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.     

Coordination Chemistry of Gold Catalysts in Solution: A Detailed NMR Study

Coordination chemistry of gold catalysts bearing eight different ligands [L=PPh₃, JohnPhos (L2), Xphos (L3), DTBP, IMes, IPr, dppf, S‐tolBINAP (L8)] has been studied by NMR spectroscopy in solution at room temperature. Cationic or neutral mononuclear complexes LAuX (L=L2, L3, IMes, IPr; X=charged or neutral ligand) underwent simple ligand exchange without giving any higher coordinate complexes. For L2AuX the following ligand strength series was determined: MeOH?hex‐3‐yne <MeCN≈OTf^??Me₂S<2,6‐lutidine<4‐picoline<CF₃CO₂^?≈DMAP<TMTU<PPh₃<OH^?≈Cl^?. Some heteroligand complexes DTBPAuX exist in solution in equilibrium with the corresponding symmetrical species. Binuclear complexes dppf(AuOTf)₂ and S‐tolBINAP(AuOTf)₂ showed different behavior in exchange reactions with ligands depending on the ligand strength. Thus, PPh₃ causes abstraction of one gold atom to give mononuclear complexes LLAuPPh₃⁺ and (Ph₃P)_nAu⁺, but other N and S ligands give ordinary dicationic species LL(AuNu)₂²⁺. In reactions with different bases, LAu⁺ provided new oxonium ions whose chemistry was also studied: (DTBPAu)₃O⁺, (L2Au)₂OH⁺, (L2Au)₃O⁺, (L3Au)₂OH⁺, and (IMesAu)₂OH⁺. Ultimately, formation of gold hydroxide LAuOH (L=L2, L3, IMes) was studied. Ligand‐ or base‐assisted interconversions between (L2Au)₂OH⁺, (L2Au)₃O⁺, and L2AuOH are described. Reactions of dppf(AuOTf)₂ and S‐tolBINAP(AuOTf)₂ with bases provided more interesting oxonium ions, whose molecular composition was found to be [dppf(Au)₂]₃O₂²⁺, L8(Au)₂OH⁺, and [L8(Au)₂]₃O₂²⁺, but their exact structure was not established. Several reactions between different oxonium species were conducted to observe mixed heteroligand oxonium species. Reaction of L2AuNCMe⁺ with S^2? was studied; several new complexes with sulfide are described. For many reversible reactions the corresponding equilibrium constants were determined.     

A vectorial algorithm with finite element method for prediction of powder segregation in metal injection molding

The design of the mold and the choice of the injection parameters for metal injection molding (MIM) is required to maintain homogeneity of the filled mixture. However, powder segregation is unavoidable in MIM because of the significant difference in densities of the metallic powder and the polymer binder. To achieve an effective prediction of segregation effect, a biphasic model based on mixture theory is employed. The viscous behaviors of each phase and the interaction coefficient between the flows of the two phases should be determined. The solution of two coupled Navier–Stokes equations results in a tremendous computation effort. The previous development of an explicit algorithm makes the biphasic simulation much faster than that of the classic methods. However, it is strongly desired to reduce or even eliminate the numerous global solutions for pressure fields at each time step. Hence, a new vectorial algorithm is proposed and developed to perform the simulation only by vectorial operations. It provides the anticipated efficiency in the simulation of biphasic modeling, and the advantage to use the classic elements of equal‐order interpolations. Some results produced by the two algorithms are compared with the experimental values to validate the new vectorial algorithm. Copyright © 2012 John Wiley & Sons, Ltd.     

Interlayer shear strength of single crystalline graphite

Reported values(0.2 MPa-7.0 GPa) of the interlayer shear strength(ISS) of graphite are very dispersed.The main challenge to obtain a reliable value of the ISS using conventional measuring methods was the unavailability of sufficiently large single crystalline graphite.Here we present a novel experimental method to measure the ISS,and obtain the value as ～0.14 GPa.Our result can serve as an important basis for understanding mechanical behavior of graphite or graphene-based materials.     

Existence of Surface Waves and Band Gaps in Periodic Heterogeneous Half-spaces

We find a sufficient condition for the existence of surface (Rayleigh) waves based on the Rayleigh-Ritz variational method. When specialized to a homogeneous half-space, the sufficient condition recovers the known criterion for the existence of subsonic surface waves. A simple existence criterion in terms of material properties is obtained for periodic half-spaces of general anisotropic materials. Further, we numerically compute the dispersion relation of the surface waves for a half-space of periodic laminates of two materials and demonstrate the existence of surface wave band gaps.     

认知无线电网络中提高传输层端到端吞吐率的跨层参数配置

在认知无线电网络中, 传输层端到端(TCP)吞吐率是衡量网络性能的重要指标. 前期相关研究大都具有以下两方面缺点: 第一, 大部分研究只考虑了协议底层参数来优化物理链路性能, 对传输层性能有所忽略; 第二, 目前的研究大都基于马尔可夫决策过程建模, 这需要网络具有完全知识, 使得这类模型的应用受到很大限制. 针对以上问题, 本文提出一种新的算法: 网络中每个节点通过联合配置物理层调制方式、发射功率、 链路层信道接入和TCP拥塞控制因子来找到传输层端到端近似最优吞吐率. 由于无线设备对环境感知存在误差, 本文将网络模型建模为部分可观测马尔可夫决策过程, 并将其转换成信念状态马尔可夫决策过程, 采用Q值迭代找到近似最优策略. 仿真分析表明, 提出的算法能在动态无线环境下以一定的误差限收敛于最优策略, 能在功率受限条件下, 有效提高传输层端到端吞吐率.     

氘化对KH2PO4晶体微观缺陷影响的正电子湮没研究

采用传统降温法从不同程度氘化(x=0, 0.51, 0.85)的生长溶液中生长氘化KH₂PO₄(KDP) 晶体, 利用正电子湮没技术(正电子寿命谱和多普勒展宽谱)、结合X射线衍射谱(XRD) 结构分析, 对KDP晶体氘化生长的微观缺陷进行了研究, 讨论了氘化程度对晶体内部微观结构特性、缺陷类型和浓度的影响. XRD结果显示晶胞参数a, b值随氘含量的增加而增加, c值无明显变化; 正电子寿命谱结果发现随着氘化浓度的提高, KDP晶体内部中性填隙缺陷以及氧缺陷不断增加, 引起晶体晶格畸变; 氢空位、K空位、杂质替位缺陷不断发生缔合反应形成复合缺陷, 缺陷浓度不断减少; 团簇、微空洞等大尺寸缺陷也在不断发生聚合反应, 缺陷浓度表现为不断减少. 多普勒实验结果表明随着氘化程度的提升, 晶体内部各类缺陷表现为同步变化. 实验结果表明, KDP晶体在低浓度氘化生长(50%以内)下缺陷反应较弱, 而在高浓度氘化(50%以上)下的缺陷反应显著增强.     

油水饱和球管孔隙模型弛豫的理论计算与计算机模拟

根据Brownstein-Tarr理论,采用特征函数展开法,通过求解基于扩散效应的Bloch控制方程,给出了油水饱和球管孔隙模型弛豫的理论计算公式.理论计算结果表明,在水润湿条件下,油的弛豫过程只与含油饱和度有关,而与岩石的孔隙结构无关.根据理论计算结果对球管模型中水的弛豫进行了数值模拟,模拟结果显示,球和管的主弛豫过程是一个单指数函数,其余部分与之相比可以忽略,即球管模型中水的弛豫可近似为一个双指数衰减过程. 关键词： 核磁共振 弛豫 球管孔隙模型 Bloch控制方程     

Comparison between relay propagation and direct propagation of Gaussian-Schell-model beam in turbulent atmosphere along a slant path

The relay propagation of Gaussian-Schell-model in turbulent atmosphere along a slant path is studied in this paper. Based on the extended Huygens-Fresnel principle and a quadratic approximation, an analytical formula of average intensity for Gaussian-Schell-model beams in turbulent atmosphere along a slant path is derived, and some special cases are discussed. From the study and the comparison with the direct propagation, we can see that the relay propagation has an advantage over the direct propagation. When the altitude of the target is low, the peak intensity of relay propagation is much larger than that of direct propagation. However, because of the limitation of the relay system aperture for relay propagation and the variation of coherence length for direct propagation, the difference in peak intensity between the two propagations decreases with the increase of the target altitude.