134 resultados para THEORETICAL APPROACH

em Biblioteca Digital da Produção Intelectual da Universidade de São Paulo (BDPI/USP)


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Structured meaning-signal mappings, i.e., mappings that preserve neighborhood relationships by associating similar signals with similar meanings, are advantageous in an environment where signals are corrupted by noise and sub-optimal meaning inferences are rewarded as well. The evolution of these mappings, however, cannot be explained within a traditional language evolutionary game scenario in which individuals meet randomly because the evolutionary dynamics is trapped in local maxima that do not reflect the structure of the meaning and signal spaces. Here we use a simple game theoretical model to show analytically that when individuals adopting the same communication code meet more frequently than individuals using different codes-a result of the spatial organization of the population-then advantageous linguistic innovations can spread and take over the population. In addition, we report results of simulations in which an individual can communicate only with its K nearest neighbors and show that the probability that the lineage of a mutant that uses a more efficient communication code becomes fixed decreases exponentially with increasing K. These findings support the mother tongue hypothesis that human language evolved as a communication system used among kin, especially between mothers and offspring.

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New molecular species HSeCl, HClSe, and SeCl were investigated at a high level of theory, CCSD(T), with a series of correlation consistent basis sets with extrapolation to the CBS limit. Account has been taken for valence-only and core-valence correlation effects, and of anharmonic effects on the vibrational frequencies. HSeCl is 43.25 kcal mol (1) more stable than HClSe. A barrier (Delta G(#)) of 47.20 kcal mol (1) separates these species. Internuclear distances are generally overestimated by 0.008 angstrom in the valence-only correlation calculations. Inclusion of anharmonicity leads to much improved vibrational frequencies. For SeCl, we estimate Delta H(f) (0 K) = 23.96 and Delta H(f) (298.15 K) = 24.64 kcal mol (1); for HSeCl, we had 4.20 and 4.97 kcal mol (1), respectively. (C) 2010 Elsevier B.V. All rights reserved.

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This work reports theoretical and experimental studies on the first hyperpolarizability (beta) of aminophenols, evaluating the influence of the NH(2) group position relative to the OH group on the hyperpolarizability. A new extension of hyper-Rayleigh scattering technique using picosecond pulse trains was employed to obtain the experimental absolute values of (beta). The theoretical static beta(0) values were calculated using AMI method implemented in the AMPAC program. The theoretical and experimental data show a clear dependence between beta and the relative position of the electron donor (D) and acceptor (A) groups, presenting the 2-aminophenol the higher values. Moreover, calculations show excellent qualitative agreement between theoretical and experimental data, which are improved when the simulations considering the solvated molecule in a combination of discrete solvent molecules interacting with the solute and the application of continuous dielectric model. Besides, the study indicates that the experimental hyperpolarizabilities seem to be a property of the solute-solvation shell system. These facts have affirmed that the theoretical approach employed can be successfully used to foresee the variation in beta due to modifications in the D/A position. Moreover, a theoretical study of the ground state absorption is performed and compared with experimental data. (C) 2008 Elsevier B.V. All rights reserved.

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A high level theoretical approach is used to characterize for the first time a manifold of doublet and quartet A + S and Omega states correlating with the first two dissociation channels of an as yet experimentally unknown molecular species, SI, sulfur monoidide. A set of spectroscopic constants is determined, including vibrationally averaged spin-orbit coupling constants, vibrationally averaged dipole moments, and dissociation energies. The transition dipole moment function for the spin-forbidden transition a (4)Sigma -X (2)Pi, and the associated radiative lifetimes were also evaluated. Two possibilities to detect transitions experimentally and to derive spectroscopic constants are suggested. (C) 2011 Elsevier B. V. All rights reserved.

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Após um século de reflexões e investigações, como era de se esperar, a Psicologia Moral apresenta sinais de esgotamento de seus referenciais teóricos clássicos. Consequentemente, novas perspectivas se abrem, entre elas a abordagem teórica que leva o nome de 'personalidade ética', cuja tese é: para compreendermos os comportamentos morais (deveres) dos indivíduos, precisamos conhecer a perspectiva ética (vida boa) adotadas por eles. Entre os invariantes psicológicos de realização de uma 'vida boa', está a necessidade de 'expansão de si próprio'. Como tal expansão implica ter 'representações de si' de valor positivo, entre elas poderão estar aquelas relacionadas à moral. Se estiverem, o sujeito experimentará o sentimento de dever, do contrário, a motivação para a ação moral será inexistente ou fraca.

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This work clarifies the relation between network circuit (topology) and behaviour (information transmission and synchronization) in active networks, e.g. neural networks. As an application, we show how one can find network topologies that are able to transmit a large amount of information, possess a large number of communication channels, and are robust under large variations of the network coupling configuration. This theoretical approach is general and does not depend on the particular dynamic of the elements forming the network, since the network topology can be determined by finding a Laplacian matrix (the matrix that describes the connections and the coupling strengths among the elements) whose eigenvalues satisfy some special conditions. To illustrate our ideas and theoretical approaches, we use neural networks of electrically connected chaotic Hindmarsh-Rose neurons.

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The transition of plasmons from propagating to localized state was studied in disordered systems formed in GaAs/AlGaAs superlattices by impurities and by artificial random potential. Both the localization length and the linewidth of plasmons were measured by Raman scattering. The vanishing dependence of the plasmon linewidth on the disorder strength was shown to be a manifestation of the strong plasmon localization. The theoretical approach based on representation of the plasmon wave function in a Gaussian form well accounted for by the obtained experimental data.

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This paper presents an analysis of a reconfigurable patch filter based on a triple-mode circular patch resonator with four radial slots. The analysis has been carried out thanks to the development of a new theoretical approach of the tunable patch filter based on the coupling matrix. The coefficients of the coupling matrix related to the tunable behavior have been identified and some rules for their evolution have been derived. For a proof-of-concept, a bandpass filter has been designed with a continuous tunability obtained with varactors connected across the slots. State-of-the-art results have been obtained, with a frequency tuning range of 27% from 1.95 to 2.43 GHz and a change in fractional bandwidth from 8.5% to 31.5% for the respective frequencies. In the entire tuning range, the return loss is better than 10 dB and the maximum insertion loss is 2 dB. Due to the newly developed coupling matrix, measurements, simulations, and theory showed great agreement.

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The microtube is a simple and cheap emitter that was widely used throughout the world in the early days of drip irrigation. Its length can be adjusted according to the pressure distribution along the lateral line and the discharge from the microtube can be adjusted by its length. This not only counters the pressure loss due to pipe friction but also makes it suitable for undulating and hilly conditions, where pressure in the lateral line varies considerably according to the differences in elevation. This is the major problem facing the designer, i.e., emitter flow changes as the acting pressure head changes. In this study, a novel micro-sprinkler system is proposed that uses microtube as the emitter and where the length of the microtube can be varied in response to pressure changes along the lateral to give uniformity of emitter discharges. The objective of this work is to develop and validate empirical and semi-theoretical equations for the emitter hydraulics. Laboratory testing of two microtube emitters of different diameter over a range of pressures and discharges was used in the development of the equations relating pressure and discharge, and pressure and length for these emitters. The equations proposed will be used in the design of the micro-sprinkler system, to determine the length of microtube required to give the nominal discharge for any given pressure. The semi-theoretical approach underlined the importance of accurate measurements of the microtube diameter and the uncertainty in the estimation of the friction factor for these tubes.

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The main objective of this experiment is to determine the amount of nicotine in commercial brand cigarettes by means of a nonaqueous acid-base titration. A simple glass device simulating a smoker is proposed, which allows the determination of the volatilized, filter retained, and inhaled portions. Students will readily see that the amount of nicotine/cigarette stated on the label (similar to 0.5-1.0 mg) refers indeed to the inhaled portion only, rather than to the total amount/cigarette (usually more than 10 mg). Even so, values for inhaled nicotine may be significantly higher than those reported for several brands. Students will also be able to make a critical evaluation of the true content of nicotine in the inhaled portion and confront it with the reported value for a given brand. In addition, the theoretical approach, supported by HPLC data, provides an excellent experience on nonaqueous acid-base volumetric analysis.

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For many learning tasks the duration of the data collection can be greater than the time scale for changes of the underlying data distribution. The question we ask is how to include the information that data are aging. Ad hoc methods to achieve this include the use of validity windows that prevent the learning machine from making inferences based on old data. This introduces the problem of how to define the size of validity windows. In this brief, a new adaptive Bayesian inspired algorithm is presented for learning drifting concepts. It uses the analogy of validity windows in an adaptive Bayesian way to incorporate changes in the data distribution over time. We apply a theoretical approach based on information geometry to the classification problem and measure its performance in simulations. The uncertainty about the appropriate size of the memory windows is dealt with in a Bayesian manner by integrating over the distribution of the adaptive window size. Thus, the posterior distribution of the weights may develop algebraic tails. The learning algorithm results from tracking the mean and variance of the posterior distribution of the weights. It was found that the algebraic tails of this posterior distribution give the learning algorithm the ability to cope with an evolving environment by permitting the escape from local traps.

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We study the nuclear quadrupole interaction at the nitrogen sites in the molecular and crystalline phases of the imidazole compound. We use PAW which is a state-of-the-art method to calculate the electronic structure and electric field gradient at the nucleus in the framework of the density functional theory. The quadrupole frequencies at both imino and amino N sites are in excellent agreement with measurements. This is the first time that the electric field gradient at crystalline imidazole is correctly treated by an ab initio theoretical approach.

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New lanthanide complexes with benzeneseleninic (ABSe) and 4-chloro-benzeneseleninic (ABSeCl) acids have been synthesized and characterized by elemental analysis, infrared and UV-visible spectroscopies. The emission spectra of the trivalent europium complexes presented the typical electronic (5)D(0) -> (7)F(j) transitions of the ion (J = 0-4). The ground-state geometries of the europium complexes have been calculated by using the Sparkle/AM1 model. From these results, the 4f-4f intensity parameters and energies of the ligand singlet and triplet excited states have been obtained. The lower emission quantum yield for the [Eu(ABSe)(3)(H(2)O)(2)](H(2)O)(2) compound, as compared to the [Eu(Al(3)SeCl)(3)(H(2)O)(2)] one, can be associated to the higher numbers of water molecules, in the first and second coordination spheres, that contribute to the luminescence quenching. The [Eu(Al(3)Se)(3)(H(2)O)(2)](H(2)O)(2) complex presents an intermediate state whose energy difference with respect to the first excited singlet state is resonant with three phonons from the water molecules, favouring a multiphonon relaxation process from the singlet state followed by a fast internal conversion process; this effect is less pronounced in the complex with the ABSeCl ligand. The luminescence decay curves of the gadolinium complexes indicate that the level responsible for the intramolecular energy transfer process has a triplet character for both compounds. The nephelauxetic effect in these compounds was investigated under the light of a recently proposed covalency scale based on the concept of overlap polarizability of the chemical bond. (C) 2009 Elsevier B.V. All rights reserved.

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Structural, energetic, and vibrational properties of new molecular species, HSeF and HFSe, the associated transition state, and dissociation fragments are investigated using a state-of-the-art theoretical approach, CCSD(T)/CBS. HSeF is a normal covalently bonded molecule 38.98 kcal mol (1) more stable than the complex HF-Se, which shows an unusual structure with a central fluorine atom and a bond angle of 101.8 degrees.A barrier (Delta G(#)) of 49.01 kcal mol (1) separates the two species. Vibrational frequencies are also quite distinct. Heats of formation are evaluated for the diatomic fragments and HSeF. Final Delta(f)H values depend on the experimental accuracy of those of Se(g) and H(2)Se. (c) 2009 Elsevier B.V. All rights reserved.

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Structural, vibrational, and energetic properties of new molecular species, HSI and HIS are investigated for the first time using a state-of-the-art theoretical approach. These molecules can be easily differentiated by their geometric parameters and vibrational spectra. HSI is much more stable, and a direct unimolecular isomerization is very unlikely. Kinetics estimates predict that only at low temperatures there is a possibility of isolating HIS. For HS-I, we estimate a bond dissociation energy of 46.25 kcal/mol, and a heat of formation at 298.15 K of 12.84 kcal/mol. For the H(2)S + I(2) -> HSI + HI reaction enthalpy, we found 8.40 kcal/ mol. (C) 2008 Elsevier B.V. All rights reserved.