CONFORMATIONAL STABILITY, BARRIERS TO INTERNAL ROTATION, VIBRATIONAL ASSIGNMENT, AND AB INITIO CALCULATIONS OF TRANS-1,3-DICHLOROPROPENE

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1991

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Ohio State University

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The far infrared spectrum of gaseous trans-1,3-dichloropropene has been recorded at a resolution of $0.10 cm^{-1}$ in the region of 350 - 50 $cm^{-1}$. The fundamental asymmetric torsional frequencies of the more stable gauche and the higher energy cis conformations have been observed at 85 and 130 $cm^{-1}$, respectively. Several excited states falling to lower frequencies were observed for the cis conformation. From these data the asymmetric torsional potential function governing the internal rotation about the C-C bond has been determined. From studies of the Raman spectrum at variable temperatures, the conformational enthalpy difference has been determined. A complete assignment of the vibrational fundamentals observed from the infrared spectra (3300 - 50 $cm^{-1}$ of the gas and solid and the Raman spectra (3200 - 10 $cm^{-1}$) of all three physical states is proposed. All of these data are compared to the corresponding quantities obtained from ab initio Hartree-Fock gradient calculations employing both the 3-21$G^{*}$ and 6-31$G^{*}$ basis sets.

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Author Institution: Department of Chemistry, University of South Carolina; Departments of Chemistry and Physics, The University of the South

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