TIME-DEPENDENT CALCULATION OF THERMALLY AVERAGED REACTION-RATE CONSTANTS - DYNAMIC DISPLACEMENT OPERATOR TREATMENT

The time-dependent operator formulation of tbe reactive flux-side correlation function [J. Chem. Phys. 1991, 94, 4949], whose long-time limit yields the quantum mechanical Boltzmann-averaged rate constant, is optimized by including displacement operators in the expansion of the complex time evolution operator. The advantage of this new treatment is that very few terms are needed for the representation of the propagator, thus significantly reducing the numerical effort required in the calculation.