A quantized classical path approach for calculations of quantum mechanical rate constants

Abstract

A practical method for calculations of quantized rate constants is examined and illustrated. The method, which is referred to as the «quantized classical path» approach, evaluates quantum mechanical activation energies by propagating trajectories of the classical particles to generate the centroid positions for the quantum mechanical calculations. This provides a stable and effective way for evaluating quantized activation energies of processes in multidimensional systems. In fact, the present approach was used before in studies of proton-transfer and hydride-transfer reactions in solution and proteins (Hwang et al. J. Phys. Chem. 1991, 95, 8445), but its validity was not established in well-defined test cases