Different Flavors of Exact-Factorization-Based Mixed Quantum-Classical Methods for Multistate Dynamics

Evaristo Villaseco Arribas, Patricia Vindel-Zandbergen, Saswata Roy, Neepa T. Maitra, accepted in Physical Chemistry Chemical Physics as “accepted manuscript” (2023)

The exact factorization approach has led to the development of new mixed quantum-classical methods for simulating coupled electron-ion dynamics. We compare their performance for dynamics when more than two electronic states are occupied at a given time and analyze: (1) the use of coupled versus auxiliary trajectories in evaluating the electron-nuclear correlation terms, (2) the approximation of using these terms within surface-hopping and Ehrenfest frameworks, and (3) the relevance of the exact conditions of zero population transfer away from nonadiabatic coupling regions and total energy conservation. Dynamics through the three-state conical intersection in the uracil radical cation as well as polaritonic models in one dimension are studied.

URL: https://doi.org/10.1039/D3CP03464J