Electronic structure and local environment of substitutional V3+ in grossular garnet Ca3Al2(SiO4)3: K-edge X-ray absorption spectroscopy and first-principles modeling - CNRS - Centre national de la recherche scientifique Accéder directement au contenu
Article Dans Une Revue The American Mineralogist Année : 2010

Electronic structure and local environment of substitutional V3+ in grossular garnet Ca3Al2(SiO4)3: K-edge X-ray absorption spectroscopy and first-principles modeling

Résumé

The V K-edge spectrum of a V-bearing grossular garnet (tsavorite) single crystal has been measured by high-energy resolution fluorescence detected X-ray absorption spectroscopy (HERFD-XAS). First-principles calculations based on the density functional theory (DFT) reproduce the experimental spectra well, including the angular dependence of the pre-edge. The latter arises from pure electric quadrupole transitions since vanadium is incorporated in a centrosymmetric site, which inhibits the electric dipole transitions. An interpretation of the spectral features is given using a monoelectronic description of the transitions involved in the X-ray absorption process. The assignment of experimental pre-edge peaks in terms of 1s-3d transitions makes it possible to determine the magnitude of the 3d-splitting, which is similar to the 10 Dq crystal-field value determined from optical absorption spectroscopy. DFT calculations also indicate a full structural relaxation around V3+ substituting Al3+ in the garnet structure. The angular dependence only causes weak variations of the pre-edge intensity, which supports the use of V-bearing grossular garnet as a reference compound for octahedral V3+.
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Dates et versions

hal-00537425 , version 1 (18-11-2010)

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Amélie Bordage, Christian Brouder, Eetienne Balan, Delphine Cabaret, Amélie Juhin, et al.. Electronic structure and local environment of substitutional V3+ in grossular garnet Ca3Al2(SiO4)3: K-edge X-ray absorption spectroscopy and first-principles modeling. The American Mineralogist, 2010, 95 (8-9), pp.1161-1171. ⟨10.2138/am.2010.3432⟩. ⟨hal-00537425⟩
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