Carbene and nitrene rearrangements: A theoretical study of cyclic allenes and carbenes, carbodiimides, and azirines

B3LYP/6-31G(d) calculations of structures, energies, and infrared spectra of several rearrangement products of (hetero)aromatic nitrenes and carbenes are reported. 3-Isoquinolylnitrene 36 ring closes to the azirine 37 prior to ring expansion to the potentially stable but unobserved seven-membered-ring carbodiimide 38 and diazacycloheptatrienylidene C-s-39S. A new, stable cycloheptatrienylidene, C-s-19S, is located on the naphthylcarbene energy surface. 4-Quinolylnitrene undergoes reaction via the azirine 50 in solution, but ring expansion to the stable seven-membered-ring ketenimine 47 under Ar matrix photolysis conditions. There is excellent agreement between calculated infrared spectra of 1,5-diazacyclohepta-1,2,4,6-tetraene 54 (obtained by photolysis of 4-pyridyl azide), 1-azacyclohepta-1,2,4,6-tetraene 5, 1-azacyclohepta-1,3,5,6-tetraene 55, and 1-azacyclohepta-1,3,4,6-tetraene 56 and the available experimental data.

A theoretical study of the origin of rotational barriers in push-pull ethylenes

Using the B3LYP/6-31G* ab initio method, we have studied the rotation about the C=C bonds in 15 push-pull ethylenes of the general formula (X,Y)C=C(CHO)(2) [X, Y = NH2, NHCH3, N(CH3)(2), OCH3, SCH3] in the gas phase. Two stationary points (minimum and transition state) were located for all compounds. The geometry, dipole moments, natural bond orbital atomic charges, as well as the rotational barriers were examined. The torsion angle 0 depends essentially on the presence or absence of intramolecular hydrogen bonds, and the barrier is a function of the torsion angle. (C) 2002 Elsevier Science B.V. All rights reserved.

Modelling of Lamb waves in composite laminated plates excited by interdigital transducers

The technique of permanently attaching interdigital transducers (IDT) to either flat or curved structural surfaces to excite single Lamb wave mode has demonstrated great potential for quantitative non-destructive evaluation and smart materials design, In this paper, the acoustic wave field in a composite laminated plate excited by an IDT is investigated. On the basis of discrete layer theory and a multiple integral transform method, an analytical-numerical approach is developed to evaluate the surface velocity response of the plate due to the IDTs excitation. In this approach, the frequency spectrum and wave number spectrum of the output of IDT are obtained directly. The corresponding time domain results are calculated by applying a standard inverse fast Fourier transformation technique. Numerical examples are presented to validate the developed method and show the ability of mode selection and isolation. A new effective way of transfer function estimation and interpretation is presented by considering the input wave number spectrum in addition to the commonly used input frequency spectrum. The new approach enables the simple physical evaluation of the influences of IDT geometrical features such as electrode finger widths and overall dimension and excitation signal properties on the input-output characteristics of IDT. Finally, considering the convenience of Mindlin plate wave theory in numerical computations as well as theoretical analysis, the validity is examined of using this approximate theory to design IDT for the excitation of the first and second anti-symmetric Lamb modes. (C) 2002 Elsevier Science Ltd. All rights reserved.

Practical scheme for quantum computation with any two-qubit entangling gate

Which gates are universal for quantum computation? Although it is well known that certain gates on two-level quantum systems (qubits), such as the controlled-NOT, are universal when assisted by arbitrary one-qubit gates, it has only recently become clear precisely what class of two-qubit gates is universal in this sense. We present an elementary proof that any entangling two-qubit gate is universal for quantum computation, when assisted by one-qubit gates. A proof of this result for systems of arbitrary finite dimension has been provided by Brylinski and Brylinski; however, their proof relies on a long argument using advanced mathematics. In contrast, our proof provides a simple constructive procedure which is close to optimal and experimentally practical.

The Limits of Rational Choice: New Institutionalism in the Test Bed of Central Banking Politics in Australia

This paper tests the explanatory capacities of different versions of new institutionalism by examining the Australian case of a general transition in central banking practice and monetary politics: namely, the increased emphasis on low inflation and central bank independence. Standard versions of rational choice institutionalism largely dominate the literature on the politics of central banking, but this approach (here termed RC1) fails to account for Australian empirics. RC1 has a tendency to establish actor preferences exogenously to the analysis; actors' motives are also assumed a priori; actor's preferences are depicted in relatively static, ahistorical terms. And there is the tendency, even a methodological requirement, to assume relatively simple motives and preference sets among actors, in part because of the game theoretic nature of RC1 reasoning. It is possible to build a more accurate rational choice model by re-specifying and essentially updating the context, incentives and choice sets that have driven rational choice in this case. Enter RC2. However, this move subtly introduces methodological shifts and new theoretical challenges. By contrast, historical institutionalism uses an inductive methodology. Compared with deduction, it is arguably better able to deal with complexity and nuance. It also utilises a dynamic, historical approach, and specifies (dynamically) endogenous preference formation by interpretive actors. Historical institutionalism is also able to more easily incorporate a wider set of key explanatory variables and incorporate wider social aggregates. Hence, it is argued that historical institutionalism is the preferred explanatory theory and methodology in this case.

A genetic algorithm/method of moments approach to the optimization of an RF coil for MRI applications - Theoretical considerations - Abstract

A Combined Genetic Algorithm and Method of Moments design methods is presented for the design of unusual near-field antennas for use in Magnetic Resonance Imaging systems. The method is successfully applied to the design of an asymmetric coil structure for use at 190MHz and demonstrates excellent radiofrequency field homogeneity.

Theoretical and experimental studies of unbraced tubular trusses allowing for torsional stiffness

This paper describes the buckling phenomenon of a tubular truss with unsupported length through a full-scale test and presents a practical computational method for the design of the trusses allowing for the contribution of torsional stiffness against buckling, of which the effect has never been considered previously by others. The current practice for the design of a planar truss has largely been based on the linear elastic approach which cannot allow for the contribution of torsional stiffness and tension members in a structural system against buckling. The over-simplified analytical technique is unable to provide a realistic and an economical design to a structure. In this paper the stability theory is applied to the second-order analysis and design of the structural form, with detailed allowance for the instability and second-order effects in compliance with design code requirements. Finally, the paper demonstrates the application of the proposed method to the stability design of a commonly adopted truss system used in support of glass panels in which lateral bracing members are highly undesirable for economical and aesthetic reasons.

O estado da reforma: balan??o da literatura em gest??o p??blica (1994/2002)

O objetivo deste paper ?? demonstrar a todos aqueles que trabalham com a disciplina Administra????o P??blica quais s??o os principais autores e obras da literatura nacional/internacional recente, articulando-os sob os aspectos anal??tico, metodol??gico e te??rico-conceitual, no sentido de contribuir para a cumulatividade da gera????o do conhecimento e forma????o de panorama nessa ??rea, no per??odo selecionado (1994/2002). Para tanto, foi adotada metodologia espec??fica para esse objetivo, apresentada por KEINERT (2000) em fun????o das caracter??sticas estruturais da disciplina. A literatura foi agrupada em cinco loci contemplando a vertente p??s-burocr??tica da gest??o p??blica, os impactos da globaliza????o no aparelho do Estado, as condicionantes do ordenamento pol??tico e econ??mico nacional e internacional, as novas tend??ncias no ciclo de pol??ticas p??blicas e a gest??o de pol??ticas sociais.As principais conclus??es da pesquisa apontam para a adequa????o do instrumental anal??tico adotado para compreens??o da literatura em Administra????o P??blica e tamb??m para a baixa verticalidade e cumulatividade da pesquisa nesse campo, com pouca sistematiza????o e densidade anal??tica no que se refere a determinados temas.

Gest??o do conhecimento como sistema de gest??o para o setor p??blico

O conhecimento e a gest??o do conhecimento t??m sido focos de uma intensa discuss??o sobre como as organiza????es privadas podem obter vantagens competitivas e atingir elevados patamares de flexibilidade, produtividade e inova????o, sem que, no entanto, esta disciplina seja devidamente debatida e/ou incorporada pelo setor p??blico brasileiro. A partir da perspectiva dos autores de maior prest??gio no assunto, este trabalho apresenta os principais conceitos e aspectos relacionados a este novo paradigma de gest??o organizacional, de modo a identificar quais seriam os principais desafios para a implanta????o de projetos de gest??o do conhecimento no ??mbito da administra????o p??blica. Adicionalmente, este trabalho prop??e a ado????o de um novo modelo de gest??o do conhecimento, mais consistente e adequado ??s organiza????es p??blicas. O modelo de gest??o apresentado prop??e-se a servir como susbs??dio para um debate te??rico e metodol??gico sobre como a gest??o do conhecimento poderia ser incorporada ?? tarefa de buscar melhores n??veis de gest??o para as organiza????es p??blicas brasileiras, de forma a torn??-las mais capacitadas a fazerem frente ??s interfer??ncias que j?? provocaram a fal??ncia das inst??ncias de planejamento e or??amento no setor p??blico, o abandono da padroniza????o e da melhoria dos procedimentos administrativos, a desestrutura????o da fun????o p??blica e das pol??ticas de recursos humanos, a persistente descontinuidade de projetos e de pol??ticas p??blicas, assim como permita resgatar a credibilidade nos mecanismos internos de repress??o e de puni????o ??queles agentes que adotam pr??ticas ou condutas que v??o de encontro aos princ??pios morais e ??s normas jur??dicas estabelecidas.

O t??nel no fim da luz: a privatiza????o do setor el??trico em Mato Grosso

Este artigo tem por objetivo analisar a forma????o de consensos sociais e pol??ticos para a reforma do Estado e de seu aparelho em n??vel estadual, conforme a governabilidade democr??tica. Optou-se por uma pesquisa sobre a privatiza????o das Centrais El??tricas Mato- Grossenses S.A. (Cemat), considerada representativa tanto da reforma empreendida pelo Estado de Mato Grosso quanto das dificuldades do setor el??trico em n??vel nacional. O referencial metodol??gico dessa pesquisa ?? composto de um problema e de quatro hip??teses de trabalho. Trata-se de estudo de caso da esp??cie ???provas de plausibilidade???, em que, por uma aplica????o iterativa, apresenta-se uma proposi????o te??rica inicial e, em seguida, as conclus??es da pesquisa s??o comparadas, o que permite sua revis??o e compara????o. Para tanto, descrevem-se a privatiza????o da Cemat e os problemas da desestatiza????o do setor el??trico brasileiro no seu conjunto. Por fim, na conclus??o, verifica-se a validade das hip??teses e fazem-se algumas considera????es finais sobre a pesquisa.

A pesquisa em psicologia : construindo outros planos de análise

O texto procura traçar um quadro teórico do qual pretende derivar questões para uma discussão que visa a levantar alguns aspectos para o debate sobre a forma com está colocada hoje a questão da pesquisa em psicologia e os efeitos produzidos no plano político/subjetivo, dada a indissociabilidade desses planos. Oferece um certo ponto de vista sobre o problema do conhecimento a partir de algumas referências metodológicas que problematizam a racionalidade na qual estão apoiadas as ciências humanas, pautadas numa lógica que persegue verdades inquestionáveis sobre uma realidade já dada. Propõe novas perguntas sobre a produção de conhecimento que possam reorientar as práticas de pesquisa no campo da psicologia, pois toda concepção de produção de conhecimento/pesquisa envolve sempre uma certa política, não possui apenas um sentido técnico e/ou metodológico.