Mapping State Space to Quasiclassical Trajectory Dynamics in Coherence-Controlled Nonadiabatic Simulations for Condensed Phase Problems.

Abstract

Recently a coherence controlled (CC) approach to nonadiabatic dynamics was proposed by one of the authors based on the mapping between the decomposed classical state space and different types of nuclear dynamics. Here we elaborate the state-space decomposition scheme and the corresponding state-space-to-dynamics mapping of the CC approach in a general high-dimensional framework. In the CC formalism, dynamical properties such as the full electronic matrix can be evaluated by means of the ensemble of trajectories in the active state space, which consists of single-state domains and coherence domains. The feasibility of the state space decomposition and related mappings and the performance of the CC approach are demonstrated by the implementation to benchmark problems of nonadiabatic molecular dynamics in condensed phase including the spin-boson model and the excitation energy transfer problem in photosynthesis. The results obtained from the CC approach are in reasonably good agreement with exact or benchmark calculations, and it is also shown that the CC approach satisfies the detailed balance approximately and is capable of efficiently describing condensed phase nonadiabatic molecular dynamics at reasonable accuracy.