The atomistic simulations of charge transfer reactions in complex systems remains a significant challenge, particular where quantum dynamic effects including coupled electron-nuclear motion play an important role. We address this challenge by developing path integral based methods that employ classical molecular dynamics trajectories to describe quantum effects. We demonstrate accuracy and efficiency of one such approximate dynamics, Ring Polymer Molecular Dynamics (RPMD), in an atomistic simulation of the Cobalt Hexammine(II/III) self-exchange reaction. We then introduce new methods based on RPMD that extend its applicability to multi-state, multi-electron thermal reactions as well as to photo-initiated excited state dynamics in the condensed phase. We demonstrate the accuracy of these new techniques in a variety of model systems, and we discuss their regimes of applicability and their use in large-scale simulations.

Path integral methods for nonadiabatic dynamics: Quantum transitions from classical trajectories

253rd National Meeting (2017)

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