A first principles derivation of energy-conserving momentum jumps in surface hopping simulations.
| Autor: | Huang DM; University of California, Irvine, California 92697-2025, USA., Green AT; University of California, Irvine, California 92697-2025, USA., Martens CC; University of California, Irvine, California 92697-2025, USA. |
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| Jazyk: | angličtina |
| Zdroj: | The Journal of chemical physics [J Chem Phys] 2023 Dec 07; Vol. 159 (21). |
| DOI: | 10.1063/5.0178534 |
| Abstrakt: | The fewest switches surface hopping (FSSH) method proposed by Tully in 1990 [Tully, J. Chem. Phys. 93, 1061 (1990)]-along with its many later variations-forms the basis for most practical simulations of molecular dynamics with electronic transitions in realistic systems. Despite its popularity, a rigorous formal derivation of the algorithm has yet to be achieved. In this paper, we derive the energy-conserving momentum jumps employed by FSSH from the perspective of quantum trajectory surface hopping (QTSH) [Martens, J. Phys. Chem. A 123, 1110 (2019)]. In the limit of localized nonadiabatic transitions, simple mathematical and physical arguments allow the FSSH algorithm to be derived from first principles. For general processes, the quantum forces characterizing the QTSH method provide accurate results for nonadiabatic dynamics with rigorous energy conservation, at the ensemble level, within the consistency of the underlying stochastic surface hopping without resorting to the artificial momentum rescaling of FSSH. (© 2023 Author(s). Published under an exclusive license by AIP Publishing.) |
| Databáze: | MEDLINE |
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