Debunking The Catastrophic Anthropogenic Global Warming Hypothesis

“Anyone who’s studied particle physics knows CAGW (Catastrophic Anthropogenic Global Warming caused by CO2) is a politicized scam.”

Debunking The Catastrophic Anthropogenic Global Warming Hypothesis

By Reader ‘Up far too late’

Anyone who’s studied particle physics knows CAGW (Catastrophic Anthropogenic Global Warming caused by CO2) is a politicized scam with the ulterior motive of implementing a totalitarian world government and deindustrializing / depopulating the planet so the elites can live like kings while the rest of us live like paupers… UN officials have even outright admitted the IPCC agenda has nothing to do with climate change.

CO2 does not and cannot cause global warming… that’s a scientific fact.

A Comprehensive Debunking Of The Catastrophic Anthropogenic Global Warming (CAGW) Hypothesis Utilizing Particle Physics First Principles

First, you’ll notice the title states “the CAGW hypothesis”, rather than “the CAGW theory”… that is deliberate.

The words “fact”, “theory”, “hypothesis” and “law” have very specific definitions in science:
Hypothesis: A tentative explanation of an empirical observation that can be tested, but which has little or no validation. It is merely an educated guess.

Fact: An empirical observation that has been confirmed so many times that scientists can accept it as true without having to retest its validity each time they experience whatever phenomenon they’ve empirically observed.

Law: A mathematically rigorous description of how some aspect of the natural world behaves.

Theory: An explanation of an empirical observation which is rigorously substantiated by tested hypotheses, facts and laws.

Laws explain how things behave in the natural world, whereas theories explain why they behave the way they do.

For instance, we have the law of gravity which explains how an object will behave in a gravitational field, but we’re still looking for a gravitational theory which fits into quantum mechanics and the Standard Model and explains why objects behave the way they do in a gravitational field.

Climate science as it is currently studied has barely reached the level of hypothesis, but rather than testing their hypothesis via (non-cherry-picked) data and empirical observation, the climate alarmist “scientists” have defenestrated the Scientific Method, choosing instead to cherry-pick data, outright manufacture data, skew existing data to fit their hypothesis, and validate their hypothesis with computer models, which are nothing more than other hypotheses!

This is not scientific, which is exemplified by the fact that they then crow about some percentage “consensus” as an appeal to authority, while attempting to set themselves up as the very authority they seek to appeal to!

And they do this while dismissing any possibility that their “science” has become corrupted by group-think, political ideology and grant-troughing, as we saw in the ClimateGate 1.0, ClimateGate 2.0, ClimateGate 3.0 emails, and the Mann v. Steyn lawsuit discovery.

There has been an awful lot of scientific fraud perpetrated, and those responsible for that fraud need to be called to account to save the credibility of all of science.

Why Is Will Happer Leading The Climate Review Team?
The atmosphere consists of atoms and molecules. Those atoms and molecules obey the laws which particle physics has discovered. There is no magic occurring in the atmosphere and there are no exceptions to those laws, no matter what any climate “scientist” claims.

This is why Will Happer is now leading the team to review climate science. Happer is a retired particle physicist, specialized in optics and spectroscopy, and had a long research career studying physics closely related to the ‘greenhouse effect’, for example, absorption and emission of visible and infrared radiation, and fluid flow dynamics.

Happer, while at Princeton, extended Princeton’s amazing history of scientific discovery, and has written dozens of peer-reviewed papers on the topic of particle physics. He is eminently qualified to lead the team tasked with reviewing climate science.

The basic premise behind CAGW (Catastrophic Anthropogenic Global Warming) is that the CO2 molecule absorbs ~15 micron radiation, becomes vibrationally excited in one of its bending modes, collides with a nitrogen or oxygen molecule, and imparts that vibrational energy to the translational energy of the other molecule via a process known as collisional de-excitation, thereby increasing the temperature of the atmosphere.

Quantum mechanics dictates that all atoms and molecules are harmonic oscillators (with anharmonic force constants complicating the wave equation in the case of molecules). Atoms have only electronic mode quantum states, whereas molecules have vibrational, rotational and electronic mode quantum states. These modes are activated via absorption of electromagnetic radiation at specific frequencies. For vibrational and/or rotational modes, there must exist a magnetic dipole for photon absorption to occur. The molecule is unaffected by nonresonant frequencies, and if the molecule is already excited, even radiation at the correct frequency will be rejected (scattered) by the molecule.

The time-independent Schrodinger Equation treats translational molecular movement (which we sense as temperature) differently than it treats vibrational, rotational and electronic mode quantum states because the quantum states are quantized (have discrete energy levels) whereas translational movement is not quantized.

The 2nd Law of Thermodynamics states that energy cannot flow from a lower-energy region to a higher-energy region… not directly, not via excitation of a molecule’s vibrational, rotational and/or electronic mode quantum states then transferred to translational motion of other molecules via collisional de-excitation, not ever.

Kirchhoff’s Law states that the frequency at which an atom or molecule absorbs radiation is also the frequency at which it will emit radiation. That is, however, affected by fine structure rotational mode quantum states and by Doppler broadening.

Doppler broadening of the absorption / emission spectrum is caused by two factors… translational motion and collisional frequency (which is determined by density (and thus partial pressure) and temperature).

If a molecule is moving in the same direction as the incoming radiation, that radiation is red-shifted in the reference frame of the molecule, thus a higher-frequency photon could be absorbed, broadening the absorption spectrum.

If a molecule is moving in the opposite direction to the incoming radiation, that radiation is blue-shifted in the reference frame of the molecule, thus a lower-frequency photon could be absorbed, broadening the absorption spectrum.

The Equipartition Theorem states that energy is shared equally amongst all energetically accessible degrees of freedom of a system. “Energetically accessible” being a proviso that the energy must be sufficient to occupy the quantized energy states of rotational or vibrational modes for it to be shared in those modes. At prevalent atmospheric temperatures, collisional energy imparted to the CO2 molecule is sufficient to occupy rotational mode quantum states, whereas it is generally insufficient to occupy vibrational mode quantum states (typically ~3.6% of CO2 molecules are vibrationally excited to the lowest (v1) vibrational mode quantum state, and 1.024% of CO2 molecules are vibrationally excited to the highest (v3) vibrational mode quantum state via molecular collision at prevalent tropospheric temperature).

According to the Equipartition Theorem, molecular collisions maintain an equilibrium distribution of molecules in higher rotational mode quantum states and vibrational mode quantum states. As stated above, at prevalent atmospheric temperature, ~3.6% of CO2 molecules are vibrationally excited to the lowest (v1) vibrational mode quantum state, and 1.024% of CO2 molecules are vibrationally excited to the highest (v3) vibrational mode quantum state via molecular collision, whereas nearly all CO2 molecules are in excited rotational mode quantum states. The radiative lifetime of the vibrational mode quantum states is on the order of 200 milliseconds due to the small matrix elements for transition moments (which scales as the cube of the wavelength, or inversely as the square of the electric dipole matrix element), whereas the mean time between collisions is on the order of only 3.45 ns.

The momentum of photons in the atmosphere is insufficient to directly affect translational kinetic energy of the atmospheric molecules absorbing them, and thus cannot directly raise atmospheric gas temperature. That energy goes into changing the vibrational mode and rotational mode quantum states of the molecules.

The amount of IR radiation the planet’s surface receives from the atmosphere and the amount of IR radiation the planet’s surface emits are not closely correlated. The amount of IR the planet’s surface receives from the atmosphere is almost entirely dependent upon atmospheric molecular composition and temperature. The two are loosely coupled in that the IR emission from the planet’s surface affects air temperature, which in turn affects IR emission from the atmosphere, but the linkage is weak, other factors such as convective heat transfer affect air temperature much more.

Only a molecule’s vibrational and rotational modes can interact with infrared radiation, and this interaction can take place only if the molecule exhibits a non-zero magnetic dipole, which implies asymmetry in the distribution of electronic charge. For CO2, this non-zero magnetic dipole occurs when the alignment of the atoms comprising the CO2 molecule is distorted in the asymmetric stretch (v3) mode and bending (v2) modes.

All singular photons are circularly polarized either parallel or antiparallel to their direction of motion. This is a feature of their being massless, which precludes their exhibiting the third state expected of a spin-1 particle. A macroscopic electromagnetic wave is the tensor product of many singular photons, and thus may be linearly polarized if all singular photons comprising the macroscopic electromagnetic wave are not circularly polarized in the same direction.

When an atom or molecule emits a photon, there is a probability distribution of emission direction, with maximum emission probability perpendicular to the dipole moment and zero emission probability parallel to the dipole moment.

Similarly, when an atom or molecule absorbs a photon, there is a probability distribution of absorption direction, with maximum absorption probability perpendicular to the dipole moment and zero absorption probability parallel to the dipole moment.

While the angular momentum selection rules in the immediately-above two paragraphs don’t imply any overall direction of emission of photons from a molecule, they do imply that the emitted photon will be either roughly parallel or antiparallel to the vector of the absorbed photon, disregarding molecule rotation and dependent upon photon polarization direction.

Blackbodies absorb and emit at a wide range of wavelengths exemplified by the Planck curve, whereas a gas absorbs and emits at specific spectral lines. As a first approximation, atmospheric gases cannot and do not emit as a blackbody. The dominant source of blackbody radiation is transient oscillating dipoles induced by inter-molecular thermal vibrations within a material. Solids, liquids, plasma of sufficient density and gases of sufficient density can emit blackbody radiation, but our atmosphere cannot simply because the gas molecules spend the majority of their time relatively distant from each other, and thus they cannot sustain the inter-molecular oscillations necessary for blackbody radiation. As gas density increases, blackbody radiation production increases and eventually dominates the discrete emission spectra.

A body can absorb radiation from another body which is at a higher temperature but it can only emit radiation at or below its own temperature. Thus the temperature of outgoing radiation can only be less than or equal to the temperature of incoming radiation. This means that energy cannot flow from a cooler to a warmer body simply because any radiation from the cooler body incident upon the warmer body will experience a temperature already higher than that radiation’s temperature, thus that radiation will be reflected, not absorbed. Since gasses cannot really reflect radiation, for a gas the radiation would be scattered.

Blackbody radiative flux scales as the fourth-power with temperature (ie: for a doubling of temperature, radiative flux increases 16 times). So any heating at the surface of our planet is quickly damped by increased radiative flux, the main reason our planet’s temperature has been relatively stable for billions of years.

An atmospheric greenhouse gas enables a planet’s atmosphere to radiate at a temperature lower than the surface temperature if there is cold air aloft. All other factors held constant, this would cause the surface temperature in balance with a given amount of absorbed solar radiation to be higher than would be the case if the atmosphere were transparent to IR. Of course, all other factors are not held constant… radiative flux and convection in particular increase. This is why Clough and Iacono’s study (linked below) showed CO2 to exhibit a spectral cooling rate at all altitudes from surface to thermosphere, except for a slight warming at the tropopause.

The only way our planet can shed heat is via radiative transmission of energy to space. N2 and O2 (the two largest constituents of the atmosphere) are homonuclear diatomic molecules, so they have no net magnetic dipole and thus cannot effectively emit (nor absorb) infrared, and thus cannot shed energy to space. CO2 has been shown to cool the troposphere, the stratosphere, the mesosphere and the thermosphere (studies below). Indeed, CO2 is the largest contributor to upper atmosphere cooling. Without CO2, the planet would heat up due to a reduced ability to radiate energy to space. If the upper atmosphere cannot cool via CO2 radiative emission to space, the air below would not be able to convect upward, thus quickly warming the entirety of the atmosphere. Thus CO2 acts as a cooling gas, not a ‘heat-trapping’ gas. More CO2 will cause more radiative emission to space, thus the upper atmosphere will cool more, thus tropospheric air can convect more easily, thus cooling the troposphere more effectively. Indeed, this is exactly what is observed (studies below).

The Rule of Mutual Exclusion states that for molecules like carbon dioxide, which are centrosymmetric, quantum state vibrational modes that are IR-active are Raman-inactive, and vice versa. Thus carbon dioxide has 1 Raman band and two IR bands.

The total energy of a molecule equates to the sum of the translational kinetic energy, electronic mode quantum state energy, vibrational mode quantum state energy and rotational mode quantum state energy of the molecule.

The molecule’s translational kinetic energy is non-quantized. It is represented by what we classically know as temperature.

The molecule’s electronic mode quantum state energy is quantized. It is represented by the equation E = h^2 / m * a^2. Typically, visible range and ultraviolet photons are necessary to excite this quantum state.

The molecule’s vibrational mode quantum state energy is quantized. It is represented by the equation E = h^2 / a^2 * SqRt(mM). Typically, thermal and near infrared photons are necessary to excite this quantum state.

The molecule’s rotational mode quantum state energy is quantized. It is represented by the equation E = h^2 / M * a^2. Typically, microwave and far infrared photons are necessary to excite this quantum state.

Particle Physics Of CO2
The CO2 molecule (a triatomic linearly symmetric molecule with an axis of symmetry along the nuclei and a plane of symmetry perpendicular to this axis) has two rotational mode quantum states, and four fundamental vibrational mode quantum states at 3 radiation wavelength bands centered on:
– 4.25695 micron (v3; 2349.1 cm-1 wavenumber) { v20(0) -> v3(1) }
Asymmetric stretch mode, this mode is very IR-active, but the dipole moment oscillates parallel to the molecule’s symmetric axis, and therefore Delta_J = 0 Q-branch transition is forbidden, making this very narrow-band. The radiance at this narrow frequency band is also minimal, falling at the minima between the Planck curves of solar (incoming) and terrestrial (outgoing) radiation. As discussed below, however, this vibrational mode quantum state is the main route for transfer of energy from vibrationally-excited N2 to CO2.

– 7.20357 micron (v1; 1388.2 cm–1 wavenumber) { v20(0) -> v1(1) }
Symmetric stretch mode; this mode is IR-inactive, it cannot absorb radiation since the molecule has no change in net magnetic dipole moment unless the molecule is perturbed via collision at the same time that it absorbs a photon.

– 14.98352 micron (v2; 667.4 cm-1 wavenumber) { v20(0) -> v21(1) }
2 degenerate bending modes.

There is also a narrow absorption band centered on 2.7 micron, but it is swamped by the v3 (asymmetric stretch) fundamental of H2O centered at 3490 cm-1, the v1 (symmetric stretch) fundamental of H2O centered at 3280 cm-1 and the {v2 + v3} band of H2O centered at ~5000 cm-1, and thus has little radiance available to it except in extremely low humidity locales:
– 2.76785 micron (v20(0) -> v22(2) + v3(1); 3612.91 cm-1 wavenumber)

– 2.69209 micron (v20(0) -> v1(1) + v3(1); 3714.59 cm-1 wavenumber)

…the only one of those vibrational modes which has any appreciable radiance available to it, and which is IR-active is 14.98352 micron, and hence this wavelength band is the largest contributor to CO2 quantum energy states from IR absorption.
Adapted from image at:
Note that the lowest excited vibrational mode quantum state of N2 has a (very) slightly lower energy level than the highest vibrational mode quantum state of CO2. This energy is more than made up by translational kinetic energy during collision, as discussed below. Were this not so, CO2 lasers could not work.
Reference: Journal of Geophysical Research: Atmospheres; Vibrational-vibrational and vibrational-thermal energy transfers of CO2 with N2 from MIPAS high-resolution limb spectra, Jurado-Navarro et al.; p. 8008

The Interaction of O3, N2 and CO2:
Satellites see CO2 and (a bit of) water vapor radiating at the temperature of the lower stratosphere all over the planet. This is because ozone (O3, excited by incoming solar radiation) and collisional processes excite nitrogen (N2) to its v1 (symmetric stretch) vibrational mode, and N2 then transfers energy to the v3 (asymmetric stretch) mode of CO2 via collision as shown in the image, whereupon the vibrationally excited CO2 partially de-excites by dropping from the v3 (asymmetric stretch) mode to either the v1 (symmetric stretch) mode by emitting a 10.6 micron photon, or to the v2 (bending) mode by emitting a 9.6 micron photon.

This is the same method by which a CO2 laser works… the laser filling gas within the discharge tube consists of around 10–20% carbon dioxide (CO2), around 10–20% nitrogen (N2), and a few percent hydrogen (H2) and/or xenon (Xe), and the remainder helium (He). Electron impact vibrationally excites the N2 to its first vibrational mode quantum state {v1(1)}, the N2 collides with CO2, the CO2 becomes excited in the asymmetric stretch vibrational mode quantum state {v3(1)}, and de-excites to its v1 or v2 vibrational modes by emission of 9.6 micron or 10.6 micron radiation as described above. The helium is used to fully de-excite the N2 to the ground state after it’s collided with CO2 to maintain population inversion, but this is unimportant to the process of energy transfer from vibrationally excited N2 to CO2 in the atmosphere. The process by which the N2 becomes vibrationally excited (in the case of a CO2 laser via electron impact; in the atmosphere via translational-to-vibrational collisional processes and via vibrational-to-vibrational collisional processes with solar-excited O3) is similarly unimportant… the concept of energy flowing from N2 to CO2 is the same. Laser wavelength can be tuned by altering the carbon and oxygen isotopes comprising the CO2 molecules in the discharge tube. Similarly, in the atmosphere, we can determine the ratio of anthropogenic CO2 (which consists primarily of 13C) and natural CO2 (which consists primarily of 12C) via spectral analysis.

Radiation transmitted by the atmosphere
Adapted from image at:
You’ll note the immediately-above two paragraphs describe the energy flow from vibrationally-excited N2 to CO2, which then emits at either 9.6 microns or 10.6 microns, both of which are in the Atmospheric Infrared Window. Thus this radiation has a nearly unfettered path out to space.

Remember, N2 is a homonuclear diatomic, thus it has no net magnetic dipole, and thus it cannot emit (nor absorb) infrared radiation. So once it is vibrationally excited, its vibrational states are metastable and relatively long-lived… much longer-lived than the average emission time of CO2. Thus CO2 will emit radiation and break Local Thermodynamic Equilibrium, whereupon there are more N2 molecules waiting to excite it again. Thus energy must flow from N2 to CO2, just as it does in a CO2 laser.

The Equipartition Theorem states that energy is shared equally amongst all energetically accessible degrees of freedom of a system… in this case it means that just as much energy flows from CO2 vibrational mode quantum states to O2 or N2 molecule translational energy as flows from O2 or N2 molecule translational energy to CO2 vibrational mode quantum states (barring violation of Local Thermodynamic Equilibrium conditions via radiative emission… and in this instance, CO2 is the only molecule which can radiatively emit, so net energy must flow from N2 to CO2)… in other words, at best it’s a wash and therefore CO2 cannot cause atmospheric warming… which is why, despite years of looking, scientists haven’t been able to find the mid-tropospheric ‘hotspot’ their models predicted.

They thought they had found it, but it was satellite drift error:

Santer and Sherwood completely ignored the millions of weather balloons with direct-recording thermometers, and attempted to use wind speed as a proxy for temperature, then reported that they’d ‘found’ the missing hotspot hidden in the temperature noise… they were soundly rebutted and laughed at for their desperate and transparent ploy.
On the left is the data collected by millions of weather balloons. On the right is what the climate models say was happening. The theory (as per the climate models) is incompatible with the observations. In both diagrams the horizontal axis shows latitude, and the right vertical axis shows height in kilometers. Image from Dr. David Evans

Indeed, as CO2 concentration increased, OLR (Outgoing Longwave Radiation) increased. The computer climate models predicted it would decrease, thereby heating the atmosphere (their claim that CO2 ‘traps’ heat in the atmosphere).

Further, the very graphic the climate alarmists use to claim that CO2 causes warming proves the exact opposite:
Brightness Temperature vs. Wavenumber graphic

Brightness temperature is the temperature a black body in thermal equilibrium with its surroundings would have to be to duplicate the observed intensity of a grey body object at a frequency v (nu) .

A brightness temperature lower than the equivalent blackbody temperature implies that energy is flowing from that equivalent blackbody temperature to the matter with that brightness temperature, which is shedding energy via radiative emission.

Matter emits according to the law: B=Sigma*T^4
Sigma is the Stephan-Boltzmann constant, B is the brightness and T is the absolute temperature

Therefore a lower Brightness Temperature implies an absolute temperature below the temperature of the environment from which CO2 is attaining its energy. In this case, it means CO2 is radiatively cooling the atmosphere, as explicated in the studies below.

The average kinetic energy of CO2 molecules at prevalent atmospheric temperature (288 K) is given by:
KE_avg = [1/2 mv^2] = 3/2 kT
… which gives an average kinetic energy of 0.03722663 eV and a mean CO2 molecular translational speed of 372.227941 m/s. This thermal energy is equivalent to the energy of a 33.3283159 micron photon. You’ll note the thermal energy is LESS THAN the energy necessary to excite a CO2 molecule’s vibrational mode quantum states. So one would simplistically assume that the opposite applies, that the vibrational mode quantum state energy of CO2 is greater than the translational energy of N2 or O2 molecules (which would be approximately the same as calculated above, due to the Equipartition Theorem) and therefore a photon-excited CO2 molecule will de-excite via a thermalizing collision with N2 or O2, thereby raising atmospheric temperature… except that assumes N2 and O2 are in their ground vibrational mode quantum states; it neglects the energy in vibrational mode quantum states of N2 and O2.

The wavenumber of any transition is related to its corresponding energy by the equation:
1 cm-1 = 11.9624 J mol-1
667.4 cm-1 = 667.4 * 11.9624 / 1000 = 7.9837 kJ mol-1
The Boltzmann Factor at 288 K has the value exp(-7983.7 / 288R) = 0.03607 which means that only 3.607% of the CO2 molecules are in the lowest state of the lowest vibrationally excited mode {ie: v21(1)}. These are the molecules that form the lower energy state for the next higher transitions which have an even lower population.

The v2 vibrational (bending) mode of CO2 in its lowest vibrational state {v21(1)} requires ~0.08279 eV, equivalent to an ~14.98576 micron photon (per VR Molecules Pro molecular modeler). The first vibrational mode quantum state of N2 has quantum energy of ~0.291929 eV, more than enough to activate CO2’s v2 (bending) vibrational mode quantum state. Thus, given that the Equipartition Theorem indicates that the thermal (kinetic, translational) energy of both molecules is similar, during a collision the vibrational mode quantum state energy of a vibrationally-excited N2 molecule will flow to the non-excited CO2 molecule, not the other way around.

1 cm-1 = 11.9624 J mol-1
2349.3 cm-1 = 2349.3 * 11.9624 / 1000 = 28.1032 kJ mol-1
The Boltzmann Factor at 288 K has the value exp(-28100.8 / 288R) = 0.010247 which means that only 1.024% of the CO2 molecules are in the lowest state of the highest vibrationally excited mode {ie: v3(1)}.

The v3 (asymmetric stretch) mode quantum state of CO2 requires ~0.291477 eV, equivalent to an ~4.256 micron photon. The lowest vibrational mode {v1} of N2 in its lowest energy state {v1(1)} has, surprisingly enough, nearly exactly the same energy as the highest vibrational mode {v3) lowest quantum state {v3(1)} of CO2, differing by only 4.3 cm-1 (equivalent to a very low-energy 2325.58 micron photon, or 0.0005335 eV; equivalent to a blackbody temperature of -271.9038 C or 1.2463 K, which is colder than the temperature of outer space at ~3.74 K) when accounting for N2 anharmonicity, centrifugal distortion and vibro-rotational interaction, which is more than covered by the distribution of translational kinetic energy as calculated above. So N2 exhibits strong collisional coupling to this vibrational mode quantum state of CO2, and during a collision the vibrational mode quantum state energy of a vibrationally-excited N2 molecule will flow to the non-excited CO2 molecule, not the other way around (simply for the fact that CO2 can radiatively emit, whereas N2 cannot, so the net energy flow must be from N2 to CO2). If this were not so, CO2 lasers could not work.

This, of course, assumes that N2 in the atmosphere is vibrationally excited to at least its first vibrational mode quantum state. And a good percentage of it is…
Vibrationally Excited Molecules In Atmospheric Reactions
“It follows from the solar ultraviolet intensities quoted by Watanabe and Hinteregger that the production of N2* through Eq. 21 will be of the order of 10^10 cm-2 sec-1. Most of the N2* will be in low vibrational levels.”

{Comment: That’s 10,000,000,000 per square centimeter per second)

We can again use the Boltzmann Factor to determine the vibrationally excited population of N2 due to collisional processes. While the N2 molecule is IR-inactive due to no change in magnetic dipole, it is Raman-active. Further, it can be vibrationally excited by a UV-excited O3 (ozone) molecule in the stratosphere, and via collision with another molecule with sufficient translational energy.
N2 v1(1) (stretch) mode at 2345 cm-1 (4.26439 micron), correcting for anharmonicity, centrifugal distortion and vibro-rotational interaction
1 cm-1 = 11.9624 J mol-1
2345 cm-1 = 2345 * 11.9624 / 1000 = 28.051828 kJ mol-1
The Boltzmann factor at 288 K has the value exp(-2805.1828 / 288R) = 0.102667 which means that 10.2667% of N2 molecules are in the N2 v1(1) excited state.

“But wait!”, you may exclaim, “The energy differential in your calculations between N2 and CO2 isn’t 18 cm-1 as most graphics show!”

{Sigh} I just covered that above. Because I’ve accounted for N2 anharmonicity, centrifugal distortion and vibro-rotational interaction, this lowers the quantum state energy differential between N2 and CO2 to a mere 4.3 cm-1.

And you should be glad I’ve accounted for anharmonicity, centrifugal distortion and vibro-rotational interaction… without doing so, the N2 molecule total energy is 18 cm-1 higher energy than CO2. And that would destroy your CAGW argument. I’m giving your whacky hypothesis every chance I can, but it still fails.

Considering the total molecular energy E_tot:
CO2 {v3(1)}: E_tot = 1174.7 + 2349.3 = 3524 cm-1
N2 {v1(1)}: E_tot = 1176 + 2345 = 3521 cm-1
… gives a differential of only 3 cm-1. This is equivalent to a 3333.333 micron photon, or 0.0003722 eV with an equivalent Wien’s Displacement Law temperature of only 0.8694000008694001 K.

That’s why N2 {v1(1)} and CO2 {v3(1)} are so closely collisionally coupled, they are nearly perfectly resonant. Random thermal energy variations (ie: the speed distribution of molecules) completely overwhelms the energy differential. A mere 20.453 m/s speed differential (for CO2, moving at an average of 372.227941 m/s at 288 K) or 25.194 m/s (for N2, moving at an average of 458.5489 m/s at 288 K) is enough to overwhelm the energy differential. The Maxwell Speed Distribution Function gives a far wider speed distribution than that. Thus, since CO2 is the only molecule of the two which can emit radiation (and thus break Local Thermodynamic Equilibrium conditions), the net energy flow is FROM N2 TO CO2.

When the molar mass of any gas is divided by the density of that gas at a pressure of 1 atmosphere and a temperature of 288 K, the value 23.633 L/mol is obtained. So when looking at any 23.633 liter volume of the atmosphere, there will be one mol of N2 and one mol of CO2, when assuming that CO2 is a well-mixed gas.

The mol of N2 in that 23.633 liter volume will contain 28.051 kJ of energy, whereas the mol of CO2 in its v2 mode quantum state will contain 7.98 kJ of energy.
Similarly, the mol of N2 in that 23.633 liter volume will contain 28.051 kJ of energy, whereas the mol of CO2 in its v3 mode quantum state will contain 28.1 kJ of energy.

Given that CO2 constitutes 0.041% of the atmosphere (410 ppm), and N2 constitutes 78.08% of the atmosphere (780800 ppm), this means that 14.7969 ppm of CO2 is excited to its v1 mode quantum state via collisional translational-to-vibrational (t-v) processes, whereas 80162.3936 ppm of N2 is excited via the same t-v processes. This is a ratio of 1 vibrationally excited CO2 to 5417 vibrationally excited N2. You’ll note this is 2.845 times higher than the total CO2:N2 ratio of 1:1904, and 195 times more excited N2 molecules than ALL CO2 molecules (vibrationally excited or not).

Similarly, 4.1984 ppm of CO2 is excited to its v3 mode quantum state via collisional translational-to-vibrational (t-v) processes, whereas 80162.3936 ppm of N2 is excited via the same (t-v) processes. This is a ratio of 1 vibrationally excited CO2 to 19093 vibrationally excited N2. You’ll note this is 10.028 times higher than the total CO2:N2 ratio of 1:1904, and 195 times more excited N2 molecules than ALL CO2 molecules (vibrationally excited or not).

N2 has a molar mass of 28.014 g / mol. Thus 4.518 grams of N2 in that 23.633 liter volume will be vibrationally excited in its v1 mode quantum state.

CO2 has a molar mass of 44.009 g / mol. Thus 1.587 grams of CO2 in that 23.633 liter volume will be vibrationally excited in its v2 mode quantum state, and 0.451 grams will be vibrationally excited in its v3 mode quantum state.

As you can see, the quantity and mass of excited N2 molecules in any given 23.633 liter volume of the atmosphere swamps the quantity and mass of excited CO2 molecules (indeed, it swamps the total number of CO2 molecules in that volume, excited or not). Hence, energy flows FROM N2 TO CO2.

Now granted, the ratio of excited CO2 molecules which will radiatively de-excite rather than collisionally de-excite is on the order of 1 in 100,000 at low altitudes… but consider how many CO2 molecules there are, and you’ll quickly conclude that this still gives a lot of radiative de-excitation, which is why we see CO2’s radiation signature in the atmosphere (at 9.6 micron, 10.6 micron and 15 micron). And as altitude increases, that probability increases until nearly all CO2 emits rather than undergoing collisional de-excitation. At the same time, the mean free path length of the emitted radiation (at the altitude at which CO2 radiative emission becomes prevalent over collisional de-excitation) becomes longer as altitude increases. This is why CO2 molecules collisionally-deexciting with ground-state vibrational mode N2 molecules cause the air at low altitudes to convect upward… they (barely, considering the Equipartition Theorem) heat the low-altitude air and (significantly) cool the high-altitude air. Indeed, without “greenhouse” gases, there would be very little convection! Without “greenhouse” gases, the only way IR-inactive gases (O2 and N2, for instance) can convect upward is if they gain heat via conduction by contacting the planet’s surface. So in fact, CO2 helps to *cool* the atmosphere via convection at low altitudes and via radiative emission at high altitudes… as we see in many studies below. Without CO2, our planet would heat up. The upper atmosphere could not effectively radiatively shed heat to space and would thus heat up, making the air below it unable to convect upward, which very little of it would want to do because it would only be able to pick up energy by directly contacting the surface of the planet.

We should see an increase in convective airflow as a signature of increasing CO2…

CO2 Cools The Troposphere, The Stratosphere, The Mesosphere And the Thermosphere
“Based on all the foregoing discussion, of the log-dependence of CO2 forcing (Myhre et al., GRL, 1998, vol. 25, doi: org/10.1029/98GLO1908) and its possible climate-cooling effect, I have a simpler hypothesis on the ineffectiveness of CO2 in warming the climate. I realize that this explanation is unacceptable to the IPCC and to many climate-warming advocates. I believe that the ‘gap’, now 40 years long, according to Christy, has existed throughout the Industrial Revolution — and probably during the whole of the Holocene. In other words, I consider that the ‘pause’ may be permanent.”

The Thermosphere Has Cooled:

The Stratosphere Has Cooled:
The graph shows multiple analyses of data from radiosondes that have measured stratospheric temperature for several decades. Graph adapted from Figure 2.7 in Bulletin of the American Meteorological Society, State of the Climate, 2011.

Cooling of Atmosphere Due to CO2 Emission
“Abstract: The writers investigated the effect of CO2 emission on the temperature of atmosphere. Computations based on the adiabatic theory of greenhouse effect show that increasing CO2 concentration in the atmosphere results in cooling rather than warming of the Earth’s atmosphere.”

How increasing CO2 leads to an increased negative greenhouse effect in Antarctica

Why CO2 cools the middle atmosphere – a consolidating model perspective

Observations of infrared radiative cooling in the thermosphere on 2 daily to multiyear timescales from the TIMED/SABER instrument
“Abstract:. We present observations of the infrared radiative cooling by carbon dioxide (CO2) and nitric oxide (NO) in Earth’s thermosphere.”

A Guide to CO2 and Stratospheric Cooling

Cooling of the mesosphere and lower thermosphere due to doubling of CO2
The sensitivity of the mesosphere and lower thermosphere (MLT) to doubling of CO2 has been studied. The thermal response in the MLT is mostly negative (cooling) and much stronger than in the lower atmosphere. An average cooling at the stratopause is about 14 K. It gradually decreases to approximately 8 K in the upper mesosphere and again increases to about 40–50 K in the thermosphere.
The enhanced cooling produced by the increasing CO2 should result in a more contracted thermosphere, where many satellites, including the International Space Station, operate. The contraction of the thermosphere will reduce atmospheric drag on satellites and may have adverse consequences for the already unstable orbital debris environment, because it will slow the rate at which debris burn up in the atmosphere.

Climate “Science” on Trial; Evidence Shows CO2 COOLS the Atmosphere

Spectral Cooling Rates For the Mid-Latitude Summer Atmosphere Including Water Vapor, Carbon Dioxide and Ozone

Note the CO2-induced spectral cooling rate (positive numbers in the scale at right) extend right down to the surface of the planet, whereas CO2 shows just a slight bit of warming (negative numbers in the scale at right) only at the tropopause (ie: just above the clouds, where it absorbs a greater percentage of reflected solar insolation).

References and Additional Reading:
For an earlier take on this topic, refer to:

For a comprehensive treatise on heat transfer via infrared radiation in the atmosphere, refer to the standard reference on the subject, the 1942 Harvard Meteorological Studies No. 6 tome, entitled “Heat Transfer By Infrared Radiation In The Atmosphere” by Walter Maurice Elsasser.

Feynmen Lectures:

A discussion of angular momentum selection rules:

Vibrational-vibrational and vibrational-thermal energy transfers of CO2 with N2 from MIPAS high-resolution limb spectra
Because of the strong collisional coupling of CO2 with N2(1) via V-V energy transfer, vibrational populations of N2(1) are also included in the non-LTE model. The SEE (Statistical Equilibrium Equation) for N2(1) is coupled into the SEE for the main CO2 isotope. The CO2 levels are connected by 695 radiative transitions, 39 of them considering full radiative transfer in the atmosphere. These 39 transitions involve vibrational states up to (4,1) for the main isotope; (3,0) and (2,1) for the 636 isotope; and (1,1) for the 628 and 627 isotopes.

Georgia State University – Department of Physics and Astronomy
HyperPhysics thermal energy, molecular speed and photon-equivalent energy calculations:

VR Molecules Pro molecular modeler:
In the simulation, all vibration frequencies and atom equilibrium positions are “exact” (v.g. not calculated by a molecular modeling software but obtained from handbooks or public databases), while displacements of atoms in the various vibration modes are calculated using the simple (classical) models used in most of the literature.

Absorption Spectra of Water Vapor and Carbon Dioxide in the Region of 2 .7 Microns

Maayke, Huisman, Stal, Matthijs – Colorful niches of phototrophic microorganisms shaped by vibrations of the water molecule.

Lidar-measured atmospheric N2 vibrational-rotational Raman spectra and consequent temperature retrieval

A. Dalgarno, Department of Applied Mathematics, The Queen’s University of Belfast
Planetary Space Science, 1963, pp. 19 – 28
Vibrationally Excited Molecules In Atmospheric Reactions…18…19D

Steven DeWitte, N. Clerbaus – Decadal Changes of Earth’s Outgoing Longwave Radiation’s_Outgoing_Longwave_Radiation
In this paper, decadal changes of the Outgoing Longwave Radiation (OLR) as measured by the Clouds and Earth’s Radiant Energy System from 2000 to 2018, the Earth Radiation Budget Experiment from 1985 to 1998, and the High-resolution Infrared Radiation Sounder from 1985 to 2018 are analysed. The OLR has been rising since 1985, and correlates well with the rising global temperature. An observational estimate of the derivative of the OLR with respect to temperature of 2.93 +/- 0.3 W/m^2 K is obtained.
C. Crevoisier – Use of Hyperspectral Infrared Radiances to Infer Atmospheric Trace Gases
“Infrared channels are intrinsically sensitive to temperature; greenhouse gases, such as CO2, CH4, or N2O, have a significant but minor impact, difficult to separate from this dominant signal. For instance, a variation of 1% (~4 ppm) of CO2 only induces a variation of 0.1 K at 670 cm- 1. Moreover, the typical radiometric noise of the IASI channels is 0.25 K at this wavelength (more than twice the CO2 signal), and the channels are mostly sensitive to atmospheric temperature variations, with a moderate variation of 1 K of the atmospheric temperature profile inducing an 0.8 K variation of brightness temperature!”

“For present-day Earth, the only important continuum is the water vapor continuum in the window around 1000 cm-1. Carbon dioxide continua are unimportant for conditions which have prevailed on Earth during the past several billion years, but they are important for plugging the gaps in the line spectra for the dense CO2 atmospheres of Venus and early Mars. Diatomic homoatomic molecules like N2, which are transparent to IR in Earthlike conditions, have collisional continua that become important in cold, dense atmospheres. For example, the continuum makes N2 one of the most important greenhouse gases on Saturn’s largest moon, Titan.
– Infrared Radiation And Planetary Temperature, Raymond T. Pierrehumbert (Louis Block Professor in Geophysical Sciences at University of Chicago), Physics Today, January 2011, p. 35 (

19 thoughts on “Debunking The Catastrophic Anthropogenic Global Warming Hypothesis”

  1. How long before all those Summer Snow Caps around the Planet work to change Global Weather patterns and cool things down even further? This coming Winter should be an eye opener.

  2. From above: “When the molar mass of any gas is divided by the density of that gas at a pressure of 1 atmosphere and a temperature of 288 K, the value 23.633 L/mol is obtained. So when looking at any 23.633 liter volume of the atmosphere, there will be one mol of N2 and one mol of CO2, when assuming that CO2 is a well-mixed gas.”

    A mole of a gas is avagadro’s number of molecules of that gas. You have just implied above that 23.633 liters of atmosphere has the same number of molecules of N2 as CO2. That is obviously not true.

  3. Is this most interesting paper gong to be polished and “officially” published in a conventional journal?

    It really deserves a wide and learned readership.

    Well done.


  4. Enjoyed reading this article, mostly because it was debunking CO2 as the principal cause of non-existent global warming. I do not agree with it though. CO2 has no meaningful effect on the earth’s heat balance. Water and most particularly, Water vapor is the principal gas which interacts with the Sun’s energy and modulates the atmosphere in which live. CO2(g) is denser than air, and water vapor (g)) is less dense than air, that’s all you need to know to know that CO2 based global warming is B.S.

  5. I will be the first to admit… this article goes COMPLETELY over my head! Not saying that’s a bad thing… just acknowledging that.

    And I have enough confidence in my self and my smarts not to be intimidated by the fact that I do not understand EVERYTHING. I do have my areas of expertise and don’t need to fake it.

    But it illustrates a point I think is important. What I am seeing in today’s “Millennials” is a lot of people who are afraid to admit they are not experts in all subjects. So they listen to “professors”, politicians, celebrities and the media… who spew forth sound bites that they don’t understand either… and push those “ideas” out to everyone else and ridicule anyone who disagrees or admits there’s something they don’t understand.

    The real problem is also with corrupt and unscrupulous “scientists” pushing out the sound bites in the first place… to further their own personal agenda and instant wealth generating schemes.

  6. Thank you for this very comprehensive report.
    Somehow I must print out a copy of this.
    Much to study.

  7. NASA put up the 0=C=0 satellite and it measured COOLING. CO2 up there captures the linear stream of high energy photons and then re-radiates them in all directions and the net effect is cooling.

    So that means the primary assumption of CO2 up there warms is wrong. CO2 in the upper atmosphere cools, not warms. OOPS!

    I can hardly pick myself up from the floor I am laughing so hard.

  8. Here is the one chart that destroys the AGW hypothesis:

    There is no correlation between CO2 and temperature. In past Ice Ages (which can last tens of millions of years) CO2 was above 4,000 ppm.

    This means the current Ice Age will continue and CO2 levels will have no effect on temperature (but plants will grow better).

  9. And yet

    “All of the planets and moons in our solar system emit strongly in the infrared. This infrared emission is the heat from atmospheres and surfaces which peaks in the mid to far-infrared (15-100 microns – a micron is 1 millionth of a meter). Solar system objects also reflect infrared radiation from the Sun.”

    Now all of the gas giants have atmospheres with tiny quantities of so-called “greenhouse gases” or what they really should be called – infra-red active absorbing gases.

    Combine this with the fact that the outer planets receive solar radiation of such low levels there is zero probability of any “greenhouse effect” and almost no “greenhouse gases” yet they have temperatures deep in their atmosphere that rival the surface temperature of the Sun –

    “The temperature in the clouds of Jupiter is about minus 145 degrees Celsius (minus 234 degrees Fahrenheit). The temperature near the planet’s center is much, much hotter. The core temperature may be about 24,000 degrees Celsius (43,000 degrees Fahrenheit). That’s hotter than the surface of the sun!” What is Jupiter/NASA.

    Thus if ONLY IR Active gases can emit infra-red and the solar radiation at the outer planets is so low that temperatures of a maximum of ~173 Kelvin or minus 100°C at Jupiter (and getting colder as we head further out) are possible due to solar radiation how can any of these “emit strongly in the infrared” ??

    Climate science’s hypotheses are just plain wrong.

  10. An excellent piece of work deserving a closer investigation!

    I have studied just these days Tom Vonk’s 2010 posting and found that his main assumption that the collision rate for the process
    CO2(*) + N2 -> CO2 + N2(+)
    equals to that of the reverse process
    CO2 + N2(+) -> CO2(*) + N2
    in local thermodynamic equilibrium [where (*) stands for the vibrational excitation and (+) for a translational energy] is not correct.

    To arrive at this conclusion, I have repeated arguments presented in a paper by Harde 2013 ( who has formulated a master equation-type of approach to formulate all the relevant collision and radiation processes. Harde then uses spectroscopy measurements (such as linewidth, etc.) to determine the Einstein coefficients for spontaneous emission and absorption of photons for the CO2 and also the collision rates between CO2 and other molecules under given conditions (pressure, temperature, density,…). Using these computations Harde comes to the conclusion that photons with lambda=15 micro m are absorbed within a few hundred meters of atmosphere.

    Your hint of vibrational excited N2(*) colliding with CO2 leading to a vibrational excited CO2(*) however is new to me and changes the entire story. It truly deserves a thorough analysis. One should write these things up once and for all and then submit it for publication in a decent physics journal.

    What a pity that BSc or MSc courses in meteorology in Germany do include physics courses in classical mechanics and electrodynamics (in conjunction with the physics department) but not in quantum mechanics.

  11. Our atmosphere is not heated to any significant degree by radiation.

    As one realises that and accepts that conduction between heated surfaces and air and convection of that heated air is the primary method of heating the atmosphere the rest of the unproven hypothesis makes no sense at all.

    If anything adding more IR active gases should cause a faster cooling rate due to increased radiation of IR to space.

    I can heat a thermometer to 50°C using a PAR spotlight while the surrounding air does not change temperature to any significant degree due to its not absorbing the radiation and the huge mass imbalances.

    At 400 ppm CO2 constitutes approximately 814 MILLIGRAMS per kilogram of air. At 4% (probably the maximum, not average, value at ambient temperatures) water vapour constitutes approximately 3174 MILLIGRAMS per kilogram of air.

    I don’t care what anyone says ~4 grams per kilogram controls nothing – it is 1/4 % !

  12. Science today is in a very bad state. 9 tenths of this stuff is theoretical “maybe”s and “itis thought”s or “likely caused by” s.
    Just look at the compendium of what we know about how molecules collide and transfer radiation here and there and h squared divided by the mass …. yet not one has figured out why water does what it does. It just refuses to coerrelate ha ha.
    I would urge readers interested in the science of thermal radiation and the Ideal Gas Laws and Black Bodies to reas Michael Robiataille. You tube channel SkyScholar.
    Lastly, the confirmation bias that condemned CO2 to being the mother of all GHGs was the discovery that the surface temp of Venus is super hot and its atmosphere is 99% plant food. It is notable that Velikovsky predicted both of these discoveries

  13. I have to study the article, despite that I remark that ‘the greenhouse gas’ is not about science but about how to maintain political support. A lot of science has been developped to support political decisions and nowadays these decisions are almost only made by experts in the decision-field, i.e. scientists. As politicians felt that they were loosing control over society, people, due to multinaltionals and banks, they pushed ‘greenhouse’ mixed with creating jobs and a clean environment more and more into the throat of humans..

  14. Sad but true:
    One video by Ray Stevens will change more minds than 50 scientific treatises.

    I necessarily skimmed over the above article, but aren’t they saying that CO2 causes global cooling? The climate change fanatics don’t care if if it warms up or cools down, as long as they can blame it on us.

    So, thanks a lot, dudes…

  15. The above has been updated to tighten up the language and provide more information. If you want the updated version to replace the above (so the alarmists have less to attack), let me know.

    Specifically, I tightened up the language as regards Wien Displacement Law equivalent temperature and energy of photons.

    I also broke down what ‘backradiation’ was prevalent, showing that CO2 only emits radiation with enough energy to raise the 288K average tropospheric temperature when it is excited by N2{v1(1)} to its CO2{v3(1)} vibrational mode quantum state, whereupon the CO2 radiatively emits a 9.6 micron photon by dropping to the CO2{v20(2)} vibrational state. This type of emission only occurs in the stratosphere (where the N2 picks up sufficient energy from solar-excited O3 (ozone)).

  16. Scott Scarborough is correct about my molar calculations. The text has been updated to correct this.

    Anyone wishing to use the text above, feel free. I choose to remain pseudonymous simply because I don’t want the snowflake rage-mob’s ire directed my way. I’m not looking for credit, I’m looking to kill CAGW before the whackos who believe in CAGW destroy our way of life via deindustrialization and carbon taxation.

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