posted on 2017-02-08, 00:00authored byGuohua Tao, Na Shen
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.