Electronic structure of SrFe4+O3 and related Fe perovskite oxides

A. E. Bocquet, A. Fujimori, Takashi Mizokawa, T. Saitoh, H. Namatame, S. Suga, N. Kimizuka, Y. Takeda, M. Takano

Research output: Contribution to journalArticle

299 Citations (Scopus)

Abstract

The electronic structure of SrFeO3 has been investigated by x-ray photoemission and ultraviolet photoemission spectroscopy. We find that the ground state consists of heavily mixed d4 and d5L states, reflecting the large covalency. The Fe 3s core-level splitting, together with a subsequent cluster-model configuration-interaction calculation, shows that a high-spin t2g3eg ground state is stabilized. The Fe 2p core levels have been interpreted using a p-d charge-transfer cluster-model calculation. The charge-transfer energy eff, defined with respect to the lowest multiplet levels of the d4 and d5L configurations, is negative, which means that a large amount of charge is transferred via Fe-O bonds from the O 2p bands to the metal d orbitals and that the ground state is dominated by the d5L configuration. This reduces the charge on the ionic sites, leading to only a small chemical shift between the Fe3+ and Fe4+ compounds. The band-gap energy Egap, calculated using the cluster model for the high-spin d4 configuration, is small due to the small charge-transfer energy and the large exchange stabilization of the adjacent d5 configuration. This small value for Egap leads to the presence of itinerant d electrons in the periodic lattice, causing metallic conductivity in SrFeO3 and charge disproportionation in CaFeO3.

Original languageEnglish
Pages (from-to)1561-1570
Number of pages10
JournalPhysical Review B
Volume45
Issue number4
DOIs
Publication statusPublished - 1992
Externally publishedYes

Fingerprint

Perovskite
Oxides
Ground state
Electronic structure
Charge transfer
Core levels
electronic structure
oxides
charge transfer
configurations
ground state
photoelectric emission
Chemical shift
Photoemission
Photoelectron spectroscopy
Ultraviolet spectroscopy
Energy gap
Stabilization
Metals
configuration interaction

ASJC Scopus subject areas

  • Condensed Matter Physics

Cite this

Bocquet, A. E., Fujimori, A., Mizokawa, T., Saitoh, T., Namatame, H., Suga, S., ... Takano, M. (1992). Electronic structure of SrFe4+O3 and related Fe perovskite oxides. Physical Review B, 45(4), 1561-1570. https://doi.org/10.1103/PhysRevB.45.1561

Electronic structure of SrFe4+O3 and related Fe perovskite oxides. / Bocquet, A. E.; Fujimori, A.; Mizokawa, Takashi; Saitoh, T.; Namatame, H.; Suga, S.; Kimizuka, N.; Takeda, Y.; Takano, M.

In: Physical Review B, Vol. 45, No. 4, 1992, p. 1561-1570.

Research output: Contribution to journalArticle

Bocquet, AE, Fujimori, A, Mizokawa, T, Saitoh, T, Namatame, H, Suga, S, Kimizuka, N, Takeda, Y & Takano, M 1992, 'Electronic structure of SrFe4+O3 and related Fe perovskite oxides', Physical Review B, vol. 45, no. 4, pp. 1561-1570. https://doi.org/10.1103/PhysRevB.45.1561
Bocquet, A. E. ; Fujimori, A. ; Mizokawa, Takashi ; Saitoh, T. ; Namatame, H. ; Suga, S. ; Kimizuka, N. ; Takeda, Y. ; Takano, M. / Electronic structure of SrFe4+O3 and related Fe perovskite oxides. In: Physical Review B. 1992 ; Vol. 45, No. 4. pp. 1561-1570.
@article{8a0d4d9be83a4f5d86d2cf330ee5ba58,
title = "Electronic structure of SrFe4+O3 and related Fe perovskite oxides",
abstract = "The electronic structure of SrFeO3 has been investigated by x-ray photoemission and ultraviolet photoemission spectroscopy. We find that the ground state consists of heavily mixed d4 and d5L states, reflecting the large covalency. The Fe 3s core-level splitting, together with a subsequent cluster-model configuration-interaction calculation, shows that a high-spin t2g3eg ground state is stabilized. The Fe 2p core levels have been interpreted using a p-d charge-transfer cluster-model calculation. The charge-transfer energy eff, defined with respect to the lowest multiplet levels of the d4 and d5L configurations, is negative, which means that a large amount of charge is transferred via Fe-O bonds from the O 2p bands to the metal d orbitals and that the ground state is dominated by the d5L configuration. This reduces the charge on the ionic sites, leading to only a small chemical shift between the Fe3+ and Fe4+ compounds. The band-gap energy Egap, calculated using the cluster model for the high-spin d4 configuration, is small due to the small charge-transfer energy and the large exchange stabilization of the adjacent d5 configuration. This small value for Egap leads to the presence of itinerant d electrons in the periodic lattice, causing metallic conductivity in SrFeO3 and charge disproportionation in CaFeO3.",
author = "Bocquet, {A. E.} and A. Fujimori and Takashi Mizokawa and T. Saitoh and H. Namatame and S. Suga and N. Kimizuka and Y. Takeda and M. Takano",
year = "1992",
doi = "10.1103/PhysRevB.45.1561",
language = "English",
volume = "45",
pages = "1561--1570",
journal = "Physical Review B-Condensed Matter",
issn = "0163-1829",
publisher = "American Institute of Physics Publising LLC",
number = "4",

}

TY - JOUR

T1 - Electronic structure of SrFe4+O3 and related Fe perovskite oxides

AU - Bocquet, A. E.

AU - Fujimori, A.

AU - Mizokawa, Takashi

AU - Saitoh, T.

AU - Namatame, H.

AU - Suga, S.

AU - Kimizuka, N.

AU - Takeda, Y.

AU - Takano, M.

PY - 1992

Y1 - 1992

N2 - The electronic structure of SrFeO3 has been investigated by x-ray photoemission and ultraviolet photoemission spectroscopy. We find that the ground state consists of heavily mixed d4 and d5L states, reflecting the large covalency. The Fe 3s core-level splitting, together with a subsequent cluster-model configuration-interaction calculation, shows that a high-spin t2g3eg ground state is stabilized. The Fe 2p core levels have been interpreted using a p-d charge-transfer cluster-model calculation. The charge-transfer energy eff, defined with respect to the lowest multiplet levels of the d4 and d5L configurations, is negative, which means that a large amount of charge is transferred via Fe-O bonds from the O 2p bands to the metal d orbitals and that the ground state is dominated by the d5L configuration. This reduces the charge on the ionic sites, leading to only a small chemical shift between the Fe3+ and Fe4+ compounds. The band-gap energy Egap, calculated using the cluster model for the high-spin d4 configuration, is small due to the small charge-transfer energy and the large exchange stabilization of the adjacent d5 configuration. This small value for Egap leads to the presence of itinerant d electrons in the periodic lattice, causing metallic conductivity in SrFeO3 and charge disproportionation in CaFeO3.

AB - The electronic structure of SrFeO3 has been investigated by x-ray photoemission and ultraviolet photoemission spectroscopy. We find that the ground state consists of heavily mixed d4 and d5L states, reflecting the large covalency. The Fe 3s core-level splitting, together with a subsequent cluster-model configuration-interaction calculation, shows that a high-spin t2g3eg ground state is stabilized. The Fe 2p core levels have been interpreted using a p-d charge-transfer cluster-model calculation. The charge-transfer energy eff, defined with respect to the lowest multiplet levels of the d4 and d5L configurations, is negative, which means that a large amount of charge is transferred via Fe-O bonds from the O 2p bands to the metal d orbitals and that the ground state is dominated by the d5L configuration. This reduces the charge on the ionic sites, leading to only a small chemical shift between the Fe3+ and Fe4+ compounds. The band-gap energy Egap, calculated using the cluster model for the high-spin d4 configuration, is small due to the small charge-transfer energy and the large exchange stabilization of the adjacent d5 configuration. This small value for Egap leads to the presence of itinerant d electrons in the periodic lattice, causing metallic conductivity in SrFeO3 and charge disproportionation in CaFeO3.

UR - http://www.scopus.com/inward/record.url?scp=0001208774&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001208774&partnerID=8YFLogxK

U2 - 10.1103/PhysRevB.45.1561

DO - 10.1103/PhysRevB.45.1561

M3 - Article

VL - 45

SP - 1561

EP - 1570

JO - Physical Review B-Condensed Matter

JF - Physical Review B-Condensed Matter

SN - 0163-1829

IS - 4

ER -