The mechanism of ethylene polymerization by nickel salicylaldiminato catalysts - Agostic interactions and their kinetic isotope effects

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 (k_H/k_D = 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.     

Quadrilateral surface meshes without self-intersecting dual cycles for hexahedral mesh generation

Several promising approaches for hexahedral mesh generation work as follows: Given a prescribed quadrilateral surface mesh they first build the combinatorial dual of the hexahedral mesh. This dual mesh is converted into the primal hexahedral mesh, and finally embedded and smoothed into the given domain. Two such approaches, the modified whisker weaving algorithm by Folwell and Mitchell, as well as a method proposed by the author, rely on an iterative elimination of certain dual cycles in the surface mesh. An intuitive interpretation of the latter method is that cycle eliminations correspond to complete sheets of hexahedra in the volume mesh.

Although these methods can be shown to work in principle, the quality of the generated meshes heavily relies on the dual cycle structure of the given surface mesh. In particular, it seems that difficulties in the hexahedral meshing process and poor mesh qualities are often due to self-intersecting dual cycles. Unfortunately, all previous work on quadrilateral surface mesh generation has focused on quality issues of the surface mesh alone but has disregarded its suitability for a high-quality extension to a three-dimensional mesh.

In this paper, we develop a new method to generate quadrilateral surface meshes without self-intersecting dual cycles. This method reuses previous b-matching problem formulations of the quadrilateral mesh refinement problem. The key insight is that the b-matching solution can be decomposed into a collection of simple cycles and paths of multiplicity two, and that these cycles and paths can be consistently embedded into the dual surface mesh.

A second tool uses recursive splitting of components into simpler subcomponents by insertion of internal two-manifolds. We show that such a two-manifold can be meshed with quadrilaterals such that the induced dual cycle structure of each subcomponent is free of self-intersections if the original component satisfies this property. Experiments show that we can achieve hexahedral meshes with a good quality.     

Current correlators to all orders in the quark masses

The contributions to the coefficient functions of the quark and the mixed quark-gluon condensate to mesonic correlators are calculated for the first time to all orders in the quark masses, and to lowest order in the strong coupling constant. Existing results on the coefficient functions of the unit operator and the gluon condensate are reviewed. The proper factorization of short- and long-distance contributions in the operator product expansion is discussed in detail. It is found that to accomplish this task rigorously the operator product expansion has to be performed in terms ofnon-normal-ordered condensates. The resulting coefficient functions are improved with the help of the renormalization group. The scale invariant combination of dimension 5 operators, including mixing with the mass operator, which is needed for the renormalization group improvement, is calculated in the leading order.Supported by the German Bundesministerium für Forschung und Technologie, under the contract 06 TM 761     

Moderate Deviations for Longest Increasing Subsequences: The Lower Tail

We derive a moderate deviation principle for the lower tail probabilities of the length of a longest increasing subsequence in a random permutation. It refers to the regime between the lower tail large deviation regime and the central limit regime. The present article together with the upper tail moderate deviation principle in Ref. 12 yields a complete picture for the whole moderate deviation regime. Other than in Ref. 12, we can directly apply estimates by Baik, Deift, and Johansson, who obtained a (non-standard) Central Limit Theorem for the same quantity.     

Upper Bounds to the Number of Vertices in a k-Critically n-Connected Graph

 Let k≤n be positive integers. A finite, simple, undirected graph is called k-critically n-connected, or, briefly, an (n,k)-graph, if it is noncomplete and n-connected and the removal of any set X of at most k vertices results in a graph which is not (n−|X|+1)-connected. We present some new results on the number of vertices of an (n,k)-graph, depending on new estimations of the transversal number of a uniform hypergraph with a large independent edge set. Received: April 14, 2000 Final version received: May 8, 2001     

A parallel version of the preconditioned conjugate gradient method for boundary element equations

The parallel version of precondition techniques is developed for matrices arising from the Galerkin boundary element method for two-dimensional domains with Dirichlet boundary conditions. Results were obtained for implementations on a transputer network as well as on an nCUBE-2 parallel computer showing that iterative solution methods are very well suited for a MIMD computer. A comparison of numerical results for iterative and direct solution methods is presented and underlines the superiority of iterative methods for large systems.