Valence Bond Crystal Research Articles

Designer Spin Models in Tunable Two-Dimensional Nanographene Lattices.

Motivated by recent experimental breakthroughs, we propose a strategy for designing two-dimensional spin-lattices with competing interactions that lead to nontrivial emergent quantum states. We consider S = 1/2 nanographenes with C3 symmetry as building blocks, and we leverage the potential to control both the sign and the strength of exchange with first neighbors to build a family of spin models. Specifically, we consider the case of a Heisenberg model in a triangle-decorated honeycomb lattice with competing ferromagnetic and antiferromagnetic interactions whose ratio can be varied in a wide range. On the basis of the exact diagonalization of both Fermionic and spin models, we predict a quantum phase transition between a valence bond crystal of spin singlets with triplon excitations living in a Kagomé lattice and a Néel phase of effective S = 3/2 in the limit of dominant ferromagnetic interactions.

Abundance of Hard-Hexagon Crystals in the Quantum Pyrochlore Antiferromagnet.

We propose a simple family of valence-bond crystals as potential ground states of the S=1/2 and S=1 Heisenberg antiferromagnet on the pyrochlore lattice. Exponentially numerous in the linear size of the system, these can be visualized as hard-hexagon coverings, with each hexagon representing a resonating valence-bond ring. This ensemble spontaneously breaks rotation, inversion, and translation symmetries. A simple, yet accurate, variational wave function allows a precise determination of the energy, confirmed by the density matrix renormalization group and numerical linked cluster expansion, and extended by an analysis of excited states. The identification of the origin of the stability indicates applicability to a broad class of frustrated lattices, which we demonstrate for the checkerboard and ruby lattices. Our work suggests a perspective on such quantum magnets, in which unfrustrated motifs are effectively uncoupled by the frustration of their interactions.

Nature of the 1/9-magnetization plateau in the spin- 12 kagome Heisenberg antiferromagnet

The nature of the 1/9-magnetization plateau of the spin-1/2 kagome Heisenberg antiferromagnet remains controversial due to the exotic physical properties and high complexity induced by the geometrical frustration. Instead of a Z3 quantum spin liquid revealed on a cylinder, we show on an infinite-size lattice that the 1/9 plateau can be described by a valence bond crystal (VBC) that breaks spatial translational invariance. Consistent results are achieved by two accurate tensor network methods, namely the full-update infinite projected-entangled pair states and the projected-entangled simplex states. The VBC exhibits an hourglass pattern with $\sqrt{3}\times\sqrt{3}$ spatial symmetry, demonstrated by magnetizations, bond energies, and three-body correlators. The spatial inversion symmetry in the $\sqrt{3}\times\sqrt{3}$ VBC is instantly broken with the presence of the difference between the coupling strengths in the up and down triangles, suggesting the existence of gapless excitations. The gapless nature of the 1/9 plateau is further indicated by the scaling behaviors of the entanglement entropy and the correlation length, which indicate a c=1 conformal field theory.

Tensor network study of the spin- 12 Heisenberg antiferromagnet on the shuriken lattice

We investigate the ground state of the spin $S=\frac{1}{2}$ Heisenberg antiferromagnet on the shuriken lattice, also in the presence of an external magnetic field. To this end, we employ two-dimensional tensor network techniques based on infinite projected entangled pair and simplex states considering states with different sizes of the unit cells. We show that a valence bond crystal with resonances over length six loops emerges as the ground state (at any given finite bond dimension) yielding the lowest reported estimate of the ground state energy ${E}_{0}/J=\ensuremath{-}0.4410\ifmmode\pm\else\textpm\fi{}0.0001$ for this model, estimated in the thermodynamic limit. We also study the model in the presence of an external magnetic field and find the emergence of 0, $\frac{1}{3}$, and $\frac{2}{3}$ magnetization plateaus. The $\frac{1}{3}$ and $\frac{2}{3}$ plateau states respect translation and point group symmetries and feature loop-four plaquette resonances.

Orbital-selective metallicity in the valence-bond liquid phase of Li2RuO3

${\mathrm{Li}}_{2}{\mathrm{RuO}}_{3}$ (LRO) forms a valence bond crystal at room temperature. It undergoes a high temperature phase transition that involves structural, magnetic, and electronic changes leading to an exotic valence bond liquid state. The orbital degrees of freedom are thought to be fundamental to the evolution of LRO properties across the phase transition. We report temperature dependent broadband $(100--26\phantom{\rule{0.16em}{0ex}}000\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{--1})$ reflectance measurements on single crystals of LRO to elucidate structural and transport properties. Specifically, the phonon and electronic properties of LRO were investigated through the phase transition. We report that above the transition temperature $({T}_{\mathrm{c}}\ensuremath{\approx}500\phantom{\rule{0.16em}{0ex}}\mathrm{K})$, the optical band gap closes for electrons in the ${d}_{\mathrm{xz}}/{d}_{\mathrm{yz}}$ orbitals, but the ${d}_{\mathrm{xy}}$ electrons remain gapped. This behavior at high temperature can be associated with an orbital selective metallic state which to our knowledge has not been previously reported in LRO.

Pinwheel valence bond crystal ground state of the spin- 12 Heisenberg antiferromagnet on the shuriken lattice

We investigate the nature of the ground-state of the spin-$\frac{1}{2}$ Heisenberg antiferromagnet on the $shuriken$ lattice by complementary state-of-the-art numerical techniques, such as variational Monte Carlo (VMC) with versatile Gutzwiller-projected Jastrow wave functions, unconstrained multi-variable variational Monte Carlo (mVMC), and pseudo-fermion/Majorana functional renormalization group (PF/PM-FRG) methods. We establish the presence of a quantum paramagnetic ground state and investigate its nature, by classifying symmetric and chiral quantum spin liquids, and inspecting their instabilities towards competing valence-bond-crystal (VBC) orders. Our VMC analysis reveals that a VBC with a pinwheel structure emerges as the lowest-energy variational ground state, and it is obtained as an instability of the U(1) Dirac spin liquid. Analogous conclusions are drawn from mVMC calculations employing accurate BCS pairing states supplemented by symmetry projectors, which confirm the presence of pinwheel VBC order by a thorough analysis of dimer-dimer correlation functions. Our work highlights the nontrivial role of quantum fluctuations via the Gutzwiller projector in resolving the subtle interplay between competing orders.

Possible electron doping of geometrically perfect spin-1/2 kagome-lattice barlowite by reduced graphene oxide

Doping of quantum spin liquid (QSL) insulators by electron or hole leads to intriguing phase transitions to metallic and superconducting states. The barlowite family with geometrically perfect $S=1/2$ kagome planes and tunable interkagome coupling is an emerging platform to realize spin-ordered, valence bond crystal, QSL states. Theoretical investigations on electron doping revealed localized states in the band gap of barlowite unlike metallicity in cuprate (${\mathrm{Nd}}_{2}\mathrm{Cu}{\mathrm{O}}_{4}$). We present successful anchoring of phase-pure barlowite crystallites onto reduced graphene oxide (rGO). The resulting barlowite-rGO system was found to be an electrical semiconductor with Arrhenius activation energy of 0.07 eV. Semiconducting properties of the barlowite-rGO system were further modulated with retention of structural integrity. We have attributed such a transformation of electrical transport response to plausible electron doping thereby making charge-doping experiments on barlowite and its analogs propitious.

Effects of spin-phonon coupling in frustrated Heisenberg models

The existence and stability of spin-liquid phases represent a central topic in the field of frustrated magnetism. While a few examples of spin-liquid ground states are well established in specific models (e.g. the Kitaev model on the honeycomb lattice), recent investigations have suggested the possibility of their appearance in several Heisenberg-like models on frustrated lattices. An important related question concerns the stability of spin liquids in the presence of small perturbations in the Hamiltonian. In this respect, the magnetoelastic interaction between spins and phonons represents a relevant and physically motivated perturbation, which has been scarcely investigated so far. In this work, we study the effect of the spin-phonon coupling on prototypical models of frustrated magnetism. We adopt a variational framework based upon Gutzwiller-projected wave functions implemented with a spin-phonon Jastrow factor, providing a full quantum treatment of both spin and phonon degrees of freedom. The results on the frustrated $J_1-J_2$ Heisenberg model on one- and two-dimensional (square) lattices show that, while a valence-bond crystal is prone to lattice distortions, a gapless spin liquid is stable for small spin-phonon couplings. In view of the ubiquitous presence of lattice vibrations, our results are particularly important to demonstrate the possibility that gapless spin liquids may be realized in real materials.

Insights into Nature of Magnetization Plateaus of a Nickel Complex [Ni4(μ-CO3)2(aetpy)8](ClO4)4 from a Spin-1 Heisenberg Diamond Cluster

Magnetic and magnetocaloric properties of a spin-1 Heisenberg diamond cluster with two different coupling constants are investigated with the help of an exact diagonalization based on the Kambe’s method, which employs a local conservation of composite spins formed by spin-1 entities located in opposite corners of a diamond spin cluster. It is shown that the spin-1 Heisenberg diamond cluster exhibits several intriguing quantum ground states, which are manifested in low-temperature magnetization curves as intermediate plateaus at 1/4, 1/2, and 3/4 of the saturation magnetization. In addition, the spin-1 Heisenberg diamond cluster may also exhibit an enhanced magnetocaloric effect, which may be relevant for a low-temperature refrigeration achieved through the adiabatic demagnetization. It is evidenced that the spin-1 Heisenberg diamond cluster with the antiferromagnetic coupling constants J1/kB = 41.4 K and J2/kB = 9.2 K satisfactorily reproduces a low-temperature magnetization curve recorded for the tetranuclear nickel complex [Ni4(μ-CO3)2(aetpy)8](ClO4)4 (aetpy = 2-aminoethyl-pyridine) including a size and position of intermediate plateaus detected at 1/2 and 3/4 of the saturation magnetization. A microscopic nature of fractional magnetization plateaus observed experimentally is clarified and interpreted in terms of valence-bond crystal with either a single or double valence bond. It is suggested that this frustrated magnetic molecule can provide a prospective cryogenic coolant with the maximal isothermal entropy change −ΔSM=10.6 J·K−1·kg−1 in a temperature range below 2.3 K.

Quantum-classical crossover in the spin- 12 Heisenberg-Kitaev kagome magnet

The spin-1/2 Heisenberg kagome antiferromagnet is one of the paradigmatic playgrounds for frustrated quantum magnetism, with an extensive number of competing resonating valence bond (RVB) states emerging at low energies, including gapped and gapless spin liquids and valence bond crystals. Here we revisit the crossover from this quantum RVB phase to a semiclassical regime brought about by anisotropic Kitaev interactions, and focus on the precise mechanisms underpinning this crossover. To this end, we introduce a simple parametrization of the classical ground states (GSs) in terms of emergent Ising-like variables, and use this parametrizaton: i) to construct an effective low-energy description of the order-by-disorder mechanism operating in a large part of the phase diagram, and ii) to contrast, side by side, exact diagonalization data obtained from the full basis with that obtained from the restricted (orthonormalized) basis of classical GSs. The results reveal that fluctuation corrections from states outside the restricted basis are strongly quenched inside the semiclassical regime (due to the large anisotropy spin gaps), and that the RVB phase survives up to a relatively large value of Kitaev anisotropy $K$. We further find that the pure Kitaev model admits a subextensive number of one-dimensional symmetries, which explains naturally the absence of classical and quantum order by disorder reported previously.

Materializing rival ground states in the barlowite family of kagome magnets: quantum spin liquid, spin ordered, and valence bond crystal states

The spin-frac{1}{2} kagome antiferromagnet is considered an ideal host for a quantum spin liquid (QSL) ground state. We find that when the bonds of the kagome lattice are modulated with a periodic pattern, new quantum ground states emerge. Newly synthesized crystalline barlowite (Cu4(OH)6FBr) and Zn-substituted barlowite demonstrate the delicate interplay between singlet states and spin order on the spin-frac{1}{2} kagome lattice. Comprehensive structural measurements demonstrate that our new variant of barlowite maintains hexagonal symmetry at low temperatures with an arrangement of distorted and undistorted kagome triangles, for which numerical simulations predict a pinwheel valence bond crystal (VBC) state instead of a QSL. The presence of interlayer spins eventually leads to an interesting pinwheel q = 0 magnetic order. Partially Zn-substituted barlowite (Cu3.44Zn0.56(OH)6FBr) has an ideal kagome lattice and shows QSL behavior, indicating a surprising robustness of the QSL against interlayer impurities. The magnetic susceptibility is similar to that of herbertsmithite, even though the Cu2+ impurities are above the percolation threshold for the interlayer lattice and they couple more strongly to the nearest kagome moment. This system is a unique playground displaying QSL, VBC, and spin order, furthering our understanding of these highly competitive quantum states.

SU(4) Heisenberg model on the honeycomb lattice with exchange-frustrated perturbations: Implications for twistronics and Mott insulators

The SU(4)-symmetric spin-orbital model on the honeycomb lattice was recently studied in connection to correlated insulators such as the $e_{g}$ Mott insulator Ba$_{3}$CuSb$_{2}$O$_{9}$ and the insulating phase of magic-angle twisted bilayer graphene at quarter filling. Here we provide a unified discussion of these systems by investigating an extended model that includes the effects of Hund's coupling and anisotropic, orbital-dependent exchange interactions. Using a combination of mean-field theory, linear flavor-wave theory, and variational Monte Carlo, we show that this model harbors a quantum spin-orbital liquid over a wide parameter regime around the SU(4)-symmetric point. For large Hund's coupling, a ferromagnetic antiferro-orbital ordered state appears, while a valence-bond crystal combined with a vortex orbital state is stabilized by dominant orbital-dependent exchange interactions.

Critical colored-RVB states in the frustrated quantum Heisenberg model on the square lattice

We consider a family of SU(2)-symmetric Projected Entangled Paired States (PEPS) on the square lattice, defining colored-Resonating Valence Bond (RVB) states, to describe the quantum disordered phase of the J_1-J_2J1−J2 frustrated Heisenberg model. For J_2/J_1\sim 0.55J2/J1∼0.55 we show the emergence of critical (algebraic) dimer-dimer correlations – typical of Rokhsar-Kivelson (RK) points of quantum dimer models on bipartite lattices – while, simultaneously, the spin-spin correlation length remains short. Our findings are consistent with a spin liquid or a weak Valence Bond Crystal in the neighborhood of an RK point.

Quantum thermal Hall effect of chiral spinons on a kagome strip

We develop a theory for the thermal Hall coefficient in a spin-$\frac{1}{2}$ system on a strip of Kagome lattice, where a chiral spin-interaction term is present. To this end, we model the Kagome strip as a three-leg $XXZ$ spin-ladder, and use Bosonization to derive a low-energy theory for the spinons in this system. Introducing further a Dzyaloshinskii-Moriya interaction ($D$) and a tunable magnetic field ($B$), we identify three distinct $B$-dependent quantum phases: a valence-bond crystal (VBC), a "metallic" spin liquid (MSL) and a chiral spin liquid (CSL). In the presence of a temperature difference $\Delta T$ between the top and the bottom edges of the strip, we evaluate the net heat current $J_h$ along the strip, and consequently the thermal Hall conductivity $\kappa_{xy}$. We find that the VBC-MSL-CSL transitions are accompanied by a pronounced qualitative change in the behavior of $\kappa_{xy}$ as a function of $B$. In particular, analogously to the quantum Hall effect, $\kappa_{xy}$ in the CSL phase exhibits a quantized plateau centered around a commensurate value of the spinon filling factor $\nu_s\propto B/D$.

Quantum dimer models emerging from large-spin ultracold atoms

We propose an experimental protocol for using cold atoms to create and probe quantum dimer models, thereby exploring the Pauling-Anderson vision of a macroscopic collection of resonating bonds. This process can allow the study of exotic crystalline phases, fractionalization, topological spin liquids, and the relationship between resonating dimers and superconductivity subjects which have been challenging to address in solid-state experiments. Our key technical development is considering the action of an off-resonant photoassociation laser on large spin atoms localized at the sites of a deep optical lattice. The resulting superexchange interaction favors nearest-neighbor singlets. We derive an effective Hamiltonian in terms of these dimer degrees of freedom, finding that it is similar to well-known quantum dimer models, which boast a rich variety of valence bond crystal and spin liquid phases. We numerically study the ground state, explain how to tune the parameters, and develop a protocol to directly measure the dimers and their resonating patterns.

Unified phase diagram of antiferromagnetic SU( N ) spin ladders

Motivated by near-term experiments with ultracold alkaline-earth atoms confined to optical lattices, we establish numerically and analytically the phase diagram of two-leg SU($N$) spin ladders. Two-leg ladders provide a rich and highly non-trivial extension of the single chain case on the way towards the relatively little explored two dimensional situation. Focusing on the experimentally relevant limit of one fermion per site, antiferromagnetic exchange interactions, and $2\leq N \leq 6$, we show that the phase diagrams as a function of the interchain (rung) to intrachain (leg) coupling ratio $J_\perp/J_\Vert$ strongly differ for even vs. odd $N$. For even $N=4$ and 6, we demonstrate that the phase diagram consists of a single valence bond crystal (VBC) with a spatial period of $N/2$ rungs. For odd $N=3$ and 5, we find surprisingly rich phase diagrams exhibiting three distinct phases. For weak rung coupling, we obtain a VBC with a spatial period of $N$ rungs, whereas for strong coupling we obtain a critical phase related to the case of a single chain. In addition, we encounter intermediate phases for odd $N$, albeit of a different nature for $N=3$ as compared to $N=5$. For $N=3$, we find a novel gapless intermediate phase with $J_\perp$-dependent incommensurate spatial fluctuations in a sizeable region of the phase diagram. For $N=5$, there are strong indications for a narrow potentially gapped intermediate phase, whose nature is not entirely clear.

Persistence of the gapless spin liquid in the breathing kagome Heisenberg antiferromagnet

The nature of the ground state of the spin $S=1/2$ Heisenberg antiferromagnet on the kagome lattice with breathing anisotropy (i.e., with different superexchange couplings $J_{\vartriangle}$ and $J_{\triangledown}$ within elementary up- and down-pointing triangles) is investigated within the framework of Gutzwiller projected fermionic wave functions and Monte Carlo methods. We analyze the stability of the U(1) Dirac spin liquid with respect to the presence of fermionic pairing that leads to a gapped $\mathbb{Z}_{2}$ spin liquid. For several values of the ratio $J_{\triangledown}/J_{\vartriangle}$, the size scaling of the energy gain due to the pairing fields and the variational parameters are reported. Our results show that the energy gain of the gapped spin liquid with respect to the gapless state either vanishes for large enough system size or scales to zero in the thermodynamic limit. Similarly, the optimized pairing amplitudes (responsible for opening the spin gap) are shown to vanish in the thermodynamic limit. Our outcome is corroborated by the application of one and two Lanczos steps to the gapless and gapped wave functions, for which no energy gain of the gapped state is detected when improving the quality of the variational states. Finally, we discuss the competition with the "simplex" $\mathbb{Z}_{2}$ resonating-valence-bond spin liquid, valence-bond crystal, and nematic states in the strongly anisotropic regime, i.e., $J_{\triangledown} \ll J_{\vartriangle}$.

Microscopic theory of the nearest-neighbor valence bond sector of the spin- 12 kagome antiferromagnet

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

Emergent spin-1 trimerized valence bond crystal in the spin- 12 Heisenberg model on the star lattice

We explore the frustrated spin-$1/2$ Heisenberg model on the star lattice with antiferromagnetic (AF) couplings inside each triangle and ferromagnetic (FM) inter-triangle couplings ($J_e<0$), and calculate its magnetic and thermodynamic properties. We show that the FM couplings do not sabotage the magnetic disordering of the ground state due to the frustration from the AF interactions inside each triangle, but trigger a fully gapped inversion-symmetry-breaking trimerized valence bond crystal (TVBC) with emergent spin-1 degrees of freedom. We discover that with strengthening $J_e$, the system scales exponentially, either with or without a magnetic field $h$: the order parameter, the five critical fields that separate the $J_e$-$h$ ground-state phase diagram into six phases, and the excitation gap obtained by low-temperature specific heat, all depend exponentially on $J_e$. We calculate the temperature dependence of the specific heat, which can be directly compared with future experiments.

Emergence of chiral spin liquids via quantum melting of noncoplanar magnetic orders

Quantum spin liquids (QSLs) are long-range entangled states of quantum magnets which lie beyond the Landau paradigm of classifying phases of matter via broken symmetries. A physical route to arriving at QSLs is via frustration-induced quantum melting of ordered states such as valence bond crystals or magnetic orders. Here, we show, using extensive exact diagonalization (ED) and density-matrix renormalization group (DMRG) studies of concrete $SU(2)$ invariant spin models on honeycomb, triangular and square lattices, that chiral spin liquids (CSLs) emerge as descendants of triple-$Q$ spin crystals with tetrahedral magnetic order and a large scalar spin chirality. Such ordered-to-CSL melting transitions may yield lattice realizations of effective Chern-Simons-Higgs field theories. Our work provides a distinct unifying perspective on the emergence of CSLs, and suggests that materials with magnetic skyrmion crystal order might provide a good starting point to search for CSLs.