Magnetic bistability of isolated giant-spin centers in a diamagnetic crystalline matrix

Polynuclear single-molecule magnets (SMMs) were diluted in a diamagnetic crystal lattice to afford arrays of independent and iso-oriented magnetic units. Crystalline solid solutions of an Fe(4) SMM and its Ga(4) analogue were prepared with no metal scrambling for Fe(4) molar fractions x down to 0.01. According to high-frequency EPR and magnetic measurements, the guest SMM species have the same total spin (S=5), anisotropy, and high-temperature spin dynamics found in the pure Fe(4) phase. However, suppression of intermolecular magnetic interactions affects magnetic relaxation at low temperature (40 mK), where quantum tunneling (QT) of the magnetization dominates. When a magnetic field is applied along the easy magnetic axis, both pure and diluted (x=0.01) phases display pronounced steps at evenly spaced field values in their hysteresis loops due to resonant QT. The pure Fe(4) phase exhibits additional steps which are firmly ascribed to two-molecule QT transitions. Studies on the field-dependent relaxation rate showed that the zero-field resonance sharpens by a factor of five and shifts from about 8 mT to exactly zero field on dilution, in agreement with the calculated variation of dipolar interactions. The tunneling efficiency also changes significantly as a function of Fe(4) concentration: the zero-field resonance is significantly enhanced on dilution, while tunneling at ±0.45 T becomes less efficient. These changes were rationalized on the basis of a dipolar shuffling mechanism and transverse dipolar fields, whose effect was analyzed by using a multispin model. Our findings directly prove the impact of intermolecular magnetic couplings on SMM behavior and disclose the magnetic response of truly isolated giant spins in a diamagnetic crystalline environment.     

Thermal characteristics of thermosets formed by free radical photocuring

We have studied the compound MnAs with a giant magnetocaloric effect, which has a magneto-structural transition at 316 K. The magnetic phase diagram has been deduced from adiabatic heat-capacity measurements and from cooling and heating curves. The ferroto paramagnetic transition changes with field from 316 K at 0 T to 335.3 K at 6 T. There is a strong thermal hysteresis between 10 and 5 K, depending on field. Direct measurements of the adiabatic temperature change caused by the application of magnetic field were made and compared with the values deduced from heat-capacity data.Moreover, adiabatic field cycles were performed quasi-statically between 0 and 6 T around the phase coexistence region, showing the strength of the effect in each phase and on the coexistence lines.     

Gd3Ga5O12∶Eu3+发光纳米晶的燃烧合成及性质

以尿素为燃烧剂,乙二醇为分散剂采用燃烧法制备了Gd3Ga5O12∶Eu3+纳米晶。利用X射线衍射、电镜和荧光光谱对前驱体和热处理后样品的结构、形貌和发光性能进行了表征。XRD结果表明:700℃热处理2 h即可获得立方结构Gd3Ga5O12∶Eu3+纳米晶。根据Scherrer公式估算经700℃和900℃热处理2 h获得的纳米晶的一次性粒径分别为28 nm和42 nm。发射光谱和激发光谱的结果表明:特征发射峰来自于5D0-7FJ跃迁,而来自于Eu3+的5D0→7F1的磁偶极跃迁发射最强;宽激发带主要来自于Eu-O电荷迁移带和Gd3Ga5O12基质吸收。发射强度和激发强度随热处理温度的提高而增强。     

Effects of isovalent substitution in the manganese sublattice on magnetic, thermal, and structural properties of BiMnO3: BiMn1-xMxO3 (M=Al, Sc, Cr, Fe, Ga; 0<or=x<or=0.2)

Solid solutions BiMn1-xMxO3 with M=Al, Sc, Cr, Fe, and Ga and 0相似文献   

Ultracold O2 + O2 collisions in a magnetic field: on the role of the potential energy surface

The collision dynamics of (17)O(2)((3)Σ(g)(-)) + (17)O(2)((3)Σ(g)(-)) in the presence of a magnetic field is studied within the close-coupling formalism in the range between 10 nK and 50 mK. A recent global ab initio potential energy surface (PES) is employed and its effect on the dynamics is analyzed and compared with previous calculations where an experimentally derived PES was used [T. V. Tscherbul et al., New J. Phys 134, 055021 (2009)]. Compared to the results using the older PES, magnetic-field dependence of the low-field-seeking state in the ultracold regime is characterized by a very large background scattering length, a(bg), and cross sections exhibit broader and more pronounced Feshbach resonances. The marked resonance structure is somewhat surprising considering the influence of inelastic scattering but it can be explained by resorting to the analytical van der Waals theory, where the short-range amplitude of the entrance channel wavefunction is enhanced by the large a(bg). This strong sensitivity to the short range of the ab initio PES persists up to relatively high energies (10 mK). After this study and despite quantitative predictions are very difficult, it can be concluded that the ratio between elastic and spin relaxation scattering is generally small, except for magnetic fields which are either low or close to an asymmetric Fano-type resonance. Some general trends found here, such as a large density of quasibound states and a propensity toward large scattering lengths, could be also characteristic of other anisotropic molecule-molecule systems.     

聚甲醛在强磁场下结晶的形貌分析

采用电子显微分析、X射线衍射法、傅里叶红外光谱法及差示扫描量热法分析强磁场对聚甲醛的结晶形态与片晶分布的影响, 探讨了微观组织特征与晶体学取向之间的关系. 研究结果表明, 聚甲醛(POM)在强磁场(12 T)作用下, 片晶厚度以及片晶间距都发生了明显的增大, 熔点升高, 分子链受到磁场的诱导而趋于定向结晶, 产生了沿磁场方向排列的类似漩涡状的结晶形貌.     

非磁性替代原子对Ce_2Co_(17)居里温度和饱和磁化强度的影响

用真空电弧熔炼法制备了Ce2 Co17-xMx(M =Ga ,Al和Si)化合物。通过X射线衍射和磁性测量手段 ,研究了非磁性替代原子Ga,Al和Si的加入对Ce2 Co17化合物的居里温度和饱和磁化强度的影响 ,其中Si在Ce2 Co17化合物中的固溶度最小 ,并使居里温度和饱和磁化强度下降幅度最大。     

The Magnetocaloric Effect and Heat Capacity of Suspensions of High-Dispersity Samarium Ferrite

The magnetocaloric effect and specific heat capacity of an aqueous suspension of samarium ferrite were determined calorimetrically over the temperature range 288–343 K in magnetic fields of 0–0.7 T. The data obtained were used to calculate changes in the magnetic component of the molar heat capacity and entropy of the magnetic phase and changes in the enthalpy of the process under an applied magnetic field. The magnetocaloric effect was found to increase nonlinearly as the magnetic field induction grew. The corresponding temperature dependences contained a maximum at 313 K related to the second-order magnetic phase transition at the Curie point. The field and temperature dependences of heat capacity contained a maximum in fields of 0.4 T and a minimum at the magnetic phase transition temperature.     

Dual-action molecular superconductors with magnetic anions

Dual-action organic superconductors, whose conducting properties can be sharply controlled by an external magnetic field, have been discovered in systems consisting of organic conduction layers based on bis(ethylenedithio)tetraselenafulvalene (BETS) molecules and magnetic anions. Owing to the metamagnetic nature of the anion layers, the superconducting state of kappa-BETS2FeBr4 can be switched on or off by applying the external field. In lambda-BETS2Fe0.4Ga0.6Cl4, exhibiting a field-induced superconducting transition for the field parallel to the conduction plane, the insulating, metallic, and superconducting states can be realized in a stepwise manner by slightly tuning the external magnetic field.     

Influence of Jahn-Teller coupling on the magnetic properties of transition metal complexes with orbital triplet ground terms: magnetization and electronic Raman studies of the titanium(III) hexa-aqua cation

Magnetization and electronic Raman data are presented for salts of the type Cs[Ga:Ti](SO(4))(2) x 12H(2)O, which enable a very precise definition of the electronic structure of the [Ti(OH(2))(6)](3+) cation. The magnetization data exhibit a spectacular deviation from Brillouin behavior, with the magnetic moment highly dependent on the strength of the applied field at a given ratio of B/T. This arises from unprecedented higher-order contributions to the magnetization, and these measurements afford the determination of the ground-state Zeeman coefficients to third-order. The anomalous magnetic behavior is a manifestation of Jahn-Teller coupling, giving rise to low-lying vibronic states, which mix into the ground state through the magnetic field. Electronic Raman measurements of the 1%-titanium(III)-doped sample identify the first vibronic excitation at approximately 18 cm(-1), which betokens a substantial quenching of spin-orbit coupling by the vibronic interaction. The ground-state Zeeman coefficients are strongly dependent on the concentration of titanium(III) in the crystals, and this can be modeled as a function of one parameter, representing the degree of strain induced by the cooperative Jahn-Teller effect. This study clearly demonstrates the importance that the Jahn-Teller effect can have in governing the magnetic properties of transition metal complexes with orbital triplet ground terms.     

Modification in structure, phase transition, and magnetic property of metallic gallium driven by atom-molecule interactions

The present work supports a novel paradigm in which the surface structure and stacking behavior of metallic gallium (Ga) were significantly influenced by the preparation process in the presence of organic small molecules (ethanol, acetone, dichloromethane, and diethyl ether). The extent of the effect strongly depends on the polarity of the molecules. Especially, a series of new atom-molecule aggregates consisting of metallic Ga and macrocyclic hosts (cyclodextrins, CDs) were prepared and characterized by various techniques. A comprehensive comparative analysis between free metallic Ga and the Ga samples obtained provides important and at present rare information on the modification in structure, phase transition, and magnetic property of Ga driven by atom-molecule interactions. First, there is a notable difference in microstructure and electronic structure between the different types of Ga samples. Second, differential scanning calorimetry analysis gives us a complete picture (such as the occurrence of a series of metastable phases of Ga in the presence of CDs) that has allowed us to consider that Ga atoms were protected by the shielding effect provided by the cavities of CDs. Third, the metallic Ga distributed in the aggregates exhibits very interesting magnetic property compared to free metallic Ga, such as the uniform zero-field-cooled and field-cooled magnetization processes, the enhanced responses in magnetization to temperature and applied field, and the fundamental change in shape of magnetic hysteresis loops. These significant changes in structural transformation and physical property of Ga provide a novel insight into the understanding of atom-molecule interactions between metallic atoms and organic molecules.     

Behavior of liquid crystals confined to mesoporous materials as studied by 13C NMR spectroscopy of methyl iodide and methane as probe molecules

The behavior of thermotropic nematic liquid crystals (LCs) Merck Phase 4 and ZLI 1115 confined to mesoporous controlled pore glass materials was investigated using 13C nuclear magnetic resonance spectroscopy of probe molecules methyl iodide and methane. The average pore diameters of the materials varied from 81 to 375 A, and the temperature series measurements were performed on solid, nematic, and isotropic phases of bulk LCs. Chemical shift, intensity, and line shape of the resonance signals in the spectra contain lots of information about the effect of confinement on the state of the LCs. The line shape of the 13C resonances of the CH3I molecules in LCs confined into the pores was observed to be even more sensitive to the LC orientation distribution than, for example, that of 2H spectra of deuterated LCs or 129Xe spectra of dissolved xenon gas. The effect of the magnetic field on the orientation of LC molecules inside the pores was examined in four different magnetic fields varying from 4.70 to 11.74 T. The magnetic field was found to have significant effect on the orientation of LC molecules in the largest pores and close to the nematic-isotropic phase transition temperature. The theoretical model of shielding of noble gases dissolved in LCs based on pairwise additivity approximation was utilized in the analysis of CH4 spectra. For the first time, a first-order nematic-isotropic phase transition was detected to take place inside such restrictive hosts. In the larger pores a few degrees below the nematic-isotropic phase transition of bulk LC the 13C quartet of CH3I changes as a powder pattern. Results are compared to those derived from 129Xe NMR measurements of xenon gas in similar environments.     

Kieselgelstandards für die Bestimmung von Spurenelementen in pulverförmigen Proben mit leichter Matrix durch Röntgenfluorescenzanalyse

The paper deals with homogeneous magnetic fields and added chemical substances both affecting the spectrochemical results obtained in arc excitation studies. The influence of a homogeneous magnetic field on the total intensity of lines of various analysis elements (Hg, Zn, Ga, Tl) in graphite has been examined. Furthermore, the axial and radial distributions of line intensities in arc plasma were determined. Parameters used were the magnetic field strength (0, 0.01, 0.02, 0.04 T) and the physical data of the analysis elements. It was found that the effect of the magnetic field varies with the ionization potential of the elements involved, their atomic mass and the strength of the magnetic field applied. A non-destructive method of measuring was introduced for studying the effects of a homogeneous magnetic field on the rates of evaporation. The results showed increased evaporation rates in presence of magnetic fields as a function of the evaporation heat of the elements involved. Effects of Ga₂O₃ additive on the line intensities of impurity elements are governed by the Ga₂O₃ concentration and the ionization potential of the elements examined.     

Schiff碱类向列液晶熔融与清亮过程热力学

用差示扫描量热法及热台显微镜法研究了Schiff碱类向列液晶PEBAB及PBAPB的熔融与清亮过程.给出PEBAB的Tm=378.53K,△Hm=26.48±0.20kJ/mol,△Sm=69.96±0.53J/K.mol,Tc=399.80K,△Hc=929±53J/mol,△Sc=2.32±0.13J/K.mol;对于PBAPB,Tm(II)=352.86K,Tm(I)=354.74K,Tc=384.54K,△Hc=866±25J/mol,△Sc=2.25±0.07J/K.mol.在通过二次加热法消除熔前效应后,得到△Hm(I+II)=12.36±0.17kJ/mol,它不随升温速率改变而变化.本工作测得的清亮焓,在3%的偏差范围内符合平均场理论要求;△H1/△H2=T1/T2;所得清亮熵也与大多数向列型液晶相近.在PBAPB中,在318K左右,还观察到固→固相变等情况,相变焓是13.96±0.35kJ/mol.     

Magnetic Bistability of Isolated Giant‐Spin Centers in a Diamagnetic Crystalline Matrix

Polynuclear single‐molecule magnets (SMMs) were diluted in a diamagnetic crystal lattice to afford arrays of independent and iso‐oriented magnetic units. Crystalline solid solutions of an Fe₄ SMM and its Ga₄ analogue were prepared with no metal scrambling for Fe₄ molar fractions x down to 0.01. According to high‐frequency EPR and magnetic measurements, the guest SMM species have the same total spin (S=5), anisotropy, and high‐temperature spin dynamics found in the pure Fe₄ phase. However, suppression of intermolecular magnetic interactions affects magnetic relaxation at low temperature (40 mK), where quantum tunneling (QT) of the magnetization dominates. When a magnetic field is applied along the easy magnetic axis, both pure and diluted (x=0.01) phases display pronounced steps at evenly spaced field values in their hysteresis loops due to resonant QT. The pure Fe₄ phase exhibits additional steps which are firmly ascribed to two‐molecule QT transitions. Studies on the field‐dependent relaxation rate showed that the zero‐field resonance sharpens by a factor of five and shifts from about 8 mT to exactly zero field on dilution, in agreement with the calculated variation of dipolar interactions. The tunneling efficiency also changes significantly as a function of Fe₄ concentration: the zero‐field resonance is significantly enhanced on dilution, while tunneling at ±0.45 T becomes less efficient. These changes were rationalized on the basis of a dipolar shuffling mechanism and transverse dipolar fields, whose effect was analyzed by using a multispin model. Our findings directly prove the impact of intermolecular magnetic couplings on SMM behavior and disclose the magnetic response of truly isolated giant spins in a diamagnetic crystalline environment.     

Melting of alloy clusters: effects of aluminum doping on gallium cluster melting

Calorimetry measurements have been performed as a function of temperature for size-selected Ga(n-1)Al+ clusters with n = 17, 19, 20, 30-33, 43, 46, and 47. Heat capacities determined from these measurements are compared with previous results for pure Ga(n)+ clusters. Melting transitions are identified from peaks in the heat capacities. Substituting an aluminum atom appears to have only a small effect on the melting behavior. For clusters that show melting transitions, the melting temperatures and latent heats for the Ga(n-1)Al+ clusters are similar to those for the Ga(n)+ analogs. For Ga(n)+ clusters that do not show first-order melting transitions (n = 17, 19, and 30) the Ga(n-1)Al+ analogs also lack peaks in their heat capacities. The results suggest that the aluminum atom is not localized to a specific site in the solid-like Ga(n-1)Al+ clusters.     

Thermal Stability of Haemoglobin Solutions Under DC and AC Magnetic Field and UV and IR Radiation

The influence of electromagnetic field in wide range of frequency (extra low frequency magnetic field, monochromatic laser light 840 nm, ultraviolet light) and static magnetic field on the stability of aqueous and NaCl 0.9% haemoglobin solutions was studied using differential scanning calorimetry (DSC) method. Three steps of denaturation process can be derived from experimental data. The shifts of transition temperatures are more marked for NaCl 0.9% than for aqueous solutions. The results suggest that static magnetic field is effective in protecting protein, while ultraviolet radiation destabilises haemoglobin. The laser light and alternating magnetic field have a little effect on the thermal stability of haemoglobin. This revised version was published online in July 2006 with corrections to the Cover Date.     

Role of magnetic forces in electrochemical reactions at microstructures

The effect of an external magnetic field (up to 0.8 T) on the anodic dissolution of microstructures has been investigated systematically. Copper and silver wires (100 microm in diameter) were embedded in epoxy resin and dissolved potentiostatically while a magnetic field was periodically switched on and off. A special feature of the thus prepared structures is that they show a smooth transition from an inlaid disk to a recessed disk electrode. An increase or a decrease of the limiting current density in the presence of B was found depending on the orientation of the magnetic field and the hydrodynamic conditions in the cell (natural or forced convection). The magnetic forces which are responsible for this are the Lorentz force and the gradient force. We propose a model which discusses the interaction of these forces with the natural and the forced convection to explain the experimental results.     

Pt/TiO2上苯和乙烯光催化氧化过程的磁场效应

以Pt/TiO₂为催化剂和365 nm紫外光为光源, 在低于0.2 T的磁场强度范围考察了磁场对苯和乙烯光催化氧化反应的影响. 实验发现, 当用紫外灯管作光源并靠近磁场磁极或者置于磁场磁极间隙内照射反应器时, 磁场可显著提高气相苯和乙烯的光催化转化率和矿化率; 而当光源远离磁场磁极而通过光导纤维传导照射到反应器上时, 磁场对这两个反应没有促进作用. 在前一种情况下, 紫外灯管的发光强度随磁场的增强而提高, 磁场对这两个光催化降解反应的促进作用被证实是由于磁场提高了紫外灯管的发光强度, 进而为反应提供了更多的光能和使反应温度升高所致；在后一种光照方式下, 由于光源不受磁场影响, 磁场对这两个光催化反应不产生影响. 这一研究结果表明, 在所研究磁场强度范围, 磁场对气-固相光催化反应没有任何本征影响.     

Thermodynamic properties of Ga27Si3 cluster using density functional molecular dynamics

Density functional molecular dynamical calculations have been carried out to explore the effect of silicon impurities on thermodynamic properties of Ga(30). We have obtained 500 distinct low energy equilibrium geometries of Ga(27)Si(3) in order to obtain reliable ground state geometry. The specific heat has been calculated using multiple histogram techniques and compared with that of Ga(30). We demonstrate that silicon impurities have a dramatic effect on the thermodynamic properties of the host cluster. In contrast to Ga(30), the specific heat of Ga(27)Si(3) shows a clear melting peak at ≈500 K, changing the character of Ga(30) from a nonmelter to a melter.