期刊
JOURNAL OF CHEMICAL PHYSICS
卷 129, 期 21, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.3031215
关键词
Jahn-Teller effect; organic compounds; potential energy surfaces; wave functions
资金
- UK Engineering and Physical Sciences Research Council (EPSRC)
- Engineering and Physical Sciences Research Council [EP/D077958/1] Funding Source: researchfish
- EPSRC [EP/D077958/1] Funding Source: UKRI
A recent approach [S. C. Althorpe, J. Chem. Phys. 124, 084105 (2006)] for interpreting geometric phase (GP) effects in a nuclear wave function confined to the lower of two conically intersecting potential energy surfaces is extended to treat coupled dynamics on both surfaces. The approach is exact, and uses simple topology to separate the wave function into contributions from Feynman paths that wind different numbers of times, and in different senses, around the conical intersection. We derive the approach first, by mapping the time-dependent wave packet describing the coupled dynamics onto a double space, and second, by classifying the Feynman paths within a time-ordered expansion of the path integral. The approach is demonstrated numerically for a simple Exe Jahn-Teller system and for a model of the B-1(1)-S-0 intersection in pyrrole. The approach allows one to investigate and interpret the effect of the GP on population transfer between the surfaces, and also to extract contributions to the coupled nuclear wave function from different reaction paths.
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