期刊
INORGANIC CHEMISTRY
卷 56, 期 7, 页码 3861-3866出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.6b02688
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资金
- Ministry of Education and Science of the Russian Federation [4.1346.2017/PP]
- Act 211 Government of the Russian Federation [02.A03.21.0011]
- Russian Foundation for Basic Research [16-08-01043]
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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