The time-dependent operator formulation of the 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.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry