Character of the insulating state in NiO: A mixture of charge-transfer and Mott-Hubbard character

Abstract

Using site-specific soft x-ray emission and absorption spectroscopy in conjunction with site-specific x-ray photoelectron spectroscopy, we present measurements of the valence and conduction band states of NiO. Significant hybridization between the Ni and the O electronic states near the Fermi energy is observed throughout both the valence and conduction bands, in accordance with density-functional theory calculations also presented. The relationship between our emission and absorption measurements also shows direct similarities to other techniques used to measure the non-dipole-allowed $d\text{\penalty1000-\hskip0pt}d$ transitions within NiO, addressing questions concerning the character of the insulating band gap of this system. NiO has previously been described as a large-gap, charge-transfer insulator, while our data show the valence and conduction states at the Fermi energy to be primarily of Ni $d$--character hybridized with a small amount of O $p$--character states, suggesting a mixture of charge-transfer and Mott-Hubbard character as described by the Zaanen-Sawatzky-Allen model.