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Intensities of Transitions in Non-Totally Symmetric Vibrations in the Electronic Spectra of Polyatomic Molecules

✍ Scribed by W.L. Smith

Publisher
Elsevier Science
Year
1996
Tongue
English
Weight
125 KB
Volume
176
Category
Article
ISSN
0022-2852

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✦ Synopsis

The effect of the noncorrespondence of normal coordinates on the Franck-Condon factors governing the appearance of non-totally symmetric vibrations in electronic spectra is examined. In a two-dimensional symmetry species containing vibrations 1 and 2, transitions such as 1 1 0 2 1 0 , 1 1 0 2 3 0 , etc. are given zero intensity in the usual theory, but it is shown using a simple model that noncorrespondence leads to their appearance with an intensity determined by the elements of the matrix connecting the normal coordinates in the two states. When applied to the 2600A ˚system of benzene the theory suggests that the transition 6 1 0 14 1 0 15 1 0 should have an observable intensity and this leads to a plausible assignment. This work suggests that the usual theory of non-totally symmetric vibrations needs to be modified to recognize that transitions of the sort 1 1 0 2 1 0 , and not 1 4 0 2 0 0 , are likely to be the most important after the leading member 1 2 0 2 0 0 .

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