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Direct crystallographic evidence of charge ordering in the novel double perovskite mixed-valence (NaMn3)Mn4O12

Abstract : By means of high-resolution synchrotron X-ray powder diffraction measurements, we studied in detail the temperature-dependent crystal structure of the mixed-valence manganese oxide, (NaMn3)Mn4O12. At 176 K, we observed a static ordering of the Jahn-Teller distortion of the Mn^3+O6 octahedra that drives a cubic-monoclinic structural transition concomitant to the Mn^3+-Mn^4+ charge ordering of the octahedral B-sites of the double-perovskite structure AA'3B4O12. This transition is followed by a CE-type magnetic ordering of these sites at 125K and by an independent antiferromagnetic ordering of the Mn A' sites at 90 K. Remarkably, both neutron [1] and X-ray data show that the charge ordering is intrinsic to the low symmetry phase, resulting in the setting up of two distinct MnO6 octahedra with very different average Mn-O distances. A bond valence sum analysis shows that these two Mn sites exactly correspond to 3+ and 4+ formal valence states. This direct evidence of charge disproportionation has never been reported in half-doped manganites, where charge order has been believed to occur only from controversial analysis of structural modulations.
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https://hal-insu.archives-ouvertes.fr/insu-00356449
Contributor : Béatrice Pibaret-Bourdon <>
Submitted on : Tuesday, January 27, 2009 - 3:09:20 PM
Last modification on : Friday, July 10, 2020 - 7:58:31 AM

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  • HAL Id : insu-00356449, version 1

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A. Prodi, B. Schmitt, F. Gozzo, Q. Huang, J. W. Lynn, et al.. Direct crystallographic evidence of charge ordering in the novel double perovskite mixed-valence (NaMn3)Mn4O12. APS March Meeting, 2005, Los Angeles, United States. ⟨insu-00356449⟩

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