Electronic structure of 3d-transition-metal compounds by analysis of the 2p core-level photoemission spectra

A. E. Bocquet, Takashi Mizokawa, T. Saitoh, H. Namatame, A. Fujimori

Research output: Contribution to journalArticle

433 Citations (Scopus)

Abstract

The electronic structures of a wide range of transition-metal compounds, including Cu, Ni, Co, Fe, and Mn oxides and sulfides, with metal valences ranging from 2+ to 4+, have been investigated by a cluster-type configuration-interaction analysis of the core-level 2p x-ray photoemission spectra. We show that by including the d-d exchange interaction (retaining only diagonal terms) and an anisotropic metal-ligand hybridization in the model, these spectra can be well reproduced, and so can be used to deduce quantitatively values for the ligand-to-metal charge-transfer energy Δ, the on-site d-d Coulomb repulsion energy U, and the metal-ligand transfer integrals T. Systematics for Δ and U are generally consistent with those found from previous valence-band studies and follow expected chemical trends. By using values of Δ and U found from this model, we show that most of the transition-metal compounds studied in this work can be classified in the charge-transfer regime of the Zaanen-Sawatzky-Allen diagram. A few exceptions to these systematics have been found. Small U values found for pyrite-type CoS2 and FeS2 and large T values for Mn perovskite oxides, as well as the neglect of other mechanisms such as exciton satellites, may indicate a limitation of the local-cluster model.

Original languageEnglish
Pages (from-to)3771-3784
Number of pages14
JournalPhysical Review B
Volume46
Issue number7
DOIs
Publication statusPublished - 1992
Externally publishedYes

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Transition metal compounds
Core levels
metal compounds
Photoemission
Electronic structure
photoelectric emission
Metals
transition metals
electronic structure
Ligands
metals
Oxides
ligands
Charge transfer
charge transfer
valence
oxides
Pyrites
Exchange interactions
Sulfides

ASJC Scopus subject areas

  • Condensed Matter Physics

Cite this

Electronic structure of 3d-transition-metal compounds by analysis of the 2p core-level photoemission spectra. / Bocquet, A. E.; Mizokawa, Takashi; Saitoh, T.; Namatame, H.; Fujimori, A.

In: Physical Review B, Vol. 46, No. 7, 1992, p. 3771-3784.

Research output: Contribution to journalArticle

Bocquet, A. E. ; Mizokawa, Takashi ; Saitoh, T. ; Namatame, H. ; Fujimori, A. / Electronic structure of 3d-transition-metal compounds by analysis of the 2p core-level photoemission spectra. In: Physical Review B. 1992 ; Vol. 46, No. 7. pp. 3771-3784.
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