Influence of the crystal field stabilization energy of metal(II) ions on the structural distortion of matrix-isolated SO4(2-) guest ions in selenate matrices

Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy
D Stoilova

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 3 and 1. An adequate measure for the SO42- guest ion distortion is the site group splitting deltanuas (deltanuab and deltanuac in the case of a doublet and a triplet for 3, respectively; a, being the highest wavenumbered component of nu3) and deltanumax (the difference between the highest and the lowest wave numbered 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 nu3 modes as deduced from the site group analysis and deltanuab approximately equal to deltanubc. When SO42- guest ions are incorporated in the...Continue Reading

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