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Vibronic spectral behavior of molecules. XIII. Theoretical contribution to the vibronic coupling and the dushinsky effect on the S1 ← S0 absorption and the S1 → S0, S2 → S1, and S2 → S0 fluorescences of azulene

✍ Scribed by Klaus Gustav; Michael Storch

Publisher
John Wiley and Sons
Year
1990
Tongue
English
Weight
797 KB
Volume
38
Category
Article
ISSN
0020-7608

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✦ Synopsis

Abstract

Based on the completely optimized S~0~, S~1~, and S~2~ molecular geometries of azulene, the vibronic structure of the S~1~ ← S~0~ absorption as well as of the S~1~ → S~0~, S~2~ → S~1~, and S~2~ → S~0~ fluorescences is investigated theoretically within the adiabatic approximation. By means of theory‐experiment comparisons, the influence of non‐Condon terms and of the Dushinsky effect on the vibronic structure of azulene spectral behavior is discussed. Typical for the S~1~ ← S~0~ absorption and the S~1~ → S~0~ fluorescence are vibronic transition moment contributions of Condon type, whereas the interpretation of azulene S~2~ → S~1~ and S~2~ → S~0~ fluorescences is successful only within the scope of the Herzberg–Teller approach by taking into account vibronic coupling terms and, additionally, the Dushinsky effect in the latter case. An analysis of the relevant vibrational modes is given.

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