THE STRUCTURE, THE INTERNAL ROTATION OF $N_{2}$ AND THE ROTATION OF THE ELECTRONIC TRANSITION MOMENT IN THE PARA-DIFLUOROBENZENE-$N_{2}$ VAN DER WAALS COMPLEX
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Date
1998
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Ohio State University
Abstract
Cold jet $S_{1}\leftarrow S_{0}$ rotational band contours have been obtained at $0.3 cm^{-1}$ resolution for the p-difluorobenzene-$N_{2} (pDFBN_{2})$ van der Waals complex and analyzed with an asymmetric top simulation program. Satisfactory simulation is possible only if it is assumed that the in-plane electronic transition moment of $pDFB-N_{2}$ rotates about $37^{\circ}$ towards the F-F axis from its position normal to that axis in free pDFB. The vdW bond distances from the ring plane to the $N_{2}$ bond parallel to that plane are 3.47 {\AA} and 3.42 {\AA} in the $S_{1}$ and $S_{0}$ states, respectively. Several transitions involving the internal rotation of $N_{2}$ about an axis perpendicular to the ring plane have been assigned. The band positions are consistent with two-fold rotational barriers of $14.0 cm^{-1}$ and $19.0 cm^{-1}$ for the $S_{0}$ and $S_{1}$ states, respectively. These barriers are in agreement with those $recently^{a}$ determined from the assignments of different internal rotor transitions seen in the R2PI spectra.
Description
$^{a}$Y. Hu. W. Lu and S. Yang, J. Photoch. Photobio. A. 106, 91(1997).
Author Institution: Department of Chemistry, Indiana University
Author Institution: Department of Chemistry, Indiana University