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

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

Type de publication:

Journal Article

Source:

American Mineralogist, Volume 95, Ticket 8-9, p.1161-1171 (2010)

ISBN:

0003-004X

Numéro d'accès:

ISI:000281220900005

URL:

http://ammin.geoscienceworld.org/content/95/8-9/1161

Mots-clés:

UMR 7154 ; Minéralogie ; N° Contribution : 2608

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+.

Notes:

Bordage, Amélie Brouder, Christian Balan, Etienne Cabaret, Delphine Juhin, Amélie Arrio, Marie-Anne Sainctavit, Philippe Calas, Georges Glatzel, Pieter