SEP SPECTROSCOPY OF THE HCCS RADICAL

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2000

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Ohio State University

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Stimulated Emission Pumping (SEP) spectroscopy has been applied to the study of the ground state vibronic structure of a linear tetra-atomic free radical, HCCS, which has two Renner-Teller active bending modes. The radical was produced in a supersonic jet by a pulsed discharge in a $C_{2}H_{2}$ and $CS_{2}$ mixture diluted in Ar. Two Nd YAG laser pumped dye lasers with linewidths $0.02 cm^{-1}$ are used to observe SEP spectra. Eight vibronic bands in the ground electronic states were observed from the $^{2} \Pi_{3/2}$ origin band excitation, and 4 bands from the $^{2}\Pi_{1/2}$ origin band excitation. Three of the observed bands are assigned to the CS stretching mode, and others to overtones and combinations of two bending modes with $\Pi$ vibronic symmetry. The observed vibronic energy levels are successfully analyzed by taking into accunt the Renner-Teller interaction including the cross vibronic terms. The determined parameters agree with previous ab initio $calculations^{a}$ and mm-wave $spectroscopy^{b}$.

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$^{a}$P. G. Szalay, J. Chem. Phys., 105, 2735 (1996), Y. Li and S. Iwata, Chem. Phys. Lett., 273, 91 (1997). $^{b}$J. Tang and S. Saito, J. Chem. Phys., 105, 8022 (1996).
Author Institution: Department of Basic Sciences, Graduate School of Arts and Sciences, University of Tokyo.

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