Communication: The correct interpretation of surface hopping trajectories: How to calculate electronic properties
Abstract
In a recent paper, we presented a road map for how Tully's fewest switches surface hopping (FSSH) algorithm can be derived, under certain circumstances, from the mixed quantum-classical Liouville equation. In this communication, we now demonstrate how this new interpretation of surface hopping can yield significantly enhanced results for electronic properties in nonadiabatic calculations. Specifically, we calculate diabatic populations for the spin-boson problem using FSSH trajectories. We show that, for some Hamiltonians, without changing the FSSH algorithm at all but rather simply reinterpreting the ensemble of surface hopping trajectories, we recover excellent results and remove any and all ambiguity about the initial condition problem.
- Authors:
-
- Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, Pennsylvania 19104 (United States)
- Publication Date:
- OSTI Identifier:
- 22251284
- Resource Type:
- Journal Article
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 139; Journal Issue: 21; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ALGORITHMS; BOLTZMANN-VLASOV EQUATION; BOSONS; HAMILTONIANS; SPIN; SURFACES
Citation Formats
Landry, Brian R., Falk, Martin J., and Subotnik, Joseph E. Communication: The correct interpretation of surface hopping trajectories: How to calculate electronic properties. United States: N. p., 2013.
Web. doi:10.1063/1.4837795.
Landry, Brian R., Falk, Martin J., & Subotnik, Joseph E. Communication: The correct interpretation of surface hopping trajectories: How to calculate electronic properties. United States. https://doi.org/10.1063/1.4837795
Landry, Brian R., Falk, Martin J., and Subotnik, Joseph E. 2013.
"Communication: The correct interpretation of surface hopping trajectories: How to calculate electronic properties". United States. https://doi.org/10.1063/1.4837795.
@article{osti_22251284,
title = {Communication: The correct interpretation of surface hopping trajectories: How to calculate electronic properties},
author = {Landry, Brian R. and Falk, Martin J. and Subotnik, Joseph E.},
abstractNote = {In a recent paper, we presented a road map for how Tully's fewest switches surface hopping (FSSH) algorithm can be derived, under certain circumstances, from the mixed quantum-classical Liouville equation. In this communication, we now demonstrate how this new interpretation of surface hopping can yield significantly enhanced results for electronic properties in nonadiabatic calculations. Specifically, we calculate diabatic populations for the spin-boson problem using FSSH trajectories. We show that, for some Hamiltonians, without changing the FSSH algorithm at all but rather simply reinterpreting the ensemble of surface hopping trajectories, we recover excellent results and remove any and all ambiguity about the initial condition problem.},
doi = {10.1063/1.4837795},
url = {https://www.osti.gov/biblio/22251284},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 21,
volume = 139,
place = {United States},
year = {Sat Dec 07 00:00:00 EST 2013},
month = {Sat Dec 07 00:00:00 EST 2013}
}