Breakdown of an intermediate plateau in the magnetization process of anisotropic spin-1 Heisenberg dimer: Theory vs. experiment

The magnetization process of the spin-1 Heisenberg dimer model with the uniaxial or biaxial single-ion anisotropy is particularly investigated in connection with recent experimental high-field measurements performed on the single-crystal sample of the homodinuclear nickel(II) compound [Ni₂(Medpt)₂(μ-ox)(H₂O)₂](ClO₄)₂·2H₂O (Medpt=methyl-bis(3-aminopropyl)amine). The results obtained from the exact numerical diagonalization indicate a striking magnetization process with a marked spatial dependence on the applied magnetic field for arbitrary but finite single-ion anisotropy. It is demonstrated that the field range, which corresponds to an intermediate magnetization plateau emerging at a half of the saturation magnetization, basically depends on a single-ion anisotropy strength as well as a spatial orientation of the applied field. The breakdown of the intermediate magnetization plateau is discussed at length in relation to the single-ion anisotropy strength.     

Micromechanical and thermal behaviour of gel grown pure- and sodium-modified copper tartrate crystals

Results regarding micromechanical characteristics of gel grown pure- and sodium-modified copper tartrate crystals, bearing composition CuC₄H₄O₆·3H₂O, (Cu)_0.77(Na)_0.23C₄H₄O₆·3H₂O and (Cu)_0.65(Na)_0.35C₄H₄O₆·H₂O, as obtained on using indentation induced hardness testing technique are reported. Thermal behaviour of these crystals in the temperature ranging from room temperature (∼25 °C) to about 600 °C is also reported. Pure copper tartrate crystals are found to be thermally more stable than the sodium-modified ones. Dependence of Vickers’ hardness number H_v on load ranging from 0.049 to 2.94 N on two different planes for all the three compositions is analyzed. It is shown that after initial rise in the value of H_v, the same achieves saturation at a load of 0.49 N. Modification of copper tartrate crystal by introducing sodium in its lattice brings about a change in the micromechanical characteristics. The saturation value of H_v decreases with increase in the concentration of sodium ions. The results on (0 0 1) and (1 1 1) planes for both pure and modified copper tartrate crystals suggest hardness anisotropy. Relative difference of hardness between the two planes and yield strength for both pure and modified copper tartrate crystals is worked out. The experimental results are analyzed for applicability of Meyer’s law and Proportional Specimen Resistance Model. It is suggested that the experimental results indicating reverse ISE phenomenon may be explained in terms of the existence of a distorted zone near the crystal-medium interface. The integral method of Coats and Redfern approximation applied to the thermoanalytical data suggests “Random Nucleation Model” for the reaction kinetics of these crystals. Non-isothermal kinetic parameters such as activation energy, frequency factor and order of reaction are calculated.     

Syntheses of two new hybrid metal-organic polymers using flexible aliphatic dicarboxylates and pyrazine: Crystal structures and magnetic studies

The reaction of metal ions, flexible aliphatic dicarboxylates and pyrazine in aqueous solution afford two new metal-organic coordination polymers, {[Cu₂(μ₂-η²-O₂C(CH₂)₂CO₂-η²-μ₂)₂(H₂O)₂]·2H₂O}_n (1) and [Eu₂(μ₂-η²-O₂CCH₂CO₂-η¹-μ₁)₂(μ₂-η²-O₂CCH₂CO₂-η²-μ₂)(H₂O)₆]_n (2). Polymer 1 contains the paddle-wheel cage dicopper(II) units, forming a one-dimensional (1D) double-stranded chain structure along the a-axis, in which the copper(II) atoms are bridged by the carboxylate groups of four succinates. The intradimer Cu-Cu distance is 2.613(2) Å; the interdimer Cu?Cu distance is 6.473 Å. To our knowledge, compound 1 represents the first example of a double-stranded chain structure containing dinuclear paddle-wheel type cage. In the three-dimensional (3D) compound 2, each central Eu(III) ion have a distorted monocapped square antiprism coordination geometry. The structure is built up from two types of polymeric chains with [EuO₆(H₂O)₃]_n units as tethers, resulting in microporous framework. The magnetic behavior of 1 shows that the occurrence of a strong antiferromagnetic coupling between the copper(II) ions through the short bridges via the carboxyl groups can be obtained; the best fittings to the experimental magnetic susceptibilities gave −2J=314 cm⁻¹.     

Phase- and shape-controlled synthesis of cadmium hydroxyl chloride microstructures via an ammonia-assisted conversion of 1D CdQCl (Q=quinoline) complex microwires

In this paper we reported a NH₃·H₂O-assisted solvothermal route for successful synthesis of cadmium hydroxyl chlorides (Cd_x(OH)_yCl_z) microstructures with different phases and shapes, employing 1D CdQCl (Q=quinoline) complex microwires as the precursor. Experiments contained two processes: firstly, CdQCl complex microwires with 500–600 nm in diameter and several hundreds of micrometers in length were prepared by the complexation between CdCl₂·2.5H₂O and quinoline at room temperature; then, CdQCl microwires were solvothermally treated at 150 °C for 10 h in the presences of different amounts of NH₃·H₂O to produce Cd_x(OH)_yCl_z microstructures with various phases and shapes. The as-obtained precursor and Cd_x(OH)_yCl_z microstructures were characterized by scanning electron microscopy, transmission electron microscopy, Infrared spectrometry and X-ray powder diffraction. Experiments showed that hexagonal Cd(OH)Cl was obtained from water–methanol system, while rhombohedral Cd₄(OH)₅Cl₃ from methanol system. Also, it was found that the shapes of Cd_x(OH)_yCl_z could be tuned by the amounts of NH₃·H₂O. Furthermore, the UV diffuse reflection and photoluminescence spectra of the precursor and Cd_x(OH)_yCl_z were also investigated.     

EPR characterization of a nanoporous metal-organic framework exhibiting a bulk magnetic ordering

Magnetic properties of the open-framework structure [Cu₃(PTMTC)₂(py)₆(CH₃CH₂OH)₂(H₂O)] as well as those of a related evacuated sample have been analyzed on the basis of combined SQUID and EPR measurements. Such combined experiments demonstrate unambiguously the key role played by the radical ligand PTMTC in the promotion in both molecular magnets of magnetic exchange interactions through the open-framework structure.     

Structural characterisation of [Cu2(bptd) (H2O) Cl4] and [Ni2(bptd)2(H2O)4] Cl4·3H2O; evidence of null intramolecular exchanges by EPR and magnetic measurements

Using the 2,5-bis(2-pyridyl)-1,3,4-thiadiazole (bptd), we recently prepared [Cu₂(bptd) (H₂O) Cl₄] and [Ni₂(bptd)₂ (H₂O)₄] Cl₄, 3H₂O in which the magnetic centres are connected through one diazine+one chloro and two diazine ligand bridges, respectively. These two compounds are the first examples that show null intramolecular magnetic interactions despite M-M distances close to 3.7 Å within perfectly planar edifices:Down to , [Cu₂(bptd)Cl₄(H₂O)] is paramagnetic while, below T_t, half of the Cu²⁺ions interact, leading to residual paramagnetism of one Cu²⁺/f.u. Magnetic susceptibility measurements, EPR and pulsed EPR study indicate the original intermolecular nature of AF exchanges.[Ni₂(bptd)₂(H₂O)₄]Cl₄·3H₂O susceptibility obeys a Curie-law involving pure paramagnetism. Moreover, its EPR spectrum can be interpreted on the basis of virtual S=1 monomers. Below 70 K, Zero Field Splitting (D∼275 G) due to dipolar interactions without magnetic exchanges could be responsible for the LT spectra splitting. For both compounds, the thia role is suggested as partially responsible for the null-in-plane magnetic exchanges.     

Pinning efficiency of splayed columnar defects in Bi-2212 single crystal: Evidence of a cage pinning effect

A three-directional configuration of columnar defects has been induced in a Bi₂Sr₂CaCu₂O₈ single crystal by irradiation with heavy ions of high energy. Persistent current densities have been extracted, using the Bean model, from hysteresis loops recorded in the orientation H||c. We have shown that improvements in pinning properties are larger in this three-directional splayed configuration than in the one obtained with columnar defects parallel to the c-axis. This effect exists only for H larger than H_Φ, where H_Φ is the matching field, and disappears as temperature is increased and vortices become less stiff. This is the first time that such a beneficial effect is reported for a compound of such a high electronic anisotropy.     

Structural, vibrational and dielectric properties of new potassium hydrogen sulfate arsenate: K4(SO4)(HSO4)2(H3AsO4)

A new compound, K₄(SO₄)(HSO₄)₂(H₃AsO₄) was synthesized from water solution of KHSO₄/K₃H(SO₄)₂/H₃AsO₄. This compound crystallizes in the triclinic system with space group P1¯ and cell parameters: a=8.9076(2) Å, b=10.1258(2) Å, c=10.6785(3) Å; α=72.5250(14)°, β=66.3990(13)°, γ=65.5159(13)°, V=792.74(3) Å³, Z=2 and ρ_cal=2.466 g cm⁻³. The refinement of 3760 observed reflections (I>2σ(I)) leads to R₁=0.0394 and wR₂=0.0755. The structure is characterized by SO₄²⁻, HSO₄⁻ and H₃AsO₄ tetrahedra connected by hydrogen bridge to form two types of dimer (H(16)S(3)O₄⁻?S(1)O₄²⁻ and H(12)S(2)O₄⁻?H₃AsO₄). These dimers are interconnected along the [1¯ 1 0] direction by the hydrogen bonds O(3)-H(3)?O(6). They are also linked by the hydrogen bridge assured by the hydrogen atoms H(2), H(3) and H(4) of the H₃AsO₄ group to build the chain S(1)O₄?H₃AsO₄ which are parallel to the “a” direction. The potassium cations are coordinated by eight oxygen atoms with K-O distance ranging from 2.678(2) to 3.354(2) Å.Crystals of K₄(SO₄)(HSO₄)₂(H₃AsO₄) undergo one endothermic peak at 436 K. This transition detected by differential scanning calorimetry (DSC) is also analyzed by dielectric and conductivity measurements using the impedance spectroscopy techniques. The obtained results show that this transition is protonic by nature.     

Characterizations of octahedral zinc oxide synthesized by sonochemical method

The ultrasonic reaction of zinc nitrate hexahydrate (Zn(NO₃)₂·6H₂O) and hexamethylenetetramine (C₆H₁₂N₄) was investigated by varying the concentration of the reactants, the irradiation time, and the type of sonicator. The morphology, composition, and phase structure of the products were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier Transform Infrared (FTIR) and ultraviolet-visible (UV-vis) spectroscopy. Octahedral zinc oxide (ZnO) micropowders were formed at low concentrations, 0.05 M, of Zn(NO₃)₂·6H₂O and C₆H₁₂N₄ in both lab-made sonicator and commercial ultrasonic bath. However, at concentrations between 0.1 and 1.0 M Zn(NO₃)₂-C₆H₁₂N₄ mainly plate-like zinc hydroxide nitrate hydrate (Zn₅(OH)₈(NO₃)₂(H₂O)₂) resulted with only a small fraction of ZnO, irrespective of the irradiation time employed, highlighting the sensitivity of the system to the concentration of the starting materials. Heat treatment of Zn₅(OH)₈(NO₃)₂(H₂O)₂ at 350 °C in air affords a ZnO phase of irregular morphology. Octahedral ZnO is found to exhibit slightly lower IR absorption and similar UV absorption to that of commercial prismatic hexagonal ZnO, although an extra peak due to small quantities of Zn₅(OH)₈(NO₃)₂(H₂O)₂ is observed.     

Upper critical field of the 122-type iron pnictide superconductors

The upper critical fields (H_c2) of the single crystals (Sr,Na)Fe₂As₂ and Ba_0.55K_0.45Fe₂As₂ were determined by means of measuring the electrical resistivity, ρ_xx(μ₀H), using the facilities of pulsed magnetic field at Los Alamos. In general, these compounds possess a very large upper critical field (H_c2(0)) with a weak anisotropic effect. The detailed curvature of H_c2(T_c) may depend on the magnetic field orientation and the sample compositions. We argue that such a difference mainly results from the multi-band effect, which might be modified via doping.     

Large upper critical field in non-centrosymmetric superconductor Y2C3

We determine the upper critical field μ₀H_c2(T_c) of non-centrosymmetric superconductor Y₂C₃ using two distinct methods: the bulk magnetization M(T) and the tunnel-diode oscillator (TDO) based impedance measurements. It is found that the upper critical field reaches a value of 30 T at zero temperature which is above the weak-coupling Pauli paramagnetic limit. We argue that the observation of such a large μ₀H_c2(0) in Y₂C₃ could be attributed to the admixture of spin-singlet and spin-triplet pairing states as a result of broken inversion symmetry.     

Full potential calculation of structural, elastic properties and high-pressure phase of binary noble metal carbide: ruthenium carbide

We present in this paper the results of an ab initio theoretical study within the local density approximation (LDA) to determine in rock-salt (B1), cesium chloride (B2), zinc-blende (B3), and tungsten carbide (WC) type structures, the structural, elastic constants, hardness properties and high-pressure phase of the noble metal carbide of ruthenium carbide (RuC).The ground state properties such as the equilibrium lattice constant, elastic constant, the bulk modulus, its pressure derivative, and the hardness in the four phases are determined and compared with available theoretical data. Only for the three phases B1, B3, and WC, is the RuC mechanically stable, while in the B2 phase it is unstable, but in B3 RuC is the most energetically favourable phase with the bulk modulus 263 GPa, and at sufficiently high pressure (P_t=19.2 GPa) the tungsten carbide (WC) structure would be favoured, where ReC-WC is meta-stable.The highest bulk modulus values in the B3, B2, and WC structures and the hardnesses of H(B3)=36.94 GPa, H(B1)=25.21 GPa, and H(WC)=25.30 GPa indicate that the RuC compound is a superhard material in B3, and is not superhard in B1 and WC structures compared with the H(diamond)=96 GPa.     

Mixed valence states in cobalt iron cyanide

Cobalt iron cyanide with both Co and Fe in mixed valence states were prepared and characterized. In this mixed valence system the cobalt atom is found both as high spin Co(2+) and low spin Co(III) while iron always appears in low spin state to form two solid solutions: Co(2+)Co(III) hexacyanoferrates (II,III), and Co(2+)Co(III) hexacyanoferrate (II). Such solid solutions have the following formula units: (Co²⁺)_x(Co^III)_1−xK[(Fe^II)_1−x(Fe^III)_x(CN)₆]·H₂O and (Co²⁺)_1.5x(Co^III)_1−xK[Fe^II(CN)₆]·yH₂O (0?x?1, 1?y?14). Compounds within these two series were characterized from Infrared, Mössbauer, X-ray diffraction and thermo-gravimetric data, and magnetic measurements at low temperature. A model for their crystal structure is proposed and the structure for a representative composition refined from XRD powder patterns using the Rietveld method. A simple and reproducible procedure to prepare these solid solutions is provided. Within hexacyanoferrates, such mixed valence states system in both metal centres shows unique features, which are discussed from the obtained data.     

Effect of polymers doping on flux pinning behavior of MgB2

The effects of polymers doping on irreversibility field (H_irr) and critical current density (J_c) of MgB₂ have been investigated in this work. It is found that both J_c, and H_irr, are improved by doping at relative lower temperature region. The J_c−B curves of all samples studied in this work are well fitted using J_c(B) formula in percolation model. The values of upper critical field anisotropy (γ) are obtained from the fitting result at various temperatures. It is observed that values of γ for polymers doping samples are reduced at these temperatures. This is considered to be responsible for the enhancement of values of J_c for doped samples. Moreover, the percolation threshold, p_c, is found to be enhanced with increasing temperature. It is believed that the grain boundary pinning is still dominating in MgB₂, while the deviation of experimental data from the theoretical values is due to the percolation of suppercurrent in polycrystalline MgB₂.     

The physical properties of borocarbide superconductor Y1−xSmxNi2B2C (x≦0.25) and Y1−xSmxPd5B3C0.4 (x≦0.4)

We have investigated the magnetic and transport properties of borocarbide superconductors YNi₂B₂C and YPd₅B₃C_0.4 with Yttrium partially substituted by Samarium. The upper critical fields H_C2 are determined by the scaling analysis of the thermal fluctuation magnetoconductivity. Around the transition region, the thermal fluctuation magnetoconductivity can be scaled by a universal function for all applied magnetic fields. The formula H_C2(T)=H_C2(0)[1−(T/T_C)^3/2]^3/2 of a narrow-band pairing mechanism gives an excellent fit to the value of upper critical field H_C2(0)=7.6 T in the Y_0.8Sm_0.2Pd₅B₃C_0.4 compound. The superconducting coherence length ξ is determined to be 6.58 nm, the Ginzburg-Landau parameter κ is 29 and the penetration depth λ is 191 nm.     

Crystal field and exchange interactions in rare earth transition metal salen compounds containing bipyridine, pyrazole complexes

Crystal field parameters for Pr³⁺ in {[Ni(salen)Pr-(hfac)₃](H₂O)} (noted as NiPr) and {[Ni(salen)Pr(hfac)₃(pyr)]-(CHCl₃)} (noted as NiPrpyr) have been found from a fit to the thermal variation in the magnetic susceptibility of NiPr and NiPrpyr. The nature of exchange interaction in [Cu(salen)Pr(hfac)3(pyr)] (noted as CuPrpyr), {[{Cu(salen)Pr(hfac)₃}₂(pyz)](H₂O)₃} (noted as Cu₂Pr₂pyz) and {[{Cu(salen)Pr(hfac)₃}₂(bpy)]-(CHCl₃)₂} (noted as Cu₂Pr₂bpy, bpy=4,4_-bipyridine) have been found using the derived results for NiPr and NiPrpyr. All the exchange interactions give significant contribution to the thermal variation in magnetic susceptibility below 50 K. The contribution due to Pr-Cu interaction is positive while that of the Cu-Cu and Pr-Pr interactions are negative. The behaviors below 10 K for Pr-Cu and Pr-Pr are difficult to explain, and point to a possible change in structure of CuPrpyr, Cu₂Pr₂pyz and Cu₂Pr₂bpy below 10 K. The theoretical thermal variations in the magnetic specific heat of NiPr and NiPrpyr are computed and discussed.     

Synthesis and magnetic properties of three-dimensional metal (II) organophosphates

A new series of metal (II) organophosphates with the formula M(II) 2(H₂O)₂[O₃PCH₂(C₆H₄)CH₂PO₃] (M=Mn, Fe and Ni) have been prepared by hydrothermal synthesis. The structure consisted of two-dimensional metal–oxygen inorganic layers is pillared by p-xylylenediphosphonate to form a three dimensional framework. The layers are constructed by corner-sharing metal oxygen polyhedron. A study on the magnetism of the materials indicates the presence of spin canted antiferromagnetc interactions. The manganese and iron compounds represent the interesting 3D metal organophosphate molecular metamagnet due to spin canted antiferromagnetic with high critical temperature (40 K for Mn; 16 K for Fe). The infinite M–O–M layers are believed to be responsible for this high performance.     

A new isomorph of ferrous chloride tetrahydrate: A Fe Mössbauer and X-ray crystallography study

This paper outlines the discovery of a newly characterised isomorph of ferrous chloride tetrahydrate, Fe(H₂O)₆·FeCl₄(H₂O)₂, which was initially identified by X-ray crystallography and confirmed by Mössbauer spectroscopy. The X-ray analysis identified the space group as P2₁/c with essentially the same unit cell dimensions as the well-known isomorph, FeCl₂·4H₂O, except that one edge is doubled due to two discrete [Fe(H₂O)₆]²⁺ and [FeCl₄(H₂O)₂]²⁻ species per unit cell. Time-series Mössbauer studies revealed this new isomorph to be unstable upon atmospheric exposure, decaying to the well-known structure over a period of days. Density functional theory calculations support an energetically favourable catalytic interconversion involving adsorbed water. A high-precision redetermination on the FeCl₂·4H₂O crystal structure, which is also in space group P2₁/c, is also reported, providing the unit cell parameters: a=5.8765(3) Å, b=7.1100(3) Å, c=8.4892(5) Å and β=111.096(1)°.     

Synthesis, crystal structure, Cu doped EPR, thermal and voltammetric studies of [Ni(isonicotinamide)2(H2O)4]·(sac)2 single crystal

The single crystal of [Ni(ina)₂(H₂O)₄]·(sac)₂, (NINS), (ina is isonicotinamide and sac is saccharinate) complex has been prepared and its structural, spectroscopic and thermal properties have been determined. The title complex crystallizes in monoclinic system with space group P2₁/c, Z=2. The octahedral Ni(II) ion, which rides on a crystallographic centre of symmetry, is coordinated by two monodentate ina ligands through the ring nitrogen and four aqua ligands to form discrete [Ni(ina)₂(H₂O)₄] unit, which captures two saccharinate ions in up and down positions, each through intermolecular hydrogen bands. The magnetic environment of copper(II) doped NINS crystal has also been identified by electron paramagnetic resonance (EPR) technique. The g and A values of Cu²⁺ doped NINS single crystal were calculated from the EPR spectra recorded in three mutually perpendicular planes. These values indicated that the paramagnetic centre has a rhombic symmetry with the Cu²⁺ ion having distorted octahedral environment. The complex exhibits only metal centred electroactivity in the potential range of −2.00, 1.25 V versus Ag/AgCl reference electrode.     

Synthesis of basic magnesium carbonate microrods with a “house of cards” surface structure using rod-like particle template

Basic magnesium carbonate (Mg₅(CO₃)₄(OH)₂·4H₂O) microrods with a surface structure of “house of cards” have been synthesized without any alkaline reagent, using rod-like particles, magnesium carbonate trihydrate, as templates. The product was characterized by X-ray diffraction (XRD) and field-emission scanning electron microscopy (FE-SEM). The transformation process from rod-like MgCO₃·3H₂O particles to Mg₅(CO₃)₄(OH)₂·4H₂O microrods with a surface structure of “house of cards” was recorded. Preliminary discussions on possible growth mechanisms of Mg₅(CO₃)₄(OH)₂·4H₂O microrods are also proposed in this paper.