Polarization IR spectra of the hydrogen bond in 1-naphthylacetic and 2-naphthylacetic acid crystals: H/D isotopic effects. Temperature and polarization effects

This paper deals with experimental studies and with the quantitative interpretation of the polarized IR crystalline spectra of 1-naphthylacetic and 2-naphthylacetic acid. The spectra were measured in the nO–H and in the nO–D band frequency ranges, at the temperatures of 298 and 77 K. The intensity distribution in the bands was quantitatively reproduced on the basis of the strong-coupling model, when assuming that the isolated (COOH)2 and (COOD)2 cycles were the source of the spectral properties of the crystals. Such approach appeared to be sufficient for explaining most of the isotopic and the temperature effects in the spectra. A vibronic mechanism, promoting the symmetry forbidden transition in the IR, for the totally symmetric proton stretching vibrations in centrosymmetric hydrogen bond dimers, was found to be of a considerably minor importance, when compared with analogous spectral properties of arylcarboxylic acid crystals. Also no Fermi resonance impact on the nO–H band shape was identified in the 1-naphthylacetic and 2-naphthylacetic acid crystal spectra. These effects were ascribed to weakening of electronic couplings between the hydrogen bonds and the phenyl rings, due to the separation of these molecular fragments by methylene groups in 1-naphthylacetic and 2-naphthylacetic acid molecules. q 2004 Elsevier B.V. All rights reserved