Theoretical study of the thermal rearrangement of chloromethylsilanes, and its mechanism

The thermal rearrangement reactions of chloromethylsilane, (chloromethyl)dimethylsilane, and (chloromethyl)vinylsilane have been studied by use of the density functional theory method at the B3LYP/6-311G(d, p) level. The structures of the reactants, transition states, and the products were determined and fully optimized. The geometries of the different stationary points and the harmonic vibrational frequencies were calculated at the same level. The results showed that thermal rearrangement of the chloromethylsilanes occurred via one pathway. The chlorine atom migrated from the carbon atom to the silicon atom, and the hydrogen atom migrated simultaneously from the silicon atom to the carbon atom through a double-three-membered-ring transition state, forming methylchlorosilane, trimethylchlorosilane, and vinylmethylchlorosilane. The energy barriers of the three rearrangements calculated at the B3LYP/6-311G(d, p) level were 217.4, 201.6, and 208.7 kJ mol^?1, respectively. The effects of alkyl substituents on silicon atom are discussed. Changes of thermodynamic functions, equilibrium constant, and reaction rate constant were calculated in accordance with Eyring transition-state theory over the temperature range 400–1,500 K.     

Homogenization of layered elastoplastic composites: Theoretical results

Exact closed-form solutions are derived that completely characterize the effective behavior of a composite material made of elastic-perfectly plastic parallel plane layers perfectly bonded together. The derivation is framed within a rigorous theory of homogenization for elastoplastic composites, and based on the fundamental fact that the in-plane part of the strain tensor and the out-of-plane part of the stress tensor are uniform throughout the composite provided no free-edge effects occur. The obtained expressions are coordinate-free and valid in the general anisotropic case. As an example, a layered composite material with isotropic constituents is examined in detail.     

Discontinuous crack-bridging model for fracture toughness analysis of nacre

Studying the structure–property relation of biological materials can not only provide insight into the physical mechanisms underlying their superior properties and functions but also benefit the design and fabrication of advanced biomimetic materials. In this paper, we present a microstructure-based fracture mechanics model to investigate the toughening effect due to the crack-bridging mechanism of platelets. Our theoretical analysis demonstrates the crucial contribution of this mechanism to the high toughness of nacre. It is found that the fracture toughness of nacre exhibits distinct dependence on the sizes of platelets, and the optimized ranges for the thickness and length of platelets required to achieve higher fracture toughness are given. In addition, the effects of such factors as the mechanical properties of the organic phase (or interfaces), the effective elastic modulus of nacre, and the stacking pattern of platelets are also examined. Finally, some guidelines for the biomimetic design of novel materials are proposed based on our theoretical analysis.     

A DOUBLE-TEMPERATURE-GRADIENT TECHNIQUE FOR THE GROWTH OF PURE C60 SINGLE CRYSTALS FROM THE VAPOR PHASE

Pure C₆₀ single crystals were grown by a sublimation-condensation method in an evacuated dosed quartz tube situated in a double-temperature-gradient furnace. Large C₆₀ single crystals, up to a size of 0.6 mm×1.0 mm×2.0 mm with quite smooth and shiny faces, were obtained. X-ray diffraction, electron diffraction and X-ray morphology were carried out and showed that the quality of large C₆₀ single crystals grown by the double-temperature-gradient technique is excellent. In this paper the experimental results of the growth of large C₆₀ single crystals are reported and the morphological and structural characterizations are discussed in detail.     

H^＋注入锗酸铋晶体表面层的性质

Ｈ＾＋注入锗酸铋（Ｂｉ４Ｇｅ３Ｏ１２或ＢＧＯ）晶体引起某些效应，如辐射损伤，光学吸收和近表层区域的晶体分解。经Ｈ＾＋注入后，ＢＧＯ晶体的颜色变成棕色，但实验中证实不了该变化是由色心的产生所引起。此外，实验中也示观察到Ｈ＾＋注入ＢＧＯ晶体中有离子束诱发的光学活性变化。可见在注入过程中，未发生从Ｂｉ４Ｇｅ３Ｏ１２转变到Ｂｉ１２ＧｅＯ２０的结构相变，由此预见，注入过程中可能发生离子束引起的晶体分解。Ｈ＾     

On the ε-expansion procedure in the RNG theory of turbulence

Rescaling the equations of eliminating small scales, the physical justification for the-expansion procedure in the RNG theory of turbulence is proposed, in terms of that the inertial effects are small comparing with the viscous effects at the vicinity of the Kolmogorov dissipation wavenumber.We are grateful to Professor Chao-Hao Gu for numerous helpful suggestions. We would also like to acknowledge Professor Ke-Lin Wang and Bing-Hong Wang for many stimulating discussions of these problems.     

富镧混合稀土-镍贮氢材料CO,O2和H2O中毒的表面特征

本文用UPS,XPS研究了贮氢材料MlNi₅(Ml=La,Ce,Pr,Nd)的CO,O₂和H₂O的中毒,在UPS谱中,我们观察到在E_F以下峰α(0.3eV)和峰b(1.2eV)强度随中毒气体暴露量增加有显著变化,并向低动能端位移,逐渐形成肩峰,与此同时,峰c(6eV)和峰d(9.5eV)的强度随暴露量增加而增加,并有能量位移,配合XPS分析,分别确定相应的化学态。氧中毒后的MlNi₅,经300℃加氢还原,从UPS谱可以看到峰α,b强度增加;H₂O和CO中毒后,在超高真空条件下,分别经300℃加热处理,和Ar⁺剥离方法,均获得类似的效果,XPS分析进一步证实了这些结果。实验给出了贮氢材料MlNi₅中过渡金属镍的d电子与气体自由分子轨道间电荷转移的信息,为在实际应用中认识此类贮氢合金的表面催化中毒和再生提供了依据。 关键词：     

光解水α-Fe2O3电极表面的研究

本文利用Ar⁺轰击正分的α-Fe₂O₃表面,证明了轰击后的表面呈类FeO性质,存在Fe⁺⁺。提出了由于表面Fe⁺⁺的3d电子的催化作用,Fe⁺⁺能把吸附在它上面的H₂O先分解成OH-和H⁺,因而有助于提高光解水的效率的看法。用UPS和XPS等技术证实了类FeO表面吸附水后存在OH^-,确认Fe^{++关键词：}     

关于《强大数定律成立的充要条件》一文的补正

In this note we point out a mistake of the article ＜The sufficient and necessary condition of SLLN＞.     

相位—啁啾调控对高次谐波光谱的影响

理论研究了在激光相位和啁啾调控共同影响下高次谐波光谱的变化。结果表明：当激光相位为0时,一阶啁啾调控使谐波能量延伸。二阶啁啾调控会呈现高强度谐波平台区。当激光相位为0.5π时,一阶啁啾调控可以获得连续平台区,但是强度较弱。在二阶啁啾调控下,谐波能量得到明显增大。通过谐波时频分析给出了不同激光波形下产生高次谐波光谱的原因。