期刊
JOURNAL OF CHEMICAL PHYSICS
卷 139, 期 15, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.4826163
关键词
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资金
- NSF [CHE-0911635]
- DOE [DE-SC0006598]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1301157] Funding Source: National Science Foundation
- U.S. Department of Energy (DOE) [DE-SC0006598] Funding Source: U.S. Department of Energy (DOE)
A partial linearized path integral approach is used to calculate the condensed phase electron transfer (ET) rate by directly evaluating the flux-flux/flux-side quantum time correlation functions. We demonstrate for a simple ET model that this approach can reliably capture the transition between non-adiabatic and adiabatic regimes as the electronic coupling is varied, while other commonly used semi-classical methods are less accurate over the broad range of electronic couplings considered. Further, we show that the approach reliably recovers the Marcus turnover as a function of thermodynamic driving force, giving highly accurate rates over four orders of magnitude from the normal to the inverted regimes. We also demonstrate that the approach yields accurate rate estimates over five orders of magnitude of inverse temperature. Finally, the approach outlined here accurately captures the electronic coherence in the flux-flux correlation function that is responsible for the decreased rate in the inverted regime. (C) 2013 AIP Publishing LLC.
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