Application of the forward–backward initial value representation to molecular energy transfer

Publisher Website
Google Scholar
Abstract
It is shown how the forward–backward (FB) approximation to the semiclassical initial value representation (IVR) can be used to calculate the probability (or cross section) for molecular energy transfer. Specifically, the probability P(ΔE A ) for a molecule A to gain (or lose) an amount of internal energy ΔE A by collision with a bath molecule B is given by the Fourier transform of a time correlation function C(t), which is in turn given by a single phase space average over the initial conditions of classical trajectories of the A+B collision system. Application to energy transfer of H 2 by collision with He is carried out to demonstrate that the FB-IVR provides a good description of quantum effects in P(ΔE A ).