Exact-Factorization-Based Surface-Hopping for Multi-State Dynamics

Patricia Vindel-Zandbergen, Spiridoula Matsika and Neepa T. Maitra, Chem. Theory Comput. 2021, 17, 7, 3852–3862 (2021)

Abstract
A surface-hopping algorithm recently derived from the exact factorization approach, SHXF, [Ha, Lee, Min, J. Phys. Chem. Lett. 9, 1097 (2018)] introduces an additional term in the electronic equation of surface-hopping, which couples electronic states through the quantum momentum. This term not only provides a first-principles description of decoherence but here we show it is crucial to accurately capture non-adiabatic dynamics when more than two states are occupied at any given time. Using a vibronic coupling model of the uracil cation, we show that the lack of this term in traditional surface-hopping methods, including those with decoherence-corrections, leads to failure to predict the dynamics through a three-state intersection, while SHXF performs similarly to the multi-configuration time dependent Hartree quantum dynamics benchmark.