期刊
JOURNAL OF CHEMICAL PHYSICS
卷 140, 期 6, 页码 -出版社
AIP Publishing
DOI: 10.1063/1.4863919
关键词
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资金
- National Science Foundation (NSF) CAREER Award [CHE-1057112]
- (U.S.) Department of Energy (DOE) [DE-SC0006598]
- Office of Naval Research (ONR) [N00014-10-1-0884]
- Camille and Henry Dreyfus Foundation New Faculty Award
- Alfred P. Sloan Foundation Research Fellowship
- U.S. Department of Energy (DOE) [DE-SC0006598] Funding Source: U.S. Department of Energy (DOE)
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1057112] Funding Source: National Science Foundation
We extend ring-polymer molecular dynamics (RPMD) to allow for the direct simulation of general, electronically non-adiabatic chemical processes. The kinetically constrained (KC) RPMD method uses the imaginary-time path-integral representation in the set of nuclear coordinates and electronic states to provide continuous equations of motion that describe the quantized, electronically non-adiabatic dynamics of the system. KC-RPMD preserves the favorable properties of the usual RPMD formulation in the position representation, including rigorous detailed balance, time-reversal symmetry, and invariance of reaction rate calculations to the choice of dividing surface. However, the new method overcomes significant shortcomings of position-representation RPMD by enabling the description of non-adiabatic transitions between states associated with general, many-electron wave-functions and by accurately describing deep-tunneling processes across asymmetric barriers. We demonstrate that KC-RPMD yields excellent numerical results for a range of model systems, including a simple avoided-crossing reaction and condensed-phase electron-transfer reactions across multiple regimes for the electronic coupling and thermodynamic driving force. (C) 2014 AIP Publishing LLC.
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