期刊
JOURNAL OF CHEMICAL PHYSICS
卷 135, 期 7, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.3624766
关键词
charge exchange; molecular dynamics method; quantum theory; reaction kinetics theory; reaction rate constants; tunnelling
资金
- U.S. Office of Naval Research (USONR) [N00014-10-1-0884]
- National Science Foundation (NSF) [CHE-1057112]
- Camille and Henry Dreyfus Foundation
- Alfred P. Sloan Foundation
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1057112] Funding Source: National Science Foundation
The use of ring polymer molecular dynamics (RPMD) for the direct simulation of electron transfer (ET) reaction dynamics is analyzed in the context of Marcus theory, semiclassical instanton theory, and exact quantum dynamics approaches. For both fully atomistic and system-bath representations of condensed-phase ET, we demonstrate that RPMD accurately predicts both ET reaction rates and mechanisms throughout the normal and activationless regimes of the thermodynamic driving force. Analysis of the ensemble of reactive RPMD trajectories reveals the solvent reorganization mechanism for ET that is anticipated in the Marcus rate theory, and the accuracy of the RPMD rate calculation is understood in terms of its exact description of statistical fluctuations and its formal connection to semiclassical instanton theory for deep-tunneling processes. In the inverted regime of the thermodynamic driving force, neither RPMD nor a related formulation of semiclassical instanton theory capture the characteristic turnover in the reaction rate; comparison with exact quantum dynamics simulations reveals that these methods provide inadequate quantization of the real-time electronic-state dynamics in the inverted regime. (C) 2011 American Institute of Physics. [doi:10.1063/1.3624766]
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