A semiclassical non-adiabatic phase-space approach to molecular translations and rotations: A new picture of surface hopping and electronic inertial effects

TL;DR

This paper introduces a new semiclassical phase-space surface hopping method that accurately models electronic inertial effects in molecular translations and rotations, surpassing existing approaches and enabling detailed studies of complex phenomena.

Contribution

It develops a novel phase-space surface hopping approach that captures electronic inertial effects and reduces non-adiabatic transitions, extending beyond the Born-Oppenheimer approximation.

Findings

Accurately models electronic inertial effects during nuclear motion.

Eliminates non-adiabatic transitions between electronic states.

Enables investigation of angular momentum transfer and chiral effects.

Abstract

We present a novel semiclassical phase-space surface hopping approach that goes beyond the Born-Oppenheimer approximation and all existing surface hopping formalisms. We demonstrate that working with a correct phase-space electronic Hamiltonian can capture electronic inertial effects during pure nuclear translational and rotational motion and completely eliminate (at least to very high order) non-adiabatic transitions between electronic eigenstates. This work opens many new avenues for quantitatively investigating complex phenomena, including angular momentum transfer between chiral phonons and electrons as well as chiral-induced spin selectivity effects.