Theoretical study on the alkaline hydrolysis of methyl thioacetate in aqueous solution

A base-catalyzed hydrolysis reaction of thiolester has been studied in both gas and solution phases using two ab initio quantum mechanics calculations such as Gaussian09 and CPMD. The free-energy surface along the reaction path is also constructed using a configuration sampling technique, namely, the metadynamics method. While there are two different reaction paths obtained for the potential profile of the base-catalyzed hydrolysis reaction for thiolester in the gas phase, a triple-well reaction path is computed for the reaction in the solution phase by two quantum mechanics calculations. Unlike the S(N)2 mechanism (a concerted mechanism) found for the gas-phase reaction, a nucleophilic attack from the hydroxide ion on the carbonyl carbon to yield a tetrahedral intermediate (a stepwise mechanism) is observed for the solution-phase reaction. Moreover, the energy profiles computed by these two theoretical calculations are found to be very comparable with those determined experimentally.     

KBiMS4 (M=Si, Ge): Synthesis, structure, and electronic structure

Two new bismuth sulfides KBiSiS₄ and KBiGeS₄ have been synthesized by means of the reactive flux method. They adopt the RbBiSiS₄ structure type and crystallize in space group P2₁/c of the monoclinic system. The structure consists of (M=Si, Ge) layers separated by bicapped trigonal-prismatically coordinated K atoms. The M atom is tetrahedrally coordinated to four S atoms and the Bi atom is coordinated to a distorted monocapped trigonal prism of seven S atoms. The optical band gap of 2.25(2) eV for KBiSiS₄ was deduced from the diffuse reflectance spectrum. From a band structure calculation, the optical absorption for KBiSiS₄ originates from the layer. The Si 3p orbitals, Bi 6p orbitals, and S 3p orbitals are highly hybridized near the Fermi level. The orbitals of K have no contributions on both the upper of valence band and the bottom of conduction band.     

Wrinkle engineering: a new approach to massive graphene nanoribbon arrays

Wrinkles are often formed on CVD-graphene in an uncontrollable way. By designing the surface morphology of growth substrate together with a suitable transfer technique, we are able to engineer the dimension, density, and orientation of wrinkles on transferred CVD-graphene. Such kind of wrinkle engineering is employed to fabricate highly aligned graphene nanoribbon (GNR) arrays by self-masked plasma-etching. Strictly consistent with the designed wrinkles, the density of GNR arrays varied from ～0.5 to 5 GNRs/μm, and over 88% GNRs are less than 10 nm in width. Electrical transport measurements of these GNR-based FETs exhibit an on/off ratio of ～30, suggesting an opened bandgap. Our wrinkle engineering approach allows very easily for a massive production of GNR arrays with bandgap-required widths, which opens a practical pathway for large-scale integrated graphene devices.     

基于传播圆补偿像散的被动锁模激光器谐振腔设计方法

由于超短脉冲激光器的谐振腔大都采用多镜折叠的形式,像散已成为影响锁模激光器性能优劣的重要问题.本文提出了一种基于传播圆补偿像散的被动锁模激光器谐振腔设计方法,该方法简单、直观、高效,容易找到补偿像散的最佳位置.理论研究表明,当SESAM位于子午和弧矢传播圆交汇处附近时,SESAM处的子午光斑和弧矢光斑大小几乎相等,像散得到补偿.该谐振腔对外界干扰引起的腔镜振动和热透镜焦距的变化均不敏感,谐振腔的抗干扰性很强.实验研究表明,当SESAM位于子午和弧矢传播圆交汇处附近时,锁模激光器可获得稳定连续的锁模激光脉冲,且激光器的抗干扰性很强.本文的理论研究与实验结果相一致.     

Electrical and thermal transport properties of CdO ceramics

High temperature electrical and thermal transport properties, that is, electrical conductivity, Seebeck coefficient and thermal conductivity, of CdO ceramics have been investigated. Because of the good electrical properties and low thermal conductivity, the dimensionless figure-of-merit ZT of the CdO ceramics reaches 0.34 at 1023 K. This value is comparable to the best reported ZT for the n-type oxide ceramic thermoelectric materials and remains as potential to be further improved by porosity controlling or nanostructuring.     

黏弹性层合圆柱壳的蠕变分岔屈曲

采用Boltzmann积分型本构关系描述铺设单层的黏弹性力学行为,基于DMV扁壳假定和Kármán- Donnell几何非线性关系,研究了对称铺设黏弹性层合圆柱壳的前屈曲变形特征和分岔蠕变屈曲．对玻璃纤维/环氧树脂基复合材料层合圆柱壳的分析结果表明,在前屈曲阶段,挠曲变形和环向薄膜力随时间的变化趋势主要取决于圆柱壳的铺设方式,可以呈现完全相反的变化特征;层合短圆柱壳两端的边界条件对其蠕变分岔屈曲行为有决定性的影响,径厚比的增加将使分岔形式的延迟失稳现象更加明显．     

Chow’s Theorem for Semi-abelian Varieties and Bounds for Splitting Fields of Algebraic Tori

A theorem of Chow concerns homomorphisms of two abelian varieties under a primary field extension base change. In this paper, we generalize Chow's theorem to semi-abelian varieties. This contributes to different proofs of a well-known result that every algebraic torus splits over a finite separable field extension. We also obtain the best bound for the degrees of splitting fields of tori.     

粘性可压混合层时间稳定性对称紧致差分求解

基于可压扰动方程组的一阶改型 ,将高精度对称紧致格式引入边值法数值线性稳定性分析。对所获非线性离散特征值问题给出了一个通用形式二阶迭代局部算法 ,实现了时间模式和空间模式的统一求解 ,并将扰动特征值及其特征函数同时得到。据此分析了可压平面自由混合层时间稳定性 ,涉及二维 /三维扰动波、粘性 /无粘扰动波、第一 /第二模态、特征函数、伪特征值谱等。研究表明 ,压缩性效应和粘性效应对最不稳定扰动波数和增长率呈相似的减抑作用 ;在 Mc=1附近 ,从高波数段开始 ,粘性效应可强化二维不稳定扰动波由第一模态向第二模态的过渡     

A new approach to the synthesis of α-chlorocycloalkanones

α-Chlorocycloalkanones(Ⅳ) were synthesized from cycloalkanones via potassiumα-oxocycloalkylsulfonates(Ⅱ).A two-step mechanism was proposed to explain the formation ofⅣfromⅡ.