SINGLE ROTATIONAL LEVEL PHOTOPHYSICS OF $S_{1}$ THIOFORMALDEHYDE
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Date
1989
Journal Title
Journal ISSN
Volume Title
Publisher
Ohio State University
Abstract
Measurements of collision-free single rotational level fluorescence lifetimes and relative quantum yields are reported for the $4{^{1}}_{0}$ band of the $S_{1}-S_{0}$ absorption system of thioformaldehyde ($H_{2}CS$). These data are compared to spectroscopic $evidence^{1}$ for internal conversion and intersystem crossing from the $S_{1}$ state. The radiative lifetime is found to be approximately $170 \mu$s substantially longer than previously reported values, with a number of levels having even longer lifetimes. These anomalously long lifetimes can be explained by the dilution of the oscillator strength due to coupling with dark levels in the ground and first excited triplet states. Quantum yield measurements indicate that some of the long-lived levels have a nonradiative decay component in the coupled state. The results are interpreted in terms of a qualitative model involving level specific coupling between $s_{1}$ and levels in $T_{1}$ and $s_{0}$.
Description
${1}$ J. C. Petersen and D. A. Ramsay, Chem. Phys. Lett. 124. 406 (1986) and references therein.
Author Institution: Department of Chemistry, University of Kentucky; Department of Chemistry, University of Wisconsin-Parkside.
Author Institution: Department of Chemistry, University of Kentucky; Department of Chemistry, University of Wisconsin-Parkside.