Les nanocavités à cristal photonique ont été largement étudiées au cours de la dernière décennie du fait de leur aptitude à fortement confiner la lumière (faible volume modal) et de leurs faibles pertes optiques (grand facteur de qualité). Parmi le grand nombre de géométries proposées, nous nous intéressons ici au cas de la cavité L3 étudiée par Noda et al. (trois trous manquants dans la direction K du réseau triangulaire sous-jacent) utilisée dans plusieurs applications et notamment pour la réalisation de nano-lasers et d’interrupteurs optiques. Cependant, l’injection ou l’extraction de lumière dans de telles nanocavités s’avère extrêmement difficile du fait de la diffraction importante dont souffrent ces structures. Différentes approches en champ proche ont été récemment développées et notamment le couplage évanescent utilisant des guides d’onde nanostructurés ou des fibres optiques étirées. Dans le but de pallier à la faible efficacité de couplage à l’espace libre, nous développons une conception récemment proposée par De Rossi et al. afin de changer radicalement le profil du diagramme de rayonnement. Cette approche utilise la méthode de repliement des bandes qui consiste à introduire au sein d’un réseau triangulaire de période (a), un sous-réseau de trous de période (2a) qui améliore considérablement l’efficacité de couplage dans la direction verticale. Bien que certaines mesures de l’efficacité de collection et du coefficient de qualité aient déjà été mentionnées dans la littérature, aucune mesure directe des diagrammes de rayonnement de ces nanocavités n’a été réalisée jusqu’alors. Nous étudions dans ce travail différents types de nanocavités et de molécules L3 à cristaux photoniques présentant des profils de champ lointain optimisés. Les diagrammes de rayonnement de cavités non-repliées et repliées incorporées dans des membranes actives suspendues en InP sont systématiquement mesurés et comparés. Un bon accord entre les simulations numériques et les diagrammes de champ lointain mesurés expérimentalement est obtenu, montrant des lobes d’émission très directionnels le long de la normale à l’échantillon. En outre, des expériences de couplage à l’espace libre ont été réalisées montrant des efficacités de couplage d’environ 15% pour des coefficients de qualité supérieurs à 10 000. Ces résultats valident ainsi la technique de repliement des bandes dans les cavités L3 qui, une fois repliées, conservent un faible volume modal et un coefficient de qualité élevé ainsi qu’une grande efficacité de couplage à l’espace libre, à la fois dans les configurations nanocavité unique et nanocavités couplés. Nous montrons aussi expérimentalement que l’écart spectral inter-modal dans deux cavités L3 couplées de manière évanescente peut être contrôlé grâce à l’ingénierie de la barrière photonique. La « barrière de potentiel » est formée par les trous d’air séparant les deux cavités. L’écart en fréquence entre les modes peut être fortement réduit et augmentée via une diminution ou une augmentation du rayon des trous de la rangée centrale de la barrière jusqu’à ∼ −30% ou ∼ 30% de sa valeur initiale. En outre, le signe de la l’écart spectral entre les modes peut être inversé de telle sorte que le mode fondamental peut être soit symétrique ou anti-symétrique et ce, sans modifier ni la géométrie de la cavité, ni la distance inter-cavité. / Photonic crystal (PhC) nanocavities have been intensively investigated during the last decade due to their capabilities of achieving tight light confinement and low optical losses simultaneously. Among the different geometries, the cavity proposed by Noda et al., namely a L3 cavity (three holes missing in the K direction of the underlying triangular lattice) with shifted end-holes has been widely used in several applications including laser emission and switching devices. However, input/output free space light coupling of such nanocavities is quite challenging. In this regard, near field coupling schemes have been recently developed, such as evanescent coupling using tapered optical fibers. In order to overcome the poor free space coupling, a new cavity design has been recently proposed by De Rossi et al. that totally changes the radiation pattern. This is based on a band folding approach introducing a modulation of the holes size at twice the period of the underlying PhC, which considerably increases the coupling efficiency in the vertical direction. While some measurements of the Q-factor and coupling efficiency were performed, no direct characterization of the far-field of such cavities has been performed so far. In this work we have studied different types of L3 photonic crystal cavities and L3 photonic molecules with optimized far-field profiles. Radiation patterns from « folded » and « unfolded » cavities incorporated in suspended InP active membranes were systematically measured and compared. Good agreement between simulations and experimental far-field patterns has been found, demonstrating highly directional emission lobes along the sample normal. Furthermore, free space input coupling experiments have been performed showing coupling efficiency of about 15% of contrast with quality factors exceeding 10 000. These results validate the « folded » L3 cavities as good candidates for small volume and high Q cavities with efficient free space coupling, either in single or coupled cavity configurations. We also experimentally show that the mode splitting in two-evanescently coupled Photonic Crystal L3 cavities can be controlled through photonic barrier engineering. The « potential barrier » is formed by the air-holes in between the two cavities. By changing the hole radius of the central row in the barrier up to ∼ 30% or down to ∼ −30% , the frequency splitting can be strongly increased or reduced. Moreover, the sign of the splitting can be reversed in such a way that the fundamental mode can be either the symmetric or the anti-symmetric one without altering neither the cavity geometry nor the inter-cavity distance.

Le problème de tournées de véhicules (Vehicle Routing Problem - VRP) est un problème d'optimisation combinatoire utilisé généralement pour modéliser et résoudre des différents problèmes rencontrés dans les systèmes logistiques et de transport. Dans cette thèse, nous nous sommes intéressés à l'étude et la résolution d'une classe de problèmes du VRP appelée les problèmes de courses d'orientation (Team Orienteering Problem - TOP). Dans cette catégorie de problèmes, il est a priori impossible de visiter tous les clients en raison de ressources limitées. On associe plutôt un profit à chaque client qui représente sa valeur. Ce profit est collecté lorsque le client est visité par l'un des véhicules disponibles. L'objectif est donc de sélectionner un sous ensemble de clients à servir tout en maximisant le profit total collecté. Dans un premier temps, nous avons introduit une nouvelle généralisation pour le TOP que nous avons appelé le Clustered TOP ou CluTOP. Dans cette variante, les clients sont regroupés en sous-ensembles appelés clusters auxquels nous associons des profits. Pour résoudre cette variante, nous avons proposé un schéma exact basé sur l'approche des plans sécants avec des inégalités valides supplémentaires et des pré-traitements. Nous avons également conçu une méthode heuristique basée sur l'approche order first-cluster second. Cette heuristique hybride combine une heuristique de type Adaptive Large Neighborhood Search qui explore l'espace des solutions et une procédure de découpage qui explore l'espace de recherche des tours géants. De plus, la procédure de découpage est renforcée par une recherche locale afin de mieux explorer l'espace de recherche. Le deuxième problème traité dans ce travail s'appelle le Synchronized Team Orienteering Problem with Time Windows (STOPTW). Cette variante avait été initialement proposée afin de modéliser des scénarios liés à la protection des infrastructures stratégiques menacées par l'avancée des feux de forêts. En plus des contraintes de fenêtres de temps et des visites synchronisées, cette variante considère le cas d'une flotte de véhicules hétérogène. Pour résoudre ce problème, nous avons proposé une méthode heuristique basée sur l'approche GRASP×ILS qui est parvenue à dominer la seule approche existante dans la littérature. La dernière variante du TOP abordée dans cette thèse s'appelle le Set Orienteering Problem (SOP). Les clients dans cette variante sont regroupés en sous-ensembles appelés clusters. Un profit est associé à chaque groupe qui n'est obtenu que si au moins un client est desservi par le véhicule disponible. Nous avons proposé une méthode de coupes avec deux procédures de séparation pour séparer les contraintes d'élimination des sous-tours. Nous avons également proposé un algorithme Mémétique avec une procédure de découpage optimale calculée à l'aide de la programmation dynamique. / The Vehicle Routing Problem (VRP) is a family of Combinatorial Optimization Problems generally used to solve different issues related to transportation systems and logistics. In this thesis, we focused our attention on a variant of the VRP called the Team Orienteering Problem (TOP). In this family of problems, it is a priory impossible to visit all the customers due to travel time limitation on vehicles. Instead, a profit is associated with each customer to represent its value and it is collected once the customer is visited by one of the available vehicles. The objective function is then to maximize the total collected profit with respect to the maximum travel time. Firstly, we introduced a new generalization for the TOP that we called the Clustered TOP (CluTOP). In this variant, the customers are grouped into subsets called clusters to which we associate profits. To solve this variant, we proposed an exact scheme based on the cutting plane approach with additional valid inequalities and pre-processing techniques. We also designed a heuristic method based on the order first-cluster second approach for the CluTOP. This Hybrid Heuristic combines between an ANLS heuristic that explores the solutions space and a splitting procedure that explores the giant tours search space. In addition, the splitting procedure is enhanced by local search procedure in order to enhance its coverage of search space. The second problem treated in this work is called the Synchronized Team Orienteering Problem with Time Windows (STOPTW). This variant was initially proposed in order to model scenarios related to asset protection during escaped wildfires. It considers the case of a heterogeneous fleet of vehicles along with time windows and synchronized visits. To solve this problem, we proposed a heuristic method based on the GRASP×ILS approach that led to a very outstanding results compared to the literature. The last variant of the TOP tackled in this thesis called the Set Orienteering Problem (SOP). Customers in this variant are grouped into subsets called clusters. Each cluster is associated with a profit which is gained if at least one customer is served by the single available vehicle. We proposed a Branch-and-Cut with two separation procedures to separate subtours elimination constraints. We also proposed a Memetic Algorithm with an optimal splitting procedure based on dynamic programming.

O presente trabalho teve como objetivo geral estudar a influência do manejo florestal no rendimento e na qualidade tecnológica da madeira serrada de uma população plantada de Eucalyptus grandis, de 21 anos de idade, manejada pelo sistema de desbastes seletivos com aplicação de fertilizantes na época do início dos desbastes. Os fatores utilizados foram três intensidades de desbastes seletivos (37, 50 e 75%), presença ou ausência de fertilizantes, três classes de diâmetro e três posições verticais ao longo da altura do fuste comercial.As influências dos fatores e de suas combinações nas tensões de crescimento das árvores foram avaliadas de forma indireta através das rachaduras de extremidade de tora, rachadura de extremidade de tábua úmidas e secas, encurvamento e arqueamento de tábua úmida e deslocamento da medula em relação à sua normal posição central. Foram avaliadas, também, porcentagem de casca e conicidade de toras, que são variáveis que interferem no rendimento em madeira serrada; massa específica da madeira à umidade de equilíbrio ao ar; módulo de elasticidade estrutural na flexão estática não destrutiva, determinado em tábuas secas de dimensões comerciais e um sistema de classificação de tábuas segundo diferentes classes de qualidade. O deslocamento da medula, conicidade, porcentagem de casca e o índice de rachaduras de topo de tora não sofreram nenhuma influência significativa dos fatores desbaste, adubação e classe de diâmetro. As rachaduras de extremidade de tábua serrada seca ou verde, encurvamento, arqueamento e o módulo de elasticidade estrutural sofreram influências dos fatores desbaste, adubação e classe de diâmetro em algumas situações específicas. O índice de rachadura de tábuas serrada verde ou seca diminui da medula para a casca enquanto que o encurvamento de peça serrada e o módulo de elasticidade estrutural aumentam da medula para a casca. O arqueamento das tábuas não apresenta nenhuma tendência de variação ao longo do raio da tora. A metodologia não destrutiva utilizada para avaliação do módulo de elasticidade estrutural à flexão estática demonstrou-se ser simples, prática e eficiente.Na classificação das tábuas serradas foi constatado que a posição relativa da tábua no raio interfere nas classes de qualidade da madeira. A freqüência de tábuas de 1ª classe aumenta da medula para a casca enquanto que as tábuas de refugo diminuem da medula para casca. A massa específica da madeira à umidade de equilíbrio ao ar sofreu influência do fator adubo e aumenta significativamente da medula para a casca. A intensidade de 75% de desbaste propiciou, de maneira geral, maior homogeneidade de qualidade da madeira ao longo do raio. Observa-se boas relações positivas entre rachadura de tábua seca e rachadura de tábua verde, mas a melhor relação foi observada entre o rendimento em madeira serrada seca e o rendimento em madeira serrada verde com destopo. / The study had the general objective of studying the influence of forest thinning on the some yield and technological quality indicators of sawn wood from a 21 year old grown Eucalyptus grandis stand managed by selective thinning with the use of fertilizers at 6 years old. The thinning intensities (37, 50 and 75%), presence or absence of fertilizers, two diameter classes, two vertical positions along the stem commercial height and three longitudinal position along the tree radius were taken as the study factors. The influences of the factors treatments and their combinations on tree growth stresses were evaluate indirectly through log end splitting, green and dry sawn lumber end splitting, green sawn lumber bow and spring and pith displacement from it normal central position. The percentage of bark and log taper which are variables that interfere on the sawn wood yield was also evaluated. Structural modulus of elasticity at static bending determined in commercial dimensions dry sawn lumber and a grading system of sawn pieces were determined. Thinning and fertilization had no significant effect on pith displacement, log tapering, bark percentage and log end splitting index. Green and dry sawn lumber, bow, spring and structural modulus of elasticity were influenced by thinning, fertilization and diameter class in some specific situations. Green or dry sawn lumber end splitting index decreases from pith to bark although green sawn lumber bow and the structural modulus of elasticity increase toward the periphery of the tree. Green lumber spring presents no variation tendency along the log radius. The methodology of non-destructive testing used for structural modulus of elasticity evaluation at static bending had demonstrated to be simple, practical and efficient. It was observed during sawn lumber grading operation that the relative position of a piece in the tree radius interferes on its class grade. The frequency of first class lumber increases from pith to bark while the refused pieces number decreases toward the outer part of the tree. In general the 75% thinning intensity slightly promoted a better homogeneity of sawn wood quality along the tree radius.

No description available.

Seismic anisotropy at continental regions, mainly at stable areas, gives important information about past and present tectonic events, and helps us in understanding patterns of upper mantle flow in a way not achieved by other methods. The measurement of shear wave splitting (SWS), at individual stations, from core refracted phases (such as SKS phases), indicates the amount and orientation of the seismic anisotropy in the upper mantle. Previous studies of SWS in South America concentrated mainly along the Andes and in southeast Brazil. Now we add extra measurements extending to all Brazilian territory, especially in the Pantanal and Paraná-Chaco basins, as part of the FAPESP 3-Basins Thematic Project. The results from both temporary deployments and from the Brazilian permanent network provide a more complete and robust anisotropy map of the South America stable platform. In general the fast polarization orientations have an average E-W orientation. Significant deviations to ESE-WNW or ENE-WSW are observed in many regions. We compare our results with different anisotropy proxies: absolute plate motion given by the hotspot reference frame HS3-NUVEL-1A, a recent model of time dependent upper mantle flow induced by the Nazca plate subduction, global anisotropy from surface wave tomography, and geologic trends. We observe a poor correlation of the anisotropy directions with geological trends, with the exception of a few stations in northern Brazil and a better correlation with the mantle flow model. Therefore, our observed anisotropy is mainly due to upper-mantle flow, with little contribution from frozen lithospheric anisotropy. Also, deviations from the mantle flow model, which includes a thicker lithosphere at the Amazon craton, are mainly due to flow surrounding cratonic nuclei not used in the model: the keel of the São Francisco craton and a possible cratonic nucleus beneath the northern part of the Paraná Basin (called Paranapanema block). Large delay times at the Pantanal Basin may indicate a stronger asthenospheric channel, a more coherent flow, or a thicker asthenosphere. Small delays beneath the northern Paraná Basin and central Amazon craton may indicate thinner anisotropic asthenosphere. / Anisotropia sísmica em regiões continentais, principalmente em áreas estáveis, nos dá informações importantes sobre eventos tectônicos do passado e do presente, e nos ajuda a entender padrões de fluxo do manto superior de forma não alcançada por outros métodos geofísicos. A medida de separação de ondas cisalhantes (SWS), em estações individuais, de fases refratadas no núcleo (fases SKS, por exemplo), indica a intensidade e orientação da anisotropia sísmica no manto superior. Estudos prévios de SWS na América do Sul se concentraram principalmente ao longo dos Andes e no sudeste do Brasil. Agora adicionamos medidas extras que se extendem por todo território Brasileiro e alguns países vizinhos, especialmente nas bacias do Pantanal e do Chaco-Paraná, como parte do \"Projeto Temático 3-Bacias\" da FAPESP. Os resultados tanto das estações temporárias quanto da rede permanente Brasileira mostram um mapa de anisotropia mais robusto e completo da plataforma estável da América do Sul. Em geral, as direções de polarização rápida tem em média direção L-O. Desvios significantes nas direções LSL-ONO ou LNL-OSO são observadas em muitas regiões. Comparamos nossos resultados com diferentes representantes da anisotropia: movimento absoluto de placa dado pelo sistema de referência de hotspot HS3-NUVEL-1A, um modelo recente dependente do tempo de fluxo do manto superior induzido pela subducção da placa de Nazca, anisotropia global de tomografia de ondas de superfície, e tendências geológicas. Observamos pouca correlação das direções de anisotropia com tendências geológicas, com exceção de algumas estações no norte do Brasil e uma melhor correlação com o modelo de fluxo do manto. Portanto, nossa anisotropia observada é devida principalmente a fluxo do manto superior, com pouca contribuição de anisotropia \"congelada\" litosférica. Também, desvios do modelo de fluxo do manto, o qual inclui uma litosfera mais espessa no cráton da Amazônia, são devido ao fluxo ao redor de núcleos cratônicos não usados no modelo: a quilha do cráton do São Francisco e um possível núcleo cratônico abaixo da região norte da bacia do Paraná (chamado bloco do Paranapanema). Atrasos de tempo grandes na bacia do Pantanal podem indicar um canal astenosférico mais forte, um fluxo mais coerente ou uma astenosfera mais espessa. Pequenos atrasos abaixo da parte norte da bacia do Paraná e no centro do cráton da Amazônia podem indicar uma astenosfera mais fina.

To design an efficient solar energy conversion device, theoretical input is extremely important to provide the basic guideline for experimental scientists, to fabricate the most efficient, cheap, and stable device with less efforts. This desire can be made possible if computational scientist use a proper theoretical protocol, design an energy material, then the experimentalist will only invest weeks or months on the synthetic effort. This thesis highlights my recent efforts in this direction. Monoclinic BiVO4 is has been using as a photocatalyst due to its stability, cheap, easily synthesizable, narrow band gap and ideal VB (-6.80 eV vs vacuum) but inappropriate CB (-4.56 eV vs vacuum) edge position, responsible for its low efficiency. We have carried out a comprehensive experimental and periodic density functional theory (DFT) simulations of the pristine, Oxygen defective (Ov), Se doped monoclinic BiVO4 and heterojunction with Selenium (Se-BiVO4), to improve not only its CB edge position but photocatalytic and charge carrier properties. It is found that Ov (1% Oxygen vacancy) and mild doped BiVO4 (1 to 2% Se) are thermodynamically stable, have ideal band edges ~ -4.30 eV), band gaps (~1.96 eV), and small effective masses of electrons and holes. We have also investigated the contribution of Se to higher performance by effecting morphology, light absorption and charge transfer properties in heterojunction. Finally, it is found that Se makes a direct Z-scheme (band alignments) with BiVO4 where the photoexcited electron of BiVO4 recombine with the VB of Se, consequences electron-hole separation at Se and BiVO4, respectively, as a result, enhanced photocurrent is obtained. Theoretical study of β-TaON in the form of primitive unit cell, supercell and its N, Ta, and O terminated surfaces are carried out with the help of periodic DFT. Optical and electronic properties of all these different species are simulated, which predict TaON as the best candidate for photocatalytic water splitting contrast to their Ta2O5 and Ta3N5 counterparts. The calculated bandgap, valence band, and conduction band edge positions predict that β-TaON should be an efficient photoanodic material. The valence band is made up of N 2p orbitals with a minor contribution from O 2p, while the conduction band is made up of Ta 5d. Turning to thin films, the valence band maximum; VBM (−6.4 eV vs. vacuum) and the conduction band minimum; CBM (−3.3 eV vs. vacuum) of (010)-O terminated surface are respectively well below and above the redox potentials of water as required for photocatalysis. Charge carriers have smaller effective masses than in the (001)-N terminated film (VBM −5.8 and CBM −3.7 eV vs. vacuum). However, due to wide band gap (3.0 eV) of (010)-O terminated surface, it cannot absorb visible wavelengths. On the other hand, the (001)-N terminated TaON thin film has a smaller band gap in the visible region (2.1 eV) but the bands are not aligned to the redox potential of water. Possibly a mixed phase material would produce an efficient photoanode for solar water splitting, where one phase performs the oxidation and the other reduction. Computational study of an optically transparent, near-infrared-absorbing low energy gap conjugated polymer, donor−acceptor−donor (D-A-D) with promising attributes for photovoltaic application is reported herein. The D and A moiety on the polymeric backbone have been found to be responsible for tuning the band gap, optical gap, open circuit (Voc) and short-circuit current density (Jsc) in the polymers solar cells (PSC). Reduction in the band gap, high charge transformation, and enhanced visible light absorption in the D-A-D system is because of strong overlapping of molecular orbitals of D and A. In addition, the enhanced planarity and weak steric hindrance between adjacent units of D-A-D, resulted in red-shifting of its onset of absorption. Finally, PSC properties of the designed D-A-D was modeled in the bulk heterojunction solar cell, which gives theoretical Voc of about 1.02 eV. DFT study has been carried out to design a new All-Solid-State dye-sensitized solar cell (SDSC), by applying a donor-acceptor conjugated polymer instead of liquid electrolyte. The typical redox mediator (I1−/I3−) is replaced with a narrow band gap, hole transporting material (HTM). A unique “upstairs” like band energy diagram is created by packing N3 between HTM and TiO2. Our theoretical simulations prove that the proposed configuration will be highly efficient as the HOMO level of HTM is 1.19 eV above the HOMO of sanitizer (dye); providing an efficient pathway for charge transfer. High short-circuit current density and power conversion efficiency is promised from the strong overlapping of molecular orbitals of HTM and sensitizer. A low reorganization energy of 0.21 eV and exciton binding energy of 0.55 eV, confirm the high efficiency of HTM. Theoretical and experimental studies of a series of four porphyrin-furan dyads were designed and synthesized, having anchoring groups, either at meso-phenyl or pyrrole-β position of a zinc porphyrin based on donor–π–acceptor (D–π–A) approach. The porphyrin macrocycle acts as donor, furan hetero cycle acts as π-spacer and either cyanoacetic acid or malonic acid group acts as acceptor. Optical bandgap, natural bonding, and molecular bonding orbital (HOMO–LUMO) analysis confirm the high efficiency pyrrole-β substituted zinc porphyrins contrast to meso-phenyl dyads. DFT study of polypyrrole-TiO2 composites has been carried out to explore their optical, electronic and charge transfer properties for the development of an efficient photocatalyst. Titanium dioxide (Ti16O32) was interacted with a range of pyrrole (Py) oligomers to predict the optimum composition of nPy-TiO2 composite with suitable band structure for efficient photocatalytic properties. The study has revealed that Py-Ti16O32 composites have narrow band gap and better visible light absorption capability compared to individual constituents. A red-shifting in λmax, narrowing band gap, and strong intermolecular interaction energy (-41 to −72 kcal/mol) of nPy-Ti16O32 composites confirm the existence of strong covalent type interactions. Electron−hole transferring phenomena are simulated with natural bonding orbital analysis where Py oligomers found as donor and Ti16O32 as an acceptor in nPy-Ti16O32 composites. Sensitivity and selectivity of polypyrrole (PPy) towards NH3, CO2 and CO have been studied at DFT. PPy oligomers are used both, in the doped (PPy+) and neutral (PPy) form, for their sensing abilities to realize the best state for gas sensing. Interaction energies and amount of charges (NBO and Mulliken charge analysis) are simulated which reveal the sensing ability of PPy towards these gases. PPy, both in doped and neutral state, is more sensitive to NH3 compared to CO2 and CO. More interestingly, NH3 causes doping of PPy and de-doping of PPy+, providing evidence that PPy/PPy+ is an excellent sensor for NH3 gas. UV-vis and UV-vis-near-IR spectra of nPy, nPy+, and nPy/nPy+-X complexes demonstrate strong interaction of PPy/PPy+ with these atmospheric gases. The applications of graphene (GR) and its derivatives in the field of composite materials for solar energy conversion, energy storage, environment purification and biosensor applications have been reviewed. The vast coverage of advancements in environmental applications of GR-based materials for photocatalytic degradation of organic pollutants, gas sensing and removal of heavy metal ions is presented. Additionally, the presences of graphene composites in the bio-sensing field have been also discussed in this review.

Nous abordons le développement d'une nouvelle génération de méthodes numériques pour la résolution des EDP évolutives qui modélisent des phénomènes multi-échelles en temps et en espace issus de divers domaines applicatifs. La raideur associée à ce type de problème, que ce soit via le terme source chimique qui présente un large spectre d'échelles de temps caractéristiques ou encore via la présence de fort gradients très localisés associés aux fronts de réaction, implique en général de sévères difficultés numériques. En conséquence, il s'agit de développer des méthodes qui garantissent la précision des résultats en présence de forte raideur en s'appuyant sur des outils théoriques solides, tout en permettant une implémentation aussi efficace. Même si nous étendons ces idées à des systèmes plus généraux par la suite, ce travail se focalise sur les systèmes de réaction-diffusion raides. La base de la stratégie numérique s'appuie sur une décomposition d'opérateur spécifique, dont le pas de temps est choisi de manière à respecter un niveau de précision donné par la physique du problème, et pour laquelle chaque sous-pas utilise un intégrateur temporel d'ordre élevé dédié. Ce schéma numérique est ensuite couplé à une approche de multirésolution spatiale adaptative permettant une représentation de la solution sur un maillage dynamique adapté. L'ensemble de cette stratégie a conduit au développement du code de simulation générique 1D/2D/3D académique MBARETE de manière à évaluer les développements théoriques et numériques dans le contexte de configurations pratiques raides issue de plusieurs domaines d'application. L'efficacité algorithmique de la méthode est démontrée par la simulation d'ondes de réaction raides dans le domaine de la dynamique chimique non-linéaire et dans celui de l'ingénierie biomédicale pour la simulation des accidents vasculaires cérébraux caractérisée par un terme source "chimique complexe''. Pour étendre l'approche à des applications plus complexes et plus fortement instationnaires, nous introduisons pour la première fois une technique de séparation d'opérateur avec pas de temps adaptatif qui permet d'atteindre une précision donnée garantie malgré la raideur des EDP. La méthode de résolution adaptative en temps et en espace qui en résulte, étendue au cas convectif, permet une description consistante de problèmes impliquant une très large palette d'échelles de temps et d'espace et des scénarios physiques très différents, que ce soit la propagation des décharges répétitives pulsées nanoseconde dans le domaine des plasmas ou bien l'allumage et la propagation de flammes dans celui de la combustion. L'objectif de la thèse est l'obtention d'un solveur numérique qui permet la résolution des EDP raides avec contrôle de la précision du calcul en se basant sur des outils d'analyse numérique rigoureux, et en utilisant des moyens de calculs standard. Quelques études complémentaires sont aussi présentées comme la parallélisation temporelle, des techniques de parallélisation à mémoire partagée et des outils de caractérisation mathématique des schémas de type séparation d'opérateur. / We tackle the development of a new generation of numerical methods for the solution of time dependent PDEs modeling general time/space multi-scale phenomena issued from various application fields. This type of problem induces well-known numerical restrictions and potentially large stiffness, which stem from the broad spectrum of time scales in the nonlinear chemical terms as well as from steep, spatially very localized, spatial gradients in the reaction fronts. Therefore, dedicated numerical strategies are needed to ensure the accuracy of the numerical approximations from a theoretical point of view, taking also into account adequate practical implementations to reduce computational costs. In order to cope with these problems, this study introduces a few mathematical and numerical elements for the solution of stiff reaction-diffusion systems, extensible in practice to more general configurations. The core of the numerical strategy is thus based on a specially conceived operator splitting method with dedicated high order time integration schemes for each subproblem. An appropriate choice of splitting time steps allows us the simulation of the solution within a prescribed accuracy, according to the overall physics of the problem. The resulting numerical scheme is properly coupled with an adaptive multiresolution technique for dynamic spatial mesh representations of the solution. Such an approach has led to the conception of the academic, generic 1D/2D/3D MBARETE code in order to evaluate the proposed theoretical and numerical developments in practical stiff configurations arising in several research fields. The algorithmic efficiency of the method is assessed by the simulation of propagating stiff reaction waves issued from nonlinear chemical dynamics and from biomedical engineering applications for a brain stroke model with "detailed chemical mechanisms''. Moreover, in order to extend the applicability of the method to more complex and unsteady problems, we consider for the first time a time adaptive splitting scheme for stiff PDEs, that yields dynamic time stepping within the prescribed accuracy. The fully time/space adaptive method allows us then a consistent description of reaction-diffusion-convection problems disclosing a broad spectrum of time/space scales as well as different physical scenarios, such as highly nanosecond repetitively pulsed discharges or self-ignition and propagation of flames for, respectively, plasma and combustion applications. The main goal of this work is hence to numerically solve stiff PDEs with reasonable, standard computational resources and based on a mathematical background that ensures robust, general and accurate numerical schemes. Further studies are also presented that include time parallelization strategies, parallel computing techniques for shared memory architectures and complementary mathematical characterization of splitting schemes.

Seismic anisotropy at continental regions, mainly at stable areas, gives important information about past and present tectonic events, and helps us in understanding patterns of upper mantle flow in a way not achieved by other methods. The measurement of shear wave splitting (SWS), at individual stations, from core refracted phases (such as SKS phases), indicates the amount and orientation of the seismic anisotropy in the upper mantle. Previous studies of SWS in South America concentrated mainly along the Andes and in southeast Brazil. Now we add extra measurements extending to all Brazilian territory, especially in the Pantanal and Paraná-Chaco basins, as part of the FAPESP 3-Basins Thematic Project. The results from both temporary deployments and from the Brazilian permanent network provide a more complete and robust anisotropy map of the South America stable platform. In general the fast polarization orientations have an average E-W orientation. Significant deviations to ESE-WNW or ENE-WSW are observed in many regions. We compare our results with different anisotropy proxies: absolute plate motion given by the hotspot reference frame HS3-NUVEL-1A, a recent model of time dependent upper mantle flow induced by the Nazca plate subduction, global anisotropy from surface wave tomography, and geologic trends. We observe a poor correlation of the anisotropy directions with geological trends, with the exception of a few stations in northern Brazil and a better correlation with the mantle flow model. Therefore, our observed anisotropy is mainly due to upper-mantle flow, with little contribution from frozen lithospheric anisotropy. Also, deviations from the mantle flow model, which includes a thicker lithosphere at the Amazon craton, are mainly due to flow surrounding cratonic nuclei not used in the model: the keel of the São Francisco craton and a possible cratonic nucleus beneath the northern part of the Paraná Basin (called Paranapanema block). Large delay times at the Pantanal Basin may indicate a stronger asthenospheric channel, a more coherent flow, or a thicker asthenosphere. Small delays beneath the northern Paraná Basin and central Amazon craton may indicate thinner anisotropic asthenosphere. / Anisotropia sísmica em regiões continentais, principalmente em áreas estáveis, nos dá informações importantes sobre eventos tectônicos do passado e do presente, e nos ajuda a entender padrões de fluxo do manto superior de forma não alcançada por outros métodos geofísicos. A medida de separação de ondas cisalhantes (SWS), em estações individuais, de fases refratadas no núcleo (fases SKS, por exemplo), indica a intensidade e orientação da anisotropia sísmica no manto superior. Estudos prévios de SWS na América do Sul se concentraram principalmente ao longo dos Andes e no sudeste do Brasil. Agora adicionamos medidas extras que se extendem por todo território Brasileiro e alguns países vizinhos, especialmente nas bacias do Pantanal e do Chaco-Paraná, como parte do \"Projeto Temático 3-Bacias\" da FAPESP. Os resultados tanto das estações temporárias quanto da rede permanente Brasileira mostram um mapa de anisotropia mais robusto e completo da plataforma estável da América do Sul. Em geral, as direções de polarização rápida tem em média direção L-O. Desvios significantes nas direções LSL-ONO ou LNL-OSO são observadas em muitas regiões. Comparamos nossos resultados com diferentes representantes da anisotropia: movimento absoluto de placa dado pelo sistema de referência de hotspot HS3-NUVEL-1A, um modelo recente dependente do tempo de fluxo do manto superior induzido pela subducção da placa de Nazca, anisotropia global de tomografia de ondas de superfície, e tendências geológicas. Observamos pouca correlação das direções de anisotropia com tendências geológicas, com exceção de algumas estações no norte do Brasil e uma melhor correlação com o modelo de fluxo do manto. Portanto, nossa anisotropia observada é devida principalmente a fluxo do manto superior, com pouca contribuição de anisotropia \"congelada\" litosférica. Também, desvios do modelo de fluxo do manto, o qual inclui uma litosfera mais espessa no cráton da Amazônia, são devido ao fluxo ao redor de núcleos cratônicos não usados no modelo: a quilha do cráton do São Francisco e um possível núcleo cratônico abaixo da região norte da bacia do Paraná (chamado bloco do Paranapanema). Atrasos de tempo grandes na bacia do Pantanal podem indicar um canal astenosférico mais forte, um fluxo mais coerente ou uma astenosfera mais espessa. Pequenos atrasos abaixo da parte norte da bacia do Paraná e no centro do cráton da Amazônia podem indicar uma astenosfera mais fina.

Dans une société qui peine à renoncer à l'utilisation des énergies fossiles, la production d'hydrogène à partir d'eau par photocatalyse solaire est une alternative que les chimistes se doivent d'explorer. La mise en place de cette solution est conditionnée à la résolution de deux problèmes majeurs : augmenter l'efficacité de la conversion solaire par le développement de nouveaux semi-conducteurs, et améliorer la réactivité en surface par le développement de co-catalyseurs efficaces. Dans un premier temps, nous avons contribué à l'étude d'une nouvelle famille de semi-conducteurs par des calculs ab initio DFT. Différentes propriétés clés ont été calculées et comparées aux valeurs expérimentales. Nous avons montré que pour une même famille de matériaux, l'absorption peut être contrôlée par modification de la composition.Ensuite, nous nous sommes focalisés sur la réaction d'oxydation de l'eau (OER). Pour cette réaction les catalyseurs de type oxyhydroxydes et leurs dérivés sont très prometteurs car à la fois efficaces et contenant des éléments abondants sur Terre, mais la compréhension de son mécanisme reste limitée. Sur le composé modèle CoOOH, nous en avons réalisé une analyse approfondie par une étude exhaustive des intermédiaires ainsi que par modélisation explicite du potentiel électrochimique. Nos études ont montré la nécessite de prendre en compte plusieurs sites réactionnels dans la détermination des mécanismes d'oxydation de l'eau sur la surface de ces catalyseurs. Enfin, une étude préliminaire de l'utilisation de la biomasse a été menée, dans le but de combiner valorisation de la biomasse et production d'hydrogène. Le cas de l'oxydation du glycérol est envisagé. / In a society struggling to waive the use of fossil fuels, hydrogen production from water by solar photocatalysis is a alternative chemists have to consider. Setting up of this solutions asks to tackle two major issues : increase solar energy conversion by developing new semiconductors, and enhance the surface reactivity by developing efficient cocatalysts.First, DFT \emph{ab initio} calculations were carried out on a new family of semiconductor materials. Different key properties were computed and compared to experimental values. We showed that for a same material family, absorption can be controlled by changing the composition.Then, we focused on Oxygen Evolution Reaction (OER). For this reaction oxyhydroxides catalysts and their derivatives seem promising as both efficient and containing earth-abundant elements, but the understanding of its mechanism still remains unclear. On CoOOH model compound, we realised an extended analysis by a comprehensive study of intermediates and by explicit modelling of electrochemical potential. Our studies showed that taking into account several reactive sites is necessary to determine the OER mechanism on these catalysts' surface.Last, a preliminary study of biomass use was carried, in order to combine its valorization along with hydrogen production. The case of glycerol photoreforming is considered.

Ce travail est consacré à la construction de méthodes numériques permettant la simulation de processus d'implosion de coquilles en fusion par confinement inertiel (FCI) avec prise en compte des termes de champ magnétique auto-généré. Dans ce document, on commence par décrire le modèle de magnétohydrodynamique résistive à deux températures considéré ainsi que les relations de fermeture utilisées. Le système d'équations ainsi obtenu est alors divisé en sous-systèmes selon la nature de l'opérateur mathématique sous-jacent pour lesquels l'on propose ensuite des schémas numériques adaptés. On insiste notamment sur le développement de schémas volumes finis pour l'opérateur hyperbolique, ce dernier correspondant aux équations d'Euler ou de la magnétohydrodynamique idéale selon que l'on tienne compte ou non des termes de champ magnétique. Plus précisement, on propose une nouvelle classe de schémas d'ordre élevé à directions alternées construits dans le formalisme Lagrange + projection sur grille cartésienne qui présentent l'originalité d'être particulièrement bien adaptés aux calculateurs modernes grâce, entre autres, au traitement par directions alternées et à l'utilisation de techniques de viscosité artificielle. Cette propriété est illustrée par des mesures de performance séquentielle et d'efficacité parallèle. On combine ensuite les schémas hyperboliques développés avec des méthodes de type volumes finis permettant letraitement semi-implicite des termes de conduction thermique et résistive et une prise en compte explicite des termes de champ magnétique auto-générés. Afin d'étudier les caractéristiques et les effets des champs magnétiques auto-générés, on présente enfin un cas test de capsule FCI simulée à partir du début de la phase de décélération.