A computational study of stereospecifity in the thermal elimination reaction of menthyl benzoate in the gas phase

This paper reports a theoretical study, at the B3LYP/6–31 + G(d,p) and M05‐2X/6–31G + (d,p) levels, on the thermal decomposition of menthyl benzoate (2‐isopropyl‐5‐methylcyclohexyl benzoate). It undergoes a unimolecular first‐order elimination to give 3‐menthene (1‐isopropyl‐4‐methylcyclohexene), 2‐menthene (3‐isopropyl‐6‐methylcyclohexene), and benzoic acid. We studied two possible mechanisms trying to explain the formation of 2‐ and 3‐menthene, via six‐membered or four‐membered cyclic transition states. Rate constants were calculated at two temperatures, 587.1 and 598.6 K, and they agree well with the experimentally determined values. We verify that 3‐menthene is the product mainly formed at both temperatures. The progress of the reactions has been followed by means of the Wiberg bond indices. Intrinsic reaction coordinate (IRC) calculations have been carried out to verify that the localized transition state structures connect with the reactants and products and also to verify that the parent compound, menthyl benzoate, is taking the cis‐configuration needed in the reaction. Copyright © 2009 John Wiley & Sons, Ltd.     

特殊工件磨削加工问题研究

对特殊工件的磨削加工过程进行抽象、建模和求解.将砂轮和底座看成刚性坐标系,将工件所在的下台、中台、上台看成可平移旋转的变换坐标系,基于工件母线方程,以砂轮和工件母线相切为紧约束,运用平面坐标变换理论设计加工方案,并对方案进行了误差分析,最后考虑砂轮的实际磨损,分别提出圆柱形和轮式砂轮修整磨削策略.     

A ghost fluid Lattice Boltzmann method for complex geometries

A ghost fluid Lattice Boltzmann method (GF‐LBM) is developed in this study to represent complex boundaries in Lattice Boltzmann simulations of fluid flows. Velocity and density values at the ghost points are extrapolated from the fluid interior and domain boundary via obtaining image points along the boundary normal inside the fluid domain. A general bilinear interpolation algorithm is used to obtain values at image points which are then extrapolated to ghost nodes thus satisfying hydrodynamic boundary conditions. The method ensures no‐penetration and no‐slip conditions at the boundaries. Equilibrium distribution functions at the ghost points are computed using the extrapolated values of the hydrodynamic variables, while non‐equilibrium distribution functions are extrapolated from the interior nodes. The method developed is general, and is capable of prescribing Dirichlet as well as Neumann boundary conditions for pressure and velocity. Consistency and second‐order accuracy of the method are established by running three test problems including cylindrical Couette flow, flow between eccentric rotating cylinders and flow over a cylinder in a confined channel. Copyright © 2011 John Wiley & Sons, Ltd.     

VIBRATIONAL SPECTRA AND NORMAL COORDINATE ANALYSIS OF 1,2-BIS(2-FORMYLGLYCINEBENZENESULFENYL) ETHANE Pd(II) DICHLORIDE COMPLEX

The normal coordinate analysis of the title complex, 1,2-bis(2-formylglycinebenzenesulfenyl) ethane Pd(II) dichloride has been carried out by using the Urey-Bradley force field. According to the molecular structure determined by x-ray crystallographic analysis, 182 internal coordinates were established and 112 theoretical vibration frequencies agree well with the observed values with the average difference of 2.53 cm^?1 and the maximum deviation of 16.0 cm^?1.     

Two‐dimensional modeling for stability analysis of two‐phase stratified flow

The effect of wavelength and relative velocity on the disturbed interface of two‐phase stratified regime is modeled and discussed. To analyze the stability, a small perturbation is imposed on the interface. Growth or decline of the disturbed wave, relative velocity, and surface tension with respect to time will be discussed numerically. Newly developed scheme applied to a two‐dimensional flow field and the governing Navier–Stokes equations in laminar regime are solved. Finite volume method together with non‐staggered curvilinear grid is a very effective approach to capture interface shape with time. Because of the interface shape, for any time advancement, a new grid is performed separately on each stratified field, liquid, and gas regime. The results are compared with the analytical characteristics method and one‐dimensional modeling. This comparison shows that solving the momentum equation including viscosity term leads to physically more realistic results. In addition, the newly developed method is capable of predicting two‐phase stratified flow behavior more precisely than one‐dimensional modeling. It was perceived that the surface tension has an inevitable role in dissipation of interface instability and convergence of the two‐phase flow model. Copyright © 2009 John Wiley & Sons, Ltd.     

DYNAMIC CHARACTERISTICS IN INCOMPRESSIBLE HYPERELASTIC CYLINDRICAL MEMBRANES

In this paper, the dynamic characteristics are examined for a cylindrical membrane composed of a transversely isotropic incompressible hyperelastic material under an applied uniform radial constant pressure at its inner surface. A second-order nonlinear ordinary differential equation that approximately describes the radial oscillation of the inner surface of the membrane with respect to time is obtained. Some interesting conclusions are proposed for different materials, such as the neo-Hookean material, the Mooney-Rivlin material and the Rivlin-Saunders material. Firstly, the bifurcation conditions depending on the material parameters and the pressure loads are determined. Secondly, the conditions of periodic motion are presented in detail for membranes composed of different materials. Meanwhile, numerical simulations are also provided.     

Cylindrical polymer brushes

In recent years, research on cylindrical polymer brushes (or molecular bottlebrushes) has received significant attention. In this article, we discuss various strategies for their synthesis and the unique properties arising from their regular multibranched structure. Some recent advances in the application of cylindrical polymer brushes are highlighted. Amphiphilic core– shell cylindrical polymer brushes, for example, have been successfully used as single molecular templates for inorganic nanoparticle formation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3461–3481, 2005     

Design of electromagnetic cloaks and concentrators using form-invariant coordinate transformations of Maxwell’s equations

The technique of applying form-invariant, spatial coordinate transformations of Maxwell’s equations can facilitate the design of structures with unique electromagnetic or optical functionality. Here, we illustrate the transformation-optical approach in the designs of a square electromagnetic cloak and an omni-directional electromagnetic field concentrator. The transformation equations are described and the functionality of the devices is numerically confirmed by two-dimensional finite element simulations. The two devices presented demonstrate that the transformation optic approach leads to the specification of complex, anisotropic and inhomogeneous materials with well directed and distinct electromagnetic behavior.