O espalhamento de ondas eletromagnéticas por partículas isoladas, com propriedades ópticas e formatos arbitrários, encontra aplicações nas mais diversas áreas do conhecimento. Usualmente, o espalhamento eletromagnético é investigado via grandezas auferidas na região de campo distante. Para partículas inomogêneas, no entanto, as ressonâncias nas seções de choque de espalhamento podem não corresponder a um aumento de intensidade do campo eletromagnético nas vizinhanças imediatas da partícula (região de campo próximo). Esse efeito pode ser induzido em nanopartículas dielétricas com revestimentos plasmônicos e foi recentemente explicado em termos da ressonância de Fano. Essa ressonância resulta da interferência entre um modo eletromagnético não ressonante (processo de fundo) e um modo discreto ressonante (ressonância de plásmon), produzindo um formato assimétrico de linha espectral. Para o entendimento de como os modos de superfície no campo próximo acoplam-se às ressonâncias nas seções de choque, é necessário o cálculo de funcionais dos campos eletromagnéticos internos às partículas ou em suas vizinhanças imediatas. Neste estudo, calculamos a energia eletromagnética no interior de centros espalhadores nas geometrias esférica e cilíndrica. Fazemos aqui o vínculo dos campos internos às grandezas de espalhamento no campo distante via seção de choque de absorção e conservação de energia. Aplicamos nossos resultados a metamateriais dispersivos, estudando as propriedades do espalhamento por esferas revestidas e por esferas quirais, no regime de refração negativa, e por cilindros revestidos sob incidência oblíqua de radiação. Mediante a energia interna às partículas, demonstramos novos efeitos de aumento de intensidade de campo interno fora da ressonância de espalhamento e fornecemos resultados analíticos para a análise dessas ressonâncias, tanto em espalhamento simples quanto múltiplo. / Electromagnetic wave scattering by single particles with both shapes and optical properties arbitrary finds applications in several areas of knowledge. Usually, the electromagnetic scattering is investigated via measured quantities in the far-field region. However, for inhomogeneous particles, resonances in scattering cross sections may not correspond to the electromagnetic field enhancement in the vicinity of a particle (near-field). This effect can be induced in dielectric nanoparticles with plasmonic coatings, and it has recently been explained in terms of the Fano resonance. The Fano resonance results from the interference between a non-resonant electromagnetic mode (background or continuous) and a resonant discrete mode (localized plasmon resonance), leading to an asymmetric lineshape. To understand how the surface modes in the near-field are connected to the cross section resonances, functionals of the electromagnetic fields within scatterers or in their vicinity are required. In this study, we calculate the electromagnetic energy inside scatterers in both cylindrical and spherical geometries. We obtain a connection between the internal energy and the scattering quantities in the far-field via absorption cross section and energy conservation. We apply our results to dispersive metamaterials, studying scattering properties of coated and chiral spheres in the negative refraction regime, and coated cylinders under oblique incidence of radiation. By the electromagnetic energy inside particles, we demonstrate new off-resonance field enhancement effects and provide analytical tools to analyze these resonances in both single and multiple scattering regimes.

The recent development of free-electron lasers operating at XUV and X-ray wavelengths are proving vital for the exploration of matter in extreme conditions. The ultra-short pulse length and high peak brightness these light sources provide, combined with a tunable X-ray wavelength range, makes them ideally suited both for creating high energy density samples and for their subsequent study. In this thesis I describe the work done on the XUV free-electron laser FLASH in Hamburg, aimed at creating homogeneous samples of warm dense matter through the process of volumetric XUV photo-absorption, and the theoretical work undertaken to understand the process of high-intensity laser-matter interactions. As a first step, we have successfully demonstrated intensities above 10¹⁷ Wcm-2 at a wavelength of 13.5 nm, by focusing the FEL beam to micron and sub-micron spot sizes by means of a multilayer-coated off-axis parabolic mirror. Using these record high intensities, we have demonstrated for the first time saturable absorption in the XUV. The effect was observed in aluminium and magnesium samples and is due to the bleaching of a core-state absorption channel by the intense radiation field. This result has major implications for the creation of homogeneous high energy density systems, as a saturable absorption channel allows for a more homogeneous heating mechanism than previously thought possible. Further, we have conducted soft X-ray emission spectroscopy measurements which have delivered a wealth of information on the highly photo-excited system under irradiation, immediately after the excitation pulse, yet before the system evolves into the warm dense matter state. Such strongly photo-excited samples have also been studied theoretically, by means of density functional theory coupled to molecular dynamics calculations, yielding detailed electronic structure information. The use of emission spectroscopy as a probe for solid-density and finite-temperature systems is discussed in light of these results. Theoretical efforts have further been made in the study of the free-free absorption of aluminium as the system evolves from the solid state to warm dense matter. We predict an absorption peak in temperature as the system heats and forms a dense plasma. The physical significance of this effect is discussed in terms of intense light-matter interactions on both femtosecond and picosecond time-scales.

Il y a plus d'un siècle, les conditions de travail ont fortement évolué sous l'influence de l'industrialisation et notamment à partir de nouvelles méthodes de travail du type Tayloriennes. Des bureaux ouverts à l'Action Office des années 50, c'est plus de 60% de la population active qui est concernée aujourd'hui en Europe. L'évolution des réglementations, liée à la prise de conscience collective des effets psychosomatiques des nuisances sonores, entraîne l'implication par les maîtrises d'ouvrages de bureaux d'études acoustiques pour la préconisation et la mise en œuvre dans la construction et la réhabilitation des espaces tertiaires. La rencontre d'acteurs scientifiques et industriels a donné lieu à ce travail de thèse, étudiant la propagation de l'énergie acoustique pour des espaces dont une des dimensions est différente des autres.La méthode se réduit à la conservation du tenseur énergie-impulsion puis à un système d'équations couplées sur l'intensité acoustique et sur la densité d'énergie. C'est un système hyperbolique d'équations linéaires aux dérivés partielles du premier ordre. Une méthode d'intégration sur une à deux dimensions de l'espace permet d'introduire les coefficients d'absorption et de diffusion moyens. Nous introduisons le potentiel d'intensité et nous écrivons le système sous la forme d'une équation hyperbolique linéaire aux dérivées partielles du second ordre impliquant la densité d'énergie, l'intensité acoustique ou le potentiel d'intensité sur une ou deux dimensions. Nous proposons une méthode analytique approchée permettant de vérifier les résultats à une dimension.Pour la conception acoustique des plateaux de bureaux, la modélisation informatique est un outil remarquable souffrant pourtant de limitations restreignant ses applications. Nous résolvons le formalisme introduit dans ce travail par la méthode des différences finies dans le domaine temporel sur une et deux dimensions. Les schémas utilisés sont stables et explicites et peu couteux en mémoires informatiques. Le fait que nous nous intéressions à une variable énergétique permet de considérer un pas de modélisation spatial important - de l'ordre du mètre - et d'accélérer d'autant les calculs.Le partenariat industriel nous a notamment permis d'accéder à des espaces de type plateaux de bureaux. Nous comparons les résultats des modélisations avec des mesures in situ conduites avec un microphone SoundField ST250 permettant l'estimation de la densité d'énergie et de l'intensité acoustique. / More than a century ago, working conditions have evolved under the influence of industrialization and especially of new management methods such as the Taylorism. From Open-Spaces to Action Offices in the 1950s, more than 60 % of the European working population is concerned today. The evolution of regulations, linked to the collective awareness of the psychosomatic effects of noise, has led clients to request the involvement of acoustical consultants for giving recommendations and supervising their implementation in constructions and rehabilitations of office spaces. This is why scientific and industrial stakeholders joined forces for this thesis dedicated to the propagation of sound energy within rooms characterized by one dimension different from the others.The method developed in this thesis reduces the conservation of the energy-stress tensor to a system of coupled equations for the sound intensity and the sound energy density. It is a hyperbolic system of linear, partial differential equations of first order. Integrating this system on one or two space dimensions leads to the introduction of the mean absorption and diffusion coefficients. We then introduce an intensity potential and write the system in the form of a linear hyperbolic equation involving partial derivatives of second order for the energy density, the sound intensity, or the intensity potential in one or two dimensions. We also propose an analytical approximated method to verify the results in one dimension.For the acoustic design of open-space offices, computer modelling is an outstanding tool. Yet limitations restrict its applications. We solve the equations introduced in this work by the finite-difference time-domain method in the one- and two-dimensional cases. We use stable and explicit schemes that require little computer memory. Considering energy variables allows the use of large spatial steps - of the order of the metre - and accelerates the calculations.The industrial partnership notably gave us access to open-space offices. We compare the results of the modelling with in situ measurements carried out with a SoundField ST250 microphone that makes it possible to estimate the sound energy density and the sound intensity.

Standard crystalline silicon photovoltaic (PV) modules are designed to continuously convert solar energy into electricity for 25 years. However, the continual generation of electricity by the PV modules throughout their designed service life has been a concern. The key challenge has been the untimely fatigue failure of solder interconnections of solar cells in the modules due to accelerated thermo-mechanical degradation. The goal of this research is to provide adequate information for proper design of solar cell solder joint against fatigue failure through the study of cyclic thermo-mechanical stresses and strains in the joint. This is carried-out through finite element analysis (FEA) using ANSYS software to develop the solar cell assembly geometric models followed by simulations. Appropriate material constitutive model for solder alloy is employed to predict number of cycles to failure of solder joint, hence predicting its fatigue life. The results obtained from this study indicate that intermetallic compound thickness (TIMC); solder joint thickness (TSJ) and width (WSJ) have significant impacts on fatigue life of solder joint. The impacts of TIMC and TSJ are such that as the thicknesses increases solder joint fatigue life decreases. Conversely, as solder joint width (WSJ) increases, fatigue life increases. Furthermore, optimization of the joint is carried-out towards thermo-mechanical reliability improvement. Analysis of results shows the design with optimal parameter setting to be: TIMC -2.5μm, TSJ -20μm and WSJ -1000μm. In addition, the optimized model has 16,264 cycles to failure which is 18.82% more than the expected 13,688 cycles to failure of a PV module designed to last for 25 years.

In the late 1970s, a method was developed to estimate acoustic intensity in one dimension by taking the cross-spectral density of two closely-spaced microphone signals. Since then, multimicrophone probes have been developed to measure three-dimensional intensity as well as energy density. Their usefulness has led to the design of various types of multimicrophone probes, the most common being the four-microphone orthogonal, the four-microphone regular tetrahedron, and the six-microphone designs. These designs generally either consist of microphones suspended in space near each other or mounted on the surface of a sphere. This work analytically compares the relative merits of each probe design in measuring acoustic intensity and investigates the various finite-sum and finite-difference processing methods used with each. The analysis is limited to probes consisting of perfect point sensors in plane wave fields. The comparison is given in terms of average and maximum errors for intensity magnitude and direction as a function of angle of incidence as well as the spread between maximum and minimum errors for intensity magnitude. After existent probe geometries are reviewed, optimization techniques are introduced to predict what the optimal probe geometry would be for any given scenario. The probe is optimized to give the lowest intensity error averaged over angle of incidence of plane waves. This is done for full-space and half-space scenarios.

Dans cette thèse, nous développons un modèle collectif de la structure du noyau préservant les symétries, basé sur la théorie des fonctionnelles de la densité relativistes. Les états de référence à déformation quadrupole/octupole et à symétrie axiale sont générés en résolvant les équations de Hartree-Bogoliubov relativistes. Nous employons la fonctionnelle avec couplage ponctuel covariant DD-PC1 dans le canal particule-trou de l'interaction effective, tandis que la force d'appariement non-relativiste séparable dans l'espace des impulsions est utilisée dans le canal particule-particule. Les corrélations collectives relatives à la restauration des symétries brisées sont prises en compte en projetant les états de référence à la fois sur les bonnes valeurs du moment angulaire, de la parité et du nombre de particules. L'étape suivante consiste à combiner les états à symétries restaurées à l'aide du formalisme de la méthode de la coordonnée génératrice. Ceci nous permet d'obtenir des prédictions spectroscopiques détaillées, incluant les énergies d'excitation, les moments multipolaires électromagnétiques et les taux de transition, ainsi que les facteurs de forme élastique et inélastique. La méthode décrite est globale et peut être employée pour l'étude de la structure de nucléides très divers. Comme première application de ce modèle, nous étudierons la formation de clusters dans les noyaux légers. Le clustering nucléaire peut être considéré comme étant un phénomène de transition entre les phases liquide quantique et solide des noyaux finis. En contraste avec l'image conventionnelle du liquide quantique homogène, la localisation spatiale des particules alpha donne une image du noyau atomique similaire à une molécule. Nous réalisons en particulier une analyse complète de la collectivité quadrupole-octupole et des structures de cluster dans les isotopes du néon. Une attention particulière est accordée au cas de l'isotope ²⁰Ne, dans lequel il semble que les structures de cluster apparaissent dès l'état fondamental. Nous étudions également la structure à basse énergie de l'isotope ¹²C. Nous concentrons notre analyse sur la structure en bandes construite à partir d'états 0⁺ qui manifestent une grande variété de formes, notamment les configurations triangulaires de la bande de Hoyle ainsi que des chaînes linéaires 3-alpha dans des états de plus haute énergie. / In this thesis we develop a symmetry-conserving collective model for nuclear structure studies based on the relativistic energy density functional framework. Axially-symmetric quadrupole- and octupole-deformed reference states are generated by solving the relativistic Hartree-Bogoliubov equations. In the particle-hole channel of the effective interaction we employ the covariant point-coupling DD-PC1 functional, while the non-relativistic pairing force separable in momentum space is used in the particle-particle channel. Collective correlations related to restoration of broken symmetries are accounted for by simultaneously projecting reference states on good values of angular momenta, parity, and particle numbers. In the next step, symmetry-restored states are mixed within the generator coordinate method formalism. This enables us to obtain detailed spectroscopic predictions, including excitation energies, electromagnetic multipole moments and transition rates, as well as both the elastic and inelastic form factors. The described framework is global and it can be employed in various nuclear structure studies across the entire nuclide chart. As a first application, we will study formation of clusters in light nuclei. Nuclear clustering is considered to be a transitional phenomenon between quantum-liquid and solid phases in nuclei. In contrast to the conventional homogeneous quantum-liquid picture, spatial localization of alpha-particles gives rise to a molecule-like picture of atomic nuclei. In particular, we carry out a comprehensive analysis of quadrupole-octupole collectivity and cluster structures in neon isotopes. A special attention is paid to the case of self-conjugate ²⁰Ne isotope, where cluster structures are thought to form already in the ground state. Finally, we study the low-lying structure of ¹²C isotope. We focus on the structure of bands built on 0⁺ states that are known to manifest a rich variety of shapes, including the triangular configurations of the Hoyle band and 3-alpha linear chains in higher states.

In der vorliegenden Arbeit wird die Darstellung neuer organischer Polyazide dokumentiert, die durch einfache nucleophile Substitution mittels NaN3 dargestellt werden können. Organische Azide mit der Formel RN3 können sich unter Stickstoff-Abspaltung in exothermen, teilweise explosionsartigen Reaktionen zersetzen. Sie sind daher prinzipiell als energiereiche Materialien (HEDM) für entsprechende Anwendungen geeignet. Die als Treibladungsmaterialien potentiell geeignetsten, handhabungssicheren, dendritischen Polyazide werden unter anderem mittels Thermogravimetrie und Differenzkalorimetrie analysiert. In einer neuen Synthesemethode können die wenig bekannten Heteroazidomethane aus Tris(azidomethyl)amin erzeugt werden. Von besonderem Interesse ist dabei die Synthese neuartiger Azidohalogenmethane. Diese können durch analytische Gas-Chromatographie charakterisiert und mittels präparativer Gas-Chromatographie isoliert werden. Durch die 1,3-dipolare Cycloaddition mit Cyclooctin konnten einige Heteroazidomethane zu Triazolen abgefangen und so einer Einkristall-Röntgen-Strukturanalyse zugeführt werden. Als letztes in der homologen Reihe der Azidomethane noch fehlendes Azid konnte Tetraazidomethan synthetisiert werden. Das Perazidomethan besitzt mit 93.3% den für organische Azide höchstmöglichen Stickstoffgehalt. Seine Existenz wurde bislang lediglich durch molekültheoretische Berechnungen nahegelegt. Die Synthese dieses homoleptischen Kohlenstoffazides gelang durch die Behandlung von Trichloracetonitril mit Natriumazid. Es ließ sich durch präparative GC als extrem explosive, farblose Flüssigkeit isolieren. Mit Hilfe der analytischen GC konnten sowohl der Siedepunkt als auch die Polarität von C(N3)4 abgeschätzt werden. C(N3)4 wird desweiteren durch IR, MS, 13C-NMR und 15N-NMR-Spektroskopie sowie durch Einkristall-Röntgen-Strukturanalysen seiner Abfangprodukte mit Cyclooctin charakterisiert. Mit Wasser zeigt C(N3)4 eine quantitative Hydrolyse unter Bildung von Carbonyldiazid. Durch Austauschprozesse mit Na15N3 konnte die mögliche Dissoziation von C(N3)4 nachgewiesen werden. Reaktionen von C(N3)4 mit Phosphinen führen zu Cyanamidderivaten, mit Norbornen sowie Norbornadien wurden über vielstufige Reaktionsmechanismen Aminotetraazole erhalten.

On‐chip micro‐supercapacitors (MSCs), as promising power candidates for microdevices, typically exhibit high power density, large charge/discharge rates, and long cycling lifetimes. However, as for most reported MSCs, the unsatisfactory areal energy density (<10 µWh cm−2) still hinders their practical applications. Herein, a new‐type Zn‐ion hybrid MSC with ultrahigh areal energy density and long‐term durability is demonstrated. Benefiting from fast ion adsorption/desorption on the capacitor‐type activated‐carbon cathode and reversible Zn stripping/plating on the battery‐type electrodeposited Zn‐nanosheet anode, the fabricated Zn‐ion hybrid MSCs exhibit remarkable areal capacitance of 1297 mF cm−2 at 0.16 mA cm−2 (259.4 F g−1 at a current density of 0.05 A g−1), landmark areal energy density (115.4 µWh cm−2 at 0.16 mW cm−2), and a superb cycling stability without noticeable decay after 10 000 cycles. This work will inspire the fabrication and development of new high‐performance microenergy devices based on novel device design.

<div>For decades, the response of high-energy (HE) density materials at extreme conditions of pressure and temperature from strong insults like burning or impact have been studied in depth by the shock community. Shock physicists aim to develop a fundamental understanding for coupled chemical and physical processes across orders of magnitude spatial and temporal regimes. In order to succeed, this requires extensive collaboration between experiments and simulations, ranging from the electronic to the engineering scales. The end goals would be to develop predictive multiscale models capable of explaining ignition and initiation of HE systems and composites. The collected works in this thesis detail my contributions to the field of HE materials, specifically addressing the chemical reactivity at the atomistic level using reactive molecular dynamics (MD) simulations.</div><div><div>Through this endeavor, we aim to develop a critical understanding for the decomposition processes of HE materials. We begin with a validation the reactive force field, ReaxFF, by addressing the very strong anisotropic shock sensitivity in 2,2-Bis[(nitrooxy)methyl]propane-1,3-diyl dinitrate (PETN) through direct comparison of time-evolved spectra between experiments and simulations. Such strong orientation dependence is thought to relate to the initial decomposition events. Therefore we compare spectra at three different shock pressures, where we observe similar timescales for the disappearance of the NO2 symmetric and antisymmetric stretch modes. A more detailed chemical species analysis indicates that the NO2 molecular species could be considered the primary intermediate which initiates the decomposition process. Furthermore, these results suggest that the combination of explicit MD simulations and ultrafast spectroscopy will be key to the development of a detailed understanding of chemistry at extreme conditions.</div></div><div><div>Following the validation study, we further our understanding of reactivity in HE systems by investigating the differences in kinetics between an ordered and disordered system. It has been shown that shocked material is often severely strained, causing a loss in crystalline order. This in turn results in the disordered materials, such as amorphous solids, having</div><div>faster reactivity due to their higher internal energy and/or lower thermal conductivity. Our results indicate that extra energy is required to break the long-range order in bulk crystalline systems, thus resulting in slower decomposition rates. Further analyses of thermal hotspots point towards slightly faster chemical propagation in the amorphous samples due to lower thermal conductivity. These results provide an understanding for how molecular disorder can be attributed to increased reactivity.</div></div><div><div>After developing an understanding for the initial decomposition processes of HE materials, we turn our attention to a growing interest in the community which is the developing reduced order chemistry models for use in multiscale efforts. Many schemes report mechanisms that are obtained from experiments, which can have large error bars depending on the apparatus and/or extraction technique, or from gas phase simulations, which may not be relevant at shock conditions. To circumvent these issues, we develop a coarse-grained chemical kinetics model from all-atom reactive MD simulations by taking advantage of an unsupervised dimensionality reduction machine learning technique called non-negative matrix factorization. Doing so allows us to represent the overall decomposition chemistry as latent concentrations akin to reactants, intermediates, and products, which we then use to extract kinetics parameters and heats of reaction. These values are implemented into a continuum model, where we could simulate the criticality of thermal hotspots at regimes beyond the reach of MD, as well as verify how uncertainties in the parameters vary as a function of hotspot sizes.</div></div><div><div>Finally, we close with significant progress made towards on-going and future work, where we address two of the most challenging ideas in the field of HE materials: 1) developing definitive chemistry models at extreme conditions, and 2) improving coarse-grained descriptions for multiscale modeling.</div></div>

Dans le cadre de la fusion par confinement inertiel, une capsule contenant le combustible de deutérium-tritium est implosée soit par irradiation laser (attaque directe, interaction laser – cible de numéro atomique faible), soit par un rayonnement de corps noir émis par une cavité convertissant le rayonnement laser (attaque indirecte, interaction laser – cible de numéro atomique élevé).Dans les deux cas, une modélisation correcte du transport électronique est cruciale pour avoir des simulations hydro-radiatives prédictives. Cependant, il a été montré très tôt que les hypothèses d'un mécanisme de transport linéaire ne sont pas applicables dans le cadre de l'irradiation d'une cible solide par un laser de puissance (I~10^14 W/cm²). Cela est dû d'une part à des gradients de température très importants (effets cinétiques dits « non-locaux ») ainsi qu'à la présence d'un champ magnétique auto-généré par effet thermo-électrique. Enfin, le flux de chaleur et le champ magnétique sont fortement couplés au travers de deux mécanismes : le transport du champ magnétique par le flux de chaleur (effet Nernst) et la rotation et inhibition du flux de chaleur par la magnétisation du plasma (effet Righi-Leduc).Dans le présent manuscrit, nous commencerons par exposer les différents modèles de transport électronique, et en particulier le modèle non-local avec champ magnétique, implémenté dans le code hydro-radiatif FCI2. Par la suite, nous chercherons à valider ce modèle par des comparaisons avec un code cinétique, puis avec une expérience lors de laquelle le champ magnétique a été mesuré par radiographie proton. Cela fait, nous utiliserons le code FCI2 pour expliquer la source et le transport du champ, ainsi que son effet sur l'interaction.Enfin, nous étudierons la reconnexion du champ magnétique, lors de l'irradiation d'une cible par deux faisceaux lasers. / In the framework of the inertial confinement fusion, a pellet filled with the deuterium-tritium fuel is imploded, either through laser irradiation (direct drive, laser – low atomic number target interaction) or by the black body radiation from a cavity converting the laser radiation (indirect drive, laser – high atomic number target interaction).In both cases, a correct modeling of the electron transport is of first importance in order to have predictive hydro-radiative simulations. Nonetheless, it has been shown early on that the hypothesis of the linear transport are not valid in the framework of a solid target irradiated by a high power laser (I~1014 W/cm²). This is due in part to very steep temperature gradients (kinetic effects, so-called « non-local ») and because of a magnetic field self-generated through the thermo-electric effect. Finally, the heat flux and the magnetic field are strongly coupled through two mecanisms: the advection of the field with the heat flux (Nernst effect) and the rotation and inhibition of the heat flux by the plasma's magnetization (Righi-Leduc effect).In this manuscript, we will first present the various electron transport models, particularly the non-local with magnetic field model included in the hydro-radiative code FCI2. Following, in order to validate this model, we will compare it first against a kinetic code, and then with an experiment during which the magnetic field has been probed through proton radiography. Once the model validated, we will use FCI2 simulations to explain the source and transport of the field, as well as its effect on the interaction.Finally, the reconnection of the magnetic field, during the irradiation of a solid target by two laser beams, will be studied.