Colloquium : Herbertsmithite and the search for the quantum spin liquid

With strong geometric frustration and quantum fluctuations, S=1/2 quantum Heisenberg antiferromagnets on the Kagome lattice has long been considered as an ideal platform to realize spin liquid (SL), a novel phase with no symmetry breaking and fractionalized excitations. A recent numerical study of Heisenberg S=1/2 Kagome lattice model (HKLM) show that in contrast to earlier studies, the ground state is a singlet-gapped SL with signatures of Z2 topological order. Motivated by this numerical discovery, we use projective symmetry group to classify all 20 possible Schwinger-fermion mean-field states of Z2 SLs on Kagome lattice. Among them we found only one gapped Z2 SL (which we call Z2[0,\pi]\beta state) in the neighborhood of U(1)-Dirac SL state, whose energy is found to be the lowest among many other candidate SLs including the uniform resonating-valentce-bond states. We thus propose this Z2[0,\pi]\beta state to be the numerically discovered SL ground state of HKLM.

Recent numerical studies have provided strong evidence for a gapped $Z_2$ quantum spin liquid in the kagome lattice spin-1/2 Heisenberg model. A special feature of spin liquids is that symmetries can be fractionalized, and different patterns of symmetry fractionalization imply distinct phases. The symmetry fractionalization pattern for the kagome spin liquid remains to be determined. A popular approach to studying spin liquids is to decompose the physical spin into partons obeying either bose (Schwinger bosons) or fermi (Abrikosov fermions) statstics, which are then treated within the mean-field theory. A longstanding question has been whether these two approaches are truly distinct, or describe the same phase in complementary ways. Here we show that all 8 $Z_2$ spin liquid phases in Schwinger-boson mean-field (SBMF) construction can also be described in terms of Abrikosov fermions, unifying pairs of theories that seem rather distinct. The key idea is that for $Z_2$ spin liquid states that admit a SBMF description on kagome lattice, the symmetry fractionalization of visions is uniquely fixed. Two promising candidate states for kagome Heisenberg model, Sachdev's $Q_{1}=Q_{2}$ SBMF state and Lu-Ran-Lee's $Z_2[0,\pi]\beta$ Abrikosov fermion state, are found to describe the same symmetric spin liquid phase. We expect these results to aid in a complete specification of the numerically observed spin liquid phase. We also discuss a set of $Z_2$ spin liquid phases in fermionic parton approach, where spin rotation and lattice symmetries protect gapless edge states, that do not admit a SBMF description.

There is growing evidence from both experiment and numerical studies that low half-odd integer quantum spins on a kagome lattice with predominant antiferromagnetic near neighbor interactions do not order magnetically or break lattice symmetries even at temperatures much lower than the exchange interaction strength. Moreover, there appear to be a plethora of low energy excitations, predominantly singlets but also spin carrying, which suggest that the putative underlying quantum spin liquid is a gapless ``critical spin liquid'' rather than a gapped spin liquid with topological order. Here, we develop an effective field theory approach for the spin-1/2 Heisenberg model with easy-plane anisotropy on the kagome lattice. By employing a vortex duality transformation, followed by a fermionization and flux-smearing, we obtain access to a gapless yet stable critical spin liquid phase, which is described by (2+1)-dimensional quantum electrodynamics (QED$_3$) with an emergent $\mathrm{SU}(8)$ flavor symmetry. The specific heat, thermal conductivity, and dynamical structure factor are extracted from the effective field theory, and contrasted with other theoretical approaches to the kagome antiferromagnet.

We study the quantum phase diagram of the spin-$1/2$ Heisenberg model on the kagom\'e lattice with first-, second-, and third-neighbor interactions $J_1$, $J_2$, and $J_3$ by means of density matrix renormalization group. For small $J_2$ and $J_3$, this model sustains a time-reversal invariant quantum spin liquid phase. With increasing $J_2$ and $J_3$, we find in addition a $q=(0,0)$ N\'{e}el phase, a chiral spin liquid phase, a valence-bond crystal phase, and a complex non-coplanar magnetically ordered state with spins forming the vertices of a cuboctahedron known as a cuboc1 phase. Both the chiral spin liquid and cuboc1 phase break time reversal symmetry in the sense of spontaneous scalar spin chirality. We show that the chiralities in the chiral spin liquid and cuboc1 are distinct, and that these two states are separated by a strong first order phase transition. The transitions from the chiral spin liquid to both the $q=(0,0)$ phase and to time-reversal symmetric spin liquid, however, are consistent with continuous quantum phase transitions.

Geometric frustration of magnetic ions can lead to a quantum spin liquid ground state where long range magnetic order is avoided despite strong exchange interactions. The physical realization of quantum spin liquids comprises a major unresolved area of contemporary materials science. One prominent magnetically-frustrated structure is the kagome lattice. The naturally occurring minerals herbertsmithite [ZnCu$_3$(OH)$_6$Cl$_2$] and Zn-substituted barlowite [ZnCu$_3$(OH)$_6$BrF] both feature perfect kagome layers of spin-$1/2$ copper ions and display experimental signatures consistent with a quantum spin liquid state at low temperatures. To investigate other possible candidates within this material family, we perform a systematic first-principles combinatorial exploration of structurally related compounds [$A$Cu$_3$(OH)$_6B_2$ and $A$Cu$_3$(OH)$_6BC$] by substituting non-magnetic divalent cations ($A$) and halide anions ($B$, $C$). After optimizing such structures using density functional theory, we compare various structural and thermodynamic parameters to determine which compounds are most likely to favor a quantum spin liquid state. Convex hull calculations using binary compounds are performed to determine feasibility of synthesis. We also estimate the likelihood of interlayer substitutional disorder and spontaneous distortions of the kagome layers. After considering all of these factors as a whole, we select several promising candidate materials that we believe deserve further attention.

The structural-magnetic models of 25 antiferromagnetic kagome cuprates similar to herbertsmithite (ZnCu3(OH)6Cl2)—a perspective spin liquid—have been calculated and analyzed. Main correlations between the structure and magnetic properties of these compounds were revealed. It has been demonstrated that, in all AFM kagome cuprates, including herbertsmithite, there exists the competition between the exchange interaction and the antisymmetric anisotropic exchange one (the Dzyaloshinskii–Moriya interaction), as magnetic ions are not linked to the center of inversion in the kagome lattice. This competition is strengthened in all the kagome AFM, except herbertsmithite, by one more type of the anisotropy (duality) of the third in length J3 magnetic couplings (strong J3(J12) next-to-nearest-neighbor couplings in linear chains along the triangle edges and very weak FM or AFM J3(J d) couplings along the hexagon diagonals). The above couplings are crystallographically identical, but are divided to two types of different in strength magnetic interactions. The existence of duality of J3 couplings originated from the structure of the kagome lattice itself. Only combined contributions of dual J3 couplings with anisotropic Dzyaloshinskii–Moriya interactions are capable to suppress frustration of kagome antiferromagnetics. It has been demonstrated that the possibility of elimination of such a duality in herbertsmithite, which made it a spin liquid, constitutes a rare lucky event in the kagome system. Three crystal chemistry criteria of the existence of spin liquids on the kagome lattice have been identified: first, the presence of frustrated kagome lattices with strong dominant antiferromagnetic nearest-neighbor J1 couplings competing only with each other in small triangles; second, magnetic isolation of these frustrated kagome lattices; and third, the absence of duality of the third in length J3 magnetic couplings.

The spin-1/2 Heisenberg model on the kagome lattice, which is closely\nrealized in layered Mott insulators such as ZnCu$_3$(OH)$_6$Cl$_2$, is one of\nthe oldest and most enigmatic spin-1/2 lattice model. While the numerical\nevidence has accumulated in favor of a quantum spin liquid, the debate is still\nopen as to whether it is a $Z_2$ spin liquid with very short-range correlations\n(some kind of Resonating Valence Bond spin liquid), or an algebraic spin-liquid\nwith power-law correlations. To address this issue, we have pushed the program\nstarted by Rokhsar and Kivelson in their derivation of the effective quantum\ndimer model description of Heisenberg models to unprecedented accuracy for the\nspin-1/2 kagome, by including all the most important virtual singlet\ncontributions on top of the orthogonalization of the nearest-neighbor valence\nbond singlet basis. Quite remarkably, the resulting picture is a competition\nbetween a $Z_2$ spin liquid and a diamond valence bond crystal with a 12-site\nunit cell, as in the DMRG simulations of Yan, Huse and White. Furthermore, we\nfound that, on cylinders of finite diameter $d$, there is a transition between\nthe $Z_2$ spin liquid at small $d$ and the diamond valence bond crystal at\nlarge $d$, the prediction of the present microscopic description for the 2D\nlattice. These results show that, if the ground state of the spin-1/2 kagome\nantiferromagnet can be described by nearest-neighbor singlet dimers, it is a\ndiamond valence bond crystal, and, a contrario, that, if the system is a\nquantum spin liquid, it has to involve long-range singlets, consistent with the\nalgebraic spin liquid scenario.\n

The Kitaev-Heisenberg model on the honeycomb lattice has been studied for the purpose of finding exotic states such as quantum spin liquid and topological orders. On the kagome lattice, in spite of a spin-liquid ground state in the Heisenberg model, the stability of the spin-liquid state has hardly been studied in the presence of the Kitaev interaction. Therefore, we investigate the ground state of the classical and quantum spin systems of the kagome Kitaev-Heisenberg model. In the classical system, we obtain an exact phase diagram that has an eight-fold degenerated canted ferromagnetic phase and a subextensive degenerated Kitaev antiferromagnetic phase. In the quantum system, using the Lanczos-type exact diagnalization and cluster mean-field methods, we obtain two quantum spin-liquid phases, an eight-fold degenerated canted ferromagnetic phase similar to the classical spin system, and an eight-fold degenerated $\bf q=0$ $120^\circ$ ordered phase induced by quantum fluctuation. These results may provide a crucial clue to recently observed magnetic structures of the rare-earth-based kagome lattice compounds $A_2$RE$_3$Sb$_3$O$_{14}$ ($A$ = Mg, Zn; RE = Pr, Nd, Gd, Tb, Dy, Ho, Er, Yb).

We present a general review of the projective symmetry group classification of fermionic quantum spin liquids for lattice models of spin $S=1/2$. We then introduce a systematic generalization of the approach for symmetric $\mathbb{Z}_2$ quantum spin liquids to the one of chiral phases (i.e., singlet states that break time reversal and lattice reflection, but conserve their product). We apply this framework to classify and discuss possible chiral spin liquids on triangular and kagome lattices. We give a detailed prescription on how to construct quadratic spinon Hamiltonians and microscopic wave functions for each representation class on these lattices. Among the chiral $\mathbb{Z}_2$ states, we study the subset of U(1) phases variationally in the antiferromagnetic $J_1$-$J_2$-$J_d$ Heisenberg model on the kagome lattice. We discuss static spin structure factors and symmetry constraints on the bulk spectra of these phases.

The properties of ground state of spin-\frac{1}{2}12 kagome antiferromagnetic Heisenberg (KAFH) model have attracted considerable interest in the past few decades, and recent numerical simulations reported a spin liquid phase. The nature of the spin liquid phase remains unclear. For instance, the interplay between symmetries and Z_2Z2 topological order leads to different types of Z_2Z2 spin liquid phases. In this paper, we develop a numerical simulation method based on symmetric projected entangled-pair states (PEPS), which is generally applicable to strongly correlated model systems in two spatial dimensions. We then apply this method to study the nature of the ground state of the KAFH model. Our results are consistent with that the ground state is a U(1)U(1) Dirac spin liquid rather than a Z_2Z2 spin liquid.

By using the variational Monte Carlo technique, we study the spin-1/2 XXZ antiferromagnetic model (with easy-plane anisotropy) on the kagome lattice. A class of Gutzwiller projected fermionic states with a spin Jastrow factor is considered to describe either spin liquids [with U(1) or Z(2) symmetry] or magnetically ordered phases [with q = (0,0) or q = (4 pi/3,0)]. We find that the magnetic states are not stable in the thermodynamic limit. Moreover, there is no energy gain to break the gauge symmetry from U(1) to Z(2) within the spin-liquid states, as previously found in the Heisenberg model. The best variational wave function is therefore the U(1) Dirac state, supplemented by the spin Jastrow factor. Furthermore, a vanishing S = 2 spin gap is obtained at the variational level, in the whole regime from the XY to the Heisenberg model.

Despite rapid progress in understanding gapped topological states, much less is known about gapless topological phases of matter, especially in strongly correlated electrons. In this work, we discuss a large class of robust gapless quantum spin liquids in frustrated magnets made of half-integer spins, which are described by gapless fermionic spinons coupled to dynamical ${\mathbb{Z}}_{2}$ gauge fields. Requiring $\text{U}(1)$ spin conservation, time-reversal, and certain space-group symmetries, we show that certain spinon symmetry fractionalization class necessarily leads to a gapless spectrum. These gapless excitations are stable against any perturbations, as long as the required symmetries are preserved. Applying these gapless criteria to spin-$\frac{1}{2}$ systems on square, triangular, and kagome lattices, we show that all gapped symmetric ${\mathbb{Z}}_{2}$ spin liquids in Abrikosov-fermion representation can also be realized in Schwinger-boson representation. This leads to 64 gapped ${\mathbb{Z}}_{2}$ spin liquids on square lattice, and 8 gapped states on both kagome and triangular lattices.

We report variational Monte Carlo calculations for the spin-$\frac{1}{2}$ Heisenberg model on the kagome lattice in the presence of both nearest-neighbor $J_1$ and next-nearest-neighbor $J_2$ antiferromagnetic superexchange couplings. Our approach is based upon Gutzwiller projected fermionic states that represent a flexible tool to describe quantum spin liquids with different properties (e.g., gapless and gapped). We show that, on finite clusters, a gapped $\mathbb{Z}_{2}$ spin liquid can be stabilized in the presence of a finite $J_2$ superexchange, with a substantial energy gain with respect to the gapless $U(1)$ Dirac spin liquid. However, this energy gain vanishes in the thermodynamic limit, implying that, at least within this approach, the $U(1)$ Dirac spin liquid remains stable in a relatively large region of the phase diagram. For $J_2/J_1 \gtrsim 0.3$, we find that a magnetically ordered state with ${\bf q}={\bf 0}$ overcomes the magnetically disordered wave functions, suggesting the end of the putative gapless spin-liquid phase.

This review synthesizes recent developments in identifying emergent quantum spin liquids in the Heisenberg model on the kagome lattice. We review a subset of progresses on the discovery of the gapped chiral spin liquid and the gapless Dirac spin liquid. We discuss several powerful numerical techniques for directly dissecting the topological order of quantum spin liquids, including entanglement measures and adiabatic topological pumping to overcome traditional limitations of calculations.

The quantum spin liquid (QSL) state is of great interest in relation to quantum computation and superconductivity and the search for new QSL materials is a current challenge in chemistry. Existing inorganic and molecular QSL compounds have two-dimensional structures, with spins arranged on triangular and kagome lattices, whereas three-dimensional structures with QSL characteristics are rare. In the copper-oxalate framework compound [(C2H5)3NH]2Cu2(C2O4)3, Cu(II) is coordinated with three bisbidentate oxalate bridges to form a three-dimensional (10,3) lattice and this produces a strong antiferromagnetic interaction between Cu2+ (S = 1/2) atoms (θ = -180 K). No long-range ordering (LRO) was observed in either magnetic susceptibility or specific heat measurements down to 2 K. Absence of LRO was further confirmed by μSR measurements down to 60 mK, indicating that it is a gapless QSL with f > 3000. Due to Jahn-Teller distortion and partial dimerization, the effective dimensionality of the magnetic lattice is reduced. This compound nevertheless highlights the great potential for obtaining QSLs of varying dimensionality from metal-organic frameworks.