Semiclassical Theory of Vibrational Excitation for Diatomic Molecules with Conserved Collision Energy

Abstract

The semiclassical method for calculating collision induced vibrational transitions in diatomic molecules is extended to account for conservation of energy. Asymmetric distortions of the collision perturbation are found to have little effect on the transition probability, but symmetric distortions, associated with energy transiently stored in vibrational modes at the collision turning point, decrease the transition probability by factors of about 1.5 to 2. This correction does not significantly change the interaction potentials deduced from vibrational relaxation data.