On detailed balance in nonadiabatic dynamics: From spin spheres to equilibrium ellipsoids

TL;DR

This paper introduces an ellipsoid spin-mapping approach that restores detailed balance in nonadiabatic dynamics simulations, improving the accuracy of equilibrium distributions and enabling more efficient sampling.

Contribution

The authors develop a flexible spin-ellipsoid mapping method that ensures detailed balance and correct equilibrium populations in mixed quantum-classical simulations.

Findings

The ellipsoid mapping recovers correct long-time populations.

It solves the negative population problem in previous methods.

The approach enables efficient sampling of thermal distributions.

Abstract

Trajectory-based methods that propagate classical nuclei on multiple quantum electronic states are often used to simulate nonadiabatic processes in the condensed phase. A long-standing problem of these methods is their lack of detailed balance, meaning that they do not conserve the equilibrium distribution. In this article, we investigate ideas for how to restore detailed balance in mixed quantum--classical systems by tailoring the previously proposed spin-mapping approach to thermal equilibrium. We find that adapting the spin magnitude can recover the correct long-time populations but is insufficient to conserve the full equilibrium distribution. The latter can however be achieved by a more flexible mapping of the spin onto an ellipsoid, which is constructed to fulfill detailed balance for arbitrary potentials. This ellipsoid approach solves the problem of negative populations that has plagued previous mapping approaches and can therefore be applied also to strongly asymmetric and anharmonic systems. Because it conserves the thermal distribution, the method can also exploit efficient sampling schemes used in standard molecular dynamics, which drastically reduces the number of trajectories needed for convergence. The dynamics does however still have mean-field character, as is observed most clearly by evaluating reaction rates in the golden-rule limit. This implies that although the ellipsoid mapping provides a rigorous framework, further work is required to find an accurate classical-trajectory approximation that captures more properties of the true quantum dynamics.