화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.111, No.13, 2498-2506, 2007
Vibrational spectroscopy of 1,1-difluorocyclopropane-d(0), -d(2), and -d(4): The equilibrium structure of difluorocyclopropane
IR and Raman spectra are reported for 1,1-difluorocyclopropane-d(0), -d(2), and -d(4), and complete assignments of vibrational fundamentals are given for these species. These assignments are consistent with predictions of frequencies, intensities, and Raman depolarization ratios computed with the B3LYP/cc-pVTZ quantum chemical (QC) model. Ground state rotational constants for five C-13 and deuterium isotopomers, obtained from published microwave spectra, were "corrected" into equilibrium rotational constants. The needed vibration-rotation interaction constants were computed with QC models after scaling the force constants. A semi-experimental equilibrium structure, fitted to the equilibrium moments of inertia, is r(C1C) = 1.470(1) angstrom, r(CC) = 1.546(1) angstrom, r(CF) = 1.343(1) angstrom, r(CH) = 1.078(1) angstrom, alpha(FCF) = 109.5(1), alpha(FCC) = 119.4(1)degrees, alpha(HCH) = 116.7(1)degrees, alpha(C1CH) = 117.4(1)degrees, and alpha(CCH) = 117.1(1)degrees. This structure agrees within the indicated uncertainties with the ab initio structure obtained from an extrapolated set of CCSD(T)/aug-cc-pVnZ calculations except for r(CC) = 1.548 angstrom. The F2C-CH2 bonds are significantly shortened and strengthened; the H2C-CH2 bond is significantly lengthened and weakened.