The electronic structure of charge-ordered magnetite $\left({\mathrm{Fe}}_3{\mathrm{O}}_4\right)$ below the Verwey transition and Mn-, Co-, or Ni-substituted ${\mathrm{Fe}}_3{\mathrm{O}}_4$ are investigated theoretically from first principles, using the fully relativistic Dirac linear muffin-tin orbital band-structure method. The electronic structure is obtained with the local spin-density approximation (LSDA), as well as with the so-called $\mathrm{LSDA}+U$ approach, for which the charge ordering is found to be a stable solution in contrast to a metallic state given by the LSDA. The x-ray absorption spectra as well as the x-ray magnetic circular dichroism spectra at the K, $L_{2,3},$ and $M_{2,3}$ edges for transition metal sites are calculated. A good agreement between theory and experiment is obtained.

• Received 24 May 2002

DOI:https://doi.org/10.1103/PhysRevB.67.024417