LASER EXCITATION SPECTRA FOR THE VINOXY-Ar RADICAL VAN DER WAALS COMPLEX
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Date
1986
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Ohio State University
Abstract
Electronic spectra for the vinoxy-argon van der Waals complex $(C_{2}H_{3}O^{-}Ar)$ have been recorded for the first time. The complex was formed by photolytically generating vinoxy radicals in the early stages of an Ar free jet expansion. The spectrum was observed by laser excitation of the bands associated with the vinoxy $\tilde{B}^{2} A^{\prime\prime}-\tilde{X}{^{2}}A^{\prime\prime}$ system. A pair of bands belonging to the complex appeared in conjuction with each of the stronger vibronic bands of the vinoxy excitation $spectrum^{1}$ $(0_{0}^{1}, 1_{0}^{1}, 2_{0}^{1}, 3_{0})$. The complex bands were red shifted from the vinoxy bands by approximately $76 cm^{-1}$ and $36 cm^{-1}$, indicating that electronic excitation strengthens the van der Waals interaction. The influence of the expansion source pressure on the relative band intensities was investigated and found to be consistent with both features arising from a complex which contains a single Ar atom. Thus they are either members of a vibrational progression or bands corresponding to two different structrual isomers. In order to distinguish between these possibilities, we are currently analysing rotational contours (recorded at $0.10 cm^{-1}$ resolution) of the complex bands. (1) L.J. DiMaouro, M.C. Heaven and T.A. Miller, J. Chem. Phys. 81, 2339 (1984).
Description
Address of van de Burgt, Maliekal and Heaven: Department of Chemistry, Illinois Institute of Technology, Chicago, Illinois 60616.
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