The effect of intermolecular forces upon the vibrations of molecules in the crystalline state I. The out-of-plane bending of the carbonate ion in aragonite minerals

Abstract

The infra-red absorption of polycrystalline BaCO 3 , SrCO 3 , and CaCO 3 , the latter in both the aragonite and calcite modifications, has been measured in the region 600 to 2000 cm -1 . Absolute intensities were determined for each of the three fundamental bands of the carbonate ion, by the method of extrapolation to infinite dilution of the carbonate in the alkali halide matrix. The band due to the out-of-plane bending mode was examined under high resolution, the samples employed having been enriched to a 50/50 ratio of 12 C/ 13 C. Intermolecular coupling in this band, which is revealed by the isotopic solid solution, has been interpreted as arising primarily from interaction of the dipoles produced during the vibration. The dipole derivatives calculated from this coupling agree fairly well with those estimated from the absolute intensities. Various sources of error are discussed, and in particular, an estimate is made of the dipole-dipole energy summed over the entire lattice, instead of merely for nearest neighbours. The carbon-oxygen bond moment during the vibration has an effective value of from 1.3 to 1.7 debyes.