Calculated vibration spectrum of calcium hexahydroxodizincate dihydrate (qatranaite).

On the basis of first-principles electronic structure calculations, crystallographic parameters have been refined for calcium hydroxozincate (Qatranaite mineral), and the vibration properties (frequencies and eigenvectors) calculated. A detailed analysis of vibration modes is done, in the context of comparison with infrared and Raman spectra previously available. Special attention is paid to a posteriori symmetry analysis of vibration modes, discussing the latters' attribution to four irreducible representations of the P 2 1 / c space group, and to identifying stretchings and bendings of particular chemical bonds, pronounced in different vibrations. It turns out that high-frequency (> 700 cm−1) vibrations of hydroxyl groups bridging the Ca or Zn cations differ quite considerably for crystallographically distinct hydroxyl positions. It is shown that the vibrations involving hydroxyl groups and crystalline water typically come about in quadruplets at very close frequencies, whereby different irreducible representations reflect different combinations of similar "molecular" vibrations of four identical entities (of each hydroxyl or water) present in the unit cell. However, some vibrations show exceptions from this rule. In addition to interpretation of earlier experimental investigations, our study indicates that the low-frequency (< 700 cm−1) vibrations within the cation–hydroxyl connected skeleton are of more "solid-state-like" character and cannot be reasonably interpreted in terms of "molecular" vibrations within ZnO 4 or CaO 6 units. [Display omitted] • Projection of vibration eigenvectors according to different criteria is suggested. • Contributions from different stretchings and bendings are naturally identified. • Molecular-type vibrations make almost degenerate symmetry-constrained combinations. • Vibrations throughout metal-oxygen cages make a dense quasi-continuous spectrum. [ABSTRACT FROM AUTHOR]