Effective-mode representation of non-Markovian dynamics: A hierarchical approximation of the spectral density. II. Application to environment-induced nonadiabatic dynamics

Abstract

The non-Markovian approach developed in the companion paper [Hughes et al., J. Chem. Phys. 131, 024109 (2009)], which employs a hierarchical series of approximate spectral densities, is extended to the treatment of nonadiabatic dynamics of coupled electronic states. We focus on a spin-boson-type Hamiltonian including a subset of system vibrational modes which are treated without any approximation, while a set of bath modes is transformed to a chain of effective modes and treated in a reduced-dimensional space. Only the first member of the chain is coupled to the electronic subsystem. The chain construction can be truncated at successive orders and is terminated by a Markovian closure acting on the end of the chain. From this Mori-type construction, a hierarchy of approximate spectral densities is obtained which approach the true bath spectral density with increasing accuracy. Applications are presented for the dynamics of a vibronic subsystem comprising a high-frequency mode and interacting with a low-frequency bath. The bath is shown to have a striking effect on the nonadiabatic dynamics, which can be rationalized in the effective-mode picture. A reduced two-dimensional subspace is constructed which accounts for the essential features of the nonadiabatic process induced by the effective environmental mode. Electronic coherence is found to be preserved on the shortest time scale determined by the effective mode, while decoherence sets in on a longer time scale. Numerical simulations are carried out using either an explicit wave function representation of the system and overall bath or else an explicit representation of the system and effective-mode part in conjunction with a Caldeira-Leggett master equation.