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P. A. van Aken, T. H?che, F. Heyroth, R. Keding, R. Uecker
Insights into oxygen-cation bonding in fresnoite-type structures from OK- and Ti L-23-electron energy-loss spectra and ab initio calculations of the electronic structure
Phys. Chem. Minerals 31, 8 (2004), 543-552

O K- and Ti L-23-core-loss spectra of fresnoite Ba2TiSi2O8 (BTS) and Sr2TiSi2O8 (STS), which is isotypic to BTS, have been measured by electron energy-loss spectroscopy (EELS). The energy-loss near-edge structures (ELNES) of the O K edge have been identified on the basis of theoretical simulations and interpretations of the X-ray absorption near-edge structures (XANES), which have been modelled in the framework of self-consistent full multiple-scattering (FMS) theory using FEFF8. Herewith, the K-absorption spectra of oxygen mu(E) and the local partial electron density of states (DOS) of all atoms have been calculated. For BTS, the observed spectral features in the O K-edge spectra are interpreted in terms of mixing between the central O p and neighbouring Ba 5d and 4f, Si 3p and 3d, and Ti 3d orbitals. The observed differences in the O K-edge spectra for STS and BTS can mainly be attributed to three properties: (1) The lack of high local partial Sr unoccupied DOS with 4f symmetry near the Fermi level compared to the high Ba 4f unoccupied DOS results in differences of overlapping O 2p cation orbitals. (2) The differences in the ionic radii of Sr and Ba result in a larger unit cell for BTS and, thus, in larger oxygen-cation bonding distances. (3) In comparison to STS, the strength of the incommensurate 2-D structural modulation is significantly weaker in BTS, i.e. distortions of coordination polyhedra occur to a much lesser extent. All these effects alter the oxygen-cation hybridization and, hence, result in a variation of the O 1s --> p transition and consequently of the O K-edge spectral shape. The observed peak broadening in Ti L-23 ELNES of STS compared to BTS is correlated with strong displacive modulations hosted in STS.

Keywords: Fresnoite, Ab initio full multiple-scattering calculations, PDOS calculations, Incommensurate 2-D structural modulation, EELS
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