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Spectroscopic properties of \(\hbox {Cr}^{3+}\) in the spinel solid solution \(\hbox {ZnAl}_{2-x}\hbox {Cr}_{x}\hbox {O}_4\)

Abstract

The evolution of the structural environment of \(\hbox {Cr}{^{3+}}\) along the solid solution \(\hbox {ZnAl}_{2-x}\hbox {Cr}_{x}\hbox {O}_4\) has been investigated using a multi-analytical approach. X-ray diffraction confirms that the system follows Vegard’s law. Diffuse reflectance spectra show a decrease of the crystal field parameter with the Cr content, usually related to the increase of the Cr–O bond length in a point charge model. This interpretation is discussed and compared to the data obtained by first-principle calculations based on density functional theory. X-ray absorption near edge structure spectra at the Cr K-edge show a pronounced evolution in the pre-edge with the Cr content, characterised by the appearance of a third feature. Calculations enable to assign the origin of this feature to Cr neighbours. The colour change from pink to brownish pink and eventually green along the solid solution has also been quantified by calculating the L*, a*, b* and x, y coefficients in the system defined by the International Commission on Illumination.

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Acknowledgments

This work was supported by the Réseau Francilien sur les oxydes fonctionnels (DIM Oxymore) and the Région Ile-de-France. We acknowledge the European Synchrotron Radiation Facility for provision of synchrotron radiation facilities at beamline ID21, through the proposal HG43. The calculations were partly performed using HPC resources from GENCI-IDRIS (100172-2015). L.V. acknowledges M. Chassé for his help with the chromaticity parameters and fruitful discussions. E.R. gratefully acknowledges the support of the Postdoctoral Fellowship of the Hungarian Academy of Sciences, the European Research Council (ERC Starting Grant No. 259709), and the French-Hungarian Balaton-TéT bilateral research program (Project No. TET_11_FR-XTHEOEXP) as well.

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Correspondence to Laurent Cormier.

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Verger, L., Dargaud, O., Rousse, G. et al. Spectroscopic properties of \(\hbox {Cr}^{3+}\) in the spinel solid solution \(\hbox {ZnAl}_{2-x}\hbox {Cr}_{x}\hbox {O}_4\) . Phys Chem Minerals 43, 33–42 (2016). https://doi.org/10.1007/s00269-015-0771-8

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Keywords

  • \(\hbox {Cr}{^{3+}}\)
  • Spinel
  • XANES
  • Optical spectroscopy
  • DFT
  • Pre-edge
  • Solid solution
  • Cr-K edge