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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
-
Amélie Bordage
,
Christian Brouder
Veröffentlicht/Copyright:
2. April 2015
Abstract
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). Firstprinciples 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+.
Keywords: Vanadium; garnet; HERFD-XAS; DFT calculations; K pre-edge; angular dependence; structural relaxation; crystal-field splitting
Received: 2009-10-23
Accepted: 2010-3-24
Published Online: 2015-4-2
Published in Print: 2010-8-1
© 2015 by Walter de Gruyter Berlin/Boston
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Schlagwörter für diesen Artikel
Vanadium;
garnet;
HERFD-XAS;
DFT calculations;
K pre-edge;
angular dependence;
structural relaxation;
crystal-field splitting
Artikel in diesem Heft
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- Uranyl phosphate sheet reconstruction during dehydration of metatorbernite [Cu(UO2)2(PO4)2·8H2O]
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- Elbrusite-(Zr)—A new uranian garnet from the Upper Chegem caldera, Kabardino-Balkaria, Northern Caucasus, Russia
- What drives the distribution in nature of 3T vs. 2M1 polytype in muscovites and phengites? A general assessment based on new data from metamorphic and igneous granitoid rocks
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