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Density Functional Theory Analysis of the Interplay between Jahn−Teller Instability, Uniaxial Magnetism, Spin Arrangement, Metal−Metal Interaction, and Spin−Orbit Coupling in Ca3CoMO6 (M = Co, Rh, Ir)
| Content Provider | Scilit |
|---|---|
| Author | Zhang, Yuemei Kan, Erjun Xiang, Hongjun Villesuzanne, Antoine Whangbo, Myung-Hwan |
| Copyright Year | 2011 |
| Abstract | In the isostructural oxides $Ca_{3}CoMO_{6}$ (M = Co, Rh, Ir), the $CoMO_{6}$ chains made up of face-sharing $CoO_{6}$ trigonal prisms and $MO_{6}$ octahedra are separated by Ca atoms. We analyzed the magnetic and electronic properties of these oxides on the basis of density functional theory calculations including on-site repulsion and spin−orbit coupling, and examined the essential one-electron pictures hidden behind results of these calculations. Our analysis reveals an intimate interplay between Jahn−Teller instability, uniaxial magnetism, spin arrangement, metal−metal interaction, and spin−orbit coupling in governing the magnetic and electronic properties of these oxides. These oxides undergo a Jahn−Teller distortion, but their distortions are weak, so that their trigonal-prism $Co^{n+}$ (n = 2, 3) ions still give rise to strong easy-axis anisotropy along the chain direction. As for the d-state split pattern of these ions, the electronic and magnetic properties of $Ca_{3}CoMO_{6}$ (M = Co, Rh, Ir) are consistent with $d_{0}$ < $(d_{2}$, $d_{−2}$) < $(d_{1}$, $d_{−1}$) but not with $(d_{2}$, $d_{−2}$) < $d_{0}$ < $(d_{1}$, $d_{−1}$). The trigonal-prism $Co^{3+}$ ion in $Ca_{3}Co_{2}O_{6}$ has the L = 2 configuration (d_{0})^{1}$(d_{2}$, d_{−2})^{3}$(d_{1}$, d_{−1}$)^{2}$ because of the metal−metal interaction between adjacent $Co^{3+}$ ions in each $Co_{2}O_{6}$ chain, which is mediated by their $z^{2}$ orbitals, and the spin−orbit coupling of the trigonal-prism $Co^{3+}$ ion. The spins in each $CoMO_{6}$ chain of $Ca_{3}CoMO_{6}$ prefer the ferromagnetic arrangement for M = Co and Rh but the antiferromagnetic arrangement for M = Ir. The octahedral $M^{4+}$ ion of $Ca_{3}CoMO_{6}$ has the $(1a)^{1}(1e)^{4}$ configuration for M = Rh but the $(1a)^{2}(1e)^{3}$ configuration for M = Ir, which arises from the difference in the spin−orbit coupling of the $M^{4+}$ ions and the Co···M metal−metal interactions. |
| Related Links | http://arxiv.org/pdf/1101.0644 |
| Ending Page | 1766 |
| Page Count | 9 |
| Starting Page | 1758 |
| ISSN | 00201669 |
| e-ISSN | 1520510X |
| DOI | 10.1021/ic1022278 |
| Journal | Inorganic Chemistry |
| Issue Number | 5 |
| Volume Number | 50 |
| Language | English |
| Publisher | American Chemical Society (ACS) |
| Publisher Date | 2011-01-19 |
| Access Restriction | Open |
| Subject Keyword | Journal: Inorganic Chemistry Inorganic Chemistry Trigonal Prism Orbit Coupling |
| Content Type | Text |
| Resource Type | Article |
| Subject | Physical and Theoretical Chemistry Inorganic Chemistry |
