A Phase Space Approach to Vibrational Circular Dichroism

TL;DR

This paper demonstrates that a phase-space non-Born-Oppenheimer Hamiltonian approach can accurately reproduce vibrational circular dichroism spectra and may reveal new physics related to chiral phenomena beyond spectroscopy.

Contribution

It introduces a practical phase-space quantum chemistry method that improves vibrational circular dichroism modeling and suggests potential for discovering novel dynamical effects.

Findings

Accurately reproduces vibrational circular dichroism spectra

Shows phase-space approach conserves total nuclear and electronic momentum

Suggests new physics beyond traditional spectroscopy methods

Abstract

We show empirically that a phase-space non-Born-Oppenheimer electronic Hamiltonian approach to quantum chemistry (where the electronic Hamiltonian is parameterized by both nuclear position and momentum, (H(R,P)) is both a practical and accurate means to recover vibrational circular dichroism spectra. We further hypothesize that such a phase space approach may lead to very new dynamical physics beyond spectroscopy circular dichroism, with potential implications for understanding chiral induced spin selectivity (CISS), noting that classical phase space approaches conserve the total nuclear plus electronic momentum, whereas classical Born-Oppenheimer approaches do not (they conserve only the nuclear momentum)