Ab initio study of the vibrational properties of acetic acid monomers and dimers

Abstract

The vibrational spectra of CH₃COOH, CH₃COOD, CD₃COOH and CD₃COOD, either monomeric or in two dimeric structures (centrosymmetric or side-on linear, with two bent hydrogen bonds), were studied by ab initio calculations at the DFT/B3LYP/6-31++G** level. The force field, the potential energy distribution and the derivatives of the electric dipole moment with respect to internal coordinates were analysed in addition to the vibration wavenumbers. A comprehensive discussion of the infrared intensities between 1150 and 1500 cm⁻¹ is made for the twelve structures studied. The calculated infrared intensities of monomers are in close agreement with the experimental spectra. In particular, the puzzling wavenumber increase that had been observed in argon matrices for the intense band assigned to the COH angle bending δCOH, by substituting OD for OH, is explained without invoking the previous hypothesis of the tunnelling of the H atom between the two O atoms. It is related to the decoupling of δCOH from a mode involving the stretching of the C–C and C–O bonds with opposite phases.