Vibrational and rotational energy transfer upon molecular collisions

Abstract

The cross section of the rotational and vibrational energy transfer is derived by using the first Born approximation which quantizes the translational motion of the colliding particles. The theory developed here integrates the intermolecular potential V( R) over all regions of the internuclear distance R by obtaining a Fourier transform of V( R). This differs from previous semiclassical (impact-parameter) treatments which either considered the short-range repulsive interaction or expanded V( R) into a long-range multipole expansion. The cross section obtained here is expressed in a very simple algebraic expression which can be readily calculated. This will be illustrated by examples of CO 2(001)+N 2(υ=0)=CO 2(000)+N 2(υ=1)+18.6 cm −1 and CO(υ=1)+CO(υ=1)=CO(υ=0)+CO(υ=2)+27 cm −1. Calculations have been made both for the exothermic and for the endothermic reactions. The comparison of the present results with experimental results as well as with previously calculated results will be discussed.