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The multiconfiguration time-dependent Hartree-Fock (MCTDHF) and multiconfiguration time-dependent Hartree (MCTDH) methods are employed to investigate nonperturbative multielectron dynamics in finite quantum systems. MCTDHF is a powerful tool that allows for the investigation of multielectron dynamics in strongly perturbed quantum systems. We have developed an MCTDHF code that is capable of treating problems involving three dimensional (3D) atoms and molecules exposed to strong laser fields. This code will allow for the theoretical treatment of multielectron phenomena in attosecond science that were previously inaccessible. These problems include complex ionization processes in pump-probe experiments on noble gas atoms, the nonlinear effects that have been observed in Ne atoms in the presence of an x-ray free-electron laser (XFEL) and the molecular rearrangement of cations after ionization. An implementation of MCTDH that is optimized for two electrons, each moving in two dimensions (2D), is also presented. This implementation of MCTDH allows for the efficient treatment of 2D spin-free systems involving two electrons; however, it does not scale well to 3D or to systems containing more that two electrons. Both MCTDHF and MCTDH were used to treat 2D problems in nanophysics and attosecond science. MCTDHF is used to investigate plasmon dynamics and the quantum breathing mode for several electrons in finite lateral quantum dots. MCTDHF is also used to study the effects of manipulating the potential of a double lateral quantum dot containing two electrons; applications to quantum computing are discussed. MCTDH is used to examine a diatomic model molecular system exposed to a strong laser field; nonsequential double ionization and high harmonic generation are studied and new processes identified and explained. An implementation of MCTDHF is developed for nonuniform tensor product grids; this will allow for the full 3D implementation of MCTDHF and will provide a means to investigate a wide variety of problems that cannot be currently treated by any other method. Finally, the time it takes for an electron to tunnel from a bound state is investigated; a definition of the tunnel time is established and the Keldysh time is connected to the wavefunction dynamics.

The multiconfiguration time-dependent Hartree-Fock (MCTDHF) and multiconfiguration time-dependent Hartree (MCTDH) methods are employed to investigate nonperturbative multielectron dynamics in finite quantum systems. MCTDHF is a powerful tool that allows for the investigation of multielectron dynamics in strongly perturbed quantum systems. We have developed an MCTDHF code that is capable of treating problems involving three dimensional (3D) atoms and molecules exposed to strong laser fields. This code will allow for the theoretical treatment of multielectron phenomena in attosecond science that were previously inaccessible. These problems include complex ionization processes in pump-probe experiments on noble gas atoms, the nonlinear effects that have been observed in Ne atoms in the presence of an x-ray free-electron laser (XFEL) and the molecular rearrangement of cations after ionization. An implementation of MCTDH that is optimized for two electrons, each moving in two dimensions (2D), is also presented. This implementation of MCTDH allows for the efficient treatment of 2D spin-free systems involving two electrons; however, it does not scale well to 3D or to systems containing more that two electrons. Both MCTDHF and MCTDH were used to treat 2D problems in nanophysics and attosecond science. MCTDHF is used to investigate plasmon dynamics and the quantum breathing mode for several electrons in finite lateral quantum dots. MCTDHF is also used to study the effects of manipulating the potential of a double lateral quantum dot containing two electrons; applications to quantum computing are discussed. MCTDH is used to examine a diatomic model molecular system exposed to a strong laser field; nonsequential double ionization and high harmonic generation are studied and new processes identified and explained. An implementation of MCTDHF is developed for nonuniform tensor product grids; this will allow for the full 3D implementation of MCTDHF and will provide a means to investigate a wide variety of problems that cannot be currently treated by any other method. Finally, the time it takes for an electron to tunnel from a bound state is investigated; a definition of the tunnel time is established and the Keldysh time is connected to the wavefunction dynamics.

Halo nuclei are among the strangest nuclear structures. They are viewed as a core containing most of the nucleons surrounded by one or two loosely bound nucleons. These have a high probability of presence at a large distance from the core. Therefore, they constitute a sort of halo surrounding the other nucleons. The core, remaining almost unperturbed by the presence of the halo is seen as a usual nucleus. <P> The Coulomb breakup reaction is one of the most useful tools to study these nuclei. It corresponds to the dissociation of the halo from the core during a collision with a heavy (high <I>Z</I>) target. In order to correctly extract information about the structure of these nuclei from experimental cross sections, an accurate theoretical description of this mechanism is necessary. <P> In this work, we present a theoretical method for studying the Coulomb breakup of one-nucleon halo nuclei. This method is based on a semiclassical approximation in which the projectile is assumed to follow a classical trajectory. In this approximation, the projectile is seen as evolving in a time-varying potential simulating its interaction with the target. This leads to the resolution of a time-dependent Schrödinger equation for the projectile wave function. <P> In our method, the halo nucleus is described with a two-body structure: a pointlike nucleon linked to a pointlike core. In the present state of our model, the interaction between the two clusters is modelled by a local potential. <P> The main idea of our method is to expand the projectile wave function on a three-dimensional spherical mesh. With this mesh, the representation of the time-dependent potential is fully diagonal. Furthermore, it leads to a simple representation of the Hamiltonian modelling the halo nucleus. This expansion is used to derive an accurate evolution algorithm. <P> With this method, we study the Coulomb breakup of three nuclei: ¹¹Be, ¹⁵C and ⁸B. ¹¹Be is the best known one-neutron halo nucleus. Its Coulomb breakup has been extensively studied both experimentally and theoretically. Nevertheless, some uncertainty remains about its structure. The good agreement between our calculations and recent experimental data suggests that it can be seen as a <I>s1/2</I> neutron loosely bound to a ¹⁰Be core in its 0⁺ ground state. However, the extraction of the corresponding spectroscopic factor have to wait for the publication of these data. <P> ¹⁵C is a candidate one-neutron halo nucleus whose Coulomb breakup has just been studied experimentally. The results of our model are in good agreement with the preliminary experimental data. It seems therefore that ¹⁵C can be seen as a ¹⁴C core in its 0⁺ ground state surrounded by a <I>s1/2</I> neutron. Our analysis suggests that the spectroscopic factor corresponding to this configuration should be slightly lower than unity. <P> We have also used our method to study the Coulomb breakup of the candidate one-proton halo nucleus ⁸B. Unfortunately, no quantitative agreement could be obtained between our results and the experimental data. This is mainly due to an inaccuracy in the treatment of the results of our calculations. Accordingly, no conclusion can be drawn about the pertinence of the two-body model of ⁸B before an accurate reanalysis of these results. <P> In the future, we plan to improve our method in two ways. The first concerns the modelling of the halo nuclei. It would be indeed of particular interest to test other models of halo nuclei than the simple two-body structure used up to now. The second is the extension of this semiclassical model to two-neutron halo nuclei. However, this cannot be achieved without improving significantly the time-evolution algorithm so as to reach affordable computational times.

Corrosion of reinforcing bars is the major cause of deterioration of reinforced concrete (RC) structures in North America, Europe, the Middle East, and many coastal regions around the world. This deterioration leads to a loss of serviceability and functionality and ultimately affects the structural safety. The objective of this research is to formulate and implement a general stochastic finite element analysis (SFEA) framework for the time-dependent reliability analysis of RC beams with corroding flexural reinforcement. The framework is based on the integration of nonlinear finite element and reliability analyses through an iterative response surface methodology (RSM). Corrosion-induced damage is modelled through the combined effects of gradual loss of the cross-sectional area of the steel reinforcement and the reduction bond between steel and concrete for increasing levels of corrosion. Uncertainties in corrosion rate, material properties, and imposed actions are modelled as random variables. Effective implementation of the framework is achieved by the coupling of commercial finite element and reliability software. Application of the software is demonstrated through a case study of a simply-supported RC girder with tension reinforcement subjected to the effects of uniform (general) corrosion, in which two limit states are considered: (i) a deflection serviceability limit state and (ii) flexural strength ultimate limit state. The results of the case study show that general corrosion leads to a very significant decrease in the reliability of the RC beam both in terms of flexural strength and maximum deflections. The loss of strength and serviceability was shown to be predominantly caused by the loss of bond strength, whereas the gradual reduction of the cross-sectional area of tension reinforcement was found to be insignificant. The load-deflection response is also significantly affected by the deterioration of bond strength (flexural strength and stiffness). The probability of failure at the end of service life, due to the effects of uniform corrosion-induced degradation, is observed to be approximately an order of magnitude higher than in the absence of corrosion. Furthermore, the results suggest that flexural resistance of corroded RC beams is controlled by the anchorage (bond) of the bars and not by the yielding of fully bonded tensile reinforcement at failure. This is significant since the end regions can be severely corroded due to chloride, moisture, and oxygen access at connections and expansion joints. The research strongly suggests that bond damage must be considered in the assessment of the time-dependent reliability of RC beams subjected to general corrosion.

The time-dependent wettability of nickel nanorod arrays was studied by measuring their water contact angles as a function of "aging" time in air. The nickel nanorod arrays were deposited on silicon substrates by DC magnetron sputtering using an oblique angle of 85° with respect to the substrate normal. By changing the deposition time from 10 to 90 min., the diameter, height, and separation of the nanorods were varied. The water contact angles of each sample were then periodically measured from a minimum aging time of 30 min. after deposition and exposure to air, up to a maximum aging time of three months. The initial water contact angles for all samples were approximately equal to 8o, indicating that the nickel nanorod arrays were initially superhydrophilic. As the samples aged in air, however, they all showed increasing contact angles as a function of time that were nonlinear with different rates. The results can be grouped into two categories: thinner samples with shorter deposition times (10 to 55 min) demonstrated faster rates of increase in contact angle, and thicker samples with longer deposition times (60 and 90 min.) showed slower rates. The increase in contact angle with time indicates that the Ni nanorods become more hydrophobic with aging time in air. Surface chemical analysis demonstrates that this increase in hydrophobicity may be due to oxidization and hydrocarbon contamination, which depend on the nanorod morphology. X-ray photoelectron spectroscopy results indicate that thinner samples (10-55 min. deposition time) have more adsorbed carbon as compared to thicker samples (60 and 90 min.). It appears that the reactivity of the Ni nanorods with air ambient is enhanced for shorter, smaller-diameter nanorods.

Doctor of Philosophy / Department of Chemistry / Christine M. Aikens / Small silver and gold clusters (less than 2 nm) display a discrete absorption spectrum characteristic of molecular systems whereas larger particles display a strong, broad absorption band in the visible. The latter feature is due to the surface plasmon resonance, which is commonly explained by the collective dipolar motion of free electrons across the particle, creating charged surface states. The evolution between molecular properties and plasmon is investigated. Time-dependent density functional theory (TDDFT) calculations are performed to study the absorption spectrum of cluster-size silver and gold nanorods. The absorption spectrum of these silver nanorods exhibits high-intensity longitudinal and transverse modes (along the long and short axis of the nanorod respectively), similar to the plasmons observed experimentally for larger nanoparticles. These plasmon modes result from a constructive addition of the dipole moments of nearly degenerate single-particle excitations. The number of single-particle transitions involved increases with increasing system size, due to the growing density of states available. Gold nanorods exhibit a broader absorption spectrum than their silver counterpart due to enhanced relativistic effects, affecting the onset of the longitudinal plasmon mode. The high-energy, high-intensity beta-peak of acenes also results from a constructive addition of single-particle transitions and I show that it can be assigned to a plasmon. I also show that the plasmon modes of both acenes and metallic nanoparticles can be described with a simple configuration interaction (CI) interpretation. The evolution between molecular absorption spectrum and plasmon is also investigated by computing the density of states of spherical thiolate-protected gold clusters using a charge-perturbed particle-in-a-sphere model. The electronic structure obtained with this model gives good qualitative agreement with DFT calculations at a fraction of the cost. The progressive increase of the density of states with particle size observed is in accordance with the appearance of a plasmon peak. The optical properties of nanoparticles can be tuned by varying their composition. Therefore, the optical behavior of the bimetallic Au[subscript](25-n)Ag[subscript]n(SH)[subscript]18[superscript]- cluster for different values of n using TDDFT is analyzed. A large blue shift of the HOMO-LUMO absorption peak is observed with increasing silver content, in accordance with experimental results.

Neste trabalho será investigado o comportamento de escoamentos de fluidos newtonianos e não-newtonianos em microcanais. O problema não-newtoniano, consiste em resolver as equações que regem o movimento para o caso de um escoamento de fluidos cujas propriedades reológicas possam ser estudadas pelo modelo constitutivo de Phan-Thien-Tanner, como por exemplo os materiais poliméricos. Uma das características interessantes de alguns destes materiais é que eles podem ser misturados com solventes apropriados, como uma solução eletrolítica, e o resultado é que este fluido como um todo passa a ter propriedades elétricas. Assim, além das propriedades viscoelásticas, será investigada a eletrocinética do escoamento, que é diretamente influenciado pela aplicação de um campo elétrico externo. Em particular o fenômeno de eletrosmose será estudado neste trabalho por meio de simulações numéricas em canais planos e bocais. Escoamentos através de bocais podem ser úteis na realização da mistura de fluidos. Neste trabalho, apresentamos uma aproximação numérica para a simulação dos vórtices que ocorrem logo após a passagem do fluido pela contração no bocal. Além disso, foram feitas simulações com potenciais dependentes do tempo e as variações nas propriedades do fluido viscoelástico para este tipo de escoamento. O movimento das cargas na solução é descrito pelas equações de Poisson-Nernst-Planck e para resolver numericamente este problema será aplicado o método das diferenças finitas generalizadas. O código para as simulações de escoamentos eletrosmóticas foi implementado como uma parte do sistema chamado HiG-Fow, que é capaz de realizar simulações de outros tipos de escoamentos além dos investigados nesta tese. A modularidade desse sistema possibilita ao usuário a implementação de pacotes de acordo com o tipo de escoamento a ser estudado. Os resultados obtidos indicam que a tensão viscoelástica é resistente a mudanças bruscas no escoamento, isto é, as oscilações da tensão normal dependem da frequência aplicada. Quanto maior a frequência menor é a amplitude do tensor. Esperamos que este trabalho contribua para um melhor entendimento de escoamentos dependente do tempo, possibilitando melhorias na tecnologia de dispositivos microfluidicos. / In this work the behavior of newtonian and non-Newtonian fluids in microchannels will be investigated. The non-Newtonian problem consists in solving the governing equations of the movement take into account a fluid flow whose rheological properties can be studied by the Phan- Thien-Tanner constitutive model, for example the polymeric materials. One of the interesting features of some of these materials is that they can be mixed with appropriate solvents, such as an electrolyte solution, and the resulting fluid has electrical properties. Thus, besides the viscoelastic properties, the electrokinetics of the flow will be investigated, which is directly influenced by the application of an external electric field. In particular the phenomenon of electro-osmosis will be studied in this work through numerical simulations in flat channels and nozzles. Flows through nozzles may be useful in performing the fluid mixture. In this work, we propose a numerical approximation for the simulation of the vortices that occur soon after the passage of the fluid by the contraction in the nozzle. In addition, simulations were made with time dependent potentials and the variations in viscoelastic fluid properties for this type of flow. The motion of the charges in the solution is described by the Poisson-Nernst-Planck equations and to solve numerically this problem will be applied the generalized finite difference method. The code for the simulations of electroosmotic flows was implemented as a part of the HiG-Fow system, which is able to perform simulations of other types of flows beyond those investigated in this thesis. The modularity of this system enables the user to implement packages according to the type of flow to be studied. The results indicate that the viscoelastic stress is resistant to abrupt changes on the flow, that is, the oscillations of the normal stress depend on the applied frequency. The higher the frequency the smaller the tensor amplitude. We hope that this work contributes to a better understanding of time-dependent flows, enabling improvements in the technology of microfluidic devices.

La production d’énergie, et en particulier la production d’électricité, est la principale responsable de l’émission de gaz à effet de serre au niveau mondial. Le secteur résidentiel étant le plus consommateur d’énergie, il est essentiel d’agir au niveau personnel afin de réduire ces émissions. Avec le développement de l’informatique ubiquitaire, il est désormais aisé de récolter des données de consommation d’électricité des appareils électriques d’un logement. Cette possibilité a permis le développement des technologies eco-feedback, dont l’objectif est de fournir aux consommateurs un retour sur leur consommation dans le but de la diminuer. Dans cette thèse nous proposons une méthode de visualisation de données temporelles personnelles basée sur une interaction what if, qui signifie que les utilisateurs peuvent appliquer des changements de comportement de manière virtuelle. En particulier notre méthode permet de simuler une modification de l’utilisation des appareils électriques d’un logement, puis d’évaluer visuellement l’impact de ces modifications sur les données. Cette méthode a été implémentée dans le système Activelec, que nous avons évalué avec des utilisateurs sur des données réelles. Nous synthétisons les éléments de conception indispensables aux systèmes eco-feedback dans un état de l’art. Nous exposons également les limitations de ces technologies, la principale étant la difficulté rencontrée par les utilisateurs pour trouver des modifications de comportement pertinentes leur permettant de consommer moins d’énergie.Nous présentons ensuite trois contributions. La première contribution est la conception d’une méthode what if appliquée à l’eco-feedback ainsi que son implémentation dans le système Activelec. La seconde contribution est l’évaluation de notre méthode grâce à deux expérimentations menées en laboratoire. Dans ces expérimentations nous évaluons si des participants utilisant notre méthode trouvent des modifications qui économisent de l’énergie et qui nécessitent suffisamment peu d’efforts pour être appliquées en vrai. Enfin la troisième contribution est l’évaluation in-situ du système Activelec dans des logements personnels pour une durée d’environ un mois. Activelec a été déployé dans trois appartements privés afin de permettre l’évaluation de notre méthode en contexte domestique réel. Dans ces trois expérimentations, les participants ont pu trouver des modifications d’utilisation des appareils qui économiseraient une quantité d’énergie significative, et qui ont été jugées faciles à appliquer en réalité. Nous discutons également de l’application de notre méthode what if au-delà des données de consommation électrique au domaine de la visualisation personnelle, qui est définie comme l’analyse visuelle des données personnelles. Nous présentons ainsi plusieurs applications possibles à d’autres données temporelles personnelles, par exemple concernant l’activité physique ou les transports. Cette thèse ouvre de nouvelles perspectives pour l’utilisation d’un paradigme d’interaction what if pour la visualisation personnelle. / The production of energy, in particular the production of electricity, is the main responsible for the emission of greenhouse gases at world scale. The residential sector being the most energy consuming, it is essential to act at a personal scale to reduce these emissions. Thanks to the development of ubiquitous computing, it is now easy to collect data about the electricity consumption of electrical appliances of a housing. This possibility has allowed the development of eco-feedback technologies, whose objective is to provide to consumers a feedback about their consumption with the aim to reduce it. In this thesis we propose a personal visualization method for time-dependent data based on a what if interaction, which means that users can apply modifications in their behavior in a virtual way. Especially our method allows to simulate the modification of the usage of electrical appliances of a housing, and then to evaluate visually the impact of the modifications on data. This approach has been implemented in the Activelec system, which we have evaluated with users on real data.We synthesize the essential elements of conception for eco-feedback systems in a state of the art. We also outline the limitations of these technologies, the main one being the difficulty faced by users to find relevant modifications in their behavior to decrease their energy consumption. We then present three contributions. The first contribution is the development of a what if approach applied to eco-feedback as well as its implementation in the Activelec system. The second contribution is the evaluation of our approach with two laboratory studies. In these studies we assess if participants using our method manage to find modifications that save energy and which require a sufficiently low effort to be applied in reality. Finally the third contribution is the in-situ evaluation of the Activelec system. Activelec has been deployed in three private housings and used for a duration of approximately one month. This in-situ experiment allows to evaluate the usage of our approach in a real domestic context. In these three studies, participants managed to find modifications in the usage of appliances that would savea significant amount of energy, while being judged easy to be applied in reality.We also discuss of the application of our what if approach to the domain of personal visualization, beyond electricity consumption data, which is defined as the visual analysis of personal data. We hence present several potential applications to other types of time-dependent personal data, for example related to physical activity or to transportation. This thesis opens new perspectives for using a what if interaction paradigm for personal visualization.

Modelos multi-estados têm sido utilizados para descrever o comportamento de unidades amostrais cuja principal resposta é o tempo necessário para a ocorrência de seqüências de eventos. Consideramos um modelo multi-estados markoviano, não homogêneo, que incorpora covariáveis cujos efeitos podem variar ao longo do tempo (efeitos dinâmicos), o que permite a generalização dos modelos usualmente empregados. Resultados assintóticos mostram que procedimentos de estimação baseados no método histograma crivo convergem para um processo gaussiano. A metodologia proposta mostra-se adequada na modelagem de dados reais para comparação de desenvolvimento de recém-nascidos pré-termo com os a termo. Estudos com dados gerados artificialmente confirmam os resultados teóricos obtidos. / Multi-state models have been used to describe the behavior of sample units where the principal response is the time needed for the occurrence of a sequence of events. We consider a non-homogeneous Markovian multi-state model that incorporates covariates with time-dependent coefficient (dynamic effects), generalizing models usually employed. The asymptotic results show that the estimators based on the method of histogram sieves converge to a Gaussian process. The proposed methodology revels adequated for modeling data related to the comparison of developement of preterm infants with term infants. The studies with artificially generated data confirm the asymptotic results.