Global fit analysis including the ν9 + ν4 − ν4 hot band of ethane: Evidence of an interaction with the ν12 fundamental

The ν₉ fundamental band of ethane occurs in the 12 μm region. It is the strongest band of ethane in a terrestrial window and is commonly used for the identification of ethane in the Jovian planets. The ν₉ + ν₄ − ν₄ band occurs in the same region; neither can be analysed as an isolated band, since both are embedded in the torsional bath of the ground vibrational state. We report here two global fit models including data from both of these bands as well as the ν₃ fundamental and the ν₄, 2ν₄ − ν₄, and 3ν₄ torsional transitions. The first is restricted to −5 ? KΔK ? 15 in the hot band and gives an excellent fit to the included data. Three resonant interactions are identified in this fit—a Coriolis interaction with two resonant cases between the ν₉ torsional stack and that of the ground vibrational state (gs) and a resonant Fermi interaction between the ν₃ fundamental and the gs. Hot band lines with KΔK < −5 are influenced by a fourth perturbation, with a crossing at −11 < KΔK < −10, which has been attributed to an interaction with the ν₁₂ fundamental. A second fit, demonstrating a promising treatment of this interaction, is also presented.     

Dendrimers as scaffolds for multifunctional reversible addition–fragmentation chain transfer agents: Syntheses and polymerization

The synthesis and characterization of novel first‐ and second‐generation true dendritic reversible addition–fragmentation chain transfer (RAFT) agents carrying 6 or 12 pendant 3‐benzylsulfanylthiocarbonylsulfanylpropionic acid RAFT end groups with Z‐group architecture based on 1,1,1‐hydroxyphenyl ethane and trimethylolpropane cores are described in detail. The multifunctional dendritic RAFT agents have been used to prepare star polymers of poly(butyl acrylate) (PBA) and polystyrene (PS) of narrow polydispersities (1.4 < polydispersity index < 1.1 for PBA and 1.5 < polydispersity index < 1.3 for PS) via bulk free‐radical polymerization at 60 °C. The novel dendrimer‐based multifunctional RAFT agents effect an efficient living polymerization process, as evidenced by the linear evolution of the number‐average molecular weight (M_n) with the monomer–polymer conversion, yielding star polymers with molecular weights of up to M_n = 160,000 g mol^?1 for PBA (based on a linear PBA calibration) and up to M_n = 70,000 g mol^?1 for PS (based on a linear PS calibration). A structural change in the chemical nature of the dendritic core (i.e., 1,1,1‐hydroxyphenyl ethane vs trimethylolpropane) has no influence on the observed molecular weight distributions. The star‐shaped structure of the generated polymers has been confirmed through the cleavage of the pendant arms off the core of the star‐shaped polymeric materials. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5877–5890, 2004     

Choice of modelling technique for evaluating health care interventions

Economic evaluation, such as cost effectiveness analysis, provides a method for comparing healthcare interventions. These evaluations often use modelling techniques such as decision trees, Markov processes and discrete event simulations (DES). With the aid of examples from coronary heart disease, the use of these techniques in different health care situations is discussed. Guidelines for the choice of modelling technique are developed according to the characteristics of the health care intervention.The choice of modelling technique is shown to depend on the acceptance of the modelling technique, model ‘error’, model appropriateness, dimensionality and ease and speed of model development. Generally decision trees are suitable for acute interventions but they cannot model recursion and Markov models are suitable for simple chronic interventions. It is further recommended that population based models be used in order to provide health care outcomes for the likely cost, health benefits and cost effectiveness of the intervention. The population approach will complicate the construction of the model. DES will allow the modeller to construct more complex, dynamic and accurate systems but these may involve a corresponding increase in development time and expense. The modeller will need to make a judgement on the necessary complexity of the model in terms of interaction of individuals and model size and whether queuing for resources, resource constraints or the interactions between individuals are significant issues in the health care system.     

Fluoride effect on the palladium–phenanthroline catalyzed carbonylation of nitroarenes to carbamates

Fluorides promote the palladium–phenanthroline catalyzed carbonylation of nitroarenes to carbamates. The effect is more evident on the rate of the reaction at short reaction times, but a positive effect on selectivity is also observed under certain conditions. The effect is observed even under conditions under which chloride inhibits the reaction. Tetraethylammonium is a better countercation than sodium. Copyright © 2007 John Wiley & Sons, Ltd.     

A duality relation for busy cycles inGI/G/1 queues

Using a generalization of the classical ballot theorem, Niu and Cooper [7] established a duality relation between the joint distribution of several variables associated with the busy cycle inM/G/1 (with a modified first service) and the corresponding joint distribution of several related variables in its dualGI/M/1. In this note, we generalize this duality relation toGI/G/1 queues with modified first services; this clarifies the original result, and shows that the generalized ballot theorem is superfluous for the duality relation.     

The implementation of ab initio quantum chemistry calculations on transputers

Summary The RHF and geometry optimization sections of the ab initio quantum chemistry code, GAMESS, have been optimized for a network of parallel microprocessors, Inmos T800-20 transputers, using both indirect and direct SCF techniques. The results indicate great scope for implementation of such codes on small parallel computer systems, very high efficiencies having been achieved, particularly in the cases of direct SCF and geometry optimization with large basis sets.The work, although performed upon one particular parallel system, the Meiko Computing Surface, is applicable to a wide range of parallel systems with both shared and distributed memory.     

Surface chemical studies of the influence of In and Al on the decomposition of TEG on GaAs(100)

The interaction of triethylgallium (TEG) with the Ga-stabilized GaAs(100) surface in the presence of In and Al has been investigated using AES (Auger electron spectroscopy), HREELS (high resolution electron energy loss spectroscopy) and TDS (thermal desorption spectroscopy) techniques. Al is shown to greatly increase the saturation surface coverage of TEG on the surface and to suppress the desorption of TEG and diethylgallium (DEG). Etching of the surface Al by TEG is observed, resulting in the formation of gas phase Al organic species. Alkyl migration from GA to Al centres occurs, and the presence of Al substantially enhances the irreversible deposition of C. In is found to enhance DEG desorption and to lower the temperature at which absorbed ethyl groups decompose to gas phase ethene. Computer modelling has been carried out to extract kinetic parameters from measured thermal desorption spectra. These parameters are then used to calculate expected partial growth rates of GaAs during the growth of Ga_xAl_1−xAs and Ga_xIn_1−xAs using TEG. The data provide a molecular level understanding of the GaAs pa rtial growth rate variations arising during the deposition of III–V ternary materials.