SUB-DOPPLER OPTOTHERMAL SPECTROSCOPY AND INTRAMOLECULAR DYNAMICS OF THE $\nu_{1}$ AND 2$\nu_{1}$ BANDS IN $SF_{5}CCH$

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1994

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Ohio State University

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Abstract

The high resolution spectra of the fundamental and first overtone of the acetylenic CH stretch in $SF_{5}CCH$ have been measured in a collimated molecular beam. The fundamental spectrum ($\rho_{A1} = 191/cm^{-1}$) is only slightly perturbed at low J, K corresponding to an ``effective” lifetime of 2 nsec. Four other weak bands are present in this region and their origin is hypothesized as being due to isotopes and near resonant perturbing states. In the spectrum of the first overtone ($\rho_{A1} = 1 \times 10^{5}/cm^{-1}$), the features have a Lorentzian lineshape and from their average width an intramolecular vibrational relaxation (IVR) lifetime of 1.5 nsec is calculated. The long lifetimes of both bands can be explained by the lack of low order anharmonic resonances.

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Author Institution: Laboratorio Europeo di Spettoscopie Non-lineari (LENS); Department of Chemistry, Princeton University; Department of Chemistry, Portland State University

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