Restoring detailed balance in the Landau–Teller probabilities for collision-induced vibrational transitions

Abstract

The general quasi-classical treatment for collision-induced vibrational transitions in diatomic molecules, under near-adiabatic conditions, is used to derive quantum corrections for probabilities, calculated in the external field approximation originally used by Landau and Teller. The quantum corrections are expressed through the Landau–Teller classical collision time. The first-order correction to the classical exponent restores detailed balance for up- and down-transitions and does not depend on the properties of the bath except for its temperature. The limits of applicability of the first-order correction are discussed.