ELECTRONIC TRANSITIONS OF THE $HC_{4}S$ AND $HC_{6}S$ RADICALS STUDIED BY LASER INDUCED FLUORESCENCE SPECTROSCOPY

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2002

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Ohio State University

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Laser induced fluorescence spectra of two new vibronic band systems have been observed by discharging a mixture gas, $C_{2}H_{2} 0.5%/CS_{2} 0.3%$ diluted in Ar, in a supersonic jet. All the bands were assigned to ${^{2}}\Pi_{3/2} - {^{2}}\Pi_{3/2}$ transitions by measuring rotationally resolved spectra. Based on the chemical composition and the ground state combination differences, the spectral carriers were assigned to the $HC_{4}S$ and $HC_{6}S$ radicals. The homogeneous width of the excitation spectra of the $HC_{6}S$ radical is larger than that of $HC_{4}S$ by $0.02 cm^{-1}$ (FWHM), which was interpreted as the lifetime broadening of the excited state, corresponding to 270 ps. Vibronic origin of $HC_{4}S$ is located at 500.5 nm, and that of $HC_{6}S$ is at 589.6 nm. Main progressions of both the vibronic systems are assigned to the excitations of the C-S stretching modes, of which frequencies were determined to $505 cm^{-1}$ for $HC_{4}S, 435 cm^{-1}$ for $HC_{6}S$.

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Author Institution: Department of Basic Science, Graduate School of Arts and Science, The University of Tokyo

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