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Fluorescence excitation spectrum of the trans,trans-1,3,5,7-octatetraene(OT)-Xe van der Waals clusters formed in supersonic jet expansions has been obtained. The transition lines corresponding to the van der Waals clusters of OT with Xe are observed in the lower frequency side of the OT band origin. Based on the spectral shifts, fluorescence lifetimes, and concentration dependence of the peak intensities, most of the transition lines are assigned to the OT-Xen (n = 1, 2, 3, 4) clusters. Long progressions of a van der Waals vibrational mode are observed for n = 1, 2, 3 and 4 clusters and assigned to rocking of the OT moiety with respect to the Xe atom with the help of ab initio quantum mechanical calculation.

Fluorescence Excitation Spectroscopy of Octatetraene-Xe van der Waals Clusters