Absorption and emission of radiation in the region of an avoided level crossing

The spectrum for absorption and emission of radiation by colliding atoms or a diatomic molecule is calculated for spectral regions dominated by an avoided level crossing. Example processes are absorption during an atom-atom collision with separation to either crossing atomic state, total absorption to both crossing states, and spontaneous emission during a collision with either state initially populated. Absorption and emission by bound diatomic molecules (including photodissociation) is described by the theory, and as an example it is applied to the ${\mathrm{Cs}}_2$ A-X band. Spectra due to single-velocity and impact-parameter collisions, as well as thermal and impact-parameter averages, are given. The shapes of the resulting spectra are parametrized by the interaction strength (or excitation transfer probability) between the crossing levels and the slopes of the ground- and excited-state potentials (assumed constant) in the region of the level crossing. The theory is applied to two observations of such regions that have been reported. We conclude that measurements of spectra in the region of level crossing is a very powerful diagnostic of the potentials and transfer probability in the level-crossing region, which is responsible for most inelastic atom-atom energy-transfer processes.