Theory of non-adiabatic vibrational relaxation in atom-molecular collisions

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Abstract
The transition complex method is used for calculating the rate constant of non-adiabatic vibrational deactivation of diatomic molecules in the 2II electronic state upon collisions with inert gas atoms. The main contribution to the rate constant comes from vibronic transition caused by spin-orbital and orbital-rotational couplings. The two-dimensional Landau-Zener approximation is considered in connection with calculation of the nonadiabatic transition near the crossing line of two potential surfaces, and the limitations of ideas concerning the activated complex are discussed. The general expression for the rate constant derived from the diatomic molecule-atom collision is correlated with that for the atomic collision.

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