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Hauptverfasser: Ji, Liang-Wen, Wu, Si-Qi, Li, Bai-Zhuo, Yang, Wu-Zhang, Song, Shi-Jie, Liu, Yi, Li, Jing, Ren, Zhi, Cao, Guang-Han
Format: Preprint
Veröffentlicht: 2024
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Online-Zugang:https://arxiv.org/abs/2410.15327
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author Ji, Liang-Wen
Wu, Si-Qi
Li, Bai-Zhuo
Yang, Wu-Zhang
Song, Shi-Jie
Liu, Yi
Li, Jing
Ren, Zhi
Cao, Guang-Han
author_facet Ji, Liang-Wen
Wu, Si-Qi
Li, Bai-Zhuo
Yang, Wu-Zhang
Song, Shi-Jie
Liu, Yi
Li, Jing
Ren, Zhi
Cao, Guang-Han
contents The antiferromagnetism in transition metal compounds is mostly mediated by the bridging anions through a so-called superexchange mechanism. However, in materials like normal spinels $AB_2X_4$ with local moments only at the $A$ site, such an anion-mediated superexchange needs to be modified. Here we report a new spinel compound Co$_{1+x}$Ir$_{2-x}$S$_4$ ($x$ = 0.3). The physical property measurements strongly suggest an antiferromagnetic-like transition at 292 K in the Co($A$) diamond sublattice. The first-principle calculations reveal that the nearest-neighbor Co($A$) spins align antiferromagnetically with an ordered magnetic moment of 1.67 $μ_\mathrm{B}$, smaller than the expected $S = 3/2$ for Co$^{2+}$. In the antiferromagnetic state, there exists an inter-cation charge-transfer gap between the non-bonding Ir-$t_\mathrm{2g}$ orbitals at the valence band maximum and the Co-S antibonding molecular orbitals at the conduction band minimum. The small charge transfer energy significantly enhances the virtual hopping between these two states, facilitating a robust long-range superexchange interaction between two neighboring CoS$_4$ complexes, which accounts for the high Néel temperature in Co$_{1+x}$Ir$_{2-x}$S$_4$. This inter-cation charge transfer mediated magnetic interaction expands the traditional superexchange theory, which could be applicable in complex magnetic materials with multiple cations.
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institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Inter-Cation Charge Transfer Mediated Antiferromagnetism in Co$_{1+x}$Ir$_{2-x}$S$_4$
Ji, Liang-Wen
Wu, Si-Qi
Li, Bai-Zhuo
Yang, Wu-Zhang
Song, Shi-Jie
Liu, Yi
Li, Jing
Ren, Zhi
Cao, Guang-Han
Materials Science
Strongly Correlated Electrons
The antiferromagnetism in transition metal compounds is mostly mediated by the bridging anions through a so-called superexchange mechanism. However, in materials like normal spinels $AB_2X_4$ with local moments only at the $A$ site, such an anion-mediated superexchange needs to be modified. Here we report a new spinel compound Co$_{1+x}$Ir$_{2-x}$S$_4$ ($x$ = 0.3). The physical property measurements strongly suggest an antiferromagnetic-like transition at 292 K in the Co($A$) diamond sublattice. The first-principle calculations reveal that the nearest-neighbor Co($A$) spins align antiferromagnetically with an ordered magnetic moment of 1.67 $μ_\mathrm{B}$, smaller than the expected $S = 3/2$ for Co$^{2+}$. In the antiferromagnetic state, there exists an inter-cation charge-transfer gap between the non-bonding Ir-$t_\mathrm{2g}$ orbitals at the valence band maximum and the Co-S antibonding molecular orbitals at the conduction band minimum. The small charge transfer energy significantly enhances the virtual hopping between these two states, facilitating a robust long-range superexchange interaction between two neighboring CoS$_4$ complexes, which accounts for the high Néel temperature in Co$_{1+x}$Ir$_{2-x}$S$_4$. This inter-cation charge transfer mediated magnetic interaction expands the traditional superexchange theory, which could be applicable in complex magnetic materials with multiple cations.
title Inter-Cation Charge Transfer Mediated Antiferromagnetism in Co$_{1+x}$Ir$_{2-x}$S$_4$
topic Materials Science
Strongly Correlated Electrons
url https://arxiv.org/abs/2410.15327