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The use of ring polymer molecular dynamics (RPMD) for the direct simulationof electron transfer (ET) reaction dynamics is analyzed in the context ofMarcus theory, semiclassical instanton theory, and exact quantum dynamicsapproaches. For both fully atomistic and system-bath representations ofcondensed-phase ET, we demonstrate that RPMD accurately predicts both ETreaction rates and mechanisms throughout the normal and activationless regimesof the thermodynamic driving force. Analysis of the ensemble of reactive RPMDtrajectories reveals the solvent reorganization mechanism for ET that isanticipated in the Marcus rate theory, and the accuracy of the RPMD ratecalculation is understood in terms of its exact description of statisticalfluctuations and its formal connection to semiclassical instanton theory fordeep-tunneling processes. In the inverted regime of the thermodynamic drivingforce, neither RPMD nor a related formulation of semiclassical instanton theorycapture the characteristic turnover in the reaction rate; comparison with exactquantum dynamics simulations reveals that these methods provide inadequatequantization of the real-time electronic-state dynamics in the inverted regime.

journal of chemical physics online/the journal of chemical physics/journal of chemical physics

Direct simulation of electron transfer using ring polymer molecular  dynamics: Comparison with semiclassical instanton theory and exact quantum  methods