60 resultados para Linguistic computacional theory
em Scielo Saúde Pública - SP
Resumo:
A study was carried out on the urea geometries using ab initio calculation and Monte Carlo computational simulation of liquids. The ab initio calculated results showed that urea has a non-planar conformation in the gas phase in which the hydrogen atoms are out of the plane formed by the heavy atoms. Free energies associated to the rotation of the amino groups of urea in water were obtained using the Monte Carlo method in which the thermodynamic perturbation theory is implemented. The magnitude of the free energy obtained from this simulation did not permit us to conclude that urea is non-planar in water.
Resumo:
A computational quantum chemistry experiment is described on the determination of the most reactive atom in a molecule for a reaction. The reaction studied was the S N2 of 4-(dimethylamino)pyridine and methyl iodide. Several indexes (HOMO coefficent, (c), charges, (q), nucleophilic softness, (s+), and Fukui index, (f+)) were employed to verify which correctly describe what nitrogen will react. The calculations were made by AM1 and HF/STO-3G methods. The correct reactivity order is only reproduced by s+ and f+. The lack of agreement of FMO based indexes was discussed.
Resumo:
A computational quantum chemistry experiment is described of Diels-Alder reactions between 2-cycloenones and cyclopentadiene. The effects of FMO-Frontier Molecular Orbitals (HOMO-LUMO) and of the withdrawing nature of substituents at the C=C bond of cycloenones were evaluated. The calculations were made using HF/STO-3G and B3LYP/6-31+G(d,p) methods. The FMO based indexes are in agreement with the experimentally observed reactivity order. NBO - Natural Bond Orbitals - analysis was used to ascertain the effect of C=C substituents on the dienophile reactivity.
Resumo:
The first computational implementation that automates the procedures involved in the calculation of infrared intensities using the charge-charge flux-dipole flux model is presented. The atomic charges and dipoles from the Quantum Theory of Atoms in Molecules (QTAIM) model was programmed for Morphy98, Gaussian98 and Gaussian03 programs outputs, but for the ChelpG parameters only the Gaussian programs are supported. Results of illustrative but new calculations for the water, ammonia and methane molecules at the MP2/6-311++G(3d,3p) theoretical level, using the ChelpG and QTAIM/Morphy charges and dipoles are presented. These results showed excellent agreement with analytical results obtained directly at the MP2/6-311++G(3d,3p) level of theory.
Resumo:
Composite methods using ONIOM and different basis sets have been used to calculate proton and electron affinities for a set of alcohols at QCISD(T)/6-311++G(2df,p) level of theory. The study was carried out considering HF, MP2 and DFT (25 exchange correlation functional) methods. The calculation performed at ONIOM2(QCISD(T)/6-311++G(2df,p):HF/6-31G(d))//ONIOM2(O3LYP/6-31G(d):HF/6-31G(d)) resulted in the smallest average absolute deviation for AP and AE, 4,75 kJ/mol e 0,43 eV, respectively.
Resumo:
Several recent works in history and philosophy of science have re-evaluated the alleged opposition between the theses put forth by logical empiricists such as Carnap and the so-called "post-positivists", such as Kuhn. Although the latter came to be viewed as having seriously challenged the logical positivist views of science, recent authors (e.g., Friedman, Reisch, Earman, Irzik and Grünberg) maintain that some of the most notable theses of the Kuhnian view of science have striking similarities with some aspects of Carnap's philosophy. Against that reading, Oliveira and Psillos argue that within Carnap's philosophy there is no place for the Kuhnian theses of incommensurability, holism, and theory-ladenness of observations. This paper presents each of those readings and argues that Carnap and Kuhn have non-opposing views on holism, incommensurability, the theory-ladenness of observations, and scientific revolutions. We note at the very end - without dwelling on the point, however - that they come apart on other matters, such as their views on metaphysics and on the context of discovery/justification distinction.
Resumo:
This article advances the theoretical integration between securitization theory and the framing approach, resulting in a set of criteria hereby called security framing. It seeks to make a twofold contribution: to sharpen the study of the ideational elements that underlie the construction of threats, and to advance towards a greater assessment of the audience's preferences. The case study under examination is the 2011 military intervention of the countries of the Gulf Cooperation Council in Bahrain. The security framing of this case will help illuminate the dynamics at play in one of the most important recent events in Gulf politics.
Resumo:
O uso de programas computacionais no setor agrícola permite atingir objetivos específicos na área. Dentre esses, um dos mais complexos é a seleção adequada de máquinas e implementos agrícolas visando à otimização de operações agrícolas, devido, principalmente, à grande variedade de equipamentos existentes no mercado e a gama de tarefas e situações de trabalho que estas são submetidas no campo. O objetivo deste trabalho foi desenvolver um programa computacional para calcular a potência requerida de máquinas e implementos agrícolas normalmente utilizados na condução de operações de campo, desde o preparo do solo até as operações de implantação de culturas. Desenvolvido em linguagem PHP, o programa computacional baseia-se na norma ASAE D497.4 - Agricultural Machinery Management Data como referência para desenvolvimento de cálculos. A partir do programa desenvolvido, tornou-se possível a execução de tarefas para cálculos de avaliação da demanda de potência de máquinas e implementos agrícolas de forma simplificada pela internet.