EXTENSIVE VIBRATIONAL STATE MIXING OF INDIVIDUAL ROTATIONAL LEVELS IN 1-BUTYNE NEAR $3333 CM^{-1}$

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1987

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Ohio State University

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An infrared absorption spectrum of jet-cooled (3K) 1-butyne is recorded by monitoring the attenuation of a scanned single-mode F-center laser beam. Rigorous are made by comparison of combination-differences with microwave data on this near-prolate asymmetric top. Levels with $K_{-1} =0$ are heavily mixed for all J and appear as a clump of 4 or more. The density of coupled states approximates the calculated total density of vibrational states $(-60 per cm^{-1})$. The $K_{-1}=1$ levels are apparently unperturbed for $J\le 3$ but heavily mixed for higher $J (\ge 7)$. The little information available on $K_{-1}=2$ indicates that it is strongly mixed even for low J. As compared to $K_{-1}=0,2, K_{-1}=1$ is anomolously noninteractive with the bath of vibrational levels. From a kinetic point of view, the data provide a detailed picture of collisionless intramolecular vibrational redistribution (IVR) in the energy region where it is ``turning on''.

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Author Institution: Department of Chemistry, The University of Akron

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