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.     

Forecasting call frequency at a financial services call centre

A forecasting model is developed for the number of daily applications for loans at a financial services telephone call centre. The purpose of the forecasts and the associated prediction intervals is to provide effective staffing policies within the call centre. The model building process is constrained by the availability of only 2 years and 7 months of data. The distinctive feature of the data is that demand is driven in the main by advertising. The analysis given focuses on applications stimulated by press advertising. Unlike previous analyses of broadly similar data, where ARIMA models were used, a model with a dynamic level, multiplicative calendar effects and a multiplicative advertising response is developed and shown to be effective.     

Issues in Managing Information Technology

This paper describes three case studies which investigated issues relating to the implementation and management of advanced information technology. The benefits derived from information technology were found to vary from one organization to another. These studies provide further evidence to support earlier research findings that senior management has an important role to play in the effective exploitation of information technology, and that the investment approach taken by an organization has a significant effect on the development of computer-based information systems. The effectiveness of a system depends not only on applying the appropriate technology, but also on how successfully technical and behavioural issues are resolved.     

Optimal tristance anticodes in certain graphs

For z₁,z₂,z₃∈Zⁿ, the tristance d₃(z₁,z₂,z₃) is a generalization of the L₁-distance on Zⁿ to a quantity that reflects the relative dispersion of three points rather than two. A tristance anticodeA_d of diameter d is a subset of Zⁿ with the property that d₃(z₁,z₂,z₃)?d for all z₁,z₂,z₃∈A_d. An anticode is optimal if it has the largest possible cardinality for its diameter d. We determine the cardinality and completely classify the optimal tristance anticodes in Z² for all diameters d?1. We then generalize this result to two related distance models: a different distance structure on Z² where d(z₁,z₂)=1 if z₁,z₂ are adjacent either horizontally, vertically, or diagonally, and the distance structure obtained when Z² is replaced by the hexagonal lattice A₂. We also investigate optimal tristance anticodes in Z³ and optimal quadristance anticodes in Z², and provide bounds on their cardinality. We conclude with a brief discussion of the applications of our results to multi-dimensional interleaving schemes and to connectivity loci in the game of Go.     

A warehouse-based design model for reverse logistics

In this paper, an MILP formulation is proposed for the design of a reverse logistics network based on a warehouse location–allocation model, which optimizes, simultaneously, the forward and reverse networks. A single product model with unlimited capacity is first defined. Subsequently, the model is extended to a multi-product capacitated recovery network model, where capacity limitations and a multi-product system can be considered. The proposed model is compared to published work in the field, where different model assumptions have been proposed. Two cases are described so as to gain a better insight into the model and allow a comparative analysis.     

Electroactive conducting polymers for corrosion control

There is an intensive effort underway to develop new corrosion control coatings for structural metals. In part, this effort has been motivated by the desire to replace chromium(VI)-containing coatings currently used for corrosion control of iron and aluminum alloys. Cr(VI) has been shown to be hazardous to the environmental and to human health, and its use in many countries will be sharply curtailed in the coming years. Electroactive conducting polymers (ECPs) represent a class of interesting materials currently being explored for use in corrosion control coating systems, possibly as a replacement for Cr(VI)-based coatings. The electroactivity and the electronic conductivity (or semiconductivity) of ECPs set them apart from traditional organic coatings. As with chromate, interesting and potentially beneficial interactions of ECPs with active metal alloys such as steel and aluminum are anticipated, with concomitant alteration of their corrosion behavior. A review of this active research area will be presented in two parts. Here in Part 1, a general introduction to the topic of corrosion control by ECPs will be presented, including an overview of corrosion and its control by traditional methods, an introduction to ECPs and their properties, and a discussion of the processing issues surrounding the use of ECPs as coatings. Part 1 also includes a review of the literature on the use of ECPs as coatings (or components of coatings) on non-ferrous active metals, principally aluminum and aluminum alloys, although some work on zinc, copper, silver, titanium and silicon will also be described. In Part 2 of this review (to be published in the next issue of this journal), the rather extensive literature on the use of ECPs for the corrosion control of ferrous alloys (steels) will be reviewed. Electronic Publication     

Quadratic data envelopment analysis

Data Envelopment Analysis (DEA) offers a piece-wise linear approximation of the production frontier. The approximation tends to be poor if the true frontier is not concave, eg in case of economies of scale or of specialisation. To improve the flexibility of the DEA frontier and to gain in empirical fit, we propose to extend DEA towards a more general piece-wise quadratic approximation, called Quadratic Data Envelopment Analysis (QDEA). We show that QDEA gives statistically consistent estimates for all production frontiers with bounded Hessian eigenvalues. Our Monte-Carlo simulations suggest that QDEA can substantially improve efficiency estimation in finite samples relative to standard DEA models.     

Effective dimensionality approach to the RKKY interaction in multilayer systems

We consider RKKY interaction in a quasi 2D system with nonparabolic dispersion. In our paper we calculate the RKKY range function assuming the in-layer confinement via effective dimensionality approach. We show, that indirect magnetic exchange in our system can be modelled by the effective spectral dimension which equals one.     

A Language for Teaching Discrete-event Simulation

Courses which teach discrete-event simulation are based on many different simulation languages. The requirements for a language to support teaching simulation are discussed. In particular, it is recommended that such languages separate into distinct modules those aspects of simulation which are taught as separate topics. Implementation of the separation is discussed. The SEESIM language, developed as a teaching aid, is described, and examples of its use are given. Straightforward use of SEESIM can be learned quickly, yet the language provides facilities for a staged introduction to advanced concepts of simulation.