Vibrational spectra and dispersion analysis of K2Ni(SeO4)2·6H2O Tutton salt single crystal doped with K2Ni(SO4)2·6H2O

Abstract

Dispersion analysis of the polarized IR reflectance spectra of K2Ni(SeO4)2·6H2O doped with K2Ni(SO4)2·6H2O has been performed. Vibrational parameters like oscillator strength, attenuation constant and frequency of the transversal phonons for the modes of Au symmetry type plus the orientation of the transition dipole moments for the modes of Bu symmetry type in the ac crystal plane have been obtained. The spectra-structure correlation of the H2O stretching vibrations show that bands appearing in the spectra for polarization of the external radiation oriented along the b axis are mainly due to the H2O stretching vibrations of one of the three crystallographically distinct sets of water molecules. The orientation of the transition dipoles of stretching vibrations of the selenate ion differ from the characteristic spectra of the sulfate analog in that no mutually perpendicular transition dipoles are found in the ac crystal plane. Water librational bands masked with the bands of the ν4(SO4(2-)) mode in the sulfate analog have now been unveiled and assigned. The ratio between the oscillator strength and the attenuation constant appears to be a helpful tool in the assignment of the sulfate stretching vibrations and water librations. The vibrational and orientational characteristics of the ν4(SeO4(2-)) modes were obtained. Тhe ν3(SO4(2-)) frequency region of the isomorphously isolated SO4(2-) ion in the K2Ni(SeO4)2·6H2O matrix was investigated in some detail. Contrary to the expected three, four bands can be identified. Three of them were assigned to ν3(SO4(2-)) based on the orientation of the transition dipole moments. On the basis of the IR, but also Raman spectra of the pure and mixed crystals, a discussion of the influence of the potential field and the hydrogen bonds with the change in the volume of the unit cell is given.