Covalency-driven collapse of strong spin-orbit coupling in face-sharing iridium octahedra

TL;DR

This study reveals that in Ba$_5$CuIr$_3$O$_{12}$, strong covalency due to face-sharing IrO$_6$ octahedra leads to molecular orbital formation, deviating from the traditional $j_{eff}=1/2$ model for iridates.

Contribution

It demonstrates that face-sharing geometry induces covalency-driven molecular orbitals, challenging the $j_{eff}=1/2$ paradigm in iridates with IrO$_6$ octahedra.

Findings

Identification of a three-peak structure in the electronic excitation spectrum.

Verification of molecular orbital formation via Raman scattering.

Deviation from the $j_{eff}=1/2$ model in face-sharing iridates.

Abstract

We report $\textit{ab-initio}$ density functional theory calculation and Raman scattering results to explore the electronic structure of Ba$_5$CuIr$_3$O$_{12}$ single crystals. This insulating iridate, consisting of face-sharing IrO$_6$ octahedra forming quasi-one-dimensional chains, cannot be described by the local $j_{\rm eff}$=1/2 moment picture commonly adopted for discussing electronic and magnetic properties of iridate compounds with IrO$_6$ octahedra. The shorter Ir-Ir distance in the face-sharing geometry, compared to corner- or edge-sharing structures, leads to strong covalency between neighboring Ir. Then this strong covalency results in the formation of molecular orbitals (MO) at each Ir trimers as the low-energy electronic degree of freedom. The theoretically predicted three-peak structure in the joint density of states, a distinct indication of deviation from the $j_{\rm eff}$=1/2 picture, is verified by observing the three-peak structure in the electronic excitation spectrum by Raman scattering.