Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 11, Issue 4, Pages 1375-1382Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jctc.5b00072
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Funding
- Natural Sciences and Engineering Research Council of Canada (NSERC)
- Chemistry Department of the University of Toronto
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Adequate simulation of nonadiabatic dynamics through conical intersection requires accounting for a nontrivial geometric phase (GP) emerging in electronic and nuclear wave functions in the adiabatic representation. Popular mixed quantum-classical (MQC) methods, surface hopping and Ehrenfest, do not carry a nuclear wave function to be able to incorporate the GP into nuclear dynamics. Surprisingly, the MQC methods reproduce ultrafast interstate crossing dynamics generated with the exact quantum propagation so well as if they contained information about the GP. Using two-dimensional linear vibronic coupling models we unravel how the MQC methods can effectively mimic the most significant dynamical GP effects: (1) compensation for repulsive diagonal second-order nonadiabatic couplings and (2) transfer enhancement for a fully cylindrically symmetric component of a nuclear distribution.
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