Understanding Complex Interplay among Different Instabilities in Multiferroic BiMn<sub>7</sub>O<sub>12</sub> Using <sup>57</sup>Fe Probe Mössbauer Spectroscopy
Here, we report the results of a Mössbauer study on hyperfine electrical and magnetic interactions in quadruple perovskite BiMn<sub>7</sub>O<sub>12</sub> doped with <sup>57</sup>Fe probes. Measurements were performed in the temperature range of 10 K < <i>...
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MDPI AG
2024-01-01
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| author | Iana S. Soboleva Vladimir I. Nitsenko Alexey V. Sobolev Maria N. Smirnova Alexei A. Belik Igor A. Presniakov |
| author_facet | Iana S. Soboleva Vladimir I. Nitsenko Alexey V. Sobolev Maria N. Smirnova Alexei A. Belik Igor A. Presniakov |
| author_sort | Iana S. Soboleva |
| collection | DOAJ |
| description | Here, we report the results of a Mössbauer study on hyperfine electrical and magnetic interactions in quadruple perovskite BiMn<sub>7</sub>O<sub>12</sub> doped with <sup>57</sup>Fe probes. Measurements were performed in the temperature range of 10 K < <i>T</i> < 670 K, wherein BiMn<sub>6.96</sub><sup>57</sup>Fe<sub>0.04</sub>O<sub>12</sub> undergoes a cascade of structural (<i>T</i><sub>1</sub> ≈ 590 K, <i>T</i><sub>2</sub> ≈ 442 K, and <i>T</i><sub>3</sub> ≈ 240 K) and magnetic (<i>T</i><sub>N1</sub> ≈ 57 K, <i>T</i><sub>N2</sub> ≈ 50 K, and <i>T</i><sub>N3</sub> ≈ 24 K) phase transitions. The analysis of the electric field gradient (EFG) parameters, including the dipole contribution from Bi<sup>3+</sup> ions, confirmed the presence of the local dipole moments <i>p</i><sub>Bi</sub>, which are randomly oriented in the paraelectric cubic phase (<i>T</i> > <i>T</i><sub>1</sub>). The unusual behavior of the parameters of hyperfine interactions between <i>T</i><sub>1</sub> and <i>T</i><sub>2</sub> was attributed to the dynamic Jahn–Teller effect that leads to the softening of the orbital mode of Mn<sup>3+</sup> ions. The parameters of the hyperfine interactions of <sup>57</sup>Fe in the phases with non-zero spontaneous electrical polarization (<i>P</i><sub>s</sub>), including the <i>P</i>1 ↔ <i>Im</i> transition at <i>T</i><sub>3</sub>, were analyzed. On the basis of the structural data and the quadrupole splitting Δ(<i>T</i>) derived from the <sup>57</sup>Fe Mössbauer spectra, the algorithm, based on the Born effective charge model, is proposed to describe <i>P</i><sub>s</sub>(<i>T</i>) dependence. The <i>P</i><sub>s</sub>(<i>T</i>) dependence around the <i>Im</i> ↔ <i>I</i>2/<i>m</i> phase transition at <i>T</i><sub>2</sub> is analyzed using the effective field approach. Possible reasons for the complex relaxation behavior of the spectra in the magnetically ordered states (<i>T</i> < <i>T</i><sub>N1</sub>) are also discussed. |
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| spelling | doaj.art-a89e875ebcff47d28b0c53676a96f10b2024-02-09T15:13:14ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672024-01-01253143710.3390/ijms25031437Understanding Complex Interplay among Different Instabilities in Multiferroic BiMn<sub>7</sub>O<sub>12</sub> Using <sup>57</sup>Fe Probe Mössbauer SpectroscopyIana S. Soboleva0Vladimir I. Nitsenko1Alexey V. Sobolev2Maria N. Smirnova3Alexei A. Belik4Igor A. Presniakov5Department of Chemistry, Lomonosov Moscow State University, Moscow 119991, RussiaDepartment of Chemistry, Lomonosov Moscow State University, Moscow 119991, RussiaDepartment of Chemistry, Lomonosov Moscow State University, Moscow 119991, RussiaDepartment of Chemistry, Lomonosov Moscow State University, Moscow 119991, RussiaResearch Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), Namiki 1-1, Tsukuba 305-0044, Ibaraki, JapanDepartment of Chemistry, Lomonosov Moscow State University, Moscow 119991, RussiaHere, we report the results of a Mössbauer study on hyperfine electrical and magnetic interactions in quadruple perovskite BiMn<sub>7</sub>O<sub>12</sub> doped with <sup>57</sup>Fe probes. Measurements were performed in the temperature range of 10 K < <i>T</i> < 670 K, wherein BiMn<sub>6.96</sub><sup>57</sup>Fe<sub>0.04</sub>O<sub>12</sub> undergoes a cascade of structural (<i>T</i><sub>1</sub> ≈ 590 K, <i>T</i><sub>2</sub> ≈ 442 K, and <i>T</i><sub>3</sub> ≈ 240 K) and magnetic (<i>T</i><sub>N1</sub> ≈ 57 K, <i>T</i><sub>N2</sub> ≈ 50 K, and <i>T</i><sub>N3</sub> ≈ 24 K) phase transitions. The analysis of the electric field gradient (EFG) parameters, including the dipole contribution from Bi<sup>3+</sup> ions, confirmed the presence of the local dipole moments <i>p</i><sub>Bi</sub>, which are randomly oriented in the paraelectric cubic phase (<i>T</i> > <i>T</i><sub>1</sub>). The unusual behavior of the parameters of hyperfine interactions between <i>T</i><sub>1</sub> and <i>T</i><sub>2</sub> was attributed to the dynamic Jahn–Teller effect that leads to the softening of the orbital mode of Mn<sup>3+</sup> ions. The parameters of the hyperfine interactions of <sup>57</sup>Fe in the phases with non-zero spontaneous electrical polarization (<i>P</i><sub>s</sub>), including the <i>P</i>1 ↔ <i>Im</i> transition at <i>T</i><sub>3</sub>, were analyzed. On the basis of the structural data and the quadrupole splitting Δ(<i>T</i>) derived from the <sup>57</sup>Fe Mössbauer spectra, the algorithm, based on the Born effective charge model, is proposed to describe <i>P</i><sub>s</sub>(<i>T</i>) dependence. The <i>P</i><sub>s</sub>(<i>T</i>) dependence around the <i>Im</i> ↔ <i>I</i>2/<i>m</i> phase transition at <i>T</i><sub>2</sub> is analyzed using the effective field approach. Possible reasons for the complex relaxation behavior of the spectra in the magnetically ordered states (<i>T</i> < <i>T</i><sub>N1</sub>) are also discussed.https://www.mdpi.com/1422-0067/25/3/1437manganitesMössbauer spectroscopymultiferroicsJahn–Teller effect |
| spellingShingle | Iana S. Soboleva Vladimir I. Nitsenko Alexey V. Sobolev Maria N. Smirnova Alexei A. Belik Igor A. Presniakov Understanding Complex Interplay among Different Instabilities in Multiferroic BiMn<sub>7</sub>O<sub>12</sub> Using <sup>57</sup>Fe Probe Mössbauer Spectroscopy International Journal of Molecular Sciences manganites Mössbauer spectroscopy multiferroics Jahn–Teller effect |
| title | Understanding Complex Interplay among Different Instabilities in Multiferroic BiMn<sub>7</sub>O<sub>12</sub> Using <sup>57</sup>Fe Probe Mössbauer Spectroscopy |
| title_full | Understanding Complex Interplay among Different Instabilities in Multiferroic BiMn<sub>7</sub>O<sub>12</sub> Using <sup>57</sup>Fe Probe Mössbauer Spectroscopy |
| title_fullStr | Understanding Complex Interplay among Different Instabilities in Multiferroic BiMn<sub>7</sub>O<sub>12</sub> Using <sup>57</sup>Fe Probe Mössbauer Spectroscopy |
| title_full_unstemmed | Understanding Complex Interplay among Different Instabilities in Multiferroic BiMn<sub>7</sub>O<sub>12</sub> Using <sup>57</sup>Fe Probe Mössbauer Spectroscopy |
| title_short | Understanding Complex Interplay among Different Instabilities in Multiferroic BiMn<sub>7</sub>O<sub>12</sub> Using <sup>57</sup>Fe Probe Mössbauer Spectroscopy |
| title_sort | understanding complex interplay among different instabilities in multiferroic bimn sub 7 sub o sub 12 sub using sup 57 sup fe probe mossbauer spectroscopy |
| topic | manganites Mössbauer spectroscopy multiferroics Jahn–Teller effect |
| url | https://www.mdpi.com/1422-0067/25/3/1437 |
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