The mechanism of ethylene polymerization by nickel salicylaldiminato catalysts - Agostic interactions and their kinetic isotope effects

The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (k_H/k_D = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active.     

Rank 2 Ample Vector Bundles on Some Smooth Rational Surfaces

Several classification results for ample vector bundles of rank 2 on Hirzebruch surfaces, and on Del Pezzo surfaces, are obtained. In particular, we classify rank 2 ample vector bundles with _c2 less than seven on Hirzebruch surfaces, and with _c2 less than four on Del Pezzo surfaces.     

Scattering of Laser Light from Mixed Micelles

Dynamic and static scattering of light was employed to investigate mixed micelles of two homologous anionic surfactants-sodium octyl sulfate and sodium hexadecyl sulfate, above the phase boundary temperature and critical micelle concentrations (cmc). The results indicate that the mixed micelles change from prolate to sphcrical as the molar ratio SOS/SHS increases from 1 to 8. Below 1 or above 8, the formation of micelles is due to one surfactant dissolving the other.     

An Improved Gradient Projection-based Decomposition Technique for Support Vector Machines

In this paper we propose some improvements to a recent decomposition technique for the large quadratic program arising in training support vector machines. As standard decomposition approaches, the technique we consider is based on the idea to optimize, at each iteration, a subset of the variables through the solution of a quadratic programming subproblem. The innovative features of this approach consist in using a very effective gradient projection method for the inner subproblems and a special rule for selecting the variables to be optimized at each step. These features allow to obtain promising performance by decomposing the problem into few large subproblems instead of many small subproblems as usually done by other decomposition schemes. We improve this technique by introducing a new inner solver and a simple strategy for reducing the computational cost of each iteration. We evaluate the effectiveness of these improvements by solving large-scale benchmark problems and by comparison with a widely used decomposition package.     

Multicriteria decision making under uncertainty

Formalization for problems of multicriteria decision making under uncertainty is constructed in terms of guaranteed and weak estimates. A relevant definition of the vector maximinimax value is given. Parameterization and approximation of maximum, minimax, and maximinimax values based on the inverse logical convolution are suggested. An application for multicommodity networks is considered. Received: December 13, 2000 / Accepted: August 21, 2001?Published online May 8, 2002     

原子力显微镜在生物物理领域的新应用

介绍了原子力显微镜在生物物理领域的最新应用:蛋白质去折叠、DNA拉伸、生物膜受力,通过分析实验得到的力谱,可以获取关于蛋白质、DNA、生物膜结构信息.原子力显微镜不仅能反映测量体系的力学性质,由于其具有独特的时间、空间分辨及实时成像,因而能提供更多信息.     

B_2分子X~3Σ_g~-和A~3Σ_u~-态的势能函数

使用SAC/SAC-CI方法,利用D95(d),6-311g**以及cc-PVTZ等基组,对B2分子的基态(X3Σg-)和第一激发态(A3Σu-)的平衡结构和谐振频率进行了优化计算.通过对3个基组的计算结果的比较,得出了D95(d)基组为3个基组中的最优基组的结论;使用D95(d)基组,利用SAC的GSUM(Group Sum of Operators)方法对基态(X3Σg-),SAC-CI的GSUM方法对激发态(A3Σu-)进行单点能扫描计算,用正规方程组拟合Murrell-Sorbie函数,得到了相应电子态的完整势能函数;从得到的势能函数计算了与基态(X3Σg-)和第一激发态(A3Σu-)相对应的光谱常数(Be,αe,ωe和ωeχe),结果与实验数据吻合.     

On the Boltzmann Equation for Fermi–Dirac Particles with Very Soft Potentials: Averaging Compactness of Weak Solutions

The paper considers macroscopic behavior of a Fermi–Dirac particle system. We prove the L ¹-compactness of velocity averages of weak solutions of the Boltzmann equation for Fermi–Dirac particles in a periodic box with the collision kernel b(cos θ)|ρ−ρ _*|^γ, which corresponds to very soft potentials: −5 < γ ≤ −3 with a weak angular cutoff: ∫₀ ^π b(cos θ)sin ³θ dθ < ∞. Our proof for the averaging compactness is based on the entropy inequality, Hausdorff–Young inequality, the L ^∞-bounds of the solutions, and a specific property of the value-range of the exponent γ. Once such an averaging compactness is proven, the proof of the existence of weak solutions will be relatively easy.     

第五讲新型光纤水听器和矢量水听器

光纤水听器和矢量水听器作为当前水声研究领域最具有代表性的两大技术倍受业界关注。光纤水听器的重要贡献在于，从一个全新的角度出发，试图解决传统的水声传感和声纳数据传输一体化设计和实现的一系列问题，这有助于改善声纳系统的可靠性，并且有可能降低其制造、使用和维护的总成本。矢量水听器则由于其特有的指向性和矢量一相位处理方法，在低频和甚低频水声微弱目标探测方面具有潜在的优势．经过不懈的努力，光纤水听器和矢量水听器系统已经从实验室逐渐进入到工程应用阶段．这些对未来声纳系统的发展会产生相当重要的影响．文章尝试从声纳设计的角度对这两者的技术现状进行简要综述，包括它们各自的物理基础、工作原理、关键技术和应用领域．