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Exact-Factorization-Based Surface Hopping for Multistate Dynamics

Cite this: J. Phys. Chem. Lett. 2022, 13, 7, 1785–1790
Publication Date (Web):February 16, 2022
https://doi.org/10.1021/acs.jpclett.1c04132
Copyright © 2022 American Chemical Society

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    Abstract

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    A surface-hopping algorithm recently derived from the exact factorization approach, SHXF [Ha et al. J. Phys. Chem. Lett.2018, 9, 1097], introduces an additional term in the electronic equation of surface hopping that 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 nonadiabatic 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 multiconfiguration time-dependent Hartree quantum dynamics benchmark.

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    We note that this is not the same as starting in the diabatic state because it represents an incoherent mixture rather than a coherent initial state; however, it approximates the initial populations of the reference calculation more accurately than starting in the adiabatic state.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpclett.1c04132.

    • Additional computational details and tables with the parameters of the LVC model; additional figures including analysis of hops between states, illustration of internal consistency in the different surface-hopping methods, comparison with full-dimensional calculations, and plots of geometries (PDF)

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    Cited By

    This article is cited by 9 publications.

    1. Evaristo Villaseco Arribas, Lea M. Ibele, David Lauvergnat, Neepa T. Maitra, Federica Agostini. Significance of Energy Conservation in Coupled-Trajectory Approaches to Nonadiabatic Dynamics. Journal of Chemical Theory and Computation 2023, 19 (21) , 7787-7800. https://doi.org/10.1021/acs.jctc.3c00845
    2. Arkajit Mandal, Michael A.D. Taylor, Braden M. Weight, Eric R. Koessler, Xinyang Li, Pengfei Huo. Theoretical Advances in Polariton Chemistry and Molecular Cavity Quantum Electrodynamics. Chemical Reviews 2023, 123 (16) , 9786-9879. https://doi.org/10.1021/acs.chemrev.2c00855
    3. Sophya Garashchuk, Julian Stetzler, Vitaly Rassolov. Factorized Electron–Nuclear Dynamics with an Effective Complex Potential. Journal of Chemical Theory and Computation 2023, 19 (5) , 1393-1408. https://doi.org/10.1021/acs.jctc.2c01019
    4. Javier Segarra-Martí, Thierry Tran, Michael J. Bearpark. 3-Methylation alters excited state decay in photoionised uracil. Physical Chemistry Chemical Physics 2022, 24 (44) , 27038-27046. https://doi.org/10.1039/D2CP03460C
    5. Kai T. Liu, Feng-Feng Song, David N. Beratan, Peng Zhang. Suppressing the entanglement growth in matrix product state evolution of quantum systems through nonunitary similarity transformations. Physical Review B 2022, 106 (10) https://doi.org/10.1103/PhysRevB.106.104306
    6. Julian Stetzler, Vitaly A. Rassolov. Comparison of Born–Oppenheimer approximation and electron-nuclear correlation. Molecular Physics 2022, 10 https://doi.org/10.1080/00268976.2022.2106321
    7. Evaristo Villaseco Arribas, Federica Agostini, Neepa T. Maitra. Exact Factorization Adventures: A Promising Approach for Non-Bound States. Molecules 2022, 27 (13) , 4002. https://doi.org/10.3390/molecules27134002
    8. Francesco Talotta, David Lauvergnat, Federica Agostini. Describing the photo-isomerization of a retinal chromophore model with coupled and quantum trajectories. The Journal of Chemical Physics 2022, 156 (18) , 184104. https://doi.org/10.1063/5.0089415
    9. Lea M. Ibele, Carlotta Pieroni, Francesco Talotta, Basile F.E. Curchod, David Lauvergnat, Federica Agostini. Exact Factorization of the Electron-Nuclear Wavefunction: Fundamentals and Algorithms. 2022https://doi.org/10.1016/B978-0-12-821978-2.00030-1

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