Quantum decoherence in mixed quantum-classical systems: Nonadiabatic processes

Abstract

We address the issue of quantum decoherence in mixed quantum-classical simulations. We demonstrate that restricting the classical paths to a single path among all the quantum paths affects a coarse graining of the quantum paths. Such coarse graining causes the quantum paths to lose coherence as the various possible classical paths associated with each quantum state diverge. This defines a reduction mapping of the quantum density matrix, and we derive a quantum master equation suitable for mixed quantum-classical systems. The equation includes two terms: first, the ordinary quantum Liouvillian which is parametrized by a single classical path, and second, a quantum decoherence term that includes both a coherence time and length scale which are determined by the dynamics of the classical paths. Model calculations for electronic coherence loss in nonadiabatic mixed quantum-classical dynamics are presented as examples. For a model charge transfer chemical reaction with nonadiabatic transitions, application of the present formulation reveals that nonadiabaticity is diminished as the decoherence timescale becomes shorter and adiabatic dynamics are recovered in the limit of rapid decoherence.