Non-Adiabatic Quantum Molecular Dynamics with Detailed Balance

TL;DR

This paper introduces a novel non-adiabatic molecular dynamics method that combines classical and quantum descriptions, ensuring detailed balance and thermal equilibrium without wave function propagation.

Contribution

The authors develop a first-principles approach for non-adiabatic dynamics that inherently satisfies detailed balance and does not require wave function propagation.

Findings

Method naturally satisfies detailed balance at equilibrium

Can describe evolution to thermal equilibrium from arbitrary states

Does not require explicit wave function propagation

Abstract

We present an approach for carrying out non-adiabatic molecular dynamics simulations of systems in which non-adiabatic transitions arise from the coupling between the classical atomic motions and a quasi-continuum of electronic quantum states. Such conditions occur in many research areas, including chemistry at metal surfaces, radiation damage of materials, and warm dense matter physics. The classical atomic motions are governed by stochastic Langevin-like equations, while the quantum electron dynamics is described by a master equation for the populations of the electronic states. These working equations are obtained from a first-principle derivation. Remarkably, unlike the widely used Ehrenfest and surface-hopping methods, the approach naturally satisfies the principle of detailed balance at equilibrium and, therefore, can describe the evolution to thermal equilibrium from an arbitrary initial state. In addition, unlike other schemes, there is no need to explicitly propagate wave functions in time.