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|Title: ||Structural studies of the rhombohedral and orthorhombic monouranates: CaUO4, α-SrUO4, β-SrUO4 and BaUO4|
|Authors: ||Murphy, G|
|Keywords: ||Trigonal lattices|
|Issue Date: ||1-May-2016|
|Publisher: ||Elsevier B.V.|
|Citation: ||Murphy, G., Kennedy, B. J., Johannessen, B., Kimpton, J. A., Avdeev, M., Griffith, C. S., Thorogood, G. J., & Zhang, Z. (2016). Structural studies of the rhombohedral and orthorhombic monouranates: CaUO 4, α-SrUO 4, β-SrUO 4 and BaUO 4. Journal of Solid State Chemistry, 237, 86-92. doi:/10.1016/j.jssc.2016.01.019|
|Abstract: ||The structures of some AUO4 (A=Ca, Sr, or Ba) oxides have been determined using a combination of neutron and synchrotron X-ray diffraction, supported by X-ray absorption spectroscopic measurements at the U L3-edge. The smaller Ca cation favours a rhombohedral AUO4 structure with 8-coordinate UO8 moieties whilst an orthorhombic structure based on UO6 groups is found for BaUO4. Both the rhombohedral and orthorhombic structures can be stabilised for SrUO4. The structural studies suggest that the bonding requirements of the A site cation play a significant role in determining which structure is favoured. In the rhombohedral structure, Bond Valence Sums demonstrate the A site is invariably overbonded, which, in the case of rhombohedral α-SrUO4, is compensated for by the formation of vacancies in the oxygen sub-lattice. The uranium cation, with its flexible oxidation state, is able to accommodate this by inducing vacancies along its equatorial coordination site as demonstrated by neutron powder diffraction. © 2016 Elsevier Inc.|
|Appears in Collections:||Journal Articles|
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