Abstract
Infrared (IR) spectra in the gas phase are reported for CF2-CHD and CF2-CD2 in the region 350-4000 cm-1. Ab initio calculations of an harmonic force-field and anharmonicity constants have been made with an MP2/aug-cc-pVTZ model. These enable a number of Fermi resonances in each species to be analyzed and a complete set of “observed” harmonic frequencies to be derived. The latter are combined with similar data for CF2-CH2 in a scaling of the model harmonic force field to both anharmonic and harmonic frequencies. Inspection of the scale factors reveals minor defects of the model, evident in the out-of-plane wagging modes and in the CF stretch/CF stretch interaction force constant. Fermi resonance treatments involved in all isotopomers studied are compatible with the overall force-field refinement results. The treatment leaves a small anomaly in the 13C shift on ¿1. Improved microwave spectra are reported for five isotopic species, and a semiexperimental equilibrium structure for F2C-CH2 is determined and compared favorably with the structure obtained from new high-level ab initio calculations. Centrifugal distortion constants are predicted for the five isotopic species, and those for F2C-CH2 are compared with values fit to microwave spectra.
Original language | English |
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Pages (from-to) | 9309-9318 |
Number of pages | 10 |
Journal | Journal of Physical Chemistry A |
Volume | 114 |
Issue number | 34 |
Early online date | 6 Aug 2010 |
DOIs | |
Publication status | Published - 2 Sept 2010 |