Submitted by Nelson Bretanha (physikosmos@gmail.com) on 2016-01-01T12:55:20Z No. of bitstreams: 1 Métodos Semi-Empíricos (Princípios Básicos e Aplicações).pdf: 4755970 bytes, checksum: 0e2d74ff6ffd8de112da824ec714d84e (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2016-01-05T18:04:11Z (GMT) No. of bitstreams: 1 bretanhaneto_ne_me_rcla.pdf: 4755970 bytes, checksum: 0e2d74ff6ffd8de112da824ec714d84e (MD5) / Made available in DSpace on 2016-01-05T18:04:11Z (GMT). No. of bitstreams: 1 bretanhaneto_ne_me_rcla.pdf: 4755970 bytes, checksum: 0e2d74ff6ffd8de112da824ec714d84e (MD5) Previous issue date: 2015-12-18 / Neste trabalho investigamos os efeitos decorrentes da presença de heteroátomos numa folha de “supercoroneno” (molécula C58H18 utilizada como uma primeira aproximação para o grafeno). Mais especificamente, utilizando método semi-empírico PM6, implementado no pacote computacional MOPAC2012®, estudamos as diferentes curvas de energia (calor de formação). As curvas estudadas foram obtidas pela passagem de um átomo de carbono sobre uma folha de supercoroneno na qual existe um heteroátomo (foram utilizadas três diferentes estruturas: C57H18Si, C57H18Ge e C57H18Sn). Nesse contexto, estudamos também o efeito destes heteroátomos sobre a densidade eletrônica e os orbitais HOMO e LUMO das diferentes estruturas. / In this work we investigate the effects of the presence of heteroatoms on a “supercoronene” sheet (C58H18 molecule used as a molecular model for graphene). Specifically, we used the semiempirical method PM6 as implemented in MOPAC2012® software to study several (formation) energy curves. The energy curves were obtained by positioning a carbon atom over a “supercoronene” sheet in which there is a heteroatom (this was done for three different structures: C57H18Si, C57H18Ge and C57H18Sn). In this context, the effect of these heteroatoms on the electronic density distributions, as well as their effect on HOMO and LUMO orbitals were also investigated.

Orientador: Paulo Cardieri / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Elétrica e de Computação / Made available in DSpace on 2018-08-26T02:54:38Z (GMT). No. of bitstreams: 1 Goes_AdrianoAlmeida_D.pdf: 4041752 bytes, checksum: 3aebfc7442e100b6011a6873be01c5f9 (MD5) Previous issue date: 2014 / Resumo: Resultados de campanhas de medição realizadas visando o desenvolvimento de uma fer-ramenta para o projeto, implantação e análise de sistemas de RFID são mostrados nesse traba-lho. Particularmente, a perda de percurso de rádio a partir de um leitor de RFID até um TAG, e de volta para o leitor é caracterizada na banda 915 MHz, para diferentes distâncias de separação leitor-TAG, alturas de TAG e de antena do leitor. Vários cenários de propagação foram considerados, incluindo ambientes exteriores e in-teriores, para os quais foi colhido um extenso número medidas. Os dados de campo são, então, comparados a uma versão melhorada do modelo clássico perda caminho 2-ray, ajustada para incluir também os padrões de radiação da antena não omnidirecionais no leitor. Além disso, foi investigado, por meio da análise de medidas de campo, o efeito da mobi-lidade do TAG no sinal recebido no leitor. Para a coleta das medidas, foi construído um aparato composto de uma esteira de velocidade controlada, onde foram instalados TAGs de teste. Os resultados de medida mostraram que a mobilidade do TAG provoca uma diminuição do valor médio e um aumento da variância do sinal recebido no leitor. Essa atenuação extra e a variância do sinal não são fortemente afetadas pelo valor da velocidade. Por fim, esses efeitos de propagação são incorporados em um modelo matemático, que pode ser utilizado para a simulação e planejamento de sistemas RFID / Abstract: Results of measurement campaigns carried out aiming at the development of a tool for design, deployment, and analysis of RFID systems are shown. Particularly, the radio path loss from an RFID reader towards the test TAG and back to the reader is characterized at the 915 MHz band. The path loss is estimated based on the received signal strength measured at the reader, for different reader¿TAG separation distances and different antenna TAG heights. Several propagation scenarios have been considered, including outdoor and indoor environments for which an extensive number of typical real manufacturing plants have been chosen. The field data are then compared to a proposed novel, improved version of the classical 2-ray path loss model, adjusted to include non-omnidirectional antenna radiation patterns at the reader. In addition, the effect of TAG mobility in the received signal at the reader was also investigated, by means of field measurements. To collect the field measurements, an apparatus was designed and constructed, consisting of a mat of controlled speed, on which test TAGs were installed. The results showed that TAG mobility decreases the average value increases the variance of the received signal at the reader. This extra attenuation and the increased variance of the signal are not strongly affected by the value of speed. Finally, these two effects are incorporated into a mathematical model that can be used for simulation and planning of RFID systems / Doutorado / Telecomunicações e Telemática / Doutor em Engenharia Elétrica

Esta tesis analiza los métodos estáticos, los cuales comprenden los métodos analíticos y semi empíricos que son utilizados para determinar la capacidad de carga teórica en pilotes, y los compara con las pruebas de carga dinámica, las cuales brindan el resultado real de la capacidad de carga de un pilote. El análisis realizado recopila las teorías de Therzaghi, Hansen, Meyerhof y Bowles, en cuanto a los modelos analíticos, y las teorías de Aoki Velloso, Decourt Quaresma, Pedro Paulo Velloso y Texeira, por parte de las teorías semi empíricas. / This thesis analyzes the static methods, which include the analytical and semi-empirical methods that are used to determine the theoretical load capacity in piles, and compares them with the dynamic load tests, which provide the real result of the load capacity of a pile. The analysis compiles the theories of Therzaghi, Hansen, Meyerhof and Bowles, regarding the analytical models, and the theories of Aoki Velloso, Decourt Quaresma, Pedro Paulo Velloso and Texeira, by the semi-empirical theories. / Tesis

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Cette thèse est consacrée à l'étude de deux systèmes, à la fois proches et différents par leur comportement : Co-Pt, système emblématique de l'ordre chimique, et Pt-Ag, système hybride présentant à la fois un ordre chimique et une tendance à la démixtion, ainsi qu'une forte tendance à la ségrégation. Afin de répondre à ces diverses questions, nous adoptons une approche semi-empirique à travers un potentiel à $N$-corps, permettant les relaxations atomiques, dans l'approximation du second moment de la densité d'états (SMA), couplé à des simulations Monte Carlo dans différents ensembles. Des agrégats de différentes tailles (allant de 1000 à 10000 atomes) et de différentes morphologies (octaèdre tronqué, décaèdre, ou icosaèdre) sont analysés en terme de composition chimique sur les différents sites inéquivalents (sommet, arête, facettes (100) et (111) et coeur) puis comparés aux systèmes de référence (surfaces, volume) sur toute la gamme de concentration. Pour le système Co-Pt, nous observons des structures ordonnées similaires à celles du volume pour le coeur et similaires à celles des surfaces pour les facettes. L'impact de la phase bidimensionnelle (√3×√3)R30◦ propre à la surface, est d'autant plus important sur l'ordre chimique au coeur que la nanoparticule est de petite taille. Pour le système Pt-Ag, nous observons une importante ségrégation de l'Ag en surface, ainsi qu'un enrichissement de Pt en sous-surface, et la stabilisation de la phase ordonnée L1$_{1}$ au coeur. Cette structure peut apparaître en un seul variant ou bien en adoptant tous les variants possibles, conduisant ainsi à une structure en pelures d'oignon. / Due to the correlation between atomic arrangement and physical properties, ordered nanoalloys are particularly interesting in the field of catalysis, magnetism, or optics. By reducing the system size, from alloy to nanoalloy, a lot of questions arise: Is chemical ordering conserved? What is the morphology of nanoalloys? What is the properties evolution as a size function? Is there a coupling between segregation and core ordering? This thesis is dedicated to two systems: Co-Pt, a typical example of ordering and Pt-Ag, hybrid system between ordering and demixion. To answer these questions, we performed Monte Carlo simulations in different ensembles with semi-empirical many-body potential within the Second Moment Approximation (SMA) of the density of states which allows atomic relaxations. Nanoparticles of different sizes (from 1000 to 10000 atoms) and shapes (truncated octahedra, decahedra, or icosahedra) are analyzed considering chemical composition on each site (vertex, edge, (111) and (100) facets and core) and compared to reference systems (surfaces and bulk) on the whole range of composition. For Co-Pt, we get ordered structures similar to the bulk ones and similar to surfaces for facets. The bidimensional phase (√3×√3)R30◦, purely due to surface effect, impacts core ordering, even more for small clusters. For Pt-Ag, we get a strong Ag segregation on surface coupled with a Pt sub-surface enrichment, and a stable L1$_{1}$ phase in the core. This ordered structure may appear with a single variant or with multiple variants, leading to an onion-like structure.

Orientador: Douglas Soares Galvão / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-09-27T13:47:49Z (GMT). No. of bitstreams: 1 Troche_KarlaSouza_M.pdf: 1255427 bytes, checksum: 17251baf9cd0c68ce5c4f8e8adefec0b (MD5) Previous issue date: 2003 / Resumo: Neste trabalho apresentamos estudos de estrutura-atividade realizados para 81 hidrocarbonetos policíclicos aromáticos (PAHs) tentando identificar compostos carcinogênicos. Em particular, empregamos uma nova metodologia desenvolvida para tratar o problema da correlação estrutura geométrica com atividade biológica, denominada Metodologia de Índices Eletrônicos (MIE). Utilizamos três métodos semi-empíricos para estudar a dependência entre a qualidade dos resultados obtidos pela MIE e o Hamiltoniano utilizado. Para validarmos os descritores utilizados pela MIE, investigamos a relação entre a atividade experimental dos PAHs e descritores teóricos através de cinco metodologias de reconhecimento de padrões: a Análise de Componentes Principais (PCA), Análise Hierárquica de Agrupamentos (HCA), K-ésimo vizinho mais próximo (KNN), Soft Independent Modeling of Class Analogies (SIMCA) e as Redes Neurais Artificiais (NN). Para estas investigações distintas pudemos correlacionar a atividade dos PAHs estudados com parâmetros teóricos, em sua maioria eletrônicos, onde os parâmetros utilizados na MIE foram selecionados pelos diferentes métodos. Este estudo valida estatisticamente a MIE como uma nova metodologia capaz de identificar compostos biologicamente ativos, e com um custo computacional menor que técnicas convencionais de Relação estrutura-atividade (SAR) e apresentando um desempenho, em geral superior / Abstract: In this work we present the study structure-activity realized for 81 polycyclic aromatic hydrocarbons (PAHs) trying to identify carcinogenic compounds. Particularly, we used a new methodology developed to deal with the problem of correlation between geometrical structure and biological activity, the Electronic Indices Methodology (EIM). We used three semi-empirical methods to analyze the dependence between the quality of results obtained through EIM and the Hamiltonian used. In order to validate the descriptors used in EIM, we investigated the relationship between the experimental activity of PAHs and the theorical descriptors through five methodologies of pattern recognition: Principal Component Analysis (PCA), Hierarchical Cluster Analysis (HCA), Kth Nearest Neighbor (KNN), Soft Independent Modeling of Class Analogies (SIMCA) and Neural Networks (NN). From these different investigations, we could correlate the activity of PAHs studied with theorical parameters, almost all electronic, where the used parameters on EIM were selected with the different methods. These studies validate the statistical value of electronic parameters derived from EIM analysis and their ability to identify active compounds. The EIM out performed more standard Structure-Activity Relationship (SAR) methodologies / Mestrado / Física da Matéria Condensada / Mestre em Física

In this study, the semi-empirical approach is introduced to accurately estimate the probability distribution of complex non-linear random variables in the field of wavestructure interaction. The structural form of the semi-empirical distribution is developed based on a mathematical representation of the process and the model parameters are estimated directly from utilization of the sample data. Here, three probability distributions are developed based on the quadratic transformation of the linear random variable. Assuming that the linear process follows a standard Gaussian distribution, the three-parameter Gaussian-Stokes model is derived for the second-order variables. Similarly, the three-parameter Rayleigh-Stokes model and the four-parameter Weibull- Stokes model are derived for the crests, troughs, and heights of non-linear process assuming that the linear variable has a Rayleigh distribution or a Weibull distribution. The model parameters are empirically estimated with the application of the conventional method of moments and the newer method of L-moments. Furthermore, the application of semi-empirical models in extreme analysis and estimation of extreme statistics is discussed. As a main part of this research study, the sensitivity of the model statistics to the variability of the model parameters as well as the variability in the samples is evaluated. In addition, the sample size effects on the performance of parameter estimation methods are studied. Utilizing illustrative examples, the application of semi-empirical probability distributions in the estimation of probability distribution of non-linear random variables is studied. The examples focused on the probability distribution of: wave elevations and wave crests of ocean waves and waves in the area close to an offshore structure, wave run-up over the vertical columns of an offshore structure, and ocean wave power resources. In each example, the performance of the semi-empirical model is compared with appropriate theoretical and empirical distribution models. It is observed that the semi-empirical models are successful in capturing the probability distribution of complex non-linear variables. The semi-empirical models are more flexible than the theoretical models in capturing the probability distribution of data and the models are generally more robust than the commonly used empirical models.

This thesis was concerned on the investigation of mechanical properties of centrally notched and unnotched AS-4/PEEK (APC-2) composite laminates due to static tensile and tension-tension (T-T) fatigue tests empirically and systematically. Then, statistical analyses were used to determine and quantify the significant thermomechanical variables that influence the durability/life of the composite laminates. Typical laminates were made from sixteen prepregs of APC-2 and manufactured by a modified curing process. After drilling one hole with various diameters in the center of the samples respectively, the lay-ups were conducted on tension fracture and T-T fatigue test at different temperatures. From the parametric study we achieved the important results as follows. The cross-ply laminate possesses the higher ultimate strength, fatigue strength and longitudinal stiffness than those of the quasi-isotropic at the same temperature. Notch effect decays the laminate strength seriously, but changes the stiffness irregularly. As test temperature rising both strength and stiffness of lay-ups degrade significantly. Combining both effects of notch and temperature under severe environmental condition, it is found the cross-ply laminate possesses more resistance than that of the quasi-isotropic to cyclic loading. However, the quasi-isotropic laminate is more capable of sustaining the original strength than that of the cross-ply. Finally, the multiple regression analysis results showed that the hygrothermal environmental effects and cyclic loading were decoupled for APC-2 composite system. A semi-empirical model, reliably set up after the said programs, predicts conservative values, and should be adequate for use in preliminary designs. That is the main contribution in this study. Also, for the purposes of design and application, the predicted models efficiently treat experimental data instead of conventional curve-fitting methods.

Orientador: Douglas Soares Galvão / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-09T02:37:49Z (GMT). No. of bitstreams: 1 Autreto_PedroAlvesdaSilva_M.pdf: 14908796 bytes, checksum: 389f8f28e3d38fbfe32aeab511893f6e (MD5) Previous issue date: 2007 / Resumo: As melaninas constituem uma classe de pigmentos biológicos de destaque devido, sobretudo, a sua predominante presença nos tecidos dos mamíferos. Há fortes evidências que sugerem que a pigmentação por melanina tem por objetivo proteger a pele contra efeitos prejudiciais da radiação ultravioleta. Além deste papel de fotoproteção, outras funções biológicas são especuladas em razão da presença do pigmento em regiões não iluminadas do corpo como por exemplo no cérebro em que há uma aparente destruição preferencial das células que contém melanina quando ocorrem doenças como o mal de Parkinson. Apesar de décadas de investigações, nenhuma amostra de melanina foi estruturalmente bem caracterizada. Dentre os diversos obstáculos que são responsáveis pelo lento progresso que marca a pesquisa deste pigmento, o maior deles é que as melaninas naturais são altamente insolúveis e de presumido alto peso molecular. Pesquisas recentes desenvolvem sínteses alternativas para as melaninas utilizando outros solventes e demonstram que até 20 % da estrutura desta pode ser composta por água. Assim, neste trabalho investigamos, por métodos quânticos, a geometria e estrutura eletrônica das moléculas 5,6 indolquinona, suas formas reduzidas (semiquinona e hidroquinona) e 27 dímeros obtidos a partir destas, em seus estados neutros e iônicos ( ± 1 e ± 2), no vácuo e nos solventes DMF(dimetilformamida), DMSO (dimetilsulfóxido) e água. Verificamos como o solvente altera as propriedades eletrônicas e espectroscópicas destas estruturas e como este pode ser fundamental para a determinação de suas geometrias. Utilizamos dois modelos para simular o solvente: um modelo contínuo, COSMO (Conductor-like Screening Model) e um discreto, que considera explicitamente cada molécula do solvente e é baseado em simulações Monte Carlo. Notamos que o solvente altera a propriedade de aceitador de dois elétrons de diversas estruturas, fato até então não observado e de importante consequência biológica, visto as eumelaninas poderem ser base de um mecanismo de defesa celular contra radicais livres. Os picos dos espectros de absorção, de um modo geral, são deslocados para o vermelho e, em alguns casos, tem um alargamento. Isto poderia contribuir para a constrção da larga banda característica das eumelaninas. Diversos outros aspectos importantes, em excelente acordo com dados experimentais, são também apresentados ao se considerar o solvente. Um dos mais relevantes mostra que o solvente tem forte influência na geometria da molécula com o menor custo de dimerização, o que nos leva a concluir que esta pode ser de fato a semente de "nucleação" para a formação do polímero de melanina. / Abstract: Melanins belong to an important class of biological pigments due to its abundant presence in mamal tissues. There are strong evidences that suggest that the pigmentation due to melanin would protect the skin against the biochemical devastation induced by solar exposure. Besides the photo-protection feature, other biological functions have been speculated to melanin due to its presence in non-illuminated areas of the body and the apparent preferential destruction of melanin-containing cells in the substancia nigra of the brain in Parkinsonism. Unfortunately, in what concerns structural and chemical composition, no melanin sample has been fully and unambiguously characterized yet, despite the enormous amount of experimental work done so far. The main difficulty for that is that melanin is insoluble in most organic solvents and has high molecular weight. A new synthetic route for melanins, using organic solvents, has been recently achieved and it was demonstrated that about 20 % of the structure of the pigment is composed by water. In this work we have investigated using quantum methods the geometries and electronic structure of 5,6 indolquinone, their redox forms (semiquinone and hidroquinone) and 27 dimers associated, in their neutral and ionic states ( ± 1 e ± 2). The calculation were carried in vacuum and in the solvents dimethyl sulfoxide (DMSO), N,N-dimethyl formamide (DMF) and water. We study the effect of the solvent on the electronic and spectroscopic properties and its importance to determine eumelanin structure. Two models for solvents were used. The first was a continuum model, COSMO (Conductor-like Screening Model), and the second one (based on Monte Carlo simulations) explicitly considers each molecule of the solvent. The results showed that the solvents affected the electron accepton properties allowing the acceptance of two electrons. These aspects have been not been observed before from vacuum calculations and it is of important biological consequence because the melanins can be the base of mechanism of cellular defense against free radicals. The peaks of absorption spectra of the solvated structure are dislocated from red and broadened. This could contribute to the characteristic broad band of eumelanins. Many others important aspects are in better agreement with experimental data when solvent aspects are explicitly taken into account. One of most important results was the observation that solvent effects can alter the order of the lowest energy dimer configuration in relation to the structures in vacuum. This dimer was suggested to be the nucleation seed for the polymer formation. / Mestrado / Física Atômica e Molecular / Mestre em Física