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

We report ab initio density functional theory calculation and Raman scattering results to explore the electronic structure of Ba₅CuIr₃O₁₂ single crystals. This insulating iridate, consisting of face-sharing IrO₆ octahedra forming quasi-one-dimensional chains, cannot be described by the local j₄₅₅=1/2 moment picture commonly adopted for discussing the electronic and magnetic properties of iridate compounds with IrO₆ 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 (MOs) at each Ir trimer 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 j₄₅₅=1/2 picture, is verified by observing the three-peak structure in the electronic excitation spectrum by Raman scattering.