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1.
Alexander Zeller 《Journal of organometallic chemistry》2006,691(21):4379-4385
The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (kH/kD = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active. 相似文献
2.
Exact closed-form solutions are exhibited for the Hopf equation for stationary incompressible 3D Navier-Stokes flow, for the cases of homogeneous forced flow (including a solution with depleted nonlinearity) and inhomogeneous flow with arbitrary boundary conditions. This provides an exact method for computing two- and higher-point moments, given the mean flow. 相似文献
3.
In this work we study nonnegativity and positivity of a discrete quadratic functional with separately varying endpoints. We introduce a notion of an interval coupled with 0, and hence, extend the notion of conjugate interval to 0 from the case of fixed to variable endpoint(s). We show that the nonnegativity of the discrete quadratic functional is equivalent to each of the following conditions: The nonexistence of intervals coupled with 0, the existence of a solution to Riccati matrix equation and its boundary conditions. Natural strengthening of each of these conditions yields a characterization of the positivity of the discrete quadratic functional. Since the quadratic functional under consideration could be a second variation of a discrete calculus of variations problem with varying endpoints, we apply our results to obtain necessary and sufficient optimality conditions for such problems. This paper generalizes our recent work in [R. Hilscher, V. Zeidan, Comput. Math. Appl., to appear], where the right endpoint is fixed. 相似文献
4.
本文对具有有限时滞的泛函微分方程建立了关于依照两种测度的实际稳定性的Razumikhin型判定定理,其中未采用通常的辅助函数,且可运用多个含有状态变量x的部分变元的Lyapunov函数,得出部分变远实际稳定性的判定定理,从而改进了已有的结果。 相似文献
5.
Modulo some natural generalizations to noncompact spaces, we show in this Letter that Moyal planes are nonunital spectral triples in the sense of Connes. The action functional of these triples is computed, and we obtain the expected result, i.e. the noncommutative Yang–Mills action associated with the Moyal product. In particular, we show that Moyal gauge theory naturally fits into the rigorous framework of noncommutative geometry. 相似文献
6.
线性泛函方程解的振动性的新结果 总被引:1,自引:0,他引:1
本文研究高阶泛函方程x(g(t))=P(t)x(t)+Q1(t)x(g2(t))+…+Qk(t)x(gk+1(t))解的振动性,得到了一些新的振动条件.改进和推广了已有结果. 相似文献
7.
Ren‐Shen Lee Jen‐Ming Yang Tz‐Feng Lin 《Journal of polymer science. Part A, Polymer chemistry》2004,42(10):2303-2312
Water‐soluble poly(ester‐carbonate) having pendent amino and carboxylic groups on the main‐chain carbon is reported for the first time. This article describes the melt ring‐opening/condensation reaction of trans‐4‐hydroxy‐N‐benzyloxycarbonyl‐L ‐proline (N‐CBz‐Hpr) with 5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one (MBC) at a wide range of molar fractions. The influence of reaction conditions such as catalyst concentration, polymerization time, and temperature on the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of the copolymers was investigated. The polymerizations were carried out in bulk at 110 °C with 3 wt % stannous octoate as a catalyst for 16 h. The poly(ester‐carbonate)s obtained were characterized by Fourier transform infrared spectroscopy, 1H NMR, differential scanning calorimetry, and gel permeation chromatography. The copolymers synthesized exhibited moderate molecular weights (Mn = 6000–14,700 g mol?1) with reasonable molecular weight distributions (Mw/Mn = 1.11–2.23). The values of the glass‐transition temperature (Tg) of the copolymers depended on the molar fractions of cyclic carbonate. When the MBC content decreased from 76 to 12 mol %, the Tg increased from 16 to 48 °C. The relationship between the poly(N‐CBz‐Hpr‐co‐MBC) Tg and the compositions was in approximation with the Fox equation. In vitro degradation of these poly(N‐CBz‐Hpr‐co‐MBC)s was evaluated from weight‐loss measurements and the change of Mn and Mw/Mn. Debenzylation of 3 by catalytic hydrogenation led to the corresponding linear poly(ester‐carbonate), 4 , with pendent amino and carboxylic groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2303–2312, 2004 相似文献
8.
A new grid‐free upwind relaxation scheme for simulating inviscid compressible flows is presented in this paper. The non‐linear conservation equations are converted to linear convection equations with non‐linear source terms by using a relaxation system and its interpretation as a discrete Boltzmann equation. A splitting method is used to separate the convection and relaxation parts. Least squares upwinding is used for discretizing the convection equations, thus developing a grid‐free scheme which can operate on any arbitrary distribution of points. The scheme is grid free in the sense that it works on any arbitrary distribution of points and it does not require any topological information like elements, faces, edges, etc. This method is tested on some standard test cases. To explore the power of the grid‐free scheme, solution‐based adaptation of points is done and the results are presented, which demonstrate the efficiency of the new grid‐free scheme. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
9.
Gabriele Bonanno 《Journal of Global Optimization》1998,12(1):101-104
In this note we introduce a suitable class of functionals, including the class of integral functionals, and prove that any (strict) local minimum of a functional of this class, defined on a decomposable space, is a (strict) global minimum. So, the recent result obtained by Giner in [1] is specified and extended. 相似文献
10.
The purpose of this paper is to give the Reid ``Roundabout Theorem' for quadratic functionals with general boundary conditions.
In particular, we describe the so-called coupled point and regularity condition introduced in [16] in terms of Riccati equation
solutions.
Accepted 27 February 1996 相似文献