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The high temperature structural behaviour of the uranium perovskites Ba2CaUO6 and BaSrCaUO6 has been investigated using a combination of synchrotron X-ray and neutron powder diffraction. Ba2CaUO6 undergoes a complex sequence of structures associated with the progressive loss of cooperative octahedral tilting: P21/n → I2/m → I2/m → I4/m → Fm3[combining macron]m. The observation of the intermediate tetragonal structure, I4/m, in this, contrasts with the previously reported rhombohedral R3[combining macron] intermediate formed by the Ba2SrUO6 oxide. The importance of π-bonding in determining the structural sequence is discussed.
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Reynolds et al. (2015) studied this question.
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