2021/12/06 by Patricia Vindel-Zandbergen, Vindel-Zandbergen, Patricia, Spiridoula Matsika +3 · 1 citation
Chemistry · Physics and Astronomy · #Advanced Chemical Physics Studies #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Molecular spectroscopy and chirality #Quantum Physics (quant-ph) #Spectroscopy and Quantum Chemical Studies #physics.chem-ph #quant-ph
paper · pdf · doi:10.48550/arxiv.2112.02727
openalex publication_date 2021/12/06 · arxiv created 2022/02/07 · arxiv updated 2022/02/08 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
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.