Effect of the geometric phase on nuclear dynamics at a conical intersection: Extension of a recent topological approach from one to two coupled surfaces.
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 (1)B(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.
Althorpe
Stuart C
SC
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
Stecher
Thomas
T
Bouakline
Foudhil
F