The Kitaev spin model offers an exact quantum spin liquid in the ground state, which has stimulated exploration of its material realization over the last decade. Thus far, most of the candidates are found in $4d$- and $5d$-electron compounds, in which the low-spin $d^5$ electron configuration subject to strong spin-orbit coupling comprises a Kramers doublet with the effective angular momentum $j_{\rm eff}=1/2$ and gives rise to the bond-dependent anisotropic interactions in the Kitaev model. Here we theoretically investigate other candidates in $4f$-electron compounds with the $f^1$ electron configuration on both quasi-two-dimensional honeycomb and three-dimensional hyperhoneycomb structures, $A_2$PrO$_3$ with $A$=Li, Na, K, Rb, and Cs. Based on {\it ab initio} calculations, we show that the electronic structures of these compounds host a spin-orbital entangled Kramers doublet with $j_{\rm eff}=1/2$ in the $Γ_7$ state. By constructing the tight-binding Hamiltonian and performing a perturbation expansion, we find that the low-energy magnetic properties of $A_2$PrO$_3$ are well described by an effective spin model with the $J$-$K$-$Γ'$ model. The most remarkable feature is that the Kitaev interaction $K$ is antiferromagnetic, in contrast to the ferromagnetic one in the $d^5$ candidates at hand. The exchange interactions are systematically modulated by changing the $A$-site cations. As a consequence, the compounds with $A$=Li and Na may have a dominant antiferromagnetic $K$, but $J$ dominates $K$ and $Γ'$ in the cases with $A$=Rb and Cs. Also, by computing the ground states of the $J$-$K$-$Γ'$ model by using the exact diagonalization, we map out the systematic evolution of the model parameters in the phase diagram. Our results will stimulate material exploration of the antiferromagnetic Kitaev interaction in $f$-electron compounds.
We present a thorough experimental study of the three-dimensional hyperhoneycomb Kitaev magnet $β$-Li$_2$IrO$_3$, using a combination of inelastic neutron scattering (INS), time-domain THz spectroscopy, and heat capacity measurements. The main results include a massive low-temperature reorganization of the INS spectral weight that evolves into a broad peak centered around 12 meV, and a distinctive peak in the THz data at 2.8(1) meV. A detailed comparison to powder-averaged spin-wave theory calculations reveals that the positions of these two features are controlled by the anisotropic $Γ$ coupl…
We study the finite temperature phase diagram of the Heisenberg-Kitaev model on a three dimensional hyperhoneycomb lattice. Using semiclassical analysis and classical Monte-Carlo simulations, we investigate quantum and thermal order-by-disorder, as well as the magnetic ordering temperature. We find the parameter regime where quantum and thermal fluctuations favor different magnetic orders, which leads to an additional finite temperature phase transition within the ordered phase. This transition, however, occurs at a relatively low temperature and the entropic effects may dominate most of the f…
We report the existence of a phase transition at high temperature in the 3D Kitaev candidate material, $β$-Li$_2$IrO$_3$. We show that the transition is bulk, intrinsic and orders a tiny magnetic moment with a spatially anisotropic saturation moment. We show that even though this transition is global, it does not freeze the local Ir moments, which order at much lower temperatures into an incommensurate state. Rather, the ordered moment has an orbital origin that is coupled to spin correlations, likely of a Kitaev origin. The separate ordering of spin-correlated orbital moments and of local Ir …
The recently-synthesized iridate $β$-Li$_2$IrO$_3$ has been proposed as a candidate to display novel magnetic behavior stabilized by frustration effects from bond-dependent, anisotropic interactions (Kitaev model) on a three-dimensional "hyperhoneycomb" lattice. Here we report a combined study using neutron powder diffraction and magnetic resonant x-ray diffraction to solve the complete magnetic structure. We find a complex, incommensurate magnetic order with non-coplanar and counter-rotating Ir moments, which surprisingly shares many of its features with the related structural polytype "strip…
Motivated by recent experiments on $β-$Li$_2$IrO$_3$, we study the phase diagram of the Heisenberg-Kitaev model on a three dimensional lattice of tri-coordinated Ir$^{4+}$, dubbed the hyperhoneycomb lattice by Takagi et. al. The lattice geometry of this material, along with Ir$^{4+}$ ions carrying $J_{\rm eff}=1/2$ moments, suggests that the Heisenberg-Kitaev model may effectively capture the low energy spin-physics of the system in the strong-coupling limit. Using a combination of semiclassical analysis, exact solution and slave-fermion mean field theory, we find, in addition to the spin-liqu…
We present a theoretical study of the static and dynamical properties of the Kitaev magnet $β$-Li$_2$IrO$_3$ based on the minimal $J$-$K$-$Γ$ model. We argue that the incommensurate magnetic order of $β$-Li$_2$IrO$_3$ can be qualitatively understood in terms of a long-wavelength twisting of a nearby commensurate, period-3 state, that shares the same symmetry, propagation vector, counter-rotation of the two spin sublattices, and non-coplanarity. This period-3 state shows very different structure when either the Kitaev interaction $K$ or the off-diagonal exchange anisotropy $Γ$ is dominant, feat…
We discuss magnetically ordered states, arising in Heisenberg-Kitaev and related spin models, on three-dimensional (3D) harmonic honeycomb lattices. For large classes of ordered states, we show that they can be mapped onto two-dimensional (2D) counterparts on the honeycomb lattice, with the classical energetics being identical in the 2D and 3D cases. As an example, we determine the phase diagram of the classical nearest-neighbor Heisenberg-Kitaev model on the hyperhoneycomb lattice in a magnetic field: This displays rich and complex behavior akin to its 2D counterpart, with most phases and pha…
A polycrystalline sample of the hyperhoneycomb iridate $β$-ZnIrO$_3$ was synthesized via a topochemical reaction, and its structural, magnetic, and thermodynamic properties were investigated. The magnetization and heat capacity data show the absence of long-range magnetic order at least down to 2 K. A positive Curie-Weiss temperature $θ_W \sim 45$ K probed by the temperature dependence of magnetic susceptibility indicates that a Kitaev interaction is dominant. These observations suggest that a quantum spin liquid may have been realized. Furthermore, the observation of linear temperature-depend…
We present numerical evidence for the presence of a finite-temperature ($T$) phase transition separating paramagnet and quantum spin liquid in a three-dimensional variant of the Kitaev model defined on a hyperhoneycomb lattice in the limit of strong anisotropy; the model is mapped onto an effective Ising-type model, where elementary excitations consist of closed loops of flipped Ising-type variables. Analyzing this effective model by Monte Carlo simulation, we find a phase transition from quantum spin liquid to paramagnet at a finite critical temperature $T_c$. We also compute the magnetic pro…
The family of edge-sharing tri-coordinated iridates and ruthenates has emerged in recent years as a major platform for Kitaev spin liquid physics, where spins fractionalize into emergent magnetic fluxes and Majorana fermions with Dirac-like dispersions. While such exotic states are usually pre-empted by long-range magnetic order at low temperatures, signatures of Majorana fermions with long coherent times have been predicted to manifest at intermediate and higher energy scales, similar to the observation of spinons in quasi-1D spin chains. Here we present a Resonant Inelastic X-ray Scattering …
We explore the response of Ir $5d$ orbitals to pressure in $β$-$\mathrm{Li_2IrO_3}$, a hyperhoneycomb iridate in proximity to a Kitaev quantum spin liquid (QSL) ground state. X-ray absorption spectroscopy reveals a reconstruction of the electronic ground state below 2 GPa, the same pressure range where x-ray magnetic circular dichroism shows an apparent collapse of magnetic order. The electronic reconstruction, which manifests a reduction in the effective spin-orbit (SO) interaction in $5d$ orbitals, pushes $β$-$\mathrm{Li_2IrO_3}$ further away from the pure $J_{\rm eff}=1/2$ limit. Although l…
We present a unified description of the response of the hyperhoneycomb Kitaev magnet $β$-$\text{Li}_2\text{IrO}_3$ to applied magnetic fields along the orthorhombic directions ${\bf a}$, ${\bf b}$ and ${\bf c}$. This description is based on the minimal nearest-neighbor $J$-$K$-$Γ$ model and builds on the idea that the incommensurate counter-rotating order observed experimentally at zero field can be treated as a long-distance twisting of a nearby commensurate order with six spin sublattices. The results reveal that the behavior of the system for ${\bf H}\parallel{\bf a}$, ${\bf H}\parallel{\bf…
The quantum spin liquid is an enigmatic quantum state in insulating magnets, in which conventional long-range order is suppressed by strong quantum fluctuations. Recently, an unconventional phase transition was reported between the low-temperature quantum spin liquid and the high-temperature paramagnet in the Kitaev model on a three-dimensional hyperhoneycomb lattice. Here, we show that a similar "liquid-gas" transition takes place in another three-dimensional lattice, the hyperoctagon lattice. We investigate the critical phenomena by adopting the Green-function based Monte Carlo technique wit…
Evolution of crystal field and intraionic interactions in the ilmenite $A$IrO$_3$ ($A$ = Mg, Zn, Cd) and hyperhoneycomb $β$-ZnIrO$_3$
Tokyo University of Agriculture and Technology（东京农工大学）；National Institutes for Quantum and Radiological Science and Technology（量子与放射线科学研究所）；Tohoku University（东北大学）
$^7$Li nuclear magnetic resonance (NMR) and terahertz (THz) spectroscopies are used to probe magnetic excitations and their field dependence in the hyperhoneycomb Kitaev magnet $β$-Li$_2$IrO$_3$. Spin-lattice relaxation rate ($1/T_1$) measured down to 100\,mK indicates gapless nature of the excitations at low fields (below $H_c\simeq 2.8$\,T), in contrast to the gapped magnon excitations found in the honeycomb Kitaev magnet $α$-RuCl$_3$ at zero applied magnetic field. At higher temperatures in $β$-Li$_2$IrO$_3$, $1/T_1$ passes through a broad maximum without any clear anomaly at the Néel tempe…
We study the 3D Kitaev and Kitaev-Heisenberg models respectively on the hyperhoneycomb and hyperoctagon lattices, both at zero and finite-temperature, in the thermodynamic limit. Our analysis relies on advanced tensor network (TN) simulations based on graph Projected Entangled-Pair States (gPEPS). We map out the TN phase diagrams of the models and characterize their underlying gapped and gapless phases both at zero and finite temperature. In particular, we demonstrate how cooling down the hyperhoneycomb system from high-temperature leads to fractionalization of spins to itinerant Majorana ferm…
Hyperhoneycomb iridate $β$-Li$_2$IrO$_3$ is a three-dimensional analogue of two-dimensional honeycomb iridates, such as $α$-Li$_2$IrO$_3$, which recently appeared as another playground for the physics of Kitaev-type spin liquid. $β$-Li$_2$IrO$_3$ shows a non-collinear spiral ordering of spin-orbital-entangled $J_{\rm eff}$ = 1/2 moments at low temperature, which is known to be suppressed under a pressure of $\sim$2 GPa. With further increase of pressure, a structural transition is observed at $P_{\rm S}$ $\sim$ 4 GPa at room temperature. Using the neutron powder diffraction technique, the crys…
We investigate possible quantum ground states as well as the classical limit of a frustrated J1-J2 Heisenberg model on the three-dimensional (3D) hyperhoneycomb lattice. Our study is inspired by the recent discovery of beta-Li2IrO3, where Ir^{4+} ions form a 3D network with each lattice site being connected to three nearest neighbors. We focus on the influence of magnetic frustration caused by the second-nearest neighbor spin interactions. Such interactions are likely to be significant due to large extent of 5d orbitals in iridates or other 5d transition metal oxides. In the classical limit, t…
There have been tremendous experimental and theoretical efforts toward discovery of quantum spin liquid phase in honeycomb-based-lattice materials with strong spin-orbit coupling. Here the bond-dependent Kitaev interaction between local moments provides strong magnetic frustration and if it is the only interaction present in the system, it will lead to an exactly solvable quantum spin liquid ground state. In all of these materials, however, the ground state is in a magnetically ordered phase due to additional interactions between local moments. Recently, it has been reported that the magnetic …
The family of "Kitaev materials" provides an ideal platform to study quantum spin liquids and their neighboring magnetic orders. Motivated by the possibility of a quantum spin liquid ground state in pressurized hyperhoneycomb iridate $β$-Li$_2$IrO$_3$, we systematically classify and study symmetric quantum spin liquids on the hyperhoneycomb lattice, using the Abrikosov-fermion representation. Among the 176 symmetric $U(1)$ spin liquids (and 160 $Z_2$ spin liquids), we identify 8 "root" $U(1)$ spin liquids in proximity to the ground state of the solvable Kitave model on hyperhonecyomb lattices.…
We propose that resonant inelastic X-ray scattering (RIXS) is an effective probe of the fractionalized excitations in three-dimensional (3D) Kitaev spin liquids. While the non-spin-conserving RIXS responses are dominated by the gauge-flux excitations and reproduce the inelastic-neutron-scattering response, the spin-conserving (SC) RIXS response picks up the Majorana-fermion excitations and detects whether they are gapless at Weyl points, nodal lines, or Fermi surfaces. As a signature of symmetry fractionalization, the SC RIXS response is suppressed around the $Γ$ point. On a technical level, w…
The magnetic field response of the Mott-insulating honeycomb iridate Na$_{2}$IrO$_{3}$ is investigated using torque magnetometry measurements in magnetic fields up to 60 tesla. A peak-dip structure is observed in the torque response at magnetic fields corresponding to an energy scale close to the zigzag ordering ($\approx 15~K$) temperature. Using exact diagonalization calculations, we show that such a distinctive signature in the torque response constrains the effective spin models for these classes of Kitaev materials to ones with dominant ferromagnetic Kitaev interactions, while alternative…
Topological phases in magnetic materials offer novel tunability of topological properties via varying the underlying magnetism. We show that three dimensional Kitaev materials can provide a great opportunity for controlling symmetry-protected topological nodal magnons. These materials are originally considered as strong candidates for the Kitaev quantum spin liquid due to the bond-dependent frustrating spin exchange interactions. As a concrete example, we consider the symmetry and topology of the magnons in the canted zig-zag ordered state in the hyperhoneycomb $β\text{-}\mathrm{Li_2IrO_3}$, w…
The recently discovered three-dimensional hyperhoneycomb iridate, $β$-Li$_2$IrO$_3$, has raised hopes for the realization of dominant Kitaev interaction between spin-orbit entangled local moments due to its near-ideal lattice structure. If true, this material may lie close to the sought-after quantum spin liquid phase in three dimensions. Utilizing ab-initio electronic structure calculations, we first show that the spin-orbit entangled basis, $j_{\rm eff}$=1/2, correctly captures the low energy electronic structure. The effective spin model derived in the strong coupling limit supplemented by …
Motivated by recent experiments, we consider a generic spin model in the $j_{\text{eff}}=1/2$ basis for the hyperhoneycomb and harmonic-honeycomb iridates. Based on microscopic considerations, the effect of an additional bond-dependent anisotropic spin exchange interaction ($Γ$) beyond the Heisenberg-Kitaev model is investigated. We obtain the magnetic phase diagrams of the hyperhoneycomb and harmonic-honeycomb ($\mathcal{H}\text{--}1$) lattices via a combination of the Luttinger-Tisza approximation, single-$\mathbf{Q}$ variational ansatz, and classical Monte Carlo simulated annealing. The res…
The unconventional magnetic orderings found in Kitaev spin liquid candidates suggest frustration of spin interactions, and raise a possibility of nearby spin liquid phases. In particular, counter-rotating spiral ordering in three-dimensional (3D) iridates is striking, and understanding the microscopic mechanism of such ordering may provide routes to 3D Kitaev spin liquids. We study a minimal 3D model including Kitaev $K$ and a symmetric off-diagonal bond-dependent $Γ$ interaction on the hyperhoneycomb lattice using exact diagonalization. We first show that a 12-site unitary transformation unve…
A three-dimensional Kitaev model on a hyperhoneycomb lattice is investigated numerically at finite temperature. The Kitaev model is one of the solvable quantum spin models, where the ground state is given by gapped and gapless spin liquids, depending on the anisotropy of the interactions. This model can be rewritten as a free Majorana fermion system coupled with $Z_2$ variables. The density of states of Majorana fermions shows an excitation gap in the gapped region, while it is semimetallic in the gapless region reflecting the Dirac node. Performing the Monte Carlo simulation, we calculate the…
We investigate the magnetic excitations of the hyperhoneycomb Kitaev magnet $β$-$\text{Li}_2\text{IrO}_3$ by means of inelastic Raman scattering. The spectra exhibits a coexistence of a broad scattering continuum and two sharp low-energy peaks at 2.5 meV and 3 meV, with a distinctive polarization dependence. While the continuum is suggestive of fractional quasi-particles emerging from a proximate quantum spin liquid phase, the sharp peaks provide the first experimental signature of the `non-Loudon-Fleury' one-magnon scattering processes proposed recently [Phys. Rev. B 104, 144412 (2021)]. The …
We theoretically propose a family of $f$-electron based magnets that realizes Kitaev-type bond-dependent anisotropic interactions. Based on {\it ab initio} calculations, we show that $A_2$PrO$_3$ ($A$: alkali metals) crystalize in a triclinic structure with honeycomb layers of edge-sharing PrO$_6$ octahedra. Each Pr$^{4+}$ cation has a $4f$ electron in the $Γ_7$ doublet, which comprises a spin-orbital entangled Kramers pair with the effective moment $J_{\rm eff}=1/2$. By using the Wannier orbitals from the {\it ab initio} calculations, we find that the effective interactions between the $J_{\r…
The layered honeycomb magnet $α$-Li$_2$IrO$_3$ has been theoretically proposed as a candidate to display novel magnetic behaviour associated with Kitaev interactions between spin-orbit entangled $j_{\rm eff}=1/2$ magnetic moments on a honeycomb lattice. Here we report single crystal magnetic resonant x-ray diffraction combined with powder magnetic neutron diffraction to reveal an incommensurate magnetic order in the honeycomb layers with Ir magnetic moments counter-rotating on nearest-neighbour sites. This type of magnetic structure has not been reported experimentally before in honeycomb magn…
The fractionalization of quantum numbers in interacting quantum-many body systems is a central motif in condensed matter physics with prominent examples including the fractionalization of the electron in quantum Hall liquids or the emergence of magnetic monopoles in spin-ice materials. Here we discuss the fractionalization of magnetic moments in three-dimensional Kitaev models into Majorana fermions (and a $\mathbb Z_2$ gauge field) and their emergent collective behavior. We analytically demonstrate that the Majorana fermions form a Weyl superconductor for the Kitaev model on the recently synt…
The long-sought quantum spin liquid is a quantum-entangled magnetic state leading to the fractionalization of spin degrees of freedom. Quasiparticles emergent from the fractionalization affect not only the ground state properties but also thermodynamic behavior in a peculiar manner. We here investigate how the spin dynamics evolves from the high-temperature paramagnet to the quantum spin liquid ground state, for the Kitaev spin model describing the fractionalization into itinerant matter fermions and localized $Z_2$ gauge fluxes. Beyond the previous study [J. Yoshitake, J. Nasu, and Y. Motome,…
We revisit the theory of magnetic Raman scattering in Mott insulators with strong spin-orbit coupling, with a major focus on Kitaev materials. We show that Kitaev materials with bond-anisotropic interactions are generally expected to show both one- and two-magnon responses. It is further shown that, in order to obtain the correct leading contributions to the Raman vertex operator $\mc{R}$, one must take into account the precise, photon-assisted microscopic hopping processes of the electrons and that, in systems with multiple hopping paths, $\mc{R}$ contains terms beyond those appearing in the …
Temperature-pressure phase diagram of the Kitaev hyperhoneycomb iridate $β$-Li$_2$IrO$_3$ is explored using magnetization, thermal expansion, magnetostriction, and muon spin rotation ($μ$SR) measurements, as well as single-crystal x-ray diffraction under pressure and ab initio calculations. The Neel temperature of $β$-Li$_2$IrO$_3$ increases with the slope of 0.9 K/GPa upon initial compression, but the reduction in the polarization field $H_c$ reflects a growing instability of the incommensurate order. At 1.4 GPa, the ordered state breaks down upon a first-order transition giving way to a new …
Motivated by the recent synthesis of two insulating Li$_2$IrO$_3$ polymorphs, where Ir$^{4+}$ $S_{eff}$=1/2 moments form 3D ("harmonic") honeycomb structures with threefold coordination, we study magnetic Hamiltonians on the resulting $β$-Li$_2$IrO$_3$ hyperhoneycomb lattice and $γ$-Li$_2$IrO$_3$ stripyhoneycomb lattice. Experimentally measured magnetic susceptibilities suggest that Kitaev interactions, predicted for the ideal 90$^\circ$ Ir-O-Ir bonds, are sizable in these materials. We first consider pure Kitaev interactions, which lead to an exactly soluble 3D quantum spin liquid (QSL) with …
