Electronic structure and magnetism in P4/nmm KCoO2

Abstract

KCoO2 has been found in 1975 to exist in a unique structure with P4/nmm spacegroup with Co in a square pyramidal coordination with the Co atoms in the plane linked by O in a square arrangement reminiscent of the cuprates but its electronic structure has not been studied until now. Unlike Co atoms in LiCoO2 and NaCoO2 in octahedral coordination, which are non-magnetic band structure insulators, the unusual coordination of d6 Co^{3+} in KCoO2 is here shown to lead to a magnetic stabilization of an insulating structure with high magnetic moments of 4μB per Co. The electronic band structure is calculated using the quasiparticle self-consistent (QS)GW method and the basic formation of magnetic moments is explained in terms of the orbital decomposition of the bands. The optical dielectric function is calculated using the Bethe-Salpeter equation including only transitions between equal spin bands. The magnetic moments are shown to prefer an antiferromagnetic ordering along the [110] direction. Exchange interactions are calculated from the transverse spin susceptibility and a rigid spin approximation. The Néel temperature is estimated using the mean-field and Tyablikov methods and found to be between approximately 100 and 250 K. The band structure in the AFM ordering can be related to the FM ordering by band folding effects. The optical spectra are similar in both structures and show evidence of excitonic features below the quasiparticle gap of about 4 eV.