Mixed quantum-classical approach to model non-adiabatic electron-nuclear dynamics: Detailed balance and improved surface hopping method

Abstract

We develop a density matrix formalism to describe coupled electron-nuclear dynamics. To this end we introduce an effective Hamiltonian formalism that describes electronic transitions and small (quantum) nuclear fluctuations along a classical trajectory of the nuclei. Using this Hamiltonian we derive equations of motion for the electronic occupation numbers and for the nuclear coordinates and momenta. We show that in the limit when the number of nuclear degrees of freedom coupled to a given electronic transition is sufficiently high (i.e., the strong decoherence limit), the equations of motion for the electronic occupation numbers become Markovian. Furthermore the transition rates in these (rate) equations are asymmetric with respect to the lower-to-higher energy transitions and vice versa. In thermal equilibrium such asymmetry corresponds to the detailed balance condition. We also study the equations for the electronic occupations in non-Markovian regime and develop a surface hopping algorithm based on our formalism. To treat the decoherence effects we introduce additional "virtual" nuclear wavepackets whose interference with the "real" (physical) wavepackets leads to the reduction in coupling between the electronic states (i.e., decoherence) as well as to the phase shifts that improve the accuracy of the numerical approach. Remarkably, the same phase shifts lead to the detailed balance condition in the strong decoherence limit.