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%.

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.

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.

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.

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.

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.

Syntheses, Structure, and 2/5 Magnetization Plateau of a 2D Layered Fluorophosphate Na3Cu5(PO4)4F·4H2O.

A new two-dimensional (2D) fluorophosphate compound Na3Cu5(PO4)4F·4H2O with a Cu5 cluster has been synthesized using a conventional hydrothermal method. The compound crystallizes in the orthorhombic crystal system with space group Pnma. The 2D layered structure is formed by cap-like {Cu5(PO4)4F} building units consisting of a Cu4O12F cluster plus a residual cap Cu2+ ion. Magnetic susceptibility exhibits a broad maximum at T2 = 19.2 K due to low-dimensional character followed by a long-range antiferromagnetic ordering at T1 = 11.5 K, which is further confirmed by the specific heat data. High-field magnetization measurement demonstrates a 2/5 quantum magnetization plateau above 40 T. The ESR data indicate the presence of magnetic anisotropy, in accordance with the 2D structure of the system.

Octa-Kagomé Lattice Compounds Showing Quantum Critical Behaviors: Spin Gap Ground State versus Antiferromagnetic Ordering.

Search for a new geometrically frustrated lattice is a great challenge. Herein, we report on a successful synthesis of two new layered compounds BiOCu2(XO3)(SO4)(OH)·H2O [X = Te (1) and Se (2)] with a new type of geometrically frustrated lattice (i.e., the octa-kagomé lattice) between kagomé and star motifs. Magnetic measurements confirmed that 1 exhibits a spin gap ground state, while 2 possesses a typical antiferromagnetic ordering at low-temperature. Such different magnetic behaviors between two isostructural compounds are suggested to originate from a slightly structural modification induced by nonmagnetic XO3 anionic groups. Theoretical simulations suggest that the origin of gapped ground state in 1 may be due to the dimerization of Cu2+ ions, while 2 may break the limiting of such dimerization, leading to an antiferromagnetic ordering.

Magnetic Tuning of an Anionic CoII -MOF through Deionization of the Framework: Spin-Canting, Spin-Flop, and Easy-Plane Magnetic Anisotropy.

An anionic CoII -MOF, (Me2 NH2 )[Co3 (Me2 NH)3 (OH)(SDBA)3 ] (1) (H2 SDBA=4,4'-sulfonyldibenzoic acid) consisting of highly symmetric CoII3 (µ3 -OH) triangles exhibits spin-canting, spin-flop, and easy-plane magnetic anisotropy. Measurement on a single crystal shows that the ab plane of 1 is the easy magnetization plane. After structural modification through simultaneous removal of the coordinated dimethylamine (DMA) molecule at the Co center and the ionic groups DMA+ and OH- , the resulting neutral amorphous framework 2 displays an enhanced spin frustration effect. The deionization of 1 does not result in the collapse of the framework, showing the high stability of the backbone structure.

Layered Cu7(TeO3)2(SO4)2(OH)6 with Diluted Kagomé Net Containing Frustrated Corner-Sharing Triangles.

The half-spin Kagomé antiferromagnet is one of the most promising candidates for the realization of a quantum spin liquid state because of its inherent frustration and quantum fluctuations. The search for candidates for quantum spin liquids with novel spin topologies is still a challenge. Herein, we report a new diluted Kagomé lattice in Cu7(TeO3)2(SO4)2(OH)6, showing a 9/16-depleted triangle lattice, where the corner-sharing triangle units [Cu5(OH)6O8] are separated by CuO2(OH)2. Magnetic measurements show that the title compound does not exhibit long-range antiferromagnetic order down to 2 K, suggesting strong spin frustration with f > 19.

Synthesis, Structure, and Magnetic Properties of A2Cu5(TeO3)(SO4)3(OH)4 (A = Na, K): The First Compounds with a 1D Kagomé Strip Lattice.

Two new tellurite-sulfates A2Cu5(TeO3)(SO4)3(OH)4 (A = Na, K) have been synthesized by a conventional hydrothermal method. Both compounds feature 1D kagomé strip structure built by distorted CuO6 octahedra, which can be regarded as the dimensional reduction of kagomé lattice. Magnetic measurements confirmed that the titled compounds possess antiferromagnetic ordering at low temperature, while a field-induced magnetic transition can be observed at critical field. To the best of our knowledge, this is the first time to obtain distorted kagomé strip compounds.

Syntheses and magnetic properties of new tellurite-sulfate compounds M2(TeO3)(SO4)·H2O (M = Co, Mn) with a layer structure showing a distorted honeycomb spin-lattice.

New tellurite-sulfate compounds M2(TeO3)(SO4)·H2O (M = Co, Mn) are synthesized by a conventional hydrothermal method. Two compounds are found to exhibit a similar structure, which both crystallize in the orthorhombic system of space group Pbcm. Te(4+) ions are coordinated by three O atoms, forming a quite distorted TeO3 trigonal pyramid with lone-pair electrons, while magnetic Co(2+) or Mn(2+) ions construct a wavelike layer with a distorted honeycomb spin-lattice. Magnetic measurements confirm that two isostructural compounds display different magnetic behaviors, in which Co2(TeO3)(SO4)·H2O shows a canted antiferromagnetic ordering at ∼15 K, while Mn2(TeO3)(SO4)·H2O shows a collinear antiferromagnetic ordering at ∼28 K. The nature of different magnetic behaviors between two isostructural compounds is also discussed.

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.

Synthesis and magnetic properties of a new borophosphate SrCo2BPO7 with a four-column ribbon structure.

A new borophosphate SrCo2BPO7 is synthesized by a conventional high-temperature solid-state reaction. The titled compound is found to crystallize in monoclinic system with space group P21/c, which displays a distorted four-column ribbon structure. Both BO3 triangles and PO4 tetrahedra are isolated, while irregular triangles built by Co(2+) ions are found to exist between the connecting ribbons. Magnetic behaviors are investigated by means of susceptibility, magnetization, and heat capacity measurements. The results confirm that SrCo2BPO7 possesses a three-dimensional antiferromagnetic ordering at 25 K. The possible spin arrangements in the system are also suggested.

Syntheses, characterization, and optical properties of ternary Ba-Sn-S system compounds: acentric Ba7Sn5S15, centric BaSn2S5, and centric Ba6Sn7S20.

Three new ternary Ba-Sn-S system compounds, acentric Ba(7)Sn(5)S(15), centric BaSn(2)S(5), and centric Ba(6)Sn(7)S(20) have been designed and synthesized by a conventional high-temperature solid-state reaction method using the evacuated silica tubes. The crystal structure of Ba(7)Sn(5)S(15) shows the coexistence of a SnS(4) tetrahedral and a Sn(2)S(3) trigonal bipyramid. Importantly, the larger dipole moment of the [Sn(2)S(3)](2-) trigonal bipyramid group and the polarity enhancement of the bipyramidal arrangements result in a strong SHG effect at 2.05 µm, which is 10 times of the SHG intensity of the benchmark AgGaS(2) with the particle size of 30-46 µm and twice as much as that with the particle size of 150-212 µm. Evidently, the acentric Ba(7)Sn(5)S(15) is a novel IR NLO crystal material with a wide mid-IR window and a strong SHG effect, which is the first reported among the Ba-Sn-S ternary system. Moreover, Ba(7)Sn(5)S(15) can achieve type-I phase-matching that can be used for practical applications. In the centric BaSn(2)S(5,) all Sn atoms are coordinated by five S atoms to form novel SnS(5) trigonal bipyramid polyhedrons. In the other centric Ba(6)Sn(7)S(20), there is the coexistence of the two coordination patterns with a SnS(5) trigonal bipyramid and SnS(4) tetrahedral polyhedrons, featuring a special crystal structure in the Ba-Sn-S system.

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.