Infrared Spectra of 12CF212CH2 and 12CF213CH2, Quantum-Chemical Calculations of Anharmonicity, and Analyses of Resonances

Abstract

Infrared spectra obtained in gas and liquid argon phases are reported for 12CF212CH2 and 12CF213CH2. These spectra firmly establish the positions of ν3 (A1) and ν6 (A2) for both isotopomers. Using anharmonicity constants from MP2 calculations, Fermi resonances affecting ν1 (A1), ν2 (A1), ν3, and ν8 (B1) are analyzed. Deperturbed fundamental frequencies from these analyses are used in conjunction with unaffected fundamentals and ab initio anharmonicity data to predict all 12 “observed” harmonic frequencies. A Darling−Dennison type resonance between 2ν6 and ν11 + ν12 is diagnosed, the calculation of which from ab initio data requires modification of the existing second-order treatment of such constants, where Fermi resonance type terms are also present. Predictions are made of many overtone and combination band frequencies, aiding assignment of observed spectra. From the isolated CH stretching frequency obtained here of 3125.4 cm−1, the C−H equilibrium bond length is predicted to be 1.0762(11) Å.

Publisher

American Chemical Society

Publication Date

5-1-2010

Publication Title

Journal of Physical Chemistry A

Department

Chemistry and Biochemistry

Document Type

Article

DOI

https://dx.doi.org/10.1021/jp100438z

Keywords

Correlated molecular calculations, Resolution ftir spectrum, Gaussian-basis sets, Force-fields, Vibrational anharmonicity, Fermi, Resonance, 1, 1-difluoroethylene, cf2=ch2, Bands, Spectroscopy, Chemistry, physical, Physics, atomic, molecular & chemical

Language

English

Format

text

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