Perturbation theory for vibrational transitions induced by bimolecular reactions

Abstract

The analytical expressions are obtained for the amplitudes of vibrational transitions induced by the collinear reaction A + BC → AB + C with Eckart potential barrier. The calculation is performed in the first perturbation order using adiabatic basic functions as a zero approximation. The translational motion is treated semiclassically. The dependence of the transition probability on the curvature of the reaction coordinate is investigated, and, in particular, on the relative arrangement of the barrier and the reaction coordinate bending region. The limiting cases of large and small kinetic energy are compared.