Theoretical kinetic study of the reaction between dimethyl disulfide and OH radicals

The potential energy profile of the reaction between dimethyl disulfide and OH^? radicals is explored by utilizing ab initio and hybrid meta density functional theory methods. Having the energies and structural data of the stationary points, statistical rate theories, such as transition state theory and variable reaction coordinate-transition state theory, are employed to compute the overall rate constants, and discuss the mechanism and product channels. On the basis of the calculations, the overall rate coefficient is predicted to be 2.49?×?10^?10?cm³?molecule^?1?s^?1 at 298?K. It is found that in the most favorable pathway, the reaction proceeds via formation of the relatively unstable intermediate CH₃S^?(OH)SCH₃ decomposing rapidly to yield CH₃S^?+CH₃SOH.     

Ab initio calculations of the NO2 fission for CL-20 conformers

NO₂ fission is regarded to be the most important initial decomposition process of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20). In this study, four CL-20 conformers based on the ε-CL-20 were obtained after the optimization at m062x/cc-pvtz level, and the bond length, bond order and bond dissociation energy of the N-N bonds were examined to investigate the stability of these bonds. In addition, the rate constants and activation energy of the NO₂ fission were evaluated using the microcanonical variational transition state theory (μVT). The calculation results have shown that N-N bonds in the case of pseudo-equatorial and axial of nitro groups are the most stable and the least stable, respectively, by evaluating the bond length, bond order and minimum energy path (MEP). The NO₂ fission rate constants are affected by not only the stability of N-N bonds but also the repulsion forces from the other nitro groups, and the fission process for pseudo-equatorial positioning of nitro groups is easier to be accelerated due to the increase of the repulsion forces. The decomposition of CL-20 conformer may mainly originate from the fission of the pseudo-equatorial positioning of nitro groups, especially for CL-20 III conformer because of the significant low activation energy.     

Intrinsic dielectric behavior of Mg2TiO4 spinel ceramic

In the work, we focused on the intrinsic dielectric behavior of Mg₂TiO₄ spinel ceramic by P–V–L theory and infrared spectra analysis. Ti–O bonds have larger bond ionicity values, thus playing an important role in dielectric polarization. The theoretical dielectric constant was predicted by calculating the bond susceptibility of each chemical bond. Furthermore, Ti(1)–O bonds are responsible for the structural stability of Mg₂TiO₄ ceramic. Based on classical dispersion theory, permittivity and loss corresponding to each infrared active mode were quantified, and then the crucial contribution of low-frequency modes to intrinsic dielectric properties were determined.     

Effects of structural characteristics on microwave dielectric properties of low-loss (Zn1-xNix)ZrNbTaO8 ceramics

Low-loss (Zn_1-xNi_x)ZrNbTaO₈ (0.02?≤?x?≤?0.10) ceramics possessing single wolframite structure are initiatively synthesized by solid-state route. Based on the results of Rietveld refinement, complex chemical bond theory is used to establish the correlation between structural characteristics and microwave performance in this ceramic system. A small amount of Ni²⁺ (x?=?0.06) in A-site with the fixed substitution of Ta⁵⁺ in B-site can effectually raise the Q?×?f value of ZnZrNb₂O₈ ceramic, embodying a dense microstructure and high lattice energy. The dielectric constant and τ_f are mainly affected by bond ionicity and the average octahedral distortion. The (Zn_0.94Ni_0.06)ZrNbTaO₈ ceramic sample sintered at 1150?°C for 3?h exhibits an outstanding combination of microwave dielectric properties: ε_r =?27.88, Q?×?f?=?128,951?GHz, τ_f =?–39.9?ppm/°C. Thus, it is considered to be a candidate material for the communication device applications at high frequency.     

Effects of sintering in a high magnetic field on properties of vitrified bond and vitrified CBN composites

Vitrified bond CBN grinding wheels are being widely used due to their superior performance. Also, advantages of vitrified grinding wheels are high elastic modulus, stable chemical property, and low thermal expansion coefficient. Brittleness and low strength are key factors restricting the development of vitrified bond CBN grinding wheels. In this paper, the sintering in a high magnetic field was innovatively introduced into the manufacturing of vitrified bond CBN grinding wheels, and the effects of sintering in a high magnetic field on properties on vitrified bond and vitrified CBN composites were systematically investigated. Vitrified bond was characterized using three-point bending, scanning electron microscopy, X-ray diffraction. It was observed that microstructure of vitrified bond could be changed, grain orientation could be controlled and average grain size could be decreased in a high magnetic field, while vitrified bond strength could be simultaneously improved. High quality vitrified bond could be obtained by appropriately adjusting the strength and direction of high magnetic field. Results demonstrated that vitrified bond properties were improved when the magnetic field strength was 6?T. In order to highlight the high magnetic field effect on the vitrified CBN composites, the ordinary CBN abrasives and nickel plated CBN abrasives were used respectively. Microstructures, bending strengths of vitrified CBN composites were compared in different high magnetic fields. When the magnetic field strength was appropriate (less than 6?T), the binding characteristic of vitrified bond CBN composites with nickel plated CBN abrasives was greatly improved. The highest bending strength value of vitrified CBN composites was 79.5?MPa in 6?T high magnetic field.     

An application of chemometric techniques to analyze the effects of the wave function modifications on the intermolecular stretching frequencies of the hydrogen-bonded complexes

Factorial design and principal component models are used to determine how ab initio H-bond stretching frequencies depend on characteristics of the molecular orbital wave functions of acetylene–HX, ethylene–HX and cyclopropane–HX π-type hydrogen complexes with X=F, Cl, CN, NC and CCH. The results obtained for the three sets of complexes show that factorial design and principal component analyses complement each other. Factorial design calculations clearly show that these frequencies are affected mostly by inclusion of electron correlation on the calculation level. On average, their values are increased by about 25 cm⁻¹ due to a change from the Hartree–Fock (HF) to Möller–Plesset 2 (MP2) level. Valence, diffuse and polarization main effects as well as valence–diffuse, diffuse–correlation and polarization–correlation interaction effects are also important to better describe a factorial model to the H-bond stretching frequencies of these hydrogen complexes. This simplified model has been successful in reproducing the complete ab initio results, which correspond to two hundred and forty calculations. Principal component analyses applied only to hydrogen-bonded complexes whose experimental frequencies are known, has revealed that the six-dimensional original space can be accurately represented by a bidimensional space defined by two principal components. Its graphical representation reveals that the experimental intermolecular stretching frequencies are in closest agreement with the MP2/6–31+G and MP2/6–311+G ab initio results.     

H-bond and conformations of donors and acceptors in model polyether based polyurethanes

The molecular mechanics (MM) method with COMPASS force field was used to study the H-bonds in the polyether based polyurethane model molecules. Availability of the calculation was firstly verified in comparison of some H-bonded model molecules, which were studied by using ab initio calculation, and those calculated by MM. Based on a urethane model molecule 1,3-dimethylcarbamate, which can be donor or acceptor and behaves in various conformations, it is reasonable to have a large number of H-bond interactions between various conformational donors and acceptors. For examining all the possible interaction patterns, we studied 57H-bond complexes. This systematic modeling covers well-known four types of interaction patterns, such as NH?OC (Type I), NH?O-CO (Type II), NH?NH (Type III), NH?COC (Type IV) in the system. Obtained H-bond energies were used to analyze the probabilities of the complexes. For the interaction within the hard segments, or Type I, Type II and Type III, a predominant H-bond complex has been found in the present study, which belongs to Type I. For the interaction between the hard segment and the soft segment, two conformations of Type IV were calculated to be existed.     

国际工程承包项目中的银行保函实务

在国际工程承包中,银行保函是一种常用的担保形式,也是商业银行表外业务的一种。笔者主要介绍保函的种类、办理银行保函的一般程序、开具银行保函的注意事项等内容,为从事国际工程承包业务的管理提供参考。     

聚苯硫醚复合涂层的耐磨性能

研究了用固体润滑石墨、碳化硅、二硫化钼等填料改性的聚苯硫醚 (PPS)涂层的耐磨性能。实验结果表明 ,聚苯硫醚复合涂层具有优良的耐磨性 ;加入适量 ( 3 0 % )的石墨、碳化硅等固体润滑剂 (石墨 :碳化硅 =2∶3 ) ,可以有效提高涂层的耐磨性能 ,而二硫化钼和三氧化二铬的减摩效果更佳     

温和条件下碳氢单键直接官能团化的新方法

介绍了近年来国内外在温和条件下碳氢单键直接官能团化反应的最新进展。官能团化反应的特点是，在常温常压和紫外光促进下，用过渡金属配合物催化碳氢单链活化，使烷烃、芳烃等烃类的碳氢单键直接官能团化，从而达到直接利用各种烷烃及芳烃作为化工原料合成有机化工产品的目的。通过紫外光催化可以使反应在常温常压下进行，能克服传统工艺能耗高、选择性差的缺陷。经不断深入研究，该反应可望在２１世纪成为环境友好的有机合成工艺。