期刊
JOURNAL OF CHEMICAL PHYSICS
卷 140, 期 19, 页码 -出版社
AIP Publishing
DOI: 10.1063/1.4875702
关键词
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资金
- Computational Materials and Chemical Sciences Network (CMCSN) project at the Brookhaven National Laboratory [DE-AC02-98CH10886]
- U.S. Department of Energy
- Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences
- Science Foundation Ireland (SFI) SIRG Program [11/SIRG/E2172]
- U.S. Department of Energy [DE-SC0006527]
We present a new semiclassical approach for description of decoherence in electronically nonadiabatic molecular dynamics. The method is formulated on the grounds of the Ehrenfest dynamics and the Meyer-Miller-Thoss-Stock mapping of the time-dependent Schrodinger equation onto a fully classical Hamiltonian representation. We introduce a coherence penalty functional (CPF) that accounts for decoherence effects by randomizing the wavefunction phase and penalizing development of coherences in regions of strong non-adiabatic coupling. The performance of the method is demonstrated with several model and realistic systems. Compared to other semiclassical methods tested, the CPF method eliminates artificial interference and improves agreement with the fully quantum calculations on the models. When applied to study electron transfer dynamics in the nanoscale systems, the method shows an improved accuracy of the predicted time scales. The simplicity and high computational efficiency of the CPF approach make it a perfect practical candidate for applications in realistic systems. (C) 2014 AIP Publishing LLC.
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