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DOE OSTI · 2998479

Exact-Factorization-Based Surface Hopping without Velocity Adjustment

Dupuy, Lucien·Rikus, Anton·Maitra, Neepa T.
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Abstract

While surface hopping has emerged as a powerful method for simulating non-adiabatic dynamics in large molecules, the ad hoc nature of the necessary velocity adjustments and decoherence corrections in the algorithm somewhat reduces its reliability. Here we propose a new scheme that eliminates these aspects by combining the nuclear equation from the quantum-trajectory surface-hopping approach with the electronic equation derived from the exact-factorization approach. Furthermore, the resulting method, denoted QTSH-XF, yields a surface-hopping method on firmer ground than previous and is shown to successfully capture dynamics in Tully models and in a linear vibronic coupling model of the photoexcited uracil cation.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICSAlgorithmsComputational ChemistryElectrical EnergyEnergyQuantum Mechanics

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Dupuy, Lucien, Rikus, Anton, Maitra, Neepa T.. 2024-02-29. Exact-Factorization-Based Surface Hopping without Velocity Adjustment. https://doi.org/10.1021/acs.jpclett.4c00115

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