Microwave Spectroscopy of Chiral Astrochemical Candidate Vinyloxirane: The Missing Gauche Conformer.

The recent detection of a chiral molecule, propylene oxide, in the interstellar medium provides impetus for investigation of related analogues as candidates for discovery of a second chiral species. Vinyloxirane (VO) shares many of the characteristics of propylene oxide that favored its remote detection such as modest size, appreciable dipole moment and modest adsorption to water ice. The microwave spectrum of vinyloxirane at room temperature has been studied in the 18 - 26 GHz region. Rotational transitions of the previously undetected gauche -1 conformer have been assigned and fitted. The quantum number range of anti conformer transitions has been greatly expanded, providing improved molecular constants. Vibrational satellite transitions were assigned and fitted for the lowest frequency ν 27 torsion mode, for 2ν 27 , and for the ν 26 C=CC bend of anti VO, along with ν 27 satellites of gauche -1. The rovibrational analyses were assisted by anharmonic vibrational calculations at B3LYP-D3/aug-cc-PVTZ, B2PLYPD3/cc-pVTZ, and DSDPBEP86/cc-pVTZ levels. Experimental peak intensities provide a population ratio N gauche-1 / N anti of 0.36 ± 0.06, corresponding to a Gibbs free energy difference of 2.5 ± 0.4 kJ mol -1 in favor of the anti conformer, in agreement with the density functional theory results. In the gauche -1 conformer, the torsional angle between vinyl group and oxirane ring, τ C=CCM , is optimized at -35° to favor an intramolecular C vinyl H 11 ...O interaction. The gauche -2 conformer with τ C=CCM of + 74° suffers from C vinyl H 11 ...HC cyclopropyl repulsion so that it is calculated to be 8-9 kJ mol -1 higher than gauche -1. Reinterpretation of earlier Raman spectra suggests that the gauche -2 conformer had not been observed as reported.