title: Infrared and Raman spectra, conformational stability, ab initio calculations and vibrational assignments for trans-3-chloropropenoyl chloride.
abstract: The infrared (3500-30 cm(-1)) spectra of gaseous and solid and the Raman (3500-200 cm(-1)) spectra of the liquid with quantitative depolarization ratios and solid trans-3-chloropropenoyl chloride (trans-ClCHCHCClO) have been recorded. These data indicate that both the anti (carbonyl bond trans to the carbon-carbon double bond) and syn conformers are present in the fluid states but only the anti conformer is present in the crystalline state. The mid-infrared spectra of the sample dissolved in liquid xenon as a function of temperature (-55 to -100 degrees C) have been recorded. Utilizing conformer pairs at 870 and 725 cm(-1), 1215 and 1029 cm(-1), and 1215 and 1228 cm(-1), the enthalpy difference has been determined to be 136+/-5 cm(-1) (389+/-14 cal mol(-1)) with the anti conformer the more stable form. Optimized geometries and conformational stabilities were obtained from ab initio calculations at the levels of RHF/6-31G(d), MP2/6-31G(d), MP2/6-311 + + G(d,p), MP2/6-311 + + G(2d,2p) and MP2/6-311 + + G(2df,2pd) with only the latter two calculations predicting the anti rotamer to be the more stable form. The vibrational frequencies, harmonic force constants and infrared intensities were obtained from the MP2/6-31G(d) calculations, whereas the Raman activities and depolarization values were obtained from the RHF/6-31G(d) calculations. The spectra are interpreted in detail and the results are compared with those obtained for some related molecules.
authors.affiliation: Department of Chemistry, University of Missouri-Kansas City, 64110-2499, USA. durigj@umkc.edu
authors.forename: J R
authors.initials: JR
authors.lastname: Durig
authors.forename: B R
authors.initials: BR
authors.lastname: Drew
authors.forename: C E
authors.initials: CE
authors.lastname: Reese
authors.forename: P A
authors.initials: PA
authors.lastname: Brletic
mesh_terms: D000179:Acrylates / Q000737:chemistry*; D008968:Molecular Conformation; D017550:Spectroscopy, Fourier Transform Infrared; D013059:Spectrum Analysis, Raman; D013696:Temperature
chemical_list: C419880:3-chloropropenoyl chloride; D000179:Acrylates