Le sujet de cette thèse est à l’interface entre l’étude de composés à base de nitrure et des structures émergeantes formées par les matériaux bidimensionnels (2D) d’épaisseur atomique. Ce travail se consacre sur l’hybridation des propriétés électriques et optiques des semi-conducteurs à larges bandes interdites que sont les nitrures et des performances mécaniques, électriques et optiques des matériaux lamellaires, récemment isolé à l’échelle d’un plan atomique, qui sont aujourd’hui considérées avec attention aux regards de futures applications et d’études plus fondamentales. En particulier, une étude des propriétés électroniques, optiques et structurelles d’hétérostructures composées de plusieurs matériaux lamellaires et d’interfaces entre matériaux 2D et 3D a été réalisé par des moyens de microscopie et de spectroscopie tel que la spectroscopie Raman, de photoémission et d’absorption.Ce manuscrit traite dans un premier temps des propriétés structurelles et électroniques du nitrure de bore hexagonal (h-BN), matériau isolant aux propriétés optiques exotiques et essentiel dans la future intégration de ce type de matériaux 2D permettant de mettre en valeur leurs propriétés intrinsèques.En utilisant le graphène comme substrat les problèmes de mesures par photoémission rencontrés pour des matériaux isolant ont pu être surmonté dans le cas du h-BN et une étude des défauts structurels a pu être réalisée. Par conséquent, les premières mesures directes de la structure de bande électronique de plusieurs plans de h-BN sont présentées dans ce manuscrit.Dans un second temps, une approche d’intégration de ces matériaux 2D différente a été étudiée en formant une hétérostructure 2D/3D. L’interface de cette hétérojonction, composée d’un plan de disulfure de molybdène (MoS2) de dopage intrinsèque N associé à 300 nm de nitrure de gallium (GaN) intentionnellement dopé P à l’aide de magnésium, a été caractérisée. Un transfert de charge du GaN vers le MoS2 a pu être identifié suggérant un contrôle des propriétés électroniques de ce type de structure par le choix de matériaux.Ces travaux ont permis de révéler les diagrammes de bandes électroniques complet des structures étudiées a pu être obtenu permettant une meilleur compréhension de ces systèmes émergeants. / This thesis is at the interface between the study of nitride based compounds and the emerging structures formed by atomically thin bi-dimensional (2D) materials. This work consists in the study of the hybridization of the properties of large band gap materials from the nitride family and the mechanical, electronic and optical performances of layered materials, recently isolated at the monolayer level, highly considered due to their possible applications in electronics devices and fundamental research. In particular, a study of electronics and structural properties of stacked layered materials and 2D/3D interfaces have been realised with microscopic and spectroscopic means such as Raman, photoemission and absorption spectroscopy.This work is firstly focused on the structural and electronic properties of hexagonal boron nitride (h-BN), insulating layered material with exotic optical properties, essential in in the purpose of integrating these 2D materials with disclosed performances. Using graphene as an ideal substrate in order to enable the measure of insulating h-BN during photoemission experiments, a study of structural defects has been realized. Consequently, the first direct observation of multilayer h-BN band structure is presented in this manuscript. On the other hand, a different approach consisting on integrating bi-dimensional materials directly on functional bulk materials has been studied. This 2D/3D heterostructure composed of naturally N-doped molybdenum disulphide and intentionally P-doped gallium nitride using magnesium has been characterised. A charge transfer from GaN to MoS2 has been observed suggesting a fine-tuning of the electronic properties of such structure by the choice of materials.In this work present the full band alignment diagrams of the studied structure allowing a better understanding of these emerging systems.

Orientador: Aguinaldo Robinson de Souza / Banca: Americo Sheitiro Tabata / Banca: Nelson Henrique Morgon / O Programa de Pós Graduação em Ciência e Tecnologia de Materiais, PosMat, tem caráter institucional e integra as atividades de pesquisa em materiais de diversos campi / Resumo: A teoria cinética dos gases tem como primeira aproximação o comportamento observado considerando o gás como tendo um comportamento ideal, isto é, pode ser modelado através da lei do gás ideal. As equações de estado conhecidas, como a equação do gás ideal e de van der Waals descrevem, dentro das aproximações do modelo, situações bastante diversas. Neste trabalho iremos utilizar a lei dos gases ideais, ou mais especificamente a implementação da Equação de van der Waals para o entendimento do fenômeno de colisões que entre átomos e moléculas / Abstract: The kinetic theory of gases has a a first approximation the observed behavior considering the gas to have an ideal behavior, ie it can be modeled by the ideal bas law. The equations of state known as the ideal gas equation and Van der Waals describe, within the approximations of the model, very different situations. In this paper we use the ideal gas law, or more specifically the implementation of the Vann der Waals equation for understandign the phenomenon of collisions between atoms and molecules / Mestre

Diese Arbeit setzt sich mit der Messung und Modellierung von Haftkräften auf rauen Oberflächen auseinander, wobei Filtermaterialien aus dem Sonderforschungsbereich 920 mittels Rasterkraftmikroskopie-Methoden untersucht wurden. Durch eine Vielzahl an Haftkraftmessungen konnte gezeigt werden, dass für schlecht benetzende Oberflächen die Rauheit zur Erhöhung der attraktiven Kräfte führt, da vermehrt mit Kapillarwechselwirkungen zu rechnen ist. Aus diesem Grund erfolgte eine Charakterisierung der Oberflächenmorphologien der Filtermaterialproben und eine kritische Bewertung von Modellen, welche aus Kontaktwinkeldaten die Oberflächenenergien ermitteln. Im Modellierungsteil der Arbeit wurden gängige van der Waals-Kraftmodelle mit Berücksichtigung von Retardationseffekten untersucht. Weiterhin wurden AFM-Scans mit dem Schichtmodell von Dagastine verbunden sowie für die Bewertung von Kapillarkraftmodellen verwendet.:Abbildungsverzeichnis Tabellenverzeichnis 1 Einleitung 2 Stand der Technik 2.1 Reinigung von Metallschmelzen 2.1.1 Stellung des Sonderforschungsbereichs 920 innerhalb der Thematik der Metallschmelzereinigung 2.1.2 Inklusionen in Metallschmelzen - Schmelzprozess, relevante Einschlusstypen und Problematik verunreinigter Gussprodukte 2.1.3 Möglichkeiten der Metallschmelzereinigung 2.1.4 Metallschmelzefiltration 2.2 Rasterkraftmikroskopie 2.2.1 Funktionsweise, Kraftspektroskopie und Imaging 2.2.2 Colloidal Probe Technik 2.3 Benetzung und deren Phänomene 2.3.1 Ansätze zur Quantifizierung von Benetzungsgrößen 2.3.2 Diskussion bezüglich der Oberflächenenergiemodelle 2.3.3 Realsystem: Benetzungsphänomene bei Metallschmelzen auf Keramiken am Beispiel Aluminium 2.4 Haftkräfte und deren Berechnung 2.4.1 DLVO-Kräfte: van der Waals-Wechselwirkungen 2.4.2 nonDLVO-Kräfte 2.4.3 Nanoblasen und Kapillarkräfte 2.4.4 Haftkräfte unter erhöhten Temperaturen, Sinterung 2.4.5 Haftkräfte auf rauen Oberflächen 2.4.6 Kontaktmechanik 2.5 Genutztes Modellsystem, Abgrenzung der Arbeit 3 Material und Methoden 3.1 Material 3.1.1 Substrate 3.1.2 Partikel 3.1.3 Modellschmelze Wasser, Flüssigkeiten für die Kontaktwinkelmessung 3.2 Methoden 3.2.1 Kontaktwinkelmessgerät G10 3.2.2 Rasterkraftmikroskope XE-100 und UHV750 3.2.3 MatLAB-Skripte 3.2.4 Silanisierung 3.3 Vorbetrachtungen 3.3.1 Berechnung der Hamaker-Konstanten der untersuchten Stoffsysteme 3.3.2 Bedeutung eines einheitlichen Protokolls bei AFM- und KWMessungen 4 Auswertung 4.1 Charakterisierung der untersuchten Oberflächen bezüglich ihrer Rauheit mithilfe von AFM-Scans 4.1.1 Kontaktmechanik und sinnvolle Wahl der Scan-Größen sowie Lateral-Auflösung 4.1.2 Höhenprofile (z-Werte) der Filtermaterialien 4.1.3 Rauheitskenngrößen der AFM-Scans 4.1.4 Zusammenfassung 4.2 Kontaktwinkelmessungen und Oberflächenenergieverteilungen 4.2.1 Kontaktwinkelmessungen auf den Filtermaterialien 4.2.2 Oberflächenenergie - Komponentenansätze 4.2.3 Oberflächenenergie - Equation of State 4.2.4 Abschätzen der Hamaker-Konstanten aus der Oberflächenenergie des Feststoffs 4.2.5 Zusammenfassung 4.3 Ergebnisse Kraftspektroskopie 4.3.1 Experimentelle Ergebnisse - Einflussfaktoren Benetzbarkeit, Rauheit und Gasübersättigung 4.3.2 Sondergeometrien 4.3.3 Nachbetrachtung zu den Ergebnissen des Modellsystems 4.3.4 HT-Messungen mit dem Rasterkraftmikroskop 4.3.5 Zusammenfassung 5 Modellierung 5.1 Berücksichtigung von Retardation bei gängigen van der Waals- Kraftmodellen auf rauen Oberflächen in der Mechanischen Verfahrenstechnik 5.2 Van der Waals-Kraft-Modelle für raue Oberflächen zur Beschreibung der experimentellen Daten 5.3 Dagastines Modell in Kombination mit dem Cooper-Ansatz 5.4 Kapillarkräfte durch Nanoblasen auf rauen Oberflächen 5.4.1 Zusammenfassung 6 Zusammenfassung und Ausblick 6.1 Zusammenfassung 6.2 Ausblick 7 Anhang 7.1 Ergänzungen zum Kapitel Stand der Technik 7.2 Ergänzungen zum Kapitel Material und Methoden 7.3 Ergänzungen zum Kapitel Auswertung: Rauheit 7.4 Ergänzungen zum Kapitel Auswertung: Kontaktwinkelmessungen und Oberflächenenergien 7.5 Ergänzungen zum Kapitel Auswertung: Literatur- und Messdaten 7.6 Ergänzungen zum Kapitel Auswertung: Modellierung Literaturverzeichnis

This thesis supplies a contribution to the understanding of the interaction between carboncarbon surfaces, atoms with carbon-surfaces, and atoms with metallic surfaces. It is well established that the surface-surface and atom-surface interactions are interesting, important and challenging for reasons that vary from industrial interest up to the academic necessity of understanding it deeply. Currently, there are many measurements and simulations for the geometric and electronic properties of Graphite, these differ by more than 40%. This implies that our understanding of the nature of this material is quite poor. The interaction between small transition-metals clusters with a Graphene sheet is another example where our knowledge is very limited. There are many theoretical studies in the literature that describe the interaction between these clusters with a Graphene sheet, but they agree and disagree on many points, which calls for systematic study of this issue. In this thesis we will focus our efforts on studying the surface-surface and atom/clusters-surface interactions. This thesis is split into three projects. The first aims to contribute to the understanding of the interlayer interactions of the bulk Graphite. In the second, we intend to shed some light on comprehending the interaction of an adatom with a Graphene sheet. Both of these projects, are studied within DFT framework with the inclusion of the van der Waals (vdW) corrections. In the Graphite project, we found that the electronic and geometric properties depend on the vdW correction employed in the calculation. In the adatom supported on Graphene project, we combined a modified Anderson-Newns model to describe the coupling between the adatom with Graphene. In addition, we found the existence of competition between quantum and classical forces, which determine the type of site in which the adatom prefers to adsorb. The last project is a dynamical study of an atom that impinges upon a metallic surface. In this project, we focus on the calculation of the sticking coefficient, a measure of the amount of nuclear density attached to the metal surface after collision. At this time the project is not one 100% ready, but our preliminary results indicates that, a small part of the nuclear density stays stuck on the metal. / Esta tese ajuda a entender as interações entre duas superfícies de carbono. A natureza da interação de átomos ou aglomerados atômicos adsorvidos sobre uma superfície de carbono. Além disso, visa esclarecer a dinâmica de um átomo sendo adsorvido sobre uma superfície metálica. As interações superfície-superfície e átomos-superfícies são importantes por razões que variam desde o interesse industrial até a necessidade acadêmica para compreendê-la profundamente. Entendê-las ainda é um desafio. Diversos trabalhos apresentam medidas experimentais e simulações para as propriedades geométricas e eletrônicas do grafite. Tais medidas diferem em mais ide 40% umas da outra. Isso mostra que nossa compreensão sobre a natureza desse material ainda é bastante pobre. A interação entre pequenos grupos de metais de transição com uma folha de grapheno é outro exemplo em que nosso conhecimento é limitado. Existem muitos estudos teóricos na literatura que descrevem a interação desse tipo de aglomerado com uma folha de grafeno, porém há numerosas discordâncias. Tais controvérsias parecem suplicar por um estudo sistemático. Nesta tese focamos nossos estudos nas interações superfície-superfície e de átomos ou aglomerados atômicos com superfícies de carbono e de um metal. A tese foi dividida em três projetos. O primeiro visa compreender melhor a interação entre as camadas do grafite. No segundo, pretendemos lançar alguma luz no entendimento da interação de átomos e aglomerados atômicos com uma folha de grafeno. Esses dois projetos, são estudados à luz da Teoria do Funcional da Densidade com a inclusão das correções van der Waals (vdW). No Projecto sobre o grafite, mostramos que as propriedades eletrônicas e geométricas dependem do tipo de correção de vdW empregada no cálculo. No projeto sobre átomos e aglomerados atômicos adsorvidos no grapheno, combinamos um modelo modificado de Anderson-Newns para descrever o acoplamento entre um átomo adsorvido e o grafeno. Além disso, encontramos uma competição entre forças quânticas e clássicas, a qual determina o tipo de sítio no qual o átomo prefere ser adsorvido. O último projeto é um estudo dinâmico de um átomo colidindo contra uma superfície metálica. Nesse projeto o foco é posto no cálculo do coeficiente de aderência, o qual mede a taxa de densidade nuclear presa na superfície metálica após a colisão. Resultados preliminares indicam que, uma pequena parte da densidade nuclear permanece aderida ao metal depois da colisão.

As proteínas são moléculas que desempenham funções essenciais para a vida. Para entender a função de uma proteína é preciso conhecer sua estrutura tridimensional. No entanto, encontrar a estrutura da proteína pode ser um processo caro e demorado, exigindo profissionais altamente qualificados. Neste sentido, métodos computacionais têm sido investigados buscando predizer a estrutura de uma proteína a partir de uma sequência de aminoácidos. Em geral, tais métodos computacionais utilizam conhecimentos de estruturas de proteínas já determinadas por métodos experimentais, para tentar predizer proteínas com estrutura desconhecida. Embora métodos computacionais como, por exemplo, o Rosetta, I-Tasser e Quark tenham apresentado sucesso em suas predições, são apenas capazes de produzir estruturas significativamente semelhantes às já determinadas experimentalmente. Com isso, por utilizarem conhecimento a priori de outras estruturas pode haver certa tendência em suas predições. Buscando elaborar um algoritmo eficiente para Predição de Estruturas de Proteínas livre de tendência foi desenvolvido um Algoritmo de Estimação de Distribuição (EDA) específico para esse problema, com modelagens full-atom e algoritmos ab initio. O fato do algoritmo proposto ser ab initio é mais interessante para aplicação envolvendo proteínas com baixa similaridade, com relação às estruturas já conhecidas. Três tipos de modelos probabilísticos foram desenvolvidos: univariado, bivariado e hierárquico. O univariado trata o aspecto de multi-modalidade de uma variável, o bivariado trata os ângulos diedrais (Φ Ψ) de um mesmo aminoácido como variáveis correlacionadas. O hierárquico divide o problema em subproblemas e tenta tratá-los separadamente. Os resultados desta pesquisa mostraram que é possível obter melhores resultados quando considerado a relação bivariada (Φ Ψ). O hierárquico também mostrou melhorias nos resultados obtidos, principalmente para proteínas com mais de 50 resíduos. Além disso, foi realiza uma comparação com algumas heurísticas da literatura, como: Busca Aleatória, Monte Carlo, Algoritmo Genético e Evolução Diferencial. Os resultados mostraram que mesmo uma metaheurística pouco eficiente, como a Busca Aleatória, pode encontrar a solução correta, porém utilizando muito conhecimento a priori (predição que pode ser tendenciosa). Por outro lado, o algoritmo proposto neste trabalho foi capaz de obter a estrutura da proteína esperada sem utilizar conhecimento a priori, caracterizando uma predição puramente ab initio (livre de tendência). / Proteins are molecules that perform critical roles in the living organism and they are essential for their lifes. To understand the function of a protein, its 3D structure should be known. However, to find the protein structure is an expensive and a time-consuming task, requiring highly skilled professionals. Aiming to overcome such a limitation, computational methods for Protein Structure Prediction (PSP) have been investigated, in order to predict the protein structure from its amino acid sequence. Most of computational methods require knowledge from already determined structures from experimental methods in order to predict an unknown protein. Although computational methods such as Rosetta, I-Tasser and Quark have showed success in their predictions, they are only capable to predict quite similar structures to already known proteins obtained experimentally. The use of such a prior knowledge in the predictions of Rosetta, I-Tasser and Quark may lead to biased predictions. In order to develop a computational algorithm for PSP free of bias, we developed an Estimation of Distribution Algorithm applied to PSP with full-atom and ab initio model. A computational algorithm with ab initio model is mainly interesting when dealing with proteins with low similarity with the known proteins. In this work, we developed an Estimation of Distribution Algorithm with three probabilistic models: univariate, bivariate and hierarchical. The univariate deals with multi-modality of the distribution of the data of a single variable. The bivariate treats the dihedral angles (Proteins are molecules that perform critical roles in the living organism and they are essential for their lifes. To understand the function of a protein, its 3D structure should be known. However, to find the protein structure is an expensive and a time-consuming task, requiring highly skilled professionals. Aiming to overcome such a limitation, computational methods for Protein Structure Prediction (PSP) have been investigated, in order to predict the protein structure from its amino acid sequence. Most of computational methods require knowledge from already determined structures from experimental methods in order to predict an unknown protein. Although computational methods such as Rosetta, I-Tasser and Quark have showed success in their predictions, they are only capable to predict quite similar structures to already known proteins obtained experimentally. The use of such a prior knowledge in the predictions of Rosetta, I-Tasser and Quark may lead to biased predictions. In order to develop a computational algorithm for PSP free of bias, we developed an Estimation of Distribution Algorithm applied to PSP with full-atom and ab initio model. A computational algorithm with ab initio model is mainly interesting when dealing with proteins with low similarity with the known proteins. In this work, we developed an Estimation of Distribution Algorithm with three probabilistic models: univariate, bivariate and hierarchical. The univariate deals with multi-modality of the distribution of the data of a single variable. The bivariate treats the dihedral angles (Φ Ψ) within an amino acid as correlated variables. The hierarchical approach splits the original problem into subproblems and attempts to treat these problems in a separated manner. The experiments show that, indeed, it is possible to achieve better results when modeling the correlation (Φ Ψ). The hierarchical model also showed that is possible to improve the quality of results, mainly for proteins above 50 residues. Besides, we compared our proposed techniques among other metaheuristics from literatures such as: Random Walk, Monte Carlo, Genetic Algorithm and Differential Evolution. The results show that even a less efficient metaheuristic such as Random Walk managed to find the correct structure, however using many prior knowledge (prediction that may be biased). On the other hand, our proposed EDA for PSP was able to find the correct structure with no prior knowledge at all, so we can call this prediction as pure ab initio (biased-free).

This thesis supplies a contribution to the understanding of the interaction between carboncarbon surfaces, atoms with carbon-surfaces, and atoms with metallic surfaces. It is well established that the surface-surface and atom-surface interactions are interesting, important and challenging for reasons that vary from industrial interest up to the academic necessity of understanding it deeply. Currently, there are many measurements and simulations for the geometric and electronic properties of Graphite, these differ by more than 40%. This implies that our understanding of the nature of this material is quite poor. The interaction between small transition-metals clusters with a Graphene sheet is another example where our knowledge is very limited. There are many theoretical studies in the literature that describe the interaction between these clusters with a Graphene sheet, but they agree and disagree on many points, which calls for systematic study of this issue. In this thesis we will focus our efforts on studying the surface-surface and atom/clusters-surface interactions. This thesis is split into three projects. The first aims to contribute to the understanding of the interlayer interactions of the bulk Graphite. In the second, we intend to shed some light on comprehending the interaction of an adatom with a Graphene sheet. Both of these projects, are studied within DFT framework with the inclusion of the van der Waals (vdW) corrections. In the Graphite project, we found that the electronic and geometric properties depend on the vdW correction employed in the calculation. In the adatom supported on Graphene project, we combined a modified Anderson-Newns model to describe the coupling between the adatom with Graphene. In addition, we found the existence of competition between quantum and classical forces, which determine the type of site in which the adatom prefers to adsorb. The last project is a dynamical study of an atom that impinges upon a metallic surface. In this project, we focus on the calculation of the sticking coefficient, a measure of the amount of nuclear density attached to the metal surface after collision. At this time the project is not one 100% ready, but our preliminary results indicates that, a small part of the nuclear density stays stuck on the metal. / Esta tese ajuda a entender as interações entre duas superfícies de carbono. A natureza da interação de átomos ou aglomerados atômicos adsorvidos sobre uma superfície de carbono. Além disso, visa esclarecer a dinâmica de um átomo sendo adsorvido sobre uma superfície metálica. As interações superfície-superfície e átomos-superfícies são importantes por razões que variam desde o interesse industrial até a necessidade acadêmica para compreendê-la profundamente. Entendê-las ainda é um desafio. Diversos trabalhos apresentam medidas experimentais e simulações para as propriedades geométricas e eletrônicas do grafite. Tais medidas diferem em mais ide 40% umas da outra. Isso mostra que nossa compreensão sobre a natureza desse material ainda é bastante pobre. A interação entre pequenos grupos de metais de transição com uma folha de grapheno é outro exemplo em que nosso conhecimento é limitado. Existem muitos estudos teóricos na literatura que descrevem a interação desse tipo de aglomerado com uma folha de grafeno, porém há numerosas discordâncias. Tais controvérsias parecem suplicar por um estudo sistemático. Nesta tese focamos nossos estudos nas interações superfície-superfície e de átomos ou aglomerados atômicos com superfícies de carbono e de um metal. A tese foi dividida em três projetos. O primeiro visa compreender melhor a interação entre as camadas do grafite. No segundo, pretendemos lançar alguma luz no entendimento da interação de átomos e aglomerados atômicos com uma folha de grafeno. Esses dois projetos, são estudados à luz da Teoria do Funcional da Densidade com a inclusão das correções van der Waals (vdW). No Projecto sobre o grafite, mostramos que as propriedades eletrônicas e geométricas dependem do tipo de correção de vdW empregada no cálculo. No projeto sobre átomos e aglomerados atômicos adsorvidos no grapheno, combinamos um modelo modificado de Anderson-Newns para descrever o acoplamento entre um átomo adsorvido e o grafeno. Além disso, encontramos uma competição entre forças quânticas e clássicas, a qual determina o tipo de sítio no qual o átomo prefere ser adsorvido. O último projeto é um estudo dinâmico de um átomo colidindo contra uma superfície metálica. Nesse projeto o foco é posto no cálculo do coeficiente de aderência, o qual mede a taxa de densidade nuclear presa na superfície metálica após a colisão. Resultados preliminares indicam que, uma pequena parte da densidade nuclear permanece aderida ao metal depois da colisão.

Thermal and quantum fluctuations of the electromagnetic near field of atoms and macroscopic bodies play a key role in quantum electrodynamics (QED), as in the Lamb shift. They lead, e.g., to atomic level shifts, dispersion interactions (Van der Waals-Casimir-Polder interactions), and state broadening (Purcell effect) because the field is subject to boundary conditions. Such effects can be observed with high precision on the mesoscopic scale which can be accessed in micro-electro-mechanical systems (MEMS) and solid-state-based magnetic microtraps for cold atoms (‘atom chips’). A quantum field theory of atoms (molecules) and photons is adapted to nonequilibrium situations. Atoms and photons are described as fully quantized while macroscopic bodies can be included in terms of classical reflection amplitudes, similar to the scattering approach of cavity QED. The formalism is applied to the study of nonequilibrium two-body potentials. We then investigate the impact of the material properties of metals on the electromagnetic surface noise, with applications to atomic trapping in atom-chip setups and quantum computing, and on the magnetic dipole contribution to the Van der Waals-Casimir-Polder potential in and out of thermal equilibrium. In both cases, the particular properties of superconductors are of high interest. Surface-mode contributions, which dominate the near-field fluctuations, are discussed in the context of the (partial) dynamic atomic dressing after a rapid change of a system parameter and in the Casimir interaction between two conducting plates, where nonequilibrium configurations can give rise to repulsion. / Thermische und Quantenfluktuationen des elektromagnetischen Nahfelds von Atomen und makroskopischen Körpern spielen eine Schlüsselrolle in der Quantenelektrodynamik (QED), wie etwa beim Lamb-Shift. Sie führen z.B. zur Verschiebung atomarer Energieniveaus, Dispersionswechselwirkungen (Van der Waals-Casimir-Polder-Wechselwirkungen) und Zustandsverbreiterungen (Purcell-Effekt), da das Feld Randbedingungen unterliegt. Mikroelektromechanische Systeme (MEMS) und festkörperbasierte magnetische Fallen für kalte Atome (‘Atom-Chips’) ermöglichen den Zugang zu mesoskopischen Skalen, auf denen solche Effekte mit hoher Genauigkeit beobachtet werden können. Eine Quantenfeldtheorie für Atome (Moleküle) und Photonen wird an Nichtgleichgewichtssituationen angepasst. Atome und Photonen werden durch vollständig quantisierte Felder beschrieben, während die Beschreibung makroskopischer Körper, ähnlich wie im Streuformalismus (scattering approach) der Resonator-QED, durch klassische Streuamplituden erfolgt. In diesem Formalismus wird das Nichtgleich- gewichts-Zweiteilchenpotential diskutiert. Anschließend wird der Einfluss der Materialeigenschaften von normalen Metallen auf das elektromagnetische Oberflächenrauschen, das für magnetische Fallen für kalte Atome auf Atom-Chips und für Quantencomputer-Anwendungen von Bedeutung ist, sowie auf den Beitrag des magnetischen Dipolmoments zum Van der Waals-Casimir-Polder-Potential im thermisch- en Gleichgewicht und in Nichtgleichgewichtssituationen untersucht. In beiden Fällen sind die speziellen Eigenschaften von Supraleitern von besonderem Interesse. Beiträge von Oberflächenmoden, die die Feldfluktuationen im Nahfeld dominieren, werden im Kontext des (partiellen) dynamischen Dressing nach einer raschen Änderung eines Systemparameters sowie für die Casimir-Wechselwirkung zweier metallischer Platten diskutiert, zwischen denen in Nichtgleichgewichtssituationen Abstoßung auftreten kann.

Resumo: O sistema de microscopia de força atômica se tornou um instrumento popular e útil para medir as forças intermoleculares com resolução atômica que pode ser aplicado em eletrônica, análises biológicas, engenharia de materiais, semicondutores, etc. Este trabalho estuda o comportamento da dinâmica não-linear da ponta da sonda causada pelo tipo da amostra e os modos de funcionamento de um microscópio de força atômica. Utilizando-se de simulações numéricas, busca-se uma solução aproximada, através do método de perturbação de múltiplas escalas e teoria de controle linear ótimo consegue-se um bom entendimento do trabalho feito e explicado a seguir. Este trabalho está dividido em três partes, na primeira apresentou-se o problema, mostrando a necessidade de se controlar o comportamento caótico no sistema a ser estudado. Mostrou-se o funcionamento do microscópio atômico com todas suas variáveis de funcionamento. Foram geradas as equações de movimento e os resultados são obtidos através de integrações numéricas das equações de movimento, obteve-se oscilações regulares e irregulares (caóticos), os quais dependem da escolha dos parâmetros do sistema. Na segunda parte do trabalho, utilizou-se o método das múltiplas escalas, efetuou-se a busca de uma solução analítica aproximada para o movimento estacionário do sistema, que foi obtida através de técnicas de perturbações. Este método foi desenvolvido foi desenvolvido por [10] para controlar estes sistemas / Abstract: The atomic force microscope system has become a popular and useful instrument to measure the intermolecular forces with atomic-resolution that can be applied in electronics, biological analysis, materials, semiconductors etc. This work studies the complex nonlinear dynamic behavior of the probe tip between the sample and cantilever of an atomic force microscope using numeral simulations, method of multiple scales, and optimal linear control. This work concerns of three parts, in the first we will make the presentation of the AFM, showing various models of AFM. In second part, regular and irregular (chaotic) behaviors depend of the physical parameters and can be observed when a numerical integration is performed. When the dynamic system of the AFM becomes a chaotic oscillator a computational and analytical study of the nonlinear dynamic behavior of the AFM oscillator is proposed and it is obtained by perturbations method. The third part is dedicated to the application and performance of the linear feedback control for the suppressing of the chaotic motion of a non ideal system, theses systems are numerically studied. We use the method developed by [10] to control both the non-ideal system. This method seeks to find an optimal linear feedback control where they find - if conditions for the application of linear control in non-linear, ensuring the stability of the problem / Orientador: José Manoel Balthazar / Coorientador: Bento Rodrigues de Pontes / Banca: Átila Madureira Bueno / Banca: Angelo Marcelo Tusset / Mestre

Nowadays, the assembly of small (<1mm) components has become an industrial reality. Many domains like MEMS, surgery, telecommunications, car industry, etc. now have large use of micro-parts. At this scale, predominant forces are different than in macroworld. The pieces often undergo adhesion problems. The adhesion forces can be splitted in different components :van der Waals, electrostatics and capillary condensation. This work focuses on capillary condensation as it often can be the major component of the adhesion force. <p><p>The first part of this work details a review of literature of different fields involved in capillary condensation. A simulation tool is then implemented and theoretically validated in the second part of the work. Finally, a test bed is presented; this bed is then used to experimentally validate the simulation results.<p><p>Experiments and simulation results are shown to concord. Therefore, the simulation tool can be used to model the force due to capillary condensation. / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

The current theoretical understanding of thermodynamics of clathrate hydrates is based on the van der Waals and Plattew (vdWP) theory developed using statistical thermodynamics approach. vdWP theory has been widely used to predict the phase equilibrium of clathrate hydrates over the decades. However, earlier studies have shown that this success could be due to the presence of a large number of parameters. In this thesis, a systematic and a rigorous analysis of vdWP theory is per-formed with the help of Monte Carlo molecular simulations for methane hydrate. The analysis revealed that long range guest-water interactions and guest-guest interactions are important, Monte Carlo integration to is superior to the spherical shell approximation for the Langmuir constant calculation and even after inclusion of all the interactions and using Monte Carlo integration for Langmuir constant, the vdWP theory still fails to regress parameters correctly. This failure of vdWP theory is attributed to the rigid water lattice approximation. To address the rigid water lattice approximation, a new method is proposed. In the proposed method, the Langmuir constant is computed in flexible water lattice, by considering the movement of water molecules. The occupancy values predicted using the proposed method are in excellent agreement with the values obtained from Monte Carlo molecular simulations for variety of hydrates, methane, ethane, carbon dioxide and tetrahydrofuran(THF) hydrates . In addition to small guest molecules like methane, ethane etc. which are mod- heled as rigid, the method is extended for large guest molecules like propane and isobutane, using configurationally bias Monte Carlo method. The phase equilib-rium and occupancy along the phase equilibrium predictions from vdWP theory are compared with the exact phase equilibrium computed from Monte Carlo molecular simulations. This comparison is done for a wide variety of hydrate systems, single hydrates , binary hydrates and quaternary hydrate. In all the cases, the vdWP theory with the flexible water lattice showed significant improvement over the rigid lattice model with significantly less absolute relative deviations in pressure. Guest-cavity interactions for hydrates are calculated using abinitio calculations. In general, these guest-cavity interaction from first principle calculations are used to develop classical force field parameters in alternative to Lorentz-Berthelot rule. In the study, comparison of guest-cavity interactions from MP2 and CCSD(T) methods revealed that less expensive MP2 method, which is generally used, is insouciant to capture the dispersion interactions accurately. These guest-cavity interactions using CCSD(T) method extrapolated to complete basis set are used to model the interaction parameters between cyclopropane and water. The potential parameters obtained from ab-initio calculations are used in the calculation of Langmuir constant using vdWP theory. Langmuir constant calculated using vdWP theory with flexible water lattice gave close agreement with the values obtained from experimental occupancy data. In addition, simulation methodology to calculate ternary hydrate phase equilibrium is extended for binary hydrates. Simulations have been successful in the prediction of sIsII and sII-sI structural transitions as observed in experiments. Predicted methane-ethane binary hydrate is also compared with the available experimental phase equilibrium data. The phase equilibrium obtained from simulations showed very good qualitative agreement with the experimental data.