Surface hopping from the perspective of quantum–classical Liouville dynamics

Abstract

Fewest-switches surface hopping is studied in the context of quantum–classical Liouville dynamics. Both approaches are mixed quantum–classical theories that provide a way to describe and simulate the nonadiabatic quantum dynamics of many-body systems. Starting from a surface-hopping solution of the quantum–classical Liouville equation, it is shown how fewest-switches dynamics can be obtained by dropping terms that are responsible for decoherence and restricting the nuclear momentum changes that accompany electronic transitions to those events that occur between population states. The analysis provides information on some of the elements that are essential for the construction of accurate and computationally tractable algorithms for nonadiabatic processes.