Ergodic collision theory of intermolecular energy transfer II. Quantum effects in the harmonic approximation

Abstract

An efficient numerical implementation of the ergodic collision theory is described and used to evaluate the average energy transfer per collision relevant to several reactant species undergoing unimolecular reaction. The full effect due to vibrational quantization in the harmonic approximation is included and found to cause only a minor shift in the results previously obtained in a quasi-classical approximation. A much simplified computational method based on the use of specific heat data for the molecules concerned is suggested and shown to account for most of this shift.