元素在石墨炉内石墨探针表面上的原子化机理研究：Ⅶ.锗的原子化机理

本文应用Ｘ－射线衍射，Ｘ－射线光电子能谱，俄歇电子能谱和其它一些实验，考察石墨炉升温过程中氟化锗，锗酸钠在石墨探针表面上的形态变化，阐明了它们的原子化机理：ＧｅＦ２与Ｎａ２ＧｅＯ３首先分解为ＧｅＯ２，ＧｅＯ２还原为ＧｅＯ，后者在＞２４００Ｋ热分解产生自由态的锗原子，ＧｅＦ２和Ｎａ２ＧｅＯ３的原子化均源于ＧｅＯ（ｇ）的气相分解。原子化的升温过程中，在１４００－２４００Ｋ ＧｅＦ２和Ｎａ２ＧｅＯ３都产     

On the exact distribution of linear combinations of order statistics from dependent random variables

We study the exact distribution of linear combinations of order statistics of arbitrary (absolutely continuous) dependent random variables. In particular, we examine the case where the random variables have a joint elliptically contoured distribution and the case where the random variables are exchangeable. We investigate also the particular L-statistics that simply yield a set of order statistics, and study their joint distribution. We present the application of our results to genetic selection problems, design of cellular phone receivers, and visual acuity. We give illustrative examples based on the multivariate normal and multivariate Student t distributions.     

A computational study into the reactivity of epichlorohydrin and epibromohydrin under basic conditions in the gas phase and solution

Ab initio molecular orbital calculations were carried out on epibromohydrin (EBH) and epichlorohydrin (ECH) in an attempt to elucidate their reactivity with respect to a hard nucleophile, hydroxide. These systems were modeled in both the gas phase and a polar solvent under basic conditions. In the gas phase, it was determined that a direct displacement mechanism (nucleophilic attack at the C1 position) was operative for EBH, while an indirect pathway (nucleophilic attack at the C3 position and subsequent intramolecular displacement) was followed for ECH. In an acetone solution, only the indirect displacement mechanism was found to occur. An electrostatic argument is advanced to account for this behavior in polar solution. Copyright © 2007 John Wiley & Sons, Ltd.     

Mechanism of the reaction of neutral and anionic N-nucleophiles with α-halocarbonyl compounds

N-Acylalkylation of neutral and anionic N-nucleophiles with α-halocarbonyl compounds was investigated by quantum chemical methods in terms of the density functional theory and by experimental methods for 2,3-dihydroimidazo[2,1-b]quinazolin-1(10)H-5-one, its N-anion, and simpler model structures. High reactivity of these reagents is determined primarily by stabilization of transition states (TS) by bridge bonds involving halogen or nitrogen atoms rather than by conjugation, as has been commonly accepted. Bridged TS are formed by both the substitution mechanism S _N 2 and the addition-elimination mechanism. α-Haloalkyl-substituted zwitterions, which are potential intermediates of stepwise N-acylalkylation of neutral N-nucleophiles, do not exist in the isolated state, but they are rather efficiently stabilized upon solvation. These zwitterions, as well as analogous O-anions generated from anionic N-nucleophiles, can serve as intermediates of N-acylalkylation, as was demonstrated by localization of the corresponding TS. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1150–1164, June, 2007.     

Small-world and the growing properties of the Chinese railway network

By using the tools of statistical physics and recent investigations of the scaling properties of different complex networks, the structural and evolving properties of the Chinese railway network (CRN) is studied. It has been verified that the CRN has the same small-world properties of the Indian railway network (IRN). According to the class of small-world networks, we believe the CRN is a single scale. In addition, a novel result is obtained. Measurements on the CRN indicate that the rate at which nodes acquire links depends on the node’s degree and follows a power law.      

纳米悬浮液热导率测量及其预测模型的探讨

纳米颗粒悬浮液具有广泛应用于强化传热的潜在优势。本文采用加入表面活性剂的方法提高纳米悬浮液的悬浮稳定性,并用瞬态热线法测量了热导率。在分析现有理论模型和纳米悬浮液热导率影响因素研究的基础上,从弹性传动和非弹性传动两方面分析了纳米尺度效应导致纳米悬浮液热导率提高的机理。发现已有的理论公式仍然存在一定欠缺,预测值比实验值偏低,有关机理尚有待于深入探讨。     

自由基-分子反应:F+Propene(CH2CHCH3)的从头算研究

采用从头算CCSD(T)/6-311 G(2d,2p)//B3LYP/6-311G(d,p)方法,研究了自由基-分子反应F CH2CHCH3的各种不同的反应通道．该反应主要是通过复合物形成机制进行,即F分别加到碳碳双键的两端形成自由基复合物1和2．这两种亚稳态自由基会解离成三种产物:H C3H5F、CH3 C2H3F和HF C3H5．理论计算结果表明,生成CH3 C2H3F是反应的主要通道,而生成H C3H5F和HF C3H5对产物也有一定的贡献．这一结果和实验符合得很好．     

Mechanism of catalytic asymmetric hydrogenation of 2-formyl-1-methylene-1,2,3,4-tetrahydroisoquinoline using Ru(CH3COO)2[(S)-binap]

The mechanism of the asymmetric hydrogenation of 2-acyl-1-alkylidene-1,2,3,4-tetrahydroisoquinolines, the first reported reaction with the Noyori-Takaya Ru(CH₃COO)₂(binap) complex, has been investigated by means of deuterium labeling, kinetics, and NMR analysis. A series of experiments has revealed that (1) a monohydride-unsaturated mechanism operates involving the initial formation of RuH followed by reaction with the enamide substrate, (2) the hydride transfer from RuH to the olefinic double bond is endothermic and reversible, and (3) the rate is determined in the hydrogenolysis step. This view is consistent with that of proposed for the BINAP-Ru catalyzed Kagan reaction.     

玻璃中CdSeS纳米晶体的生长及其性能

对掺有镉、硒、硫的玻璃在500—800℃退火2—24h,生长了不同尺寸的CdSxSe1x纳米晶体.用分光光度计和光致发光光谱(PL)分析了纳米晶体的性能.退火温度低于550℃,纳米晶体处于成核阶段,600—625℃处于正常扩散生长阶段,700—800℃处于竞争生长阶段;而650℃处于两种生长阶段之间.虽然650℃下生长的纳米晶体的尺寸分布比较窄,但纳米晶体的尺寸随退火时间的延长几乎不变,在该温度改变退火时间很难改变纳米晶体的平均尺寸.在所有样品中出现了深能级缺陷,在650℃退火时间小于4h或大于16h有利 关键词： 纳米晶体 生长机理 深能级缺陷     

基于内生信息的股票发售机制比较研究

本文在内生信息成本的基础上，通过引入投资银行的信息成本函数，考察了国际上主要股票发售机制的内在机理，并用一个统一的框架比较了各种发售机制的差异及演进趋势。本研究表明，在投资银行和投资者信息成本相同的情况下，由于固定价格发售机制须用额外的折价去解决投资者之间的信息问题，因而相对于累计投标询价制是一种处于劣势的机制选择。同时指出，具有信息成本优势的机构投资者的出现和发展，是固定价格发行向询价发行过渡的一个必要条件。