Quantum mechanics provides the basis for computing the interactions between molecules and radiation. Most of this interaction occurs when the frequency of the radiation closely matches that of the spectral lines of the molecule, determined by the quantization of the modes of vibration and rotation of the molecule. (The electronic excitations are generally not relevant for infrared radiation, 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, rather than ab initio quantum mechanical computations, provide the basis for most of the radiative transfer calculations used in studies of the atmosphere.