ROTATIONALLY RESOLVED ELECTRONIC SPECTRUM OF THE PARA-DIFLUOROBENZENE-NITROGEN VAN DER WAALS COMPLEX: STRUCTURE AND INTERNAL $MOTION^{a}$

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2003

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Ohio State University

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The rotationally resolved $S_{1} \leftarrow S_{0}$ fluorescence excitation spectra of p-difluorobenzene and its $N_{2}$ complex have been observed. While the spectrum of pDFB is pure b-type, the spectrum of the $N_{2}$ complex is a superposition of two pure c-type spectra that result from the internal rotation of the $N_{2}$ molecule. The analysis reveals that $N_{2}$ molecule lies above the center of the ring plane in the $S_{0}$ state; this distance decreases in the $S_{1}$ state. The preferred orientation and barrier to internal rotation in the two electronic states are also different. A full discussion of the factors responsible for the differences will be given.

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$^{a}$work supported by NSF.
Author Institution: Department of Chemistry, University of Pittsburgh; Laboratorium f\""{u}r Physikalische Chemie, Eidgenossische Technische Hochschule Zurich

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