Orientador: Hélio Aparecido Navarro / Banca: Vicente Luiz Scalon / Banca: Luben Cabezas Gomez / Resumo: No presente trabalho desenvolve-se um estudo de modelagem matemática e simulação numérica do escoamento bifásico gás-sólido em leito fluidizado borbulhante. Utiliza-se o modelo Euleriano de duas fases separadas formulando o tensor das tensões da fase sólida através da teoria cinética dos escoamentos granulares. As simulações numéricas são realizadas através do código fonte MFIX (Multiphase Flow with Interphase eXchanges) desenvolvido no NETL (National Energy Technology Laboratory). Os resultados de simulação numérica são avaliados por meio da análise da influência dos seguintes parâmetros: malha computacional e esquemas de discretização dos termos convectivos das equações de conservação. Com base nos estudos teóricos e resultados obtidos durante o trabalho conclui-se que esquemas de primeira, tais como FOUP são altamente difusivos, já os resultados obtidos utilizando o esquema de alta ordem, Superbee, produziu resultados de melhor qualidade para as malhas testadas neste trabalho. Além disso, os resultados mostraram-se bastante dependentes do tamanho da malha computacional. / Abstract: In the present work is described a mathematical model and numerical simulation of gas-solid two-phase flow in a bubbling fluidized bed. It is used the Eulerian gas-solid two-fluid model and the solid phase stress tensor is modeled considering the kinetic theory of granular flows. The numerical simulations were developed using the MFIX (Multiphase Flow with Interphase eXchanges) code developed in NETL (National Energy Technology Laboratory). The numerical diffusion is analyzed considering a single bubbling detachment and its movement process in a two-dimensional bubbling fluidized bed using the bubble shape as a metric for results description. The influence of computacional grid it is also analyzed. It is concluded that SuperBee scheme produces the better results and analysis about estimating uncertainty in grid refinement should be studied. / Mestre

O conjunto de funções de base gaussianas, o p-GCHF, foi gerado para os átomos Na, Al, Si, P, S e Cl pelo Método da Coordenada Geradora (MCG) através da expansão integral polinomial para discretizar (DIP) as equações de Griffin-Hill-Wheeler-Hartree-Fock (GHW-HF). A base p-GCHF, de qualidade 7Z, foi contraída por meio do programa Contract que opera segundo os preceitos de contração de Davidson. O processo de contração resultou em 9 funções do tipos e 7 funções p para os átomos de Na e Mg e de 9 funções s e 8 funções p para os átomos de Al, Si, P, S e Cl. Expoentes de polarização foram gerados através do programa Polarization em nível CISD para os átomos de H, B, C, N, O, F, Na, Mg, Al, Si, P, S e Cl. Foram necessários não mais do que 2p1d expoentes de polarização para compor a base p-GCHF para o átomo de H, 2d1f para os átomos da primeira fila e 3d2f, para os átomos da segunda fila da tabela periódica. Cálculos moleculares revelaram que a base p-GCHF é competitiva em energia com as bases cc-pVQZ e cc-pV5Z, entretanto apresentando custos computacionais bem menores que as mencionadas bases de Dunning. Análises das frequências vibracionais e das geometrias de otimização dos pontos estacionários, tanto mínimos quanto de estado de transição, também apontam similaridades entre o conjunto de base p-GCHF e a base cc-pVQZ, porém com diferenças de tempos de CPU que apontam a base gerada pelo MCG como computacionalmente vantajosa. Um conjunto de base capaz de descrever um dado sistema de maneira equivalente à célebres conjuntos de base da literatura, mas trazendo consigo o benefício da economia de tempo computacional é absolutamente oportuno principalmente àqueles que têm como objeto de estudo moléculas com um número considerável de átomos. / The gaussian basis sets p-GCHF was generated for a set of atoms from Na to Cl through the Generator Coordinate Method (GCM) based on a polynomial integral expansion to discretize the Griffin-Wheeler-Hartree-Fock equations. The p-GCHF is a 7z type basis sets and was contracted through the Contract program which works based on the Davidson\'s contraction model. The contraction process provided a set of 9s7p functions for Na and Mg atoms and 9s8p functions for Al, Si, P, S e Cl atoms. Polarizations exponents were acquired through the Polarization program at CISD level of theory for H, B, C, N, O, F, Na, Mg, Al, Si, P, S e Cl atoms. No more than 2p1d polarization exponents were necessary to compose the p-GCHF basis set for hydrogen atom, 2d1f for the first row of the periodic table and 3d2f for the second row one. Molecular calculations show that p-GCHF works like cc-pVQZ and cc-pV5Z basis sets but with less computational cost than the Dunning\'s ones. Vibrational frequency analysis and optimization geometry to the stationary points minimum as well as transition state, revealed similarities between p-GCHF and cc-pVQZ basis sets, but again with the GCM basis sets being computationally advantageous. A basis sets capable to describe a system like the main gaussian basis sets known in the literature but demanding less computational effort is very helpful above all for those who work with massive molecular systems.

A equação de Schrödinger possui solução exata para átomos monoeletrônicos, porém devido ao nível de complexidade das soluções para átomos polieletrônicos e moléculas houve a necessidade de métodos aproximados que descrevessem satisfatoriamente as propriedades de interesse. O Método da Coordenada Geradora Hartree-Fock (MCG-HF) é um método variacional que permitiu desenvolver conjuntos de base acurados para átomos, entretanto, utilizando apenas a discretização integral, os conjuntos de base requeriam um maior número de expoentes, deixando-os extensos. Barbosa e da Silva (2009) introduziram o conceito de discretização integral polinomial que diminuiu a quantidade de expoentes necessários para descrever adequadamente um átomo, gerando conjuntos de base menores. Os conjuntos de primitivas gerados pelo p-MCG-HF foram contraídos utilizando o método de contração geral para a qualidade 5Z e em seguida, polarizados, utilizando dois métodos de polarização, ou seja, a pinçada e otimizada, para descrever melhor propriedades químicas como ligação química, estados excitados, entre outros. As energias obtidas por esses métodos de polarização são semelhantes, porém o tempo computacional é menor para a polarização pinçada (na maioria dos casos). Ao comparar os resultados obtidos neste trabalho com aqueles da literatura, os resultados obtidos utilizando o p-MCG-HF são de alta qualidade e com a enorme vantagem de ter tempo computacionais muito reduzidos. Esse método já está sendo aplicado por este grupo de pesquisa para gerar conjunto base para átomos do 1º ao 2º períodos da tabela periódica e os metais de transição e têm demonstrado resultados satisfatórios. Então, no intuito de estudar todos os átomos da tabela periódica até o bário, os átomos Gálio, Germânio, Arsênio, Selênio, Bromo, Criptônio, Rubídio, Estrôncio, Índio, Estanho, Antimônio, Telúrio, Iodo, Xenônio, Césio e Bário serão o foco deste trabalho. / The Schrödinger equation has exact solution for monoelectronic atoms, but the high complexity for the exact solution for many electron systems, lead to the use of approximation methods that satisfactorily. The Hartree-Fock Generating Coordinate Method (MCG-HF) is a variational method that allows the development of accurate basis sets for atoms with many electrons. However, using only an integral discretization, the basis sets generated with the MCG-HF requires a larger number of exponentes. Barbosa and da Silva (2009) introduced the concept of integral polynomial discretization that reduced the amount of exponents required to properly describe an atom, generating smaller basis sets. The sets of primitives generated with p-MCG-HF were contracted using the general contraction method for 5Z quality and then polarized using two different polarization methods (pinched and optimized) to better describe chemical properties such as chemical bonding, excited states, etc. The energies obtained with these polarization methods are similar, but the computational cost is smaller for pinched polarization (in most cases). Comparing the results obtained in this work with those of the literature, the results obtained by using the p-MCG-HF have a high quality and a large advantage of having very reduced computational cost. This method is already being applied in ours research group to generate basis set for atoms of the 1st to 2nd period of the periodic table and the transition metals showing satisfactory results. In order to study all the atoms in the periodic table, the atoms Gallium, Germanium, Arsenic, Selenium, Bromine, Crypton, Rubidium, Strontium, Indium, Tin, Antimony, Tellurium, Iodine, Xenium, Cesium and Barium will be focused in this work.

Schwerpunkt dieser Arbeit ist die Untersuchung einer Klasse von Diskretisierungsmethoden für nichtlineare optimale Steuerungsprobleme mit gewöhnlichen Differentialgleichungen und Steuerungsbeschränkung sowie die Durchführung von numerischen Experimente. Die theoretischen Untersuchungen basieren aus einem gekoppeltes Parametrisierungs-Diskretisierungsschema aus stückweise polinomialen Ansatz für die Steuerung und einen Runge-Kutta-Verfahren zur Integration der Zustands-Differentialgleichung. Die Konvergenzordnung der Lösung wird unter Regularitätsbedingung und Optimalitätsbedingung 2.Ordnung ermittelt. Außerdem wird eine Möglichkeit zur numerischen Berechnung der Gradienten über internen numerischen Differentiation erläutert. Schließlich werden einige numerischen Resultate gegeben und die Abhängigkeiten zur den theoretischen Konvergenzresultate diskutiert. / The focal point of this work is the investigation of a class of discretization methods for nonlinear optimal control problems governed by ordinary differential equations with control restrictions, as well as the implementation of some numerical experiments. The theoretical investigations are based on a coupledparameterization-discretization pattern, a piecewise linear parameterization representation of the control, and the application of a Runge Kutta method for the integration of the differential state equation. The rate of convergence of the solution is obtained with the help of regularity conditions and the second order optimality conditions. Furthermore, we also present in this paper a possibility of the numerical computation of the gradients via numerical differentiation. Finally some numerical results are given and their relationship to the theoretical convergence results are discussed.

A afinidade eletrônica (AE) é uma importante propriedade de átomos e moléculas, sendo definida como a diferença de energia entre a espécie neutra e seu respectivo íon negativo. Uma vez que a AE é uma fração muito pequena da energia eletrônica total das espécies neutra e aniônica, é necessário que tais energias sejam determinadas com elevado grau de precisão. A receita utilizada para o cálculo teórico acurado da AE atômica e molecular baseia-se na escolha de um conjunto adequado de funções de base juntamente com o emprego de teorias com altos níveis de correlação eletrônica. Durante o cálculo, o mesmo conjunto de base é utilizado para descrever o elemento neutro e seu respectivo ânion. Geralmente, os conjuntos de base para descrever propriedades de ânions possuem seus expoentes otimizados em ambiente neutro, e sua difusibilidade é conferida pela adição de funções difusas para cada valor de momento angular, l. A ideia deste trabalho está no desenvolvimento de conjuntos de base otimizados exclusivamente em ambiente aniônico para cálculos precisos de afinidade eletrônica. Deste modo, foram escolhidos os átomos para serem estudados: B, C, O e F. Os conjuntos de base foram gerados pelo Método da Coordenada Geradora Hartree-Fock, empregando a técnica da Discretização Integral Polinomial para a solução das integrais do problema. Os conjuntos de base obtidos são compostos por (18s13p) primitivas que foram contraídos para [7s6p] via esquema de contração geral proposto por Raffenetti. Os conjuntos contraídos foram polarizados para 4d3f2g e 4d3f2g1h, sendo os expoentes otimizados em ambiente CISD através do método SIMPLEX. Avaliaram-se as funções de base no cálculo de afinidades eletrônicas, tendo seus resultados comparados aos obtidos utilizando as bases aug-cc-pVQZ e aug-cc-pV5Z. A análise dos resultados demonstrou que os conjuntos de base difusos, gerados neste trabalho, reproduzem de maneira satisfatória as afinidades eletrônicas em relação ao valor experimental. Os conjuntos difusos polarizados para 4d3f2g1h apresentaram eficiência superior aos conjuntos aug-cc-pVQZ e, em alguns casos, aos conjuntos aug-cc-pV5Z que são consideravelmente maiores. / The electron affinity (EA) is an important property of atoms and molecules defined as the energy difference between the neutral species and its negative ion. Since the EA is a very small fraction of the total electronic energy of anionic and neutral species, one must determine these energies with high accuracy. The recipe used to calculate accurate atomic and molecular EAs is based on the choice of an adequate basis set and the use of high level of electron correlation calculations. In the computation of EAs, the same basis set is used to describe both neutral and negatively charged species. In general, the basis sets designed to describe anionic properties have their exponents optimized in neutral environment, and its diffuseness is acquired through the addition of diffuse functions for each angular momentum. The main idea of this work is to develop basis sets optimized exclusively in anionic environment that would be applied in accurate calculations of electron affinity. Thus, here follows the chosen atoms to be studied: B, C, O and F. The basis sets were generated by the Generator Coordinate Hartree-Fock Method through the Polynomial Integral Discretization Method. Basis sets were obtained containing (18s13p) primitives that were contracted to [7s6p] via Raffenetti\'s general contraction scheme. The contracted basis sets were polarized to 4d3f2g and 4d3f2g1h, and the exponents of polarization were optimized in a CISD environment through the Simplex algorithm. The basis sets quality was evaluated through the calculation of the electron affinities. The results were compared to those obtained by using the aug-cc-pVQZ and aug-cc-pV5Z basis-sets. The calculation showed that our diffuse basis sets reproduce satisfactorily the electron affinities when compared to the experimental data. The diffuse basis sets polarized to 4d3f2g1h showed to be more efficient than the aug-cc-pVQZ basis sets and in some cases also better than the aug-cc-pV5Z basis sets that are considerably larger.

Cette thèse est motivée par un problème aéronautique: le ballottement du carburantdans des réservoirs d’ailes d’avion très flexibles. Les vibrations induites par le couplagedu fluide avec la structure peuvent conduire à des problèmes tels que l’inconfort des passagers,une manoeuvrabilité réduite, voire même provoquer un comportement instable. Cette thèse apour objectif de développer de nouveaux modèles d’interaction fluide-structure, en mettant enoeuvre la théorie des systèmes Hamiltoniens à ports d’interaction (pHs). Le formalisme pHsfournit d’une part un cadre unifié pour la description des systèmes multi-physiques complexeset d’autre part une approche modulaire pour l’interconnexion des sous-systèmes grâce auxports d’interaction. Cette thèse s’intéresse aussi à la conception de contrôleurs à partir desmodèles pHs. Des modèles pHs sont proposés pour les équations de ballottement du liquide en partantdes équations de Saint Venant en 1D et 2D. L’originalité du travail est de donner des modèlespHs pour le ballottement dans des réservoirs en mouvement. Les ports d’interaction sont utiliséspour coupler la dynamique du ballottement à la dynamique d’une poutre contrôlée par desactionneurs piézo-électriques, celle-ci étant préalablement modélisée sous forme pHs. Aprèsl’écriture des équations aux dérivées partielles dans le formalisme pHs, une approximation endimension finie est obtenue en utilisant une méthode pseudo-spectrale géométrique qui conservela structure pHs du modèle continu au niveau discret. La thèse propose plusieurs extensionsde la méthode pseudo-spectrale géométrique, permettant la discrétisation des systèmesavec des opérateurs différentiels du second ordre d’une part et avec un opérateur d’entrée nonborné d’autre part. Des essais expérimentaux ont été effectués sur une structure constituéed’une poutre liée à un réservoir afin d’assurer la validité du modèle pHs du ballottementdu liquide couplé à la poutre flexible, et de valider la méthode pseudo-spectrale de semi-discrétisation.Le modèle pHs a finalement été utilisé pour concevoir un contrôleur basé surla passivité pour réduire les vibrations du système couplé. / This thesis is motivated by an aeronautical issue: the fuel sloshing in tanksof very flexible wings. The vibrations due to these coupled phenomena can lead to problemslike reduced passenger comfort and maneuverability, and even unstable behavior. Thisthesis aims at developing new models of fluid-structure interaction based on the theory ofport-Hamiltonian systems (pHs). The pHs formalism provides a unified framework for thedescription of complex multi-physics systems and a modular approach for the coupling ofsubsystems thanks to interconnection ports. Furthermore, the design of controllers using pHsmodels is also addressed. PHs models are proposed for the equations of liquid sloshing based on 1D and 2D SaintVenant equations and for the equations of structural dynamics. The originality of the workis to give pHs models of sloshing in moving containers. The interconnection ports are used tocouple the sloshing dynamics to the structural dynamics of a beam controlled by piezoelectricactuators. After writing the partial differential equations of the coupled system using thepHs formalism, a finite-dimensional approximation is obtained by using a geometric pseudospectralmethod that preserves the pHs structure of the infinite-dimensional model at thediscrete level. The thesis proposes several extensions of the geometric pseudo-spectral method,allowing the discretization of systems with second-order differential operators and with anunbounded input operator. Experimental tests on a structure made of a beam connected to atank were carried out to validate both the pHs model of liquid sloshing in moving containersand the pseudo-spectral semi-discretization method. The pHs model was finally used to designa passivity-based controller for reducing the vibrations of the coupled system.

Ce travail de thèse a pour but d'étudier des écoulements non stationnaires de fluides incompressibles Newtoniens et non isothermes. Le problème est décrit par les lois de conservation de la masse, de la quantité de mouvement et de l'énergie. Nous nous intéressons au couplage entre le système de Navier-Stokes et l’équation de la chaleur hyperbolique (le résultat de la combinaison entre la loi de conservation d'énergie et la loi de Cattaneo). Cette dernière est une modification de la loi de Fourier utilisée habituellement, elle permet de surmonter « le paradoxe de la chaleur » et d'obtenir une description plus précise de la propagation de la chaleur. Le système couplé est un problème hyperbolique-parabolique dont la viscosité dépend de la température, alors que la capacité thermique et le terme de dissipation dépendent de la vitesse. Afin d’obtenir un résultat d'existence de solutions du problème couplé, nous démontrons d'abord l'existence et l'unicité de la solution du problème hyperbolique puis nous introduisons une discrétisation en temps et nous étudions la convergence des solutions approchées vers celles du problème original. Dans un deuxième temps nous étudions l'existence et l'unicité de la solution du système de Navier-Stokes muni des conditions aux limites de type Tresca puis de type Coulomb en dimension 2 et 3. Dans le chapitre 3, nous proposons une discrétisation en temps du problème d'écoulement dans le cas de la condition au limite de type Tresca et nous établissons la convergence des solutions approchées. Le dernier chapitre de ce mémoire est consacré à l'étude du problème couplé dans le cas de conditions aux limites de type Tresca. L'existence d'une solution est obtenue par un argument théorique de point fixe en dimension 2 et également par une méthode de discrétisation en temps qui conduit à résoudre sur chaque sous intervalle de temps un problème découplé pour la vitesse et la pression d'une part et la température d'autre part / The main objective of this thesis is to study nonstationary flows of incompressible Newtonian and non isothermal fluids. The problem is described by the laws of conservation of mass, momentum and energy. We consider the coupling between the Navier-Stokes system and the hyperbolic heat equation (the result of combination between the law of conservation of energy and the Cattaneo’s law). This one is a modification of the commonly used Fourier's law, it overcomes "the heat paradox" and gives a more accurate description of heat propagation. The coupled system is an hyperbolic-parabolic problem where the viscosity depends on the temperature but the thermal capacity and the dissipative term depend on the velocity. To obtain an existence result for the coupled system, we first prove the existence and uniqueness of the solution of the hyperbolic problem then we introduce a time discretization and we study the convergence of the approximate solutions to those of the original problem. In the second chapter, we study the existence and uniqueness of the solution of Navier-Stokes system with Tresca or Coulomb boundary conditions in dimension 2 and 3. In the third chapter, we propose a time discretization of the flow problem in the case of Tresca boundary conditions and we establish the convergence of the approximate solutions. The last chapter is devoted to the study of the coupled problem in the case of Tresca free boundary conditions. The existence of a solution is obtained by a theoretical argument (fixed-point theorem) in dimension 2 and also by a method of time discretization leading, on each time subinterval, to a decoupled problem for the velocity and pressure of a hand and the temperature of the other hand

O conjunto de funções de base gaussianas, o p-GCHF, foi gerado para os átomos Na, Al, Si, P, S e Cl pelo Método da Coordenada Geradora (MCG) através da expansão integral polinomial para discretizar (DIP) as equações de Griffin-Hill-Wheeler-Hartree-Fock (GHW-HF). A base p-GCHF, de qualidade 7Z, foi contraída por meio do programa Contract que opera segundo os preceitos de contração de Davidson. O processo de contração resultou em 9 funções do tipos e 7 funções p para os átomos de Na e Mg e de 9 funções s e 8 funções p para os átomos de Al, Si, P, S e Cl. Expoentes de polarização foram gerados através do programa Polarization em nível CISD para os átomos de H, B, C, N, O, F, Na, Mg, Al, Si, P, S e Cl. Foram necessários não mais do que 2p1d expoentes de polarização para compor a base p-GCHF para o átomo de H, 2d1f para os átomos da primeira fila e 3d2f, para os átomos da segunda fila da tabela periódica. Cálculos moleculares revelaram que a base p-GCHF é competitiva em energia com as bases cc-pVQZ e cc-pV5Z, entretanto apresentando custos computacionais bem menores que as mencionadas bases de Dunning. Análises das frequências vibracionais e das geometrias de otimização dos pontos estacionários, tanto mínimos quanto de estado de transição, também apontam similaridades entre o conjunto de base p-GCHF e a base cc-pVQZ, porém com diferenças de tempos de CPU que apontam a base gerada pelo MCG como computacionalmente vantajosa. Um conjunto de base capaz de descrever um dado sistema de maneira equivalente à célebres conjuntos de base da literatura, mas trazendo consigo o benefício da economia de tempo computacional é absolutamente oportuno principalmente àqueles que têm como objeto de estudo moléculas com um número considerável de átomos. / The gaussian basis sets p-GCHF was generated for a set of atoms from Na to Cl through the Generator Coordinate Method (GCM) based on a polynomial integral expansion to discretize the Griffin-Wheeler-Hartree-Fock equations. The p-GCHF is a 7z type basis sets and was contracted through the Contract program which works based on the Davidson\'s contraction model. The contraction process provided a set of 9s7p functions for Na and Mg atoms and 9s8p functions for Al, Si, P, S e Cl atoms. Polarizations exponents were acquired through the Polarization program at CISD level of theory for H, B, C, N, O, F, Na, Mg, Al, Si, P, S e Cl atoms. No more than 2p1d polarization exponents were necessary to compose the p-GCHF basis set for hydrogen atom, 2d1f for the first row of the periodic table and 3d2f for the second row one. Molecular calculations show that p-GCHF works like cc-pVQZ and cc-pV5Z basis sets but with less computational cost than the Dunning\'s ones. Vibrational frequency analysis and optimization geometry to the stationary points minimum as well as transition state, revealed similarities between p-GCHF and cc-pVQZ basis sets, but again with the GCM basis sets being computationally advantageous. A basis sets capable to describe a system like the main gaussian basis sets known in the literature but demanding less computational effort is very helpful above all for those who work with massive molecular systems.

On s'interesse aux problèmes elliptiques avec coéficients variables à travers des interfaces intérieures. La solution et ses dérivées normales peuvent subir des variations significatives à travers les frontières intérieures. On présente une méthode compacte aux différences finies sur des maillages adaptés de type octree conçues pour une résolution en parallèle. L'idée principale est de minimiser l'erreur de troncature sur la discretisation locale, en fonction de la configuration du maillage, en rapprochant une convergence à l'ordre deux. On montrera des cas 2D et 3D des résultat liés à des applications concrètes. / We consider problems governed by a linear elliptic equation with varying coéficients across internal interfaces. The solution and its normal derivative can undergo significant variations through these internal boundaries. We present a compact finite-difference scheme on a tree-based adaptive grid that can be efficiently solved using a natively parallel data structure. The main idea is to optimize the truncation error of the discretization scheme as a function of the local grid configuration to achieve second order accuracy. Numerical illustrations relevant for actual applications are presented in two and three-dimensional configurations.

This thesis focuses on optimization on a generic objective function based on reflected Brownian motion (RBM). We investigate in several approaches including the partial differential equation approach where we write our objective function in terms of a Hamilton-Jacobi-Bellman equation using the dynamic programming principle and the gradient descent approach where we use two different gradient estimators. We provide extensive numerical results with the gradient descent approach and we discuss the difficulties and future study opportunities for this problem.