钐(Ⅱ)类卡宾CH_3SmCH_2X(X=Cl、Br和Ⅰ)促进乙烯环丙烷化反应途径的理论研究(英文)

用密度泛函B3LYP方法研究了过渡金属钐类卡宾与乙烯的环丙烷化反应的机理。对三种不同的钐的SS试剂CH_3SmCH_2X(其中X=Cl、Br和Ⅰ)分别和CH_2CH_2反应的各反应物、中间体、过渡态和产物构型的全部结构几何参数进行了优化,用内禀反应坐标(IRC)计算和频率分析方法,对过渡态进行了验证。结果表明：CH_3SmCH_2X(其中X=Cl、Br和Ⅰ)与CH_2CH_2环丙烷化反应按亚甲基转移通道(通道A)和卡宾金属化通道(通道B)都可以进行,与锂类卡宾的反应机理相同,只是按亚甲基转移通道(通道A)进行反应较容易一些,而且此反应在较低的温度下就可以发生。     

The chemisorption of pentacene on Si(0 0 1)-2 × 1

Adsorption structures of the pentacene (C₂₂H₁₄) molecule on the clean Si(0 0 1)-2 × 1 surface were investigated by scanning tunneling microscopy (STM) in conjunction with density functional theory calculations and STM image simulations. The pentacene molecules were found to adsorb on four major sites and four minor sites. The adsorption structures of the pentacene molecules at the four major sites were determined by comparison between the experimental and the simulated STM images. Three out of the four theoretically identified adsorption structures are different from the previously proposed adsorption structures. They involve six to eight Si-C covalent chemical bonds. The adsorption energies of the major four structures are calculated to be in the range 67-128 kcal/mol. It was also found that the pentacene molecule hardly hopped on the surface when applying pulse bias voltages on the molecule, but was mostly decomposed.     

New feature in the Auger peak of adsorbed oxygen

Recent joint theoretical and experimental investigations of Auger core-core-valence spectra of alkali adatoms on simple metals have revealed that such technique is capable to ascertain contributions from different adsorption environments in the signal [M.I. Trioni, S. Caravati, G.P. Brivio, L. Floreano, F. Bruno, A. Morgante, Phys. Rev. Lett. 93 (2004) 206802]. Consequently, to verify if such an effect is present also for other chemical species, we study theoretically the KLV transition of oxygen either as a bulk impurity or as an adsorbate in/on Al and Ag (jellium-like). We make use of the Fermi golden rule in which the matrix elements of the interaction are calculated within DFT. We verify that the relevant physical quantity of this phenomenon is the excited local density of states (LDOS), calculated within a region centered on the core ionized atom. The Auger rate for oxygen in Ag bulk displays a single asymmetric peak, while for adsorbed oxygen a second smaller feature at lower energies, and very close to the first one, appears. This unexpected result follows from the removal of the degeneracy of the m quantum number of the 2p states of oxygen at the surface. It is only displayed on the electronically less dense metal (Ag), but not on Al.     

GLOBAL CLASSICAL SOLUTIONS WITH SMALL INITIAL TOTAL VARIATION FOR QUASILINEAR HYPERBOLIC SYSTEMS

By means of the continuous Glimm functional,a proof is given on the global existence ofclassical solutions to Cauchy problem for general first order quasilinear hyperbolic systems withsmall initial total rariation.     

Numerical differentiation from a viewpoint of regularization theory

In this paper, we discuss the classical ill-posed problem of numerical differentiation, assuming that the smoothness of the function to be differentiated is unknown. Using recent results on adaptive regularization of general ill-posed problems, we propose new rules for the choice of the stepsize in the finite-difference methods, and for the regularization parameter choice in numerical differentiation regularized by the iterated Tikhonov method. These methods are shown to be effective for the differentiation of noisy functions, and the order-optimal convergence results for them are proved.

     

QUENCHING PROBLEMS OF DEGENERATE FUNCTIONAL REACTION-DIFFUSION EQUATION

This paper is concerned with the quenching problem of a degenerate functional reaction-diffusion equation. The quenching problem and global existence of solution for the reaction-diffusion equation are derived and, some results of the positive steady state solutions for functional elliptic boundary value are also presented.     

条件泛函及其导数非参数估计的强一致收敛速度

研究了条件泛函及其导数的非参数估计,对随机与固定设计的条件泛函,分别利用核估计和非参数加权估计,在核函数及权函数满足一定条件下,证明了估计一致强收敛于待估函数的速度可达到最优。从而进一步推广和发展了Hrdle,etal.(1988)、Severini,etal.(1992)的许多结果。     

真空注入法在功能性食品加工中的试验研究

功能性食品是除具有原有的营养功能外,还具有一种或多种能够提高人的健康状况或防治疾病的靶向功能。真空注入法是一种新型的功能性新鲜果蔬的生产方法,可以在多孔产品中注入任何成分,以调整产品组成。在真空注入过程中,温度、溶液浓度和真空处理时间是影响注入量的重要参数,本文研究了这三个参数对真空注入强化萝卜钙含量的影响。     

Chemical Reactivity of Tetrasulfur Tetranitride: Synthesis,Physical Properties,and Structural Characterization of the Amorphous Phase Cu7S4N4

Tetrasulfur tetranitride, S₄N₄, reacts with elemental Cu within inert solvents to a black‐blue material of approximate composition Cu₇S₄N₄ which is totally amorphous to X‐rays and which cannot be made crystalline by either thermal treatment or electron radiation. Cu₇S₄N₄ explodes if heated above 234 °C or when subjected to mechanical shock to eventually yield copper(I) sulfide; this together with the characteristic infrared spectrum of Cu₇S₄N₄ indicates the presence of molecular S₄N₄ units inside the amorphous phase. The metastable nature of Cu₇S₄N₄ is also mirrored by electron microscopy which furthermore allows the structural characterization of its degradation products. Based on experimental EXAFS data offering characteristic Cu—N and Cu—S distances, a theoretical crystalline approximant of Cu₇S₄N₄ was suggested and structurally optimized by density‐functional total‐energy calculations including periodic boundary conditions. This model incorporates a central S₄N₄ unit bonded to three shells of Cu atoms of different functionalities; in addition, a partial rupture of the S₄N₄ unit is likely to allow for a lowering of the total energy of the metastable phase. The latter observation supports the impossibility to make Cu₇S₄N₄ crystallize using ₄N₄ crystallize using whatever kind of measures.