Forward–backward initial value representation for the calculation of thermal rate constants for reactions in complex molecular systems

Abstract

The semiclassical (SC) initial value representation (IVR) provides a potentially practical way for including quantum effects into classical molecular dynamics simulations. The forward–backward (FB) version of the IVR provides an especially attractive way for calculating time correlation functions, in particular the reactive flux correlation function which determines chemical reaction rates. This paper presents a further analysis and development of the FB-IVR approach. Applications show that it is feasible and accurate for a reaction coordinate coupled to up to 40 degrees of freedom.