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Breakdown of the born—oppenheimer approximation in radiative transitions

✍ Scribed by W.G. Breiland; C.B. Harris

Publisher: Elsevier Science
Year: 1973
Tongue: English
Weight: 711 KB
Volume: 18
Category: Article
ISSN: 0009-2614
DOI: 10.1016/0009-2614(73)80176-9

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✦ Synopsis

Evidence demojhstsating an explicit nuclear coordinate dependence bf efectr&c matrix e&&s in the tran&ion _ moment for phosphorescence to the ground state'vibration~ maRifofd has been found for substituted benzenes by an opticaliy detected microwave double resonance esperimen:. Theoretical expressions for .the experimentai obseW* tions developed within the framework of the Coridon qnd He.rzber, O-Teller approsimations f&l to cxpla?n thk results, implying that these approximations are not general enough to give a good description of radiative transitions in aromatic molecules. Additional tem'is in the Herzberg-Teller expansion and the breakdown of the Born-Opperr heimer approximation are briefly discussed as nltemativcs which can be used to explain the ~x~e~ent~ obsqa!ions '.

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