A Phase-Space Electronic Hamiltonian For Vibrational Circular Dichroism.

Abstract

We show empirically that a phase-space non-Born-Oppenheimer electronic Hamiltonian approach to quantum chemistry (where the electronic Hamiltonian is parametrized by both nuclear position and momentum, ĤPS(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 spectroscopic 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).