Exact-Factorization-Based Surface Hopping without Velocity Adjustment

Lucien Dupuy, Anton Rikus, Neepa T. Maitra, J. Phys. Chem. Lett. 15, 2643-2649 (2024)

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. 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.

URL: https://doi.org/10.1021/acs.jpclett.4c00115