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  Three Oxidation States of Manganese in the Barium Hexaferrite BaFe12-xMnxO19

Nemrava, S., Vinnik, D. A., Hu, Z., Valldor, M., Kuo, C.-Y., Zherebtsov, D. A., et al. (2017). Three Oxidation States of Manganese in the Barium Hexaferrite BaFe12-xMnxO19. Inorganic Chemistry, 56(7), 3861-3866. doi:10.1021/acs.inorgchem.6b02688.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-002D-3F8B-3 Version Permalink: http://hdl.handle.net/11858/00-001M-0000-002D-C6E8-8
Genre: Journal Article

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 Creators:
Nemrava, Sandra1, Author
Vinnik, Denis A.1, Author
Hu, Zhiwei2, Author              
Valldor, Martin3, Author              
Kuo, Chang-Yang4, Author              
Zherebtsov, Dmitry A.1, Author
Gudkova, Svetlana A.1, Author
Chen, Chien-Te1, Author
Tjeng, Liu Hao5, Author              
Niewa, Rainer1, Author
Affiliations:
1External Organizations, ou_persistent22              
2Zhiwei Hu, Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863461              
3Martin Valldor, Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863454              
4Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863445              
5Liu Hao Tjeng, Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863452              

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 Abstract: The coexistence of three valence states of Mn ions, namely, +2, +3, and +4, in substituted magnetoplumbite-type BaFe12xMnxO19 was observed by soft X-ray absorption spectroscopy at the Mn-L-2,L-3 edge. We infer that the occurrence of multiple valence states of Mn situated in the pristine purely iron(III) compound BaFe12O19 is made possible by the fact that the charge disproportionation of Mn3+ into Mn2+ and Mn4+ requires less energy than that of Fe3+ into Fe2+ and Fe4+, related to the smaller effective Coulomb interaction of Mn3+ (d(4)) compared to Fe3+ (d(5)). The different chemical environments determine the location of the differently charged ions: with Mn3+ occupying positions with (distorted) octahedral local symmetry, Mn4+ ions prefer octahedrally coordinated sites in order to optimize their covalent bonding. Larger and more ionic bonded Mn2+ ions with a spherical charge distribution accumulate at tetrahedrally coordinated sites. Simulations of the experimental Mn-L-2,L-3 XAS spectra of two different samples with x = 1.5 and x = 1.7 led to Mn2+:Mn3+:Mn4+ atomic ratios of 0.16:0.51:0.33 and 0.19:0.57:0.24.

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Language(s): eng - English
 Dates: 2017-03-142017-03-14
 Publication Status: Published in print
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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 56 (7) Sequence Number: - Start / End Page: 3861 - 3866 Identifier: ISSN: 0020-1669
CoNE: /journals/resource/0020-1669