Mixed quantum-classical equilibrium

Abstract

We present an analysis of the equilibrium limits of the two most widely used approaches for simulating the dynamics of molecular systems that combine both quantum and classical degrees of freedom. For a two-level quantum system connected to an infinite number of classical particles, we derive a simple analytical expression for the equilibrium mean energy attained by the self-consistent-field (Ehrenfest) method and show that it deviates substantially from Boltzmann. By contrast, "fewest switches" surface hopping achieves Boltzmann quantum state populations. We verify these analytical results with simulations.