Experimental Study of Magnetocaloric Effect in Tetraaquabis(Hydrogen Maleato)Nickel(II), [Ni(C<sub>4</sub>H<sub>3</sub>O<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]—A Potential Realization of a Spin-1 Spatially Anisotropic Square Lattice with Ferromagnetic Interactions
An experimental study of the magnetocaloric effect in tetraaquabis(hydrogen maleato)nickel(II), [Ni(C<sub>4</sub>H<sub>3</sub>O<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>] powder sample is presented. The magnetocaloric...
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MDPI AG
2022-09-01
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| Series: | Magnetochemistry |
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| Online Access: | https://www.mdpi.com/2312-7481/8/9/106 |
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| author | Petro Danylchenko Róbert Tarasenko Erik Čižmár Vladimír Tkáč Anna Uhrinová Alžbeta Orendáčová Martin Orendáč |
| author_facet | Petro Danylchenko Róbert Tarasenko Erik Čižmár Vladimír Tkáč Anna Uhrinová Alžbeta Orendáčová Martin Orendáč |
| author_sort | Petro Danylchenko |
| collection | DOAJ |
| description | An experimental study of the magnetocaloric effect in tetraaquabis(hydrogen maleato)nickel(II), [Ni(C<sub>4</sub>H<sub>3</sub>O<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>] powder sample is presented. The magnetocaloric properties of the studied sample were investigated using specific heat and magnetization measurements in magnetic fields up to 9 T in the temperature range from 0.4 to 50 K. A large conventional magnetocaloric effect was found at a temperature of about 3.5 K, where −Δ<i>S</i><sub>M</sub> = 8.5 Jkg<sup>−1</sup>K<sup>−1</sup> and 11.2 Jkg<sup>−1</sup>K<sup>−1</sup> for a magnetic field of 5 T and 7 T, respectively. Assuming a substantial role of the crystal field, the temperature dependence of the magnetic specific heat in a zero magnetic field was compared with an <i>S</i> = 1 model with single-ion anisotropy parameters <i>D</i> and <i>E</i> (axial and rhombic). The best agreement was found for the parameters <i>D</i>/<i>k</i><sub>B</sub> = −7.82 K and <i>E</i>/<i>k</i><sub>B</sub> = −2.15 K. On the other hand, the experimental temperature dependence of −Δ<i>S</i><sub>M</sub> shows higher values compared to the theoretical prediction for the mentioned model, indicating the presence of additional factors in the system, such as an exchange interaction between magnetic ions. The first exchange pathway can be realized through maleic rings between the nearest Ni(II) ions. The second exchange pathway can be realized through water molecules approximately along the <i>a</i> crystallographic axis. Broken-symmetry DFT calculations performed using the computational package ORCA provided the values of ferromagnetic exchange interactions, <i>J</i><sub>1</sub>/<i>k</i><sub>B</sub> = 1.50 K and <i>J</i><sub>2</sub>/<i>k</i><sub>B</sub> = 1.44 K (using B3LYP functional). The presence of such ferromagnetic correlations in the studied system may explain the enhanced magnetocaloric effect compared with the model of an anisotropic spin-1 paramagnet. |
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| last_indexed | 2024-03-09T23:20:48Z |
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| spelling | doaj.art-b561b526220a4036b815c5deb532cb4f2023-11-23T17:27:59ZengMDPI AGMagnetochemistry2312-74812022-09-018910610.3390/magnetochemistry8090106Experimental Study of Magnetocaloric Effect in Tetraaquabis(Hydrogen Maleato)Nickel(II), [Ni(C<sub>4</sub>H<sub>3</sub>O<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]—A Potential Realization of a Spin-1 Spatially Anisotropic Square Lattice with Ferromagnetic InteractionsPetro Danylchenko0Róbert Tarasenko1Erik Čižmár2Vladimír Tkáč3Anna Uhrinová4Alžbeta Orendáčová5Martin Orendáč6Institute of Physics, Faculty of Science, Pavol Jozef Šafárik University, Park Angelinum 9, 04154 Košice, SlovakiaInstitute of Physics, Faculty of Science, Pavol Jozef Šafárik University, Park Angelinum 9, 04154 Košice, SlovakiaInstitute of Physics, Faculty of Science, Pavol Jozef Šafárik University, Park Angelinum 9, 04154 Košice, SlovakiaInstitute of Physics, Faculty of Science, Pavol Jozef Šafárik University, Park Angelinum 9, 04154 Košice, SlovakiaDepartment of Chemistry, Biochemistry, and Biophysics, Institute of Pharmaceutical Chemistry, University of Veterinary Medicine and Pharmacy, Komenského 73, 04181 Košice, SlovakiaInstitute of Physics, Faculty of Science, Pavol Jozef Šafárik University, Park Angelinum 9, 04154 Košice, SlovakiaInstitute of Physics, Faculty of Science, Pavol Jozef Šafárik University, Park Angelinum 9, 04154 Košice, SlovakiaAn experimental study of the magnetocaloric effect in tetraaquabis(hydrogen maleato)nickel(II), [Ni(C<sub>4</sub>H<sub>3</sub>O<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>] powder sample is presented. The magnetocaloric properties of the studied sample were investigated using specific heat and magnetization measurements in magnetic fields up to 9 T in the temperature range from 0.4 to 50 K. A large conventional magnetocaloric effect was found at a temperature of about 3.5 K, where −Δ<i>S</i><sub>M</sub> = 8.5 Jkg<sup>−1</sup>K<sup>−1</sup> and 11.2 Jkg<sup>−1</sup>K<sup>−1</sup> for a magnetic field of 5 T and 7 T, respectively. Assuming a substantial role of the crystal field, the temperature dependence of the magnetic specific heat in a zero magnetic field was compared with an <i>S</i> = 1 model with single-ion anisotropy parameters <i>D</i> and <i>E</i> (axial and rhombic). The best agreement was found for the parameters <i>D</i>/<i>k</i><sub>B</sub> = −7.82 K and <i>E</i>/<i>k</i><sub>B</sub> = −2.15 K. On the other hand, the experimental temperature dependence of −Δ<i>S</i><sub>M</sub> shows higher values compared to the theoretical prediction for the mentioned model, indicating the presence of additional factors in the system, such as an exchange interaction between magnetic ions. The first exchange pathway can be realized through maleic rings between the nearest Ni(II) ions. The second exchange pathway can be realized through water molecules approximately along the <i>a</i> crystallographic axis. Broken-symmetry DFT calculations performed using the computational package ORCA provided the values of ferromagnetic exchange interactions, <i>J</i><sub>1</sub>/<i>k</i><sub>B</sub> = 1.50 K and <i>J</i><sub>2</sub>/<i>k</i><sub>B</sub> = 1.44 K (using B3LYP functional). The presence of such ferromagnetic correlations in the studied system may explain the enhanced magnetocaloric effect compared with the model of an anisotropic spin-1 paramagnet.https://www.mdpi.com/2312-7481/8/9/106magnetocaloric effectentropyadiabatic temperature changemagnetic anisotropycrystal field |
| spellingShingle | Petro Danylchenko Róbert Tarasenko Erik Čižmár Vladimír Tkáč Anna Uhrinová Alžbeta Orendáčová Martin Orendáč Experimental Study of Magnetocaloric Effect in Tetraaquabis(Hydrogen Maleato)Nickel(II), [Ni(C<sub>4</sub>H<sub>3</sub>O<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]—A Potential Realization of a Spin-1 Spatially Anisotropic Square Lattice with Ferromagnetic Interactions Magnetochemistry magnetocaloric effect entropy adiabatic temperature change magnetic anisotropy crystal field |
| title | Experimental Study of Magnetocaloric Effect in Tetraaquabis(Hydrogen Maleato)Nickel(II), [Ni(C<sub>4</sub>H<sub>3</sub>O<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]—A Potential Realization of a Spin-1 Spatially Anisotropic Square Lattice with Ferromagnetic Interactions |
| title_full | Experimental Study of Magnetocaloric Effect in Tetraaquabis(Hydrogen Maleato)Nickel(II), [Ni(C<sub>4</sub>H<sub>3</sub>O<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]—A Potential Realization of a Spin-1 Spatially Anisotropic Square Lattice with Ferromagnetic Interactions |
| title_fullStr | Experimental Study of Magnetocaloric Effect in Tetraaquabis(Hydrogen Maleato)Nickel(II), [Ni(C<sub>4</sub>H<sub>3</sub>O<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]—A Potential Realization of a Spin-1 Spatially Anisotropic Square Lattice with Ferromagnetic Interactions |
| title_full_unstemmed | Experimental Study of Magnetocaloric Effect in Tetraaquabis(Hydrogen Maleato)Nickel(II), [Ni(C<sub>4</sub>H<sub>3</sub>O<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]—A Potential Realization of a Spin-1 Spatially Anisotropic Square Lattice with Ferromagnetic Interactions |
| title_short | Experimental Study of Magnetocaloric Effect in Tetraaquabis(Hydrogen Maleato)Nickel(II), [Ni(C<sub>4</sub>H<sub>3</sub>O<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]—A Potential Realization of a Spin-1 Spatially Anisotropic Square Lattice with Ferromagnetic Interactions |
| title_sort | experimental study of magnetocaloric effect in tetraaquabis hydrogen maleato nickel ii ni c sub 4 sub h sub 3 sub o sub 4 sub sub 2 sub h sub 2 sub o sub 4 sub a potential realization of a spin 1 spatially anisotropic square lattice with ferromagnetic interactions |
| topic | magnetocaloric effect entropy adiabatic temperature change magnetic anisotropy crystal field |
| url | https://www.mdpi.com/2312-7481/8/9/106 |
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