A simple one-electron expression for electron rotational factors

Within the context of fewest-switch surface hopping (FSSH) dynamics, one often wishes to remove the angular component of the derivative coupling between states J and K. In a previous set of papers, Shu et al. [J. Phys. Chem. Lett. 11, 1135–1140 (2020)] posited one approach for such a removal based o...

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Bibliographic Details
Published in:The Journal of chemical physics 2024-03, Vol.160 (12)
Main Authors: Qiu, Tian, Bhati, Mansi, Tao, Zhen, Bian, Xuezhi, Rawlinson, Jonathan, Littlejohn, Robert G., Subotnik, Joseph E.
Format: Article
Language:English
Subjects:
Algorithms
Coupling
Mathematical analysis
Operators (mathematics)
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Summary:Within the context of fewest-switch surface hopping (FSSH) dynamics, one often wishes to remove the angular component of the derivative coupling between states J and K. In a previous set of papers, Shu et al. [J. Phys. Chem. Lett. 11, 1135–1140 (2020)] posited one approach for such a removal based on direct projection, while we isolated a second approach by constructing and differentiating a rotationally invariant basis. Unfortunately, neither approach was able to demonstrate a one-electron operator Ô whose matrix element JÔK was the angular component of the derivative coupling. Here, we show that a one-electron operator can, in fact, be constructed efficiently in a semi-local fashion. The present results yield physical insight into designing new surface hopping algorithms and are of immediate use for FSSH calculations.
ISSN:0021-9606
1089-7690
DOI:10.1063/5.0192083