34 resultados para First-principles calculations

em Repositório Científico do Instituto Politécnico de Lisboa - Portugal


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In this paper we develop an appropriate theory of positive definite functions on the complex plane from first principles and show some consequences of positive definiteness for meromorphic functions.

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A series of mono(eta(5)-cyclopentadienyl)metal-(II) complexes with nitro-substituted thienyl acetylide ligands of general formula [M(eta(5)-C5H5)(L)(C C{C4H2S}(n)NO2)] (M = Fe, L = kappa(2)-DPPE, n = 1,2; M = Ru, L = kappa(2)-DPPE, 2 PPh3, n = 1, 2; M = Ni, L = PPh3, n = 1, 2) has been synthesized and fully characterized by NMR, FT-IR, and UV-Vis spectroscopy. The electrochemical behavior of the complexes was explored by cyclic voltammetry. Quadratic hyperpolarizabilities (beta) of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at 1500 nm. The effect of donor abilities of different organometallic fragments on the quadratic hyperpolarizabilities was studied and correlated with spectroscopic and electrochemical data. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were employed to get a better understanding of the second-order nonlinear optical properties in these complexes. In this series, the complexity of the push pull systems is revealed; even so, several trends in the second-order hyperpolarizability can still be recognized. In particular, the overall data seem to indicate that the existence of other electronic transitions in addition to the main MLCT clearly controls the effectiveness of the organometallic donor ability on the second-order NLO properties of these push pull systems.

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Risk Based Inspection (RBI) is a risk methodology used as the basis for prioritizing and managing the efforts for an inspection program allowing the allocation of resources to provide a higher level of coverage on physical assets with higher risk. The main goal of RBI is to increase equipment availability while improving or maintaining the accepted level of risk. This paper presents the concept of risk, risk analysis and RBI methodology and shows an approach to determine the optimal inspection frequency for physical assets based on the potential risk and mainly on the quantification of the probability of failure. It makes use of some assumptions in a structured decision making process. The proposed methodology allows an optimization of inspection intervals deciding when the first inspection must be performed as well as the subsequent intervals of inspection. A demonstrative example is also presented to illustrate the application of the proposed methodology.

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In MIMO systems the antenna array configuration in the BS and MS has a large influence on the available channel capacity. In this paper, we first introduce a new Frequency Selective (FS) MIMO framework for macro-cells in a realistic urban environment. The MIMO channel is built over a previously developed directional channel model, which considers the terrain and clutter information in the cluster, line-of-sight and link loss calculations. Next, MIMO configuration characteristics are investigated in order to maximize capacity, mainly the number of antennas, inter-antenna spacing and SNR impact. Channel and capacity simulation results are presented for the city of Lisbon, Portugal, using different antenna configurations. Two power allocations schemes are considered, uniform distribution and FS spatial water-filling. The results suggest optimized MIMO configurations, considering the antenna array size limitations, specially at the MS side.

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Neste trabalho, com base na análise de diferentes formas de conceber e entender a integração didática na perspetiva curricular portuguesa e da consideração do trinómio didático - globalização da aprendizagem / motivação / ensino e aprendizagem integrados nos primeiros anos de escolaridade –, propomos, do ponto de vista científico - didático, uma reflexão sobre os princípios e fundamentos da sequenciação didática e da construção de unidades didáticas integradoras, com o objetivo de dar contributos significativos para que, desde a formação de professores, se possam criar bases teórico-práticas de definição de percursos de ensino e aprendizagem com potencial efetivo de integração nas dimensões epistemológica e curricular.

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The ruthenium(II)-cymene complexes [Ru(eta(6)-cymene)(bha)Cl] with substituted halogenobenzohydroxamato (bha) ligands (substituents = 4-F, 4-Cl, 4-Br, 2,4-F-2, 3,4-F-2, 2,5-F-2, 2,6-F-2) have been synthesized and characterized by elemental analysis, IR, H-1 NMR, C-13 NMR, cyclic voltammetry and controlled-potential electrolysis, and density functional theory (DFT) studies. The compositions of their frontier molecular orbitals (MOs) were established by DFT calculations, and the oxidation and reduction potentials are shown to follow the orders of the estimated vertical ionization potential and electron affinity, respectively. The electrochemical E-L Lever parameter is estimated for the first time for the various bha ligands, which can thus be ordered according to their electron-donor character. All complexes exhibit very strong protein tyrosine kinase (PTK) inhibitory activity, even much higher than that of genistein, the clinically used PTK inhibitory drug. The complex containing the 2,4-difluorobenzohydroxamato ligand is the most active one, and the dependences of the PTK activity of the complexes and of their redox potentials on the ring substituents are discussed. (C) 2012 Elsevier B.V. All rights reserved.

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A calibração e o controlo da qualidade de um acelerador linear são passos muito importantes num serviço de Radioterapia, para garantir a qualidade dos tratamentos prestados. O sector da Física da Unidade de Radioterapia do Hospital Cuf Descobertas implementou um rigoroso Programa de controlo de qualidade ao equipamento produtor de radiação e aos equipamentos medidores de radiação, de acordo com o Dec-Lei 180/2002 e com os protocolos internacionais. Para tal, foram implementados procedimentos, criadas folhas de cálculo, instruções de trabalho e impressos. Foram ainda implementados testes aos equipamentos com periodicidade definida: controlo de qualidade diário e controlo de qualidade após intervenções (manutenções preventivas e correctivas). No decorrer do ano de 2005, o sector da Física colaborou activamente com toda a equipa da Radioterapia na implementação da Norma ISO 9001:2000 no serviço, contribuindo com o seu know how na implementação desta, numa área tão importante como a da garantia da qualidade dos feixes de radiação e das respectivas calibrações em dose. Numa procura de melhoria contínua da qualidade dos serviços prestados aos pacientes, decorre ainda uma auditoria externa da EQUAL-ESTRO*, intercomparação postal com dosímetros termoluminescentes. A qualidade dos feixes de energias utilizados diariamente é analisada, tanto ao nível das calibrações absolutas de cada um dos feixes de fotões e de electrões, como ao nível dos cálculos de dose obtidos com o sistema de planimetria XiO da CMS. Os resultados das duas primeiras fases da intercomparação, relativa aos dois feixes de fotões de 6 MV e 15 MV e feixes de electrões de 4 MeV, 8 MeV e 12 MeV, foram considerados pela EQUAL-ESTRO num nível óptimo (desvio máximo na dose medida em relação à dose de referência |d| ≤ 3%).

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Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Mecânica

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Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Mecânica

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Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Mecânica

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Trabalho Final de Mestrado elaborado no Laboratório Nacional de Engenharia Civil (LNEC) para a obtenção do grau de Mestre em Engenharia Civil pelo Instituto Superior de Engenharia de Lisboa no âmbito do protocolo de cooperação entre o ISEL e o LNEC

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Projecto para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização em Edificações

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We consider a fluid of hard boomerangs, each composed of two hard spherocylinders joined at their ends at an angle Psi. The resulting particle is nonconvex and biaxial. The occurence of nematic order in such a system has been investigated using Straley's theory, which is a simplificaton of Onsager's second-virial treatment of long hard rods, and by bifurcation analysis. The excluded volume of two hard boomerangs has been approximated by the sum of excluded volumes of pairs of constituent spherocylinders, and the angle-dependent second-virial coefficient has been replaced by a low-order interpolating function. At the so-called Landau point, Psi(Landau)approximate to 107.4 degrees, the fluid undergoes a continuous transition from the isotropic to a biaxial nematic (B) phase. For Psi not equal Psi(Landau) ordering is via a first-order transition into a rod-like uniaxial nematic phase (N(+)) if Psi > Psi(Landau), or a plate-like uniaxial nematic (N(-)) phase if Psi < Psi(Landau). The B phase is separated from the N(+) and N(-) phases by two lines of continuous transitions meeting at the Landau point. This topology of the phase diagram is in agreement with previous studies of spheroplatelets and biaxial ellipsoids. We have checked the accuracy of our theory by performing numerical calculations of the angle-dependent second virial coefficient, which yields Psi(Landau)approximate to 110 degrees for very long rods, and Psi(Landau)approximate to 90 degrees for short rods. In the latter case, the I-N transitions occur at unphysically high packing fractions, reflecting the inappropriateness of the second-virial approximation in this limit.

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The excellent properties of elastomers are exploited to trigger wrinkling instabilities in curved shells. Micro- and nano-fibres are produced by electrospinning and UV irradiated: each fibre consists of a soft core and a stiff outer half-shell. Upon solvent de-swelling, the fibres curl because the shell and the core have different natural lengths. Wrinkling only starts after the fibre has attained a well-defined helical shape. A simple analytical model is proposed to find the curling curvature and wrinkle wavelength, as well as the transition between the “curling” and “wrinkling” regimes. This new instability resembles that found in the tendrils of climbing plants as they dry and lignify.