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arXiv · 2401.06878

Exact-factorization-based surface-hopping without velocity adjustment

Lucien Dupuy·Anton Rikus·Neepa T. Maitra
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Abstract

While surface-hopping has emerged as a powerful method to simulate 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. The resulting method, denoted QTSH-XF, places surface-hopping on a firmer ground and is shown to successfully capture dynamics in Tully models and in a linear vibronic coupling model of the photo-excited uracil cation.

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Lucien Dupuy, Anton Rikus, Neepa T. Maitra. 2024-01-12. Exact-factorization-based surface-hopping without velocity adjustment. https://arxiv.org/abs/2401.06878

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