Temperature Effect on the Structure and Formation Kinetics of Vinyltriethoxysilane-Derived Organic/Silica Hybrids

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Approximations for the generalized temperature integral: a method based on quadrature rules

The generalized temperature integral I(m, x) appears in non-isothermal kinetic analysis when the frequency factor depends on the temperature. A procedure based on Gaussian quadrature to obtain analytical approximations for the integral I(m, x) was proposed. The results showed good agreement between the obtained approximation values and those obtained by numerical integration. Unless other approximations found in literature, the methodology presented in this paper can be easily generalized in order to obtain approximations with the maximum of accurate.

Peak Separation by Derivative Spectroscopy Applied to FTIR Analysis of Hydrolized Silica

Reliable spectral analysis is only achieved if the spectrum is thoroughly investigated in regard to all hidden and overlapped peaks. This paper describes the steps undertaken to find and separate such peaks in the range of 3000 to 4000 cm(-1) in the case of three different infrared absorption spectra of the glass surface of hydrolyzed silica optical fibers. Peak finding was done by the analysis of the second and fourth derivatives of the digital data, coupled with the available knowledge of infrared spectroscopy of silica-water interaction in the investigated range. Peak separation was accomplished by curve fitting with four different models. The model with the best fit was described by a sum of pure Gaussian peaks. Shoulder limit and detection limit maps were used to validate the revealed spectral features.

Refractive index changes in photochromic SbPO4-WO3 glass by exposure to band-gap radiation

We report photoinduced photo-darkening in SbPO4-WO3 glass by exposure to 532 nm light with a power density of 143 mW/cm(2). The time of exposure was varied between 0 and 256 min following which visible photo-darkening, peaking at 850 nm was observed. Spectrophotometer measurement of absorption was performed for both treated and untreated regions of the sample. Time exposure to below band-gap light results in a single exponent Gaussian absorption function over an exceptionally wide range of wavelengths (500 nm-1600 nm), with a 1/e width of 647.5 nm. Kramers-Kronig transform of the change in the absorption indicates a negative local change in the refractive index. The dispersed refractive index change at 1550 nm, Delta n, is calculated to be similar to -5 x 10(-8). The peak absorption increases with time of exposure and the photo-darkening remains irreversible at room temperature. Crown Copyright (C) 2010 Published by Elsevier B.V. All rights reserved.

Waveguides and gratings fabrication in zirconium-based organic/inorganic hybrids

Sol-gel derived poly(oxyethylene)/siloxane organic/inorganic di-ureasil hybrids containing different amounts of methacrylic acid (McOH, CH(2)=C(CH(3))COOH)) modified zirconium oxo-clusters (Zr-OMc) were processed as thin films deposited in glassy substrates via spin coating and as transparent and shape controlled monoliths. Channel monomode waveguides and diffraction gratings were UV patterned using the Talbot interferometer and the Lloyd mirror interferometer experimental setups. The time dependence of the diffraction gratings efficiency was studied for hybrids containing different amounts of Zr-OMc. Finally, the number of propagating modes and the refractive index gradient within the waveguide region, determined as a Gaussian section located below the patterned channel, was evaluated and modeled, a maximum index contrast of 2.43 X 10(-5) being estimated.

Uncertainties in the prediction of spatial variability of soil CO2 emissions and related properties

A emissão de CO2 do solo apresenta alta variabilidade espacial, devido à grande dependência espacial observada nas propriedades do solo que a influenciam. Neste estudo, objetivou-se: caracterizar e relacionar a variabilidade espacial da respiração do solo e propriedades relacionadas; avaliar a acurácia dos resultados fornecidos pelo método da krigagem ordinária e simulação sequencial gaussiana; e avaliar a incerteza na predição da variabilidade espacial da emissão de CO2 do solo e demais propriedades utilizando a simulação sequencial gaussiana. O estudo foi conduzido em uma malha amostral irregular com 141 pontos, instalada sobre a cultura de cana-de-açúcar. Nesses pontos foram avaliados a emissão de CO2 do solo, a temperatura do solo, a porosidade livre de água, o teor de matéria orgânica e a densidade do solo. Todas as variáveis apresentaram estrutura de dependência espacial. A emissão de CO2 do solo mostrou correlações positivas com a matéria orgânica (r = 0,25, p < 0,05) e a porosidade livre de água (r = 0,27, p <0,01) e negativa com a densidade do solo (r = -0,41, p < 0,01). No entanto, quando os valores estimados espacialmente (N=8833) são considerados, a porosidade livre de água passa a ser a principal variável responsável pelas características espaciais da respiração do solo, apresentando correlação de 0,26 (p < 0,01). As simulações individuais propiciaram, para todas as variáveis analisadas, melhor reprodução das funções de distribuição acumuladas e dos variogramas, em comparação à krigagem e estimativa E-type. As maiores incertezas na predição da emissão de CO2 estiveram associadas às regiões da área estudada com maiores valores observados e estimados, produzindo estimativas, ao longo do período estudado, de 0,18 a 1,85 t CO2 ha-1, dependendo dos diferentes cenários simulados. O conhecimento das incertezas gerado por meio dos diferentes cenários de estimativa pode ser incluído em inventários de gases do efeito estufa, resultando em estimativas mais conservadoras do potencial de emissão desses gases.

Detecção de falhas em estruturas inteligentes usando otimização por nuvem de partículas: fundamentos e estudo de casos

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Aprendizado não-supervisionado em redes neurais pulsadas de base radial: um estudo da capacidade de agrupamento para a classificação de pixels

Redes neurais pulsadas - redes que utilizam uma codificação temporal da informação - têm despontado como uma promissora abordagem dentro do paradigma conexionista, emergente da ciência cognitiva. Um desses novos modelos é a rede neural pulsada com função de base radial, que é capaz de armazenar informação nos tempos de atraso axonais dos neurônios. Um algoritmo de aprendizado foi aplicado com sucesso nesta rede pulsada, que se mostrou capaz de mapear uma seqüência de pulsos de entrada em uma seqüência de pulsos de saída. Mais recentemente, um método baseado no uso de campos receptivos gaussianos foi proposto para codificar dados constantes em uma seqüência de pulsos temporais. Este método tornou possível a essa rede lidar com dados computacionais. O processo de aprendizado desta nova rede não se encontra plenamente compreendido e investigações mais profundas são necessárias para situar este modelo dentro do contexto do aprendizado de máquinas e também para estabelecer as habilidades e limitações desta rede. Este trabalho apresenta uma investigação desse novo classificador e um estudo de sua capacidade de agrupar dados em três dimensões, particularmente procurando estabelecer seus domínios de aplicação e horizontes no campo da visão computacional.

GCHF basis sets and their application in the electronic structure study of PrMnO3

The approach called generator coordinate Hartree-Fock (GCHF) method is used in the selection of Gaussian basis set [25s18p for O ((3)p), 31s21p14d for Mn (S-6), and 33s22p16d9f for Pr ((4)J)] for atoms. The role of the weight functions in the assessment of the numerical integration range of the GCHF equations is shown. These basis sets are contracted to (25s18p/9s5p), (31s21p14d/9s6p4d), and (33s22pl6d9f118sl2p5d3f) by segmented contraction scheme of Dunning and they are utilized in calculations of Restricted-Open-HF (ROHF) Total and Orbital energies of the (MnO+1)-Mn-3 and (PrO+1)-Pr-1 fragments, to evaluate their quality in molecular studies. The addition of one d polarization function in the contracted (9s5p) basis set for O(P-3) atom and their application with the contracted (9s6p4d), (18s21p5d3f) basis sets for Mn (S-6) and Pr-Pr ((4)j) atoms lead to the electronic structure study of PrMnO3. The dipole moment, the total energy, and total atomic charges properties were calculated and were carried out at ROHF level with the [PrMnO3](2) fragment. The calculated values show that PrMnO3 does not present piezoelectric properties. (C) 2004 Elsevier B.V. All rights reserved.

Theoretical and experimental study of the infrared spectrum of isonicotinamide

The IR-spectrum of the isonicotinamide molecule (C(2)H(2)NC(3)H(2)CONH(2)) is studied by means of theoretical and experimental methods. For an appropriate representation of the molecular environment, Gaussian basis sets to the atoms of these molecule are built and then contracted (5s and 6s5p). For evaluation of the quality of contracted basis sets in molecular calculations, we have accomplished calculations of the total and the orbital (HOMO and HOMO-1) energies in the HF-Roothaan method for the molecule studied. The results obtained with the contracted basis sets [5s/6s5p] are compared to values obtained with our (21s/22s14p) basis sets and with those obtained with the D95, 6-31G, and 6-311G basis sets from literature. It was added one d polarization function in the [6s5p] contracted basis set for C ((3)P) atom, which was used in combination with the basis sets for H ((2)S), N ((4)S). and O((3)P) atoms to calculate the infrared spectrum of isonicotinamide. The calculations were performed at B3LYP level and were compared to corresponding experimental values also obtained in our laboratory. The theoretical results in comparison with the corresponding experimental values indicate a very good interpretation of the IR-spectrum and that the strategy of an appropriate representation of the molecular environment through the basis sets is an effective alternative to investigate vibrational theoretical properties of the nicotinamide molecule. (c) 2006 Published by Elsevier B.V.

Ab initio study of high tridymite by the formalism generator coordinate Hartree-Fock

The Generator Coordinate Hartree-Fock (GCHF) Method is applied to generate extended 14s 8p and 17s 11p Gaussian basis sets for the atoms O and Si, respectively. The role of the weight functions in the assessment of the numerical integration range of the GCHF is shown. The Gaussian basis sets are contracted to [6s4p] O atom and [8s5p] Si atom by the Dunning's segmented contraction scheme. To evaluate the quality of our contracted [6s4p] and [8s5p] bases in molecular calculations we accomplish calculations of total and orbital energies in the Hartree-Fock-Roothaan method for O-2 and SiO molecules. We compare the results obtained with the our (14s 8p) and (17s 11p) bases sets with the of 6-311G basis and with values from the literature. The addition of one d polarization function in the silicon basis and its utilization with the basis for oxygen leads to the calculation of electronic properties and IR Spectrum of high tridymite in space group D-3d. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Investigation of piezoelectricity in perovskite (LaFeO3): A theoretical study

In a previous report we studied theoretically the piezoelectric effect in barium titanate (BaTiO3) [O. Treu Filho, J.C. Pinheiro, R.T. Kondo, J. Mol. Struct. (THEOCHEM), 671 (2004) 71]. In this article we applied the Hartree-Fock (HF) theory in the investigation of piezoelectricity in LaFeO3. Initially, the generator coordinate HF (GCHF) method was used to build 22s14p, 30s19p13d, and 32s24p17d Gaussian basis sets for O(3p), Fe(D-5), and La(D-2) atoms. Then those basis sets were contracted to [7s6p], [13s8p6d], and [18s13p7d], respectively. The quality of the contracted basis sets in polyatomic calculations was evaluated through calculations of total and orbital energies (HOMO and HOMO-1) of (FeO1+)-Fe-2 and (LaO1+)-La-1. Finally, the contracted basis sets were supplemented with polarization and diffuse functions and used to investigate the piezoelectricity in LaFeO3. The calculated properties were dipole moment, total energy, and atomic charges and the analysis of those properties showed that covalent bonds constitute the electronic structure of [LaFCO3](2) fragment. Therefore, it is reasonable to believe that LaFeO3 does not present piezoelectric properties. (C) 2006 Elsevier B.V. All rights reserved.

Collisional semiclassical approximations in phase-space representation

The Gaussian wave-packet phase-space representation is used to show that the expansion in powers of a of the quantum Liouville propagator leads, in the zeroth-order term, to results close to those obtained in the statistical quasiclassical method of Lee and Scully in the Weyl-Wigner picture. It is also verified that, propagating the Wigner distribution along the classical trajectories, the amount of error is less than that coming from propagating the Gaussian distribution along classical trajectories.

Blumenthal's theorem for Laurent orthogonal polynomials

We investigate polynomials satisfying a three-term recurrence relation of the form B-n(x) = (x - beta(n))beta(n-1)(x) - alpha(n)xB(n-2)(x), with positive recurrence coefficients alpha(n+1),beta(n) (n = 1, 2,...). We show that the zeros are eigenvalues of a structured Hessenberg matrix and give the left and right eigenvectors of this matrix, from which we deduce Laurent orthogonality and the Gaussian quadrature formula. We analyse in more detail the case where alpha(n) --> alpha and beta(n) --> beta and show that the zeros of beta(n) are dense on an interval and that the support of the Laurent orthogonality measure is equal to this interval and a set which is at most denumerable with accumulation points (if any) at the endpoints of the interval. This result is the Laurent version of Blumenthal's theorem for orthogonal polynomials. (C) 2002 Elsevier B.V. (USA).

Fluctuating dimension in a discrete model for quantum gravity based on the spectral principle

The spectral principle of Connes and Chamseddine is used as a starting point to define a discrete model for Euclidean quantum gravity. Instead of summing over ordinary geometries, we consider the sum over generalized geometries where topology, metric, and dimension can fluctuate. The model describes the geometry of spaces with a countable number n of points, and is related to the Gaussian unitary ensemble of Hermitian matrices. We show that this simple model has two phases. The expectation value , the average number of points in the Universe, is finite in one phase and diverges in the other. We compute the critical point as well as the critical exponent of . Moreover, the space-time dimension delta is a dynamical observable in our model, and plays the role of an order parameter. The computation of is discussed and an upper bound is found, < 2.