Confinement effects on C–H and C–F stretching vibrational frequencies of difluoromethane in cold inert gas matrixes: a combined infrared spectroscopy and electronic structure theory study

Abstract

Mid-infrared spectra of difluoromethane (DFM) have been recorded by confining the molecule in the matrix cages of pure argon, nitrogen and in the mixed matrixes of argon and nitrogen obtained by mixing the two gases in definite proportions. The measured spectra depict distinct confinement effects in terms of the infrared spectral shifts of the C–H and C–F stretching vibrational fundamentals as compared to the free molecules in the gas-phase, and also some remarkable changes in band appearances and relative intensities. The signs of the spectral shifts are observed to be different for the $$\upnu _{\text {C--H}}$$ and $$\upnu _{\text {C--F}}$$ transitions. Pronounced blue shifts are observed for the two $$\upnu _{\text {C--H}}$$ modes in pure nitrogen matrix, which progressively reduce in magnitude in the mixed matrixes, and is least in the pure argon matrix. On the other hand, distinct red shifts of the $$\upnu _{\text {C--F}}$$ vibrations are evident in pure nitrogen matrix, which are reduced in magnitude in the mixed matrixes, and become even less pronounced in pure argon matrix. The effect of Fermi resonances in the $$\upnu _{\text {C--H}}$$ region, that has motivated several previous investigations of DFM including high resolution gas phase studies, becomes explicit upon comparison of the matrix isolation spectrum with the gas phase spectrum. Electronic structure calculations using several DFT and DFT-D methods, in conjunction with NBO analysis, have been carried out for various sizes of $$\hbox {DFM-N}_{2}$$ and DFM-Ar complexes in order to understand the underlying interactions responsible for the observed shifts. The calculations are found to satisfactorily reproduce the observed variations in magnitude and direction of the shifts of both the $$\upnu _{\text {C--H}}$$ and $$\upnu _{\text {C--F}}$$ transitions for the change of the medium. It is inferred that the inert gas matrix environment exerts an electronic re-organization within the DFM molecule, and the consequent rehybridization of the carbon-centric hybrid orbital of the C–H and C–F bonds is responsible for the observed spectral shifts.