A HIGH RESOLUTION STUDY OF THE ELECTRONIC SPECTRA OF CONFORMERS OF 1,3 AND 1,4 DIVINYL-BENZENE: UNEXPECTED EXCITED STATE $BEHAVIOR^{a}$

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1999

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Ohio State University

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Abstract

The vibrationally resolved $S_{1} \leftarrow S_{0}$ electronic spectra of 1,3- and 1,4-divinylbenzene each exhibited two origin bands that are $^{\sim}800 cm^{-1}$ and $^{\sim}1000 cm^{-1}$ apart respectively. Intrigued by this observation, we have recorded the different bands at full rotational resolution in a molecular beam. Analyses of these data show that the two bands are the $S_{1} \leftarrow S_{0}$ of the different conformers, cis and trans, in each molecule, which are remarkably far apart. Typically, such systems exhibit more closely spaced origin bands. A model that accounts for this unexpected behavior will be discussed.

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$^{a}$ work supported by NSF.
Author Institution: Department of Chemistry, University of Pittsburgh

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