MICROWAVE SPECTROSCOPY OF THE HCCS AND DCCS RADICALS IN THE VIBRONIC EXCITED STATES
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Date
1996
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Ohio State University
Abstract
The microwave spectra of the HCCS and DCCS radicals ($X^{2}\Pi_{1}$) in both $CCS(\nu_{5})$ and $H(D)CC(\nu_{4})$ bending vibrational states were observed in the freuency range of 160 400 GH2 with a de discharge of the $C_{2}H_{2}$ (or $C_{2}D_{2}$) and $CS_{2}$ gas mixture. The rotational transition series for the vibronic $^{2}\Delta_{2, 3yz}(\nu_{5}),\mu\kappa^{2}\Sigma(\nu_{5}), ^{2}\Pi_{3/2}(2\nu_{5}), ^{2}\Delta_{5/2}(\nu_{4})$ and $\mu^{2}\Sigma(\nu_{4})$ states were assigned. The analysis of the effective molecular constants showed that the values of the $\tau_{eff}$ constants of the vibronic $\mu\kappa^{2}\Sigma$ states were different from each other by 2 3 GHz, which could not be explained by the up-to-date Renner-Teller theory for a single bending mode. This abnormal Renner-Teller effect may be understood by a new vibronic interaction theory, which was developed by us to consider the cross vibronic interaction between the two bending modes.
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Author Institution: Dept. of Molecular Structure, The Graduate University for Advanced Studies and Institute for Molecular Science