In the quest for materials hosting Kitaev spin liquids, much of the efforts have been focused on the fourth- and fifth-row transition metal compounds, which are spin-orbit coupling--assisted Mott insulators. Here we study the structural and magnetic properties of $3d$ transition metal oxides, ${\mathrm{Na}}_{2}{\mathrm{Co}}_{2}{\mathrm{TeO}}_{6}$ and ${\mathrm{Na}}_{3}{\mathrm{Co}}_{2}{\mathrm{SbO}}_{6}$. The partial occupancy of sodium in former compound is addressed using a cluster expansion, and a honeycomb lattice of sodiums is found to be energetically favored. Starting from the ab initio band structures, a many-body second-order perturbation theory leads to a pseudospin-$\frac{1}{2}$ Hamiltonian with estimated magnetic interactions. We show that the experimentally observed zigzag magnetic state is stabilized only when the first-neighbor Kitaev coupling dominates over the Heisenberg term, both of which are highly suppressed due to presence of ${e}_{g}$ orbitals. A third-neighbor Heisenberg interaction is found dominant in both these compounds. We also present a phase diagram for ${\mathrm{Na}}_{2}{\mathrm{Co}}_{2}{\mathrm{TeO}}_{6}$ by varying the electron-electron and spin-orbit interactions. The computed spin excitation spectra are found to capture essential features of recent experimental magnon spectrum, lending support to our results.
In the quest for materials hosting Kitaev spin liquids, much of the efforts have been focused on the fourth- and fifth-row transition metal compounds, which are spin-orbit coupling--assisted Mott insulators. Here we study the structural and magnetic properties of 3d transition metal oxides, Na2Co2TeO6 and Na3Co2SbO6. The partial occupancy of sodium in former compound is addressed using a cluster expansion, and a honeycomb lattice of sodiums is found to be energetically favored. Starting from the ab initio band structures, a many-body second-order perturbation theory leads to a pseudospin-21 Hamiltonian with estimated magnetic interactions. We show that the experimentally observed zigzag magnetic state is stabilized only when the first-neighbor Kitaev coupling dominates over the Heisenberg term, both of which are highly suppressed due to presence of eg orbitals. A third-neighbor Heisenberg interaction is found dominant in both these compounds. We also present a phase diagram for Na2Co2TeO6 by varying the electron-electron and spin-orbit interactions. The computed spin excitation spectra are found to capture essential features of recent experimental magnon spectrum, lending support to our results.
Can we realize Kitaev quantum spin liquids in the Jeff=1/2 honeycomb cobaltates?
The quest for Kitaev quantum spin liquids has led to great interest in honeycomb quantum magnets with strong spin-orbit coupling. It has been recently proposed that even Mott insulators with 3d transition metal ions, having nominally weak spin-orbit coupling, can realize such exotic physics. Motivated by this, we study the rhombohedral honeycomb cobaltates CoTiO3, BaCo2(PO4)2, and BaCo2(AsO4)2, using ab initio density functional theory, which takes into account realistic crystal field distortions and chemical information, in conjunction with exact diagonalization numerics. We show that these Co2+ magnets host jeff=1/2 local moments with highly anisotropic g-factors, and we extract their full spin Hamiltonians including longer-range and anisotropic exchange couplings. For CoTiO3, we find a nearest-neighbor easy-plane ferromagnetic XXZ model with additional bond-dependent anisotropies and interlayer exchange, which supports three-dimensional (3D) Dirac nodal line magnons. In contrast, for BaCo2(PO4)2 and BaCo2(AsO4)2, we find a strongly suppressed interlayer coupling, and significant frustration from additional third-neighbor antiferromagnetic exchange mediated by P/As. Such bond-anisotropic J1-J3 spin models can support collinear zig-zag or coplanar spiral ground states; we discuss their dynamical spin correlations which reveal a gapped Goldstone mode, and argue that the effective parameters of these pseudospin-1/2 models may be strongly renormalized by coupling to a low energy spin-exciton. Our results call for re-examining proposals for realizing Kitaev spin liquids in the honeycomb cobaltates.
The current efforts to find the materials hosting Kitaev model physics have been focused on Mott insulators of d5 pseudospin-1/2 ions Ir4+ and Ru3+ with t2g5(S=1/2,L=1) electronic configuration. Here we propose that the Kitaev model can be realized in materials based on d7 ions with t2g5eg2(S=3/2,L=1) configuration such as Co2+, which also host the pseudospin-1/2 magnetism. Considering possible exchange processes, we have derived the d7 pseudospin-1/2 interactions in ${90}^{\ensuremath{\circ}}$ bonding geometry. The obtained Hamiltonian comprises the bond-directional Kitaev K and isotropic Heisenberg J interactions as in the case of d5 ions. However, we find that the presence of additional spin-active eg electrons radically changes the balance between Kitaev and Heisenberg couplings. Most remarkably, we show that the exchange processes involving eg spins are highly sensitive to whether the system is in Mott ($U<\mathrm{\ensuremath{\Delta}}$) or charge-transfer ($U>\mathrm{\ensuremath{\Delta}}$) insulating regime. In the latter case, to which many cobalt compounds do actually belong, the antiferromagnetic Heisenberg coupling J is strongly suppressed and spin-liquid phase can be stabilized. The results suggest cobalt-based materials as promising candidates for the realization of the Kitaev model.
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.
By considering two ab initio-based complementary approaches, we analyze the electronic structure and extract effective spin models of BaCo2(AsO4)2, a honeycomb material which has been proposed as a candidate for Kitaev physics. Both methods show that the dominant direct hopping makes the bond-dependent Kitaev term negligible, diverting the material away from the sought-after spin-liquid regime. As a result, we present a simple three-parameter exchange model to describe the interactions of the lowest doublet of the honeycomb cobaltate BaCo2(AsO4)2. Remarkably, it is the third-neighbor interactions, both isotropic and anisotropic, that are responsible for the standout double-zigzag ground state of BaCo2(AsO4)2, stabilized by quantum fluctuations. A significantly large third-nearest-neighbor hopping, observed ab initio, supports the importance of the third-neighbor interactions in the stabilization of the unique ground state of BaCo2(AsO4)2.
The exact solution of Kitaev's spin-1/2 honeycomb spin-liquid model has sparked an intense search for Mott insulators hosting bond-dependent Kitaev interactions, of which Na2IrO3 and $\ensuremath{\alpha}\text{\ensuremath{-}}\mathrm{Ru}{\mathrm{Cl}}_{3}$ are prime examples. Subsequently, it has been proposed that also spin-1 and spin-3/2 analogs of Kitaev interactions may occur in materials with strong spin-orbit coupling. As a minimal model to describe these Kitaev materials, we study the Heisenberg-Kitaev Hamiltonian in a consistent 1/S expansion, with S being the spin size. We present a comprehensive study of this model in the presence of an external magnetic field applied along two different directions, [001] and [111], for which an intricate classical phase diagram has been reported. In both settings, we employ spin-wave theory in a number of ordered phases to compute phase boundaries at the next-to-leading order in 1/S and show that quantum corrections substantially modify the classical phase diagram. More broadly, our work presents a consistent route to investigate the leading quantum corrections in spin models that break spin-rotational symmetry.
In the search for quantum spin liquids, candidate materials for the Kitaev model and its extensions have been intensively explored during the past decade, as the models realize the exact quantum spin liquids in the ground state. Thus far, insulating magnets in the low-spin d5 electron configuration under the strong spin-orbit coupling have been studied for realizing the Kitaev-type bond-dependent anisotropic interactions between the spin-orbital entangled Kramers doublets. To extend the candidates, here we investigate the systems in a high-spin d7 electron configuration, whose ground state is described by the spin-orbital entangled Kramers doublet. By the second-order perturbation in terms of the ${t}_{2g}\ensuremath{-}{t}_{2g}$ and ${t}_{2g}\ensuremath{-}{e}_{g}$ hoppings, we show that the effective spin model possesses the anisotropic Kitaev interactions as well as the isotropic Heisenberg ones. While the Kitaev interaction is always ferromagnetic, the Heisenberg interaction can become either ferromagnetic or antiferromagnetic depending on the Coulomb interactions and the crystalline electric fields. We also derive the effective model for the low-spin d5 electron configuration within the same perturbation scheme, in which the Kitaev interaction becomes both ferromagnetic and antiferromagnetic, while the Heisenberg one is always ferromagnetic. Referring to the previous study for the Kitaev-Heisenberg model, we find that the quantum spin liquid phase exists in the reasonable parameter region in both d7 and d5 cases, while the former has a richer structure of the phase diagram. We discuss the advantages of the d7 case in comparison with the d5 case. Our results indicate that the high-spin d7 state provides another platform for the Kitaev-type quantum spin liquid.