Simulation of Coherent Nonadiabatic Dynamics Using Classical Trajectories

In this paper, we describe a trajectory-based implementation of the semiclassical-limit Liouville equation approach to molecular dynamics on multiple electronic surfaces. The formalism is briefly reviewed, and a realization of the general theory in the context of a classical trajectory-based molecular dynamics algorithm is described. The method is applied to a model problem consisting of one-dimensional motion on two coupled electronic surfaces, and the results are compared with coupled-state wave packet calculations. Excellent agreement is obtained, even for the detailed phase space structure of the nonclassical electronic coherences, demonstrating that electronic coherent effects can be included naturally in generalized classical molecular dynamics simulations.