Revealing the site selective local electronic structure of Co$_{3}$O$_{4}$ using $2p3d$ resonant inelastic X-ray scattering

TL;DR

This study uses Co 2p3d RIXS to selectively probe local electronic structures of Co$_3$O$_4$, revealing site-specific excited states and magnetic activity, with insights into covalent and ionic bonding characteristics.

Contribution

It introduces a site-selective RIXS approach to distinguish electronic states of Co$^{2+}$ and Co$^{3+}$ in Co$_3$O$_4$, providing detailed local electronic structure information.

Findings

Identification of $^4$T$_{2}$ state for Co$^{2+}$ at 0.5 eV

Detection of $^3$T$_{2g}$ state for Co$^{3+}$ at 1.3 eV

Only Co$^{2+}$ is magnetically active at low temperatures

Abstract

We investigate mixed-valence oxide Co$_3$O$_4$ using Co $2p3d$ resonant inelastic X-ray scattering (RIXS). By setting resonant edges at Co$^{2+}$ and Co$^{3+}$ ions, the $dd$ excitations on the two Co sites are probed selectively, providing detailed information on the local electronic structure of Co$_3$O$_4$. The $2p3d$ RIXS result reveals the $^4$T$_{2}$ excited state of tetrahedral Co$^{2+}$ site at 0.5 eV beyond the discriminative power of optical absorption spectroscopies. Additionally, the $^3$T$_{2g}$ excited stated at 1.3 eV is uniquely identified for the octahedral Co$^{3+}$ site. Guided by cluster multiplet simulations, the ground-state character of the Co$^{2+}$ and Co$^{3+}$ site is determined to be high-spin $^4$A$_{2}$(T$_d$) and low-spin $^1$A$_{1g}$(O$_h$), respectively. This indicates that only the Co$^{2+}$ site is magnetically active site at low-temperatures in Co$_3$O$_4$. The ligand-to-metal charge transfer analysis suggests a formation of a strong covalent bonding between Co and O ions at the Co$^{3+}$ site, while Co$^{2+}$ is rather ionic.