“Again you need to read the paper just not copy and paste it, the title is ‘Stimulated Raman pumping’, that requires two frequencies, a pump frequency, 532 cm-1, and a Stokes frequency, 607 cm-1.”

Yes, Phil… in the *Raman* *Cell*. The two Stokes beam frequencies are the pump frequencies for the *Nitrogen* *Cell*. Did you read the report, Phil?

Yes I did and unlike you I understood it. In the Nitrogen cell the pump is 532nm and the Stokes is 607nm.
Phil wrote:
“They needed those two simultaneous frequencies to create that vibrationally excited state which is why they designed the illumination system the way they did. As they say:
“we present new experimental results in which N2 molecules are laser excited to the v=1 vibrational by a process known as stimulated Raman scattering (SRS), where ωp is the laser “pump”frequency and ωs is the Stokes beam frequency.

Here’s what they did, they needed a pump beam and a Stokes beam simultaneously to illuminate the N2 in the cell to generate N2(1) via SRS. The SRS procedure requires:
“A light wave at frequency ωs is incident on the material system simultaneously with a light wave at ωp”,
The Stimulated Raman Effect, N. Bloembergen, Am J Physics 35, 989 (1967).
In order to achieve this they used a N2/He Raman cell in which about 10% of the 532nm pump was converted into either 607nm or 707nm photons. Since they wanted 607nm not 707nm they also ran a dye laser to provide some seed to favor the 607nm production by SRS.
Once they had done that they had a beam consisting of ~􏰂50 mJ of 532 nm, ~􏰂40 mJ of 607 nm, and 􏰂10 mJ of 707 nm.
The 707 nm is a side effect of the process and isn’t needed for the SRS of the N2 in the second cell (a clue is that only the 532nm and 607nm beams are shown in the schematic of the apparatus).

And the second *Stokes* beam is what is creating the enhanced Raman scattering cross-section in the Nitrogen Cell, Phil.
No, the second Stokes beam (707nm) has no role.

“Also note that 150 ns is selected for the minimum delay time in order to avoid interferences due to stray room scattering from the first and second Stokes pump beams”

Since they wanted to measure the vibrationally excited N2 concentrations using the spontaneous Raman signal from a second Nd-YAG laser any stray 607nm light from the SRS process would give a fake signal so the couldn’t make any measurements until after the SRS probe, hence the 150ns delay.

So the 0.532 um beam in the Nitrogen Cell didn’t play a part in the Stimulated Raman Scattering taking place in the Nitrogen Cell. It had a time delay of at least 150 ns. It was merely a probe beam.

No you are confusing the two 532nm beams, look at the schematic of the experiment.

“Each peak corresponds to a single Stokes vibrational band”
You omitted the important remainder of the sentence:
“(the rotational structure is unresolved)”, which relates to their comment later “While not directly relevant to this work, it is interesting to note that this exceeds the fractional population (which peaks at ~10% for J=10) in any one rotational sublevel, implying that population is moved from multiple rotational levels simultaneously.” This refers to the results from the spontaneous Raman probe and has nothing to do with the SRS process.

Again you’ve completely misunderstood the paper you linked to. You’re totally wrong, yet again.

• LOL@Klimate Katastrophe Kooks says:

Ok, Phil. I’ve toyed with and embarrassed you for your silly anti-science warmist beliefs long enough. It’s time to drive the stake through the heart of CAGW.

Today is the day your entire world changes.

Today is the day I rip out the foundation of your warmist religion.

It is entirely up to you what you replace its anti-science rhetoric with, but I’d suggest subscribing to reality via the scientific method.

As you already know, I’ve demonstrated that VRS (Vibrational Raman Scattering) occurs for N2 in the microwave, infrared and visible ranges.

As you already know, I’ve demonstrated that the lowest vibrational state of N2 has a higher vibrational temperature than the highest excitation state of CO2, thus the Laws of Thermodynamics dictate that a vibrationally-excited N2 molecule will, upon collision with CO2, transfer its vibrational quantum state energy to the CO2 molecule, which will then undergo emission relaxation by emitting a photon… and not the other way around, as you warmists claim.

As you already know, I’ve demonstrated that vibrational quantum state-VRS coupling increases significantly under photon flux. I’ve even generated an analogy (remember? “Fantastical Pedantical Phil’s Wave Machine” LOL) to roughly describe the process by which this takes place.

As you already know, I’ve demonstrated that VRS takes place throughout the depth of the atmosphere for infrared and visible range photons. Unless you’re going to now start claiming that visible and IR photons cannot reach the surface of our planet, Phil. In point of fact, the VRS probability increases with optical depth, so it occurs *more* *frequently* in the troposphere than at higher altitudes, Phil.

As you’re painfully aware of, I’ve forced you from a position of chanting your warmist mantra in outright denial (“Homonuclear diatomics have no net electric dipole, so they cannot be vibrationally excited by radiation”), to grudging acknowledgment that the processes described take place (“Ok, homonuclear diatomics can undergo vibrational Raman scattering, but it doesn’t happen much in the troposphere”), and upon my pointing this out, you scurried back to the ego-shelter of your religious belief in CAGW by reiterating your original warmist belief (and in the process, you simultaneously admitted and denied that N2 undergoes Raman scattering. LOL).

So you know you’re cornered by the facts. This is where it gets fun.

The last argument you’ve got is that the process doesn’t take place at a rate high enough in the troposphere to matter much. But that’s about to change, Phil.

Phil wrote:
“My statement is correct, the N2 in the troposphere is overwhelmingly in its vibrational ground state. The very weak Raman effect does not excite a significant number of N2 molecules in the troposphere.”

That’s the last argument you’ve got to defend your warmist religion, Phil. I’ve moved you from the standard warmist mantra of “Homonuclear diatomics have no net electric dipole and thus cannot be vibrationally excited by radiation” to your fall-back position of “Ok, homonuclear diatomics can be vibrationally excited by radiation, but it doesn’t happen much in the troposphere”.

That’s progress (notwithstanding your constant attempts to backslide into your original warmist mantra). And that means I’m winning. LOL

Of course, just last night you fell back to your original warmist mantra… and in the process both admitted and denied that N2 undergoes Raman scattering, while demonstrating that you simply don’t understand the underlying mechanics of the Raman scattering process. That was pretty hilarious. LOL

Of course, if I were to remove that last argument of yours, your warmist mantra would evaporate, wouldn’t it, Phil?

https://www.atmos-meas-tech.net/8/3767/2015/amt-8-3767-2015.pdf
“In contrast to that, vibrational Raman scattering (VRS) of N2 and O2 has often been thought to be negligible, but it also contributes.”

That states that your outdated belief that N2 and O2 (homonuclear diatomics) don’t undergo Raman scattering enough to matter, is wrong, Phil. In actuality, it accounts for ~2.3% of all atmospheric scattering (elastic and inelastic), enough to red-shift the solar spectrum.

https://i.imgur.com/SKCGC3d.png

What does that graph say, Phil? Oh, it says that the Vibrational Raman Scattering (VRS), Rotational Raman Scattering (RRS) and VibroRotational Raman Scattering (VRRS), when combined together, account for a much higher percentage of all N2 scattering (as measured at Cabannes) than previously thought… an amount sufficient to red-shift the spectrum of light we receive from the sun, and in fact, an amount even higher than the inelastic scattering by water vapor.

https://www.atmos-meas-tech.net/8/3767/2015/amt-8-3767-2015.pdf
“Due to the temperatures in the Earth’s atmosphere T , only the ground vibrational state is occupied *significantly*, thus leading only to Stokes transitions of the vibrational states. (Evib/kT ≈ 11 and 8 for N2 and O2, respectively.)” {Emphasis mine}

You’ll remember the ground vibrational state of N2 has sufficient vibrational temperature such that vibrationally excited N2 will, under all circumstances, transfer its vibrational quantum state kinetic energy to CO2 (even if CO2 is in its highest excited state, asymmetric stretch).

https://www.atmos-meas-tech.net/8/3767/2015/amt-8-3767-2015.pdf
“This spectral region (i.e. 430–440 nm) is actually the location of the strong Ca lines of the Fraunhofer spectrum, red-shifted by the excitation energy of the first vibrational eigenstate of N2. This is a first indication that this effect might indeed be relevant for measurements of atmospheric absorbers.”

The inelastic vibrational Raman scattering signal was covered up by elastic scattering Fraunhofer in-filling, so we thought Raman scattering was negligible, but it’s not.

https://i.imgur.com/sZ0yyhJ.png

Note the total (Rayleigh and Raman) scattering and RRS in the top graph, note the relative amount of scattering by N2 VRS and VRRS. You’ll note N2 VRS and VRRS contributes a significant percentage of all Raman scattering. Note especially the 420-440 nm (0.42-0.44 um) ghost lines.

https://www.atmos-meas-tech.net/8/3767/2015/amt-8-3767-2015.pdf
“Vibrational Raman scattering of N2 and O2 can contribute *significantly* to observed optical depths in passive DOAS applications.” {Emphasis mine}

This means, Phil, that a far larger percentage of N2 in the troposphere is vibrationally excited than was previously thought. So much so that the spectrum of light we receive from the sun is red-shifted by VRS, RRS and VRRS.

https://i.imgur.com/MzSqcet.png

N2, much more vibrationally excited in the atmosphere than CO2… and much more abundant as a constituent of the atmosphere (by a few orders of magnitude). So there are far more N2 molecules than CO2 molecules which are vibrationally excited, and the N2 molecules have a higher vibrational temperature, thus they will transfer their vibrational quantum state kinetic energy to CO2.

And given that the mean free path length of that radiation increases with increasing altitude (as I stated in my original post)…
https://i.imgur.com/xz3nzgH.png
…the net vector for that radiation is upward.

Thus CO2 causes cooling, not warming.

And that means you’re *wrong*, Phil. Again. LOL

Now, I’m sure your world is rocked, Phil… but the scientific method *requires* that you take into account the new data and change your viewpoint to where the data leads you… to do any less, to stick with your warmist religion, means you’re relying upon faith… and that’s anti-science, Phil.

Warmists are anti-science, Phil. Don’t be a warmist, Phil. LOL

• Phil. says:

That states that your outdated belief that N2 and O2 (homonuclear diatomics) don’t undergo Raman scattering enough to matter, is wrong, Phil. In actuality, it accounts for ~2.3% of all atmospheric scattering (elastic and inelastic), enough to red-shift the solar spectrum.

2.3% of one part per million, I think you just made my point for me.

• LOL@Klimate Katastrophe Kooks says:

Demonstrating your maff skills again, Phil? LOL

In point of fact, Raman scattering accounts for ~2.3% of *all* scattering (Rayleigh, Raman and Mie combined).

https://i.imgur.com/O4TzGNM.png
https://i.imgur.com/3OI2z0R.png
Taken via the MeteoSat satellite.

~2.3% of all scattering, Phil.

• Phil. says:

Demonstrating your maff skills again, Phil? LOL

In point of fact, Raman scattering accounts for ~2.3% of *all* scattering (Rayleigh, Raman and Mie combined).

No the paper you quoted explicitly stated:
“the observed VRS(N2) cross-section at 393 nm amounts to 2.3 ± 0.4 % of the cross-section of RRS at 433 nm under tropospheric conditions.”

And RRS in turn is parts per million.

• LOL@Klimate Katastrophe Kooks says:

Let’s open this post with a prayer. I’m going to need it.

{God, grant me the strength to refrain from mercilessly mocking the feebleminded. Amen.}

Phil wrote:
“No the paper you quoted explicitly stated:
“the observed VRS(N2) cross-section at 393 nm amounts to 2.3 ± 0.4 % of the cross-section of RRS at 433 nm under tropospheric conditions.””

Exactly as I said. And look, Phil! Its “under tropospheric conditions”.

And that’s at just one incident wavelength, Phil. Are there more wavelengths than just one, Phil?

{Pssst… hey Phil! The answer is ‘yes’. Yer welcome. LOL}

Phil wrote:
“And RRS in turn is parts per million.”

Do you even know what RRS means, Phil? Obviously not.

Nowhere in that report do they mention “PPM” or “parts per million”, because RRS is not measured in parts per million, Phil.

It’s measured in cm2 sr-1 molec-1 or Wm2 incident power density, Phil.

“The relative contribution of the cross-section of VRS of N2 to the cross-section of RRS of 2.3 % is in agreement with expected values from the theory (2–3.5 %, depending on the measurement geometry).”

What’d I say, Phil? That N2 Vibrational Raman Scattering contributed 2.3% of all scattering.

But then, you don’t even know what “RRS” is (you think it’s measured in parts per million LOL), so you have no context with which to even understand much of anything.

Another giant fail from you, Phil. I’m believing less and less your claimed “40 years of study and research in the field”, Phil. LOL

• LOL@Klimate Katastrophe Kooks says:

Let’s examine the CO2 vibrational and rotational modes:

{Note: The molecule simulator shows N2 as 2359 cm-1. It’s actually 2359.6 cm-1. This has been taken into account in the calculations used to arrive at figures below.}
——————–
https://i.imgur.com/GMtbMtK.png
CO2 in its ground state, with an old-style nomenclature of CO2(000) and a modern nomenclature of CO2[v20(0)]. The molecule is undergoing bend (v2), with vibrational quantum state 0 and rotational quantum state 0.

This quantum state cannot participate in increasing the translational kinetic energy (temperature) of N2, since N2 has a much higher vibrational temperature. In fact CO2 acts to cause cooling via the following collisional process:

N2[v1(1)] + CO2[v20(0)] === N2[v1(0)] + CO2[v3(1)]

The CO2[ν3(1)] state can then emit radiation or be degraded to the lower energy levels from which radiation may be emitted.
——————–
https://i.imgur.com/sQDTMSK.png
The only rotovibrationally excited state of CO2 which has a higher vibrational temperature than N2’s first excited vibrational mode, known as CO2 (001) in older nomenclature, and as CO2[v38(1)] in more modern nomenclature.

The CO2 molecule is undergoing asymmetric stretch (v3) with vibrational quantum number 1 and rotational quantum number 8.

CO2 in this rotovibrational excitation state, upon collision with N2, will undergo the following V-V (Vibrational-Vibrational) process, emitting a 558.6592 um photon:

C02[v38(1)] + N2[v1(0)] === C02[v20(0)] + N2[v1(1)] + 17.9 cm-1 (558.6592 um)

The molecule in this state cannot participate in increasing N2’s translational kinetic energy (temperature), since the quantum state energy transfer is V-V (Vibrational-Vibrational) rather than V-T (Vibrational-Translational), and in fact the emission of the 558.6592 um photon actually causes a loss of energy to the system.

Further, the N2[v1(1)] then goes on to collide with CO2[v20(0)], and the CO2[v20(0)] then emits a photon as described above.

Thus CO2 in this mode causes a slight amount of cooling.
——————–

If CO2[v20(0)] (ground state) cannot cause global warming, and CO2[v38(1)] (highest rotovibrational temperature of CO2) cannot cause global warming, no quantum states in between will, either. In fact, they both cause cooling. LOL

Well, that’s it, Phil. Quantum Mechanical proof that CO2 does not and cannot cause global warming.

Thus your continued warmist CAGW belief is proven to be an act of faith… a religion. Not science. LOL

• LOL@Klimate Katastrophe Kooks says:

“Further, the N2[v1(1)] then goes on to collide with CO2[v20(0)], and the consequent CO2[v3(1)] then emits a photon as described above.”

• Phil. says:

The only rotovibrationally excited state of CO2 which has a higher vibrational temperature than N2’s first excited vibrational mode, known as CO2 (001) in older nomenclature, and as CO2[v38(1)] in more modern nomenclature.

It’s not the only one, it’s the one with the lowest energy.

The CO2 molecule is undergoing asymmetric stretch (v3) with vibrational quantum number 1 and rotational quantum number 8.

CO2 in this rotovibrational excitation state, upon collision with N2, will undergo the following V-V (Vibrational-Vibrational) process, emitting a 558.6592 um photon:

The 17.9cm-1 is translational energy not a photon.

Further, the N2[v1(1)] then goes on to collide with CO2[v20(0)], and the CO2[v20(0)] then emits a photon as described above.

Thus CO2 in this mode causes a slight amount of cooling.

This is nonsense: You started with a CO2 excited state which can’t be reached by direct vibrational excitation, which you then postulate collisionally excites an N2 molecule which in turn collisionally excites another CO2 molecule which then emits a photon!
——————–

If CO2[v20(0)] (ground state) cannot cause global warming, and CO2[v38(1)] (highest rotovibrational temperature of CO2) cannot cause global warming, no quantum states in between will, either. In fact, they both cause cooling. LOL

No, IR radiation (667cm-1) excites CO2 into the 010 state which heats N2 via collisions (V-T) which causes warming.

Well, that’s it, Phil. Quantum Mechanical proof that CO2 does not and cannot cause global warming.

No a discussion of high energy states which are inaccessible in the troposphere and don’t contribute to warming at all. Rather they are active in the upper atmosphere in such phenomena as auras.

• LOL@Klimate Katastrophe Kooks says:

LOL@Klimate Katastrophe Kooks wrote:
“The only rotovibrationally excited state of CO2 which has a higher vibrational temperature than N2’s first excited vibrational mode, known as CO2 (001) in older nomenclature, and as CO2[v38(1)] in more modern nomenclature.”

Phil wrote:
“It’s not the only one, it’s the one with the lowest energy.”

Bwahahahaaa! Way to demonstrate that you know absolutely nothing about the topic, Phil. You hace been trolled. LOL

CO2[v38(1)] doesn’t exist, Phil. I made it up as a test of your knowledge, and you failed miserably. Had you even an inkling of what you were doing, you’d have realized that right off. I made it very obvious to anyone with even cursory training in quantum mechanics, which obviously excludes you.

First, Phil, in the excited state, only the odd-numbered rotational levels are populated, and CO2[v3(1)] is CO2’s highest excited state.

Second, Phil, the excited state rotational levels only go up to J=5.

So it should have been obvious to you at first glance that CO2[v38(1)] was farcical. That you not only didn’t catch it, but doubled-down by claiming it was “the one with the lowest energy” proves you’re just blathering, just flopping your hands across your keyboard and hoping not to make yet another idiotic mistake.

You should be ashamed of yourself, Phil. What with your other claim tonight that RRS was measured in (to quote you), “parts per million”, you have no standing to even be discussing any of this.

Pathetic.

But hilarious nonetheless. LOL

So I expect you’ll be back tomorrow for more humiliation, Phil? LOL

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“This is nonsense: You started with a CO2 excited state which can’t be reached by direct vibrational excitation, which you then postulate collisionally excites an N2 molecule which in turn collisionally excites another CO2 molecule which then emits a photon!”

The only one spewing nonsense is you, as the trolltrap I set for you and as your own words prove, Phil.

CO2[v38(1)] doesn’t exist, I made it up to see if you’d catch it. Not only didn’t you catch it, you called it “not the highest excited state”.

And now you’re blathering on about it not being directly vibrationally excitable.

You would have caught onto my ruse, if you knew what you were talking about, but you don’t. I made it pretty obvious.

That’s three mistakes just tonight from you, Phil. Aren’t you embarrassed for yourself? LOL

——————–
LOL@Klimate Katastrophe Kooks wrote:
“The only rotovibrationally excited state of CO2 which has a higher vibrational temperature than N2’s first excited vibrational mode, known as CO2 (001) in older nomenclature, and as CO2[v38(1)] in more modern nomenclature.”

Phil wrote:
“It’s not the only one, it’s the one with the lowest energy.”

Bwahahahaaa! Way to demonstrate that you know absolutely nothing about the topic, Phil. You hace been trolled. LOL

CO2[v38(1)] doesn’t exist, Phil. I made it up as a test of your knowledge, and you failed miserably. Had you even an inkling of what you were doing, you’d have realized that right off. I made it very obvious to anyone with even cursory training in quantum mechanics, which obviously excludes you.

First, Phil, in the excited state, only the odd-numbered rotational levels are populated, and CO2[v3(1)] is CO2’s highest excited state.

Second, Phil, the excited state rotational levels only go up to J=5.

So it should have been obvious to you at first glance that CO2[v38(1)] was farcical. That you not only didn’t catch it, but doubled-down by claiming it was “the one with the lowest energy” proves you’re just blathering, just flopping your hands across your keyboard and hoping not to make yet another idiotic mistake.

You should be ashamed of yourself, Phil. What with your other claim tonight that RRS was measured in (to quote you), “parts per million”, you have no standing to even be discussing any of this.

Pathetic.

But hilarious nonetheless. LOL

So I expect you’ll be back tomorrow for more humiliation, Phil? LOL
——————–

• LOL@Klimate Katastrophe Kooks says:

LOL@Klimate Katastrophe Kooks wrote:
“The only rotovibrationally excited state of CO2 which has a higher vibrational temperature than N2’s first excited vibrational mode, known as CO2 (001) in older nomenclature, and as CO2[v38(1)] in more modern nomenclature.”

Phil wrote:
“It’s not the only one, it’s the one with the lowest energy.”

Further, Phil, CO2[v3(1)] aka CO2(001) is CO2’s *highest* (not lowest, as you ignorantly claim) vibrational excitation state. The only way to get any more energy into the molecule from that vibrational state is via rotational quantum energy states, and those levels only go to J=5.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“The SRS procedure requires:
“A light wave at frequency ωs is incident on the material system simultaneously with a light wave at ωp”,”

On the *material system*, Phil, not simultaneously upon the individual molecule. Your aberrant pedantry precludes your comprehending simple concepts.

As I stated, the two Stokes pump frequencies (0.607 um / 0.707 um) set up two fundamental frequencies, allowing vibrational state coupling to occur. It can’t occur with a single fundamental frequency, Phil. Molecules are fundamental frequency and harmonic entities, Phil.

Remember, Phil? I even described it via analogy for you, since you were so obviously befuddled by the topic… “Fantastical Pedantical Phil’s Wave Machine”. LOL

The *residual* 0.532 um beam from the Raman Cell (pumped as *residual* into the Nitrogen Cell) was already used in the Raman Cell, so even had they used it in the Nitrogen Cell, it could have only produced 1/4th of the photon flux in the Nitrogen Cell as it made in the Raman Cell, and there was already four times as much photon flux in the Nitrogen Cell at the Stokes frequencies as that *residual* 0.532 um beam could have possibly made in the Nitrogen Cell.

Given that you’ve demonstrated your lack of understanding of the Raman scattering process via your inability to describe how it worked; and your inability to grasp how harmonic oscillators work (to the point that you were simultaneously admitting and denying that N2 could undergo Raman scattering. LOL), you haven’t the faintest clue what you’re talking about. Again.

And now you’ve scurried away from discussion of Raman scattering, instead moving on to demonstrating your profound lack of knowledge about vibrational selection rules and quantum state transitions. LOL

That’s called “compounding”, Phil… in language even you can understand, you find you’ve dug yourself into a hole, and you’re bound and determined to dig your way out of it. Far from following the old adage, you’ve decided to dig *faster*. LOL

• Phil. says:

Phil wrote:
“The SRS procedure requires:
“A light wave at frequency ωs is incident on the material system simultaneously with a light wave at ωp”,”

On the *material system*, Phil, not simultaneously upon the individual molecule. Your aberrant pedantry precludes your comprehending simple concepts.

As I stated, the two Stokes pump frequencies (0.607 um / 0.707 um) set up two fundamental frequencies, allowing vibrational state coupling to occur. It can’t occur with a single fundamental frequency, Phil. Molecules are fundamental frequency and harmonic entities, Phil.

Yes, you stated that, the authors of the papers explicitly stated that the pump for the nitrogen cell was 532nm and the Stokes was 607nm.

The *residual* 0.532 um beam from the Raman Cell (pumped as *residual* into the Nitrogen Cell) was already used in the Raman Cell, so even had they used it in the Nitrogen Cell, it could have only produced 1/4th of the photon flux in the Nitrogen Cell as it made in the Raman Cell, and there was already four times as much photon flux in the Nitrogen Cell at the Stokes frequencies as that *residual* 0.532 um beam could have possibly made in the Nitrogen Cell.

The 532nm beam power in the nitrogen cell was 50mJ and the 607nm Stokes beam was 40mJ.
You don’t have a clue about what was described in that paper.

• LOL@Klimate Katastrophe Kooks says:

Given that you’ve demonstrated twice just tonight that you haven’t the first clue what you’re talking about, Phil, you’d be well-advised to just STFU and slink away in embarrassment. LOL

The 0.532 um photon flux from the Raman Cell to the Nitrogen Cell was (to quote the report) “residual”. Do you know what “residual” means, Phil? LOL

• Phil. says:

In this context it means 532nm flux remaining after passing through the Raman cell, it is still the strongest component of the beam incident on the Nitrogen cell, 50mj vs 40mj of 607nm. The authors clearly thought it was important since 532nm and 607nm were the only two frequencies shown on their experimental apparatus figure.

• LOL@Klimate Katastrophe Kooks says:

“Also note that 150 ns is selected for the minimum delay time in order to avoid interferences due to stray room scattering from the *first* *and* *second* *Stokes* *pump* *beams*, some of which, despite baffling, was found to enter the spectrometer.” {Emphasis mine.}

So you’re wrong yet again, Phil. Yet again you display your ignorance of how harmonic oscillators work. LOL

Keep digging that hole, Phil! Some day you may dig yourself out of that giant credibility crater. Just ignore that old adage about what people should do when they find themselves in a hole. LOL

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Yes, you stated that, the authors of the papers explicitly stated that the pump for the nitrogen cell was 532nm and the Stokes was 607nm.”

No, Phil. They specifically called the two Stokes beams the pump beams, and the 0.532 beam from the Raman Cell to the Nitrogen Cell (to quote them) “residual”.

“Also note that 150 ns is selected for the minimum delay time in order to avoid interferences due to stray room scattering from the *first* *and* *second* *Stokes* *pump* *beams*, some of which, despite baffling, was found to enter the spectrometer.” {Emphasis mine.}

So you’re wrong yet again, Phil. Yet again you display your ignorance of how harmonic oscillators work. LOL

Phil wrote:
“The 532nm beam power in the nitrogen cell was 50mJ and the 607nm Stokes beam was 40mJ.”

But Phil, the Stokes beam in the Raman Cell was only 20 mJ to create the 0.607 um and 0.707 um photon flux used to pump the Nitrogen Cell.

Now Phil… what was the wavelength of that Raman Cell Stokes beam, and why did they *need* it for the process to work?

Phil wrote:
“You don’t have a clue about what was described in that paper.”

Says the guy who denies that infrared photons can cause N2 to become vibrationally excited; who claimed that N2 cannot become vibrationally excited at all under any circumstances; who didn’t know about vibronic coupling; who doesn’t understand the role of He in a CO2 laser; who claimed that because N2 is a homonuclear diatomic with no net electric dipole it could not absorb photons under any circumstances (“optically forbidden” LOL); who wants to visit the “hotter” upper atmosphere wearing flip-flops and a tank top; who couldn’t describe the Raman scattering process properly; who simultaneously admitted and denied that N2 undergoes Raman scattering; who can’t seem to grasp how harmonic oscillators work (“Fantastical Pedantical Phil’s Wave Machine” LOL); who denied that N2 could undergo Resonant Raman Scattering; who claimed that CO2[v3(1) aka CO2(001) was the lowest excitation state when it’s actually the highest; who thinks RRS (measured as an energy flux) has units of parts per million; who can’t seem to figure out a simple cascaded laser pump setup. LOL

• Phil. says:

Phil wrote:
“The 532nm beam power in the nitrogen cell was 50mJ and the 607nm Stokes beam was 40mJ.”

But Phil, the Stokes beam in the Raman Cell was only 20 mJ to create the 0.607 um and 0.707 um photon flux used to pump the Nitrogen Cell.

No the Stokes beam in the Raman cell was 607nm created in the dye laser using ~20mJ of the original 532nm laser, 707nm was not involved.

Now Phil… what was the wavelength of that Raman Cell Stokes beam, and why did they *need* it for the process to work?

It was 607nm, and they didn’t need it, they were able to create 607nm by just focussing the 532 in the Raman cell, however that also created the unwanted 707nm beam. By adding the dye laser output as a seed they were able to enhance production of 607nm by stimulated emission.
Hence the 532nm beam power in the nitrogen cell was 50mJ and the 607nm Stokes beam was 40mJ.

• LOL@Klimate Katastrophe Kooks says:

You pig-headed denialism notwithstanding, Phil, the authors state you’re wrong:
“Also note that 150 ns is selected for the minimum delay time in order to avoid interferences due to stray room scattering from the *first* *and* *second* *Stokes* *pump* *beams*, some of which, despite baffling, was found to enter the spectrometer.” {Emphasis mine.}

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“They needed those two simultaneous frequencies to create that vibrationally excited state”

No, Phil. That merely increases the Raman cross-section. It’s not that two photons are hitting the same N2 molecule at the same time (that’d have the same low probability in SRS testing as in the atmosphere, Phil), it’s that the two Stokes pump frequencies populate two different vibrational quantum levels, allowing coupling. It can’t happen with only a single vibrational quantum state populated, since there’d be no other vibrational quantum state for the excited state to couple *to* (except v=0). As vibrational quantum state increases, the vibrational quanta become smaller and therefore transitions occur more frequently due to molecular collisions.

This is why the coupling between vibrational levels increases substantially under photon flux (microwave, IR and visible range, as I’ve shown), meaning that multiquanta transitions become nearly as probable as single quantum transitions (see: Schuler, Zwanzig; J. Chem. Phys., 33, 1778 (1960)).

So you’ve yet again (unwittingly) argued for my point, Phil. LOL

• Phil. says:

Phil wrote:
“They needed those two simultaneous frequencies to create that vibrationally excited state”

No, Phil. That merely increases the Raman cross-section. It’s not that two photons are hitting the same N2 molecule at the same time (that’d have the same low probability in SRS testing as in the atmosphere, Phil),

No as usual you’re wrong. The pump beam, 532cm-1, in this case is focussed into a 100micron diameter spot where it creates an excited virtual state (which only exists for ~10^-16 secs). The Stokes beam, 607 cm-1, causes stimulated emission to the N2 first vibrational state, that can only happen if that N2 molecule is at the appropriate virtual state at the time it is hit by the Stokes photon.
The probability of the event in the test cell is much higher than in the atmosphere because the laser beams are very tightly focussed and are ~50:50 pump and Stokes photons.

• LOL@Klimate Katastrophe Kooks says:

No, as usual, you’re wrong. And as usual, you’re pulling “facts” straight from your goes-out. LOL

When you pull your premise from Wikipedia, Phil, you should check that *their* premise is correct. They say:
“Then, it simultaneously absorbs both pump and Stokes photons which then results with the occurrence of a vibrational (or rotational) transition with some probability.”

But that’s not what actually happens, as I describe above.

Phil wrote:
“The probability of the event in the test cell is much higher than in the atmosphere because the laser beams are very tightly focussed and are ~50:50 pump and Stokes photons.”

Wrong. The total power of the 0.532 um residual photon flux and the 0.607 um and 0.707 um Stokes pump photon flux (from the Raman Cell to the Nitrogen Cell) are in a ratio of ~50:50, but that doesn’t imply the photon counts are.

All you’re really saying is that the Raman Cell had an approximate 50% efficiency at converting 0.532 um radiation into 0.607 um and 0.707 um radiation.

But Phil… now think hard… the total power of those two (0.532 um and 0.607/0.707) is now equal at the output of the Raman Cell. There’s already a photon flux of the same magnitude in the Nitrogen Cell at 0.607 um and 0.707 um as *twice* the 0.532 um power could produce in the Raman Cell.

The reason they used a separate Raman Cell is because the conversion of 0.532 um to 0.607 um and 0.707 um also results in (to quote them) “excess translational energy associated with the conversion of a (Raman Cell) pump photon (532 nm) to a Stokes photon (607 nm)” in the Raman Cell. They used a helium buffer in the Raman Cell to remove that heat.

They couldn’t use helium in the Nitrogen Cell, it’d mess up their results (as would the “excess translational energy associated with the conversion of a pump photon (532 nm) to a Stokes photon (607 nm)”), so they used the output of the Raman Cell as a pump for the Nitrogen Cell, and were thus able to have a pure N2 atmosphere in the Nitrogen Cell.

So in fact, they used the 0.607 um and 0.707 um flux as their pump beams. As they stated, the 0.532 um flux from the Raman Cell to the Nitrogen Cell was “residual”.

Phil wrote:
“The probability of the event in the test cell is much higher than in the atmosphere because the laser beams are very tightly focussed and are ~50:50 pump and Stokes photons.”

But Phil, you claimed that it could not happen at all! Remember? You said homonuclear diatomics had no net dipole moment, and thus could not be vibrationally excited by radiation. I’ve proven you wrong.

Of course the density of states of the photon flux in the cited experiment was higher than in the atmosphere, but you claimed it wasn’t happening at all in the atmosphere, notably in the troposphere.

But it does happen, Phil.

The measured Raman spectra of air (atmospheric pressure) with integration times of 1s and 100s
https://i.imgur.com/MzSqcet.png

N2, much more vibrationally excited in the atmosphere than CO2… and much more abundant as a constituent of the atmosphere (by a few orders of magnitude). So there are far more N2 molecules than CO2 molecules which are vibrationally excited, and the N2 molecules have a higher vibrational temperature, thus they will transfer their vibrational quantum state kinetic energy to CO2.

Doesn’t matter the altitude, Phil. I’ve shown that visible range photons and infrared photons can vibrationally excite N2, and those photons reach the surface of the planet from the sun. If you were arguing about microwave, you might have a point, but you don’t… because yet again you’re wrong.

And that’s not to mention collisional excitation of N2’s vibrational state with other molecular constituents.

So I’ve forced you from a position of complete denial: “N2 is a homonuclear diatomic with no net electric dipole so it cannot be vibrationally excited by radiation”, to a grudging acknowledgment that the processes described do take place: “Well, OK, N2 can be vibrationally excited by incident radiation, but it doesn’t happen very much in the troposphere.”

That’s progress. And that means I’m winning. LOL

And once you’re forced to concede that N2 can indeed Raman scatter both IR and visible range photons to become vibrationally excited (all the way down to the surface of the planet, no less), in addition to continually being vibrationally excited by collision with other molecular constituents of the atmosphere (most notably, O2 and N2 itself), you’ll finally be forced to admit that the warmist claims are pure bunkum.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Consequently the N2 in the troposphere is overwhelmingly in its vibrational ground state.”

I guess Phil wasn’t aware that spontaneous radiational and collisional
cascade processes in homonuclear diatomic molecules decrease any electronic excitation, accumulating the excitation energy in the vibrational levels of the lowest metastable states. It’s known as electronic quenching.

So N2 tends to preferentially funnel any excitation energy (from collisional processes, electronic excitation, etc.) into vibrational quantum state excitation.

And as I proved, the first excited vibrational mode of N2 is higher than CO2’s highest excitation state (asymmetric stretch).

——————————————————————
http://www.barrettbellamyclimate.com/page15.htm
———————————
The existence of the ν3(1) level is highly important with regard to its collisional excitation by nitrogen molecules in their first excited vibrational mode that has a transition wavenumber of 2359.6 cm-1, almost a perfect match for the excitation of the anti-symmetric stretching vibration of CO2:

N2 [ν1(1)] + CO2 [ν20(0)] → N2 [ν1(0)] + CO2 [ν3(1)]

The CO2 [ν3(1)] state can then emit radiation or be degraded to the lower energy levels from which radiation may be emitted.
———————————

You’ll note that’s N2’s first excited vibrational mode, and CO2’s *highest* excitation mode.

But more importantly, his last sentence states exactly what I’ve been stating.

And given that the mean free path length of that radiation increases with increasing altitude (as I stated in my original post)…
https://i.imgur.com/xz3nzgH.png
…the net vector for that radiation is upward.

Thus CO2 causes cooling, not warming.
———————————

———————————
Absorption of solar radiation by CO2 in the 2.7‐ and 2.77‐μm bands (000 -> 101 and 000 -> 021) results in fluorescent emissions at 4.3 μm due to the decay of these levels via 101 -> 100 and 021 -> 020. They are an order of magnitude greater than the radiance due to the resonance transition 001 -> 000 centered at 4.26 μm.

N2 is 2359.6 cm-1, which is 4.23801 um.

This is *why* N2 will *always* transfer its vibrational quantum state kinetic energy to CO2, Phil. The Laws of Thermodynamics dictates it does so.

Exactly as the website I linked to above says:
“N2 [ν1(1)] + CO2 [ν20(0)] → N2 [ν1(0)] + CO2 [ν3(1)]”

So as I said in my original post, the warmists have it exactly backward.

And as I said in my original post, thus dies CAGW.
———————————

• Phil. says:

And as I proved, the first excited vibrational mode of N2 is higher than CO2’s highest excitation state (asymmetric stretch).

Not that it matters because this whole concept of yours is irrelevant but N2(1) is 18cm-1 lower than CO2 (000).

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Not that it matters because this whole concept of yours is irrelevant but N2(1) is 18cm-1 lower than CO2 (000).”

But Phil, that’s a V-V (Vibration-Vibration) process, not the V-T (Vibration-Translation) process you warmists claim is causing global warming.

C02(001) + N2(v = 0) === C02(000) + N2(v = 1) + 18 cm-1 (555.5556 um)

Whereupon N2 will collide with other CO2 molecules in the v3(1) state:

http://www.barrettbellamyclimate.com/page15.htm
———————————
The existence of the ν3(1) level is highly important with regard to its collisional excitation by nitrogen molecules in their first excited vibrational mode that has a transition wavenumber of 2359.6 cm-1, almost a perfect match for the excitation of the anti-symmetric stretching vibration of CO2:

N2 [ν1(1)] + CO2 [ν20(0)] → N2 [ν1(0)] + CO2 [ν3(1)]

The CO2 [ν3(1)] state can then emit radiation or be degraded to the lower energy levels from which radiation may be emitted.
———————————

So you’ve just argued my point, Phil, by providing yet another mechanism by which N2 becomes vibrationally excited. Did you mean to do that? LOL

Now Phil, if CO2 atmospheric concentration increases, does that V-V to V-T process by which CO2 accumulates energy unto itself such that it will undergo emission relaxation by emitting a photon increase in prevalence? Yeah it does!

So an increased CO2 atmospheric concentration will cause what, Phil?

Cooling.

Do you need me to school you on any other topics today, Phil? LOL

• LOL@Klimate Katastrophe Kooks says:

Should be:
“Whereupon N2 will collide with other CO2 molecules in the ν20(0) state:”

• Phil. says:

No, as usual, you’re wrong. And as usual, you’re pulling “facts” straight from your goes-out. LOL

When you pull your premise from Wikipedia, Phil, you should check that *their* premise is correct. They say:
“Then, it simultaneously absorbs both pump and Stokes photons which then results with the occurrence of a vibrational (or rotational) transition with some probability.”

But that’s not what actually happens, as I describe above.

Actually I didn’t get my premise from Wikipedia I got it from about 40 years of study and research in the field. What happens is as I described earlier, the pump laser induced a polarization in the target molecule, this is referred to as a virtual state. After a very short lifetime (~10^-16 secs) this state relaxes mostly to the initial ground state but a few molecules (~1 in a million) relax to the vibrational states (Raman). In the SRS process the virtual state is illuminated by a Stokes beam which stimulates a transition to a preferred state determined by the difference in frequency of the two beams.

So in fact, they used the 0.607 um and 0.707 um flux as their pump beams. As they stated, the 0.532 um flux from the Raman Cell to the Nitrogen Cell was “residual”.

As they say and as I said above they used 532 as the pump beam and 607 as the Stokes beam.
As indicated by their equation the difference between the pump frequency and the Stokes frequency is equal to the excitation of the N2(1) state.
532nm= 18796cm-1
607nm= 16474cm-1
difference = 2322cm-1

But Phil, you claimed that it could not happen at all! Remember? You said homonuclear diatomics had no net dipole moment, and thus could not be vibrationally excited by radiation. I’ve proven you wrong.

You certainly have not. Homonuclear diatomics have no net dipole moment, and thus can not be vibrationally excited by radiation, the authors of this paper agree with me:
“Since N2 does not have a dipole moment, the absorption of infrared radiation and accompanying direct vibrational excitation is prohibited due to basic optical selection rules.”
What happens in the Raman case is that the pump laser distorts the electrical field of the molecule allowing the otherwise forbidden interaction with light.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Actually I didn’t get my premise from Wikipedia”

He says, while using a Wikipedia image. LOL

Phil wrote:
“As they say and as I said above they used 532 as the pump beam and 607 as the Stokes beam.”

They used 0.532 um as the pump beam in the Raman Cell, Phil. As they state in their report, the 0.532 beam flowing from the Raman Call to the Nitrogen Cell was “residual”. It’d already been used in the Raman Cell, so even had they put it to use in the Nitrogen Cell, it could only have produced 1/4 of the Stokes photon flux as it made in the Raman Cell… because it was *residual*, Phil.

Phil wrote:
“Homonuclear diatomics have no net dipole moment, and thus can not be vibrationally excited by radiation”

Unbelievable! You’ve just discussed for several days a process by which electromagnetic radiation is absorbed by N2, part of the photon’s energy is absorbed by the N2 to increase its vibrational quantum state kinetic energy and the rest is emitted as another photon… and yet you cling to the warmist line!

The cognitive dissonance in your skull must be deafening, Phil. LOL

As I’ve already discussed, Phil, they most certainly do not agree with you.

They state (emphasis mine):
“Since N2 does not have a dipole moment, the absorption of *infrared* radiation and accompanying *direct* vibrational excitation is prohibited due to basic optical selection rules.”

You’re wrong on two counts… first, we’re not discussing direct vibrational quantum state excitation, we’re discussing vibrational quantum state-Raman coupling and the fact that it exhibits a substantially increased cross-section under photon flux (which I described in a prior post, and which I proved does indeed include IR radiation); and not all radiation in the atmosphere is *infrared*, Phil.

They used *visible* *range* photons in the Nitrogen Cell, Phil.

You’re being pedantic again in an attempt at salvaging what little remains of your warmist mantra, Phil.

• Phil. says:

LOL@Klimate Katastrophe Kooks

Phil wrote:
“As they say and as I said above they used 532 as the pump beam and 607 as the Stokes beam.”

They used 0.532 um as the pump beam in the Raman Cell, Phil. As they state in their report, the 0.532 beam flowing from the Raman Call to the Nitrogen Cell was “residual”. It’d already been used in the Raman Cell, so even had they put it to use in the Nitrogen Cell, it could only have produced 1/4 of the Stokes photon flux as it made in the Raman Cell… because it was *residual*, Phil.

And yet in the fig 1 in their paper showing the experimental setup they only show 532nm and 607nm and disregard 707nm entirely.
In the Nitrogen cell there was 50mJ of 532nm as the pump and 40mJ of the Stokes (607nm), you’d expect this to be more efficient at producing the 607nm than the dye laser seed in the Raman cell because of the better match of the band width. The use of the dye laser as a seed still improved the efficiency of generating the 606 nm Stokes beam by a factor of 2.
Stimulated Raman using 606nm (40mJ) as a pump and 707nm (10mJ) as the Stokes would not generate as much N2 (v=1).

• LOL@Klimate Katastrophe Kooks says:

You’re forgetting (again), Phil, about vibrational quantum state coupling. Did you forget the lesson I schooled you on as regards how the molecule requires two fundamental Stokes frequencies in order to couple two vibrational quantum states (“Fantastical Pedantical Phil’s Wave Machine” LOL)?

You’re talking about regular Raman scattering (which they used in the Raman Cell to produce the Stokes lines)… this is Stimulated Scattering in the Nitrogen Cell, Phil.

What’s this say, Phil?
https://bernstein.harvard.edu/research/SRS.htm
“In contrast to the CARS (Coherent Anti-Stokes Raman Spectroscopy) signal that is generated at the anti-Stokes frequency, SRG (Stimulated Raman Gain) and SRL (Stimulated Raman Loss) occur *at* *the* *frequency* *of* *the* *excitation* beams*.” {Emphasis mine.}

Now Phil, what two frequencies were they measuring in the Nitrogen Cell? What frequencies are shown on the graphs on page 3 of 8, Phil?

Were they not using Q-branch Raman scattering in the Nitrogen Cell? You do understand what Q-branch Raman scattering implies, yes, Phil? It means SRG (Stimulated Raman Gain) and SRL (Stimulated Raman Loss) occur *at* *the* *frequency* *of* *the* *excitation* *beams*, Phil.

So the 0.607 um and 0.707 um beams they were measuring in the monochromator were the Q-branch frequencies of the pump frequencies, Phil, and the 0.532 um beam from the Raman Cell to the Nitrogen Cell was (as they said) “residual”.

Do you understand what Q branch Raman scattering means, Phil? It means *you* *are* *wrong*.

That’s why they wrote:
“Also note that 150 ns is selected for the minimum delay time in order to avoid interferences due to stray room scattering from the *first* *and* *second* *Stokes* *pump* *beams*, some of which, despite baffling, was found to enter the spectrometer.” {Emphasis mine.}

So you’re wrong yet again, Phil. You’ve demonstrated yet again that you haven’t the first faint clue what you’re talking about. You ought to be embarrassed. *I’m* embarrassed for you. You keep ramming your face into the fist of reality… and you’re so delusional that you actually think you’re ‘winning’. LOL

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“the pump laser induced a polarization in the target molecule, this is referred to as a virtual state. After a very short lifetime (~10^-16 secs) this state relaxes mostly to the initial ground state but a few molecules (~1 in a million) relax to the vibrational states (Raman).”

Phil trips over his warmist belief again:
“Homonuclear diatomics have no net dipole moment, and thus can not be vibrationally excited by radiation.”

You seem a bit confused about the Raman scattering process, Phil. The incident photon will *always* drive the molecule to a virtual state under Raman scattering upon absorption of the photon. That’s why Raman scattering isn’t a resonant process, it can happen with any frequency photon. The energy difference between the absorbed and emitted photon corresponds to the energy difference between two resonant states of the material and is independent of the absolute energy of the photon. The vibrationally excited state of the molecule is the end result of the Raman process.

So in your stating that “Homonuclear diatomics have no net dipole moment, and thus can not be vibrationally excited by radiation”, you’re denying that N2 can even undergo Raman scattering at all!

Of course, we know it can, don’t we, Phil?

40 years of study and research in the field, down the drain. LOL

• Phil. says:

So in your stating that “Homonuclear diatomics have no net dipole moment, and thus can not be vibrationally excited by radiation”, you’re denying that N2 can even undergo Raman scattering at all!

Of course, we know it can, don’t we, Phil?

Raman involves an induced dipole, the vast majority of those virtual states end up back at the ground state. We’re not talking about shining powerful laser beams through the atmosphere

• LOL@Klimate Katastrophe Kooks says:

Raman scattering, Phil, does indeed involve an induced dipole.

And you keep bleating about N2 not having a net electric dipole.

You’re conflating two different things (steady state and induced), Phil… another display of your errant pedantry.

Further, Phil… does N2 have a net magnetic dipole? Sure it does! Is the electromagnetic fundamental force symmetry broken in your fantasy world, Phil? From your words, it does appear to be so.

So yet again you’re wrong, and yet again you demonstrate your shallow knowledge of the Raman scattering process.

Just for kicks, Phil, can you go back to simultaneously admitting and denying that N2 can undergo Raman scattering? I literally laughed out loud when I read that twaddle from you. LOL

• LOL@Klimate Katastrophe Kooks says:

Here’s some questions you’ve dodged, Phil:

Where does the energy come from to vibrationally excite the N2 molecule undergoing Raman scattering? Does it just pop into existence from nowhere? Were you not aware that a vibrationally excited molecule is the end result of Raman scattering, Phil, and is the most significant marker of Raman scattering?

If, as you state, Phil, “the vast majority of those virtual states end up back at the ground state”, where does the vibrational quantum state energy go? Does it just disappear? Did you forget about virtual state-vibrational state coupling, Phil?

• Phil. says:

“the vast majority of those virtual states end up back at the ground state”, where does the vibrational quantum state energy go? Does it just disappear?

It’s called Rayleigh scattering.

• Phil. says:

Very good, Phil! But why were you describing it as though it were Raman scattering (and in the process simultaneously admitting and denying that N2 undergoes Raman scattering)? LOL

Rayleigh scattering is the light scattered from the virtual state without change in frequency and is the predominant form of scattering, Raman scattering is the light scattered from the virtual state with a change in frequency and is orders of magnitude smaller.

• LOL@Klimate Katastrophe Kooks says:

Been hitting Wikipedia again, Phil? LOL

In actuality, Phil, Raman scattering accounts for ~2.3% of all scattering (elastic and inelastic combined). It is of such magnitude that it red-shifts the solar spectra. It most definitely is not negligible, and at ~2.3%, it’s not “orders of magnitude smaller”. It is, at most, one order of magnitude smaller, which is two orders of magnitude greater than previously thought.

Math classes might help. You should give them a try. LOL

• Phil. says:

In actuality, Phil, Raman scattering accounts for ~2.3% of all scattering (elastic and inelastic combined). It is of such magnitude that it red-shifts the solar spectra. It most definitely is not negligible, and at ~2.3%, it’s not “orders of magnitude smaller”. It is, at most, one order of magnitude smaller, which is two orders of magnitude greater than previously thought.

You misread the paper you quoted that from, they said that the VRS contributed ~2.3 % of the RRS (which in turn is about 1 part per million). That was at 393nm, given the 1/𝜆-4 dependence of the cross-section that will be even smaller in the visible and IR.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“You misread the paper you quoted that from, they said that the VRS contributed ~2.3 % of the RRS (which in turn is about 1 part per million). That was at 393nm, given the 1/𝜆-4 dependence of the cross-section that will be even smaller in the visible and IR.”

Bwahaha! You did it again! You’re never going to live down this, your most explicit demonstration of inaptitude, Phil. You’ll be mocked and smirked at by everyone, Phil.

——————–
Let’s open this post with a prayer. I’m going to need it.

{God, grant me the strength to refrain from mercilessly mocking the feebleminded. Amen.}

Phil wrote:
“No the paper you quoted explicitly stated:
“the observed VRS(N2) cross-section at 393 nm amounts to 2.3 ± 0.4 % of the cross-section of RRS at 433 nm under tropospheric conditions.””

Exactly as I said. And look, Phil! Its “under tropospheric conditions”.

And that’s at just one incident wavelength, Phil. Are there more wavelengths than just one, Phil?

{Pssst… hey Phil! The answer is ‘yes’. Yer welcome. LOL}

Phil wrote:
“And RRS in turn is parts per million.”

Do you even know what RRS means, Phil? Obviously not.

Nowhere in that report do they mention “PPM” or “parts per million”, because RRS is not measured in parts per million, Phil.

It’s measured in cm2 sr-1 molec-1 or Wm2 incident power density, Phil.

“The relative contribution of the cross-section of VRS of N2 to the cross-section of RRS of 2.3 % is in agreement with expected values from the theory (2–3.5 %, depending on the measurement geometry).”

What’d I say, Phil? That N2 Vibrational Raman Scattering contributed 2.3% of all scattering.

But then, you don’t even know what “RRS” is (you think it’s measured in parts per million LOL), so you have no context with which to even understand much of anything.

Another giant fail from you, Phil. I’m believing less and less your claimed “40 years of study and research in the field”, Phil. LOL
——————–

• Phil. says:

Phil wrote:
“No the paper you quoted explicitly stated:
“the observed VRS(N2) cross-section at 393 nm amounts to 2.3 ± 0.4 % of the cross-section of RRS at 433 nm under tropospheric conditions.””

Exactly as I said. And look, Phil! Its “under tropospheric conditions”.

Not “as you said”, you said “of all scattering (elastic and inelastic combined)”.

And that’s at just one incident wavelength, Phil. Are there more wavelengths than just one, Phil?

And given the strong fall-off with the reciprocal 4th power of the wavelength they’ll have much smaller cross-sections.

Phil wrote:
“And RRS in turn is parts per million.”

Do you even know what RRS means, Phil? Obviously not.

You clearly don’t since you refer to it as ‘all scattering’ whereas it’s actually rotational Raman scattering. Since Rayleigh is about 1000x stronger than Raman the VRS contribution to ‘all scattering (elastic and inelastic combined)’ would be about 1 in 100,000 not 2%.

Nowhere in that report do they mention “PPM” or “parts per million”, because RRS is not measured in parts per million, Phil.

It’s measured in cm2 sr-1 molec-1 or Wm2 incident power density, Phil.

Yeah and Raman is typically about 10^-30 cm2 sr-1 compared with Rayleigh at about 10^-27 cm2 sr-1 for N2. The fact that Rayleigh is about 1000x stronger than Raman (which I mentioned in an earlier post) is the reason why when performing Raman spectroscopy it’s essential to filter out the Rayleigh signal.

By comparison with CO2 absorption of 667cm-1 in the atmosphere which has a cross section of ~10^-18 cm2 sr-1 you can see how trivial the Raman contribution is.

I was clearly being overgenerous in saying ‘parts per million’.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“And given the strong fall-off with the reciprocal 4th power of the wavelength they’ll have much smaller cross-sections.”

“fall-off”?! Demonstrating your maff skills again, Phil? LOL

At shorter wavelengths does not the cross-section increase, Phil? Is the cross-section not proportional to the inverse of wavelength, Phil?

So according to you, it not a “strong fall-off” with decreasing wavelength, it’s a “strong increase”. You’ve just argued my point (unwittingly) yet again, Phil. LOL

So in the visible range (which reaches all the way to the surface of the planet) and at BOA (where Raman scattering probability is highest because the probability increases for increasing path length), N2 will have the highest probability for Raman scattering.

{Pssst… hey Phil! That’s in the troposphere! LOL}

On top of the fact that there is a much greater abundance of vibrationally-excited N2 in the troposphere than previously thought, the V-T process you’re talking about has a low probability because energy transfers which don’t result in molecular motion are favored over those that do (ie: V-T deactivation is highly inefficient for all quantum states and all molecular masses, whereas V-V processes are practically instantaneous).

Even further, the rate constant for the particular V-T transfer the warmists are claiming happens between CO2 and N2 or O2 is actually ~2083.33 times more likely to happen with H2O.

And there’s nothing humanity can do about water vapor in the atmosphere, Phil, nor would we want to.

On top of all that, CO2 only has an induced dipole in its v3 state (the *highest* vibrational excitation state, Phil… you’ve claimed it’s not the highest, yet again showing your shallow knowledge. LOL). So CO2 has to be highly vibrationally excited to absorb any radiation, which reduces the photon collisional cross-section of CO2. That’s why CO2 usually *gives* *off* radiation, not absorbs it, Phil, in the process described below.

Phil wrote:
“You clearly don’t since you refer to it as ‘all scattering’ whereas it’s actually rotational Raman scattering. Since Rayleigh is about 1000x stronger than Raman the VRS contribution to ‘all scattering (elastic and inelastic combined)’ would be about 1 in 100,000 not 2%.”

All inelastic scattering results in vibrational excitation, Phil. Thus the total amount of N2 being vibrationally excited in the atmosphere is much higher than we previously thought, thus the CO2 to N2 V-T process has an even lower probability than previously thought.

In fact, Phil, the 14.9925 um radiation in the atmosphere wouldn’t even be there if it were not for N2 colliding with and imparting translational energy *to* CO2, which undergoes P-branch emission relaxation:

N2[v1(1)] + CO2[v20(0)] === N2[v1(0)] + CO2[v3(1)] + 2331 cm-1 (14.9925 um)

That it’s P-branch emission relaxation means the N2 was more excited than the CO2, Phil, and imparted energy from N2 to CO2, not the other way around.

http://www.barrettbellamyclimate.com/page15.htm
———————————
The existence of the ν3(1) level is highly important with regard to its collisional excitation by nitrogen molecules in their first excited vibrational mode that has a transition wavenumber of 2359.6 cm-1, almost a perfect match for the excitation of the anti-symmetric stretching vibration of CO2:

N2 [ν1(1)] + CO2 [ν20(0)] → N2 [ν1(0)] + CO2 [ν3(1)]

The CO2 [ν3(1)] state can then emit radiation or be degraded to the lower energy levels from which radiation may be emitted.
———————————

As I said, the warmists have it exactly backward. And given your multiple errors (you’re the guy who denies that infrared photons can cause N2 to become vibrationally excited; who claimed that N2 cannot become vibrationally excited at all under any circumstances; who didn’t know about vibronic coupling; who doesn’t understand the role of He in a CO2 laser; who claimed that because N2 is a homonuclear diatomic with no net electric dipole it could not absorb photons under any circumstances (“optically forbidden” LOL); who wants to visit the “hotter” upper atmosphere wearing flip-flops and a tank top; who couldn’t describe the Raman scattering process properly; who simultaneously admitted and denied that N2 undergoes Raman scattering; who can’t seem to grasp how harmonic oscillators work (“Fantastical Pedantical Phil’s Wave Machine” LOL); who denied that N2 could undergo Resonant Raman Scattering; who claimed that CO2[v3(1) aka CO2(001) was the lowest excitation state when it’s actually the highest; who thinks RRS (measured as an energy flux) has units of parts per million; who can’t seem to figure out a simple cascaded laser pump setup), I’d say you’re a prototypical warmist. LOL

• LOL@Klimate Katastrophe Kooks says:

Should be:
“In fact, Phil, the 14.9925 um radiation in the atmosphere wouldn’t even be there if it were not for CO2 colliding with N2 and imparting translational energy *to* N2, which undergoes P-branch emission relaxation:

C02[v21(1) + N2[v1(0)] === C02[v20(0)] + N2[v1(1)] + 667 cm-1 (14.9925 um)

This results in a loss of heat from the system, as all emitting radiative processes do.”

Somehow my spreadsheet switched the 667 cm-1 and 2331 cm-1 cells. I guess the spreadsheet table rotation bug still exists.

And the rate constant is still ~2083.33 times more likely to happen between CO2 and water vapor than CO2 and N2… and there’s nothing we can do about atmospheric water vapor, nor would we want to.

• Phil. says:

Should be:
“In fact, Phil, the 14.9925 um radiation in the atmosphere wouldn’t even be there if it were not for CO2 colliding with N2 and imparting translational energy *to* N2, which undergoes P-branch emission relaxation:

C02[v21(1) + N2[v1(0)] === C02[v20(0)] + N2[v1(1)] + 667 cm-1 (14.9925 um)

More nonsense, the 15𝜇m band radiation passing through the atmosphere originates with blackbody radiation from the surface. When absorbed by CO2 it can be emitted in either the P, Q or R bands.
http://www.barrettbellamyclimate.com/PQRA.jpg

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“More nonsense, the 15𝜇m band radiation passing through the atmosphere originates with blackbody radiation from the surface. When absorbed by CO2 it can be emitted in either the P, Q or R bands.”

Seems you’re on quite a streak of being wrong, Phil. LOL

https://i.imgur.com/C5pNIGM.png

You’re talking about CO2 + γ ↔ CO2*, Phil… not about V-T energy transfers. That causes an increase of system energy, whereas photon emission always results in a loss of system energy. Don’t you even know basic thermodynamics, Phil? LOL

Further, Phil, you’re now going to have to argue against a physicist who is on the WattsUpWithThat.com site:

https://wattsupwiththat.com/2010/08/05/co2-heats-the-atmosphere-a-counter-view/
“The LTE conditions with the energy equipartition law give immediately the answer : “These rates are exactly equal .” This means that for every collision where a vibrationally excited CO2* transfers energy to N2 , there is a collision where N2⁺ transfers the same energy to CO2 and excites it vibrationally . There is no net energy transfer from CO2 to N2 through the vibration-translation interaction .”

You’re wrong, Phil. Your warmist religion continues to crumble by the day.

• Phil. says:

“More nonsense, the 15𝜇m band radiation passing through the atmosphere originates with blackbody radiation from the surface. When absorbed by CO2 it can be emitted in either the P, Q or R bands.”

Which is correct, although in the troposphere collisional deactivation, such as is indicated in the first line (a) of the V-T processes shown below, occurs. For those not familiar with the terminology ‘M’ refers to any collisional partner, in the atmosphere predominantly N2 and O2.

https://i.imgur.com/C5pNIGM.png

No problem arguing with Vonk, he was wrong about that then and on other matters.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Which is correct, although in the troposphere collisional deactivation, such as is indicated in the first line (a) of the V-T processes shown below, occurs. ”

Ah, so you admit I’m right, Phil. Good of you. LOL

Phil wrote:
“No problem arguing with Vonk, he was wrong about that then and on other matters.”

The only thing he was incorrect about is that chemical kinetics dictate that with the three orders-of-magnitude greater concentration of N2 in the atmosphere than CO2 (and thus greater partial pressure), it is energetically favorable for energy to flow from the vibrational state of N2 to CO2, whereupon the CO2 will undergo emission relaxation, which always results in a loss of energy from the system.

Remember, N2 and CO2 have very closely resonant excitation levels, and V-T transfers are highly inefficient in comparison to the nearly instantaneous V-V transfer.

So, Phil… I’m ‘more right’ than a physicist. You’re not arguing against me, Phil, you’re arguing against the reality of equations which were empirically derived long ago by people far smarter than you, and proven to be accurate in modeling our world.

But arguing against reality is kind of what you leftist warmists do, now isn’t it, Phil? That is, after all, why you’re all laughingstocks. LOL

The really funny part, Phil? Even Nick Stokes knows and admits this (from the comments on that page):
“To put it another way, in any interaction between a CO2 and a N2, it is much more likely that the CO2 will be excited than the N2 (because of the disparity in numbers).”

• Phil. says:

You posted this:
It means that the maximum vibrational temperature of CO2 doesn’t come anywhere close to enough energy to excite N2 from its vibrational ground state upon collision.

To which I replied:
Phil.
Garbage, it’s V-T transfer not V-V transfer!
The excited CO2 has more vibrational energy than 95% of the surrounding N2 molecules have translational energy so no 2LOT violation.

Remember, N2 and CO2 have very closely resonant excitation levels, and V-T transfers are highly inefficient in comparison to the nearly instantaneous V-V transfer.

The resonant excitation levels are only at the vibrationally excited N2 frequency whereas the N2 in the troposphere is predominantly in the vibrational ground state which receives translational energy from the vibrationally excited CO2, via V-T.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“The resonant excitation levels are only at the vibrationally excited N2 frequency whereas the N2 in the troposphere is predominantly in the vibrational ground state which receives translational energy from the vibrationally excited CO2, via V-T.”

Did you forget the Equipartition Theorem, Phil?

Under Local Thermodynamic Equilibrium, there is *no* *net* *energy* *transfer* between N2 and CO2 translationally.

Given that homonuclear diatomics tend to couple their excitation states such that they preferentially increase their vibrational excitation levels over translational or electronic (quenching), that means that every time a CO2 molecule impinges upon a N2 molecule, that translational energy will either nearly immediately be transferred right back to another molecule (no net change in system energy), or (preferentially, given that intra-molecular coupling is much faster than inter-molecule translational energy transfer) increase its vibrational quantum state, whereupon it will impinge upon a CO2 molecule, imparting sufficient vibrational quantum state energy such that the CO2 molecule can undergo emission relaxation by emitting a photon, resulting in a loss of energy from the system.

https://i.imgur.com/MzSqcet.png
N2, much more vibrationally excited in the atmosphere than CO2… and much more abundant as a constituent of the atmosphere (by a few orders of magnitude). So there are far more N2 molecules than CO2 molecules which are vibrationally excited, and the N2 molecules have a higher vibrational temperature, thus they will transfer their vibrational quantum state kinetic energy to CO2.

And given that the mean free path length of that emitted radiation is upward (as I stated in my original post)…
https://i.imgur.com/xz3nzgH.png
… the net vector for that radiation is upward.

Thus CO2 causes cooling, not warming.

• Phil. says:

Phil wrote:
“And given the strong fall-off with the reciprocal 4th power of the wavelength they’ll have much smaller cross-sections.”

“fall-off”?! Demonstrating your maff skills again, Phil? LOL

At shorter wavelengths does not the cross-section increase, Phil? Is the cross-section not proportional to the inverse of wavelength, Phil?

Do you not understand the meaning of the word ‘reciprocal’ Kook? Perhaps it hadn’t occurred to you that 393nm is near the minimum wavelength in the troposphere and that the other wavelengths you refer to will be longer not shorter?

On top of the fact that there is a much greater abundance of vibrationally-excited N2 in the troposphere than previously thought,

Not true, as your own source says:
“Note that anti-Stokes lines are very weak under atmospheric conditions, since only a small fraction of the N2 and O2 molecules is vibrationally excited.”

On top of all that, CO2 only has an induced dipole in its v3 state (the *highest* vibrational excitation state, Phil… you’ve claimed it’s not the highest, yet again showing your shallow knowledge. LOL). So CO2 has to be highly vibrationally excited to absorb any radiation, which reduces the photon collisional cross-section of CO2. That’s why CO2 usually *gives* *off* radiation, not absorbs it, Phil, in the process described below.
Again not true, CO2 absorbs in the v2 state.
v2 (000) to v2(010) 667cm-1
So CO2 absorbs in its ‘lowest’ vibrationally excited state!

Phil wrote:
“You clearly don’t since you refer to it as ‘all scattering’ whereas it’s actually rotational Raman scattering. Since Rayleigh is about 1000x stronger than Raman the VRS contribution to ‘all scattering (elastic and inelastic combined)’ would be about 1 in 100,000 not 2%.”

All inelastic scattering results in vibrational excitation, Phil. Thus the total amount of N2 being vibrationally excited in the atmosphere is much higher than we previously thought,

As they show it’s still a tiny proportion just a bit higher than previously thought.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Not true, as your own source says:
“Note that anti-Stokes lines are very weak under atmospheric conditions, since only a small fraction of the N2 and O2 molecules is vibrationally excited.””

Bwahahahaa! Phil yet again demonstrates that he doesn’t know what he’s talking about.

Phil… is there a difference between Stokes and Anti-Stokes?

That should have read:”Note that anti-Stokes lines are very weak under atmospheric conditions because the temperature is low enough that N2 and O2 molecules are insufficiently vibrationally excited to generate anti-Stokes lines.”

That has nothing to do with Stokes lines, Phil, which are the result of nearly all inelastic scattering in the atmosphere. You’ll note that anti-Stokes lines *are* generated in the atmosphere, Phil, despite the low temperature… so the Stokes lines will be stronger. LOL

As I proved, Phil, the prevalence of vibrationally-excited N2 in the atmosphere is much higher than previously thought… so much so that it was discovered that the inelastic scattering red-shifted the spectrum of light we receive from the sun. That’s not an insignificant amount of scattering, Phil.

Phil wrote:
“Again not true, CO2 absorbs in the v2 state.
v2 (000) to v2(010) 667cm-1
So CO2 absorbs in its ‘lowest’ vibrationally excited state!”

You just keep beating your head against that brick wall, huh, Phil? LOL

You don’t even understand the nomenclature! What the heck is “v2 (000) to v2(010)”, Phil? The v2 state is not (000). You’re attempting to mix two nomenclatures, and you don’t understand either one! Good grief, educate yourself, Phil.

Fantastical Pedantical Phil’s Craptacular Fails List:
===============
Phil is the Klimate Katastrophe Kook who denies that infrared photons can cause N2 to become vibrationally excited; who claimed that N2 cannot become vibrationally excited at all under any circumstances; who didn’t know about vibronic coupling; who doesn’t understand the role of He in a CO2 laser; who claimed that because N2 is a homonuclear diatomic with no net electric dipole it could not absorb photons under any circumstances (“optically forbidden” LOL); who wants to visit the “hotter” upper atmosphere wearing flip-flops and a tank top; who couldn’t describe the Raman scattering process properly; who simultaneously admitted and denied that N2 undergoes Raman scattering; who can’t seem to grasp how harmonic oscillators work (“Fantastical Pedantical Phil’s Wave Machine” LOL); who denied that N2 could undergo Resonant Raman Scattering; who didn’t know that inelastic scattering always results in vibrational excitation; who claimed that CO2[v3(1) aka CO2(001) was the lowest vibrational excitation state when it’s actually the highest; who thinks RRS (measured as an energy flux) has units of parts per million; who can’t seem to figure out a simple cascaded laser pump setup; who thinks that shorter wavelengths result in a “strong fall-off” in Raman scattering cross-section when it’s actually the opposite; who thinks Raman scattering only happens in the upper atmosphere (when in actuality the cross-section increases with optical depth); who doesn’t know the difference between Stokes and anti-Stokes lines; who thinks that “v2 (000)” is a vibrational excitation state. LOL
===============

In CO2’s first (v1) vibrational state (CO2(180◦|X1A′)… that’s a third nomenclature you won’t be able to grasp, Phil. LOL), otherwise known as symmetric stretch, it has 0 D dipole moment, thus it cannot absorb photons. You’ll note this is different than N2 because CO2 has 3 atoms, whereas N2 has two. Thus dipole vector cancellation will always equate to zero for CO2 in the v1 state, whereas the changing separation distance between the two N2 atoms can induce a dipole since there is no vector cancellation. This means that CO2 cannot absorb photons in the v1 symmetric stretch mode.

The v2 bend mode typically has no net dipole, with a few exceptions of a very weak dipole. The exceptions:
———-
CO2(72◦|X1A′), with fundamental vibrational frequencies at 1495 cm-1, 666 cm-1 and 683 cm-1, with a weak dipole moment of -0.25 D.

CO2(118◦|21A′) with fundamental vibrational frequencies at 1336 cm-1, 576 cm-1 and 846 cm-1, with a weak dipole moment of 0.99 D.

CO2(119◦|13A′) with fundamental vibrational frequencies at 1378 cm-1, 602 cm-1 and 1095 cm-1, with a weak dipole moment of 0.46 D.

CO2(127◦|11A′′) with fundamental vibrational frequencies at 1282 cm-1, 671 cm-1 and 904 cm-1, with a weak dipole moment of 0.36 D.

CO2(128◦|13A′′) with fundamental vibrational frequencies at 1088 cm-1, 651 cm-1 and 614 cm-1, with a weak dipole moment of 0.25 D.

CO−2 (138◦|12A′) with fundamental vibrational frequencies of 650 cm-1, 1172 cm-1 and 1657 cm-1, with a weak dipole moment of 0.27 D.
———-
So the bend (v2) mode of CO2 has extremely weak absorption bands (because the C atom never moves far from the O atoms)… so weak that they’re typically ignored except for CO2(72◦|X1A′) (aka CO2[v20(2)]) because its fundamental is a second overtone of one of the v3 mode’s fundamentals. In the rest of the v2 modes, CO2 has no net dipole because of dipole vector subtraction, so it cannot absorb radiation.

So the only mode in which CO2 is considered as dipole active is the asymmetric stretch mode (v3) and one v2 mode with a weak dipole moment. That’s why, Phil, there’s only one transition path from the v2 to the v3 state at 1063.7 cm-1 (9.40115 um).

https://i.imgur.com/ZRgZ1OG.jpg

Seriously, Phil… are you not embarrassed that you continue to spew utterly wrong blather, not once bothering to verify what you’re writing? LOL

• Phil. says:

Phil wrote:
“Not true, as your own source says:
“Note that anti-Stokes lines are very weak under atmospheric conditions, since only a small fraction of the N2 and O2 molecules is vibrationally excited.””

If you look at the diagram below carefully you’ll see that in order to get an anti-Stokes line you need the N2 to first be in a vibrationally excited state. As pointed out by your source the very weak anti-Stokes shows that” only a small fraction of the N2 molecules is vibrationally excited”. However, you’ve been blathering on here for ~4 days claiming that vibrationally excited N2 is being created in the atmosphere by vibrational Raman! As I’ve pointed out several times N2 is predominantly in its vibrational ground state in the atmosphere, confirmed by your own source.
http://rsif.royalsocietypublishing.org/content/royinterface/13/118/20160182/F2.large.jpg

As I proved, Phil, the prevalence of vibrationally-excited N2 in the atmosphere is much higher than previously thought…
You ‘proved’ nothing of the sort, you linked to a paper which showed the following result:
https://i.imgur.com/SKCGC3d.png
What those results show is that the Rayleigh scattering (elastic) cross-section is ~2×10^-27, the rotational N2 Raman (inelastic) is ~2×10^-30, and the vibrational N2 Raman is ~1×10^-32.
So the inelastic components comprise about one-thousanth of the total scattering and the vibrational Raman comprises only ~1% of the inelastic component. Their results do not support your contention that “the prevalence of vibrationally-excited N2 in the atmosphere is much higher than previously thought”.

You don’t even understand the nomenclature! What the heck is “v2 (000) to v2(010)”, Phil? The v2 state is not (000).
(000) is the ground state, absorption of 667cm-1 excites it to the first excited state of the v2 mode (010).
http://www.aml.engineering.columbia.edu/ntm/level1/ch05/html/Image432.gif

So the bend (v2) mode of CO2 has extremely weak absorption bands
Flat out false, for a guy who witters on about how strong the vibrational Raman is to say that this mode is extremely weak when it is ~10^14 times stronger than the Raman is laughable!
http://3.bp.blogspot.com/_ltlOkpoAR8o/S5FQpqpxlMI/AAAAAAAABLM/ye5RMbQcUww/s320/CO2-abs+microns.bmp

The v2 bend mode typically has no net dipole, with a few exceptions of a very weak dipole.

Apparently you are unaware that those examples you cite are electronic excited states not the ground state and first vibrational excited states that we encounter in the atmosphere.
The CO2(72) version is a triangular ring structure, nothing like the linear ground state molecule in the atmosphere!

https://qph.fs.quoracdn.net/main-qimg-667bb7d8a70c64c1f9100e0085e4ce65-c

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“If you look at the diagram below carefully you’ll see that in order to get an anti-Stokes line you need the N2 to first be in a vibrationally excited state.”

Still showing your shallow depth of knowledge, Phil?

In order to get an anti-Stokes line, you need the N2 to first be in a *sufficiently* *vibrationally* *excited* *state*, Phil.

Now, Phil… is the anti-Stokes line not of a higher energy than the Stokes line? Sure it is. So all that article states is that the atmosphere’s temperature isn’t sufficiently high such that the vibrational quantum state energy of N2 is sufficient to generate much in the way of the more-energetic anti-Stokes lines.

You’ll note that anti-Stokes lines *are* still produced in the atmosphere, but the anti-Stokes signal is weak… the Stokes line, however, is much stronger because the Stokes line consists of less-energetic photons and thus requires less vibrational excitation energy of N2.

Phil wrote:
“So the inelastic components comprise about one-thousanth of the total scattering and the vibrational Raman comprises only ~1% of the inelastic component.”

Showing your maff skills again, Phil? LOL

“The relative contribution of the cross-section of VRS of N2 to the cross-section of RRS of 2.3 % is in agreement with expected values from the theory (2–3.5 %, depending on the measurement geometry).”

According to Phil, 2.3% = 1%. Which correlates to the Rules for Libtards, Rule #1: “They are notoriously bad at math.” LOL

https://i.imgur.com/sZ0yyhJ.png

Note the total (Rayleigh and Raman) scattering and RRS in the top graph, note the relative amount of scattering by N2 VRS and VRRS. You’ll note N2 VRS and VRRS contributes a significant percentage of all Raman scattering. Note especially the 420-440 nm (0.42-0.44 um) ghost lines.

https://www.atmos-meas-tech.net/8/3767/2015/amt-8-3767-2015.pdf
“Vibrational Raman scattering of N2 and O2 can contribute *significantly* to observed optical depths in passive DOAS applications.” {Emphasis mine}

This means, Phil, that a far larger percentage of N2 in the troposphere is vibrationally excited than was previously thought. So much so that the spectrum of light we receive from the sun is red-shifted by VRS, RRS and VRRS.

https://i.imgur.com/MzSqcet.png

N2, much more vibrationally excited in the atmosphere than CO2… and much more abundant as a constituent of the atmosphere (by a few orders of magnitude). So there are far more N2 molecules than CO2 molecules which are vibrationally excited, and the N2 molecules have a higher vibrational temperature, thus they will transfer their vibrational quantum state kinetic energy to CO2.

And given that the mean free path length of that radiation increases with increasing altitude (as I stated in my original post)…
https://i.imgur.com/xz3nzgH.png
…the net vector for that radiation is upward.

Thus CO2 causes cooling, not warming.

And that means you’re *wrong*, Phil. Again. But don’t let that stop you from ‘clinging to your gun and Bible’ of CAGW, Phil… your continued insistence on arguing against the empirically-derived mathematical formulas which have had more than a century of proofs that they accurately model our reality constitutes your continued arguing against reality… which means you’re delusional, Phil. LOL

Phil wrote:
“What those results show is that the Rayleigh scattering (elastic) cross-section is ~2×10^-27”

Bwahahaa! Phil’s showing his maff and reading comprehension skills again. LOL

Rayleigh wasn’t even mentioned on that chart, Phil. In point of fact, the N2 Raman scattering cross-section was ~2×10^-27, which throws off all of your calculations. LOL

Phil wrote:
“Flat out false, for a guy who witters on about how strong the vibrational Raman is to say that this mode is extremely weak when it is ~10^14 times stronger than the Raman is laughable!
http://3.bp.blogspot.com/_ltlOkpoAR8o/S5FQpqpxlMI/AAAAAAAABLM/ye5RMbQcUww/s320/CO2-abs+microns.bmp

Now Phil is mixing his units *and* displaying his maff skills again. LOL

https://i.imgur.com/kLxOjRo.png
CO2 has a cross-section at 15 um of 300×10^-21, Phil. And as the graph above says, N2 has a cross-section of ~2×10^-27.

So what is 2e-26/3e-18, Phil? 6.66e-09, not your claimed “~10^14”. So you were only off by 5 orders of magnitude. Is that the type of maff you used during your “40 years of study and research in the field”, Phil? LOL

Phil wrote:
“Apparently you are unaware that those examples you cite are electronic excited states not the ground state and first vibrational excited states that we encounter in the atmosphere.”

Yeah, that was kind of the point, Phil… the only one which has any appreciable absorption cross-section is CO2(72◦|X1A′) (aka CO2[v20(2)]) because its fundamental is a second overtone of one of the v3 mode’s fundamentals… but you just called that vibrational mode “electronic excited state”, Phil… yet again you’re wrong. LOL

Remember my stating:
“Now Phil, given the vibrational selection rules, can you tell everyone how CO2[v20(2)] can get to CO2[v3(1)] without violating the vibrational selection rules?

I bet you can’t. LOL”

Now I *know* you can’t. LOL

• Phil. says:

Phil wrote:
“If you look at the diagram below carefully you’ll see that in order to get an anti-Stokes line you need the N2 to first be in a vibrationally excited state.”

Exactly that’s how it works, didn’t you look at the diagram?
The Raman ‘pump’ is always of sufficient energy to produce both Stokes and anti-Stokes lines, the ratio of the two depends on the relative populations of the initial states. The excitation energy in both cases is the same. If the anti-Stokes line is weak it means that there is very little N2 in the first vibrationally excited state, but you’re constantly telling us that N2 is “much more vibrationally excited in the atmosphere than CO2”. If that were the case you’d have stronger N2 anti-Stokes.

You’ll note that anti-Stokes lines *are* still produced in the atmosphere, but the anti-Stokes signal is weak… the Stokes line, however, is much stronger because the Stokes line consists of less-energetic photons and thus requires less vibrational excitation energy of N2.

No they both require the same excitation energy.

Phil wrote:
“So the inelastic components comprise about one-thousanth of the total scattering and the vibrational Raman comprises only ~1% of the inelastic component.”

Showing your maff skills again, Phil? LOL

“The relative contribution of the cross-section of VRS of N2 to the cross-section of RRS of 2.3 % is in agreement with expected values from the theory (2–3.5 %, depending on the measurement geometry).”

According to Phil, 2.3% = 1%. Which correlates to the Rules for Libtards, Rule #1: “They are notoriously bad at math.” LOL
I don’t know anything about ‘Libtards’ but I’m very good at math. According to Fig. 1 the RRS signal peaks at ~2×10^-30 and the VRS peaks at ~1.5×10^-32, which I rounded to ~1%. Where you are getting confused is that they compared that VRS value for 393nm with the RRS for 433nm which leads to an adjustment by 1/𝜆-4, hence the higher percentage.

Phil wrote:
“What those results show is that the Rayleigh scattering (elastic) cross-section is ~2×10^-27”

Bwahahaa! Phil’s showing his maff and reading comprehension skills again. LOL

Yes it shows that they’re excellent, unlike yours, apparently you hadn’t realized that the authors referred to the Rayleigh line as the Cabannes line. Oops.

Rayleigh wasn’t even mentioned on that chart, Phil. In point of fact, the N2 Raman scattering cross-section was ~2×10^-27, which throws off all of your calculations. LOL

So again I was right and you are wrong.

Phil wrote:
“Flat out false, for a guy who witters on about how strong the vibrational Raman is to say that this mode is extremely weak when it is ~10^14 times stronger than the Raman is laughable!

CO2 has a cross-section at 15 um of 300×10^-21, Phil. And as the graph above says, N2 has a cross-section of ~2×10^-27.

So correcting your error the vibrational N2 Raman cross-section is ~1×10^-32, using your value for CO2 cross-section as 3×10^-19 we get 3×10^-19/1×10^-32 = 3×10^13
That’s close enough to 10^14 for me!

Yeah, that was kind of the point, Phil… the only one which has any appreciable absorption cross-section is CO2(72◦|X1A′) (aka CO2[v20(2)]) because its fundamental is a second overtone of one of the v3 mode’s fundamentals… but you just called that vibrational mode “electronic excited state”, Phil… yet again you’re wrong. LOL

CO2(72◦|X1A′) is not aka CO2[v20(2)], it’s known as dioxiranylidene, which is a three-membered ring compound which is an isomer of carbon dioxide. In case you don’t know what an isomer is, it is a compound that contains the same number of atoms of the same elements but differs in structure and properties. So it has nothing to do with Carbon dioxide!

So not a good post for you, you got everything wrong, that must be some sort of a record even for you!

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Exactly that’s how it works, didn’t you look at the diagram?
The Raman ‘pump’ is always of sufficient energy to produce both Stokes and anti-Stokes lines, the ratio of the two depends on the relative populations of the initial states.”

You seem to be hitting Wikipedia pretty frequently, Phil. LOL

Your non sequitur answer doesn’t address the topic, Phil, and you’re attempting to attribute to me your own non sequitur waffling as means of creating a strawman you can build up, knock down and declare ‘victolly!’.

It’s not working, Phil. LOL

About your “populations of the initial states”, Phil… isn’t that exactly what I wrote when I schooled you about vibrational quantum state coupling (“Fantastical Pedantical Phil’s Wave Machine”)? So you’re agreeing with me, which means I was right. LOL

Phil wrote:
“The excitation energy in both cases is the same.”

Only in terms of frequency offset from the exciting frequency. But they are not the same in terms of thermal and therefore quantum state vibrational energy levels, Phil, nor in the exciting photon energy. They do not require the same frequency (and thus energy) photons, the exciting photons for anti-Stokes is higher frequency therefore higher energy (Planck-Einstein relation).

Anti-Stokes has a lower population density, therefore Stokes and anti-Stokes are not symmetric… conversely, Stokes lines are brighter than anti-Stokes lines simply because there are more molecules in lower states than in thermally excited states (a natural consequence of the Maxwell-Boltzmann distribution).

Exactly as I said: “In order to get an anti-Stokes line, you need the N2 to first be in a *sufficiently* *vibrationally* *excited* *state*, Phil.”

Didn’t you know that temperature affects the vibrational quantum state level population, Phil? LOL

That’s why the Stimulated Raman Scattering test you’ve been blathering about for the past week (and which you were completely wrong about, Phil. LOL) requires both *Stokes* and *anti-Stokes* lines, Phil. Different photon frequencies, different photon energies for each line, Phil.

So your claim that “the excitation energy in both cases is the same” is *wrong*, Phil. But don’t let the fact that you’ve been wrong about *everything* thus far prevent you from continuing to display your utter lack of knowledge. LOL

And since you can’t seem to grasp the underlying fundamentals of Raman scattering, you probably can’t even describe the physical mechanism by which blue light is scattered at a greater angle than red light. LOL

Weep bitter tears over your being *wrong* yet again, Phil. LOL

That’s your graphic, Phil. I suggest you spend the time necessary to actually understand it, rather than Googleraping Google Images and grabbing whichever graphic you first run across which you think bolsters your point.

Phil wrote:
“Where you are getting confused is that they compared that VRS value for 393nm with the RRS for 433nm which leads to an adjustment by 1/𝜆-4, hence the higher percentage.”

More dribbling blather from you, Phil. The difference in wavelengths is *because* *of* *the* *Raman* *scattering*. They used a theoretically-derived astrophysics correction factor (used for exoplanets) on planet Earth to determine the relative cross-section magnitudes of VRS of O2 and N2, and RRS of air, since no one had bothered to do it before to determine the actual Raman scattering in our atmosphere. They found that a large portion of the VRS was being hidden by Fraunhofer line in-filling. Thus VRS accounts for a much larger proportion of inelastic scattering than previously thought.

https://www.atmos-meas-tech.net/8/3767/2015/amt-8-3767-2015.pdf
=======================
“We use the VRS correction spectra in the spectral range of 420–440 nm to determine the relative magnitude of the cross-sections of VRS of O2 and N2 and RRS of air.”

“The measurements yield in agreement with calculated scattering cross-sections that the observed VRS(N2) cross-section at 393 nm *amounts* *to* *2.3 ± 0.4 %* *of* *the* *cross-section* *of* *RRS* at 433 nm under tropospheric conditions.” {Emphasis mine.}

While the pure rotational Raman lines of N2 or O2 appear in the vicinity of the wavelength region of 393 nm, the rotational–vibrational Raman (Stokes) lines of N2 and O2 are *considerably* *red*-*shifted* according
to their different vibrational constants. VRS of O2 leads to a red-shift of the calcium-II K-absorption line of 25 nm, VRS of N2 to 40 nm.” {Emphasis mine.}
=======================
https://i.imgur.com/SKCGC3d.png
393 + 25 = 418
393 + 40 = 433

Does that simple math elude you, Phil? LOL

Is this going to be like the Stimulated Raman Scattering test, Phil? Where you spew your blathering inaptitude for weeks, then are proven to be utterly and completely wrong? LOL

Phil wrote:
“According to Fig. 1 the RRS signal peaks at ~2×10^-30 and the VRS peaks at ~1.5×10^-32, which I rounded to ~1%”

But the N2 RRS signal is actually ~9×10^-29, Phil. You’re only off by an order of magnitude. So your maff skills are improving. LOL

And you’re claiming that you’re good at maff is disputed by your attempt at converting cm^2 sr^-1 to percentage… we’ve already covered this, Phil. That’s an energy flux. You’re converting a single energy flux to a percentage! Maff. LOL

N2 VRS peaks at ~9.8×10^-29, Phil. Can’t you even read a graph?

{Hint, Phil: The Differential Cross Section axis is labeled in descending order. You’re reading it as though it were labeled in ascending order. LOL}

So yet again, you’re *wrong*, Phil. LOL

Phil wrote:
“Yes it shows that they’re excellent, unlike yours,”

Says Mr. Dunning-Kruger. LOL

But Phil, the Cabannes N2 line is at ~9×10^-26, not your claimed “~2×10^-27”. Don’t you even know how to read a graph? LOL

Baby steps, Phil. First learn how to read a graph, *then* try math. LOL

Phil wrote:
“So correcting your error the vibrational N2 Raman cross-section is ~1×10^-32, using your value for CO2 cross-section as 3×10^-19 we get 3×10^-19/1×10^-32 = 3×10^13
That’s close enough to 10^14 for me!”

Only because you can’t read a graph, and you suck at math, Phil. LOL

The N2 RRS cross-section is ~9×10^-29 (9e-28).
The N2 VRS cross-section is ~9.8×10^-29. (9.8e-28)

I’d tell you to educate yourself, Phil, but you’ve demonstrated repeatedly that your overblown bloviating ego, combined with the brutal case of Dunning-Kruger you suffer from, precludes you doing that. LOL

• Phil. says:

Phil wrote:
“Exactly that’s how it works, didn’t you look at the diagram?
The Raman ‘pump’ is always of sufficient energy to produce both Stokes and anti-Stokes lines, the ratio of the two depends on the relative populations of the initial states.”

Phil wrote:
“The excitation energy in both cases is the same.”

Didn’t you know that temperature affects the vibrational quantum state level population, Phil? LOL

Yes, but I’m not the one who keeps insisting that vibrationally excited N2 is being created in the atmosphere in great quantities.

Here’s the graphic, the blue line shows the same excitation energy in each case. In the anti-Stokes it is excited from the first vibrational level to a higher virtual state and falls back to the ground state. However that first excited state is so lowly populated that there’s very little anti-Stokes emitted, despite your protestations of much higher vibrationally excited N2.

Phil wrote:
“According to Fig. 1 the RRS signal peaks at ~2×10^-30 and the VRS peaks at ~1.5×10^-32, which I rounded to ~1%”

But the N2 RRS signal is actually ~9×10^-29, Phil. You’re only off by an order of magnitude. So your maff skills are improving. LOL
N2 VRS peaks at ~9.8×10^-29, Phil. Can’t you even read a graph?

{Hint, Phil: The Differential Cross Section axis is labeled in descending order. You’re reading it as though it were labeled in ascending order. LOL}

This is where it gets embarrassing, you don’t even know how to read a log graph!
Here’s a sample, check it out.
https://encrypted-tbn0.gstatic.com/images?q=tbn:ANd9GcS3Y7lOUWLZgNxL4sPIS36A8F6xvZu4dyC-Ov0x11jHFymJ5xpU

Baby steps, Phil. First learn how to read a graph, *then* try math. LOL

Good advice, I suggest you take it because you’ve just told everyone you don’t know how to read a log graph!

Phil wrote:
“So correcting your error the vibrational N2 Raman cross-section is ~1×10^-32, using your value for CO2 cross-section as 3×10^-19 we get 3×10^-19/1×10^-32 = 3×10^13
That’s close enough to 10^14 for me!”

Yes I read the graphs correctly and did the math correctly.

You disagreed because you can’t read a log graph, and you suck at math.

And you’re claiming that you’re good at maff is disputed by your attempt at converting cm^2 sr^-1 to percentage… we’ve already covered this, Phil. That’s an energy flux. You’re converting a single energy flux to a percentage!

It’s not an energy flux, it’s a cross section and I converted the ratio of two cross sections to a percentage (as did the authors).

I thought your errors last night were bad, but not being able to read a log graph takes the biscuit!

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Yes, but I’m not the one who keeps insisting that vibrationally excited N2 is being created in the atmosphere in great quantities.”

Your reading comprehension problems are leading to your false conclusions, Phil. I didn’t say “great quantities”, I said “much greater abundance than we had previously thought”. Seems you’re only pedantic when it suits your purpose. LOL

Phil wrote:
“Here’s the graphic, the blue line shows the same excitation energy in each case. In the anti-Stokes it is excited from the first vibrational level to a higher virtual state and falls back to the ground state. However that first excited state is so lowly populated that there’s very little anti-Stokes emitted, despite your protestations of much higher vibrationally excited N2.”

Now Phil is claiming that the ground state and the first vibrationally excited state are at the exact same frequencies! You don’t understand much of anything, do you, Phil? LOL

Phil wrote:
“It’s not an energy flux, it’s a cross section and I converted the ratio of two cross sections to a percentage (as did the authors).”

No, you first tried to convert RRS (incorrectly) to parts per million. LOL

So you admit, then that the authors were correct when they stated:
“The relative contribution of the cross-section of VRS of N2 to the cross-section of RRS of 2.3 % is in agreement with expected values from the theory (2–3.5 %, depending on the measurement geometry).”

And that’s far higher than we’d previously thought, Phil, exactly as I’ve been saying.

That’s the very first of your numerous egregious errors that you’ve ever corrected, Phil. So you are teachable. For some value of ‘teachable’. LOL

How’s it feel to know your CAGW warmist religion has been debunked, Phil? LOL

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“CO2(72◦|X1A′) is not aka CO2[v20(2)], it’s known as dioxiranylidene, which is a three-membered ring compound which is an isomer of carbon dioxide. In case you don’t know what an isomer is, it is a compound that contains the same number of atoms of the same elements but differs in structure and properties. So it has nothing to do with Carbon dioxide!”

Bwahahahaaaa! Phil claims CO2 “has nothing to do with Carbon dioxide!”

Wow, Phil… you’re never going to live this one down.

Before you copy-paste from Wikipedia, Phil, I’d suggest actually understanding the text. LOL

It’s known as “neutral bent carbon dioxide”, Phil.

https://arxiv.org/pdf/1704.03996.pdf
Infrared spectra of neutral bent carbon dioxide
“The considered isomers include the dioxiranylidene (cyclic) form of CO2 with the equilibrium valence angle of 72◦, belonging to the ground electronic state”

Now Phil, I know you want to blather out something akin to, “But you said it’s in the CO2[v20(2)] state! It’s in the ground electronic state!”

Go ahead, Phil. Make a fool of yourself again. LOL

https://arxiv.org/pdf/1704.03996.pdf
“The cyclic isomer CO2(72◦|X˜ 1A′) in the adiabatic ground state X˜ 1A′ is C2v symmetric”

What’s that say, Phil? Oh, it says it’s in the CO2[v20(2)] bend mode, with each C-O bond symmetric in length. So yet again you demonstrate that you don’t understand anything of that which you continue to bloviate, blather and bluster about. LOL

I challenge you, Phil, to provide proof of your claimed “40 years of study and research in the field”, because you don’t even appear to have the educational equivalent of a week’s worth of autodidacticism, let alone a formal education in the field.

Fantastical Pedantical Phil’s Craptacular Fails List:
—————
Phil is the Klimate Katastrophe Kook who: denies that infrared photons can cause N2 to become vibrationally excited; who claimed that N2 cannot become vibrationally excited at all under any circumstances; who didn’t know about vibronic coupling; who doesn’t understand the role of He in a CO2 laser; who claimed that because N2 is a homonuclear diatomic with no net electric dipole it could not absorb photons under any circumstances (“optically forbidden” LOL); who wants to visit the “hotter” upper atmosphere wearing flip-flops and a tank top; who couldn’t describe the Raman scattering process properly; who simultaneously admitted and denied that N2 undergoes Raman scattering; who can’t seem to grasp how harmonic oscillators work (“Fantastical Pedantical Phil’s Wave Machine” LOL); who denied that N2 could undergo Resonant Raman Scattering; who didn’t know that inelastic scattering always results in vibrational excitation; who claimed that CO2[v3(1)] aka CO2(001) was the lowest vibrational excitation state when it’s actually the highest in the troposphere; who thinks RRS (measured as an energy flux) has units of parts per million; who can’t seem to figure out a simple cascaded laser pump setup; who thinks that shorter wavelengths result in a “strong fall-off” in Raman scattering cross-section when it’s actually the opposite; who thinks Raman scattering only happens in the upper atmosphere (when in actuality the cross-section increases with optical depth); who doesn’t know the difference between Stokes and anti-Stokes lines; who thinks that “v2 (000)” is a vibrational excitation state; who used “N2(v=1)” to describe nitrogen’s rotational quantum states; who thinks that a CO2[v320(1)] P-branch transition results in 10.591 um photon emission; who thinks N2[v1(1)] requires “0.3 eV”, when in actuality it’s 0.4365 eV; who confused R branch and P branch transitions; who didn’t know that Stimulated Raman Scattering had resultant photons of the save wavelength as the incident photons; who thinks that “CO2(002) has an energy of ‘about’ 4600 cm-1 (wavelength ~2200nm)”… (CO2[v3(2)] = 4698.6 cm-1 (2.1283 um)); who claimed “CO2(72◦|X1A′) has nothing to do with Carbon dioxide!” (it’s known as neutral bent carbon dioxide). LOL
—————

• Phil. says:

Phil wrote:
“CO2(72◦|X1A′) is not aka CO2[v20(2)], it’s known as dioxiranylidene, which is a three-membered ring compound which is an isomer of carbon dioxide. In case you don’t know what an isomer is, it is a compound that contains the same number of atoms of the same elements but differs in structure and properties. So it has nothing to do with Carbon dioxide!”

Bwahahahaaaa! Phil claims CO2 dioxiranylidene “has nothing to do with Carbon dioxide!”

Wow, Phil… you’re never going to live this one down.

Before you copy-paste from Wikipedia, Phil, I’d suggest actually understanding the text. LOL

I did, I read the arxiv paper yesterday, that’s a chemical isomer of carbon dioxide, it’s totally different chemically from the carbon dioxide we’re talking about. Instead of being a linear molecule with a central C atom and two C=O double bonds, it’s a triangular molecule with a C atom with an unpaired electron and two C-O bonds and one O-O bond.
Perhaps you should try to understand the text before posting it?

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“I did, I read the arxiv paper yesterday, that’s a chemical isomer of carbon dioxide, it’s totally different chemically from the carbon dioxide we’re talking about. Instead of being a linear molecule with a central C atom and two C=O double bonds, it’s a triangular molecule with a C atom with an unpaired electron and two C-O bonds and one O-O bond.”

And it’s still carbon dioxide, Phil. Formally “neutral bent carbon dioxide”, aka CO2(72◦|X1A′), with a middle fundamental vibrational frequency band centered at 666.2 cm-1, and it’s in v2 (bend) mode.

https://arxiv.org/pdf/1704.03996.pdf
From page 18 of 26, the 666.2 cm-1 vibrational frequency corresponds to vibrational state 1, so we know it’s got to be CO2[v21(1)] (the only v2 mode with quantum state 1), because the next higher vibrational state transitions it to CO2[v3(1)] (asymmetric stretch) mode… and once it leaves bend mode, it’s not really bent anymore, now is it?

The next higher CO2(72◦|X1A′) bend mode vibrational level is CO2[v20(2)].

The next higher CO2(72◦|X1A′) bend mode after that is CO2[v2(1)+v3(1)] (bend and asymmetric stretch modes together).

Didn’t you know that the CO2 molecule cycles through its vibrational modes as its vibrational quantum state energy level increases, Phil? LOL

But Phil, you’ve emphatically stated that it “has nothing to do with Carbon dioxide!”. LOL

Unless you’re claiming that because it’s bent, that somehow magically imparts to it some other vibrational mode other than the only ones known. Are you, Phil? LOL

Phil claims “CO2(72◦|X1A′) has nothing to do with Carbon dioxide!”
It’s known as neutral bent carbon dioxide. LOL

Don’t trip over reality as you’re backpedaling, Phil. LOL

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“So correcting your ‘error’ the vibrational N2 Raman cross-section is ~1×10^-32, using your value for CO2 cross-section as 3×10^-19 we get 3×10^-19/1×10^-32 = 3×10^13
That’s close enough to 10^14 for me!”

Phil thinks he’s off by an order of magnitude and that’s close enough for him… that’s the most advanced ‘maff’ the warmists can do. LOL

You’re actually off by two orders of magnitude, so your maff skills are devolving. LOL

The Vibrational N2 Raman cross-section peak is not “~1×10^-32”, Phil.
https://i.imgur.com/SKCGC3d.png
See that black ‘+’ symbol? Yeah, that’s VRS N2, Phil.

Cabannes N2 peak: ~1.8×10^-27
RRS N2 peak: ~2.3×10^-30
VRS N2 peak: ~1.2×10^-30
VRRS N2 peak: ~1.8×10^-32

You can’t even read a log graph, Phil! LOL

So not a good post for you, you got everything wrong, that must be some sort of a record even for you! LOL

Remember, Phil… I’m a troll. I sucker you in, get you to denigrate me for a seeming error (that you’ve already made), then I have a mandate to denigrate you endlessly (by the very rules you set, no less… so you can’t complain. LOL) because you made the mistake first and unintentionally, whereas I’m just f’ing with you. LOL

Fantastical Pedantical Phil’s Craptacular Fails List:
—————
Phil is the Klimate Katastrophe Kook who: denied that infrared photons can cause N2 to become vibrationally excited; who didn’t know about vibronic coupling; who didn’t understand the role of He in a CO2 laser; who claimed that because N2 is a homonuclear diatomic with no net electric dipole it could not absorb photons under any circumstances (“optically forbidden” LOL); who wants to visit the “hotter” upper atmosphere wearing flip-flops and a tank top; who couldn’t describe the Raman scattering process properly; who simultaneously admitted and denied that N2 undergoes Raman scattering; who can’t seem to grasp how harmonic oscillators work (“Fantastical Pedantical Phil’s Wave Machine” LOL); who denied that N2 could undergo Resonant Raman Scattering; who didn’t know that inelastic scattering always results in vibrational excitation; who claimed that CO2[v3(1)] aka CO2(001) was the lowest vibrational excitation state (forgetting v1 and v2); who thought RRS (measured as an energy flux) has units of parts per million; who can’t seem to figure out a simple cascaded laser pump setup; who thought that shorter wavelengths result in a “strong fall-off” in Raman scattering cross-section (it’s the opposite); who thought Raman scattering only happens in the upper atmosphere (when in actuality the cross-section increases with optical depth); who didn’t know the difference between Stokes and anti-Stokes lines; who thought that “v2 (000)” is a vibrational excitation state; who used “N2(v=1)” to describe nitrogen’s rotational quantum states; who thought that a CO2[v320(1)] 10P20 transition results in 10.591 um photon emission; who thinks N2[v1(1)] requires “0.3 eV”, when in actuality it’s 0.4365 eV; who confused R branch and P branch transitions; who didn’t know that Stimulated Raman Scattering had resultant photons of the same wavelength as the incident photons; who thinks that “CO2(002) has an energy of ‘about’ 4600 cm-1 (wavelength ~2200nm)”… (CO2[v3(2)] = 4698.6 cm-1 (2.1283 um)); who claimed “CO2(72◦|X1A′) has nothing to do with Carbon dioxide!” (it’s known as neutral bent carbon dioxide); who uses ‘maff’ to claim that 0.2925 eV = 0.3 eV; who can’t read a logarithmic graph (he was off by two orders of magnitude!). LOL
—————

• Phil. says:

All inelastic scattering results in vibrational excitation, Phil. Thus the total amount of N2 being vibrationally excited in the atmosphere is much higher than we previously thought, thus the CO2 to N2 V-T process has an even lower probability than previously thought.

No it does not, in the paper you cited for example 99% of the inelastic scattering is rotational excitation.

• LOL@Klimate Katastrophe Kooks says:

It doesn’t matter the type of excitation, Phil… did you forget that homonuclear diatomics tend to couple all excitation such that their vibrational modes are preferentially excited?

And your maff skills are still on display, I see…
“The relative contribution of the cross-section of VRS of N2 to the cross-section of RRS of 2.3 % is in agreement with expected values from the theory (2–3.5 %, depending on the measurement geometry).”

And that’s much more than was previously thought, Phil… before, inelastic scattering was thought to be so inconsequential that it was disregarded. Now we know that it’s of such magnitude that it red-shifts the solar spectrum. That’s not an insignificant amount of scattering, Phil.

So Phil thinks 2.3% = 1%. Maff. LOL

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“I was clearly being overgenerous in saying ‘parts per million’.”

You were clearly wrong in saying ‘parts per million’, Phil. It’s an energy flux… just how does one impart units of ‘parts per million’ to an energy flux, Phil? LOL

• Phil. says:

The same way as you use %. (in case you didn’t know, % means per cent, or ‘parts per hundred’).

• LOL@Klimate Katastrophe Kooks says:

Except they did use percentages in the report cited, Phil, to denote the ratio between RRS and VRS; whereas you pulled your “parts per million” blather from your ‘puckered facts-file’ to denote the number of scattering molecules. LOL

I’d tell you to rectify your confusion, but you seem to be unable to. And with you claiming to have “40 years of study and research in the field”. Being a janitor in a research laboratory doesn’t count as “study and research in the field”, Phil. LOL

• Phil. says:

Mods: More of the same insults that you warned him about before and his sexually explicit insult referring to ‘twat’ is still up.
And with you claiming to have “40 years of study and research in the field”. Being a janitor in a research laboratory doesn’t count as “study and research in the field”,

• LOL@Klimate Katastrophe Kooks says:

You’re only running to the mods, Phil, because your pig-headed stubbornness and refusal to admit you’re wrong and that you don’t know half as much as you claim you do is leading to you getting drop-kicked half-way across WUWT.

You need to stop embarrassing yourself and go hit the books, Phil. Your Dunning-Kruger precludes you doing that, so the least you could do is simply STFU and slink away knowing that you’re wrong, even if you won’t admit it.

• Phil. says:

You’re only running to the mods, Phil, because your pig-headed stubbornness and refusal to admit you’re wrong and that you don’t know half as much as you claim you do is leading to you getting drop-kicked half-way across WUWT.

Only in your imagination! I complained to the mods because of your rudeness, particularly your sexually explicit insults. No apology from you I notice.

You need to stop embarrassing yourself and go hit the books, Phil. Your Dunning-Kruger precludes you doing that, so the least you could do is simply STFU and slink away knowing that you’re wrong, even if you won’t admit it.

I’m not embarrassing myself, I’m astonished how many errors and incorrect statements such a self confessed troll such as yourself can make. I just won’t let them go by in case someone might actually think that you know what you’re talking about.

• LOL@Klimate Katastrophe Kooks says:

What “sexually explicit insults” were those, Phil? You’ll be posting the URLs of my comments containing these purported “sexually explicit insults”, or you’ll yet again be forced to admit you’re lying.

You’ll be providing the URL of the comment where I’ve ever claimed N2[v1(1)] = 0.3 eV, or you’ll admit you’ve been caught in a lie, Phil.

Do you honestly believe you’ll win an argument with lies, Phil?

You should expect your intelligence to be insulted when you demonstrate that you lack it, Phil.

Phil wrote:
“I’m not embarrassing myself, I’m astonished how many errors and incorrect statements such a self confessed troll such as yourself can make. I just won’t let them go by in case someone might actually think that you know what you’re talking about.”

You mean like this?

Fantastical Pedantical Phil’s Craptacular Fails List:
—————
Phil is the Klimate Katastrophe Kook who: denies that infrared photons can cause N2 to become vibrationally excited; who claimed that N2 cannot become vibrationally excited at all under any circumstances; who didn’t know about vibronic coupling; who doesn’t understand the role of He in a CO2 laser; who claimed that because N2 is a homonuclear diatomic with no net electric dipole it could not absorb photons under any circumstances (“optically forbidden” LOL); who wants to visit the “hotter” upper atmosphere wearing flip-flops and a tank top; who couldn’t describe the Raman scattering process properly; who simultaneously admitted and denied that N2 undergoes Raman scattering; who can’t seem to grasp how harmonic oscillators work (“Fantastical Pedantical Phil’s Wave Machine” LOL); who denied that N2 could undergo Resonant Raman Scattering; who didn’t know that inelastic scattering always results in vibrational excitation; who claimed that CO2[v3(1)] aka CO2(001) was the lowest vibrational excitation state when it’s actually the highest in the troposphere; who thinks RRS (measured as an energy flux) has units of parts per million; who can’t seem to figure out a simple cascaded laser pump setup; who thinks that shorter wavelengths result in a “strong fall-off” in Raman scattering cross-section when it’s actually the opposite; who thinks Raman scattering only happens in the upper atmosphere (when in actuality the cross-section increases with optical depth); who doesn’t know the difference between Stokes and anti-Stokes lines; who thinks that “v2 (000)” is a vibrational excitation state; who used “N2(v=1)” to describe nitrogen’s rotational quantum states; who thinks that a CO2[v320(1)] P-branch transition results in 10.591 um photon emission; who thinks N2[v1(1)] requires “0.3 eV”, when in actuality it’s 0.4365 eV; who confused R branch and P branch vibration modes. LOL
—————

And just today, I proved conclusively that you’re wrong about the Stimulated Raman Scattering test… despite your having spent more than a week blathering on as though you knew what you were talking about.

Q-branch Raman scattering in the Nitrogen Cell, Phil. Do you even know what that means, beside the fact that it means you’re wrong yet again? LOL

Stimulated Raman Scattering, Phil… did you forget that the incident and resultant photons are of the same frequency for SRS? They were measuring 0.607 um and 0.707 um in the monochromator, meaning the pump beams were 0.607 um and 0.707 um as well… and in fact, they even stated that they had to use baffling to exclude the 0.532 um probe beam from the monochromator… yet again proving you *wrong*, Phil.

• LOL@Klimate Katastrophe Kooks says:

Now that you’ve been proven to have been babbling out utter BS for more than a week about the Stimulated Raman Scattering test, Phil, I’m wondering what kind of backpedaling defense you’ll mount. No doubt, you’ll only embarrass yourself more. LOL

On Usenet, we use an onomatopoeia to describe the drubbing you’ve just taken, Phil… it brings to mind a spanking so vicious that it echoes.

SPNAK!

• Phil. says:

Now that you’ve been proven to have been babbling out utter BS for more than a week about the Stimulated Raman Scattering test, Phil, I’m wondering what kind of backpedaling defense you’ll mount. No doubt, you’ll only embarrass yourself more. LOL

Since it is you who has been completely wrong about the the Stimulated Raman Scattering, starting with stating that it was spontaneous Raman, I think that is your problem not mine.
You said:
The 0.532 um first laser was focused in the Raman shifting cell, Phil, which had a 1:1 mixture of N2 and He. That was needed to generate the 0.607 um and 0.707 um Stokes pump photons. The 0.532 um photon flux played no part in vibrationally exciting the N2 in the Nitrogen Cell.
To which I replied:
“Again you need to read the paper just not copy and paste it, the title is ‘Stimulated Raman pumping’, that requires two frequencies, a pump frequency, 532 cm-1, and a Stokes frequency, 607 cm-1. They needed those two simultaneous frequencies to create that vibrationally excited state which is why they designed the illumination system the way they did”

• LOL@Klimate Katastrophe Kooks says:

For God’s sake, Phil, go back and read the paper for comprehension.

They used Raman scattering in the Raman Cell to generate the 0.607 um and 0.707 um beam lines, and Stimulated Raman Scattering in the Nitrogen Cell. They measured the 0.607 um and 0.707 um lines in the monochromator. They tried to use baffles to remove interference from the 0.532 um probe beam and residual 0.532 flux from the Raman Cell.

Stimulated Raman Scattering means a Q-branch transition, Phil, which means that the incident and resultant photons are of the same frequency.

Thus, Phil, since they were measuring 0.607 um and 0.707 um in the monochromator (see the graphs, Page 3 of 8), the pump beams into the Nitrogen Cell were *also* 0.607 um and 0.707 um.

“Also note that 150 ns is selected for the minimum delay time in order to avoid interferences due to stray room scattering from the *first* *and* *second* *Stokes* *pump* *beams*, some of which, despite baffling, was found to enter the spectrometer.” {Emphasis mine.}

“The SRS pump, consisting of the collinear *residual* second harmonic and first and second Stokes frequency beams, is collimated and refocused with a 300 mm focal length lens into a second cell containing pure N2 at room temperature and variable pressure between 300 and 760 Torr.” {Emphasis mine.}

And that means you’re *wrong*, Phil. Whether you admit it or not, your blather that they’re using an already-used 0.532 um beam as a pump frequency, but don’t show 532 nm on their graphs on page 3 of 8, is *wrong*, Phil.

Those graphs on page 3 of 8 show 0.607 um and 0.707 um, Phil.

The authors specifically state that the 0.607 um and 0.707 um beams are the pump beams, and the 0.532 um is “residual”, Phil.

You’re *wrong* and embarrassing yourself, Phil. You’re proving time and again that you’re utterly incapable of understand the topic, which means your claimed “40 years of study and research in the field” is a lie, Phil… or at the very best, a horrible joke played for 40 years upon your employer. LOL

Stop embarrassing yourself, Phil. LOL

• Phil. says:

What “sexually explicit insults” were those, Phil? You’ll be posting the URLs of my comments containing these purported “sexually explicit insults”,
It’s been snipped because of my complaint.
A dictionary entry:
twat- Either way, this is a very vulgar, obscene word that should be avoided. You don’t hear twat as often as some other four-letter words, but that doesn’t mean it isn’t offensive.

You’ll be providing the URL of the comment where I’ve ever claimed N2[v1(1)] = 0.3 eV, or you’ll admit you’ve been caught in a lie, Phil.</em.

Stimulated Raman Scattering, Phil… did you forget that the incident and resultant photons are of the same frequency for SRS? They were measuring 0.607 um and 0.707 um in the monochromator, meaning the pump beams were 0.607 um and 0.707 um as well…

They measured between 600 and 610nm, they did not measure at 707nm. Meaning that the Stokes beam was 606nm because it is the Stokes frequency and the resultant photons which are the same. The ‘pump’ wavelength has to be shorter than the Stokes wavelength (higher energy) indicating that the ‘pump’ was 532 nm not 707nm.

and in fact, they even stated that they had to use baffling to exclude the 0.532 um probe beam from the monochromator…

No they did not, they used baffling to exclude 607nm from the monochromator: “Another consequence of the two beams containing photons of the same frequency was limitation on the shortest time delay between the two pulses that could be achieved. This was also due to the fact that the pump and probe methods both employed the same vibrational Raman transition. The Stokes frequency of the pump beam matched the frequency of the Raman Stokes spectrum (for v=0) being collected.”
“Also note that 150 ns is selected for the minimum delay time in order to avoid interferences due to stray room scattering from the first and second Stokes pump beams, some of which, despite baffling, was found to enter the spectrometer.”
They tried baffling but it wasn’t successful which is why they were limited to a minimum time of 150 ns.

So not a good day for you, another error filled post!

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“The ‘pump’ wavelength has to be shorter than the Stokes wavelength (higher energy) indicating that the ‘pump’ was 532 nm not 707nm.”

Bwahahaaa! Yet *again* Phil proves he doesn’t understand much of anything.

Stimulated Raman Scattering, Phil, is predicated upon the exciting photons and the resultant photons being of the same frequency.

So you’re wrong yet again, Phil… not only are you wrong, you’ve yet again demonstrated that you don’t understand anything having to do with quantum mechanics.

Of course, you’re the guy who couldn’t even properly describe the Raman scattering process, and you simultaneously admitted and denied that N2 undergoes Raman scattering (which was hilarious, BTW). LOL

Fantastical Pedantical Phil’s Craptacular Fails List:
—————
Phil is the Klimate Katastrophe Kook who: denies that infrared photons can cause N2 to become vibrationally excited; who claimed that N2 cannot become vibrationally excited at all under any circumstances; who didn’t know about vibronic coupling; who doesn’t understand the role of He in a CO2 laser; who claimed that because N2 is a homonuclear diatomic with no net electric dipole it could not absorb photons under any circumstances (“optically forbidden” LOL); who wants to visit the “hotter” upper atmosphere wearing flip-flops and a tank top; who couldn’t describe the Raman scattering process properly; who simultaneously admitted and denied that N2 undergoes Raman scattering; who can’t seem to grasp how harmonic oscillators work (“Fantastical Pedantical Phil’s Wave Machine” LOL); who denied that N2 could undergo Resonant Raman Scattering; who didn’t know that inelastic scattering always results in vibrational excitation; who claimed that CO2[v3(1)] aka CO2(001) was the lowest vibrational excitation state when it’s actually the highest in the troposphere; who thinks RRS (measured as an energy flux) has units of parts per million; who can’t seem to figure out a simple cascaded laser pump setup; who thinks that shorter wavelengths result in a “strong fall-off” in Raman scattering cross-section when it’s actually the opposite; who thinks Raman scattering only happens in the upper atmosphere (when in actuality the cross-section increases with optical depth); who doesn’t know the difference between Stokes and anti-Stokes lines; who thinks that “v2 (000)” is a vibrational excitation state; who used “N2(v=1)” to describe nitrogen’s rotational quantum states; who thinks that a CO2[v320(1)] P-branch transition results in 10.591 um photon emission; who thinks N2[v1(1)] requires “0.3 eV”, when in actuality it’s 0.4365 eV; who confused R branch and P branch transitions; who didn’t know that Stimulated Raman Scattering had resultant photons of the same wavelength as the incident photons; who thinks that “CO2(002) has an energy of ‘about’ 4600 cm-1 (wavelength ~2200nm)”… (CO2[v3(2)] = 4698.6 cm-1 (2.1283 um)); who claimed “CO2(72◦|X1A′) has nothing to do with Carbon dioxide!” (it’s known as neutral bent carbon dioxide). LOL
—————

• Phil. says:

Phil wrote:
“The ‘pump’ wavelength has to be shorter than the Stokes wavelength (higher energy) indicating that the ‘pump’ was 532 nm not 707nm.”

Bwahahaaa! Yet *again* Phil proves he doesn’t understand much of anything.

Stimulated Raman Scattering, Phil, is predicated upon the exciting photons and the resultant photons being of the same frequency.

No it’s predicated on the ‘pump’ photon first creating a virtual state and a Stokes photon stimulating a transition of a photon of the same frequency as itself to populate a lower energy state. The virtual state must alway be higher than the energy level to be populated and therefore the pump beam must be a higher frequency than the Stokes.
You claim that the two beams used in the Nitrogen cell are 607 and 707nm. In that case 607nm win excite the virtual state and the 707nm will stimulate the emission. If that were the case then using 532nm as the probe beam would mean that the pump and probe methods did not both employ the same vibrational Raman transition, whereas the authors said that they did.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“No it’s predicated on the ‘pump’ photon first creating a virtual state and a Stokes photon stimulating a transition of a photon of the same frequency as itself to populate a lower energy state. The virtual state must alway be higher than the energy level to be populated and therefore the pump beam must be a higher frequency than the Stokes.”

Says Phil, yet again demonstrating that he hasn’t the first faint clue how it works as he fishes around in his down-under for more “facts”. LOL

According to you, Stimulated Raman Scattering cannot take place, since the resultant photon flux is at the same frequency (and since you’re conflating energy density and frequency, the same energy density) as the pump beam, Phil. Did you forget that the Raman signal occurs at the same frequency as the pump frequency in Stimulated Raman Scattering, Phil?

You’re conflating the frequency of the pump beams with the energy density of the pump beams and populated vibrational state, Phil. Yet again, you’re *wrong*. You’re still thinking in 2D as if you were looking at a sheet of paper with the molecule’s energy levels drawn on it. It doesn’t work that way in the real world, it’s just an analogy.

The energy *density* of either beam is going to be higher than the energy *density* of the vibrational state to be populated, Phil.

Remember, SRS is a non-linear process in which energy is transferred into the vibrational quantum states of the molecules via frequency modulation and demodulation, unlike CARS which is essentially parametric pumping. So one can use any frequency for pump and Stokes, as long as they’re resonant with the molecule’s vibrational quantum state levels, and the pump is of sufficient energy density to drive the molecule’s electron(s) to a virtual state above the vibrational states. The two Stokes frequencies are naturally resonant with the Nitrogen Cell N2’s vibrational levels… it was N2 which created them, after all, in the Raman Cell.

The .707 um and 0.607 um beams create a spatially and temporally overlapping beat-frequency representation of the vibrational frequencies of the N2 molecules in the Nitrogen Cell.

This excites two vibrational quantum states and an overtone, generating the vibrational state coupling to higher vibrational levels. This forms a Maxwell-Boltzmann distribution of the energy of these higher vibrational levels and subsequently preferentially funnels energy into the more-intense beam’s energy level. A sort of intramolecular vibrational quantum state population inversion.

After pump pulse-off, an adjustable time delayed probe pulse hits the Nitrogen Cell N2, and its transmission or reflection is measured. By monitoring the probe signal as a function of the time delay, it is possible to obtain information on the decay of the generated excitation. You’ll note pump and probe need not be the same frequency.

https://i.imgur.com/To5yycG.png
Note the higher spectral intensity of the shorter-wavelength peak in chart (a)… that energy was being preferentially driven into higher vibrational states as a result of the vibrational state coupling creating more (and higher) vibrational state overtones (and thus a steeper Maxwell-Boltzmann distribution), just as happens during quenching of electronic and translational excitation (which is why N2 will always transfer any translational energy imparted to it by CO2 via T-T or V-T into its vibrational levels, then right back into another CO2, which will undergo relaxation emission, resulting in a loss of energy from the system… because remember, homonuclear diatomics cannot undergo IR emission relaxation (if it’s not being excited somehow, it doesn’t have an induced dipole), so that energy has nowhere to go but into its vibrational levels until the molecule undergoes collision or irs energy level is high enough to allow the molecule to emit UV.).

Note also the increasing intensity of successively longer-wavelength spectra as the time delay scales from 150 to 10000 ns during relaxation. This is because that energy had been pushed into successively shorter-wavelength spectra of the Maxwell-Boltzmann distribution of vibrational states during excitation (see “A sort of intramolecular vibrational quantum state population inversion.” above).

The 0.532 um photon flux from the Raman Cell was, as the authors stated, “residual”. You’ll notice that to achieve a background-free signal, they used baffling to remove the interference between the 0.607/0.707 um and 0.532 um probe. That’s another reason they used a separate Raman Cell, Phil… they wanted to *get* *rid* *of* as much 0.532 um in the Nitrogen Cell as they could… a Nitrogen Cell 0.532 um pump beam would interfere with the 0.532 um probe beam, washing out the resulting transmission or reflection of the probe pulse and spoiling the data. That’s also why they were forced to use a minimum time delay between the pump pulse and the probe pulse, to minimize interference from the *residual* 0.532 um beam.

Because the 0.532 um beam didn’t match any molecular quantum vibrational states that were strongly coupled in the Nitrogen Cell N2, it didn’t have much of an effect in the Nitrogen Cell. If it’d had an effect, it would have resulted in excess translational energy in the Nitrogen Cell, just as it had in the Raman Cell, necessitating adding He to the Nitrogen Cell to cool it. That 0.707 um beam in the Nitrogen Cell coupling with the 0.606 um beam shifted the coupled molecular vibrational states out of the resonant frequency range of the 0.532 um beam.

That they had a strong 0.607 um resultant signal in the Nitrogen Cell and a very weak 0.707 um resultant signal means that the energy was being funneled into that beat frequency, generating a strong line of very narrow frequency.

“Also note that 150 ns is selected for the minimum delay time in order to avoid interferences due to stray room scattering from the *first* *and* *second* *Stokes* *pump* *beams*, some of which, despite baffling, was found to enter the spectrometer.” {Emphasis mine.}

Don’t you remember my schooling you on this topic, Phil? “Fantastical Pedantical Phil’s Wave Machine”. LOL

What’s this say, Phil?
https://bernstein.harvard.edu/research/SRS.htm
“In contrast to the CARS (Coherent Anti-Stokes Raman Spectroscopy) signal that is generated at the anti-Stokes frequency, SRG (Stimulated Raman Gain) and SRL (Stimulated Raman Loss) occur *at* *the* *frequency* *of* *the* *excitation* beams*.” {Emphasis mine.}

So yet again, you’ve failed, Phil. We should just start calling you Phail. LOL

• LOL@Klimate Katastrophe Kooks says:

Funnily enough, you’ve written that word 200% more than I have, Phil. Now I feel sexually harassed. LOL

Mod, can you get the sexual harasser Phil off your site? He’s creeping everyone out, running around yelling that word everywhere. LOL

You have to know, Phil, that given your weeks-long display of inaptitude, I’m going to run you ragged. You should count your blessings that you’re on a moderated website… on Usenet, I’ve driven people to the point of babbling insanity such that they’re involuntarily committed.

I’m a troll, it’s sort of what I do. And I’m very, very good at what I do.

• LOL@Klimate Katastrophe Kooks says:

Of course, we could use your favorite units, Phil… you’ve written that word 2,000,000 ppm more than I have. And that’s a Very Large Number, making your violation of this site’s TOS especially atrocious and flagrant.

You should be ashamed of yourself, Phil. LOL

• Phil. says:

I’m a troll, it’s sort of what I do. And I’m very, very good at what I do.
Perhaps you are but your knowledge of quantum mechanics and your understanding of the papers you have linked to is terrible.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Perhaps you are but your knowledge of quantum mechanics and your understanding of the papers you have linked to is terrible.”

This terrible?

Fantastical Pedantical Phil’s Craptacular Fails List:
—————
Phil is the Klimate Katastrophe Kook who: denied that infrared photons can cause N2 to become vibrationally excited; who didn’t know about vibronic coupling; who didn’t understand the role of He in a CO2 laser; who claimed that because N2 is a homonuclear diatomic with no net electric dipole it could not absorb photons under any circumstances (“optically forbidden” LOL); who wants to visit the “hotter” upper atmosphere wearing flip-flops and a tank top; who couldn’t describe the Raman scattering process properly; who simultaneously admitted and denied that N2 undergoes Raman scattering; who can’t seem to grasp how harmonic oscillators work (“Fantastical Pedantical Phil’s Wave Machine” LOL); who denied that N2 could undergo Resonant Raman Scattering; who didn’t know that inelastic scattering always results in vibrational excitation; who claimed that CO2[v3(1)] aka CO2(001) was the lowest vibrational excitation state (forgetting v1 and v2); who thought RRS (measured as an energy flux) has units of parts per million; who can’t seem to figure out a simple cascaded laser pump setup; who thought that shorter wavelengths result in a “strong fall-off” in Raman scattering cross-section (it’s the opposite); who thought Raman scattering only happens in the upper atmosphere (when in actuality the cross-section increases with optical depth); who didn’t know the difference between Stokes and anti-Stokes lines; who thought that “v2 (000)” is a vibrational excitation state; who used “N2(v=1)” to describe nitrogen’s rotational quantum states; who thought that a CO2[v320(1)] 10P20 transition results in 10.591 um photon emission; who thinks N2[v1(1)] requires “0.3 eV”, when in actuality it’s 0.4365 eV; who confused R branch and P branch transitions; who didn’t know that Stimulated Raman Scattering had resultant photons of the same wavelength as the incident photons; who thinks that “CO2(002) has an energy of ‘about’ 4600 cm-1 (wavelength ~2200nm)”… (CO2[v3(2)] = 4698.6 cm-1 (2.1283 um)); who claimed “CO2(72◦|X1A′) has nothing to do with Carbon dioxide!” (it’s known as neutral bent carbon dioxide); who uses ‘maff’ to claim that 0.2925 eV = 0.3 eV. LOL
—————

Phil claimed CO2 “has nothing to do with Carbon dioxide!”. Bwahahahaaa!

Phil doesn’t know how to calculate quantum state energies. LOL

Phil claimed that CO2[v3(1)] aka CO2(001) was the lowest vibrational excitation state. {Belly laugh}

Phil didn’t know what RRS was and tried to convert it to parts per million. {guffaw}

Phil claimed that because homonuclear diatomics have no net electric dipole they couldn’t absorb radiation under any circumstances. {snort!}

Phil thinks “v2 (000)” is a vibrational excitation level. {chortle}

Phil’s maff says 0.2925 eV = 0.3 eV. {snerk!}

Phil still doesn’t understand Stimulated Raman Scattering. {smirk}

Phil couldn’t properly explain the Raman scattering process, and in doing so he simultaneously admitted and denied that N2 undergoes Raman scattering. Hahahahaaaaa!

Phil claims he’s got “40 years of study and research in the field”. {snicker, snort, chortle……. BWAHAHAHAAAA!}

• Phil. says:

So I’ve forced you from a position of complete denial: “N2 is a homonuclear diatomic with no net electric dipole so it cannot be vibrationally excited by radiation”, to a grudging acknowledgment that the processes described do take place: “Well, OK, N2 can be vibrationally excited by incident radiation, but it doesn’t happen very much in the troposphere.”

When you put quotation marks around a statement it means that you are quoting something they said. Since I did not make that second statement you’re lying.

That’s progress. And that means I’m winning. LOL

No when you resort to lying you’ve lost!

• LOL@Klimate Katastrophe Kooks says:

Phil’s apparently never heard of the term “paraphrasing”. LOL

This is a direct quote from you, Phil:
“Homonuclear diatomics such as N2 don’t have a dipole and can’t be vibrationally excited by radiation.”

This is a direct quote from you, Phil:
“But N2 in the troposphere isn’t vibrationally excited and CO2 is!”

This is a direct quote from you, Phil:
“When N2(1) is present it will resonantly transfer its energy to CO2 via V-V but it’s not present in any significant quantity in the troposphere so it’s irrelevant.”

Yes, CO2 is vibrationally excited in the troposphere, Phil, whereupon it undergoes the V-V process I described prior:

——————–
Phil wrote:
“Not that it matters because this whole concept of yours is irrelevant but N2(1) is 18cm-1 lower than CO2 (000).”

But Phil, that’s a V-V (Vibration-Vibration) process, not the V-T (Vibration-Translation) process you warmists claim is causing global warming.

C02(001) + N2(v = 0) === C02(000) + N2(v = 1) + 18 cm-1 (555.5556 um)

Whereupon N2 will collide with other CO2 molecules in the v3(1) state:

http://www.barrettbellamyclimate.com/page15.htm
———————————
The existence of the ν3(1) level is highly important with regard to its collisional excitation by nitrogen molecules in their first excited vibrational mode that has a transition wavenumber of 2359.6 cm-1, almost a perfect match for the excitation of the anti-symmetric stretching vibration of CO2:

N2 [ν1(1)] + CO2 [ν20(0)] → N2 [ν1(0)] + CO2 [ν3(1)]

The CO2 [ν3(1)] state can then emit radiation or be degraded to the lower energy levels from which radiation may be emitted.
———————————

So you’ve just argued my point, Phil, by providing yet another mechanism by which N2 becomes vibrationally excited. Did you mean to do that? LOL

Now Phil, if CO2 atmospheric concentration increases, does that V-V to V-T process by which CO2 accumulates energy unto itself such that it will undergo emission relaxation by emitting a photon increase in prevalence? Yeah it does!

So an increased CO2 atmospheric concentration will cause what, Phil?

Cooling.

Do you need me to school you on any other topics today, Phil? LOL
——————–

• LOL@Klimate Katastrophe Kooks says:

Should be:
“Whereupon N2 will collide with other CO2 molecules in the ν20(0) state:”

• Phil. says:

Phil’s apparently never heard of the term “paraphrasing”. LOL

Yes I have and that was not what you did.

Yes, CO2 is vibrationally excited in the troposphere, Phil, whereupon it undergoes the V-V process I described prior:

CO2 is vibrationally excited at the 020 level, 667cm-1, doesn’t undergo V-V transfer, it does V-T transfer.

Now Phil, if CO2 atmospheric concentration increases, does that V-V to V-T process by which CO2 accumulates energy unto itself such that it will undergo emission relaxation by emitting a photon increase in prevalence? Yeah it does!

In the lower troposphere the V-T process transfers the energy to its neighbors thereby heating them up.

So an increased CO2 atmospheric concentration will cause what, Phil?

Cooling.

Only above the tropopause.

Do you need me to school you on any other topics today, Phil? LOL

You couldn’t if your life depended on it.

• LOL@Klimate Katastrophe Kooks says:

LOL@Klimate Katastrophe Kooks wrote:
“Phil’s apparently never heard of the term “paraphrasing”. LOL”

Phil wrote:
“Yes I have and that was not what you did.”

You’re being pedantic again, Phil.

This is a direct quote from you, Phil:
“Homonuclear diatomics such as N2 don’t have a dipole and can’t be vibrationally excited by radiation.”

I paraphrased your direct quote thusly:
“N2 is a homonuclear diatomic with no net electric dipole so it cannot be vibrationally excited by radiation.”

This is a direct quote from you, Phil:
“When N2(1) is present it will resonantly transfer its energy to CO2 via V-V but it’s not present in any significant quantity in the troposphere so it’s irrelevant.”

I paraphrased your direct quote thusly:
“Well, OK, N2 can be vibrationally excited by incident radiation, but it doesn’t happen very much in the troposphere.”

Phil wrote:
“CO2 is vibrationally excited at the 020 level, 667cm-1, doesn’t undergo V-V transfer, it does V-T transfer.”

Remember, Phil? You wrote:
“Not that it matters because this whole concept of yours is irrelevant but N2(1) is 18cm-1 lower than CO2 (000).”

Now you’re yet again pulling “facts” from your balloon knot, Phil. LOL
https://i.imgur.com/4oWzU6t.png

It has a rate constant of ~6.0e-13 cm^3 mol sec, results in vibrationally excited N2, which then collide with CO2 in the ν20(0) state, which will undergo relaxation emission by emitting a photon.

http://www.barrettbellamyclimate.com/page15.htm
———————————
The existence of the ν3(1) level is highly important with regard to its collisional excitation by nitrogen molecules in their first excited vibrational mode that has a transition wavenumber of 2359.6 cm-1, almost a perfect match for the excitation of the anti-symmetric stretching vibration of CO2:

N2 [ν1(1)] + CO2 [ν20(0)] → N2 [ν1(0)] + CO2 [ν3(1)]

The CO2 [ν3(1)] state can then emit radiation or be degraded to the lower energy levels from which radiation may be emitted.
———————————

Is there anything else you need to be schooled on today, Phil? LOL

• Phil. says:

This is a direct quote from you, Phil:
“When N2(1) is present it will resonantly transfer its energy to CO2 via V-V but it’s not present in any significant quantity in the troposphere so it’s irrelevant.”

I paraphrased your direct quote thusly:
“Well, OK, N2 can be vibrationally excited by incident radiation, but it doesn’t happen very much in the troposphere.”

Which isn’t close to being an accurate paraphrase!
An accurate one would be:
N2 can’t be vibrationally excited by incident radiation, but when created by other means (very uncommonly) in the troposphere it is able to transfer its energy to CO2 via V-V.

Remember, Phil? You wrote:
“Not that it matters because this whole concept of yours is irrelevant but N2(1) is 18cm-1 lower than CO2 (000).”

Now you’re yet again pulling “facts” from your balloon knot, Phil. LOL

https://i.imgur.com/4oWzU6t.png

It has a rate constant of ~6.0e-13 cm^3 mol sec, results in vibrationally excited N2, which then collides with CO2 in the ν20(0) state, which will undergo relaxation emission by emitting a photon.

Your equation agrees with my “facts” as you called it, so not sure what you’re trying to say. Vibrationally excited N2 is produced along with a loss of 18cm-1 of energy.
Since CO2 in the ν20(0) state is the ground state such a collision would return the CO2 to the same excited state it started from. Any emission from that state would most likely be at 1388cm-1.

You appear to be rather confused about what going on.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Not that it matters because this whole concept of yours is irrelevant but N2(1) is 18cm-1 lower than CO2 (000).”

https://i.imgur.com/4oWzU6t.png

Notice the discrepancy, Phil? Are you claiming that CO2(001) aka CO2[v38(1)] is the same as CO2(000) aka CO2[v20(0)]? Or is your knowledge so shallow that you can’t even spot your error? LOL

Somehow I’m getting the idea that your claimed “40 years of study and research in the field” was, at best, a yuuuuuuge stretch of the truth, Phil. LOL

What will you do next to embarrass yourself and display your utter inability to grasp the science of what you’re discussing, Phil? Oddly define and inaccurately describe another atmospheric process like you did for Raman scattering? LOL

How many more times will you do so before you realize you’re outmatched, outwitted, outclassed and out of your depth? LOL

You know, Phil… the problem with your now-defunct CAGW warmist religion is that when you’re getting your teeth kicked in by reality, you don’t have an actual God to turn to for solace. LOL

• Phil. says:

Phil wrote:
“Not that it matters because this whole concept of yours is irrelevant but N2(1) is 18cm-1 lower than CO2 (000).”

Congratulations, you spotted a typo, so did I but too late to edit the post, obviously that should be CO2 (001)

• LOL@Klimate Katastrophe Kooks says:

That’s not the only error you made, Phil.

——————–
LOL@Klimate Katastrophe Kooks wrote:
“The only rotovibrationally excited state of CO2 which has a higher vibrational temperature than N2’s first excited vibrational mode, known as CO2 (001) in older nomenclature, and as CO2[v38(1)] in more modern nomenclature.”

Phil wrote:
“It’s not the only one, it’s the one with the lowest energy.”

Bwahahahaaa! Way to demonstrate that you know absolutely nothing about the topic, Phil. You hace been trolled. LOL

CO2[v38(1)] doesn’t exist, Phil. I made it up as a test of your knowledge, and you failed miserably. Had you even an inkling of what you were doing, you’d have realized that right off. I made it very obvious to anyone with even cursory training in quantum mechanics, which obviously excludes you.

First, Phil, in the excited state, only the odd-numbered rotational levels are populated, and CO2[v3(1)] is CO2’s highest excited state.

Second, Phil, the excited state rotational levels only go up to J=5.

So it should have been obvious to you at first glance that CO2[v38(1)] was farcical. That you not only didn’t catch it, but doubled-down by claiming it was “the one with the lowest energy” proves you’re just blathering, just flopping your hands across your keyboard and hoping not to make yet another idiotic mistake.

You should be ashamed of yourself, Phil. What with your other claim tonight that RRS was measured in (to quote you), “parts per million”, you have no standing to even be discussing any of this.

Pathetic.

But hilarious nonetheless. LOL

So I expect you’ll be back tomorrow for more humiliation, Phil? LOL
——————–

• Phil. says:

LOL@Klimate Katastrophe Kooks wrote:
“The only rotovibrationally excited state of CO2 which has a higher vibrational temperature than N2’s first excited vibrational mode, known as CO2 (001) in older nomenclature, and as CO2[v38(1)] in more modern nomenclature.”

Phil wrote:
“It’s not the only one, it’s the one with the lowest energy.”

Bwahahahaaa! Way to demonstrate that you know absolutely nothing about the topic, Phil. You hace been trolled. LOL

CO2[v38(1)] doesn’t exist, Phil. I made it up as a test of your knowledge, and you failed miserably. Had you even an inkling of what you were doing, you’d have realized that right off. I made it very obvious to anyone with even cursory training in quantum mechanics, which obviously excludes you.

I ignored your “more modern nomenclature”, since you referred to the state in the correct manner, CO2 (001) there was no problem.

First, Phil, in the excited state, only the odd-numbered rotational levels are populated, and CO2[v3(1)] is CO2’s highest excited state.

Second, Phil, the excited state rotational levels only go up to J=5.

Really? The strongest transition in the CO2 laser between (001) and (100) is the P(20) transition between CO2(001)(J’=19) and CO2 (100)(J”=20) at 10.591.
Check this out:

https://www.star.le.ac.uk/~zrw/courses/lect4313_fig23.jpg

So it should have been obvious to you at first glance that CO2[v38(1)] was farcical.

I just ignored it since you’d actually also used the correct terminology.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“I ignored your “more modern nomenclature”, since you referred to the state in the correct manner, CO2 (001) there was no problem.”

Phil’s problem:
“It’s not the only one, it’s the one with the lowest energy.”

CO2[v3(1)] aka CO2(001) is the *highest* vibrational quantum state, Phil… but nicely backpedaled. Yet again you show that you haven’t the faintest clue. LOL

Phil wrote:
“Really? The strongest transition in the CO2 laser between (001) and (100) is the P(20) transition between CO2(001)(J’=19) and CO2 (100)(J”=20) at 10.591.”

{facepalm} You’ve just described a population inversion in a laser, Phil!

Actually, Phil, it’s a P(10),J(10) transition. If you understood what you’re babbling about, you’d know that. But you don’t, so you don’t. LOL

Do you not understand that you’re describing a forced, unnatural state in a CO2 laser, which does not and cannot exist in the atmosphere? A molecule can be *driven* to any state right up to its dissociation potential, Phil.

The CO2 molecule only has an induced dipole in its v3 (asymmetric stretch) state, Phil… meaning it can only absorb infrared radiation in its v3 state. Futher, the photon spin must match the rotational quantum state of the molecule for resonance to occur.

Further, at the wavelengths in question, the photon wavelength (the translational distance between the peaks of that spiral below) are about 10,000 times longer than the size of the CO2 molecule, further reducing the collision probability.

https://i.imgur.com/q39aAvm.png
(You’ll note the photon is depicted as a spiral… this is entirely correct. A sinusoid is a circular function.)

http://www.barrettbellamyclimate.com/page15.htm
———————————
The existence of the ν3(1) level is highly important with regard to its collisional excitation by nitrogen molecules in their first excited vibrational mode that has a transition wavenumber of 2359.6 cm-1, almost a perfect match for the excitation of the anti-symmetric stretching vibration of CO2:

N2 [ν1(1)] + CO2 [ν20(0)] → N2 [ν1(0)] + CO2 [ν3(1)]

The CO2 [ν3(1)] state can then emit radiation or be degraded to the lower energy levels from which radiation may be emitted.
———————————

Learn how harmonic oscillators work, Phil, and you’ll stop making a fool of yourself… but then, I’d be out of a job, wouldn’t I, Phil? LOL

• Phil. says:

Phil wrote:
“I ignored your “more modern nomenclature”, since you referred to the state in the correct manner, CO2 (001) there was no problem.”

Phil’s problem:
“It’s not the only one, it’s the one with the lowest energy.”

CO2[v3(1)] aka CO2(001) is the *highest* vibrational quantum state, Phil… but nicely backpedaled. Yet again you show that you haven’t the faintest clue. LOL

It isn’t the ‘highest’ vibrational quantum state of CO2, there are many higher ones, CO2(002) for example, it’s just the first one that’s higher than N2(v=1)

Phil wrote:
“Really? The strongest transition in the CO2 laser between (001) and (100) is the P(20) transition between CO2(001)(J’=19) and CO2 (100)(J”=20) at 10.591.”

{facepalm} You’ve just described a population inversion in a laser, Phil!

So what. We’re discussing collisional excitation of CO2 by vibrationally excited N2. This is the mechanism by which CO2 lasers work, it is the mechanism by which you claim vibrationally excited CO2 can be produced in the atmosphere.
In the laser the collisions can create rotational states above J=20 as I’ve showed above. Your claim is that Raman scattering in the atmosphere creates vibrationally excited N2 which then excites the CO2. But you also claim that it’s limited to J=5 or less, what is the basis for that limit? If the Raman ‘pump’ wavelength is 500nm the energy is ~2.5 eV, the N2(v=1) only needs 0.3 eV, there’s no reason why there should be a limit of J=5 as you claim.

Actually, Phil, it’s a P(10),J(10) transition. If you understood what you’re babbling about, you’d know that. But you don’t, so you don’t. LOL

No the strongest transition on the CO2 laser I used was the P(20) at 10.591 micron, not the P(10) at 10.49 micron (must be why it’s called a 10.6micron laser).

Do you not understand that you’re describing a forced, unnatural state in a CO2 laser, which does not and cannot exist in the atmosphere?

But you’re claiming that those states can be reached via Raman scattering in the atmosphere, why are you changing your tune now? I guess that’s what a troll does.

but then, I’d be out of a job, wouldn’t I, Phil? LOL

Oh you get paid for doing this, that explains a lot!

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“It isn’t the ‘highest’ vibrational quantum state of CO2, there are many higher ones, CO2(002) for example, it’s just the first one that’s higher than N2(v=1)”

It is in the troposphere, Phil, which is what we’re discussing.

What’s the energy level of the CO2[v3(2)] vibrational quantum state, Phil? What wavelength photon corresponds to that energy level, Phil? LOL

Phil wrote:
“N2(v=1) only needs 0.3 eV, there’s no reason why there should be a limit of J=5 as you claim.”

Bwahahahaaa! Phil yet again demonstrates that he hasn’t the first faint clue what he’s talking about. You’re describing the vibrational quantum state, Phil, not the rotational quantum states.

Phil wrote:
“No the strongest transition on the CO2 laser I used was the P(20) at 10.591 micron, not the P(10) at 10.49 micron (must be why it’s called a 10.6micron laser).”

Bwahahahaaaa! It just gets better and better. Take a look at the image you’ve been citing, Phil:
https://i.imgur.com/ZEU6l9I.jpg
What does it say, Phil? It says you don’t know what P, Q or R branches are. And that means you don’t understand the vibrational and rotational transition selection rules, either. LOL

It also says that transition is a P(10)/R(10) transition [ R(10) for the CO2[v311(1)] state and P(10) for the CO2[v39(1)] state] to transition to CO2[v1(1)].

Educate yourself, Phil… oh, wait… you claim you’ve got “40 years of study and research in the field”. ROTFLMAO

Fantastical Pedantical Phil’s Craptacular Fails List:
—————
Phil is the Klimate Katastrophe Kook who denies that infrared photons can cause N2 to become vibrationally excited; who claimed that N2 cannot become vibrationally excited at all under any circumstances; who didn’t know about vibronic coupling; who doesn’t understand the role of He in a CO2 laser; who claimed that because N2 is a homonuclear diatomic with no net electric dipole it could not absorb photons under any circumstances (“optically forbidden” LOL); who wants to visit the “hotter” upper atmosphere wearing flip-flops and a tank top; who couldn’t describe the Raman scattering process properly; who simultaneously admitted and denied that N2 undergoes Raman scattering; who can’t seem to grasp how harmonic oscillators work (“Fantastical Pedantical Phil’s Wave Machine” LOL); who denied that N2 could undergo Resonant Raman Scattering; who didn’t know that inelastic scattering always results in vibrational excitation; who claimed that CO2[v3(1) aka CO2(001) was the lowest vibrational excitation state when it’s actually the highest; who thinks RRS (measured as an energy flux) has units of parts per million; who can’t seem to figure out a simple cascaded laser pump setup; who thinks that shorter wavelengths result in a “strong fall-off” in Raman scattering cross-section when it’s actually the opposite; who thinks Raman scattering only happens in the upper atmosphere (when in actuality the cross-section increases with optical depth); who doesn’t know the difference between Stokes and anti-Stokes lines; who thinks that “v2 (000)” is a vibrational excitation state; who used “N2(v=1)” to describe nitrogen’s rotational quantum states; who thinks that a P(10) P-branch denotes a 10 um photon emission. LOL
—————

Phil wrote:
“Oh you get paid for doing this, that explains a lot!”

My payoff is watching warmist kook’s heads implode as their fairy tale CAGW is defenestrated. LOL

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“N2(v=1) only needs 0.3 eV, there’s no reason why there should be a limit of J=5 as you claim.”

Further, Phil:
N2[v1(1)] requires 0.1458 eV.

Did you mean N2[v1(2)], Phil?
N2[v1(2)] requires 0.4365 eV.

You haven’t been right about a single thing yet, Phil. Why don’t you hang up your hang-up on CAGW and hit the books? You need it, and you might just learn enough to realize that CAGW is a unicorn-fart powered fantasy. LOL

Fantastical Pedantical Phil’s Craptacular Fails List:
—————
Phil is the Klimate Katastrophe Kook who denies that infrared photons can cause N2 to become vibrationally excited; who claimed that N2 cannot become vibrationally excited at all under any circumstances; who didn’t know about vibronic coupling; who doesn’t understand the role of He in a CO2 laser; who claimed that because N2 is a homonuclear diatomic with no net electric dipole it could not absorb photons under any circumstances (“optically forbidden” LOL); who wants to visit the “hotter” upper atmosphere wearing flip-flops and a tank top; who couldn’t describe the Raman scattering process properly; who simultaneously admitted and denied that N2 undergoes Raman scattering; who can’t seem to grasp how harmonic oscillators work (“Fantastical Pedantical Phil’s Wave Machine” LOL); who denied that N2 could undergo Resonant Raman Scattering; who didn’t know that inelastic scattering always results in vibrational excitation; who claimed that CO2[v3(1) aka CO2(001) was the lowest vibrational excitation state when it’s actually the highest; who thinks RRS (measured as an energy flux) has units of parts per million; who can’t seem to figure out a simple cascaded laser pump setup; who thinks that shorter wavelengths result in a “strong fall-off” in Raman scattering cross-section when it’s actually the opposite; who thinks Raman scattering only happens in the upper atmosphere (when in actuality the cross-section increases with optical depth); who doesn’t know the difference between Stokes and anti-Stokes lines; who thinks that “v2 (000)” is a vibrational excitation state; who used “N2(v=1)” to describe nitrogen’s rotational quantum states; who thinks that a CO2 P(10) transition results in a 10.6 um photon emission; who thinks N2[v1(1)] requires “0.3 eV” for excitation, when in actuality, it’s 0.1458 eV. LOL
—————

• LOL@Klimate Katastrophe Kooks says:

N2[v1(0)] requires 0.1458 eV.
N2[v1(1)] requires 0.4365 eV

• Phil. says:

Phil wrote:
“N2(v=1) only needs 0.3 eV, there’s no reason why there should be a limit of J=5 as you claim.”

Further, Phil:
N2[v1(1)] requires 0.1458 eV.

Did you mean N2[v1(2)], Phil?
N2[v1(2)] requires 0.4365 eV.

Really? Most diagrams of the CO2 laser energetics show either ~0.3eV or ~2300 cm-1.
Davis gives 2330.7 cm-1, 0.28897 eV.
Further up the thread you’ve claimed:
“The molecule simulator shows N2 as 2359 cm-1. It’s actually 2359.6 cm-1. ” Or 1176cm-1, curiouser and curiouser.

• LOL@Klimate Katastrophe Kooks says:

N2[v1(0)] requires 0.1458 eV.
N2[v1(1)] requires 0.4365 eV.
N2[v1(2)] requires 0.7312 eV.

Most people (and molecule modelers) don’t account for anharmonicity, centrifugal distortion and V-R coupling. Mine does.

My molecule modeler has two molecule modes, passive and controlled. Passive shows a summary and you can’t change parameters; Controlled shows exact numbers and you can change parameters. The molecule modeler only showed the *display* of N2 as 2359 cm-1 in its passive mode, since I had a CO2 molecule in its controlled mode to compare the two.

Since I know you’re as pedantic as pedantic can be, Phil (which you’ve just proven yet again. LOL), I included a disclaimer that while the number displayed is rounded, the exact number is used in all calculations.

• Phil. says:

2359.6 cm-1
Yes 0.2925 eV, the value (~0.3 eV) you said you’d not used!

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“2359.6 cm-1
Yes 0.2925 eV, the value (~0.3 eV) you said you’d not used!”

Phil’s maff says 0.2925 eV = 0.3 eV. LOL

You’re waffling and being pedantic again, Phil, as means of squirming out of being proven wrong.

0.3 eV correlates to 2419.7 cm-1.

Besides which, Phil, your squirming in trying to wriggle out of having been proven wrong brings up the reason you started squirming on this topic in the first place:

http://www.barrettbellamyclimate.com/page15.htm
———————————
The existence of the ν3(1) level is highly important with regard to its collisional excitation by nitrogen molecules in their first excited vibrational mode that has a transition wavenumber of 2359.6 cm-1, almost a perfect match for the excitation of the anti-symmetric stretching vibration of CO2:

N2 [ν1(1)] + CO2 [ν20(0)] → N2 [ν1(0)] + CO2 [ν3(1)]

The CO2 [ν3(1)] state can then emit radiation or be degraded to the lower energy levels from which radiation may be emitted.
———————————

Which means N2 has a higher vibrational temperature than CO2, and a much higher abundance in the atmosphere (by 3 orders of magnitude). Thus N2 will transfer its vibrational quantum state energy to CO2.

https://i.imgur.com/MzSqcet.png
N2, much more vibrationally excited in the atmosphere than CO2.

That CO2 will undergo relaxation emission. And given that the mean free path length of that radiation increases with increasing altitude (as I stated in my original post)…
https://i.imgur.com/xz3nzgH.png
… the net vector of that radiation is upward.

Thus CO2 causes cooling, not warming.

You’re finding it harder and harder to escape the reality that you’ve bought into a scam in subscribing to CAGW, Phil.

• Phil. says:

What’s the energy level of the CO2[v3(2)] vibrational quantum state, Phil? What wavelength photon corresponds to that energy level, Phil? LOL

The vibrationally excited state CO2(002) has an energy of about 4600 cm-1 (wavelength ~2200nm).

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“The vibrationally excited state CO2(002) has an energy of about 4600 cm-1 (wavelength ~2200nm).”

Bwahahahaa! Yet again Phil proves he hasn’t a clue. There’s no “about” about it, Phil. Quantum mechanics is a very precise science (in fact, the most precise science).

How long did you have to Googlerape to come up with that erroneous answer, and why don’t you learn how to do the calculations yourself, so you no longer make these hilarious mistakes? Is it because your doing so would unravel the lie you’ve told that you know anything about quantum mechanics? I think everyone already knows you’re a poseur, Phil… so the only person your lie would be unraveling for is *you*. Stop lying to yourself, Phil. LOL

CO2[v3(2)] Etot = 1174.7 cm-1 + 4698.6 cm-1 = 5873.3 cm-1
CO2[v3(2)] = 4698.6 cm-1 (2.1283 um)

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“No the strongest transition on the CO2 laser I used was the P(20) at 10.591 micron, not the P(10) at 10.49 micron (must be why it’s called a 10.6micron laser).”

The P(20) transition, you say?

Here’s the graphic you’ve been citing, Phil:
https://i.imgur.com/ZEU6l9I.jpg

CO2[v311(1)]:CO2[v110(1)] = (2400.9 – 1431.3) = 969.6 cm-1 (10.3140 um)

CO2[v39(1)]:CO2[v110(1)] = (2384.5 – 1431.3) = 953.2 cm-1 (10.4910 um)

That’s close enough to 10.6 um, given that my molecule modeler takes into account quantum state anharmonicity, centrifugal distortion and V-R interaction. IOW, Phil, my molecule modeler is more accurate than the graphic you’ve been citing.

The graphic you cited, Phil, doesn’t show a P(20) transition. But let’s calculate that, too.

CO2[v320(1):CO2[v110(1)] = (2513.5 – 1431.3) = 1082.2 cm-1 (9.2405 um)

But… but… but Phil! You claimed the P(20) transition resulted in 10.6 um radiation!

Oh… you must have meant a descent *to* the P20, right? Let’s calculate that, too.

CO2[v311(1)]:CO2[v120(1)] = (2400.9 – 1552.5) = 848.4 cm-1 (11.7870 um)

No, that can’t be it.

CO2[v39(1)]:CO2(v120(1)] = (2384.5 – 1552.5) = 832 cm-1 (12.0190 um)

That’s not it, either!

Well, that proves conclusively that Phil is just blathering, and actually knows absolutely nothing about this topic. LOL

• LOL@Klimate Katastrophe Kooks says:

This:
“CO2[v320(1):CO2[v110(1)] = (2513.5 – 1431.3) = 1082.2 cm-1 (9.2405 um)”
“CO2[v320(1):CO2[v119(1)] = (2513.5 – 1536.9) = 976.6 cm-1 (10.24 um)”

But that’s still not 10.591 um radiation, Phil. LOL

• LOL@Klimate Katastrophe Kooks says:

CO2[v320(1)]:CO2[v121(1)] = (2513.5 – 1568.9) = 944.6 cm-1 (10.5870 um)

Hmmm, Phil? That’s only 0.004 um off from your stated 10.591 um radiation.

Oh, but that’d be the R branch, Phil, not the P branch… demonstrating yet again that you don’t know one tenth as much as you claim you do. LOL

Are you having fun yet, Phil? I am. LOL

Fantastical Pedantical Phil’s Craptacular Fails List:
—————
Phil is the Klimate Katastrophe Kook who denies that infrared photons can cause N2 to become vibrationally excited; who claimed that N2 cannot become vibrationally excited at all under any circumstances; who didn’t know about vibronic coupling; who doesn’t understand the role of He in a CO2 laser; who claimed that because N2 is a homonuclear diatomic with no net electric dipole it could not absorb photons under any circumstances (“optically forbidden” LOL); who wants to visit the “hotter” upper atmosphere wearing flip-flops and a tank top; who couldn’t describe the Raman scattering process properly; who simultaneously admitted and denied that N2 undergoes Raman scattering; who can’t seem to grasp how harmonic oscillators work (“Fantastical Pedantical Phil’s Wave Machine” LOL); who denied that N2 could undergo Resonant Raman Scattering; who didn’t know that inelastic scattering always results in vibrational excitation; who claimed that CO2[v3(1)] aka CO2(001) was the lowest vibrational excitation state when it’s actually the highest in the troposphere; who thinks RRS (measured as an energy flux) has units of parts per million; who can’t seem to figure out a simple cascaded laser pump setup; who thinks that shorter wavelengths result in a “strong fall-off” in Raman scattering cross-section when it’s actually the opposite; who thinks Raman scattering only happens in the upper atmosphere (when in actuality the cross-section increases with optical depth); who doesn’t know the difference between Stokes and anti-Stokes lines; who thinks that “v2 (000)” is a vibrational excitation state; who used “N2(v=1)” to describe nitrogen’s rotational quantum states; who thinks that a CO2 P(20) transition results in 10.6 um photon emission; who thinks N2[v1(1)] requires “0.3 eV”, when in actuality, it’s 0.4365 eV; who confused R branch and P branch vibration modes. LOL
—————

• Phil. says:

CO2[v320(1)]:CO2[v121(1)] = (2513.5 – 1568.9) = 944.6 cm-1 (10.5870 um)

Hmmm, Phil? That’s only 0.004 um off from your stated 10.591 um radiation.

Oh, but that’d be the R branch, Phil, not the P branch… demonstrating yet again that you don’t know one tenth as much as you claim you do. LOL
J=20 in the v3 mode and J=21 in the v1 mode, are you sure about that?
Isn’t v=3 Asymmetric stretching and v=1 symmetric stretching?
Maybe that’s what you’re doing wrong with your model.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“J=20 in the v3 mode and J=21 in the v1 mode, are you sure about that?
Isn’t v=3 Asymmetric stretching and v=1 symmetric stretching?
Maybe that’s what you’re doing wrong with your model.”

Yes, Phil, that’s known as R branch relaxation… if you knew anything about vibrational and rotational quantum state selection rules, if you knew anything about P, Q and R branches, you’d have immediately recognized it as the *only* condition under which you were getting your claimed “10.591 um” beam.

Because my molecule modeler is more accurate than the calculations used in the naming nomenclature for your “10.6 um” laser, the relaxation actually occurs at 10.587 um. No other states give anything closer than that to your claimed “10.591 um”, so this is the state you were using… not a P branch relaxation as you claim, but an R branch relaxation.

I’m not doing anything wrong with my modeler, Phil… the problem lies in your continuing inability to grasp even the flimsiest clue about the fundamentals of this subject.

You really have no excuse, what with your claimed “40 years of study and research in the field”, Phil… if I’d spent 40 years in a field and knew as little as you do about it, I’d be properly embarrassed.

You should be properly embarrassed by your continued inaptitude, and in your stubbornness in not admitting when you’re wrong, choosing instead to compound error upon error, Phil.

• Phil. says:

Phil wrote:
“J=20 in the v3 mode and J=21 in the v1 mode, are you sure about that?
Isn’t v=3 Asymmetric stretching and v=1 symmetric stretching?
Maybe that’s what you’re doing wrong with your model.”

Yes, Phil, that’s known as R branch relaxation… if you knew anything about vibrational and rotational quantum state selection rules, if you knew anything about P, Q and R branches, you’d have immediately recognized it as the *only* condition under which you were getting your claimed “10.591 um” beam.

I guess my point was too subtle for you.

Phil wrote:
“J=20 in the v3 mode and J=21 in the v1 mode, are you sure about that?
Isn’t v=3 Asymmetric stretching and v=1 symmetric stretching?

That transition is calculated from a even numbered rotational level in the v=3 mode to an odd one in the v=1 mode.
As you said yourself elsewhere “First, Phil, in the excited state, only the odd-numbered rotational levels are populated,”
So the transition you calculated would appear to be impossible.
The one I referred to:
P(20) transition between CO2(001)(J’=19) and CO2 (100)(J”=20) at 10.591
followed the rule you stated, odd to even. According to Davis:
“Transitions where J’-J”=-1 are called P-branch transitions and are also labelled by the rotational quantum number of the lower level.”
So by that rule the transition I referred to is a P branch, and properly called P(20). Yours, if it were possible, would be R(21).

Patel https://journals.aps.org/pr/pdf/10.1103/PhysRev.136.A1187
also gives P(20) as 10.5912

If you check online you’ll find many papers use the 10.591 micron line, e,g.:
“The repetition rate was 5 Hz, and ATLAS was operated in the elastic backscatter lidar mode, transmitting a wavelength of 10.591 􏰁m corresponding to the 10P20 emission line of the CO2 laser.
https://www.osapublishing.org/DirectPDFAccess/FC6B5F08-C2BA-A96E-02E0BC23A71F7E78_177211/ol-34-6-800.pdf?da=1&id=177211&seq=0&mobile=no
It appears that your modeler is at fault.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“J=20 in the v3 mode and J=21 in the v1 mode, are you sure about that?
Isn’t v=3 Asymmetric stretching and v=1 symmetric stretching?
Maybe that’s what you’re doing wrong with your model.”

LOL@Klimate Katastrophe Kooks wrote:
“Yes, Phil, that’s known as R branch relaxation… if you knew anything about vibrational and rotational quantum state selection rules, if you knew anything about P, Q and R branches, you’d have immediately recognized it as the *only* condition under which you were getting your claimed “10.591 um” beam.”

Phil wrote:
“I guess my point was too subtle for you.”

If your point was that you didn’t know about P, Q and R-branch transitions, Phil, you made that point abundantly clear in several posts over several days. LOL

Phil wrote:
“As you said yourself elsewhere “First, Phil, in the excited state, only the odd-numbered rotational levels are populated,”

Yes, Phil. In an electronically excited state. Were you, by chance, using a cascaded pump setup such that your second stage was photonically excited, thereby allowing Δv1? You know, like in the Stimulated Raman Scattering test that you continue to demonstrate that you don’t understand. LOL

If, as you claim, you were using a 10P20 setup in an electronically-excited final stage, that’d imply that the laser was descending from v3 J=X to v1 J=X+1, Phil. No descents give 10.591 um radiation.

https://i.imgur.com/rtdd3Py.png

Your confusion stems from your inability to grasp vibrational quantum states, rotational quantum states, V-R coupling, the vibrational selection rules and the rotational selection rules. See below.

Phil wrote:
“Patel https://journals.aps.org/pr/pdf/10.1103/PhysRev.136.A1187
also gives P(20) as 10.5912″

From 1964, Phil. My modeler has the most up-to-date data.

They also wrote, Phil:
“The wavelengths measured are in slight disagreement with previous measurements of the transitions in absorption.”

Phil wrote:
“The repetition rate was 5 Hz, and ATLAS was operated in the elastic backscatter lidar mode, transmitting a wavelength of 10.591 􏰁m corresponding to the 10P20 emission line of the CO2 laser.
https://www.osapublishing.org/DirectPDFAccess/FC6B5F08-C2BA-A96E-02E0BC23A71F7E78_177211/ol-34-6-800.pdf?da=1&id=177211&seq=0&mobile=no

They’re taking that 10.591 from the HITRAN database (as nearly everyone does), Phil, and it’s electronically excited. Further, the HITRAN database has errors which are constantly being found and corrected, as even HITRAN admits.

Phil wrote:
“It appears that your modeler is at fault.”

My modeler is fine, Phil. The problem lies in the fact that you’re Googleraping old out of date data, data for conditions other than atmospheric, that you’re conflating electronically excited and de-excited, and that you don’t understand the vibrational and rotational selection rules.

As I stated prior:
———————-
The vibrational wavefunctions for the doubly degenerate bending modes (v2) and the asymmetric stretch (v3) are non-totally symmetric.

Therefore, the vibrational wavefunctions are totally symmetric for even vibrational quantum numbers (v=0, 2, 4…), while the wavefunctions remain non-totally symmetric for v odd (v=1, 3, 5…).

Therefore, any value of Δv1 is possible between the upper and lower electronic state for mode v1. On the other hand, modes v2 and v3 include non-totally symmetric vibrational wavefunctions, so the vibrational quantum number can only change evenly, such as Δv= ±2, ±4, etc…
———————-

• Phil. says:

Your confusion stems from your inability to grasp vibrational quantum states, rotational quantum states, V-R coupling, the vibrational selection rules and the rotational selection rules.

No my question arises from the fact that you keep trying to calculate transitions from even numbered states in the upper level to odd ones in the lower level, whereas everyone else does the opposite.

Why don’t you try calculating the one for the 10P20 transition from J=19 to J=20 as shown in your figure. You know the transition I referred to as the P(20) transition between CO2(001)(J’=19) and CO2 (100)(J”=20) at 10.591nm.
Not CO2[v320(1):CO2[v119(1)] = (2513.5 – 1536.9) = 976.6 cm-1 (10.24 um) which is from a nonexistent even state to a nonexistent odd state (P(19)).
Oh… you must have meant a descent *to* the P20, right? Let’s calculate that, too.
Of course I meant that, it’s the way the nomenclature works, didn’t you realize that? And it was clearly shown when I first referred to it.

https://i.imgur.com/rtdd3Py.png

Special Technologies claim the following for their laser:
10P(20) 10.591micron
In
They refer to using the 10P20 line with a wavelength of 10.591043 micron (HITRAN)
You haven’t shown your calculation for that line yet. I’m sure that HITRAN would be interested to learn that the line they quote to such precision as 10.591043 is incorrect and that you can give them more accurate values.

They’re taking that 10.591 from the HITRAN database (as nearly everyone does), Phil, and it’s electronically excited. Further, the HITRAN database has errors which are constantly being found and corrected, as even HITRAN admits.

So when I said that it was the wavelength I used on my CO2 laser you said:
“Well, that proves conclusively that Phil is just blathering, and actually knows absolutely nothing about this topic.
CO2[v320(1):CO2[v119(1)] = (2513.5 – 1536.9) = 976.6 cm-1 (10.24 um)
But that’s still not 10.591 um radiation, Phil.

Despite the fact that the calculation wasn’t for the transition I referred to.
Now you’ve learned that just about everyone who uses a CO2 laser uses that same line and that the HITRAN database lists it to great precision, they’re all wrong and the calculations of a usenet troll are the only correct ones! So give us your calculated value for the 10P20 line so that we can see how much we’re out.

• LOL@Klimate Katastrophe Kooks says:

Phail wrote:
“Why don’t you try calculating the one for the 10P20 transition from J=19 to J=20 as shown in your figure. You know the transition I referred to as the P(20) transition between CO2(001)(J’=19) and CO2 (100)(J”=20) at 10.591nm.”

I’ll go you one better, Phil. I’ll calculate the descent into the lowest 3 v1 modes.

CO2[v319(1)]:CO2[v120(2)] = (2536.1 + 2497.9) – (2536.1 + 2940.8) = -404.7 cm-1

An impossible transition, Phil.

CO2[v319(1)]:CO2[v120(1)] = (2536.1 + 2497.9) – (2536.1 + 1552.5) = 945.4 cm-1 (10.5780 um)

CO2[v319(1)]:CO2[v120(0)] = (2536.1 + 2497.9) – (2536.1 + 164.2) = 2371.9 cm-1 (4.2161 um)

When you follow an old data set, most likely from decades ago that everyone takes as gospel so no one actually checks anymore, you can expect there’s going to be some slop in your numbers, Phil.

But then, you’re the guy who thinks an order of magnitude error is close enough… except you were actually off by *two* orders of magnitude. LOL

Fantastical Pedantical Phil’s Craptacular Fails List:
—————
Phil is the Klimate Katastrophe Kook who: denied that infrared photons can cause N2 to become vibrationally excited; who didn’t know about vibronic coupling; who didn’t understand the role of He in a CO2 laser; who claimed that because N2 is a homonuclear diatomic with no net electric dipole it could not absorb photons under any circumstances (“optically forbidden” LOL); who wants to visit the “hotter” upper atmosphere wearing flip-flops and a tank top; who couldn’t describe the Raman scattering process properly; who simultaneously admitted and denied that N2 undergoes Raman scattering; who can’t seem to grasp how harmonic oscillators work (“Fantastical Pedantical Phil’s Wave Machine” LOL); who denied that N2 could undergo Resonant Raman Scattering; who didn’t know that inelastic scattering always results in vibrational excitation; who claimed that CO2[v3(1)] aka CO2(001) was the lowest vibrational excitation state (forgetting v1 and v2); who thought RRS (measured as an energy flux) has units of parts per million; who can’t seem to figure out a simple cascaded laser pump setup; who thought that shorter wavelengths result in a “strong fall-off” in Raman scattering cross-section (it’s the opposite); who thought Raman scattering only happens in the upper atmosphere (when in actuality the cross-section increases with optical depth); who didn’t know the difference between Stokes and anti-Stokes lines; who thought that “v2 (000)” is a vibrational excitation state; who used “N2(v=1)” to describe nitrogen’s rotational quantum states; who thought that a CO2[v320(1)] 10P20 transition results in 10.591 um photon emission; who thinks N2[v1(1)] requires “0.3 eV”, when in actuality it’s 0.4365 eV; who confused R branch and P branch transitions; who didn’t know that Stimulated Raman Scattering had resultant photons of the same wavelength as the incident photons; who thinks that “CO2(002) has an energy of ‘about’ 4600 cm-1 (wavelength ~2200nm)”… (CO2[v3(2)] = 4698.6 cm-1 (2.1283 um)); who claimed “CO2(72◦|X1A′) has nothing to do with Carbon dioxide!” (it’s known as neutral bent carbon dioxide); who uses ‘maff’ to claim that 0.2925 eV = 0.3 eV; who can’t read a logarithmic graph (he was off by 2 orders of magnitude!). LOL
—————

• LOL@Klimate Katastrophe Kooks says:

https://i.imgur.com/ZEU6l9I.jpg

Did you make that graphic, Phil? Because it contains an error (aside from it claiming that N2[v1(1)] requires 0.3 ev for excitation)… and given all the errors you’ve made, that you created that graphic is a safe assumption. LOL

Can you spot the error, Phil?

Bet you can’t. LOL

• Phil. says:

Did you make that graphic, Phil? Because it contains an error (aside from it claiming that N2[v1(1)] requires 0.3 ev for excitation)… and given all the errors you’ve made, that you created that graphic is a safe assumption. LOL

Nothing to do with me, of course the ~0.3eV is correct as pointed out above, you’ve even used it yourself.

Can you spot the error, Phil?

Bet you can’t. LOL

I assume you mean the extra transition marked from (001) to (100)?
At least they know that the upper state has odd rotational quantum numbers and the lower one even.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Nothing to do with me, of course the ~0.3eV is correct as pointed out above, you’ve even used it yourself.”

You’ll be providing the URL of the comment where I’ve ever claimed N2[v1(1)] = 0.3 eV, or you’ll admit you’ve been caught in a lie, Phil.

No, it’s not correct, Phil. 0.3 eV correlates to 2419.7 cm-1.

Of course, we know that N2[v1(1)] is actually 3521 cm-1 (Etot = 1176 cm (0.1458 eV)-1 + 2345 cm-1 (0.2907 eV)), which is what, Phil?

N2[v1(1)] requires a total energy (Etot) of 0.4365 eV. Just as I said, Phil.

Since that diagram shows N2[v1(0)] at 0 eV, its scaling is off. N2[v1(0)] = 1175.9 cm-1 (the additional 0.1 cm-1 from N2[v1(0)] to N2[v1(1)] coming from V-R coupling). They should have used the total energy.

Phil wrote:
“I assume you mean the extra transition marked from (001) to (100)?”

Bwahahahaa! Way to demonstrate yet again that you don’t know the first thing about P, Q and R branch transitions, Phil.

That “extra transition”, as you call it, isn’t the error, nor is it an “extra transition”, it’s a perfectly valid transition.

Do continue trying to spot the error, Phil. Your credibility is all shot to hell, but the strange thing about credibility is that you can continue to lose it even after you’ve lost all of it… the extra ‘loss’ just results in raucous laughter at your expense, is all. LOL

• Phil. says:

That’s close enough to 10.6 um, given that my molecule modeler takes into account quantum state anharmonicity, centrifugal distortion and V-R interaction. IOW, Phil, my molecule modeler is more accurate than the graphic you’ve been citing.

I suggest you learn to use it better because you’re clearly doing something wrong.
My data is from: ‘Lasers and Electro-optics: Fundamentals and Engineering’, by Christopher Davis.
But… but… but Phil! You claimed the P(20) transition resulted in 10.6 um radiation!

Oh… you must have meant a descent *to* the P20, right? Let’s calculate that, too.

CO2[v311(1)]:CO2[v120(1)] = (2400.9 – 1552.5) = 848.4 cm-1 (11.7870 um)

No I quite clearly posted:
The strongest transition in the CO2 laser between (001) and (100) is the P(20) transition between CO2(001)(J’=19) and CO2 (100)(J”=20) at 10.591.”
So from the J=19 of (100) to the J=20 of (100). Don’t you understand any of this?
Based on Davis the P(20) is 10.591𝜇m
He gives the P(10) as 10.494 𝜇m
and the R(10) as 9.329 𝜇m

• Phil. says:

Obviously a typo
So from the J=19 of (100) to the J=20 of (100)
Should be from the J=19 of (001) to the J=20 of (100)

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“No I quite clearly posted:
The strongest transition in the CO2 laser between (001) and (100) is the P(20) transition between CO2(001)(J’=19) and CO2 (100)(J”=20) at 10.591.””

And you’re quite clearly wrong, Phil. The CO2[v320(1):CO2[v119(1)] P-branch transition doesn’t give 10.591 um radiation.

CO2[v320(1):CO2[v119(1)] = (2513.5 – 1536.9) = 976.6 cm-1 (10.24 um)

The only transition which gives that radiation is:
CO2[v320(1)]:CO2[v121(1)] = (2513.5 – 1568.9) = 944.6 cm-1 (10.5870 um) (accounting for anharmonicity, centrifugal distortion and V-R coupling).

But that’s an R-branch transition. No P-branch transitions give 10.591 um radiation, Phil.

Perhaps if, rather than copy-pasting from outdated books, you actually learned how to do the calculations yourself, you wouldn’t make such egregious errors, Phil. LOL

Phil wrote:
“so from the J=19 of (001) to the J=20 of (100)”

Which gives 10.24 um radiation, Phil. You’re confused. Again. LOL

So let me guess, Phil… you lied when you claimed you’ve got “40 years of study and research in the field”, you’re desperately Googleraping in an attempt at understanding the topic, your Dunning-Kruger and inflated ego prevent you admitting your mistakes (and thus learning from them), and you don’t have the depth of knowledge necessary to ascertain when you’re making a mistake, which leads to…

Fantastical Pedantical Phil’s Craptacular Fails List:
—————
Phil is the Klimate Katastrophe Kook who: denies that infrared photons can cause N2 to become vibrationally excited; who claimed that N2 cannot become vibrationally excited at all under any circumstances; who didn’t know about vibronic coupling; who doesn’t understand the role of He in a CO2 laser; who claimed that because N2 is a homonuclear diatomic with no net electric dipole it could not absorb photons under any circumstances (“optically forbidden” LOL); who wants to visit the “hotter” upper atmosphere wearing flip-flops and a tank top; who couldn’t describe the Raman scattering process properly; who simultaneously admitted and denied that N2 undergoes Raman scattering; who can’t seem to grasp how harmonic oscillators work (“Fantastical Pedantical Phil’s Wave Machine” LOL); who denied that N2 could undergo Resonant Raman Scattering; who didn’t know that inelastic scattering always results in vibrational excitation; who claimed that CO2[v3(1)] aka CO2(001) was the lowest vibrational excitation state when it’s actually the highest in the troposphere; who thinks RRS (measured as an energy flux) has units of parts per million; who can’t seem to figure out a simple cascaded laser pump setup; who thinks that shorter wavelengths result in a “strong fall-off” in Raman scattering cross-section when it’s actually the opposite; who thinks Raman scattering only happens in the upper atmosphere (when in actuality the cross-section increases with optical depth); who doesn’t know the difference between Stokes and anti-Stokes lines; who thinks that “v2 (000)” is a vibrational excitation state; who used “N2(v=1)” to describe nitrogen’s rotational quantum states; who thinks that a CO2[v320(1)] P-branch transition results in 10.591 um photon emission; who thinks N2[v1(1)] requires “0.3 eV”, when in actuality it’s 0.4365 eV; who confused R branch and P branch vibration modes. LOL
—————

Did my years of Usenet trolling and thus learning about personality types just about pin you down, Phil? LOL

Of course, you’ll deny it… that’s a component of your personality type. LOL

• Phil. says:

But that’s an R-branch transition. No P-branch transitions give 10.591 um radiation, Phil.

Perhaps if, rather than copy-pasting from outdated books, you actually learned how to do the calculations yourself, you wouldn’t make such egregious errors, Phil. LOL

So all those hundreds of research papers that use 10.591𝜇m and called it P(20) were wrong?
And the usenet troll has a model which gives the wrong numbers has got it right and everyone else is wrong!
I would suggest that it’s you who has made the egregious errors.
Do continue trying to spot the error, Phil. Your credibility is all shot to hell, but the strange thing about credibility is that you can continue to lose it even after you’ve lost all of it… the extra ‘loss’ just results in raucous laughter at your expense, is all. LOL
Since it’s obvious that it’s you who has made the error it is you who has lost any credibility you might have had. Interesting question though, does a usenet troll have credibility to lose? Among your fellow trolls will you lose credibility for having it handed to you on WUWT? Perhaps you’ll run off and hide in the bushes to cover up your embarrassment at being caught out so obviously wrong.

Did my years of Usenet trolling and thus learning about personality types just about pin you down, Phil? LOL

But it’s interesting to see someone be so persistently wrong and be so dogmatic about it, and clearly post stuff that he’d copied but not read, which he totally misunderstood.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“So all those hundreds of research papers that use 10.591𝜇m and called it P(20) were wrong?”

Given that most researchers take that nomenclature from the HITRAN database? Given that much of the wavelengths haven’t been empirically tested taking into account modern knowledge (you know, such as taking into account anharmonicity, centrifugal distortion and V-R interaction), instead relying upon data from decades ago, and given that manufacturer inertia makes changing naming conventions difficult? Yeah.

Do you honestly believe they measure the exact wavelength of the laser each time, Phil? No, they buy a laser, which the manufacturer fills with a specific gas, and that gas corresponds to a certain naming nomenclature which HITRAN correlates to a wavelength.

Phil wrote:
“Perhaps you’ll run off and hide in the bushes to cover up your embarrassment at being caught out so obviously wrong.”

Obviously wrong? I was 0.004 cm-1 off your claimed 10.591 um, Phil. Taking into account anharmonicity, centrifugal distortion and V-R interaction, it’s spot-on.

You mean like you’ve been caught out so obviously wrong? LOL

Fantastical Pedantical Phil’s Craptacular Fails List:
—————
Phil is the Klimate Katastrophe Kook who: denies that infrared photons can cause N2 to become vibrationally excited; who claimed that N2 cannot become vibrationally excited at all under any circumstances; who didn’t know about vibronic coupling; who doesn’t understand the role of He in a CO2 laser; who claimed that because N2 is a homonuclear diatomic with no net electric dipole it could not absorb photons under any circumstances (“optically forbidden” LOL); who wants to visit the “hotter” upper atmosphere wearing flip-flops and a tank top; who couldn’t describe the Raman scattering process properly; who simultaneously admitted and denied that N2 undergoes Raman scattering; who can’t seem to grasp how harmonic oscillators work (“Fantastical Pedantical Phil’s Wave Machine” LOL); who denied that N2 could undergo Resonant Raman Scattering; who didn’t know that inelastic scattering always results in vibrational excitation; who claimed that CO2[v3(1)] aka CO2(001) was the lowest vibrational excitation state when it’s actually the highest in the troposphere; who thinks RRS (measured as an energy flux) has units of parts per million; who can’t seem to figure out a simple cascaded laser pump setup; who thinks that shorter wavelengths result in a “strong fall-off” in Raman scattering cross-section when it’s actually the opposite; who thinks Raman scattering only happens in the upper atmosphere (when in actuality the cross-section increases with optical depth); who doesn’t know the difference between Stokes and anti-Stokes lines; who thinks that “v2 (000)” is a vibrational excitation state; who used “N2(v=1)” to describe nitrogen’s rotational quantum states; who thinks that a CO2[v320(1)] P-branch transition results in 10.591 um photon emission; who thinks N2[v1(1)] requires “0.3 eV”, when in actuality it’s 0.4365 eV; who confused R branch and P branch transitions; who didn’t know that Stimulated Raman Scattering had resultant photons of the same wavelength as the incident photons; who thinks that “CO2(002) has an energy of ‘about’ 4600 cm-1 (wavelength ~2200nm)”… (CO2[v3(2)] = 4698.6 cm-1 (2.1283 um)); who claimed “CO2(72◦|X1A′) has nothing to do with Carbon dioxide!” (it’s known as neutral bent carbon dioxide). LOL
—————

Are you having fun yet, Phil? LOL

Phil claims CO2 “has nothing to do with Carbon dioxide!”. Bwahahahaa!

Perhaps you’ll run off and hide in the bushes to cover up your embarrassment at being caught out so obviously wrong.

• Phil. says:

Phil wrote:
“So all those hundreds of research papers that use 10.591𝜇m and called it P(20) were wrong?”

Given that most researchers take that nomenclature from the HITRAN database? Given that much of the wavelengths haven’t been empirically tested taking into account modern knowledge (you know, such as taking into account anharmonicity, centrifugal distortion and V-R interaction), instead relying upon data from decades ago, and given that manufacturer inertia makes changing naming conventions difficult? Yeah.

And that HITRAN database quotes the P20 line as 10.591043,
do you think that they don’t use all those factors in their calculations?

Phil wrote:
“Perhaps you’ll run off and hide in the bushes to cover up your embarrassment at being caught out so obviously wrong.”

Obviously wrong? I was 0.004 cm-1 off your claimed 10.591 um, Phil. Taking into account anharmonicity, centrifugal distortion and V-R interaction, it’s spot-on.

You didn’t do the calculation for the right transition.

• LOL@Klimate Katastrophe Kooks says:

CO2[v319(1)]:CO2[v120(1)] = (2536.1 + 2497.9) – (2536.1 + 1552.5) = 945.4 cm-1 (10.5780 um)

As I said, when you follow an old dataset, most likely from decades ago, and calibrate all your equipment to that, never actually checking to be sure the data has been tested with modern equipment and updated knowledge, you can expect there’s going to be some slop in your numbers, Phil.

And when everyone is ‘standardized’ on that likely decades-old number, the inertia to change is great, especially among manufacturers.

• Phil. says:

Phil wrote:
“No I quite clearly posted:
The strongest transition in the CO2 laser between (001) and (100) is the P(20) transition between CO2(001)(J’=19) and CO2 (100)(J”=20) at 10.591.”

And you’re quite clearly wrong, Phil. The CO2[v320(1):CO2[v119(1)] P-branch transition doesn’t give 10.591 um radiation.

And it quite clearly isn’t the transition I was referring to!

• LOL@Klimate Katastrophe Kooks says:

CO2[v319(1)]:CO2[v120(2)] = (2536.1 + 2497.9) – (2536.1 + 2940.8) = -404.7 cm-1

An impossible transition, Phil.

CO2[v319(1)]:CO2[v120(1)] = (2536.1 + 2497.9) – (2536.1 + 1552.5) = 945.4 cm-1 (10.5780 um)

CO2[v319(1)]:CO2[v120(0)] = (2536.1 + 2497.9) – (2536.1 + 164.2) = 2371.9 cm-1 (4.2161 um)

Most people are still using the Born-Oppenheimer approximation, vibrational normal modes and rigid rotor approximation. It makes the math easier, but what with the power of GPUs nowadays, that should be discarded.

• LOL@Klimate Katastrophe Kooks says:

LOL@Klimate Katastrophe Kooks wrote:
“But Phil, that’s a V-V (Vibration-Vibration) process, not the V-T (Vibration-Translation) process you warmists claim is causing global warming.

C02(001) + N2(v = 0) === C02(000) + N2(v = 1) + 18 cm-1 (555.5556 um)

Whereupon N2 will collide with other CO2 molecules in the v20(0) state:

http://www.barrettbellamyclimate.com/page15.htm
———————————
The existence of the ν3(1) level is highly important with regard to its collisional excitation by nitrogen molecules in their first excited vibrational mode that has a transition wavenumber of 2359.6 cm-1, almost a perfect match for the excitation of the anti-symmetric stretching vibration of CO2:

N2 [ν1(1)] + CO2 [ν20(0)] → N2 [ν1(0)] + CO2 [ν3(1)]

The CO2 [ν3(1)] state can then emit radiation or be degraded to the lower energy levels from which radiation may be emitted.
———————————

So you’ve just argued my point, Phil, by providing yet another mechanism by which N2 becomes vibrationally excited. Did you mean to do that? LOL

Now Phil, if CO2 atmospheric concentration increases, does that V-V to V-T process by which CO2 accumulates energy unto itself such that it will undergo emission relaxation by emitting a photon increase in prevalence? Yeah it does!”

Phil wrote:
“In the lower troposphere the V-T process transfers the energy to its neighbors thereby heating them up.”

But Phil, the C02(001) + N2(v = 0) === C02(000) + N2(v = 1) + 18 cm-1 (555.5556 um) V-V process occurs in the troposphere, because the CO2 molecules in the (001) state are in the troposphere. And given that they’re in the troposphere, the N2 molecules right next to them in the troposphere being excited to (v=1) will be where, Phil?

Did they quantumly tunnel to above the tropopause, Phil? LOL

LOL@Klimate Katastrophe Kooks wrote:
“So an increased CO2 atmospheric concentration will cause what, Phil?

Cooling.”

Phil wrote:
“Only above the tropopause.”

So how are those N2(v=1) molecules (excited by CO2(001) in the troposphere) being instantaneously transported to “above the tropopause” so your fantasy world continues to work the way you say it does, Phil? Magic, or really really intense wishful thinking? LOL

• Phil. says:

Phil wrote:
“In the lower troposphere the V-T process transfers the energy to its neighbors thereby heating them up.”

Yes that is transfer from the lowest CO2 vibrationally excited level v2 (010) which is excited by the 667cm-1 IR emitted by the surface.

But Phil, the C02(001) + N2(v = 0) === C02(000) + N2(v = 1) + 18 cm-1 (555.5556 um) V-V process occurs in the troposphere, because the CO2 molecules in the (001) state are in the troposphere.

Creation of CO2 molecules in the (001) state can’t occur by absorption of 2349cm-1 radiation because it’s a forbidden transition. A way they could be created would be if the ground state CO2 collided with an N2(1) molecule but that’s a rather circular logic!
By the way the 18cm-1 is translational energy so converting it to a wavelength is a No-No, as the wavelength of 0.55mm indicates.

And given that they’re in the troposphere, the N2 molecules right next to them in the troposphere being excited to (v=1) will be where, Phil?

Did they quantumly tunnel to above the tropopause, Phil? LOL

Given that they’re not in the troposphere none of this is happening there.

Above the tropopause is a different situation since very energetic photons (UV etc) exist up there giving rise to electronically excited states with vibrational fine structure which is why the papers you keep dragging in here are about the stratosphere, mesosphere and thermosphere not the troposphere. Also lifetimes of the states are longer because collisions are less frequent.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Creation of CO2 molecules in the (001) state can’t occur by absorption of 2349cm-1 radiation because it’s a forbidden transition. A way they could be created would be if the ground state CO2 collided with an N2(1) molecule but that’s a rather circular logic!”

Did you forget the vibrational selection rules, Phil?

The vibrational wavefunctions for the doubly degenerate bending modes (v2) and the asymmetric stretch (v3) are non-totally symmetric.

Therefore, the vibrational wavefunctions are totally symmetric for even vibrational quantum numbers (v=0, 2, 4…), while the wavefunctions remain non-totally symmetric for v odd (v=1, 3, 5…).

Therefore, any value of Δv1 is possible between the upper and lower electronic state for mode v1. On the other hand, modes v2 and v3 include non-totally symmetric vibrational wavefunctions, so the vibrational quantum number can only change evenly, such as Δv= ±2, ±4, etc…

Now Phil… is it a “forbidden transition” for CO2 to go from its symmetric stretch (v1) to its asymmetric stretch (v3)? It absolutely is not!

What’s the quickest route to get from v1 to v3, Phil? Might it be by absorbing a 10.40583 um (961 cm–1) photon? Sure it is!

https://i.imgur.com/a4hYliy.png

So yet again, you’re wrong. Yet again you embarrass yourself. Yet again you demonstrate that you have absolutely no idea what you’re blathering on about. LOL

Phil wrote:
“By the way the 18cm-1 is translational energy so converting it to a wavelength is a No-No, as the wavelength of 0.55mm indicates.”

Still pulling “facts” from your coal chute, Phil? LOL
https://i.imgur.com/4oWzU6t.png

If you keep displaying your utter inaptitude in this manner, Phil, I’m going to have to get a much larger cluebat. LOL

• LOL@Klimate Katastrophe Kooks says:

Now Phil, given the vibrational selection rules, can you tell everyone how CO2[v20(2)] can get to CO2[v3(1)] without violating the vibrational selection rules?

I bet you can’t. LOL

• Phil. says:

What’s the quickest route to get from v1 to v3, Phil? Might it be by absorbing a 10.40583 um (961 cm–1) photon? Sure it is!

So you’ve first got to get to v1(1), how do you propose doing that.

• LOL@Klimate Katastrophe Kooks says:

You’re dodging the question, Phil.

Now Phil, given the vibrational selection rules, can you tell everyone how CO2[v20(2)] can get to CO2[v3(1)] without violating the vibrational selection rules?

I *know* you can’t. LOL

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Yes that is transfer from the lowest CO2 vibrationally excited level v2 (010) which is excited by the 667cm-1 IR emitted by the surface.”

But Phil, you warmists claim CO2 is undergoing high rates of V-T collisions with N2 and O2 from that CO2[v21(1)] state.

N2[v1(1)]: 2359.6 cm-1 (4.23801 um)
CO2[v21(1)]: 667.3 cm-1 (14.98576 um)

Lower wavelengths carry more energy, Phil. N2 has more energy, Phil.

So the warmist claim (of CO2 V-T transfer to N2) isn’t going to work for any CO2 quantum states except C02[v38(1)], which has +17.9 cm-1 (558.65922 um). But that undergoes a V-V transfer with other molecular constituents, such as:

C02[v38(1)] + N2[v1(0)] === C02[v20(0)] + N2[v1(1)] + 17.9 cm-1 (558.6592 um)

… whereupon N2[v1(1)] collides with CO2[v20(0)], then the consequent CO2[v3(1)] relaxes via photon emission or degradation then emission.

Further, energy transfers which don’t result in molecular motion are favored over those that do (ie: V-T deactivation is highly inefficient for all quantum states and all molecular masses, whereas V-V processes are practically instantaneous).

Even further, the rate constant for the particular V-T transfer the warmists are claiming happens between CO2 and N2 or O2 is actually ~2083.33 times more likely to happen with H2O.

And there’s nothing humanity can do about water vapor in the atmosphere, Phil, nor would we want to.

So there are no CO2 quantum states which increase N2 or O2 translational energy.

Thus CAGW fails yet again. LOL

• Phil. says:

“Yes that is transfer from the lowest CO2 vibrationally excited level v2 (010) which is excited by the 667cm-1 IR emitted by the surface.”

But Phil, you warmists claim CO2 is undergoing high rates of V-T collisions with N2 and O2 from that CO2[v21(1)] state.

N2[v1(1)]: 2359.6 cm-1 (4.23801 um)
CO2[v21(1)]: 667.3 cm-1 (14.98576 um)

Lower wavelengths carry more energy, Phil. N2 has more energy, Phil.

So the warmist claim (of CO2 V-T transfer to N2) isn’t going to work for any CO2 quantum states except C02[v38(1)], which has +17.9 cm-1 (558.65922 um). But that undergoes a V-V transfer

Of course it is because the energy exchange is with N2 in the ground vibrational state and involves the transfer of vibrational energy from the CO2 to the translational energy of the N2.

• LOL@Klimate Katastrophe Kooks says:

Yes, Phil, that V-T process takes place (at an extremely low rate… you have checked the rate constants, yes, Phil?), but energy transfers which don’t result in molecular motion are favored over those that do (ie: V-T deactivation is highly inefficient for all quantum states and all molecular masses, whereas V-V processes are practically instantaneous).

Even further, the rate constant for the particular V-T transfer the warmists are claiming happens between CO2 and N2 or O2 is actually ~2083.33 times more likely to happen with H2O.

And we can’t do anything about H2O vapor in the atmosphere, Phil, nor would we want to.

Your warmist CAGW blather is nothing more than a red herring standing in for water vapor, to push a political ideology that otherwise wouldn’t be accepted. Nor should it be… it’s socialism. And socialism has killed more than 124 million people in the last 100 years. It’s a dangerous idea pushed by those who would want to enslave you, Phil. You’re their ‘useful idiot’.

Think about it… would you rather manage your own affairs, or have someone half the globe away in a one-world government telling you what to do? Thus every time you hear someone touting a “One World Government” or a “New World Order”, you can be sure its codespeak for your servitude.

We shouldn’t have a “One World Government”, we should have 7 billion “world governments”… each person managing their own life, without nose-sticking bureaucrats infringing upon our rights and freedoms, as is their wont.

• LOL@Klimate Katastrophe Kooks says:

Let’s see if I can generate an analogy to try to explain how the process works, Phil, since you seem to be struggling with the entire concept of Raman scattering to the point that you’re simultaneously admitting and denying that it occurs for N2. Which is hilarious, BTW. LOL

Imagine that you build a machine. We’ll call it Fantastical Pedantical Phil’s Wave Machine. For every wave the machine generates, it can absorb a bit of energy, in an amount equal to the peak-to-peak amplitude of the given wave.

Now, you initially build the machine to generate two fundamental frequencies, thus it can absorb two different fundamental amounts of energy.

But wait, there’s more! For only \$1 more, you’ll also get the incredible Harmonic Wave between the two fundamental frequencies, so your machine can now absorb three amounts of energy.

Add a third fundamental frequency and you get three fundamental energies, a harmonic energy between Wave 1 and Wave 2, a harmonic energy between Wave 1 and Wave 3, and a harmonic between Wave 2 and Wave 3. That’s six amounts of energy your machine can now absorb, and that’s not even counting the harmonics between the harmonics!

That’s how vibrational quantum state-Raman coupling happens (and why vibrational quantum state-Raman coupling increases under photon flux), to a rough estimate, Phil. And that’s what the two Stokes pump beams (0.607 um and 0.707 um) in the Stimulated Raman Scattering test did.

A molecule is a wave machine, Phil. That’s why they’re called harmonic oscillators.

• LOL@Klimate Katastrophe Kooks says:

Being a decades-long Usenet troll, I’ve developed certain tactics to flush out those who are blathering utter nonsense. I employed one of those tactics above.

Namely, I intentionally included an erroneous statement. Had Phil had the first faint clue about Raman scattering, he’d have jumped all over it.

He didn’t, and that says a lot about what Phil claims he knows about the Raman scattering process.

It’s been 3 days, Phil… can’t find that intentional error? No, of course not. You don’t even know enough to know what to look for. LOL

Gotta watch me, Phil. I’m tricky like that. LOL

• Phil. says:

Being a decades-long Usenet troll, I’ve developed certain tactics to flush out those who are blathering utter nonsense. I employed one of those tactics above.

Namely, I intentionally included an erroneous statement. Had Phil had the first faint clue about Raman scattering, he’d have jumped all over it.

He didn’t, and that says a lot about what Phil claims he knows about the Raman scattering process.

Just about every statement you made has been erroneous, sorry I missed one!

Gotta watch me, Phil. I’m tricky like that. LOL

Well you’re a troll, I expect that most of what you post is wrong and haven’t been disappointed so far.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Just about every statement you made has been erroneous, sorry I missed one!”

Says the guy who denies that infrared photons can cause N2 to become vibrationally excited; who claimed that N2 cannot become vibrationally excited at all under any circumstances; who didn’t know about vibronic coupling; who doesn’t understand the role of He in a CO2 laser; who claimed that because N2 is a homonuclear diatomic with no net electric dipole it could not absorb photons under any circumstances (“optically forbidden” LOL); who wants to visit the “hotter” upper atmosphere wearing flip-flops and a tank top; who couldn’t describe the Raman scattering process properly; who simultaneously admitted and denied that N2 undergoes Raman scattering; who can’t seem to grasp how harmonic oscillators work (“Fantastical Pedantical Phil’s Wave Machine” LOL); who denied that N2 could undergo Resonant Raman Scattering; who claimed that CO2[v3(1) aka CO2(001) was the lowest excitation state when it’s actually the highest; who thinks RRS (an energy flux) has units of parts per million.

Which one did you miss, Phil? Go on, point it out for everyone.

Bet you can’t. LOL

• Phil. says:

Being a decades-long Usenet troll, I’ve developed certain tactics to flush out those who are blathering utter nonsense. I employed one of those tactics above.

Namely, I intentionally included an erroneous statement. Had Phil had the first faint clue about Raman scattering, he’d have jumped all over it.

This one?
“Raman scattering means a single photon is absorbed, and two photons are emitted, “

I just put it down to ignorance on your part.

• LOL@Klimate Katastrophe Kooks says:

Yay! Phil finally dived Wikipedia enough to figure out my intentionally-included ‘error’ meant to trip Phil up and expose him as having absolutely no knowledge of that which he keeps blathering on about… and it only took him 4 days of intense Wikipedia diving. LOL

Why didn’t you catch it immediately, if you know so much about Raman scattering, Phil?

You know… the Raman scattering you incorrectly provided an explanation for, the Raman scattering which you simultaneously admitted and denied occurred in N2… forcing you to dive into Wikipedia and scratch your head in confusion a lot, then you came back still confounded by the process and claimed the RRS scattering flux was measured in (to quote you) “parts per million”. LOL

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“To excite N2 vibrationally to its first vibrational level would require 4.3𝜇m radiation which is singularly scarce however it’s a forbidden transition anyway.”

The measured Raman spectra of air (atmospheric pressure) with integration times of 1s and 100s
https://i.imgur.com/MzSqcet.png
4300 nm (4.3 um) = 2325.58 cm–1

Spectral radiance, incoming (yellow plot) and outgoing (blue plot)
https://i.imgur.com/GC4Ik1Z.png

If you’re going to pull your “facts” straight from your nether region, Phil, do give us a C&C (Cats & Coffee) warning first, lest we spit coffee as we guffaw and thus ruin our keyboards, or scare the cats sleeping in our laps and thus get clawed half to death. LOL

• LOL@Klimate Katastrophe Kooks says:

Absorption of solar radiation by CO2 in the 2.7‐ and 2.77‐μm bands (000 -> 101 and 000 -> 021) results in fluorescent emissions at 4.3 μm due to the decay of these levels via 101 -> 100 and 021 -> 020. They are an order of magnitude greater than the radiance due to the resonance transition 001 -> 000 centered at 4.26 μm.

N2 is 2359.6 cm-1, which is 4.23801 um.

This is *why* N2 will *always* transfer its vibrational quantum state kinetic energy to CO2, Phil. The Laws of Thermodynamics dictates it does so.

Exactly as the website I linked to above says:
“N2 [ν1(1)] + CO2 [ν20(0)] → N2 [ν1(0)] + CO2 [ν3(1)]”

So as I said in my original post, the warmists have it exactly backward.

And as I said in my original post, thus dies CAGW.

• Phil. says:

Absorption of solar radiation by CO2 in the 2.7‐ and 2.77‐μm bands (000 -> 101 and 000 -> 021) results in fluorescent emissions at 4.3 μm due to the decay of these levels via 101 -> 100 and 021 -> 020. They are an order of magnitude greater than the radiance due to the resonance transition 001 -> 000 centered at 4.26 μm.

Where did you copy this from?

N2 is 2359.6 cm-1, which is 4.23801 um.

This is *why* N2 will *always* transfer its vibrational quantum state kinetic energy to CO2, Phil. The Laws of Thermodynamics dictates it does so.
There is no connection between these two statements.
When N2(1) is present it will resonantly transfer its energy to CO2 via V-V but it’s not present in any significant quantity in the troposphere so it’s irrelevant.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Where did you copy this from?”

http://www.barrettbellamyclimate.com/page15.htm
———————————
The existence of the ν3(1) level is highly important with regard to its collisional excitation by nitrogen molecules in their first excited vibrational mode that has a transition wavenumber of 2359.6 cm-1, almost a perfect match for the excitation of the anti-symmetric stretching vibration of CO2:

N2 [ν1(1)] + CO2 [ν20(0)] → N2 [ν1(0)] + CO2 [ν3(1)]

The CO2 [ν3(1)] state can then emit radiation or be degraded to the lower energy levels from which radiation may be emitted.
———————————

Phil wrote:
“There is no connection between these two statements.
When N2(1) is present it will resonantly transfer its energy to CO2 via V-V but it’s not present in any significant quantity in the troposphere so it’s irrelevant.”

You’re going to beat the warmist drum to your last breath, eh, Phil? LOL

The measured Raman spectra of air (atmospheric pressure) with integration times of 1s and 100s
https://i.imgur.com/MzSqcet.png

N2, much more vibrationally excited in the atmosphere than CO2… and much more abundant as a constituent of the atmosphere (by a few orders of magnitude).

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“To excite N2 vibrationally to its first vibrational level would require 4.3𝜇m radiation which is singularly scarce however it’s a forbidden transition anyway.”

Can’t believe I missed this one… this is a classic.

Phil, what are the vibrational selection rules for N2?

Go on, embarrass yourself. Again. LOL

• Phil. says:

To add to your other errors you don’t understand what the vibrational temperature is either! Some victory dance!

• LOL@Klimate Katastrophe Kooks says:

Phil, Phil, Phil… now you’re just throwing out denigrating denials without substantiation. Given my years of Usenet trolling, my experience tells me that that’s a sure sign of someone who’s cornered by the facts.

Vibrational temperature is just another way of expressing the vibrational quantum state energy based upon the vibrational frequency of the molecule.

Vibrational quantum state energy is quantized kinetic energy, just as translational energy is unquantized kinetic energy, Phil… you’ll note both are described in units of temperature.

Why do you suppose that is, Phil?

Are you going to start claiming that energy can flow from a lower temperature to a higher temperature, Phil?

• Phil. says:

The vibrational temperature is the temperature a molecule must exceed for its vibrational heat capacity to approach the classical value.

• LOL@Klimate Katastrophe Kooks says:

Exactly so, Phil. Notwithstanding your waffle-wording of “must exceed” and “to approach”, a vibrationally-excited molecule is at that exact vibrational temperature, thus it matches the classical value.

Temperature is temperature, Phil… a measure of kinetic energy, whether it be vibrational quantum state kinetic energy or translational kinetic energy. That’s why the units are the same, Phil… unless you’re going to claim (as you tacitly did above) that the units are named the same but denote different energy levels.

You’ll note the vibrational temperature of a vibrationally-excited N2 molecule is far higher than its translational kinetic energy could ever hope to be in the atmosphere… unless you’re going to claim that N2 in the atmosphere has a translational kinetic energy (temperature) of 3374 K.

Thus vibrational kinetic energy transitions come before translational kinetic energy transfers. And N2’s vibrational temperature is higher than CO2’s, even in CO2’s highest (asymmetric stretch) mode.

As I said, you’ve got your energy flows all mixed up, Phil.

• Phil. says:

Try reading an undergraduate Physical Chemistry text, at the Vibrational Temperature the heat capacity is within ~10% of the classical value which is why I used the words I did.
Since in the troposphere N2 is overwhelmingly in its vibrational ground state the direction of kinetic energy is from vibrationally excited CO2 to N2(0).

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Try reading an undergraduate Physical Chemistry text, at the Vibrational Temperature the heat capacity is within ~10% of the classical value which is why I used the words I did.”

Then you need to update your undergraduate Physical Chemistry text (which no doubt still uses the Equipartition Theorem with emphasis upon Classical Statistical Mechanics) to a Quantum Mechanics text with emphasis on Quantum Statistical Mechanics, Phil. Your outdated text likely assumes an ideal gas and thus only collisional interaction, and assumes energy levels form a smooth continuum .

Phil wrote:
“Since in the troposphere N2 is overwhelmingly in its vibrational ground state the direction of kinetic energy is from vibrationally excited CO2 to N2(0).”

The measured Raman spectra of air (atmospheric pressure) with integration times of 1s and 100s
https://i.imgur.com/MzSqcet.png

N2, much more vibrationally excited in the atmosphere than CO2… and much more abundant as a constituent of the atmosphere (by a few orders of magnitude).

• Phil. says:

Phil wrote:
“Try reading an undergraduate Physical Chemistry text, at the Vibrational Temperature the heat capacity is within ~10% of the classical value which is why I used the words I did.”

Then you need to update your undergraduate Physical Chemistry text (which no doubt still uses the Equipartition Theorem with emphasis upon Classical Statistical Mechanics) to a Quantum Mechanics text with emphasis on Quantum Statistical Mechanics, Phil. Your outdated text likely assumes an ideal gas and thus only collisional interaction, and assumes energy levels form a smooth continuum .

Nice waffle signifying nothing!
At 3500K Cp of N2 is 1.333 at 6000K it’s 1.369 kJ/(kgK)

• LOL@Klimate Katastrophe Kooks says:

Nice diversion signifying nothing except that you admit your outdated undergraduate Physical Chemistry text cannot compete with Quantum Mechanics, Phil. LOL

The word “waffle” was used by me first, and I subscribe to the notion that your imitation of my verbiage is the sincerest form of flattery. LOL

• Phil. says:

Nice diversion signifying nothing except that you admit your outdated undergraduate Physical Chemistry text cannot compete with Quantum Mechanics, Phil. LOL

Since my undergraduate text says that at the Vibrational Temperature the heat capacity is within ~10% of the classical value, and the data for N2 near it’s vibrational temperature is 1.333 and at a significantly higher temperature (6000K) is 1.369 I’ll back my text.

The word “waffle” was used by me first, and I subscribe to the notion that your imitation of my verbiage is the sincerest form of flattery. LOL

It’s called ‘irony’.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Since my undergraduate text says that at the Vibrational Temperature the heat capacity is within ~10% of the classical value, and the data for N2 near it’s vibrational temperature is 1.333 and at a significantly higher temperature (6000K) is 1.369 I’ll back my text.”

Well that’s exactly the reason why you’ve been so demonstrably and embarrassingly wrong about so very much, Phil. Your knowledge is outdated, and you refuse to update it.

In other words, Phil, you refuse to follow the scientific principle. And that’s part and parcel of your woes. LOL

After all, given that your religion of CAGW has now been utterly debunked on all fronts, the fact that you refuse to update your knowledge and acknowledge reality is the only reason you continue in your warmist belief.

You don’t believe in science, Phil. You believe in your CAGW religion.

Phil wrote:
“It’s called ‘irony’.”

I know what you’re getting for Christmas. A dictionary. LOL

• Phil. says:

I’ve provided graphics showing the wide absorption spectrum of N2, based upon several studies.

It’s you, Phil, who’s claiming that N2 cannot absorb photons under any circumstances
I didn’t say this you made it up!

(denying that Raman scattering occurs for N2 molecules… you do know how Raman scattering works, yes, Phil?),
Yes I’ve even published papers on the subject.

that it cannot become vibrationally excited except by collision (thereby implying that vibronic coupling doesn’t exist for N2)…
Vibronic coupling is related to electronic excitation which is not relevant to the troposphere

Now, Phil… if, as you claim, N2 can only become vibrationally excited by collision…

I don’t believe I said that, you’re making things up again.

what’s to stop N2 from becoming vibrationally excited by collision with the much more prevalent in our atmosphere water vapor and oxygen?
Well Oxygen is also a homonuclear diatomic and water doesn’t have a resonant energy level unlike CO2.

Why do you warmists claim that the only collision which can vibrationally excite N2 is that with CO2,
As far as I’m aware no one claims that, the transfer from excited CO2 in the atmosphere is translational (V-T)

which comprises only 0.041% of the atmosphere by volume, especially in light of the fact that I’ve shown that it’s energetically favorable for the energy transfer in that situation to go the other direction (in CO2 lasers, in CARS testing and in the free atmosphere)?

Remember, Phil… N2 has only one prevalent vibrational quantum state (with several vibronic coupling ranges of lesser importance)… one prevalent vibrational quantum *energy* *level*, Phil. So once N2 is vibrationally excited, the process will work the same in CO2 lasers, in CARS testing and in the free atmosphere because that N2 vibrational quantum state energy is highly resonant to CO2’s quantum state such that it’s energetically favorable for N2 to give up its vibrational quantum state energy to CO2 upon collision.

If you wish to disprove this, you’ll have to explain how it is that the vibrational quantum state of N2 somehow magically changes in the free atmosphere.

In the free atmosphere (troposphere) the necessary electric discharge to vibrationally excite the N2 isn’t available (except in lightning strikes). Of course if vibrationally excited N2 were prevalent in the atmosphere and transferred its vibrational energy to CO2 we’d expect to see a prominent 10.6𝝁m feature, we don’t.

• LOL@Klimate Katastrophe Kooks says:

Phil… are you claiming that CO2 emits from its highest excited state at 10.6 um? Did you forget that CO2 in a CO2 laser only undergoes partial relaxation, and it requires He to fully depopulate the lower energy levels, which is why CO2 in a CO2 laser only emits 10.6 um radiation?

Why is there a 15 um CO2 line, Phil?

How much He is there in the free atmosphere, Phil? LOL

• Phil. says:

Phil… are you claiming that CO2 emits from its highest excited state at 10.6 um?
That’s the state (100) it would be excited to via a collision with vibrationally excited N2, the favored emission is at 10.6𝝁m probably some at 9.6𝝁m too.

Did you forget that CO2 in a CO2 laser only undergoes partial relaxation, and it requires He to fully depopulate the lower energy levels, which is why CO2 in a CO2 laser only emits 10.6 um radiation?

Doesn’t require He for 10.6𝝁m just makes for higher power output of the laser.

Why is there a 15 um CO2 line, Phil?

Because the CO2 010 vibrational state is excited by the bb radiation from the earth’s surface. This is the lowest vibrational state and can emit 15𝝁m radiation as it returns to the ground state, if it isn’t collisionally deactivated first.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Well Oxygen is also a homonuclear diatomic and water doesn’t have a resonant energy level unlike CO2.”

Now you’re just making stuff up, Phil.

https://www.ann-geophys.net/26/1159/2008/angeo-26-1159-2008.pdf
One of the motivations for the studies was to investigate the role of collisional molecular processes in the electronic excitation and deexcitation of molecules of main atmospheric gases. The collisional lifetime of an electronically excited molecule decreases with the increase in atmospheric density and therefore intermolecular and intramolecular electron energy transfers should be dominant in the redistribution of excitation energies between various states of N2 and O2 molecules.”

So O2 and N2 interact mainly via electronic processes in the atmosphere, Phil. Do electronic states also couple to vibrational states? You betcha, they do.

In addition, they also directly interact via their vibrational quantum states… it’s just hard to generate vibrationally-excited molecules to study because homonuclear diatomics have no net electric dipole. It is, after all, a kinetic energy transfer.

https://i.imgur.com/zzP6hQh.png

You’ll note that for CO2 to contribute vibrational quantum state energy to N2, it must simultaneously also get a contribution from O2 (and how often is that going to happen?), whereas the higher energy state of vibrationally-excited N2 readily contributes vibrational quantum state energy to CO2 (that’s kind of how CO2 lasers work, after all).

Further note that the vibrational quantum state energy of N2 isn’t 2331 as the graphic shows (it’s an old graph). It’s actually 3374 K. That makes it all the more likely that N2 (vibrationally excited via enhanced quantum state-Raman coupling under IR photon flux) will contribute vibrational quantum state energy to CO2 upon collision.

Well, that’s a wrap, folks. CAGW has been utterly debunked. LOL

• Phil. says:

Phil wrote:
“Well Oxygen is also a homonuclear diatomic and water doesn’t have a resonant energy level unlike CO2.”

Now you’re just making stuff up, Phil.

https://www.ann-geophys.net/26/1159/2008/angeo-26-1159-2008.pdf
One of the motivations for the studies was to investigate the role of collisional molecular processes in the electronic excitation and deexcitation of molecules of main atmospheric gases. The collisional lifetime of an electronically excited molecule decreases with the increase in atmospheric density and therefore intermolecular and intramolecular electron energy transfers should be dominant in the redistribution of excitation energies between various states of N2 and O2 molecules.”

Yes, during an aura in the thermo/mesosphere, very relevant to the troposphere!

You’ll note that for CO2 to contribute vibrational quantum state energy to N2, it must simultaneously also get a contribution from O2 (and how often is that going to happen?),

No, not indicated on that diagram!

Further note that the vibrational quantum state energy of N2 isn’t 2331 as the graphic shows (it’s an old graph).

Yes, it’s 2330.7 cm^-1.

Well, that’s a wrap, folks. CAGW has been utterly debunked. LOL

Yes, you’ve single-handedly debunked all your points!

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Yes, during an aura in the thermo/mesosphere, very relevant to the troposphere!”

You’re waffling, Phil.

N2 vibrationally excited by photons via vibrational quantum state-Raman coupling. Not ionized, at atmospheric density and near ambient temperature, using visible range photons which also just so happen to be very near the sun’s spectral peak.

That’s about as close as one can get to the conditions in the free atmosphere while probing the vibrational states of only N2, wouldn’t you say, Phil?

Now you can’t argue that photons cannot vibrationally excite N2. Nor can you argue that the N2 was ionized. Nor can you argue about temperature or density.

And you’re in an especially tight spot, given that the photon flux used in that experiment is at the peak of the visible range of photon flux from the sun.

What will you do now, Phil? LOL

• Phil. says:

Phil wrote:
“Yes, during an aura in the thermo/mesosphere, very relevant to the troposphere!”

You’re waffling, Phil.

No, just stating facts that paper has no bearing on the troposphere.
Regarding the OSU Raman study I’ve refuted your argument above.
And you’re in an especially tight spot, given that the photon flux used in that experiment is at the peak of the visible range of photon flux from the sun.

Not really because the special conditions which had to be met by the illumination in that experiment are not met by solar irradiation.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“Regarding the OSU Raman study I’ve refuted your argument above.”

You’ve claimed they agree with you when they don’t, Phil, because you missed one word (“direct”) and you apparently don’t know how Raman scattering works.

I’ve refuted your alleged ‘refutation’ above.

Phil wrote:
“Not really because the special conditions which had to be met by the illumination in that experiment are not met by solar irradiation.”

And that further highlights the fact that you misunderstood the experiment setup, leading you to believe the N2 was being vibrationally excited by 2 incident photons… which means you also don’t understand how Raman scattering works, Phil.

• Phil. says:

Phil wrote:
“Regarding the OSU Raman study I’ve refuted your argument above.”

You’ve claimed they agree with you when they don’t, Phil, because you missed one word (“direct”) and you apparently don’t know how Raman scattering works.

I’ve refuted your alleged ‘refutation’ above.

Phil wrote:
“Not really because the special conditions which had to be met by the illumination in that experiment are not met by solar irradiation.”

And that further highlights the fact that you misunderstood the experiment setup, leading you to believe the N2 was being vibrationally excited by 2 incident photons… which means you also don’t understand how Raman scattering works, Phil.

I understand how Raman works very well, unlike you I understood that it was a stimulated Raman experiment which requires two wavelengths, a pump and a Stokes beam. You’re out of your depth Kook, give up the trolling.

• Phil. says:

Phil wrote:
“Yes, during an aura in the thermo/mesosphere, very relevant to the troposphere!”

You’re waffling, Phil.

No just the facts.

“Abstract. Relative vibrational populations of triplet B3􏰁g, W3􏰀u, B′3􏰂u− states of N2 and the b1􏰂g+ state of O2 are calculated for different altitudes of the high-latitude upper atmosphere during auroral electron precipitation“.

• LOL@Klimate Katastrophe Kooks says:

You’re still waffling, Phil.

Raman scattering (and thus vibrational excitation) cross-section increases with increasing optical depth, thus it occurs more at lower altitudes, Phil.

You claimed it only happened in the upper atmosphere, Phil.

Yet again you’re wrong, Phil. In fact, you’re the guy who didn’t even know that Raman scattering (all inelastic scattering, in fact) causes vibrational excitation. LOL

You’re the guy who denies that infrared photons can cause N2 to become vibrationally excited; who claimed that N2 cannot become vibrationally excited at all under any circumstances; who didn’t know about vibronic coupling; who doesn’t understand the role of He in a CO2 laser; who claimed that because N2 is a homonuclear diatomic with no net electric dipole it could not absorb photons under any circumstances (“optically forbidden” LOL); who wants to visit the “hotter” upper atmosphere wearing flip-flops and a tank top; who couldn’t describe the Raman scattering process properly; who simultaneously admitted and denied that N2 undergoes Raman scattering; who can’t seem to grasp how harmonic oscillators work (“Fantastical Pedantical Phil’s Wave Machine” LOL); who denied that N2 could undergo Resonant Raman Scattering; who didn’t know that inelastic scattering always results in vibrational excitation; who claimed that CO2[v3(1) aka CO2(001) was the lowest vibrational excitation state when it’s actually the highest; who thinks RRS (measured as an energy flux) has units of parts per million; who can’t seem to figure out a simple cascaded laser pump setup; who thinks that shorter wavelengths result in a “strong fall-off” in Raman scattering cross-section when it’s actually the opposite; who thinks Raman scattering only happens in the upper atmosphere (when in actuality the cross-section increases with optical depth). LOL

Keep digging that hole, Phil. LOL

• Phil. says:

CARS requires a pump laser beam, usually UV which excites the molecule of interest to a virtual state which has an extremely short lifetime (~10^-16 s) simultaneously a Stokes beam illuminates the virtual state which couples it to a real vibrational state. Simultaneously the pump beam illuminates the control volume causing a laser beam at the anti-Stokes wavelength to be emitted. I fail to see what relevance this has to the behavior of N2 in the atmosphere.

• LOL@Klimate Katastrophe Kooks says:

Well, Phil, that’s exactly the reason why you continue to defend the fallacious warmist claim that CO2 causes warming.

It matters not how the N2 molecule becomes vibrationally excited (whether it be via virtual state coupling to a vibrational state, or via electron collision excitement, or via vibrational state-Raman coupling under IR photon flux), it will, under all circumstances, transfer its vibrational quantum state energy to CO2 upon collision. The Laws of Thermodynamics dictates it does so.

And since CO2 cannot transfer that energy back to N2, it is forced to undergo relaxation emission, which is why you see a CO2 line in the atmosphere in the first place. That brightline is not a quasi-continuous spectra due to collisional broadening, so we know that CO2 is not undergoing collision to de-excite, it is merely undergoing relaxation emission.

And since the mean free path length of the radiation emitted by CO2 increases with increasing altitude, the net vector for that radiation is upward.

Thus, CO2 causes cooling, not warming.

• Phil. says:

It matters not how the N2 molecule becomes vibrationally excited (whether it be via virtual state coupling to a vibrational state, or via electron collision excitement, or via vibrational state-Raman coupling under IR photon flux), it will, under all circumstances, transfer its vibrational quantum state energy to CO2 upon collision.
Since the virtual state in Raman lasts ~10^-16 s there will be no collision with anything, it collapses back to the ground state.

• LOL@Klimate Katastrophe Kooks says:

Does the vibrational quantum state energy due to virtual state-vibrational state coupling just disappear, Phil?

• Phil. says:

You’ll further hear warmists talking about increasing CO2 atmospheric concentration causing a widening of the ‘shoulders’ of the purported absorption band of CO2… but take a look at the image above.

You are looking downward on those ‘shoulders’, and you can see that CO2 causes cooling… so a widening of those ‘shoulders’ as CO2 atmospheric concentration increases means it’ll cause cooling at a wider band of frequencies. And as CO2 atmospheric concentration increases, you’ll see the center of that rainbow of colors labeled ‘CO2’ go toward even more extreme cooling.

This utterly destroys the entire underlying basis for CAGW. It cannot continue to exist as a reasonable hypothesis. It has been nullified.

You couldn’t be more wrong! If you’d actually read the paper that plate comes from: Clough and Iacono,
https://agupubs.onlinelibrary.wiley.com/doi/10.1029/95JD01386
you’d see that they anticipated your question and produced a figure showing “Difference in spectral cooling rate profile resulting from doubling carbon dioxide” Plate 5
That figure shows the opposite of your assertion.

• LOL@Klimate Katastrophe Kooks says:

Phil wrote:
“You couldn’t be more wrong! If you’d actually read the paper that plate comes from: Clough and Iacono,
https://agupubs.onlinelibrary.wiley.com/doi/10.1029/95JD01386
you’d see that they anticipated your question and produced a figure showing “Difference in spectral cooling rate profile resulting from doubling carbon dioxide” Plate 5
That figure shows the opposite of your assertion.”

I see you suffer from reading comprehension problems, Phil.

From the study you linked to:
“Tropospheric water vapor continues to be of principal importance for the longwave region due to the spectral extent of its absorbing properties, while the absorption bands of other trace species have influence over limited spectral domains. The principal effects of adding carbon dioxide are to reduce the role of the water vapor in the lower troposphere and to provide 72% of the 13.0 K d−1 cooling rate at the stratopause.”

So… water vapor causes warming. Increased CO2 concentration “reduces the role of the water vapor in the lower troposphere”.

I’m sure you can figure it out from there, yes?

• Phil. says:

I see you suffer from reading comprehension problems, Phil.

No that would be you, I suggested you read the paper (specifically look at Plate 5) not just read (and misunderstand) the abstract!

From the study you linked to:
“Tropospheric water vapor continues to be of principal importance for the longwave region due to the spectral extent of its absorbing properties, while the absorption bands of other trace species have influence over limited spectral domains. The principal effects of adding carbon dioxide are to reduce the role of the water vapor in the lower troposphere

From the paper itself:

The role of water vapor in the troposphere is: “of critical importance with respect to the outgoing long wave radiation in the middle and upper troposphere.”
“the effect of carbon dioxide is to moderate the strong cooling associated with water vapor.”
“Consequently in the troposphere increases in uniformly mixed gases have the effect of reducing the cooling rate associated with water vapor alone while at the same time increasing the downward flux at the surface.”
“The relatively strong net heating effects in the lower troposphere are associated with the hot bands of carbon dioxide, principally at 618 and 720 cm^-1.”

The effect of increasing CO2 is shown in Plate 5 as I said before, it clearly shows that the ‘widening shoulders’ are regions of negative cooling i.e. warming.

and to provide 72% of the 13.0 K d−1 cooling rate at the stratopause.”

You do know where the stratopause is I assume?
“The cooling in the stratosphere is dominated by the v2 band of carbon dioxide at 667 cm^-1 and the v3 band of ozone at 1043 cm^-1.

So… water vapor causes warming cooling. Increased CO2 concentration “reduces the role of the water vapor in the lower troposphere”.

I’m sure you can figure it out from there, yes?

Yes I can, perhaps you could have if you’d actually read the paper.

• LOL@Klimate Katastrophe Kooks says:

Poor Phil. He believes the most prominent greenhouse gas in the atmosphere causes cooling, in direct contradiction to what NOAA and even SkepticalScience.com says. He even changed *my* wording to avoid reality.

You seem to be confused and tripping over your own belief system, Phil. Are you having problems processing reality again?

Here’s what you warmists believe:
https://www.nasa.gov/topics/earth/features/vapor_warming.html
“Increasing water vapor leads to warmer temperatures, which causes more water vapor to be absorbed into the air. Warming and water absorption increase in a spiraling cycle. ”

What other of your beliefs will you twist in your desperate attempt at assuaging the cognitive dissonance you’re experiencing as reality crashes in upon you, Phil?

Liberals appear to be allergic to red pills. LOL

• Phil. says:

Unlike you I actually read the Clough and Iacono paper.
Poor Phil. He believes the most prominent greenhouse gas in the atmosphere causes cooling, in direct contradiction to what NOAA and even SkepticalScience.com says. He even changed *my* wording to avoid reality.

I guess your reading comprehension isn’t so great, when I put quotation marks around a sentence it indicates it is a quotation from the paper, not a belief of mine.

You seem to be confused and tripping over your own belief system, Phil. Are you having problems processing reality again?

The one who has difficulty with reality is you, by failing to read the paper you have misunderstood the findings of the paper.
What Clough and Iacono said was:
“This strong water vapor cooling is attributable to three effects: (1) the rapid decrease in water vapor density as a function of decreasing temperature from the surface, (2) the dependence of the absorption in the atmospheric window region on the square of the water vapor density due to the self-broadening continuum, and (3) both the self- and foreign-broadened continua are effective in filling in the regions between water vapor lines, so that the transition from atmospheric opacity to transparency is rapid with respect to decreasing water vapor density.”
“this rapid leads to a much stronger cooling than would be associated with a uniformly mixed gas.” (such as CO2)

In the plate from the paper which you posted you’ll see a magenta band which corresponds to the cooling emissions from this rapid transition region in H2O vapor, note that magenta corresponds to a cooling rate of between 6 and 8×10^-3 K/day.cm^-1. In the region of the CO2 absorption band this drops to 1 to -1×10^-4 K/day.cm^-1.
Here is Plate 5 which shows the effect of doubling CO2 (355-710 ppm).
“The gray shades on the color scale denote heating.”
Unfortunately the URL didn’t work, the plate can be found by Googling Clough and Iacono plate 5.

• LOL@Klimate Katastrophe Kooks says:

Uh-oh, Phil. Now you’ve got some ‘splaining to do.

Here’s a paper based upon Clough and Iacano’s LBLRTM:
http://irina.eas.gatech.edu/EAS8803_Fall2009/Lec11.pdf
“NOTE: CO2 has very small radiative heating rates. Radiation emitted at one level is absorbed at nearby level having almost the same temperature. Only at the tropopause (near 15 km), where the temperature profile has a minimum, there is a small amount of heating. At higher altitudes, pressure broadening is much weaker allowing emitted radiation to escape to space with little compensating radiation downward from higher levels. ”

Gee, Phil… that’s exactly what the Clough and Iacono graphic depicted.

Now Phil, if CO2 is absorbing a photon and transferring its vibrational quantum state kinetic energy to other molecular constituents of the atmosphere via radiationless collisional transfer and thereby causing atmospheric heating (as you warmists claim), rather than undergoing emission relaxation by emitting a ~15 um photon, where is this referenced-above “emitted radiation” coming from? Hmmmm, Phil?

Seems you *do* have a reading comprehension problem, as well as a scientific-literacy problem. Are you, by any chance, a climate researcher?

And thus it seems I was right… warmists have yet again flipped things on their head, claiming that the exact opposite of reality is what is happening.

You warmists claim CO2 is absorbing a photon and transferring its vibrational quantum state kinetic energy to other molecular constituents of the atmosphere via radiationless collisional transfer and thereby causing atmospheric heating, when in reality other molecular constituents of the atmosphere are absorbing photons of shorter wavelength, increasing their vibrational quantum states, colliding with CO2, which then undergoes emission relaxation by emitting ~15 micron photons.

Seems you’ll have to rebuild your entire belief system from the ground up, Phil. Reality seems to have intruded and stomped your fairy tale world to pieces.

• Phil. says:

Uh-oh, Phil. Now you’ve got some ‘splaining to do.

Here’s a paper based upon Clough and Iacano’s LBLRTM:
http://irina.eas.gatech.edu/EAS8803_Fall2009/Lec11.pdf
“NOTE: CO2 has very small radiative heating rates. Radiation emitted at one level is absorbed at nearby level having almost the same temperature. Only at the tropopause (near 15 km), where the temperature profile has a minimum, there is a small amount of heating. At higher altitudes, pressure broadening is much weaker allowing emitted radiation to escape to space with little compensating radiation downward from higher levels. ”

Gee, Phil… that’s exactly what the Clough and Iacono graphic depicted.
Yes C&I said that CO2 resulted in cooling in the stratosphere.
They also pointed out that in the troposphere CO2 substantially reduced the strong cooling by H2O vapor. Something that you omitted to read in the lecture (not paper) you linked to:
“H2O is concentrated in the lower atmosphere resulting in the high cooling rates between 3 and 10 km. The two peaks in the profiles are associated with different absorption bands, the stronger of these being associated with the higher altitude peak.”
Funny you didn’t mention that?
Now Phil, if CO2 is absorbing a photon and transferring its vibrational quantum state kinetic energy to other molecular constituents of the atmosphere via radiationless collisional transfer and thereby causing atmospheric heating (as you warmists claim), rather than undergoing emission relaxation by emitting a ~15 um photon, where is this referenced-above “emitted radiation” coming from? Hmmmm, Phil?
Where the atmosphere gets thinner, exactly as mentioned in that lecture!
Look at the Plate from C&I that you linked to, see that bright green/yellow/orange blob at 667cm^-1 at a pressure of 1mb, that’s emission at ~60×10^-3 K/day.cm^-1. (the tropopause is at 200mb)
You warmists claim CO2 is absorbing a photon and transferring its vibrational quantum state kinetic energy to other molecular constituents of the atmosphere via radiationless collisional transfer and thereby causing atmospheric heating, when in reality other molecular constituents of the atmosphere are absorbing photons of shorter wavelength, increasing their vibrational quantum states, colliding with CO2, which then undergoes emission relaxation by emitting ~15 micron photons.

Again you’re referring to something you’ve read about what happens in the stratosphere/thermosphere and imagining that happens in the troposphere, it doesn’t.
Again you should read the paper and understand it instead of posting about something you don’t understand.

• LOL@Klimate Katastrophe Kooks says:

But… but… but Phil, it’s you warmists who claim that atmospheric gasses cause *warming*, not cooling. And now you’ve been so twisted around that you’re claiming that the predominant GHG (per you warmists) actually causes *cooling*!

Yet you ‘cling to your guns and Bible’ of CO2 causing warming… even after the physics of it has been laid out for you, even after you have *admitted* that the spectral radiance at the absorption lines of CO2 is extremely sparse.

Now, Phil… if the spectral radiance in that region is extremely sparse, just how is the warmist claim (that CO2 is absorbing photons, becoming vibrationally excited, colliding with other molecular constituents of the atmosphere, and transferring its vibrational quantum state kinetic energy to the translational energy (which we measure as temperature) of those other molecular constituents via radiationless collisional transfer) going to work?

You seem to be confused, Phil. That tends to happen to those who believe that fairy tales are reality. LOL

• Phil. says:

But… but… but Phil, it’s you warmists who claim that atmospheric gasses cause *warming*, not cooling. And now you’ve been so twisted around that you’re claiming that the predominant GHG (per you warmists) actually causes *cooling*!

The graph from the paper you quoted here shows that, that you didn’t read it isn’t my fault!

Yet you ‘cling to your guns and Bible’ of CO2 causing warming… even after the physics of it has been laid out for you, even after you have *admitted* that the spectral radiance at the absorption lines of CO2 is extremely sparse.

You haven’t laid out any physics you don’t have a clue about it. Also I have not admitted that the spectral radiance at the absorption lines of CO2 is extremely sparse. Just attempted to refute the myth that you push that CO2 emits at -80ºC.

See above for the rest.

• LOL@Klimate Katastrophe Kooks says:

Awww, Phil’s getting perturbed and starting to ad hom and strawman. LOL

That won’t work with me, Phil. I’m a usenet troll from decades back… and I’m smarter than you. LOL

How does it feel to have to argue from *my* perspective, eschewing your lockstep hivemind CAGW mantra because you know it simply doesn’t apply, Phil?

Please to be producing just *one* peer-reviewed study which conclusively proves CO2 causes CAGW, Phil.

Here’s three from my side:
How increasing CO2 leads to an increased negative greenhouse effect in Antarctica
https://agupubs.onlinelibrary.wiley.com/doi/full/10.1002/2015GL066749

Cooling of Atmosphere Due to CO2 Emission

The Four Known Scientific Ways Carbon Dioxide Cools Earth’s Climate
https://principia-scientific.org/the-four-known-scientific-ways-carbon-dioxide-cools-earth-s-climate/

And that’s in addition to all of quantum physics backing me up, and the Clough and Iacono study.

https://co2islife.files.wordpress.com/2017/01/spectralcoolingrates_zps27867ef4.png

• Phil. says:

Awww, Phil’s getting perturbed and starting to ad hom and strawman. LOL

That won’t work with me, Phil. I’m a usenet troll from decades back… and I’m smarter than you. LOL

That you’re a troll has been apparent for a while, just not a very good one! As for being smarter, well the number of mistakes you’ve made in your postings disprove that.

• LOL@Klimate Katastrophe Kooks says:

Says the guy who denies that infrared photons can cause N2 to become vibrationally excited; who claimed that N2 cannot become vibrationally excited at all under any circumstances; who didn’t know about vibronic coupling; who doesn’t understand the role of He in a CO2 laser; who claimed that because N2 is a homonuclear diatomic with no net electric dipole it could not absorb photons under any circumstances (“optically forbidden” LOL); who wants to visit the “hotter” upper atmosphere wearing flip-flops and a tank top. LOL

I get it, Phil. You’re required by your lockstep hivemind leftist indoctrination to toe the warmist line, but geez… do try to at least confine your replies to reality. LOL

And that’s “proudly a troll”, thank you very much. I live in your head, in Nick Stoke’s head, in the head of every warmist who finds their entire house-of-cards fantasy world of CAGW having its foundation shaken by the earthquake known as reality.

• LOL@Klimate Katastrophe Kooks says:

https://www.atmos-chem-phys.net/6/5025/2006/acp-6-5025-2006.pdf
Note page 3 of 6, Fig. 3, “Measurement of radiance emitted from the deep space (bottom panel) and the atmospheric limb (top panel).

Note especially the top panel, showing wavenumber ~667 cm-1 (corresponding to ~15 um) peak in radiance.

What does that tell you, Phil?

What’s really funny is that you tripped all over yourself to declare that water vapor causes cooling (even revising what *I* wrote to do so), yet you’re still bound and determined to declare CO2 to cause warming, despite the reality of quantum physics declaring you a warmist loon.

• Phil. says:

Note especially the top panel, showing wavenumber ~667 cm-1 (corresponding to ~15 um) peak in radiance.

What does that tell you, Phil?

That CO2 emits from the upper atmosphere, exactly what C&I say and surprise, surprise what that paper says. Do you read any of the material you post here?

“the FIR region is very important because most of the radiative cooling of the upper troposphere and lower stratosphere occurs there (Clough et al., 1992, 1995).”
My emphasis.

What’s really funny is that you tripped all over yourself to declare that water vapor causes cooling (even revising what *I* wrote to do so)

No I quoted the paper you linked to a diagram from!
You made a mistake which is why I corrected it, something you could have avoid by reading the paper instead of misinterpreting the abstract.

• LOL@Klimate Katastrophe Kooks says:

You’re trapped, Phil. I’ve forced you into a corner via a clever ruse which you were too dense to foresee. Now you’re so confused that you’re no longer toeing the warmist line… you’re claiming that some atmospheric gasses cause *cooling*! Most importantly, the one GHG which you warmists claim is the *predominant* GHG… water vapor.

One more small step, and you’ll be agreeing with me in full, Phil. Can you deconstruct your CAGW fantasy to get there? Do you have the intellectual honesty to do that?

Now, Phil… if the spectral radiance in that region where CO2 absorbs is extremely sparse, just how is the warmist claim (that CO2 is absorbing photons, becoming vibrationally excited, colliding with other molecular constituents of the atmosphere, and transferring its vibrational quantum state kinetic energy to the translational energy (which we measure as temperature) of those other molecular constituents via radiationless collisional transfer) going to work?

• Phil. says:

Now, Phil… if the spectral radiance in that region where CO2 absorbs is extremely sparse,

As pointed out several times this premise is false
Done several times.

• LOL@Klimate Katastrophe Kooks says:

You’ve evaded the question several times, Phil. In point of fact, the 15 um photon flux is *always* extremely sparse in relation to shorter-wavelength photon flux.

If the spectral radiance in that region where CO2 absorbs is extremely sparse, just how is the warmist claim (that CO2 is absorbing photons, becoming vibrationally excited, colliding with other molecular constituents of the atmosphere, and transferring its vibrational quantum state kinetic energy to the translational energy (which we measure as temperature) of those other molecular constituents via radiationless collisional transfer) going to work?

Stop evading the question, Phil. Do that hard work to defend your warmist religion. Show your work. I’ve shown mine.

I bet you’ll continue to evade and obfuscate… you’ve proven that’s your ‘A game’. LOL

• Phil. says:

You’ve evaded the question several times, Phil. In point of fact, the 15 um photon flux is *always* extremely sparse in relation to shorter-wavelength photon flux.

No I explicitly answered it several times. As stated before the spectral radiance at 15µm is ~95% of the peak for a bb at 288K, consequently the shorter wavelengths are about equal or mostly ‘sparser’.

• LOL@Klimate Katastrophe Kooks says:

Only for an ideal blackbody, Phil, which our planet is not.

You also forgot the incoming radiation, Phil. That’s a much higher spectral radiance, which vibrationally excites the molecular constituents of the atmosphere.
https://i.imgur.com/P4KmEPy.jpg

• LOL@Klimate Katastrophe Kooks says:

This graphic better shows the orders-of-magnitude difference in energy density between incoming and outgoing radiation, Phil.
https://i.imgur.com/cDS5zDS.png

In essence, you were arguing that the only radiation that mattered was that which was emitted by the planet, completely dismissing that giant fusion furnace in the sky!

If one were to extend the blackbody curve for the incoming radiation out to the wavelengths of the outgoing radiation, one would see that the curve for the outgoing radiation is a mere blip in comparison.

• LOL@Klimate Katastrophe Kooks says:
• Phil. says:

This graphic better shows the orders-of-magnitude difference in energy density between incoming and outgoing radiation, Phil.

Actually it doesn’t, it shows the difference in energy density leaving the sun and leaving the earth. You have forgotten to allow for the fact that the earth is 92million miles away and the inverse square law.

If one were to extend the blackbody curve for the incoming radiation out to the wavelengths of the outgoing radiation, one would see that the curve for the outgoing radiation is a mere blip in comparison.

Actually if you correctly allowed for the distance for the earth as a blackbody the area under the two curves would be equal.

• LOL@Klimate Katastrophe Kooks says:
• Felix says:

A small increase in the concentration of GHGs might not lead to warming. It all depends upon the feedback effects of more CO2 in the air.

Even where there is relatively little water vapor, the main GHG, a fourth CO2 molecule per 10,000 dry air molecules doesn’t necessarily warm the air. The dry air over the South Pole hasn’t warmed in all the time records have been kept there.

• Pop Piasa says:

“Science is about evidence supporting a contingent conclusion.”
Climate science is more about models supporting an intangent conclusion.

• Pop Piasa
You have a way with words
that makes the rest of us
seem boring.

• fonzie says:

(Richard, maybe we ARE boring… ☺️)

• Pop Piasa says:

Reading is boring to the illiterate, television/ internet fed, video generation. “The Pepsi Generation”
We are entering another period of mass-ignorance, where the bourgeois mind is molded by broadcast propaganda.

• Pop Piasa says:

Jeez, I need to lighten up! I’m being Debbie Downer…
Rest assured there are youth who are courageous enough to buck the trend.

• Curious George says:

+1. Steven, please elucidate a single-word sentence “Evidence.”
I know quite a few people – or maybe not carbon-based life forms – who want me to stop flying. They send this message from their private aircraft.

• Latitude says:

“Physics tells us that more c02 will warm the planet.”

….are you saying the climate models…that so spectacularly failed….were not based on the best CO2 physics?

• Gordon Dressler says:

SM, you posted: “Physics tells us that more C02 will warm the planet.”

Not so fast, physics tells us that gaseous CO2 has certain absorption bands, mostly in the near- to far-infrared radiation spectrum (i.e., bands scattered over 2-20 microns wavelength span). Physics also tells us that at the current .04% concentration level in the troposphere, the absorption column length in such that the bands are at the fully saturated level. A 6 times e-folding absorption length at the present CO2 level would be about 150 m. Almost all scientists agree that direct IR from Earth in the main CO2 bands is absorbed well below 1 km above Earth’s surface.

Thus, to first order, physics tells us that adding more CO2 will not mean intercepting more direct IR radiation from Earth’s surface. However, there is the secondary affect that the IR energy absorbed by CO2 is continuously being re-radiated in all directions as a result of the effective temperature of the CO2 molecules and well as the fact that CO2 molecules are transferring some of that absorbed IR energy via collisions with other atmospheric constituents (thermal re-equilibration), which then radiate in their own emission bands as well as convect energy via atmospheric circulation (thus returning a small portion of the CO2-band energy back to Earth’s surface). So that adding CO2 (expanding its effective atmospheric column height) can have a secondary (weak) effect on reducing the total heat loss to space, thereby “warming” (a real misnomer if there ever was one) the planet.

Let’s just say the physics is complicated.

• Pop Piasa says:

Seems intuitive to me that planetary albedo changes should far outweigh an additional CO2 molecule in every ten thousand molecules of air mixture. Water is the only effective temperature regulator.

• Jeff Alberts says:

“Seems intuitive to me that planetary albedo changes should far outweigh an additional CO2 molecule in every ten thousand molecules of air mixture. Water is the only effective temperature regulator.”

I don’t agree. A few years ago, highlighted here on WUWT (don’t have time to search at the moment), much of the northern hemisphere was covered in snow. Yet we didn’t dip into a deep freeze due to the sudden change in albedo.

• G. Dressler
The physics is simple.
.
There just not much of it.
.
What happens in a laboratory
is merely assumed to apply to our
atmosphere and planet,
… but that was not scary enough,
so the assumption was tripled
with the water vapor positive feedback
theory.

A little physics.
A lot of assumin’.

• Joel O'Bryan says:

speaking of hyperbole…

How’s the Berkeley Euthanasia Saves The-world plan for humane genocide coming along?

Bwahahahahah……

• Phillip Bratby says:

Physics does not tell us that more C02 will warm the planet. Physics tells us that the sun warms the planet and that CO2 is a gas that helps cool the planet.

• Gordon Dressler says:

“Physics tells us . . . that CO2 is a gas that helps cool the planet.” Actually no it doesn’t.

If there was no CO2 in Earth’s atmosphere, Earth would be able to radiate IR directly to deep space in the CO2 spectral bands where there isn’t any significant water vapor or other species absorption (the 4-5 micron wavelength band) and where there is only relatively minor absorption by an overlaying water vapor spectral band (the 13-15 micron wavelength band).

Simple physics tells us that this direct radiation loss (due to the absence of atmospheric CO2) would increase the net loss of heat from Earth compared to the current situation, and for an assumed constant solar power input—all other things (e.g., albedo) being equal—the Earth’s surface and near-surface air temperatures would therefore be lower (i.e., cooler) in the mean-equilibrium state. Thus, the presence of CO2 make Earth’s surface temperature slightly hotter than it would be otherwise.

If what you assert was true, Venus with it heavy CO2 atmosphere should be an ice block instead of having a surface temperature of about 460 C (860 F).

• Stephen Richards says:

Science is about evidence supporting a contingent conclusion.

I suggest you go away and read Feynman.

• Gary Pearse says:

Steven, laboratory radiative physics has never been in dispute by scientific literates, but this is ceteris paribus information. The planet doesnt have a ceteris paribus position. Let me explain.

I read that a Maserati auto can do zero to 60 in under 5 seconds and I can accept this. However, away from the track (laboratory), on sand, in a foot of water, in a rainstorm with a headwind, out in the weather so to speak, this physical factor is of no use whatsoever, even for approximations. I know you are not a scientist, but Im confident you understand that scientists (and engineers)design their experiments very carefully to make them ceteris paribus. Understood is radiative physics as measured in the lab IS ceteris paribus. To not understand this us ti be thinking linearly.

For homework, I assign also to look up “le Chatelier Principle” on Wiki. The discoverer of the principle himself wasnt aware that it was a more universal law than simply a finding in connection with chemical reactions that an agent added to alter an equilibrium condition is resisted by the system as a whole. This is why Willis’s temperature “governor” hypothesis is so compelling, at least to engineers. One can see this in Newton’s 3rd law and even less simply in the other two – see gyroscope and how it works. See “back EMF” in electric motors. See buffering in oceans (and othet chemical situations). And reach understanding of why warming has only been a third of projected and ‘ocean acidification’ is greatly overblown…

• HotScot says:

Gary

Can I be rude and cut across you somewhat, just to illustrate a point to Stephen.

“Tyndall explained the heat in the Earth’s atmosphere in terms of the capacities of the various gases in the air to absorb radiant heat, also known as infrared radiation. His measuring device, which used thermopile technology, is an early landmark in the history of absorption spectroscopy of gases. He was the first to correctly measure the relative infrared absorptive powers of the gases nitrogen, oxygen, water vapour, carbon dioxide, ozone, methane, etc. (year 1859). He concluded that water vapour is the strongest absorber of radiant heat in the atmosphere and is the principal gas controlling air temperature. Absorption by the other gases is not negligible but relatively small.”

And for Stephens benefit I shall repeat: “Absorption by the other gases is not negligible but relatively small.”

Include Tyndall’s antiseptic lab experiment in your excellent Maserati illustration and I suspect we are getting somewhere near the truth.

CO2 caused global warming is a triumphant concoction of science, hijacked by politics, to achieve a specific objective.

Club of Rome and UN Agenda 21 anyone?

• Pop Piasa says:

Gary, I find that reminiscent of the claim that burning coal causes acid rains downwind when in reality it more often enhances the elemental sulfur content of the soils and bolsters crop production.

• Clyde Spencer says:

Mosher,
You said, “Physics also tells us that a warmer planet is likely to have less ice.” Not really. It depends on your base level. That is, if it is very warm (above the freezing point of water) what little snow there may be, won’t last long. However, if it gets very cold, the air will be dry and there will be relatively little snow/ice. In between there is an optimum where it is cold enough for snow and ice to form, and warm enough to allow evaporation to provide water to make snow. Either side of the optimum will decrease the amount of snow, which means less glacial ice.

11. Bob Denby says:

Incongruity: Scientists attempting to answer political suppositions! (No common language!)

12. Tom Dayton says:

“Now, exactly why it is that that enhanced geothermal heat release is happening just now, is unknown.” But Voisin provided zero evidence of enhanced geothermal heat release happening just now. Zip. Nada. Zilch.

Versus abundant empirical evidence of ice loss being caused by other mechanisms that are solidly tied to global warming, which in turn is solidly, empirically tied to increases in greenhouse gases.

• goldminor says:

The melt is due to shifts in surface wind flows. CO2 has nothing to do with changing surface winds. The melt is also affected by warmer ocean waters, but the oceans are also steadily cooling in recent years. Southern sea ice is back close to the average trend line.

https://nsidc.org/arcticseaicenews/#antarctic-popup

• Enginer says:

remember, correlation does not prove causation… especially since data has shown that air temperature increases and solar insolation cause warming seas which cause CO2 increases AFTER the lower solubility of gases in the warmer oceans occurs.

• Pop Piasa says:

Henry’s law really should explain most, if not all of the rise in CO2, considering the fact that the oceans are the single biggest sink of CO2.
It is also prudent to keep in mind that the oceans store 99.9% of terrestrial heat and the atmosphere only .1%, when considering the roles that the two factors play in deciding the global temperature (if there really is such a thing).

• Pierre says:

Voisin provided zero evidence of enhanced geothermal heat release happening just now. Zip. Nada. Zilch.
Tom Dayton said “Versus abundant empirical evidence of ice loss being caused by other mechanisms that are solidly tied to global warming, which in turn is solidly, empirically tied to increases in greenhouse gases.”
Boy that is the pot calling the kettle black. You provide zero evidence that global warming is tied to green house gases. I have never seen this proof. 97% of global warming studies have been based on that missing proof. The closest I have ever found was circular arguments within climate models as proof it works in the environment like it works in a controlled lab experiment.
I have been waiting and looking for more than twenty years. IF, ever the proof were to arise I would buy into a lot more of the ancillary studies.

• Gary Pearse says:

Pierre, if you dont know this is an active volc area on land (under the ice) and on the seafloor, then you are too far back to begin your education here. Google is your friend. Better, check out Wuwt archives.

• fonzie says:

(Gary, Pierre was quoting Tom Dayton in that first paragraph there. i guess he messed up on the quotation marks)…

• Pierre says:

Was directed at Tom Dayton’s comment that green house gases are empirically, solidly tied to global warming. No such empirical evidence exists that I have found. I am well aware of the volcanism in Antarctica. Eribus has an active lava lake and has been in more or less continuous eruption for a long time. Everyone ignored it back in the ozone scare days.

• Gary Pearse says:

Nintety volcanoes! Volcanoes are hot- geothermal is heat from within. Also, the seafloor throughout the region is tufted with volcanoes not marked on the authors map. A few years ago, researchers from Washington State measured the seismics of a sub-ice eruption. Also Eribus volcano in west Ant. recently erupted. Google all this or check in WUWT archives.

• “geothermal is heat from within”
So, how much heat? And is it different to the past? And how much ice could it melt? No-one seems interested in actual numbers, despite all the chest thumping about engineers.

• Tom Dayton says:

The key word is “enhanced.” As Nick Stokes commented, Voisin provided no evidence of any enhancement (increase) in geothermal heat release.

• Pop Piasa says:

…And again, neither of you has provided any proof that CO2 enhancement is the cause of these phenomena either.
The explanation of melting in the areas outlined in this article is certainly much more logical than simply pinning it on climate change. brought about magically by CO2, emitted by those nasty Humanoids (except myself, of course) who are overpopulating poor, fragile Gaea.

• Chris says:

No, it’s not more logical. It implies there has been a substantial increase in geothermal activity without providing any evidence that is the case. Atmospheric CO2 levels have gone up, that is not in question.

• MarkW says:

Argument from ignorance.
We don’t know what else it might be, so it must be CO2.

Just showing that CO2 levels have gone up isn’t sufficient to prove anything.

• Chris says:

Ah, but the statement that geothermal is causing the Greenland and Antarctica melt without any supporting data is just fine by you? What’s the word that comes to mind….hmmmm… oh yeah, hypocrisy.

13. Sara says:

I’m continually amazed at the silliness of the Greenbeans and Ecohippies who are the short attention span people.. They don’t seem to “get” that we are thriving as a species because we’re in a warm period that allowed us to start settling in places, learn how to grow crops and domesticate animals so that we no longer needed to wander, and the Greenbeans complain bitterly about this benefit.

Well, I have a question that is related somewhat to this article, and it has to do with a proposed el Nino forming during the 2018-2019 season, as indicated in this Accuweather article:
https://www.accuweather.com/en/weather-news/what-does-el-nino-watch-mean-for-atlantic-hurricane-season-us-winter/70005235

I’m not in the butterfly wing flapping mind, but how will loss of solar activity affect this cycle this time? Is it going to be weaker or stronger (in the real world) or is it simply not going to happen at all? Since that’s a weather question, about something that does affect us all – jet stream splits, for example – is the pattern going to change? Is this possibly a long-term, semi-permanent change, because it is usually timed to the solar cycles and we’re having little to no solar sunspot activity nowadays.

There’s another thing: the Gakkel Ridge formation runs northward in the Atlantic and became active a while back, so how will this affect Greenland itself? Is it having an effect on what’s going on there? And what about Iceland? There are more volcanoes working their way toward erupting in the near future, so when that happens, what will the consequences be to the rest of the world?

All these little things are never addressed by cli-sci peeps like Mann and Hanse, and others of their ilk, because they don’t really want to have to take such variables into account. It’s easier to blame a bogeyman, an invisible gas that is produced by their lungs on a constant basis: Carbon dioxide, IDIOTS!!

So in going back to my original subject, the projected el Nino, if it doesn’t happen, or is weak, what are those cli-sci guys going to do? Blame it on more CO2? This simply gets silly after a while.

I can’t take them seriously at all.

• Alley says:

Most every El Nino is warmer than the last. Linking up El Nino years shows warming, as expected in a warming system. Linking La Nina years shows warming.

There are wheels inside of wheels. The trick is to see what wheels are the largest, and which ones oscillate and which ones are creating warming. Ocean waters move heat around, not create it. We are getting less solar irradiation. Seems tat CO2 really is the primary forcing.