Exchange model of vibrational dephasing in S1 trans-stilbene in solution and its possible correlation with the isomerization reaction
✍ Scribed by Hiro-o Hamaguchi; Koichi Iwata
- Publisher
- Elsevier Science
- Year
- 1993
- Tongue
- English
- Weight
- 595 KB
- Volume
- 208
- Category
- Article
- ISSN
- 0009-2614
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✦ Synopsis
The changes of the peak position and bandwidth of the oleftic C-C stretch Raman band of S, tram-stilbene in normal alkanes have been analyzed on the basis of an asymmetric exchange model in which the C-C stretch frequency hops to and fro between two discrete values belonging to two different electronic states. Both the time-dependent spectral changes in a single solvent and the solvent-dependent changes at a fixed delay time are successfully interpreted by this exchange model. A correlation has been found between the hopping rate and the rate of the trans to perpendicular isomerization, suggesting that the process of isomerization involves the same exchange mechanism. The proposed exchange model may be generalized and described as a time-domain expression of the solvent-induced polarization of the solute molecule.