Nonadiabatic quantum-classical reaction rates with quantum equilibrium structure

Abstract

Time correlation function expressions for quantum reaction-rate coefficients are computed in a quantum-classical limit. This form for the correlation function retains the full quantum equilibrium structure of the system in the spectral density function but approximates the time evolution of the operator by quantum-classical Liouville dynamics. Approximate analytical expressions for the spectral density function, which incorporate quantum effects in the many-body environment and reaction coordinate, are derived. The results of numerical simulations of the reaction rate are presented for a reaction model in which a two-level system is coupled to a bistable oscillator which is, in turn, coupled to a bath of harmonic oscillators. The nonadiabatic quantum-classical dynamics is simulated in terms of an ensemble of surface-hopping trajectories and the effects of the quantum equilibrium structure on the reaction rate are discussed.