VIBBATIONAL REDISTRIBUTION IN THE EXCITED STATE OF A LARGE POLYATOMIC MOLECULE

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1978

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Ohio State University

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Most SVL fluorescence experiments are from excited state $(S_{1})$ levels which contain only a modest amount of vibrational energy $(\approx 0 - 2000\;cm^{-1})$. The structured emission at low pressures is characteristic of the vibrational level excited. As the excitation energy is increased the density of vibrational levels accessible also goes up. However, because of the bias supplied by the Franck-Condon factors the excitation energy can be initially restricted to only a few levels of the many that are isoenergetic. Vibrational redistribution can then occur which in extreme cases can result in essentially unstructured emission. Such a phenomenon has not been unambiguously observed previously due primarily to sequency congestion obscuring the identity of the initially excited vibrational levels. We wish to report here experiments performed on the $^{1}B_{2u}$ electronic state of p-difluorobenzene where preliminary results indicate that vibrational redistribution becomes gradually effective with increasing excitation energy.

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Author Institution: Department of Chemistry, Indiana University

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