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Superstoichiometric Oxygen and Structural Instability of Ferrite CaBaFe4O7: ab Initio Approach

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Abstract

The pseudo-potential PAW method of the density functional theory is employed to study the localization of superstoichiometric oxygen in ferrite CaBaFe4O7 with the orthorhombic swedenborgite structure. The geometric characteristics of oxygen defects are determined by the crystal lattice relaxation procedure. It is shown that the formation of defects in calcium and barium coordination are energetically unfavorable. Oxygen intercalation into structural trigonal iron-oxygen and Kagomé layers is more favorable. In these layers, two edge-sharing Fe2O5 bipyramides are formed instead of FeO4 tetrahedra connected via one oxygen atom. The structural instability of ferrite CaBaFe4O7 is shown to be caused by the population of anti-bonding 2p O states during oxygen intercalation. The asymmetric location of the intercalated oxygen ion relative to the neighboring iron ions promotes the appearance of local electric polarization, which can induce ferroelectric effects in the presence of ferromagnetic order.

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Funding

The work was supported by the Russian Science Foundation (grant No. 22-19-00129).

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Authors and Affiliations

  1. Institute of Solid State Chemistry, Ural Branch, Russian Academy of Sciences, Ekaterinburg, Russia

    A. Yu. Suntsov, V. P. Zhukov & V. L. Kozhevnikov

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  1. A. Yu. Suntsov
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  2. V. P. Zhukov
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  3. V. L. Kozhevnikov
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Correspondence to A. Yu. Suntsov.

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Russian Text © The Author(s), 2024, published in Zhurnal Strukturnoi Khimii, 2024, Vol. 65, No. 1, 120093.https://doi.org/10.26902/JSC_id120093

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Suntsov, A.Y., Zhukov, V.P. & Kozhevnikov, V.L. Superstoichiometric Oxygen and Structural Instability of Ferrite CaBaFe4O7: ab Initio Approach. J Struct Chem 65, 36–47 (2024). https://doi.org/10.1134/S0022476624010049

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