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Crucial Role of Site Disorder and Frustration in Unusual Magnetic Properties of Quasi-2D Triangular Lattice Antimonate Na4FeSbO6

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Abstract

The effect of antisite disorder in the layered sodium iron antimonate Na4FeSbO6 was examined both experimentally and theoretically. The magnetic susceptibility and specific heat measurements show that Na4FeSbO6 does not undergo a long-range antiferromagnetic order, unlike its structural analog Li4FeSbO6. The electron spin resonance yields the complicated picture of coexistence of two magnetic subsystems corresponding to two different Fe cation positions in the lattice (regular and antisite) and driving the magnetic properties of the Na4FeSbO6. This conclusion found perfect confirmation from both the Mössbauer and X-ray absorption data which show the presence of two kinds of Fe3+ ions being in high-spin Fe3+ (S = 5/2) and low-spin Fe3+ (S = 1/2) states. These findings arise from the antisite disorder between the Fe3+ and Sb5+ ions in the (NaFeSbO6)3− layers of Na4FeSbO6. Our density functional calculations show that the Fe3+ ions located at the Sb5+ sites exist as low-spin Fe3+ ions, and that the spins of each Fe3+ (S = 5/2)–Fe3+ (S = 1/2)–Fe3+ (S = 5/2) trimer generated by the antisite disorder has a ferrimagnetic arrangement Fe3+↑–Fe3+↓–Fe3+↑, which enhances the magnetization of Na4FeSbO6 and leads to an apparently positive Curie–Weiss temperature.

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Acknowledgments

E.A.Z. and V.B.N. appreciate support from the Russian Foundation for Basic Research (grants 14-02-00245, 11-03-01101). J.-Y.L. acknowledges support from MOE-ATU and National Science Council of Taiwan under Grant No. NSC98-2112-009-005-MY3. The work at NCSU was supported by the computing resources of the NERSC Center and the HPC Center of NCSU.

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Authors and Affiliations

  1. Faculty of Physics, Moscow State University, 119991, Moscow, Russia

    Elena A. Zvereva, Tatyana V. Frantsuzenko, Olga A. Savelieva & Alexander N. Vasiliev

  2. Chemistry Faculty, Moscow State University, 119991, Moscow, Russia

    Igor A. Presniakov & Alexey V. Sobolev

  3. Department of Chemistry, North Carolina State University, Raleigh, NC, 27695-8204, USA

    Myung-Hwan Whangbo

  4. Department of Chemistry and Research Institute for Basic Sciences, Kyung Hee University, Seoul, 130-701, Republic of Korea

    Hyun-Joo Koo

  5. Chemistry Faculty, Southern Federal University, Rostov-on-Don, 344090, Russia

    Vladimir B. Nalbandyan

  6. Institute of Physics, National Chiao Tung University, Hsinchu, 30010, Taiwan

    Pei-Shan Shih, Jen-Che Chiang & Jiunn-Yuan Lin

  7. National Synchrotron Radiation Research Center, Hsinchu, 30076, Taiwan

    Jenn-Min Lee & Jin-Ming Chen

  8. Leibniz Institute for Solid State and Materials Research IFW Dresden, Dresden, 01069, Germany

    Elena A. Zvereva & Bernd Büchner

  9. Theoretical Physics and Applied Mathematics Department, Ural Federal University, 620002, Ekaterinburg, Russia

    Alexander N. Vasiliev

  10. National University of Science and Technology “MISiS”, Moscow, 119049, Russia

    Alexander N. Vasiliev

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  1. Elena A. Zvereva
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Correspondence to Elena A. Zvereva.

Appendix

Appendix

See Figs. 13, 14, 15, 16, 17 and Tables 4, 5, 6, 7.

Fig. 13
figure 13

Temperature dependence of the inverse magnetic susceptibility corrected by temperature-independent term χ d under variation of χ d value

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Fig. 14
figure 14

Distribution functions of the quadrupole splitting p(Δ) (circles) and the isomer shift p(δ) (triangles)

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Fig. 15
figure 15

Energy vs. 10Dq for various spin states with J H = 0.7 eV

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Fig. 16
figure 16

Energy vs. 10Dq for various spin states with J H = 0.8 eV

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Fig. 17
figure 17

Unit cell of the (NaFeSbO6)3− layer containing the antisite defects between Fe3+ and Sb5+ ions. The blue circles represent the Fe3+ ions, the cyan circles the Sb5+ ions, the yellow circles the Na atoms, and white circles the O atoms. The oxygen atoms numbered 1–20 are used to specify the Fe–O bond lengths and their magnetic moments. Note that the Fe(1) atom is located at an Sb5+ ion site (color figure online)

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Table 4 Atomic coordinates for the two structural models of Na4FeSbO6
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Table 5 Principal interatomic distances (Å) for the models listed in Table 4 in comparison with sums of ionic radii [33]
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Table 6 Fe–O bond distances (in Å) of the four different FeO6 octahedra in the relaxed structure of Na4FeSbO6 obtained from the DFT + U calculations for its FM state
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Table 7 Magnetic moments (in µ B) on the Fe and O atoms of the four different FeO6 octahedra in the relaxed structure of Na4FeSbO6 obtained from DFT + U calculations for its FM state
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Zvereva, E.A., Presniakov, I.A., Whangbo, MH. et al. Crucial Role of Site Disorder and Frustration in Unusual Magnetic Properties of Quasi-2D Triangular Lattice Antimonate Na4FeSbO6 . Appl Magn Reson 46, 1121–1145 (2015). https://doi.org/10.1007/s00723-015-0700-5

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