Engineering Kitaev exchange in stacked iridate layers: impact of inter-layer species on in-plane magnetism

Novel functionalities may be achieved in oxide electronics by appropriate stacking of planar oxide layers of different metallic species, MO(p) and M′O(q). The simplest mechanism allowing the tailoring of the electronic states and physical properties of such heterostructures is of electrostatic nature—charge imbalance between the M and M′ cations. Here we clarify the effect of interlayer electrostatics on the anisotropic Kitaev exchange in H(3)LiIr(2)O(6), a recently proposed realization of the Kitaev spin liquid. By quantum chemical calculations, we show that the precise position of H(+) cations between magnetically active [LiIr(2)O(6)](3–) honeycomb-like layers has a strong impact on the magnitude of Kitaev interactions. In particular, it is found that stacking with straight interlayer O–H–O links is detrimental to in-plane Kitaev exchange since coordination by a single H-ion of the O ligand implies an axial Coulomb potential at the O site and unfavorable polarization of the O 2p orbitals mediating the Ir–Ir interactions. Our results therefore provide valuable guidelines for the rational design of Kitaev quantum magnets, indicating unprecedented Kitaev interactions of ≈40 meV if the linear interlayer linkage is removed.