Quantum annealing of a frustrated magnet.

Quantum annealing, which involves quantum tunnelling among possible solutions, has state-of-the-art applications not only in quickly finding the lowest-energy configuration of a complex system, but also in quantum computing. Here we report a single-crystal study of the frustrated magnet α-CoV2O6, consisting of a triangular arrangement of ferromagnetic Ising spin chains without evident structural disorder. We observe quantum annealing phenomena resulting from time-reversal symmetry breaking in a tiny transverse field. Below ~ 1 K, the system exhibits no indication of approaching the lowest-energy state for at least 15 hours in zero transverse field, but quickly converges towards that configuration with a nearly temperature-independent relaxation time of ~ 10 seconds in a transverse field of ~ 3.5 mK. Our many-body simulations show qualitative agreement with the experimental results, and suggest that a tiny transverse field can profoundly enhance quantum spin fluctuations, triggering rapid quantum annealing process from topological metastable Kosterlitz-Thouless phases, at low temperatures.

Ba4Ni3F14·H2O: a ferrimagnetic compound with a staircase kagomé lattice.

A new crystalline fluoride Ba4Ni3F14·H2O was found to exhibit a rare S = 1 staircase kagomé lattice built by Ni2+ ions. Magnetic measurements indicate a ferrimagnetic transition at ∼28 K, while 1/3 plateau can be observed from the magnetization curve. We suggest that the hydrogen-bond interactions of O-H⋯F pathways may play an important role for magnetic properties of the system.

High-Pressure Vibrational and Structural Properties of Ni3V2O8 and Co3V2O8 up to 20 GPa.

The vibrational and structural behaviors of Ni3V2O8 and Co3V2O8 orthovanadates have been studied up to around 20 GPa by means of X-ray diffraction, Raman spectra, and theoretical simulations. Both materials crystallize in an orthorhombic Kagomé staircase structure (space group: Cmca) at ambient conditions, and no phase transition was found in the whole pressure range. In order to identify the symmetry of the detected Raman-active modes under high pressure, single crystal samples of those materials were used in a polarized Raman and infrared setup. Moreover, high-pressure powder X-ray diffraction measurements were performed for Co3V2O8, and the results confirmed the structure stability also obtained by other diagnostic techniques. From this XRD analysis, the anisotropic compressibilities of all axes were calculated and the unit-cell volume vs pressure was fitted by a Birch-Murnaghan equation of state, obtaining a bulk modulus of 122 GPa.

BaNa2Co7Te3O18 with a distorted 2-uniform lattice (T13) showing unusual magnetic behaviors.

Search for transition-metal compounds with unique spin lattices is a great challenge. Herein, we report on a successful exploration of a new compound BaNa2Co7Te3O18, featuring a unique spin network of (36; 34, 6)2-like lattice (T13), which is a typical example with distorted 2-uniform lattices. Magnetic measurements show that this compound has large magnetic anisotropy with an easy magnetization c-axis, while an unusually large magnetization loop can be observed in the magnetization curve. Furthermore, no λ-like peaks are observed in the heat capacity data, showing partial long-range order in the system, which is in good agreement with the theoretical prediction.

Influence of Barium Intercalated Ions on Magnetic Interaction in the Tellurate Compound BaNi2TeO6.

A novel transition metal tellurate single-crystal BaNi2TeO6 with layered honeycomb lattices has been successfully synthesized. The crystal structure of BaNi2TeO6 reveals that there are the Ni2+ honeycomb lattice layers and Te6+ triangle lattice layers in the ab plane. BaNi2TeO6 shows an antiferromagnetic (AFM) transition at ∼25 K, which is almost the same temperature as the Curie-Weiss temperature θ ∼ -27 K, indicating the presence of the AFM interactions without obvious magnetic frustration in the system. However, the field-induced successive magnetic transitions observed at Hc1 ∼ 16.2 T and Hc2 ∼ 42.2 T show the complicated spin structure in BaNi2TeO6. Compared with the isostructural Na2Ni2TeO6, the various magnetic properties indicate that the intercalated ions (Ba2+) can significantly affect the magnetic properties of the layered honeycomb lattices, which may be useful for exploring the spin-liquid state and valence bond liquid state in the layered honeycomb lattice compounds.

Pressure-Induced Phase Transition and Band Gap Decrease in Semiconducting ß-Cu2V2O7.

The understanding of the interplay between crystal structure and electronic structure in semiconductor materials is of great importance due to their potential technological applications. Pressure is an ideal external control parameter to tune the crystal structures of semiconductor materials in order to investigate their emergent piezo-electrical and optical properties. Accordingly, we investigate here the high-pressure behavior of the semiconducting antiferromagnetic material ß-Cu2V2O7, finding it undergoes a pressure-induced phase transition to γ-Cu2V2O7 below 4000 atm. The pressure-induced structural and electronic evolutions are investigated by single-crystal X-ray diffraction, absorption spectroscopy and ab initio density functional theory calculations. ß-Cu2V2O7 has previously been suggested as a promising photocatalyst for water splitting. Now, these new results suggest that ß-Cu2V2O7 could also be of interest with regards to barocaloric effects, due to the low phase -transition pressure, in particular because it is a multiferroic material. Moreover, the phase transition involves an electronic band gap decrease of approximately 0.2 eV (from 1.93 to 1.75 eV) and a large structural volume collapse of approximately 7%.

Approach toward Iron(II) Coordination Polymers Based on Chain Motifs with Thiolate or Mixed Thiolate/Carboxylate Bridges: Structures and Magnetic Properties.

The search for iron-sulfur-based coordination polymers (CPs) has become an attractive field in recent years. Here we demonstrate how it is possible to synthesize new iron-sulfur-based CPs by solvothermal reactions of [CpFe(CO)2]2 (Cp = cyclopentadienyl) with two positional isomeric ligands 6-mercaptonicotinic acid (6-H2mna) and 2-mercaptoisonicotinic acid (2-H2mina) in different mixed-solvent systems. The reactions afforded, in moderate yields, a variety of desired CPs, namely, [Fe(6-Hmna)2] (1), [Fe3(6-Hmna)2(6-mna)2] (2), [Fe2(6-mna)2]·H2O (3), and [Fe(2 mina)(H2O)] (4 and 5). The structures of these compounds have been characterized by single-crystal X-ray diffraction, which reveals that they all contain 1D chain motifs of iron held together in different ways by thiolate or mixed thiolate/carboxylate bridges. These chains are further connected through the ligand backbones to form 3D networks of 1-3 and 5 and a 2D sheet of 4. Moreover, magnetic investigations indicate that both 1 and 4 display canted antiferromagnetic behavior with weak ferromagnetism, while 2 and 5 possess short-range antiferromagnetic order at ∼20 K. CP 3 exhibits paramagnetic behavior down to 2 K with strong spin frustration.

Synthesis, structure and magnetic properties of two new spin-chain compounds Ca2Ni(HSeO3)2(SeO3)2 and Na2Cu(SeO3)2·2H2O.

Two new selenite compounds Ca2Ni(HSeO3)2(SeO3)2 (CaNi) and Na2Cu(SeO3)2·2H2O (NaCu) were obtained by a hydrothermal method. Both compounds crystallize in the triclinic system of space group P1̄, featuring a selenite-bridged one-dimensional (1D) spin-chain structure running along the a-axis. Magnetic measurements indicate that CaNi undergoes a long-range antiferromagnetic order (LRO) at TN = ∼3.8 K, while NaCu does not exhibit a LRO down to 2 K but the onset of a short-range correlation at TM = ∼30 K. The intrachain exchange coupling J/kB = -2.59 K for CaNi and J/kB = -47.13 K for NaCu can be estimated by a fit using the 1D spin-chain model. The thermogravimetric analyses show that both compounds are stable below 130 °C. The UV-vis diffuse reflectance spectra indicate that the band gaps of CaNi and NaCu are 4.38 eV and 3.18 eV, respectively.

E_{8} Spectra of Quasi-One-Dimensional Antiferromagnet BaCo_{2}V_{2}O_{8} under Transverse Field.

We report ^{51}V NMR and inelastic neutron scattering (INS) measurements on a quasi-1D antiferromagnet BaCo_{2}V_{2}O_{8} under transverse field along the [010] direction. The scaling behavior of the spin-lattice relaxation rate above the Néel temperatures unveils a 1D quantum critical point (QCP) at H_{c}^{1D}≈4.7 T, which is masked by the 3D magnetic order. With the aid of accurate analytical analysis and numerical calculations, we show that the zone center INS spectrum at H_{c}^{1D} is precisely described by the pattern of the 1D quantum Ising model in a magnetic field, a class of universality described in terms of the exceptional E_{8} Lie algebra. These excitations are nondiffusive over a certain field range when the system is away from the 1D QCP. Our results provide an unambiguous experimental realization of the massive E_{8} phase in the compound, and open a new experimental route for exploring the dynamics of quantum integrable systems as well as physics beyond integrability.

A pentanuclear {Co5} cluster motif forming a capped breathing kagomé lattice.

A new pentanuclear {Co5} cluster motif is found to have a D3h oblate trigonal bipyramidal geometry, which is extended into a 3D triangle network, forming a unique capped breathing kagomé lattice. Magnetic results confirmed a paramagnetism down to 2 K, accompanying the disappearance of two-thirds of the spin moment at low-temperature and the appearance of a 1/5 magnetization plateau.

A spin-1/2 gapped compound CdCu2(SeO3)2Cl2 with a ladder structure.

The exploration of two-leg spin-ladder materials is a great challenge to the chemical community since it is one of the most ideal models for the study of low-dimensional magnetism and high-Tc superconductivity. Herein, we report on a successful synthesis of a new Cu2+-based two-leg ladder compound constructed by CuO4Cl2 octahedra along the [101] direction. The magnetic results exhibit a broad peak at Tmax ∼ 265 K, and suggest that CdCu2(SeO3)2Cl2 has a spin singlet ground state. The fitting of the isolated two-leg spin-ladder model shows J⊥/kB = 429 K and J‖/kB = 21 K, leading to a large spin gap of ∼409 K.

Pb(OF)Cu3(SeO3)2(NO3): a selenite fluoride nitrate with a breathing kagomé lattice.

The Cu2+-based breathing kagomé material Pb(OF)Cu3(SeO3)2(NO3) with both corner-sharing and edge-sharing has been synthesized. Magnetic measurements suggest ferromagnetic interactions inside the layers and antiferromagnetic interactions between the neighboring layers, leading to an antiferromagnetic ground state with a field-induced spin-flip transition at low temperature.

Uniform Spin-1/2-Chain System with a Weak Interchain Interaction.

A new hydroxyl sulfate-fluoride compound, Lu2Cu(SO4)2(OH)3F·H2O, was obtained using a hydrothermal method. This compound is found to crystallize in a monoclinic space group of P21/c, exhibiting a uniform chain structure along the b axis, in which the chains are composed of elongated CuO4+2 octahedra and further separated by SO4 tetrahedra and Lu3+ ions. The shortest Cu-Cu distance inside the chains is ∼3.394(1) Å, while that between neighboring chains is ∼7.878(1) Å. Magnetic and heat capacity measurements indicate that this compound does not possess long-range magnetic order until 2 K. The fitting of spin-chain models suggests a strong intrachain interaction J and a weak interchain interaction J' with a small value of |J'/J| < 3.20(2) × 10-3, indicating that Lu2Cu(SO4)2(OH)3F·H2O may be a nearly ideal one-dimensional spin-1/2-chain system.

Co3(SeO3)(SO4)(OH)2: A Selenite-Sulfate Compound with a Distorted Kagomé Lattice.

A new selenite-sulfate compound Co3(SeO3)(SO4)(OH)2 was prepared using a typical hydrothermal reaction. This compound is found to crystallize in an orthorhombic space group of Pnma, featuring a 2D distorted kagomé structure composed of linear and zigzag Co-chains, in which the magnetic ions construct different isosceles-triangles. Our results of magnetic and specific heat measurements confirm a canted antiferromagnetic order at TN ∼ 29 K. Further, the successive field-induced metamagnetic transitions can be observed at Hc1 ∼ 1 T, Hc2 ∼ 23 T, and Hc3 ∼ 27 T, respectively. A clear magnetic hysteresis loop with a coercive field (Hc) of ∼1.4 T is also observed.

Ferromagnetic Half-Metal Cyanamides Cr(NCN)2 Predicted from First Principles Investigation.

The stability, physical properties, and electronic structures of Cr(NCN)2 were studied using density functional theory with explicit electronic correlation (GGA+U). The calculated results indicate that Cr(NCN)2 is a ferromagnetic and half-metal, both thermodynamically and elastically stable. A comparative study on the electronic structures of Cr(NCN)2 and CrO2 shows that the Cr atoms in both compounds are in one crystallographically equivalent site, with an ideal 4+ valence state. In CrO2, the Cr atoms at the corner and center sites have different magnetic moments and orbital occupancies, moreover, there is a large difference between the intra- (12.1 meV) and inter-chain (31.2 meV) magnetic couplings, which is significantly weakened by C atoms in Cr(NCN)2.

Molybdate-Tellurite Compounds with Capped-Kagomé Spin-Lattices.

Three new molybdate-tellurites, K2M9(TeO3)4(MoO4)4(OH)4 (M = NiII and CoII) and (NH4)2Cu9II(TeO3)4(MoO4)4(OH)4, have been successfully synthesized by conventional hydrothermal method. Due to the influence of the Jahn-Teller effect, these compounds crystallize in different space groups of rhombohedral R3̅m, monoclinic P21/c and triclinic P1̅ for Ni-, Co-, and Cu-analogues, respectively. The topological arrangements of magnetic ions in these compounds show that deficient capped-kagomé spin-lattices with kagomé positions exhibit different 1/6 depletion. Magnetic and specific heat measurements confirm that K2Ni9(TeO3)4(MoO4)4(OH)4 exhibits a spin-glass behavior at low temperature, while (NH4)2Cu9(TeO3)4(MoO4)4(OH)4 possesses a long-range canted antiferromagnetic ordering with TN ∼ 10.8 K and further shows a 3/5 magnetization plateau in the magnetization curve at low temperature.

Quantum Criticality of the Ising-like Screw Chain Antiferromagnet SrCo_{2}V_{2}O_{8} in a Transverse Magnetic Field.

The quantum criticality of an Ising-like screw chain antiferromagnet SrCo_{2}V_{2}O_{8}, with a transverse magnetic field applied along the crystalline a axis, is investigated by ultralow temperature NMR measurements. The Néel temperature is rapidly and continuously suppressed by the field, giving rise to a quantum critical point (QCP) at H_{C_{1}}≈7.03 T. Surprisingly, a second QCP at H_{C_{2}}≈7.7 T featured with gapless excitations is resolved from both the double-peak structure of the field-dependent spin-lattice relaxation rate 1/^{51}T_{1} at low temperatures and the weakly temperature-dependent 1/^{51}T_{1} at this field. Our data, combined with numerical calculations, suggest that the induced effective staggered transverse field significantly lowers the critical fields, and leads to an exposed QCP at H_{C_{2}}, which belongs to the one-dimensional transverse-field Ising universality.

Synthesis, Structure, and Magnetic Properties of Two Mercury Selenite Antiferromagnets HgM(SeO3)2(H2O)2 (M = Co, Ni).

Two mercury selenite compounds HgM(SeO3)2(H2O)2 (M = Co, Ni) are synthesized using a conventional hydrothermal method. Both compounds crystallize in the monoclinic structure with a C2/ c space group, and equivalent Co2+ or Ni2+ ions exhibit a stacked triangular lattice. Magnetic measurements suggest different magnetic properties between these two isostructural compounds, in which HgCo(SeO3)2(H2O)2 undergoes a canted antiferromagnetic order below TN = 7.6 K, while HgNi(SeO3)2(H2O)2 exhibits a collinear antiferromagnetic order below TN = 9.0 K. When applying a magnetic field, two successive magnetic transitions are observed at Bc1 ∼ 1 T and Bc2 ∼ 3.6 T in HgCo(SeO3)2(H2O)2, whereas only one field-induced transition is detected around 3.1 T in HgNi(SeO3)2(H2O)2.

The half magnetization plateau in Ni3V2O8 studied by electron spin resonance.

Ni3V2O8, regarded as an S = 1 kagome staircase lattice antiferromagnet, possesses a novel magnetic field-temperature phase diagram. Specifically, a half plateau region is observed in the high field magnetization curve for magnetic fields in the range of 11-19 T. This experimental observation is theoretically unexpected for a standard kagome lattice antiferromagnet, and consequently, the underlying magnetic structure is still unclear. Multi-frequency electron spin resonance results in this study strongly support a collinear magnetic arrangement at the half plateau region. The resonant modes can be well fit by only considering the antiferromagnetic interactions on a four-spin sublattice of the spine sites.

Two spin-canted antiferromagnetic orderings and a field-induced metamagnetic transition in SrMn2(VO4)2(H2O)2.

A new vanadate SrMn2(VO4)2(H2O)2 was synthesized and characterized by single-crystal X-ray analysis. It crystallizes in the monoclinic system with space group C2/m, and exhibits a quasi-one-dimensional (1D) structure. The Mn2+ ions form infinite linear-chains along the b-axis through edge-sharing oxygen atoms and further the linear-chains are connected by VO4 polyhedra into a layer in the ab-plane with Sr2+ ions residing in the space between the layers. Magnetic measurement results show that SrMn2(VO4)2(H2O)2 possesses two spin-canted antiferromagnetic orderings at ∼45 K and ∼7 K. The first ordering at ∼45 K possibly corresponds to a small deviation of spins from a strictly antiparallel arrangement. As the temperature decreases, further spin rotations occur leading to a steadier noncollinear antiferromagnetic phase, leading to the second ordering at ∼7 K. Also, a field-induced transition is observed at a critical field (0.4 T) below ∼7 K.