A Centroid Molecular Dynamics Approach for Nonadiabatic Dynamical Processes in Condensed Phases: the Spin-Boson Case

• DOI: 10.1021/jp020978d
• Publication Date: 2002-09-17T20:35:19Z
• Authors: Jie-Lou Liao; Gregory A. Voth
• Keywords: Centroid; Operator (biology)

A centroid molecular dynamics (CMD) approach [J. Chem. Phys. 1999 111, 2357; 2371] is developed to study nonadiabatic in condensed phases, as represented by the spin-boson model. The CMD variables for both electronic and nuclear degrees of freedom are defined on basis concept a quasi-density operator. initial distribution system investigated not at thermal equilibrium, operator therefore constructed using mixed Wigner representation. approximation employed motion variables, set equations then derived. For case model, consisting two states bilinearly coupled harmonic bath, stochastic (generalized Langevin-like) can also be obtained integrating out bath variables. From numerical simulations, good agreement found between calculations exact results.