Nonadiabatic transition path sampling

Sherman, M. C.

doi:10.1063/1.4959038

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Nonadiabatic transition path sampling

Sherman, M. C.

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Abstract

Fewest-switches surface hopping (FSSH) is combined with transition path sampling (TPS) to produce a new method called nonadiabatic path sampling (NAPS). The NAPS method is validated on a model electron transfer system coupled to a Langevin bath. Numerically exact rate constants are computed using the reactive flux (RF) method over a broad range of solvent frictions that span from the energy diffusion (low friction) regime to the spatial diffusion (high friction) regime. The NAPS method is shown to quantitatively reproduce the RF benchmark rate constants over the full range of solvent friction. Integrating FSSH within the TPS framework expands the applicability of both approaches and creates a new method that will be helpful in determining detailed mechanisms for nonadiabatic reactions in the condensed-phase.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY ELECTRON TRANSFER REACTION KINETICS SAMPLING SIMULATION

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Sherman, M. C.. 2016-07-21. Nonadiabatic transition path sampling. https://doi.org/10.1063/1.4959038

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