We have studied the charge disproportionation phenomenon in CaFeO3 using the local-spin density approximation with the on-site Coulomb interaction parameter U and exchange parameter J. The calculation reveals that the total number of the 3d electrons is about 5.1 for both Fe(1)(Fe5+) and Fe(2)(Fe3+) atoms, and that there are about 0.25 electron holes in the O-2p band. Therefore, the charge disproportionation can be more accurately described as 2d5L(Fe4+)=d5L2(Fe5+)+d5(Fe3+), where L denotes a hole in the oxygen 2p band, instead of 2d4(Fe4+)=d3(Fe5+)+d5(Fe3+). The hybridization between the Fe-3d and O-2p orbitals is stronger for Fe(1) than for Fe(2) due to the shorter Fe(1)-O bond. The hyperfine magnetic field contributed from conduction electron polarization is larger for Fe(2), resulting from a stronger s-d hybridization between the s orbital of Fe(2) and the d orbitals of its neighboring Fe(1) atoms. The on-site Coulomb repulsion and the exchange interaction increase the splitting between the occupied spin up and unoccupied spin down bands of Fe atoms. Fe-3d electrons become localized and the occupied d-band shifts to a lower energy range, even below the O-2p level. The calculated magnetic moments, hyperfine fields, and electron charge density agree well with the experimental data.


Materials Science and Engineering

Second Department


Third Department



United States. Department of Energy

Keywords and Phrases

Antiferromagnetic Materials; Band Structure; Calcium Compounds; Density Functional Theory; Exchange Interactions (Electron); Hyperfine Interactions; Magnetic Moments

Document Type

Article - Journal

Document Version

Final Version

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© 2005 American Institute of Physics (AIP), All rights reserved.

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