Quasimolecular electronic structure of the trimer iridate Ba\(_4\)NbIr\(_3\)O\(_{12}\)

The insulating mixed-valent Ir\(^{+3.66}\) compound Ba\(_4\)NbIr\(_3\)O\(_{12}\) hosts two holes per Ir\(_3\)O\(_{12}\) trimer unit. We address the electronic structure via resonant inelastic x-ray scattering (RIXS) at the Ir \(L_3\) edge and exact diagonalization. The holes occupy quasimolecular orbitals that are delocalized over a trimer. This gives rise to a rich intra-\(t_{2g}\) excitation spectrum that extends from 0.5 eV to energies larger than 2 eV. Furthermore, it yields a strong modulation of the RIXS intensity as a function of the transferred momentum q. A clear fingerprint of the quasimolecular trimer character is the observation of two modulation periods, \(2\pi/d\) and \(2\pi/2d\), where d and 2d denote the intratrimer Ir-Ir distances. We discuss how the specific modulation reflects the character of the wavefunction of an excited state. Our quantitative analysis shows that spin-orbit coupling \(\lambda\) of about 0.4 eV is decisive for the character of the electronic states, despite a large hopping \(t_{a_{1g}}\) of about 0.8 eV. The ground state of a single trimer is described very well by both holes occupying the bonding j=1/2 orbital, forming a vanishing quasimolecular moment with J=0.