GH effect – photon-molecule interaction

When a molecule absorbs a photon, i.e., a particle of light, the absorption energy makes the molecule
rotate faster, vibrate faster, or increases the energy of an outer shell electron. The changes in rotational
rates, vibrational rates or modes, and/or the excitation of electrons are quantized, that is they can only
rotate at discrete rotation rates, or vibrate at specific frequencies, or be excited from one well-defined
energy level to another. The transition between specific rotation rates, vibrational frequencies, and
energy levels corresponds to the wavelength or frequency of an absorption line.

Each of these absorption mechanisms corresponds to a different energy regime. Low energy photons
corresponding to microwave or millimeter wavelengths tend to excite molecular rotational modes.
Moderate energy photons corresponding to infrared wavelengths tend to excite molecular vibrational
modes. Therefore, it usually takes more energy to make a molecule vibrate than to rotate. Even higher
energy photons corresponding to visible light tend to excite outer shell electrons from one energy
level to a higher one.

(I should note that even higher energy photons corresponding to ultraviolet light and x-rays can break
molecular bonds causing molecules to break into their constituent molecules or atoms. I will ignore
this mechanism because it is not relevant to a discussion of greenhouse gases.)

Since greenhouse gases absorb infrared radiation while being transparent to visible light, greenhouse
gases tend to have one or more rotational or vibrational modes that can be excited by infrared light,
that is, they can absorb infrared light at the specific frequency of a transition between different
rotational or vibrational modes. In contrast, since greenhouse gases are transparent at visible
wavelengths, these molecules do not have electron transitions that can be excited by photons
corresponding to visible wavelengths.

More on Quantization and Quantum Weirdness

In the macroscopic, non-quantum world, a fidget spinner can be spun to rotate at any speed, and when
they slow down their speed seems to decrease continuously. In contrast, consider a fidget spinner the
size of a water molecule. Now quantum effects will be relevant. Assuming it was spinning at 1,000
rpm, a 1.0 centimeter-wavelength photon corresponding to the energy difference between the allowed
1,000 rpm rotation rate and the allowed 1,500 rpm rotation rate would cause the fidget spinner to
suddenly and discontinuously change its speed from 1,000 rpm to 1,500 rpm. In contrast, a 1.1
centimeter-wavelength that did not correspond to the energy difference between the allowed rotation
rates would not be absorbed by the fidget spinner and would instead pass right by.

More on Greenhouse Gases

Water Vapor

The most prevalent greenhouse gas is water vapor, which is a polar molecule, that is, the oxygen side
is more negatively charged than the hydrogen side, giving rise to a non-uniform electric field, denoted
by the dipole moment vector in the diagram below. As the molecule rotates, its electric field rotates.
Since the electric field rotation rates are quantized, photons that are at the right energy to cause the
transition between water vapor rotational rates will be absorbed. The energy differences between the
rotational modes give rise to a series of microwave and millimeter-wavelength absorption lines.

The water molecule’s hydrogen molecules can also vibrate in synch towards and away from the
oxygen atom, and similarly out of synch with each one alternately moving towards and away from the
oxygen atom (as shown by the red arrows). The hydrogen atoms can also move towards each other
and away from each other. Each of these vibrational modes corresponds to different sets of excitation
energies giving rise to a plethora of absorption lines in the infrared.
Carbon Dioxide

Carbon dioxide is the second most potent greenhouse gas. It is a linear molecule and therefore does
not have a dipole moment. The lack of a dipole moment means that there is no way to either
determine its orientation in space or rotation rate. Therefore, carbon dioxide does not have any
rotational modes and cannot absorb microwave or millimeter-wavelength photons.

In contrast, carbon dioxide does have a series of vibrational modes corresponding to its oxygen
molecules vibrating in synch towards and away from the central carbon atom, and similarly out of
synch alternating towards and away from the central carbon atom (as shown by the red arrows). There
are also bending vibrational modes as shown by the outer red arrows. Each of these vibrational modes
corresponds to a different set of excitation energies yielding a thicket of absorption lines in the
infrared.

Similar analyses can be used to explain the spectrum of other greenhouse gases such as methane,
ozone, nitrous oxide, and CFCs.
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Dmitry Rominski

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