Scaled quantum chemical force fields for 1,1-difluorocyclopropane and the influence of vibrational anharmonicity


Potential functions and harmonic (ωi) and anharmonic (νi) fundamental frequencies have been calculated for 1,1-difluorocyclopropane (DFCP) and its d4 and d2 isotopomers using the program Gaussian 03. B3LYP and MP2 models were employed, each with the bases 6-311++G** and cc-pVTZ. Anharmonicity corrections Δi = ωi − νi are listed and shown to be different for symmetric and antisymmetric CH stretching modes in situations where Fermi resonance appears to be absent. The same effect is missing in C2H4, for which similar calculations were made. The quadratic force fields for DFCP have been scaled in symmetry coordinate space with 15 scale factors both to observed frequencies νobsd and also to ωobsd, where ωobsd = νobsd + Δ. With νobsd especially, different scale factors are needed for the symmetric and antisymmetric CH stretching force constants due to their differing anharmonicities. The source of the latter in the quartic and cubic force field is explored. MP2 calculations of valence interaction force constants involving the stretching of bonds on a common carbon atom are preferred to those from a B3LYP model. In either model, scaling to ωobsd rather than to νobsd does not remove the necessity of varying scale factors for differing types of motion in the same group. Theoretical values of the five quartic centrifugal distortion constants are listed for the normal species and compared with new experimental data. The predictions are sufficiently good to be useful in fitting pure rotational transitions. A weakness is identified in the current Gaussian 03 code for the calculation of vibration−rotation quantities, and limitations are noted in the manner in which Fermi resonance is handled.


American Chemical Society

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Journal of Physical Chemistry A


Chemistry and Biochemistry

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