A Phase-Space Electronic Hamiltonian For Vibrational Circular Dichroism
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, <b><i>Ĥ</i></b><sub><i>PS</i></sub>(<b><i>R</i></b>,<b><i>P</i></b>)) 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).
Authors
- Yihan Shao (ORCID: https://orcid.org/0000-0001-9337-341X)
- Titouan Duston (ORCID: https://orcid.org/0000-0002-1165-5817)
- Zheng Pei (ORCID: https://orcid.org/0000-0002-1230-4664)
- Zhen Tao (ORCID: https://orcid.org/0000-0003-0511-7665)
- Xuezhi Bian (ORCID: https://orcid.org/0000-0001-6445-7462)
- Joseph Eli Subotnik (ORCID: https://orcid.org/0000-0003-2170-2020)
- Mansi Bhati (ORCID: https://orcid.org/0000-0002-8029-0516)
- Robert G. Littlejohn (ORCID: https://orcid.org/0000-0002-4438-0952)
- Jonathan Rawlinson (ORCID: https://orcid.org/0000-0001-9681-3775)
Institutions
- Nottingham Trent University (GB)
- University of Pennsylvania (US)
- University of Oklahoma (US)
- University of California, Berkeley (US)
Publication Details
- Journal
- Journal of Chemical Theory and Computation
- Published
- 2024-09-03
- DOI
- https://doi.org/10.1021/acs.jctc.4c00662
- Citations
- 10
- Primary Topic
- Molecular spectroscopy and chirality
- Type
- article
- Field-Weighted Citation Impact
- 2.41
Funders
- National Science Foundation
- Air Force Office of Scientific Research