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• W2071583362 abstract "Infrared spectra of metal(II) selenate hydrates (MeSeO4·nH2O and Na2Me(SeO4)2·2H2O; n=6, 5, 4, 1; Me=Mg, Mn, Co, Ni, Cu, Zn, Cd) containing matrix-isolated SO42− guest ions are reported and discussed with respect to the SO stretching modes ν3 and ν1. An adequate measure for the SO42− guest ion distortion is the site group splitting Δνas (Δνab and Δνac in the case of a doublet and a triplet for ν3, respectively; a, being the highest wavenumbered component of ν3) and Δνmax (the difference between the highest and the lowest wavenumbered SO stretching modes). It has been shown that the SO42− guest ion distortion depends on both the number of the sulfate oxygen atoms involved in coordinative bonds with the metal(II) ions and the electronic configuration of the metal(II) ions, i.e. their crystal field stabilization energy (CFSE) additionally to the site symmetry and the local potential at the lattice site of the host lattice. The SO42− guest ions matrix-isolated in MeSeO4·H2O (Me=Mn, Co, Zn) and in Na2Me(SeO4)2·2H2O (Me=Mn, Cu, Cd) exhibit three bands corresponding to the ν3 modes as deduced from the site group analysis and Δνab≅Δνbc. When SO42− guest ions are incorporated in the triclinic Na2Me(SeO4)2·2H2O host lattices (Me=Co, Ni, Zn) the ν3 stretching region resembles a higher local symmetry of the SO42− guest ions (an approximate (A1⊕E) splitting) than the crystallographic one (i.e. Δνab>Δνbc instead of Δνab≅Δνbc) and, hence, the ratio Δνab/Δνbc has to be taken into account (the higher value of the ratio Δνab/Δνbc, the weaker is the distortion of the SO42− guest ions). The SO42− guest ions incorporated in MeSeO4·nH2O (n=6, 5, 4) exhibit a higher local symmetry of the guest ions than that deduced from the site group analysis (D2d for the SO42− guest ions in MeSeO4·5H2O, MeSeO4·4H2O and in the monoclinic MeSeO4·6H2O host lattices and close to Td in the tetragonal MeSeO4·6H2O host lattices). The analysis of the infrared spectra of selenate host lattices containing SO42− guest ions reveals that the guest ions are stronger distorted when the adjacent metal(II) ions have CFSE≠0. These ions are more resistant to angular deformations of the MeO6-octahedra (i.e. changes in the OMeO bond angles), thus facilitating the SO42− guest ion distortion as compared to those having CFSE=0 which allow stronger angular deformations of the respective metal octahedra. Infrared spectra of kieserite-type compounds MeSeO4·H2O (Me=Mn, Co, Zn) containing matrix-isolated SO42− guest ions and Me′2+ guest ions different from those of the host ions (i.e. Me′SO4·H2O in MeSeO4·H2O) are also presented and discussed (double matrix-spectroscopy)." @default.
• W2071583362 created "2016-06-24" @default.
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• W2071583362 date "2004-08-01" @default.
• W2071583362 modified "2023-09-23" @default.
• W2071583362 title "Influence of the crystal field stabilization energy of metal(II) ions on the structural distortion of matrix-isolated SO42− guest ions in selenate matrices" @default.
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• W2071583362 doi "https://doi.org/10.1016/j.saa.2003.11.023" @default.
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