Initiation of petroleum formation and antioxidant function – a DFT study of sulfur?sulfur bond dissociation enthalpies

Experimental studies showed that sulfur radicals play the vital role in petroleum formation. 1 Sulfur‐ centered radicals also exhibit activities in antioxidant functions. Here we conduct a theoretical investigation of their precursor‐disulfides. By investigation into substituent effect on sulfur? sulfur bond dissociation enthalpies (S? S BDEs), we would like to find the most effective provider for sulfur radicals. In the present work, 50 alpha‐substituted disulfides and 16 para‐substituted aryl disulfides are studied systematically, with the general formula XS‐SX or HS‐SX. The substituent effect on S? S BDEs is found to be very eminent, ranging from 33.2 to 75.0 kcal/mol for alpha‐substituted disulfide, and from 43.7 to 59.7 kcal/mol for para‐substituted phenyl disulfides. We also evaluate the performance of 44 density functional methods to get an accurate prediction. A further study indicates that substituents play a major role in radical energies, instead of molecule energies, which is substantiated by the good linearity between XS‐SX bond dissociation enthalpy (BDE) and HS‐SX BDE. Copyright © 2007 John Wiley & Sons, Ltd.     

Investigation of Ti/TiN multilayered films in a reactive mid-frequency dual-magnetron sputtering

Influence of the process parameters like (i) sputtering gas pressure, (ii) target current, (iii) substrate bias voltage and (iv) substrate temperature of a reactive mid-frequency dual-magnetron sputtering on (a) surface defects and (b) mechanical properties of Ti/TiN multilayered films was investigated. The forming mechanisms of the observed droplets and craters were analyzed. Results showed when: (1) pressure of Ar/N₂ gases PAr/N₂ was at 0.31 Pa and substrate temperature was in certain range, the size and the density of the surface defects on the TiN films tended to decrease with increasing the target current and the pulsed bias voltage; (2) the optimal deposition parameters for accomplishing fewer surface defects were used, increasing the thickness of the Ti buffer layer decreased the microhardness in certain level, and the adhesion was firstly increased and then decreased as thickness reaching and/or beyond a critical value. Results also showed that selection of optimized process parameters evidently minimized the surface defects and improved the mechanical properties of the film.     

半球上导线不同绕法在球心处磁场的差别

在《物理学教程》中有这样一道习题：半径为R的木球上均匀绕有密集的细导线，线圈平面彼此平行，且以单层线圈覆盖住半个球面，设线圈的总匝数为N．通过线圈的电流为I．求球心O处的磁感强度．     

Generation of hyperentangled four-photon cluster state via cross-Kerr nonlinearity

We propose a scheme for generating a hyperentangled four-photon cluster state that is simultaneously entangled in polarization modes and spatial modes. This scheme is based on linear optical elements, weak cross-Kerr nonlinearity, and homodyne detection. Therefore, it is feasible with current experimental technology.     

基于荧光动力学技术的黄渤海初级生产力快速测量

浮游植物初级生产作为海洋生态系统的重要起点,是海洋食物网的基础,是衡量海水质量的重要指标.为了准确测量、监测和预测浮游植物初级生产力的时空变化及其对外部环境条件的动力学响应,研究了一种基于叶绿素荧光动力学的测量技术,研制出响应时间为1.6 min、精度为4.86％ 的快速测量仪器.仪器测得的浮游植物初级生产力与液相氧电...     

Dangling bond-induced graphitization process on the (111) surface of diamond nanoparticles

The intrinsic mechanism of graphitization occurring on the (111) surface of nanodiamonds (NDs) during the transformation from NDs into bucky diamonds are explored using density functional theory (DFT) computations in conjunction with density functional based tight-binding simulations. The DFT results indicate that dangling bonds (DBs) on the ND surfaces play an important role in the graphitization process, and the orientation of the DBs on different ND surfaces determines whether there will be a graphitization process or not. Moreover, a criterion is proposed to estimate rupturing of the C-C bonds between different layers on the [111] direction in the NDs and is verified to be applicable to illustrate the phase transformation from sp(3) into sp(2) bonding structures. The energy contributions of the four-coordinated carbon atoms located at different positions on the (111) surface are exhibited for the first time and discussed in detail to gain a clear picture for the transition from NDs into bucky diamonds. The outcome may provide a deeper understanding on the influence of DBs upon the transformation from sp(3) into sp(2) bonding structures.     

催化动力学分光光度法测定痕量铬(Ⅵ)

在pH为1-2的强酸性介质中,利用痕量铬(Ⅵ)催化溴酸钾氧化H酸-钠盐显色的指示反应,研究了显色反应的最佳反应条件,建立了催化动力学光度法测定痕量铬(Ⅵ)的新方法。本方法线性范围为:0.16μg/mL-0/04μg/mL,检测限为1.04×10-5g/L,相对标准偏差为1.43%,回收率为99-103%,将其直接用于废水中铬(Ⅵ)的测定,结果满意。     

Al2O3钝化及其在晶硅太阳电池中的应用

介绍了Al₂O₃的材料性质及其原子层沉积制备方法, 详细阐述了该材料的钝化机制(化学钝化和场效应钝化), 并从薄膜厚度、热稳定性及叠层钝化等角度阐释其优化方案. 概述了Al₂O₃钝化在晶体硅太阳电池中的应用, 主要包括钝化发射极及背面局部扩散电池和钝化发射极及背表面电池. 最后, 对Al₂O₃钝化工艺的未来研究方向和大规模的工业应用进行了展望.     

斜波导喇曼振荡器

 采用斜波导的喇曼氢气池, 使泵浦激光束在波导内部传播, 增大了受激喇曼散射的作用区域。在传播过程中光束截面逐渐被压缩, 补偿因波导内壁的反射损耗而引起的功率密度下降。在一定气压范围内提高了喇曼转换的效率, 并利用波导对激光束的均匀作用, 使输出的一阶斯托克斯光光强的均匀性获得改善。     

Theoretical studies on the mechanism of acid-promoted hydrolysis of N-formylaziridine in comparison with formamide

[reaction: see text] We present an ab initio study of the acid-promoted hydrolysis reaction mechanism of N-formylaziridine in comparison with formamide. Since the rate of amide hydrolysis reactions depends on the formation of the tetrahedral intermediate, we focused our attention mainly on the reactant complex, the tetrahedral intermediate, and the transition state connecting these two stationary points. Geometries were optimized using the density functional theory, and the energetics were refined using ab initio theory including electron correlation. Solvent effects were investigated by using polarizable continuum method calculations. The proton-transfer reaction between the O-protonated and N-protonated amides was investigated. In acidic media, despite that the N-protonated species is more stable than the O-protonated one, it is predicted that both N-protonated and O-protonated pathways compete in the hydrolysis reaction of N-formylaziridine.