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Investigation of the Fe K-edge XANES Spectra from Fe1−xGaxSbO4: Local versus Nonlocal Excitations

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Department of Chemistry, University of Saskatchewan, Saskatoon, Saskatchewan, Canada S7N 5C9
*E-mail [email protected]; phone (306) 966-4660; fax (306) 966-4730.
Cite this: J. Phys. Chem. A 2011, 115, 10, 1908–1912
Publication Date (Web):February 22, 2011
https://doi.org/10.1021/jp111520r
Copyright © 2011 American Chemical Society
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    Abstract

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    The Fe K-edge X-ray absorption near-edge (XANES) spectra from Fe1−xGaxSbO4, having a rutile-like structure, have been investigated. Similar to the Ti K-edge XANES spectrum from TiO2 (rutile), the low-energy pre-edge region observed in the Fe K-edge spectra is too broad to be representative of only a local, quadrupolar 1s → 3d excitation. The broadness of this peak results from the presence of a nonlocal transition, referred to as an intersite hybrid, which involves the excitation of 1s electrons to unoccupied 3d states of a next-nearest-neighbor Fe atom. (These 3d states overlap Fe 4p states of the absorbing atom through O 2p states.) With increasing Ga concentration, the intensity of the intersite hybrid peak decreases because of a deficiency of unoccupied next-nearest-neighbor 3d states. This observation provides important information on how the peak intensities of these nonlocal excitations are affected by substitution of the constituent elements.

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