A semiclassical non-adiabatic phase-space approach to molecular translations and rotations: Surface hopping with electronic inertial effects

Xuezhi Bian; Yanze Wu; Tian Qiu; Zhen Tao; Joseph E Subotnik

doi:10.1063/5.0242673

A semiclassical non-adiabatic phase-space approach to molecular translations and rotations: Surface hopping with electronic inertial effects

J Chem Phys. 2024 Dec 21;161(23):234114. doi: 10.1063/5.0242673.

Authors

Xuezhi Bian¹, Yanze Wu², Tian Qiu¹, Zhen Tao¹, Joseph E Subotnik^{1

3}

Affiliations

¹ Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.
² Department of Chemistry, Northwestern University, Evanston, Illinois 60208, USA.
³ Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA.

PMID: 39704569
DOI: 10.1063/5.0242673

Abstract

We demonstrate that working with a correct phase-space electronic Hamiltonian captures electronic inertial effects. In particular, we show that phase space surface hopping dynamics do not suffer (at least to very high order) from non-physical non-adiabatic transitions between electronic eigenstates during the course of pure nuclear translational and rotational motion. This work opens up 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.