Electronically Nonadiabatic Dynamics in Complex Molecular Systems: An Efficient and Accurate Semiclassical Solution

Abstract

Chemical reaction dynamics is always a central theme in chemistry research. In many important chemical processes, reaction dynamics is electronically nonadiabatic, i.e., dynamics involves coupled multiple electronic states. We demonstrate in this paper that a semiclassical (SC) treatment based on an initial value representation methodology and a classical mapping formalism for the electronic degrees of freedom is now able to provide a rigorous and practical solution to electronically nonadiabatic dynamics in complex molecular systems. The key component of this treatment is to incorporate a correlated importance sampling protocol in nonadiabatic SC calculations, which results in a speedup factor of 100 or more in comparison with that using the standard sampling approach. This is illustrated by application to a two-state model coupled with up to 10 nuclear bath modes for a benchmark nonadiabatic excitation energy transfer problem. This work provides great opportunities for the effectively theoretical investigations on reaction mechanisms in complex molecular systems, in which electronically nonadiabatic dynamics plays an importance role.