Millimeter and Submillimeter Wave ESR System: Using 30 T Pulsed Magnetic Field

New systems for millimeter and submillimeter wave ESR have been developed in Kobe University. In the previous system the pulsed magnetic field was limited up to 17 T in the temperature range from 1.8 to 86 K. Using the new systems, we can measure in the field range up to 30 T in the temperature range from 1.8 K to 4.2 K and from 18 K to room temperature. The resolution of the magnetic field has been also improved in the new ESR system. The details of our new ESR systems are presented. In addition, the measurements of Yb₂Cu₂O₅ using these new systems are presented.     

Submillimeter-wave ESR measurements of low-dimensional quantum spin systems

Temperature-dependent electron spin resonance (ESR) measurements of two low-dimensional quantum spin systems, theS = 1/2 spin-ladder system Cu₂(1,4-diazacycloheptane)₂Cl₄ (Cu₂(C₅H₁₂N₂)₂Cl₄) and the gaplessS = 1 bond-alternating one-dimensional antiferromagnettrans-Ni(333-tet)(N₃)(ClO₄), have been performed. X-band electron spin resonance (ESR) measurements of single-crystal Cu₂(C₅H₁₂N₂)₂Cl₄ show the increase of linewidth and anisotropicg-shifts below 8 K similar to those known for one-dimensional antiferromagnet. On the other hand, Ni(333-tet)(N₃)(ClO₄) has broad line-width and ESR has been observed for the first time by our high-field ESR. Its linewidth increases as the temperature is decreased, while theg-shift seems to be isotropic and theg-value decreases as the temperature is decreased. Thisg-shift can be connected to the quantum fluctuation of the system.     

Submillimeter wave ESR measurements of metamagnetic Y2Cu2O5

Submillimeter wave ESR system in Kobe University is presented. It covers the frequency region from 60 to 383GHz and can apply the pulsed magnetic field up to 30T. The measurement of Y₂Cu₂O₅ single crystals using our system is presented.     

Thermodynamic properties of the spin-1/2 antiferromagnetic ladder under magnetic field

Specific heat (C_V) measurements in the spin-1/2 Cu₂(C₂H₁₂N₂)₂Cl₄ system under a magnetic field up to H =8.25 T are reported and compared to the results of numerical calculations based on the 2-leg antiferromagnetic Heisenberg ladder. While the temperature dependences of both the susceptibility and the low-field specific heat are accurately reproduced by this model, deviations are observed above the critical field H_C1 at which the spin gap closes. In this Quantum High Field phase, the contribution of the low-energy quantum fluctuations are stronger than in the Heisenberg ladder model. We argue that this enhancement can be attributed to dynamical lattice fluctuations. Finally, we show that such a Heisenberg ladder, for H > H C1, is unstable, when coupled to the 3D lattice, against a lattice distortion. These results provide an alternative explanation for the observed low temperature ( K-0.8 K) phase (previously interpreted as a 3D magnetic ordering) as a new type of incommensurate gapped state. Received: 23 July 1998 / Accepted: 24 August 1998     

Low-temperature behavior of specific heat curves in ruthenocuprate RuSr<Subscript>2</Subscript>Gd<Subscript>1.5</Subscript>Ge<Subscript>0.5</Subscript>Cu<Subscript>2</Subscript>O<Subscript>10 − δ</Subscript>: Superconducting,magnetic and crossing-point effects

Magnetic and superconducting properties of polycrystalline samples of RuSr₂Gd_1.5Ce_0.5Cu₂O_{(10 − δ)}, asprepared (by solid-state reaction) and annealed in pure oxygen at different pressure are presented. Specific heat and magnetization were investigated in the temperature range 1.8–300 K with a magnetic field up to 8 T. Specific heat, C (T), shows a jump at the superconducting transition (with onset at T ≈ 37.5 K) and a Schottky-type anomaly below 20 K. It is found that curves C(T) taken for different values of magnetic field have the same crossing point (at T _* ≈ 2.7 K) for all samples studied. At the same time, C(H) curves taken for different temperatures have a crossing point at a characteristic field H _* ≈ 3.7 T. These effects are manifestations of the crossing-point phenomenon, which is supposed to be inherent for strongly correlated electron systems.     

An algebraic description of anharmonic diatom–diatom inelastic collisions in the semiclassical approximation

An algebraic model to describe inelastic collisions between two anharmonic diatomic molecules in the semiclassical approximation is presented. The interactions for the diatomic systems are modelled in terms of Morse potentials, while an exponential repulsive potential is taken for the interactions between the nearest atoms of the diatomic systems. This problem is treated in the interaction potential framework, where an approximation in terms of the generators of three SU(2) groups is proposed, two corresponding to the Morse oscillators and the other to the interaction. The transition probabilities are given in terms of a sum of the products of three Wigner's d(β) functions corresponding to the three SU(2) groups. As an example the systems N₂?+?N₂ and H₂?+?H₂ are described and compared with exact quantum mechanical calculations.     

An investigation of paddle wheel Cu2(μ2-O2CCH3)4 for gas molecule adsorptions

Metal organic frameworks (MOFs) have been well-known and extensively researched due to the high storage /good selectivity for gas molecules. Herein, the structures and electron paramagnetic resonance (EPR) spectra for dicopper paddle wheel MOF compound (Cu₂(µ₂-O₂CCH₃)₄ with various gas molecule are theoretically investigated by density functional theory (DFT) calculations. The adsorption energies and isotherms (including pure gas molecules and the mixed ones) are calculated for the gas molecules interacting with the unsaturated Cu₂(µ₂-O₂CCH₃)₄. Both quantities exhibit the roughly consistent orders (e.g. H₂S?>?NH₃?>?CO₂?>?CO?>?H₂O?>?N₂?>?NO?>?H₂ for isotherms and H₂S?>?NH₃?>?N₂?>?CO₂?>?NO?>?H₂O?>?H₂?>?CO for adsorption energies), possibly suggesting that this material may act as a potential adsorbent of these gas molecules. The catalytic property of Cu₂(µ₂-O₂CCH₃)₄ for oxidation of CO and NO into non-toxic molecules and splitting of H₂O into H₂ and O₂ in the solvent condition are uniformly discussed. Simulation of Grand Canonical Monte Carlo (GCMC) in MS 8.0 and calculations in Langmuir model reveal that Cu₂(µ₂-O₂CCH₃)₄ has good selectivity for CH₄ in natural gas (CH₄/CO₂/N₂) and SO₂ in fog (SO₂/NO/NO₂/H₂O/O₂), which would exhibit potential environmentally friendly applications.     

Magnetotransport and magnetotunneling in single-layer, two-layer, and three-layer Bi2Sr2Can−1CunOz (n=1,2,3) single crystals

In continuous magnetic fields H up to 28 T, we have studied the out-of-plane transport properties and tunneling characteristics of high-quality nondoped single crystals of the Bi-cuprate family: Bi₂Sr₂CuO_6+δ (Bi2201), Bi₂Sr₂CaCu₂O_8+δ (Bi2212) and Bi₂Sr₂Ca₂Cu₃O_10+δ (Bi2223) grown by an identical method. For all compounds the out-of-plane magnetotransport ρ_c(H) is negative in the temperature region where ρ_c(T) shows in the normal state a semiconducting-like temperature dependence. The negative magnetoresistance of ρ_c corresponds to the suppression of the semiconducting temperature dependence of ρ_c(T) which is found to be isotropic. For the Bi2201 compound, where the normal state can be reached in the available magnetic fields (28 T), a nearly complete suppression of the low-temperature upturn in ρ_c(T) is observed in the highest magnetic fields with a tendency towards a metallic behavior down to the lowest temperatures (0.4 K). Using the break-junction technique, especially for the Bi2212 and Bi2232 compounds, a clear superconducting gap structure can be observed. Both for temperatures above the critical temperature and for magnetic fields above the upper critical field, a pseudogap structure remains present in the tunneling spectra. The applied magnetic fields yield a stronger suppression of the superconducting state compared to that of the normal-state gap structures as manifested in ρ_c(T) transport and tunneling.     

The effects of C substitution and disorder on the field dependent critical current density in MgB2 with nano-SiC additions

In this work, nano sized SiC powders were mixed with Mg and B and reacted by either a one-step insitu or two-step method resulted in different level of C substitution. X-ray diffraction shows the presence of Mg₂Si signifying that the reaction between SiC and Mg occurred leading to the release of C in samples reacted in one-step method. Moreover, the much reduced value of a-axis indicates C substitution took place. Resistivity measurements showed higher intragrain scattering owing to a higher density of defects and/or impurities. These samples also show higher H_irr and H_c2 at 20 K in comparison to samples with mainly unreacted SiC (hence lower C substitution). More importantly, their J_c’s are more insensitive to high magnetic field (>4 T) at 6 K. However, at 20 K the effect of C content on J_c(H) is less pronounced. Finally, the order of magnitude of J_c(H) at both 6 K and 20 K is rather dominated by pinning.     

The dc magnetic field,temperature and film thickness dependence of microwave surface resistance of YBCO and DyBCO thin films

We investigated the dc magnetic field and temperature dependences of the microwave surface resistance (R_s) of YBa₂Cu₃O_y (YBCO) and DyBa₂Cu₃O_y (DyBCO) superconducting thin films. The YBCO and DyBCO thin films, each with a thickness of 300, 500, or 700 nm, were deposited on MgO (1 0 0) substrates by the thermal co-evaporation method. The R_s was measured using the dielectric resonator method. A dc magnetic field of up to 5.0 T was applied parallel to the c-axis of the superconducting thin films. The results showed that the R_s value had almost the same temperature dependence at various thicknesses in a zero-external field. The R_s of the YBCO and DyBCO thin films increased with the applied dc magnetic field. The DyBCO thin films showed weaker magnetic field dependence of R_s than the YBCO thin films. The R_s ratio (defined as R_s(5 T)/R_s(0 T)) linearly increased with the film thickness. These results show that pinning strength decreased with an increasing film thickness.     

DSC study of superionic phase transition in (NH4)4H2(SeO4)3 single crystals

DSC and complex impedance studies of the protonic conductor (NH₄)₄H₂(SeO₄)₃, which undergoes a superionic phase transition of first order at T_s = 378 K show that the activation energy of ionic conductivity d(lg σ)/dt and the ordering enthalpy ΔC_p of the crystal are proportional: d(lg σ)/dT = XΔC_p/RT_s + const, as found for MAg₄I₅ crystals undergoing a second-order superionic phase transition. Thus the short-range order environment of the species involved in fast-ion transport plays the main role in the superionic phase transition. This is also supported by the value of the entropy change at T_s, ΔS = 43 J/mole·K. A new metastable phase was found to be induced on heating the (NH₄)₄H₂(SeO₄)₃ crystal above T_s.     

Reverse phenomena of magnetic field effects and time-resolved EPR spectra in the photogenerated biradical from intramolecular electron-transfer in a phenothiazine–C60 linked compound with a semi-rigid spacer

Photoinduced electron-transfer reactions and magnetic field effects (MFEs) on the decay rates of the photogenerated biradical in a phenothiazine (Ph)–C₆₀ linked compound with a biphenyl group (Ph(BP)C₆₀) were examined in benzonitrile and benzene. Fluorescence and transient absorption spectra indicate that the intramolecular electron-transfer for Ph(BP)C₆₀ from the Ph to the singlet or triplet excited state of C₆₀ was suppressed by the biphenyl group. The decay rates of the photogenerated biradical decreased in the 0–0.2 T magnetic field range and increased in the 0.2–1 T magnetic field range. The reverse phenomena of the MFEs in Ph(BP)C₆₀ were strongly enhanced with increasing temperature and similar to those in Ph(n)C₆₀ (n = 6?12). The MFEs in Ph(BP)C₆₀ can be governed by spin-lattice relaxation and/or spin-spin relaxation mechanisms as observed in Ph(n)C₆₀ (n = 6?12). Time-resolved EPR spectra of Ph(BP)C₆₀ showed absorption, emission, absorption and emission patterns, and are quite different from those in Ph(n)C₆₀ (n = 4?12). The result indicates that the magnitude and distribution of the exchange interaction |2J| in Ph(BP)C₆₀ are smaller than those in Ph(n)C₆₀ (n = 4?12) and charge recombination occurs in the inverted region because the sign of the J is positive.     

三明治结构Tan(B3N3H6)n+1 团簇的磁性和量子输运性质

利用密度泛函理论和非平衡格林函数方法, 本文对小尺寸团簇Ta_n(B₃N₃H₆)_n+1 (n ≤ 4)的磁性和量子输运性质进行了系统的研究. 计算结果表明, 此类体系采用三明治结构作为其基态并且具有较高的稳定性. 体系的磁矩随团簇尺寸的增大而线性增大. 当把Ta_n(B₃N₃H₆)_n+1团簇耦合到Au电极上时, 形成的Au-Ta_n(B₃N₃H₆)_n+1-Au体系在有限偏压下展示出了较强的自旋过滤能力, 因而可以被看做是一类新型的低维自旋过滤器.     

Hydrostatic pressure study of the structural phase transitions and superconductivity in single crystals of (Ba1−xKx)Fe2As2 (x=0 and 0.45) and CaFe2As2

We studied the effect of hydrostatic pressure (P) on the structural phase transitions and superconductivity in the ternary and pseudo-ternary iron arsenides CaFe₂As₂, BaFe₂As₂, and (Ba_0.55K_0.45)Fe₂As₂, by means of measurements of electrical resistivity (ρ) in the 1.8-300 K temperature (T) range, pressures up to 20 kbar, and magnetic fields up to 9 T. CaFe₂As₂ and BaFe₂As₂ (lightly doped with Sn) display structural phase transitions near 170 and 85 K, respectively, and do not exhibit superconductivity in ambient pressure, while K-doped (Ba_0.55K_0.45)Fe₂As₂ is superconducting for T<30 K. The effect of pressure on BaFe₂As₂ is to shift the onset of the crystallographic transformation down in temperature at the rate of ~−1.04 K/kbar, while shifting the whole ρ(T) curves downward, whereas its effect on superconducting (Ba_0.55K_0.45)Fe₂As₂ is to shift the onset of superconductivity to lower temperatures at the rate of ~−0.21 K/kbar. The effect of pressure on CaFe₂As₂ is first to suppress the crystallographic transformation and induce superconductivity with onset near 12 K very rapidly, i.e., for P<5 kbar. However, higher pressures bring about another phase transformation characterized by reduced-resistivity, and the suppression of superconductivity, confining superconductivity to a narrow pressure dome centered near 5 kbar. Upper critical field (H_c2) data in (Ba_0.55K_0.45)Fe₂As₂ and CaFe₂As₂ are discussed.     

Quasi-two-dimensional magnetism in (CnH2n+1NH3)2CuCl4 studied by electron paramagnetic resonance

The quasi-two-dimensional magnetism in the layered transition metal compound (C_nH_2n+1NH₃)₂CuCl₄ (n=10, 14) was investigated by means of electron paramagnetic resonance (EPR) and superconducting quantum interference device measurements. As a result, the high temperature magnetic phase transitions were reflected in the EPR parameters in a sensitive manner.     

Magnetocaloric effect in Gd6Co1.67Si3 compound with a second-order phase transition

The magnetic properties and the magnetic entropy change AS have been investigated for Gd6Co1.67Si3 compounds with a second-order phase transition. The saturation moment at 5 K and the Curie temperature TC are 38.1μB and 298 K, respectively. The AS originates from a reversible second-order magnetic transition around TC and its value reaches 5.2 J/kg.K for a magnetic field change from 0 to 5T. The refrigerant capacity （RC） of Gd6Co1.67Si3 are calculated by using the methods given in Refs.[12] and [21], respectively, for a field change of 0 5T and its values are 310 and 440 J/kg, which is larger than those of some magnetocaloric materials with a first-order phase transition.     

Rapid preparation of Mg（B1-xCx）2 superconductor using hybrid microwave method

The crystal structure and the superconductivity for samples Mg（B1-xCx）2 （0〈 x 〈0.09） prepared by a hybrid microwave synthesis have been investigated. The starting material B10C is also obtained by using the microwave method. The carbon can distribute uniformly in the Mg（B1-xCx）2 samples because boron and carbon are mixed on an atomic scale in the staring material B10C. The dependences of both lattice parameters and superconducting transition temperature Tc on carbon content accord with those reported in the literature. The upper critical field He2 at 20 K can be enhanced from about 4.3 T for x = 0 to 10 T for x = 0.05. The critical current density Jc of Mg（B0.95 C0.05）2 is 1.05×10^4 A/cm^2 at 20 K and 1 T.     

Superparamagnetism and spin-glass like state for the MnFe2O4 nano-particles synthesized by the thermal decomposition method

MnFe₂O₄ nano-particles with an average size of about 7 nm were synthesized by the thermal decomposition method. Based on the magnetic hysteresis loops measured at different temperatures the temperature-dependent saturation magnetization (M_S) and coercivity (H_C) are determined. It is shown that above 20 K the temperature-dependence of the M_S and H_C indicates the magnetic behaviors in the single-domain nano-particles, while below 20 K, the change of the M_S and H_C indicates the freezing of the spin-glass like state on the surfaces. By measuring the magnetization–temperature (M–T) curves under the zero-field-cooling (ZFC) and field-cooling procedures at different applied fields, superparamagnetism behavior is also studied. Even though in the ZFC M–T curves peaks can be observed below 160 K, superparamagnetism does not appear until the temperature goes above 300 K, which is related with the strong inter-particle interaction.     

Large magnetic entropy change near room temperature in the LaFe11.5Si1.5H1.3 interstitial compound

The LaFe_11.5Si_1.5H_1.3 interstitial compound has been prepared. Its Curie temperature T_C (288 K) has been adjusted to around room temperature, and the maximal magnetic entropy change (|ΔS|～17.0 J·kg^-1·K^-1 at T_C) is larger than that of Gd (|ΔS|～9.8 J·kg^-1·K^-1 at T_C=293 K) by ～73.5% under a magnetic change from 0 to 5 T. The origin of the large magnetic entropy change is attributed to the first-order field-induced itinerant-electron metamagnetic transition. Moreover, the magnetic hysteresis of LaFe_11.5Si_1.5H_1.3 under the increase and decrease of the field is very small, which is favourable to magnetic refrigeration application. The present study suggests that the LaFe_11.5Si_1.5H_1.3 compound is a promising candidate as a room-temperature magnetic refrigerant.     

Co(S1-xSex)2系统中的铁磁量子相变

针对Co(S_1-xSe_x)₂系统在x=0.11附近发生的铁磁金属到顺磁金属相变,制备了一系列不同Se替代浓度的多晶样品.通过对其结构和电阻率-温度ρ(T)关系的系统观测,结果发现,样品铁磁相变温度T_C随着Se替代浓度x值的增加,以(1-x)^1/2关系单调下降,其二级铁磁相变转变为一级相变 关键词： 量子相变 自旋量子涨落 1-xSe_x)₂')" href="#">Co(S_1-xSe_x)₂