X-ray Absorption Near-Edge Structure (XANES) at the O K-Edge of Bulk Co3O4: Experimental and Theoretical Studies

We combine theoretical and experimental X-ray absorption near-edge spectroscopy (XANES) to probe the local environment around cationic sites of bulk spinel cobalt tetraoxide (Co3O4). Specifically, we analyse the oxygen K-edge spectrum. We find an excellent agreement between our calculated spectra based on the density functional theory and the projector augmented wave method, previous calculations as well as with the experiment. The oxygen K-edge spectrum shows a strong pre-edge peak which can be ascribed to dipole transitions from O 1s to O 2p states hybridized with the unoccupied 3d states of cobalt atoms. Also, since Co3O4 contains two types of Co atoms, i.e., Co3+ and Co2+, we find that contribution of Co2+ ions to the pre-edge peak is solely due to single spin-polarized t(2g) orbitals (dxz, dyz, and dxy) while that of Co3+ ions is due to spin-up and spin-down polarized eg orbitals (d(x2-y2) and d(z2)). Furthermore, we deduce the magnetic moments on the Co3+ and Co2+ to be zero and 3.00 mu B respectively. This is consistent with an earlier experimental study which found that the magnetic structure of Co3O4 consists of antiferromagnetically ordered Co2+ spins, each of which is surrounded by four nearest neighbours of oppositely directed spins.

Automated summary

Combining theoretical and experimental X-ray absorption near-edge spectroscopy (XANES) to probe the local environment around cationic sites in bulk spinel cobalt tetraoxide (Co3O4), we found a strong pre-edge peak in the oxygen K-edge spectrum. The contributions to the pre-edge peak from Co2+ ions are solely due to single spin-polarized t(2g) orbitals, while those from Co3+ ions are due to spin-up and spin-down polarized eg orbitals. Additionally, the magnetic moments on the Co3+ and Co2+ ions were determined to be zero and 3.00 mu B respectively, consistent with previous experimental findings of antiferromagnetically ordered Co2+ spins in Co3O4.