Restoring detailed balance in the Landau-Teller probabilities for collision-induced vibrational transitions.
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.
Nikitin
E E
EE
Max-Planck-Institut für biophysikalische Chemie, Am Fassberg 11, D-37077, Goettingen, Germany.
Troe
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J