nonadiabatic coupling; electronic states interacting with a continuum; correlation function; resonance states; predissociation; HBr cation
Abstract :
[en] The Fourier transform of an electronic spectrum leads to an autocorrelation function which provides information on the propagation of the wave packet on the potential energy surface of the electronic state reached in the transition. The formula is valid even when nonadiabatic interaction is present, i.e., when the wave packet splits at a particular surface crossing with one part branching off to another potential energy surface. An explicit expression of the correlation function is given for a model of several discrete states interacting with a continuum. Closed-form solutions are given in the case of one and two resonances. A very simple formula valid in the strong coupling limit is also derived. The method is applied to the photoelectron spectrum of state A 2Sigma+ of HBr+, which is shown to correspond to the strong couplig case.
Disciplines :
Chemistry
Author, co-author :
Dehareng, Dominique ; Université de Liège - ULiège > Centre d'ingénierie des protéines
Leyh, Bernard ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de dynamique moléculaire
Desouter-Lecomte, Michèle ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique
Lorquet, Jean-Claude ; Université de Liège - ULiège > Services généraux (Faculté des sciences) > Relations académiques et scientifiques (Sciences)
Delwiche, Jacques ; Université de Liège - ULiège > Services généraux (Faculté des sciences) > Relations académiques et scientifiques (Sciences)
Hubin-Franskin, Marie-Jeanne ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie physique, spectrométrie de masse
Language :
English
Title :
Intramolecular dynamics by photoelectron spectroscopy. II. Nonadiabatic processes.
Publication date :
1983
Journal title :
Journal of Chemical Physics
ISSN :
0021-9606
eISSN :
1089-7690
Publisher :
American Institute of Physics, New York, United States - New York
Volume :
79
Issue :
8
Pages :
3719-3724
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
FRFC - Fonds de la Recherche Fondamentale Collective [BE] FRIA - Fonds pour la Formation à la Recherche dans l'Industrie et dans l'Agriculture [BE] BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique
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