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Title: Crystal Structure, Optical Properties, and Electronic Structure of Calcium Strontium Tungsten Oxynitrides CaxSr1-xWO2N
Authors: Yashima, M
Fumi, U
Nakano, H
Omoto, K
Hester, JR
Keywords: Magnetic properties
Neutron diffraction
Issue Date: 12-Sep-2013
Publisher: American Chemical Society
Citation: Yashima, M., Fumi, U., Nakano, H., Omoto, K., & Hester, J. R. (2013). Crystal structure, optical properties, and electronic structure of calcium strontium tungsten oxynitrides CaxSr1-xWO2N. Journal of Physical Chemistry C, 117(36), 18529-18539. doi:10.1021/jp405597x
Abstract: Novel calcium strontium tungsten oxynitrides CaxSr(1-x)WO(2)N (x = 0.25 and 0.5) have been synthesized. The crystal and electronic structures, electron-density distribution, and optical properties of CaxSr(1-x)WO(2)N and CaxSr(1-x)WO(2)N (x = 0, 0.25, and 0.5) have been investigated by neutron, synchrotron, and X-ray powder diffraction; transmission electron microscopy energy-dispersive spectroscopy (TEMEDS); scanning electron microscopy; UV visible reflectance measurements; and ab initio density functional theory (DFT)based calculations. Precursor materials CaxSr(1-x)WO(2)N (x = 0, 0.25, 0.5, and 1) with a scheelite-type structure were prepared by solid-state reactions, and heated at 900 degrees C for 5 h under an ammonia flow. The main phase in the product for the composition x = 1 was metallic tungsten W, whereas cubic Pm3m perovskite-type oxynitrides CaxSr(1-x)WO(2)N were obtained for the compositions x = 0, 0.25, and 0.5. The unit-cell parameter a of the cubic perovskite-type CaxSr(1-x)WO(2)N obtained from the Rietveld analysis of synchrotron X-ray and neutron powder diffraction data decreases with an increase of Ca concentration x (0 < x < 0.5), which indicates the substitution of Ca for Sr. The existence of nitrogen in CaxSr(1-x)WO(2)N was confirmed by (I) the refined occupancy factor in the Rietveld analysis of neutron data and (2) EDS. The maximum-entropy-method electron-density analysis combined with the DFT calculations indicates W N and W-O covalent bonds in CaxSr1_xWO2N, which are formed by the overlapping of W 5d and anion 2p orbitals. The minimum electron density at the W N bond is higher than that at the W-0 one, which indicates that the W N bond is more covalent due to the smaller difference in the electronegativity between W and N atoms compared to the W and O ones: The oxidation number of W in CaxSr(1-x)WO(2)N was estimated to be 5.2 by bond valence sum, which indicates the W5+ ion with the 5di electron configuration. Precursor oxides Ca Sr,,WO, with W6* having the 5cl electron configuration are white and insulating, whereas the CaxSr(1-x)WO(2)N oxynitrides with the W5* ion having the 5di configuration are black and exhibit metallic character. These results indicate the insulator metal transition from the d oxide CaxSr(1-x)WO(2)N to the di oxynitride CaxSr(1-x)WO(2)N. © 2013, American Chemical Society.
Gov't Doc #: 5439
ISSN: 1932-7447
Appears in Collections:Journal Articles

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