p+209Bi核反应微观数据的理论计算

利用光学模型、激光模型、蒸发模型及扭曲波玻恩近似理论,对入射能量从阈能到300MeV,p+²⁰⁹Bi的中子反应截面、剩余核截面、出射粒子的多重数进行了理论计算及分析,并将计算结果与实验数据进行了比较.同时得到一组能量到50?0MeV与实验数据符合很好的光学势参数.     

Energy of formation for and liquid binary alloys

We have investigated the free energy of formation for Ag_xIn_1-x and Ag_xSn_1-x liquid binary alloys at temperatures 1173 and 1250 K, respectively. A microscopic theory based on the first order perturbation has been applied. The interionic interaction and a reference liquid are the fundamental components of the theory. The interionic interaction is described by a local pseudopotential. A liquid of hard spheres (HS) of two different effective diametres and charges is used to describe the reference system. The results of the calculations for energy of formation agree very well with the available experimental data. Our calculations also reveal that a simple perturbative approach along with appropriate effective pair potentials can produce nearly quantitative results for the concerned alloys.     

Distribution Functions in Quantum Mechanics and Wigner Functions

We formulate and solve the problem of finding a distribution function F(r,p,t) such that calculating statistical averages leads to the same local values of the number of particles, the momentum, and the energy as those in quantum mechanics. The method is based on the quantum mechanical definition of the probability density not limited by the number of particles in the system. The obtained distribution function coincides with the Wigner function only for spatially homogeneous systems. We obtain the chain of Bogoliubov equations, the Liouville equation for quantum distribution functions with an arbitrary number of particles in the system, the quantum kinetic equation with a self-consistent electromagnetic field, and the general expression for the dielectric permittivity tensor of the electron component of the plasma. In addition to the known physical effects that determine the dispersion of longitudinal and transverse waves in plasma, the latter tensor contains a contribution from the exchange Coulomb correlations significant for dense systems.     

35Cr25Ni12奥氏体耐热钢中碳化物的电子显微分析

应用扫描电镜（SEM）和透射电镜（TEM）研究了长期使用前后的35Cr25Ni12奥氏体耐热钢中的碳化物演变行为；该钢固溶时效后的组织由初晶奥氏体及M23C6共晶碳化物组成，奥氏体基体中析出了二次M23C6，二次碳化物总是与基体保持立方－立方取向关系；长期使用（3、5年）后，奥氏体中析出的二次碳化物量明显增加，部分M23C6已转变为M6C，M6C与奥氏体基体以及二次碳化物M23C6保持[001]M6C//[221]A//[221]M23C6孪晶取向关系。     

Multivariate resolution of NMR labile signals by means of hard- and soft-modelling methods

One of the difficulties frequently encountered when studying acid–base equilibria with NMR spectroscopy is the labile behaviour of the measured signal, which hinders the application of bilinear multivariate data analysis methods. In this work, a mathematical transformation is proposed for the conversion of NMR labile signals to inert signals, which make possible the application of multivariate data analysis methods, based on bilinear data models. The procedure has been applied to the analysis of NMR data corresponding to the acid–base equilibria of nucleotides dCMP and dGMP. Both hard-modelling (EQUISPEC) and soft-modelling (MCR-ALS) approaches have been applied for the analysis and resolution of transformed bilinear NMR data matrices.     

Accurate pKa determination for a heterogeneous group of organic molecules.

Single-molecule studies that allow to compute pKa values, proton affinities (gas-phase acidity/basicity) and the electrostatic energy of solvation have been performed for a heterogeneous set of 26 organic compounds. Quantum mechanical density functional theory (DFT) using the Becke-half&half and B3LYP functionals on optimized molecular geometries have been carried out to investigate the energetics of gas-phase protonation. The electrostatic contribution to the solvation energies of protonated and deprotonated compounds were calculated by solving the Poisson equation using atomic charges generated by fitting the electrostatic potential derived from the molecular wave functions in vacuum. The combination of gas-phase and electrostatic solvation energies by means of the thermodynamic cycle enabled us to compute pKa values for the 26 compounds, which cover six distinct chemical groups (carboxylic acids, benzoic acids, phenols, imides, pyridines and imidazoles). The computational procedure for determining pKa values is accurate and transferable with a root-mean-square deviation of 0.53 and 0.57 pKa units and a maximum error of 1.0 pKa and 1.3 pKa units for Becke-half&half and B3LYP DFT functionals, respectively.     

Measurement of Diffusion in Zeolites—A Never Ending Challenge?

A review is given on the main problems associated with the determination and interpretation of molecular diffusion in zeolites. It is shown that the diffusivities may most decisively depend on the relevant space and time scales of observation, as well as on the physical state under which the measurements are carried out. Special emphasis is given to the microscopic techniques and their most recent evidence on the existence of transport resistances distributed over the intracrystalline space.     

Copolymerization of butadiene and styrene with a gadolinium tricarboxylate catalyst

Homo- and copolymerizations of butadiene (BD) and styrene (St) were carried out by gadolinium catalysts having various tricarboxylate ligands [Gd(OCOR)₃: R = CH₃, CH₂Cl, CHCl₂, CCl₃, and CF₃], to investigate the effects of ligands and discuss the cis polymerization mechanism. Polymerization of BD with Gd(OCOR)₃—(i—Bu)₃Al—Et₂AlCl catalysts was carried out in hexane at 50°C. By each catalyst, poly(BD) having a high cis content (cis = 97–99%) in 22–85% yields for 2–24 h were obtained. The ligands with low pKa values increased the polymerization activity as follows: R of Gd(OCOR)₃: CF₃ > CCl₃ > CHCl₂ > CH₂Cl ～ CH₃. On the other hand, in the polymerization of St or copolymerization of BD and St under similar conditions, the highest activity was attained by a Gd(OCOCCI₃)₃- based catalyst. The difference in the optimum ligand among the homo- and copolymerization of BD and St was discussed on the basis of energy levels of the catalysts. In the copolymers of BD and St, the cis-1,4 content of the BD unit decreased with increasing St content. Furthermore, according to the diad analysis of copolymers (St content ～ 14.5 mol %) by ¹³C NMR spectroscopy, the low cis value of the BD unit was observed in the St-BD diad (cis/trans/vinyl = 24/53/23), while the high cis value of the BD unit remained in the BD-BD diad (cis/trans/vinyl = 89/10/1). These results suggest that the terminal BD unit is controlled by the cis configuration by the coordination between the penultimate cis vinylene unit and the gadolinium metal catalyst, whereas the presence of the penultimate St unit interferes with cis polymerization of the terminal BD unit. The difference in the coordination mechanism in the course of polymerization between rare earth metal and transition metal catalysts such as the Ni(acac)₂ and Co(acac)₃-based catalyst was also discussed. © 1995 John Wiley & Sons, Inc.     

神东煤液化残渣显微组分的特征与分类研究

在PSU处理能力为0.1t/d的小型连续液化装置上对神东煤进行了加氢液化试验，对其液化残渣进行了显微光学研究。结果表明，在液化过程中，原料煤中的壳质组和镜质组全部转化，惰质组部分转化，在残渣中可见未反应的惰质组，同时在残渣中出现中间相小球体和半焦等新生组分。矿物质大量富集，并基本保持煤中原有的形态特征。THF处理后残余惰质组反射率在2.0%~3.8%，略高于煤中高反射率惰质组反射率，煤中高反射率惰质组是残余惰质组的主要来源。     

高配位双环氮氧杂有机锡化合物在二甲亚砜溶剂中的酸性解离常数

本文报道了在DMSO溶剂中利用Bordwell指示剂重迭法测定六种高配位双环氮氧杂有机锡化合物的α-CH的酸性离解常数(pKa)的方法, 并对配合物的结构与其α-CH酸性的关系进行了讨论。