Effect of metal-oxygen covalent bonding on the competition between Jahn-Teller distortion and charge disproportionation in the perovskites of high-spin d(4) metal ions LaMnO(3) and CaFeO(3).
| hal.structure.identifier | Department of Chemistry | |
| dc.contributor.author | WHANGBO, Myung-Hwan | |
| hal.structure.identifier | Department of Chemistry | |
| dc.contributor.author | KOO, H.-J. | |
| hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
| dc.contributor.author | VILLESUZANNE, Antoine | |
| hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
| dc.contributor.author | POUCHARD, Michel | |
| dc.date.issued | 2002-04-08 | |
| dc.identifier.issn | 0020-1669 | |
| dc.description.abstractEn | The perovskites LaMnO(3) and CaFeO(3) consisting of high-spin d(4) transition metal ions undergo different types of distortions, i.e., a Jahn-Teller distortion in LaMnO(3) and a charge disproportionation in CaFeO(3). We investigated the electronic factor causing this difference on the basis of first principles spin-polarized electronic band structure calculations for their ideal cubic structures and also tight-binding electronic band structure calculations for their ideal cubic and distorted structures. Our study shows that a charge disproportionation is favored over a Jahn-Teller distortion in CaFeO(3) because the covalent character is strong in the Fe-O bond, while the opposite is true for LaMnO(3) because the covalent character is weak in the Mn-O bond. In spin-polarized electronic band structure calculations, the covalency of the M-O (M = Fe, Mn) bond is enhanced in the up-spin bands but is reduced in the down-spin bands. Our analysis shows that electron-electron repulsion causes the energy gap between the metal 3d and the oxygen 2p orbitals to become larger for the down-spin than for the up-spin-orbital interactions. Thus in the d-block e(g) bands of both LaMnO(3) and CaFeO(3) the metal 3d orbital contribution is larger in the down-spin than in the up-spin bands. | |
| dc.language.iso | en | |
| dc.publisher | American Chemical Society | |
| dc.subject.en | Perovskites | |
| dc.subject.en | Metal | |
| dc.subject.en | Oxygen | |
| dc.subject.en | Chemical bonding | |
| dc.subject.en | Inorganic compounds | |
| dc.title.en | Effect of metal-oxygen covalent bonding on the competition between Jahn-Teller distortion and charge disproportionation in the perovskites of high-spin d(4) metal ions LaMnO(3) and CaFeO(3). | |
| dc.type | Article de revue | |
| dc.identifier.doi | 10.1021/ic0110427 | |
| dc.subject.hal | Chimie/Matériaux | |
| bordeaux.journal | Inorganic Chemistry | |
| bordeaux.page | 1920-1929 | |
| bordeaux.volume | 41 | |
| bordeaux.issue | 7 | |
| bordeaux.peerReviewed | oui | |
| hal.identifier | hal-00712870 | |
| hal.version | 1 | |
| hal.popular | non | |
| hal.audience | Internationale | |
| hal.origin.link | https://hal.archives-ouvertes.fr//hal-00712870v1 | |
| bordeaux.COinS | ctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Inorganic%20Chemistry&rft.date=2002-04-08&rft.volume=41&rft.issue=7&rft.spage=1920-1929&rft.epage=1920-1929&rft.eissn=0020-1669&rft.issn=0020-1669&rft.au=WHANGBO,%20Myung-Hwan&KOO,%20H.-J.&VILLESUZANNE,%20Antoine&POUCHARD,%20Michel&rft.genre=article |
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