Probing the Local Magnetic Structure of the [FeIII(Tp)(CN)3]− Building Block Via Solid-State NMR Spectroscopy,Polarized Neutron Diffraction,and First-Principle Calculations

The local magnetic structure in the [Fe^III(Tp)(CN)₃]⁻ building block was investigated by combining paramagnetic Nuclear Magnetic Resonance (pNMR) spectroscopy and polarized neutron diffraction (PND) with first-principle calculations. The use of the pNMR and PND experimental techniques revealed the extension of spin-density from the metal to the ligands, as well as the different spin mechanisms that take place in the cyanido ligands: Spin-polarization on the carbon atoms and spin-delocalization on the nitrogen atoms. The results of our combined density functional theory (DFT) and multireference calculations were found in good agreement with the PND results and the experimental NMR chemical shifts. Moreover, the ab-initio calculations allowed us to connect the experimental spin-density map characterized by PND and the suggested distribution of the spin-density on the ligands observed by NMR spectroscopy. Interestingly, significant differences were observed between the pseudo-contact contributions of the chemical shifts obtained by theoretical calculations and the values derived from NMR spectroscopy using a simple point-dipole model. These discrepancies underline the limitation of the point-dipole model and the need for more elaborate approaches to break down the experimental pNMR chemical shifts into contact and pseudo-contact contributions.     

Nanoscopic scale studies of LiFePO4 as cathode material in lithium-ion batteries for HEV application

We present a review of the structural properties of LiFePO₄. Depending on the mode of preparation, different impurities can poison this material. These impurities are identified and a quantitative estimate of their concentrations is deduced from the combination of X-ray diffraction analysis, Fourier transform infrared spectroscopy, Raman spectroscopy, and magnetic measurements. An optimized preparation provides samples with carbon-coated particles free of any impurity phase, insuring structural stability and electrochemical performance that justify the use of this material as a cathode element a new generation of lithium secondary batteries.     

Synthesis and functional pharmacological effects on human bronchi of 20-hydroxyeicosatetraenoic acid

We have synthesized 20-hydroxyeicosatetraenoic acid (20-HETE) following a new route and delineated its functional effects in human bronchi. Isometric tension measurements were performed, and they demonstrated that synthetic 20-HETE induced a concentration-dependent relaxant effect in ASM on resting tone and on bronchi pre-contracted with methacholine.     

含R_2dtc配体Mo-Cu化合物的动态~(95)Mo NMR

本实验利用动态~(95)Mo NMR监测Mo-Cu系列化合物的形成过程,对反应CuCl+NaR_2dtc+MoO_nS,摩尔比3:3:1,溶剂为DMF;R=Et,n=0(Ⅰ);R=Me,n=0(Ⅱ);R=Et,n=2(Ⅲ)进行了研究,观察到具有不同簇骼的多种中间产物的存在及随反应进程相互转化等现象。     

利用宽带声场干涉结构特性对移动船只距离的连续估计

浅海移动船只的宽带辐射声场在距离-频率上通常表现为有规则的干涉条纹结构,这些条纹的特性(数目和斜率)可用波导不变量理论来表征并已被用于多种水声反演问题中,如沉积层声学参数反演和宽带声源距离的估计。基于波导不变量理论和干涉条纹的结构特性,利用扩展卡尔曼滤波器分析移动船只LOFAR图中干涉条纹的距离-频率特征可对其距离进行连续估计。该方法不需要海洋环境的信息和前向拷贝声场计算,具有较高的计算效率。海试数据处理结果和GPS数据计算结果比较一致,证实了本方法的准确性。试验数据处理同样证实该方法对初始距离的选择有着较高的稳健性。     

A general variable neighborhood search variants for the travelling salesman problem with draft limits

In this paper, we present two general variable neighborhood search (GVNS) based variants for solving the traveling salesman problem with draft limits (TSPDL), a recent extension of the traveling salesman problem. TSPDL arises in the context of maritime transportation. It consists of finding optimal Hamiltonian tour for a given ship which has to visit and deliver products to a set of ports while respecting the draft limit constraints. The proposed methods combine ideas in sequential variable neighborhood descent within GVNS. They are tested on a set of benchmarks from the literature as well as on a new one generated by us. Computational experiments show remarkable efficiency and effectiveness of our new approach. Moreover, new set of benchmarks instances is generated.     

Benders,metric and cutset inequalities for multicommodity capacitated network design

Solving multicommodity capacitated network design problems is a hard task that requires the use of several strategies like relaxing some constraints and strengthening the model with valid inequalities. In this paper, we compare three sets of inequalities that have been widely used in this context: Benders, metric and cutset inequalities. We show that Benders inequalities associated to extreme rays are metric inequalities. We also show how to strengthen Benders inequalities associated to non-extreme rays to obtain metric inequalities. We show that cutset inequalities are Benders inequalities, but not necessarily metric inequalities. We give a necessary and sufficient condition for a cutset inequality to be a metric inequality. Computational experiments show the effectiveness of strengthening Benders and cutset inequalities to obtain metric inequalities.     

高温超导线圈在大电流下稳定性的数值仿真

在电力应用中,超导磁体可能会因为线圈工作于过流状态而失超,也可能会因为交流损耗而导致失超.为此,我们模拟了一个磁体在大电流过载下的稳定性情况.我们使用了一个建立在热传导方程和麦克斯韦方程基础上的差分数值计算方法来得出磁体内部的温度分布.我们对各种不同的电流冲击情况进行了考察,我们的模型可以使磁体设计者在实际制作之前能够估计一个比较安全的操作电流水平,有着广泛的实用价值.     

Assessing the exchange coupling in binuclear lanthanide(iii) complexes and the slow relaxation of the magnetization in the antiferromagnetically coupled Dy2 derivative

We report here the synthesis and the investigation of the magnetic properties of a series of binuclear lanthanide complexes belonging to the metallacrown family. The isostructural complexes have a core structure with the general formula [Ga₄Ln₂(shi^3–)₄(Hshi^2–)₂(H₂shi^–)₂(C₅H₅N)₄(CH₃OH)_x(H₂O)_x]·xC₅H₅N·xCH₃OH·xH₂O (where H₃shi = salicylhydroxamic acid and Ln = Gd^III1; Tb^III2; Dy^III3; Er^III4; Y^III5; Y^III_0.9Dy^III_0.16). Apart from the Er-containing complex, all complexes exhibit an antiferromagnetic exchange coupling leading to a diamagnetic ground state. Magnetic studies, below 2 K, on a single crystal of 3 using a micro-squid array reveal an opening of the magnetic hysteresis cycle at zero field. The dynamic susceptibility studies of 3 and of the diluted DyY 6 complexes reveal the presence of two relaxation processes for 3 that are due to the excited ferromagnetic state and to the uncoupled Dy^III ions. The antiferromagnetic coupling in 3 was shown to be mainly due to an exchange mechanism, which accounts for about 2/3 of the energy gap between the antiferro- and the ferromagnetic states. The overlap integrals between the Natural Spin Orbitals (NSOs) of the mononuclear fragments, which are related to the magnitude of the antiferromagnetic exchange, are one order of magnitude larger for the Dy₂ than for the Er₂ complex.     

声波水平折射引起水平位移椭圆极化和声能流水平偏转

针对矢量水听器测向的应用要求,研究了三维水声传播问题中水平折射对声矢量场特性的影响。理论分析表明,水平折射可使质点水平位移从线性极化转变为椭圆极化,同时引起声能流方向的水平偏转。声能流方向的水平偏转导致波达方向偏离目标水平方位,对目标水平方位估计造成误差。采用虚源法仿真了倾角为2.86°的楔形波导中的三维声矢量场,并给出了空间各点处由水平折射引起的单矢量水听器目标方位估计误差。结果显示,部分区域中由水平折射引起的目标方位估计误差可达10°以上。