arXiv:2411.00125 · Physical review. B./Physical review. B
Quasimolecular electronic structure of the trimer iridate Ba 4 NbIr 3 O 12
M. Magnaterra, Anna Sandberg, H. Schilling, P. Warzanowski, Lara Pätzold, E. Bergamasco, Christoph J. Sahle, Blanka Detlefs, Kari O. Ruotsalainen, M. Moretti Sala, G. Monaco, P. Becker, Quentin Faure, Gohil Singh Thakur, M. Songvilay, Claudia Felser, Paul H. M. van Loosdrecht, Jeroen van den Brink, Maria Hermanns, M. Grüninger
The trimer compound Ba${}_{4}$NbIr${}_{3}$O${}_{12}$ is found to be a spin-orbit-entangled cluster Mott insulator, with two holes per trimer occupying quasimolecular orbitals. The authors employ here resonant inelastic x-ray scattering (RIXS) and exact diagonalization. The quasimolecular nature yields a characteristic interference pattern in the RIXS intensity, reflecting the character of the wavefunction. Despite a large hopping, strong spin-orbit coupling is decisive for the electronic states. This promises nontrivial magnetic moments in trimers with an odd number of holes.
The trimer compound Ba4NbIr3O12 is found to be a spin-orbit-entangled cluster Mott insulator, with two holes per trimer occupying quasimolecular orbitals. The authors employ here resonant inelastic x-ray scattering (RIXS) and exact diagonalization. The quasimolecular nature yields a characteristic interference pattern in the RIXS intensity, reflecting the character of the wavefunction. Despite a large hopping, strong spin-orbit coupling is decisive for the electronic states. This promises nontrivial magnetic moments in trimers with an odd number of holes.
The mixed-valent iridate Ba3InIr2O9 has been discussed as a promising candidate for quantum spin-liquid behavior. The compound exhibits Ir4.5+ ions in face-sharing IrO6 octahedra forming Ir2O9 dimers with three t2g holes per dimer. Our results establish Ba3InIr2O9 as a cluster Mott insulator. Strong intradimer hopping delocalizes the three t2g holes in quasimolecular dimer states while interdimer charge fluctuations are suppressed by Coulomb repulsion. The magnetism of Ba3InIr2O9 emerges from spin-orbit entangled quasimolecular moments with yet unexplored interactions, opening up a new route to unconventional magnetic properties of 5d compounds. Using single-crystal x-ray diffraction we find the monoclinic space group C2/c already at room temperature. Dielectric spectroscopy shows insulating behavior. Resonant inelastic x-ray scattering reveals a rich excitation spectrum below 1.5 eV with a sinusoidal dynamical structure factor that unambiguously demonstrates the quasimolecular character of the electronic states. Below 0.3 eV, we observe a series of excitations. According to exact diagonalization calculations, such low-energy excitations reflect the proximity of Ba3InIr2O9 to a hopping-induced phase transition based on the condensation of a quasimolecular spin-orbit exciton. The dimer ground state roughly hosts two holes in a bonding j=21 orbital and the third hole in a bonding j=23 orbital.
A comparative resonant inelastic x-ray scattering (RIXS) study of three well-known Kitaev materials is presented: $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{Li}}_{2}{\mathrm{IrO}}_{3}, {\mathrm{Na}}_{2}{\mathrm{IrO}}_{3}$, and $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{RuCl}}_{3}$. Despite similar low-energy physics, these materials show distinct electronic properties, such as the large difference in the size of the charge gap. The RIXS spectra of the spin-orbit exciton for these materials show remarkably similar three-peak features, including sharp low energy peak (peak A) as well as transitions between jeff=1/2 and jeff=3/2 states. Comparison of experimental spectra with cluster calculations reveals that the observed three-peak structure reflects the significant role that nonlocal physics plays in the electronic structure of these materials. In particular, the low-energy peak A arises from a holon-doublon pair rather than a conventional particle-hole exciton as proposed earlier. Our study suggests that while spin-orbit assisted Mott insulator is still the best description for these materials, electron itinerancy cannot be ignored when formulating low-energy Hamiltonian of these materials.
We investigate spin-flip excitations in the spin-1/2 trimer chain Cu3(P2O6OH)2, featuring an antiferromagnetic exchange motif J1-J1-J2 with J1<J2. Using density matrix renormalization group (DMRG) simulations, we demonstrate that single-spin-flip processes induced by resonant inelastic X-ray scattering (RIXS) generate emergent gapless modes governed by the underlying trimer periodicity alongside distinct high-energy excitations. By combining exact diagonalization and real-space renormalization group (RG) techniques, we attribute these features to fractionalized spinons and composite quasiparticles arising from one- and two-trimer excitations. Furthermore, we show that multi-spin RIXS excitations yield experimentally distinguishable spectral signatures of composite modes absent in single-spin-flip spectra. At the field-induced 1/3 magnetization plateau, single-spin-flip RIXS spectra evolves with the magnetic field to favor spin-polarized composite quasiparticles. This trend culminates in a gapless spectrum of spin-1 excitations beyond the plateau, paving the way for field-tuned Bose condensation of composite modes.
In the recent years, interest in TM oxides with 5d valence electrons has grown immensely due to the realization of novel spin-orbit coupled ground states. In these compounds, e.g., iridates and osmates, the intriguing situation arises where the spin-orbit and electron-electron interactions meet on the same energy scale. This has created a new window of interest in these compounds since the interplay of crystal field effects, local multiplet physics, spin-orbit couplings, and intersite hopping can offer novel types of correlated ground states and excitations. In 5d5 iridates, a spin-orbit entangled j = 1/2 Mott insulating state has been realized recently. A remarkable feature of such a ground state is that it gives rise to anisotropic magnetic interactions. The 2D honeycomb-lattice 213 iridium oxides, A2IrO3 (A=Li,Na), have been put forward to host highly anisotropic bond-dependent spin-spin interactions that resemble the Kitaev spin model, which supports various types of topological phases relevant in quantum computing. The 2D square-lattice 214 iridates Sr2IrO4 and Ba2IrO4 are, on the other hand, appealing because of their perceived structural and magnetic simi- larity to La2CuO4, the mother compound of the cuprate high-Tc superconductors. This has promoted the latter iridium oxide compounds as novel platforms for the search of high-Tc superconductivity. To put such considerations on a firm footing, it is essential to quantify the different coupling strengths and energy scales, as they for instance appear in effective Hamiltonian descriptions of these correlated systems. Moreover, it is important to correctly describe their effects. In this thesis, the electronic structure and magnetic properties of 5d5 (mainly 214 and 213) iridates are studied using wave-function-based quantum chemistry methods. These methods are fully ab initio and are capable of accurately treating the electron-electron interactions without using any ad hoc parameters. The spin-orbit entangled j = 1/2 ground state in 214, 213 and other lower symmetry Sr3CuIrO6 and Na4Ir3O8 iridates is first analyzed in detail, by studying the local electronic structure of the 5d5 Ir4+ ion. We establish that the longer-range crystal anisotropy, i.e., low-symmetry fields related to ionic sites beyond the nearest neighbor oxygen cage, strongly influence the energies of Ir d levels. The ground state in all the compounds studied is j = 1/2 like with admixture from j ≃ 3/2 states ranging from 1 – 15 %. Further, the average j ≃ 1/2 → j ≃ 3/2 excitation energy we find is around 0.6 eV. The NN magnetic exchange interactions we computed for 214 iridates are predominantly isotropic Heisenberg-like with J ~ 60 meV, 3 – 4 times smaller than found in isostructural copper oxides. However, the anisotropic interactions are an order of magnitude larger than those in cuprates. Our estimates are in excellent agreement with those extracted from experiments, e.g., resonant inelastic x-ray scattering measurements. For the 213 honeycomb-lattice Na2IrO3 our calculations show that the relevant spin Hamiltonian contains further anisotropic terms beyond the Kitaev-Heisenberg model. Nevertheless, we predict that the largest energy scale is the Kitaev interaction, 10 to 20 meV, while the Heisenberg superexchange and off-diagonal symmetric anisotropic couplings are significantly weaker. In the sister compound Li2IrO3, we find that the structural inequivalence between the two types of Ir-Ir links has a striking influence on the effective spin Hamiltonian, leading in particular to two very different NN superexchange pathways, one weakly AF (~ 1 meV) and another strongly FM (−19 meV). The latter gives rise to rigid spin-1 triplets on a triangular lattice.
Spinons are well known as the elementary excitations of one-dimensional antiferromagnetic chains, but means to realize spinons in higher dimensions is the subject of intense research. Here, we use resonant x-ray scattering to study the layered trimer iridate Ba_{4}Ir_{3}O_{10}, which shows no magnetic order down to 0.2 K. An emergent one-dimensional spinon continuum is observed that can be well described by XXZ spin-1/2 chains with a magnetic exchange of ∼55 meV and a small Ising-like anisotropy. With 2% isovalent Sr doping, magnetic order appears below T_{N}=130 K along with sharper excitations in (Ba_{1-x}Sr_{x})_{4}Ir_{3}O_{10}. Combining our data with exact diagonalization calculations, we find that the frustrated intratrimer interactions effectively reduce the system into decoupled spin chains, the subtle balance of which can be easily tipped by perturbations such as chemical doping. Our results put Ba_{4}Ir_{3}O_{10} between the one-dimensional chain and two-dimensional quantum spin liquid scenarios, illustrating a new way to suppress magnetic order and realize fractional spinons.
A recently performed resonant inelastic x-ray scattering experiment (RIXS) at the copper L3 edge in the quasi-one-dimensional Mott insulator Sr2CuO3 has revealed a significant dispersion of a single-orbital excitation (orbiton). This large and unexpected orbiton dispersion has been explained using the concept of spin-orbital fractionalization in which the orbiton, which is intrinsically coupled to the spinon in this material, liberates itself from the spinon due to the strictly one-dimensional nature of its motion. Here, we investigate this mechanism in detail by (i) deriving the microscopic spin-orbital superexchange model from the charge-transfer model for the CuO3 chains in Sr2CuO3, (ii) mapping the orbiton motion in the obtained spin-orbital model into a problem of a single hole moving in an effective half-filled antiferromagnetic chain t-J model, and (iii) solving the latter model using the exact diagonalization and obtaining the orbiton spectral function. Finally, the RIXS cross section is calculated based on the obtained orbiton spectral function and compared with the RIXS experiment.