AN OBSERVATION OF COLLISION FREE, INTRAMOLECULAR VIBRATIONAL REDISTRIBUTION IN $S_{1}$ p-FLUOROTOLUENE

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1981

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Ohio State University

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Vibrational redistribution with $\epsilon_{vib} = 1988$ $cm^{-1}$ in the $S_{1}$ state of p-fluorotoluene (pft) vapor has been followed by observation of the time evolution of electronic fluorescence spectra after initial $S_{1}$ $preparation^{1}$. A chemical timing technique using an efficient electronic state quencher ($O_{2}$) at high gas pressures has extended the time resolution to few picoseconds. A ``single’’ vibronic level of p-fluorotoluene is excited by pumping a prominent absorption feature of the p-fluorotoluene spectrum using cw laser excitation at 257.3 nm. Fluorescence observed after the natural lifetime of the molecule is congested and featureless. Fluorescence observed from pft molecules at short times exhibits sharp features which are consistent with emission from the initially prepared state.

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$^{1}$D. A. Dolson, C. S. Parmenter, and B. M. Stone, ``Fast Reactions in Energetic Systems'', Proceedings of the NATO Advanced study Institute, July, 1980.
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