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Vibronic coupling in electronic transitions with significant Duschinsky effect
Author(s) -
Peluso Andrea,
Santoro Fabrizio,
Del Re Giuseppe
Publication year - 1997
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(1997)63:1<233::aid-qua25>3.0.co;2-b
Subject(s) - diabatic , vibronic coupling , coupling (piping) , born–oppenheimer approximation , chemistry , harmonic , potential energy , valence (chemistry) , computational chemistry , physics , atomic physics , quantum mechanics , excited state , molecule , materials science , adiabatic process , metallurgy
Conceptual and mathematical difficulties arise in the study of transitions between vibronic states belonging to crossing Born‐Oppenheimer hypersurfaces with significantly different positions and shapes of the minimum‐energy nuclear configurations (Duschinsky effect). This article presents an analytic procedure for the evaluation of the pertinent coupling integrals, adopting a normal coordinate reference system for the internal nuclear motion and harmonic approximation. The Duschinsky effect is properly considered. The procedure was applied to the dynamics of electron transfer in neutral mixed valence monoradicals, using the diabatic representation. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 63: 233–244, 1997