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arxiv 2112.02727 v3 pith:A4OZD5N3 submitted 2021-12-06 physics.chem-ph quant-ph

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

classification physics.chem-ph quant-ph
keywords dynamicssurface-hoppingtermelectronicquantumshxfstatesaccurately
verification ladder T0 review T1 audit T2 compute T3 formal T4 reserved
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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.

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