Detailed balance in mixed quantum-classical mapping approaches

TL;DR

This paper analyzes the violation of detailed balance in quasiclassical methods for nonadiabatic dynamics, highlighting issues with negative populations and proposing MASH as a promising solution that guarantees correct thermalization.

Contribution

The paper demonstrates that MASH uniquely guarantees correct thermalization in quantum-classical systems, addressing a key limitation of existing approaches.

Findings

Negative populations cause unphysical trajectories.

MASH avoids inverted potentials, improving accuracy.

MASH guarantees exact thermalization behavior.

Abstract

The violation of detailed balance poses a serious problem for the majority of current quasiclassical methods for simulating nonadiabatic dynamics. In order to analyze the severity of the problem, we predict the long-time limits of the electronic populations according to various quasiclassical mapping approaches, by applying arguments from classical ergodic theory. Our analysis confirms that regions of the mapping space that correspond to negative populations, which most mapping approaches introduce in order to go beyond the Ehrenfest approximation, pose the most serious issue for reproducing the correct thermalization behaviour. This is because inverted potentials, which arise from negative electronic populations entering into the nuclear force, can result in trajectories unphysically accelerating off to infinity. The recently developed mapping approach to surface hopping (MASH) provides a simple way of avoiding inverted potentials, while retaining an accurate description of the dynamics. We prove that MASH, unlike any other quasiclassical approach, is guaranteed to describe the exact thermalization behaviour of all quantum$\unicode{x2013}$classical systems, confirming it as one of the most promising methods for simulating nonadiabatic dynamics in real condensed-phase systems.