Quantal Trajectories for Adiabatic and Nonadiabatic Regimes of Vibronic Systems

摘要

Exact and averaged nuclear pseudorotational quantal trajectories are compared for various adiabatic and vibronic states of the Longuet-Higgins E direct X implied by Jahn-Teller model. It is argued that the usual averaging over the electronic motion could be understood as being a consequence of ergodicity. The failure of the Born-Oppenheimer factorization to obey the ergodic hypothesis was examined. A quantitative separation of the electronic and nuclear time-scales is, nevertheless, achieved for all regimes. It is shown that the short-time deviations from the global "drift" of the electronic and nuclear motions are perfectly correlated.