diation, as they require energy larger than that in an infrared photon.)
The width of a spectral line is an important element in understanding its importance for the absorption of radiation. In the Earth's atmosphere these spectral widths are primarily determined by "pressure broadening", which is the distortion of the spectrum due to the collision with another molecule. Most of the infrared absorption in the atmosphere can be thought of as occurring while two molecules are colliding. The absorption due to a photon interacting with a lone molecule is relatively small. This three-body aspect of the problem, one photon and two molecules, makes direct quantum mechanical computation for molecules of interest more challenging. Careful laboratory spectroscopic measurements provide the basis for most of the radioactive transfer calculations used in studies of the atmosphere.
The molecules/atoms that constitute the bulk of the atmosphere: oxygen (O 2 ), nitrogen (N 2 ) and argon; do not interact with infrared radiation significantly. While the oxygen and nitrogen molecules can vibrate, because of their symmetry these vibrations do not create any transient charge separation. Without such a transient dipole moment, they can neither absorb nor emit infrared radiation. In the Earth's atmosphere, the dominant infrared absorbing gases are water vapor, carbon dioxide, and ozone (O 3 ). The same molecules are also the dominant infrared emitting molecules. CO 2 and O 3 have "floppy" vibration motions whose quantum states can be excited by collisions at energies encountered in the atmosphere. For example, carbon dioxide is a linear molecule, but it has an important vibrational mode in which the molecule bends with the carbon in the middle moving one way and the oxygens on the ends moving the other way, creating some charge separation, a dipole moment, thus carbon dioxide molecules can absorb IR radiation. Collisions will immediately transfer this energy to heating the surrounding gas. On the other hand, other CO 2 molecules will be vibrationally excited by collisions. Roughly 5% of CO 2 molecules are vibrationally excited at room temperature and it is this 5% that radiates. A substantial part of the greenhouse effect due to carbon dioxide exists because this vibration is easily excited by infrared radiation. CO 2 has two other vibrational modes. The symmetric stretch does not radiate, and the asymmetric stretch is at too high a frequency to be effectively excited by atmospheric temperature collisions, although it does contribute to absorption of IR radiation. The vibrational modes of water are at too high energies to effectively radiate, but do absorb higher frequency IR radiation. Water vapor has a bent shape. It has a permanent dipole moment (the O atom end is electron rich, and the H atoms electron poor) which means t...
