15min:
ELECTRONIC SPECTROSCOPY OF JET COOLED THIOPHENOXYL RADICAL.

MASARU FUKUSHIMA AND TAKASHI ISHIWATA, Faculty of Information Sciences, Hiroshima City University, Hiroshima 731-3194, Japan; KINICHI OBI, Department of Chemical and Biological Sciences, Japan Women's University, Tokyo 112-8681, Japan.

The thiophenoxyl radical, C6H5-S (~ phi-S~), is an aromatic free radical with a benzyl type pi-electronic structure. We have generated the phi-S radical by ArF laser photolysis in supersonic free jet expansions, and observed laser induced fluorescence (~LIF~) of the green-blue band. We have measured the vibrationally and rotationally resolved LIF excitation spectra and the vibrationally resolved LIF dispersed spectra from the single vibronic levels (~SVL~). On the basis of the precise vibrational analysis of the dispersed spectra, we propose new vibrational assignments to the vibronic bands on the excitation spectrum. The band types of the vibronic bands determined from the rotationally resolved excitation spectra make it possible us to give a definite assignment of the D2 12A2 -- D0 12B1, pi* leftarrow pi, electronic transition for the green-blue band of phi-S. Based on the results of the spectroscopic assignments, we will discuss the electronic and vibrational structure of phi-S both on the ground D0 12B1 and the second excited D2 12A2 states.