A Phase-Space Electronic Hamiltonian For Vibrational Circular Dichroism
Titouan Duston, Zhen Tao, Xuezhi Bian, Mansi Bhati, Jonathan Rawlinson, Robert G. Littlejohn, Zheng Pei, Yihan Shao, Joseph E. Subotnik
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, Ĥ PS ( 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).