The Journal of Physical Chemistry A · 2011 · 29 citations · 28 references
Natural SciencesChemistryMaterials ScienceElectronic MaterialsSpectroscopic AnalysisSpectroscopyElectronic Band StructureElectronic SpectroscopyInorganic SpectroscopyX-ray CrystallographyX-ray Data AnalysisX-ray SpectroscopyAbsorbing StatesConcentrationNear-edge X-ray Absorption Fine Structure SpectroscopyX-ray Absorption Near Edge StructureX-ray Absorption SpectroscopyX-ray Emission Lines
The Fe K-edge X-ray absorption near-edge (XANES) spectra from Fe(1-x)Ga(x)SbO(4), having a rutile-like structure, have been investigated. Similar to the Ti K-edge XANES spectrum from TiO(2) (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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