Analyzing the Local Electronic Structure of Co3O4 Using 2p3d Resonant Inelastic X-ray Scattering

J Phys Chem C Nanomater Interfaces. 2022 May 26;126(20):8752-8759. doi: 10.1021/acs.jpcc.2c01521. Epub 2022 May 11.

Abstract

We present the cobalt 2p3d resonant inelastic X-ray scattering (RIXS) spectra of Co3O4. Guided by multiplet simulation, the excited states at 0.5 and 1.3 eV can be identified as the 4 T 2 excited state of the tetrahedral Co2+ and the 3 T 2g excited state of the octahedral Co3+, respectively. The ground states of Co2+ and Co3+ sites are determined to be high-spin 4 A 2(T d ) and low-spin 1 A 1g (Oh ), respectively. It indicates that the high-spin Co2+ is the magnetically active site in Co3O4. Additionally, the ligand-to-metal charge transfer analysis shows strong orbital hybridization between the cobalt and oxygen ions at the Co3+ site, while the hybridization is weak at the Co2+ site.