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Quantal trajectories for adiabatic and nonadiabatic regimes of vibronic systems
Author(s) -
Carlsen Henrik,
Sjöqvist Erik,
Goscinski Osvaldo
Publication year - 1999
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1999)75:4/5<409::aid-qua7>3.0.co;2-s
Subject(s) - adiabatic process , vibronic coupling , ergodicity , born–oppenheimer approximation , ergodic theory , diabatic , factorization , vibronic spectroscopy , chemistry , statistical physics , physics , quantum mechanics , excitation , mathematics , mathematical analysis , molecule , algorithm
Exact and averaged nuclear pseudorotational quantal trajectories are compared for various adiabatic and vibronic states of the Longuet‐Higgins E ⊗ϵ 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. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 75: 409–416, 1999