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

2024/10/02 by Bian, Xuezhi, Wu, Yanze, Qiu, Tian +2
#Chemical Physics (physics.chem-ph) #FOS: Physical sciences

paper · doi:10.48550/arxiv.2410.01156

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.

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