The spin-1/2 kagome lattice antiferromagnet herbertsmithite, ZnCu$_{3}$(OH)$_{6}$Cl$_{2}$, is a candidate material for a quantum spin liquid ground state. We show that the magnetic response of this material displays an unusual scaling relation in both the bulk ac susceptibility and the low energy dynamic susceptibility as measured by inelastic neutron scattering. The quantity $χT^α$ with $α\simeq 0.66$ can be expressed as a universal function of $H/T$ or $ω/T$. This scaling is discussed in relation to similar behavior seen in systems influenced by disorder or by the proximity to a quantum critical point.
Recent evidence from magnetic torque, electron spin resonance, and second harmonic generation indicate that the prototypical quantum spin liquid candidate, herbertsmithite, has a symmetry lower than its x-ray refined trigonal space group. Here, we consider known and possible distortions of this mineral class, along with related copper kagome oxides and fluorides, relate these to possible valence bond patterns, and comment on their relevance to the physics of these interesting materials.
Employing complementary torque magnetometry and electron spin resonance on single crystals of herbertsmithite, the closest realization to date of a quantum kagome antiferromagnet featuring a spin-liquid ground state, we provide novel insight into different contributions to its magnetism. At low temperatures, two distinct types of defects with different magnetic couplings to the kagome spins are found. Surprisingly, their magnetic response contradicts the three-fold symmetry of the ideal kagome lattice, suggesting the presence of a global structural distortion that may be related to the establi…
Despite tremendous investigations, a quantum spin liquid state realized in spin-1/2 kagome Heisenberg antiferromagnet remains largely elusive. In herbertsmithite ZnCu$_3$(OH)$_6$Cl$_2$, a quantum spin liquid candidate on the perfect kagome lattice, precisely characterizing the intrinsic physics of the kagome layers is extremely challenging due to the presence of interlayer Cu/Zn antisite disorder within its crystal structure. Here we measured the specific heat and thermal conductivity of single crystal herbertsmithite in magnetic fields with high resolution. Our results are highlighted by the …
We investigate the lattice dynamics in the spin-1/2 frustrated kagome compound herbertsmithite ZnCu$_3$(OH)$_6$Cl$_2$ by a combination of infrared spectroscopy measurements and ab initio density functional theory calculations, and provide an unambiguous assignment of infrared-active lattice vibrations involving in-plane and out-of-plane atom displacements in the kagome layers. Upon cooling, non-thermal red-shifts and broadening appear specifically for modes that deform the kagome layer or affect the Cu-O-Cu bond angles, thus creating pronounced modifications of the antiferromagnetic exchange c…
To capture the high-field magnetization process of herbertsmithite (ZnCu3(OH)6Cl2), Faraday rotation (FR) measurements were carried out on a single crystal in magnetic fields of up to 190 T. The magnetization data evaluated from the FR angle exhibited a saturation behavior above 150 T at low temperatures, which was attributed to the 1/3 magnetization plateau. The overall behavior of the magnetization process was reproduced by theoretical models based on the nearest-neighbor Heisenberg model. This suggests that herbertsmithite is a proximate kagome antiferromagnet hosting an ideal quantum spin …
Low energy inelastic neutron scattering on single crystals of the kagome spin liquid compound ZnCu3(OD)6Cl2 (Herbertsmithite) reveals antiferromagnetic correlations between impurity spins for energy transfers E < 0.8 meV (~J/20). The momentum dependence differs significantly from higher energy scattering which arises from the intrinsic kagome spins. The low energy fluctuations are characterized by diffuse scattering near wavevectors (1 0 0) and (0 0 3/2), which is consistent with antiferromagnetic correlations between pairs of nearest neighbor Cu impurities on adjacent triangular (Zn) interlay…
Recently Han et al. have provided an analysis of the observed behavior of $\rm ZnCu_{3}(OH)_6Cl_2$ Herbertsmithite based on a separation of the contributions to its thermodynamic properties due to impurities from those due to the kagome lattice. The authors developed an impurity model to account for the experimental data and claimed that it is compatible with the presence of a small spin gap in the kagome layers. We argue that the model they advocate is problematic, conflicting with the intrinsic properties of $\rm ZnCu_{3}(OH)_6Cl_2$ as observed and explained in recent experimental and theore…
Measuring the specific heat of herbertsmithite single crystals in high magnetic fields (up to $34$ T) allows us to isolate the low-temperature kagome contribution while shifting away extrinsic Schottky-like contributions. The kagome contribution follows an original power law $C_{p}(T\rightarrow0)\propto T^α$ with $α\sim1.5$ and is found field-independent between $28$ and $34$ T for temperatures $1\leq T\leq4$ K. These are serious constrains when it comes to replication using low-temperature extrapolations of high-temperature series expansions. We manage to reproduce the experimental observatio…
The kagome Heisenberg antiferromagnet formed by frustrated spins arranged in a lattice of corner-sharing triangles is a prime candidate for hosting a quantum spin liquid (QSL) ground state consisting of entangled spin singlets. But the existence of various competing states makes a convincing theoretical prediction of the QSL ground state difficult, calling for experimental clues from model materials. The kagome lattice materials Zn-barlowite ZnCu$_{3}$(OD)$_{6}$FBr and herbertsmithite ZnCu$_{3}$(OD)$_{6}$Cl$_2$ do not exhibit long range order, and they are considered the best realizations of t…
Optical conductivity measurements are combined with density functional theory calculations in order to understand the electrodynamic response of the frustrated Mott insulators Herbertsmithite $\mathrm{ZnCu_{3}(OH)_{6}Cl_{2}}$ and the closely-related kagome-lattice compound $\mathrm{Y_{3}Cu_{9}(OH)_{19}Cl_{8}}$. We identify these materials as charge-transfer rather than Mott-Hubbard insulators, similar to the high-$T_c$ cuprate parent compounds. The band edge is at 3.3 and 3.6 eV, respectively, establishing the insulating nature of these compounds. Inside the gap, we observe dipole-forbidden lo…
Local spectral functions and Nuclear Magnetic Relaxation (NMR) rates, 1/T1, for the spin-half Heisenberg antiferromagnet on the Kagome Lattice are calculated using Moriyas Gaussian approximation, as well as through an extrapolation of multiple frequency moments. The temperature dependence of the calculated rates is compared with the oxygen 1/T1 NMR data in Herbertsmithite. We find that the Gaussian approximation for 1/T1 shows behavior qualitatively similar to experiments with a sharp drop in rates at low temperatures, consistent with a spin-gapped behavior. However, this approximation signifi…
Nearest-neighbor interacting S = 1/2 spins on the ideal Kagomé lattice are predicted to form a variety of novel quantum entangled states, including quantum spin-liquid (SL) and valence bond solid (VBS) phases. In real materials, the presence of additional perturbative spin interactions may further expand the variety of entangled states, which recent theoretical analyses show are identifiable through the spontaneous loss of particular discrete point group symmetries. Here we comprehensively resolve the ground state point group symmetries of the prototypical Kagomé SL candidate ZnCu$_3$(OH)$_6$C…
We report on temperature dependence of the infrared reflectivity spectra of a single crystalline herbertsmithite in two polarizations --- parallel and perpendicular to the kagome plane of Cu atoms. We observe anomalous broadening of the low frequency phonons possibly caused by fluctuations in the exotic dynamical magnetic order of the spin liquid.
Quantum spin liquids form a novel class of matter where, despite the existence of strong exchange interactions, spins do not order down to the lowest measured temperature. Typically, these occur in lattices that act to frustrate the appearance of magnetism. In two dimensions, the classic example is the kagome lattice composed of corner sharing triangles. There are a variety of minerals whose transition metal ions form such a lattice. Hence, a number of them have been studied, and were then subsequently synthesized in order to obtain more pristine samples. Of particular note was the report in 2…
The ground state of the simple Heisenberg nearest-neighbor quantum kagome antiferromagnetic model is a magnetically disordered spin liquid, yet various perturbations may lead to fundamentally different states. Here we disclose the origin of magnetic ordering in the structurally-perfect kagome material YCu$_3$(OH)$_6$Cl$_3$, which is free of the widespread impurity problem. {\it Ab-initio} calculations and modeling of its magnetic susceptibility reveal that, similar to the archetypal case of herbertsmithite, the nearest-neighbor exchange is by far the dominant isotropic interaction. Dzyaloshins…
Is Herbertsmithite far from an ideal antiferromagnet? Ab-initio answer including in-plane Dzyaloshinskii-Moriya interactions and coupling with extra-plane impurities
The structural-magnetic models of 25 AFM 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…
Herbertsmithite and Zn-doped barlowite are two compounds for experimental realization of twodimensional gapped kagome spin liquid. Theoretically, it has been proposed that charge doping a quantum spin liquid gives rise to exotic metallic states, such as high-temperature superconductivity. However, one recent experiment about herbertsmithite with successful Li-doping shows surprisingly the insulating state even under the heavy doped scenario, which can hardly be explained by many-body physics. Using first-principles calculation, we performed a comprehensive study about the Li intercalated dopin…
Realizing a quantum spin liquid (QSL) ground state in a real material is a leading issue in condensed matter physics research. In this pursuit, it is crucial to fully characterize the structure and influence of defects, as these can significantly affect the fragile QSL physics. Here, we perform a variety of cutting-edge synchrotron X-ray scattering and spectroscopy techniques, and we advance new methodologies for site-specific diffraction and L-edge Zn absorption spectroscopy. The experimental results along with our first-principles calculations address outstanding questions about the local an…
We investigate the effects of Dzyaloshinsky-Moriya (DM) interactions on the frustrated $J_1$-$J_2$ kagome-Heisenberg model using the pseudo-fermion functional-renormalization-group (PFFRG) technique. In order to treat the off-diagonal nature of DM interactions, we develop an extended PFFRG scheme. We benchmark this approach in parameter regimes that have previously been studied with other methods and find good agreement of the magnetic phase diagram. Particularly, finite DM interactions are found to stabilize all types of non-collinear magnetic orders of the $J_1$-$J_2$ Heisenberg model ($\mat…
Quantifying the Phase Diagram and Hamiltonian of $S=1/2$ Kagome Antiferromagnets: Bridging Theory and Experiment
Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory（斯坦福材料能源科学研究所，SLAC国家加速器实验室）；Department of Applied Physics, Stanford University（斯坦福大学应用物理系）；Neutron Scattering Division, Oak Ridge National Laboratory（橡树岭国家实验室中子散射部）
Synthetic barlowite, Cu4(OH)6BrF, has emerged as a new quantum spin liquid (QSL) host, containing kagome layers of S=1/2 Cu2+ ions separated by interlayer Cu2+ ions. Similar to synthetic herbertsmithite, ZnCu3(OH)6Cl2, it has been reported that Zn2+ substitution for the interlayer Cu2+ induces a QSL ground state. Here we report a scalable synthesis of single crystals of Cu4(OH)6BrF. Through x-ray, neutron, and electron diffraction measurements coupled with magic angle spinning 19F and 1H NMR spectroscopy, we resolve the previously reported positional disorder of the interlayer Cu2+ ions and fi…
A preponderance of evidence suggests that the ground state of the nearest-neighbor $S = 1/2$ antiferromagnetic Heisenberg model on the kagome lattice is a gapless spin liquid. Many candidate materials for the realization of this model possess in addition a Dzyaloshinskii-Moriya (DM) interaction. We study this system by tensor-network methods and deduce that a weak but finite DM interaction is required to destabilize the gapless spin-liquid state. The critical magnitude, $D_c/J \simeq 0.012(2)$, lies well below the DM strength proposed in the kagome material herbertsmithite, indicating a need t…
We compute the real-space spin correlations and frquency and wave-vector resolved dynamic structure factors $S(\vec q,ω)$ for the nearest-neighbor Kagome-Lattice Heisenberg Antiferromagnet (KLHM) at finite temperatures using Numerical Linked Cluster Expansion (NLCE) method. A triangle-based NLCE is used to calculate frequency moments of the dynamic structure factors in the thermodynamic limit, which show excellent convergence for $T> J/4$. A Gaussian approximation and the fluctuation-dissipation relation are used to to reconstruct the frequency dependence. We find that some features of the low…
Spinon mediation of witness spin dynamics in herbertsmithite
University of Oxford（牛津大学）；University College Cork（科克大学学院）；Cardiff University（卡迪夫大学）；University of Bristol（布里斯托大学）；Max Planck Institute for Solid State Research（马克斯·普朗克固体的研究所）；Max Planck Institute for Chemical Physics of Solids（马克斯·普朗克固体化学物理研究所）；Argonne National Laboratory（阿贡国家实验室）；Cornell University（康奈尔大学）
Arguably the most favorable situation for spins to enter the long-sought quantum spin liquid (QSL) state is when they sit on a kagome lattice. No consensus has been reached in theory regarding the true ground state of this promising platform. The experimental efforts, relying mostly on one archetypal material ZnCu$_3$(OH)$_6$Cl$_2$, have also led to diverse possibilities. Apart from subtle interactions in the Hamiltonian, there is the additional degree of complexity associated with disorder in the real material ZnCu$_3$(OH)$_6$Cl$_2$ that haunts most experimental probes. Here we resort to heat…
Ground State and Intrinsic Susceptibility of the Kagome Antiferromagnet Vesignieite as seen by 51V NMR
用51 V核磁共振测量了近kagome量子磁体vesignieite Cu 3BaV 2 O 8（OH）2的内禀磁化率和局部磁化强度。核磁共振谱线位移给出了一个精确的测量的内在磁化率的kagome网站，这非常类似的量子自旋液体herbertsmithite [A. Olariu等人，Phys. Rev. Lett. 100，087202（2008）]。因此，令人惊讶的是，在Tc ~ 9 K时，观察到向异质基态的转变。一个逐渐wipeout的一半的NMR强度表明一个缓慢波动的自旋液体成分和线宽的详细分析揭示了静态磁性的发病在其余一半的网站。我们认为这种跃迁和不寻常的基态起源于Dzyaloshinskiii-Moriya相互作用诱导的一个量子临界点附近。
In frustrated magnets the Dzyaloshinsky-Moriya interaction arising from spin-orbit coupling can induce a magnetic long-range order. Here, we report a theoretical prediction of thermal Hall effect in frustrated kagomé magnets such as KCr$_3$(OH)$_6$(SO4)$_2$ and KFe$_3$(OH)$_{6}$(SO$_{4}$)$_2$. The thermal Hall effects in these materials are induced by scalar spin chirality as opposed to DMI in previous studies. The scalar spin chirality originates from magnetic-field-induced chiral spin configuration due to non-coplanar spin textures, but in general it can be spontaneously developed as a macro…
The quantum spin liquid material herbertsmithite is described by an antiferromagnetic Heisenberg model on the kagome lattice with non-negligible Dzyaloshinskii-Moriya interaction~(DMI). A well established phase transition to the $\mathbf q=0$ long-range order occurs in this model when the DMI strength increases, but the precise nature of a small-DMI phase remains controversial. Here, we describe a new phase obtained from Schwinger-boson mean-field theory that is stable at small DMI, and which can explain the dispersionless spectrum seen in inelastic neutron scattering experiment by Han et al (…
Herbertsmithite, ZnCu$_3$(OH)$_6$Cl$_2$, is a two dimensional kagomé lattice realization of a spin liquid, with evidence for fractionalized excitations and a gapped ground state. Such a quantum spin liquid has been proposed to underlie high temperature superconductivity and is predicted to produce a wealth of new states, including a Dirac metal at $1/3$rd electron doping. Here we report the topochemical synthesis of electron-doped ZnLi$_x$Cu$_3$(OH)$_6$Cl$_2$ from $x$ = 0 to $x$ = 1.8 ($3/5$th per Cu$^{2+}$). Contrary to expectations, no metallicity or superconductivity is induced. Instead, we…
