Orientador: Renato Sprung / Tese doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-06T18:06:45Z (GMT). No. of bitstreams: 1 Villanueva_SandraBizarriaLopes_D.pdf: 2768871 bytes, checksum: ec40bbcbf8152a8c34f6d7fdd395af83 (MD5) Previous issue date: 2005 / Resumo: Materiais do tipo hidrotalcita foram sintetizados, calcinados e caracterizados, assim como utilizados na conversão catalítica de etanol. As sínteses foram realizadas com razões molares AI/(AI + Mg) iguais a 0,20; 0,25 e 0,33; em todos os casos os difratogramas de raios-X demonstraram que, efetivamente, fases de hidrotalcitas tinham sido obtidas. Esses materiais apresentaram áreas superficiais BET de cerca de 50 a 70 m2.g-l, à exceção da hidrotalcita sintetizada com agentes precipitantes contendo amônio, em que a área superficial foi de cerca de 7 m2g -I. A quimissorção de CO2 desses materiais revelou que hidrota1citas calcinadas são sólidos básicos e tal basicidade relaciona-se com o teor de magnésio substituído e também com a temperatura de ca1cinação. Os testes catalíticos foram realizados a temperaturas de 3000 C a 4000 C e verificou-se o aumento da taxa de reação com o incremento da temperatura. Os produtos de condensação éter etílico e nbutanol foram obtidos em maior proporção. Hidrotalcitas da série sódio apresentaram maior rendimento de n-butanol independentemente do teor de alumínio presente na amostra. Todas as amostras utilizadas apresentaram, a baixas conversões, quantidades significativas de n-butanol, o que pode indicar que, além da via de condensação aldólica, a formação desse produto também ocorre via condensação direta do etanol, ou seja, sem a dessorção para a fase gasosa da molécula de acetaldeído. Testes catalíticos comparativos realizados com óxido de magnésio e alumínio resultaram principalmente em acetaldeído e etileno, respectivamente. Traços de n-butanol foram identificados no óxido de magnésio quando testado a 4000 C, e éter etílico foi observado em maior quantidade no óxido de alumínio quando testado a 3000 C / Abstract: Hydrotalcites-like materiaIs were prepared, calcined and characterized as well as used in the catalytic reaction of ethanol. The synthesis were perfonned with AI/(AI + Mg) ratios of 0.20; 0.25 and 0.33; in all cases the x-ray showed hydrotalcites phases. These materiaIs resulted in BET areas of 50 at 70 m2.g-1, except for the hydrotalcite synthesized with NH3, that resulted in a BET area 00 m2g-1. The CO2 chemisorption on these materiaIs revealed that calcined hydrotalcites are basic catalysts and their basicity was related to the quantity of substituted magnesium and to the calcination temperature. The catalytic reactions were performed at 300, 350 and 4000 C; the reaction rate increasing with reaction temperature. The main reaction products identified were ether and n-butanol. The hydrotalcite synthesized with cation sodium presented the highest yield of n-butanoI independent of aluminum content present in the samples. The results of Iow conversions showed significant yield of n-butanoI, and this could indicate that the formation of that product occurs by aldoI condensation and aIso by straight condensation of ethanoI molecule, without acetaldehyde desorption to gas fase. Comparative catalytic tests performed with MgO and AI203 showed acetaldehyde and ethylene predominantly as reaction products. Traces of n-butanoI were identified with MgO when the reaction occurred at 4000 C, and ether was identified with AI203 when the reaction occurred at 3000 C / Doutorado / Desenvolvimento de Processos Químicos / Doutor em Engenharia Química

Ce travail de thèse est consacré à la conception de métalloenzymes artificielles. Un tel concept permet de combiner les avantages des catalyseurs enzymatiques et organométalliques, tels que la sélectivité catalytique élevée et l'efficacité des systèmes enzymatiques et la large portée de substrats des catalyseurs des métaux de transition. Notre approche repose sur l’utilisation de complexes de métaux de transition avec un ligand prochiral hémilabile, qui une fois insérés dans la protéine hôte sera forcé d’adopter une configuration spécifique. La chiralité sera ainsi amenée au plus près du centre métallique et permettra d’augmenter l’énantioselectivité des réactions catalysées. Dans cette thèse, nous rapportons la synthèse de nouveaux complexes de palladium à ligands pinces NCN hémilabiles prochiraux et l’étude de leurs propriétés structurales. De plus, l’ancrage supramoléculaire de ces complexes dans la β-lactoglobuline (β-LG) bovine a été étudié expérimentalement et théoriquement par modélisation moléculaire. Ces constructions ont montré une activité catalytique dans la condensation d’aldol dans l’eau, et permettent d’obtenir, dans certains cas, le produit Cis. Cette diastéréosélectivité inhabituelle résulte de la seconde sphère de coordination apportée par l'hôte protéique. Dans une deuxième partie, on rapporte la synthèse de nouveaux complexes semi-sandwich de ruthénium avec des ligands β-aminothioéther hémilabiles, ainsi que l'étude de leur insertion dans la protéine. Les hybrides catalysent l'hydrogénation par transfert d'arylcétones avec une énantiosélectivité élevée. L'amélioration de la sélectivité a été attribuée au transfert de chiralité de la protéine vers le complexe et à son tour vers le produit de réaction. / This PhD work focused on the development of artificial metalloenzymes. Such a concept allows to combine typical advantages of both enzymatic and organometallic catalysts, such as high catalytic selectivity and efficiency of enzymatic systems and wide substrate scope of transition metals catalysts. Our approach consists in the utilization of transition metal complexes with a prochiral hemilabile ligand, once embedded within the protein host, could be forced to adopt a specific stereoconfiguration. This would in turn make possible to bring the chirality centers closer to the catalytic metal center and, therefore, to increase the enantioselectivity of catalyzed reactions.In this thesis, we report the synthesis of new palladium complexes of prochiral hemilabile NCN pincer ligands and the study of their structural properties. Furthermore, the supramolecular anchoring of these complexes to bovine β-lactoglobulin (β-LG) was studied both experimentally and theorically by computational calculation. These constructs were shown to catalyze aldol condensation reactions in aqueous media, affording, in some cases, the less-favorable cis product. This unusual diastereoselectivity was ensued by the second sphere of coordination brought by the protein host. In a second part, the synthesis of new half sandwich ruthenium complexes of prochiral hemilabile β-aminothioether ligands is reported as well as the study of their insertion in the protein. The hybrids catalyzed the transfer hydrogenation of arylketones with high enantioselectivity. The enhancement of selectivity was attributed to chirality.

Dans l’industrie, des systèmes de protection collectifs doivent être mis en œuvre pour protéger aussi bien les travailleurs que l’environnement. Des filtres à fibres sont généralement disposés dans les circuits de ventilation générale pour capter ces particules en suspension dans l’air. Les performances de ces media fibreux en termes d’efficacité de collecte et consommation énergétique sont relativement bien documentées lors de leur fonctionnement dans des conditions standards (humidité et température ambiantes). Cependant, peu d’études s’intéressent à l’interaction de l’humidité de l’air avec un dépôt composé de particules nanostructurées collectées par ces media filtrants et son incidence sur l’évolution de la perte de charge. Le travail de thèse a donc consisté dans un premier temps à la mesure d’isothermes de sorption de quatre poudres nanostructurées. Un modèle semi-prédictif d’adsorption-condensation basé sur le modèle GAB et la loi de Kelvin a ensuite été proposé. La seconde partie de l’étude a permis de décrire expérimentalement la variation de perte de charge et d’épaisseur d’un milieu poreux, formé par ces mêmes particules nanostructurées, pour différentes valeurs d’humidité. Grâce à la variation d’épaisseur du milieu déterminée par trigonométrie laser et au modèle d’adsorption-condensation, la porosité pour chaque valeur d’humidité relative a pu être calculée. En incorporant les valeurs de porosité et d’épaisseur dans trois modèles de perte de charge, il a été possible de représenter de façon satisfaisante les résultats expérimentaux. Enfin, une analyse rhéologique des poudres est proposée pour quantifier leur augmentation de cohésion sous humidité / Air quality has emerged as a major public environmental and health issue. Almost all fine particles in the air are man-made or manufactured and there are many questions regarding the impact of ultrafine (<100nm) particles on human health. Thus, in most cases, institutions use large-scale protection equipment to protect workers. These institutions often use particulate air filters placed within the flow of general ventilation. Almost all of the available data corresponds to standard ambient air conditions. Despite this, few studies focus on the interaction of water moisture on the deposit formed by these accumulated nanoparticles and the impact on the pressure drop. The first part of this study consists of the measurement of sorption isotherms of four nanostructured powders. A semi-predictive sorption model based on the theory of the multimolecular adsorption (described by the GAB equation) and on the capillary condensation (Kelvin’s law) was developed. The second part of the study experimentally describes the thickness and pressure drop variation of a porous medium formed by these nanostructured particles for different values of humidity. Through the thickness variation of the media - determined by laser trigonometry - and adsorption-condensation model, the porosity for each humidity value has been calculated. Following this, three pressure drop models available in the literature have been modified by introducing cake thickness and porosity variation according to relative humidity. This allows us to model the experimental data for all the samples. Finally, a rheological analysis of powders is proposed to quantify the cohesion changes under moisture conditions

Le travail réalisé dans le cadre de cette thèse s'articule en deux volets. Le premier porte sur l'étude de l'effet des interactions entre atomes au sein d'un interféromètre atomique, dont la source est un condensat de Bose-Eintein. Nous présentons un modèle analytiquepermettant d'obtenir des expressions simples pour le déphasage induit par celles-ci. Ce modèle est comparé à des simulations numériques résolvant les équations de Gross-Pitaevskii couplées, et présente un excellent accord. Le second concerne la conception et la construction d'un nouveau dispositif expérimental visant à obtenir un condensat de Bose-Einteindans le but de réaliser des mesures de haute précision par interférométrie atomique. / The work performed during this thesis comprises two orientations. The first one is the study of the effect of interactions between atoms in an atom interferometer which source of atoms is a Bose-Einstein condensate. We present an analytical model allowing to obtain simple expressions for the phase shift induced by them. This model is compared to numerical simulations solving the coupled Gross-Pitaevskii equations and presents a good agreement. The second one is the design and construction of a new experimental set-up for the production of a Bose-Einstein condensate to perform high precision measurements with the use of atom interferometry.

Cette thèse est dédiée à l'interprétation théorique des expériences sur les gaz froids des excitons indirects dans des nanostructures semi-conductrices. La théorie proposée explique la formation de l'état des excitons macroscopiquement ordonnés ("MOES") et des taches lumineuses localisées dans les images de photoluminescence des excitons. Dans la première partie je montrerai que la séparation macroscopique de charge induite par laser mène à l'apparition d'un champ électrique situé dans le plan de la structure. A cause de ce champ les états quantiques 1s et 2p de l'exciton se croisent et son moment dipolaire s'incline. Par conséquent, l'exciton va se localiser à la frontière entre les deux domaines d'une charge différente, où le champ électrique est le plus fort. Ensuite, j'étudierai un gaz d'excitons mis dans de tels pièges bidimensionnels en négligeant sa structure de spin. J'analyserai la possibilité de la condensation de Bose-Einstein dans le système considéré en utilisant les méthodes puissantes de la théorie à N-corps développées pour des gaz atomiques. En me basant sur le Hamiltonien pour un segment du cercle bidimensionnel ("2D cigar"), je montrerai que la dispersion cohérente des excitons mène à l'autolocalisation accompagnée par une modulation périodique de la densité. L'idée principale de la théorie est, ensuite, de modéliser cet état périodique par une chaîne de condensats piégés (Le Modèle de Chaîne). Un tel modèle permettra de dire que le système peut exhiber la transition de phase de second ordre pour certaines valeurs du paramètre qui caractérise les interactions. La valeur critique de ce paramètre peut être trouvée en analysant le comportement des fluctuations de phase à la température nulle. Le nombre de condensats dans le régime où les interactions sont fortes est déterminé par la balance entre les contributions de l'énergie cinétique est l'entropie dans l'énergie libre du système. Le Modèle de Chaîne permettra aussi de révéler l'invariance d''échelle et l'universalité du phénomène. J'obtiendrai l'expression pour la température unique de la transition de phase dans le système excitonique et discuterai l'effet de désordre. Je finirai par une discussion du rôle des interactions à N-corps et des effets de spin dans la condensation de Bose-Einstein des excitons. Je proposerai un modèle de gaz idéal pour décrire les textures de polarisation linéaire observées autour de chaque tache lumineuse et chaque fragment de MOES. Selon ce modèle, le domaine central incohérent de tous ces objets est composé d'une glace excitonique quantique. / The present Thesis is devoted to theoretical interpretation of intriguing observations made recently in cold gases of indirect excitons in semiconductor quantum wells. The proposed theory provides simple intuitive explanation for the basic phenomenology of the macroscopically ordered exciton state (MOES) and the localized bright spots (LBS) in the exciton photoluminescense pattern. The Thesis is organized as follows.First, we provide an important insight into the formation process of the external ring and LBS. We show that the macroscopic charge separation induced by the photoexcitation results in appearance of an in-plane electric field in the vicinity of the boundary. The field hybridizes 1s and 2p quantum states of an indirect exciton, effectively tilting its dipole moment. Thus polarized exciton seeks for the regions with higher in-plane electric field and, hence, becomes localized at the ring-shaped boundary.As a next step, we consider a gas of spinless dipolar bosons put in such two-dimensional (2D) traps. We analyze the possibility for occurence of Bose-Einstein condensation (BEC) in the system under consideration by means of the powerful many-body theoretical methods developed for ultracold atomic gases. Starting from the Hamiltonian for a segment of the ring (2D cigar) we show, howthe coherent scattering of excitons can result in autolocalization accompanied by a buildup of the diagonal long-range order. The crucial point of the theory then consists in replacement of the periodic coherent state by a chain of harmonically trapped condensates (Chain Model). We argue, that for sufficiently strong contact interaction between the excitons the system can exhibit the true second order phase transistion at finite temperature. The critical value of the interaction parameter can be found by analyzing the behaviour of the quantum phase fluctuations at zero temperature. The number of condensates at the ring in the strongly interacting regime is defined by the balance between the kinetic energy and the entropy terms in the free energy of the system.Futhermore, the use of the Chain Model of the MOES allows one to reveal scale invariance and universality of the pnenomenon. We obtain the expression for the unique critical temperature of the second order phase transition in the exciton system and discuss the effect of disorder.Finally, we comment on the role of many-body interactions and spin degrees of freedom in excitonic BEC. We suggest that each bead (or, equivalently, LBS) has the internal structure: it consists of a solid core (Quantum Exciton Iceberg) surrounded by a coherent exciton fluid. We develop an ideal gas model for the coherent four-component exciton fluid which allows one to explain the measured linear polarization patterns.

Superhydrophobic (SHS) and lubricant-infused surfaces (LIS) exhibit exceptional non-wetting characteristics that make them attractive for energy production applications including steam condensation and fouling mitigation. The dissertation work focuses on application of non-wetting surfaces to energy production using a systematic approach examining each component of surface fabrication in three functional areas. First, SHS and LIS are fabricated using robust, scalable methods and tested for durability in heated, wet conditions and under high-energy water jet impingement. Clear performance differences are shown based on surface texturing, functionalizing agent, and infused lubricant. Second, SHS and LIS are applied to tube exteriors and evaluated for their ability to produce sustained dropwise condensation in a typical power plant condenser environment. The surfaces are shown to produce heat transfer coefficients up to 7-10 times that of film-wise condensation, with condenser effectiveness of 0.92 or better compared to effectiveness of about 0.6 in conventional condensers. Third, LIS on the interior of tubes are assessed in accelerated mineral fouling conditions. LIS are shown to mitigate calcium sulfate and calcium carbonate fouling under laminar conditions. The results of the study bear profound benefits to reducing the levelized cost of condensers and water uptake in thermoelectric power plants, that currently consume about 50% of the total water use in the U.S. / Doctor of Philosophy / Creating durable, hybrid surfaces for improved steam condensation and fouling mitigation would provide substantial impact to power generation worldwide. Bioinspired, non-wetting surfaces, such as superhydrophobic (SHS) and lubricant-infused surfaces (LIS) exhibit exceptional non-wetting characteristics that make them attractive for energy applications. Each of these non-wetting technologies, however, faces durability and scalability challenges that make them unfeasible for widespread, practical adoption. As a result, decades of materials science research have stagnated in the research laboratories with limited demonstrations of dropwise condensation and fouling mitigation in static situations. The dissertation work focuses on application of SHS and LIS to energy production using a systematic approach examining each component of surface fabrication in three functional areas. First, SHS and LIS are fabricated using robust, scalable methods and tested for durability using ASTM standard static and dynamic evaluation methods. Clear performance differences are shown based on surface texturing, functionalizing agent, and infused lubricant. Second, dropwise steam condensation on the surfaces are shown to exhibit heat transfer performance an order of magnitude greater than film-wise condensation in a typical power plant condenser environment. The surfaces are shown to produce heat transfer coefficients up to 7-10 times that of film-wise condensation, with condenser effectiveness of 0.92 or better compared to effectiveness of about 0.6 in conventional condensers. This work presents for the first time, a non-dimensional correlation for a priori prediction of LIS heat transfer performance given known qualities of the LIS. Third, challenges of fouling mitigation in power plants have been studied for over a decade. This work demonstrates for the first time that LIS applied to the interior of tubes mitigate calcium sulfate and calcium carbonate fouling in both static and laminar flow conditions.

The processing of information based on the generation of common quantum optical states (e.g. coherent states) and the measurement of the quadrature components of the light field (e.g. homodyne detection) is often referred to as continuous-variable quantum information processing. It is a very fertile field of investigation, at a crossroads between quantum optics and information theory, with notable successes such as unconditional continuous-variable quantum teleportation or Gaussian quantum key distribution. In quantum optics, the states of the light field are conveniently characterized using a phase-space representation (e.g. Wigner function), and the common optical components effect simple affine transformations in phase space (e.g. rotations). In quantum information theory, one often needs to determine entropic characteristics of quantum states and operations, since the von Neuman entropy is the quantity at the heart of entanglement measures or channel capacities. Computing entropies of quantum optical states requires instead turning to a state-space representation of the light field, which formally is the Fock space of a bosonic mode.<p>This interplay between phase-space and state-space representations does not represent a particular problem as long as Gaussian states (e.g. coherent, squeezed, or thermal states) and Gaussian operations (e.g. beam splitters or squeezers) are concerned. Indeed, Gaussian states are fully characterized by the first- and second-order moments of mode operators, while Gaussian operations are defined via their actions on these moments. The so-called symplectic formalism can be used to treat all Gaussian transformations on Gaussian states, including mixed states of an arbitrary number of modes, and the entropies of Gaussian states are directly linked to their symplectic eigenvalues.<p>This thesis is concerned with the Gaussian transformations applied onto arbitrary states of light, in which case the symplectic formalism is unapplicable and this phase-to-state space interplay becomes highly non trivial. A first motivation to consider arbitrary (non-Gaussian) states of light results from various Gaussian no-go theorems in continuous-variable quantum information theory. For instance, universal quantum computing, quantum entanglement concentration, or quantum error correction are known to be impossible when restricted to the Gaussian realm. A second motivation comes from the fact that several fundamental quantities, such as the entanglement of formation of a Gaussian state or the communication capacity of a Gaussian channel, rely on an optimization over all states, including non-Gaussian states even though the considered state or channel is Gaussian. This thesis is therefore devoted to developing new tools in order to compute state-space properties (e.g. entropies) of transformations defined in phase-space or conversely to computing phase-space properties (e.g. mean-field amplitudes) of transformations defined in state space. Remarkably, even some basic questions such as the entanglement generation of optical squeezers or beam splitters were unsolved, which gave us a nice work-bench to investigate this interplay. <p>In the first part of this thesis (Chapter 3), we considered a recently discovered Gaussian probabilistic transformation called the noiseless optical amplifier. More specifically, this is a process enabling the amplification of a quantum state without introducing noise. As it has long been known, when amplifing a quantum signal, the arising of noise is inevitable due to the unitary evolution that governs quantum mechanics. It was recently realized, however, that one can drop the unitarity of the amplification procedure and trade it for a noiseless, albeit probabilistic (heralded) transformation. The fact that the transformation is probabilistic is mathematically reflected in the fact that it is non trace-preserving. This quantum device has gained much interest during the last years because it can be used to compensate losses in a quantum channel, for entanglement distillation, probabilistic quantum cloning, or quantum error correction. Several experimental demonstrations of this device have already been carried out. Our contribution to this topic has been to derive the action of this device on squeezed states and to prove that it acts quite surprisingly as a universal (phase-insensitive) optical squeezer, conserving the signal-to-noise ratio just as a phase-sensitive optical amplifier but for all quadratures at the same time. This also brought into surface a paradoxical effect, namely that such a device could seemingly lead to instantaneous signaling by circumventing the quantum no-cloning theorem. This paradox was discussed and resolved in our work.<p>In a second step, the action of the noiseless optical amplifier and it dual operation (i.e. heralded noiseless attenuator) on non-Gaussian states has been examined. We have observed that the mean-field amplitude may decrease in the process of noiseless amplification (or may increase in the process of noiseless attenuation), a very counterintuitive effect that Gaussian states cannot exhibit. This work illustrates the above-mentioned phase-to-state space interplay since these devices are defined as simple filtering operations in state space but inferring their action on phase-space quantities such as the mean-field amplitude is not straightforward. It also illustrates the difficulty of dealing with non-Gaussian states in Gaussian transformations (these noiseless devices are probabilistic but Gaussian). Furthermore, we have exhibited an experimental proposal that could be used to test this counterintuitive feature. The proposed set-up is feasible with current technology and robust against usual inefficiencies that occur in optical experiment. <p>Noiseless amplification and attenuation represent new important tools, which may offer interesting perspectives in quantum optical communications. Therefore, further understanding of these transformations is both of fundamental interest and important for the development and analysis of protocols exploiting these tools. Our work provides a better understanding of these transformations and reveals that the intuition based on ordinary (deterministic phase-insensitive) amplifiers and losses is not always applicable to the noiseless amplifiers and attenuators.<p>In the last part of this thesis, we have considered the entropic characterization of some of the most fundamental Gaussian transformations in quantum optics, namely a beam splitter and two-mode squeezer. A beam splitter effects a simple rotation in phase space, while a two-mode squeezer produces a Bogoliubov transformation. Thus, there is a well-known phase-space characterization in terms of symplectic transformations, but the difficulty originates from that one must return to state space in order to access quantum entropies or entanglement. This is again a hard problem, linked to the above-mentioned interplay in the reverse direction this time. As soon as non-Gaussian states are concerned, there is no way of calculating the entropy produced by such Gaussian transformations. We have investigated two novel tools in order to treat non-Gaussian states under Gaussian transformations, namely majorization theory and the replica method.<p>In Chapter 4, we have started by analyzing the entanglement generated by a beam splitter that is fed with a photon-number state, and have shown that the entanglement monotones can be neatly combined with majorization theory in this context. Majorization theory provides a preorder relation between bipartite pure quantum states, and gives a necessary and sufficient condition for the existence of a deterministic LOCC (local operations and classical communication) transformation from one state to another. We have shown that the state resulting from n photons impinging on a beam splitter majorizes the corresponding state with any larger photon number n’ > n, implying that the entanglement monotonically grows with n, as expected. In contrast, we have proven that such a seemingly simple optical component may have a rather surprising behavior when it comes to majorization theory: it does not necessarily lead to states that obey a majorization relation if one varies the transmittance (moving towards a balanced beam splitter). These results are significant for entanglement manipulation, giving rise in particular to a catalysis effect.<p>Moving forward, in Chapter 5, we took the step of introducing the replica method in quantum optics, with the goal of achieving an entropic characterization of general Gaussian operations on a bosonic quantum field. The replica method, a tool borrowed from statistical physics, can also be used to calculate the von Neumann entropy and is the last line of defense when the usual definition is not practical, which is often the case in quantum optics since the definition involves calculating the eigenvalues of some (infinite-dimensional) density matrix. With this method, the entropy produced by a two-mode squeezer (or parametric optical amplifier) with non-trivial input states has been studied. As an application, we have determined the entropy generated by amplifying a binary superposition of the vacuum and an arbitrary Fock state, which yields a surprisingly simple, yet unknown analytical expression. Finally, we have turned to the replica method in the context of field theory, and have examined the behavior of a bosonic field with finite temperature when the temperature decreases. To this end, information theoretical tools were used, such as the geometric entropy and the mutual information, and interesting connection between phase transitions and informational quantities were found. More specifically, dividing the field in two spatial regions and calculating the mutual information between these two regions, it turns out that the mutual information is non-differentiable exactly at the critical temperature for the formation of the Bose-Einstein condensate.<p>The replica method provides a new angle of attack to access quantum entropies in fundamental Gaussian bosonic transformations, that is quadratic interactions between bosonic mode operators such as Bogoliubov transformations. The difficulty of accessing entropies produced when transforming non-Gaussian states is also linked to several currently unproven entropic conjectures on Gaussian optimality in the context of bosonic channels. Notably, determining the capacity of a multiple-access or broadcast Gaussian bosonic channel is pending on being able to access entropies. We anticipate that the replica method may become an invaluable tool in order to reach a complete entropic characterization of Gaussian bosonic transformations, or perhaps even solve some of these pending conjectures on Gaussian bosonic channels.<p> / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

L'objectif de c e mémoire est d'apporter une contribution à la modélisation et la simulation numérique de la convection thermosolutale de mélanges binaires de gaz parfaits contenus dans des cavités. Un modèle a été élaboré en se basant sur l'approximation de faible compressibilité. Le premier chapitre précise la démarche suivie dans la modélisation et une formulation originale en est déduite afin de traiter les différents types de conditions aux limites et de conditions de références hydrostatiques analysés dans le mémoire. Les variations de masse volumique sont déduites de la loi des gaz parfaits et la pression thermodynamique est calculée à partir de la conservation de la masse totale. La méthode numérique repose sur la méthode des volumes finis mise en uvre sur des maillages décalés. Le couplage vitesse-pression est traité par un nouvel algorithme dont l'efficacité est discutée en détail. La démarche numérique est validée via des comparaisons avec des solutions de références, en régime stationnaire comme en régime transitoire pour des écoulements transitionnels. Dans la seconde partie du mémoire, on considère d'abord la convection thermosolutale dans une cavité rectangulaire verticale dans le cas où les écoulements sont induits par des gradients horizontaux de température et de concentration. On discute en particulier les limites de l'approximation d'extrême dilution. La condensation de vapeur d'eau et l'évaporation d'un film d'eau liquide sur les parois d'une cavité sont ensuite étudiées en régime transitoire. Ces changements de phase surfaciques sont associés à la convection naturelle dans une cavité dont les températures des quatre parois varient au cours du temps / The aim of this dissertation is at modeling and numerically simulating thermosolutal convection within cavities filled by binary gas mixtures of ideal gases. A new problem formulation, based on the weakly compressible approximation, has been derived in order to account for the changes in density as well as thermodynamic pressure. The ideal gas law and global conservation of mass are invoked for the predictions of density field and thermodynamic pressure. The first part of the manuscript is devoted to the mathematical derivation of the governing equations and boundary conditions, numerical procedure implemented and, checks of the accuracy of the results through deeply comparisons with updated benchmark solutions. The emphasis is put on the efficiency of algorithm used for solving the pressure-velocity coupling for unsteady, transitional flow regimes. Thermosolutal convection without phase changes at the cavity surfaces is first considered in the second part of the manuscript. We investigated the case of vertical cavities with horizontal gradients of concentration and temperature. The results clearly show that the dilute approximation fails to be valid as soon as the maximum concentration difference exceeds a critical value function of the flow parameters. Surface condensation of water vapor or evaporation of liquid water film in vertical cavities is then considered. The specific thermal boundary conditions of uniform but time-varying temperatures of the four walls are considered. Periodic variations of the flow, temperature and relative humidity fields are discussed in detail. The evolutions of thicknesses of the water film over the four walls are also predicted

Nous investiguons dans ce travail la création d'échantillons permettant l'étude du comportement des polaritons excitoniques dans les matériaux semi-conducteurs organiques. Le couplage fort entre les états excités d'électrons et des photons impose la création de nouveaux états propres dans le milieu. Ces nouveaux états, les polaritons, ont un comportement bosonique et sont donc capables de se condenser dans un état fortement dégénéré. Une occupation massive de l'état fondamental permet l'étude de comportements explicables uniquement par la mécanique quantique. La démonstration, au niveau macroscopique, d'effets quantiques promet d'éclairer notre compréhension de la matière condensée. De plus, la forte localisation des excitons dans les milieux organiques permet la condensation des polaritons excitoniques organiques à des températures beaucoup plus hautes que dans les semi-conducteurs inorganiques. À terme, les échantillons proposés dans ce travail pourraient donc servir à observer une phase cohérente macroscopique à des températures facilement atteignables en laboratoire. Les cavités proposées sont des résonateurs Fabry-Perot ultraminces dans lesquels est inséré un cristal unique d'anthracène. Des miroirs diélectriques sont fabriqués par une compagnie externe. Une couche d'or de 60 nanomètres est ensuite déposée sur leur surface. Les miroirs sont ensuite mis en contact, or contre or, et compressés par 2,6 tonnes de pression. Cette pression soude la cavité et laisse des espaces vides entre les lignes d'or. Une molécule organique, l'anthracène, est ensuite insérée par capillarité dans la cavité et y est cristallisée par la suite. Dans leur état actuel, les cavités présentent des défauts majeurs quant à la planarité des miroirs et à l'uniformité des cristaux. Un protocole détaillé est présenté et commenté dans ce travail. Nous y proposons aussi quelques pistes pour régler les problèmes courants de l'appareil. / In this work we investigate the creation of samples for the study of the behavior of excitonic polaritons in organic semiconductor materials. The strong coupling between the excited states of electrons and photons implies the creation new eigenstates in the medium. These new states, called polaritons, are composite bosons and are therefore capable of condensing in a strongly degenerated state. A massive occupation of the ground state allows the study of behaviors that are only explainable by quantum mechanics. A macroscopic demonstration of quantum effects offers a rare opportunity for scientific research and discoveries. The strong localization of excitons in organic materials allows condensation of exciton polaritons at temperatures much higher than in inorganic semiconductors. Therefore the samples proposed in this work could ultimately be used to observe a macroscopic coherent phase at temperatures easily attainable in a laboratory. The cavities proposed in this work are Fabry-Perot resonators in which anthracene is inserted and crystalized. The mirrors used in the resonator are dielectric reflectors made by a external company according to our specifications. A gold layer of 60 nm is deposited on their surface. The mirrors are then brought into contact, gold against gold, and compressed by 2.6 tons of pressure. This pressure seals the cavity and leaves voids between the gold lines. An organic molecule, anthracene, is then inserted in by capillary inside the cavity voids and subsequently crystallized by controlled cooling. In their current state cavities have defects regarding the planarity of the mirrors and the uniformity of the crystals. A detailed protocol is presented and discussed in this work.

L'aimant organique NIT-2Py a été caractérisé expérimentalement et ses propriétés ont été simulées numériquement à partir de la théorie de la fonctionnelle de la densité. Le magnétisme dans ce matériau provient de la présence d'un électron non apparié sur chaque molécule qui a ainsi un moment magnétique non nul. Ceci a été confirmé par des simulations sur une molécule isolée. Les molécules de NIT-2Py cristallisent dans le groupe d'espace P21/c avec huit molécules par maille élémentaire pour former la structure cristalline Alpha étudiée dans ce document. Le moment effectif de la susceptibilité et l'entropie magnétique totale montre que ce matériau est un système de spins 1/2 avec un spin par molécule. Les mesures de chaleur spécifique ont mis en évidence la présence de deux phases magnétiques ordonnées à basse température qui sont séparées par un plateau en aimantation. Une première phase est observée à des champs magnétiques inférieurs à 2.2 T et a une température de transition de 1.32 K en champ nul. Les mesures de susceptibilité magnétique et d'aimantation ont permis d'établir que cette phase ordonnée est antiferromagnétique. Ceci est confirmé par les simulations numériques. La deuxième phase est induite par le champ magnétique avec une température de transition de 0.53 K à 6 T. L'information disponible sur cette phase est limitée et l'étude du système à l'extérieur des phases ordonnées en donne une meilleure compréhension. Un modèle de spins S=1/2 isolés et de dimères S=0 isolés reproduit bien les mesures d'aimantation et de chaleur spécifique au-dessus de 3 K. L'application d'un champ magnétique réduit l'écart d'énergie entre le singulet et le triplet du dimère jusqu'au croisement qui se produit à 6 T. La phase induite émerge précisément à ce croisement et on spécule l'existence d'un condensat de Bose-Einstein des états triplets. / The organic magnet built from NIT-2Py molecules has been characterized experimentally and its properties have been simulated using density functional theory. In this material, an unpaired electron carrying a magnetic moment on each molecule is responsible for the magnetism. This has been confirmed by numeric simulations on an isolated molecule. NIT-2Py molecules crystallize in space group P21/c with eight molecules per unit cell to form crystalline phase Alpha studied in this document. The effective moment obtained from magnetic susceptibility and the total magnetic entropy show that this material is a spin 1/2 system with one spin per molecule. Specific heat measurements have highlighted the presence of two magnetically ordered phases at low temperature, which are separated by a plateau in magnetization. A first phase is observed at magnetic field lower than 2.2 T and has a transition temperature of 1.32 K in zero field. Magnetic susceptibility and magnetization measurements have established that this ordered phase is antiferromagnetic. This is confirmed by numeric simulations. The second phase is induced by a magnetic field and has a transition temperature of 0.53 K at 6 T. Information concerning the field induced phase is limited and a study of the system above the transition temperatures helps to gain a better understanding. A model of isolated spins S=1/2 and isolated dimers S=0 reproduces nicely the specific heat and magnetization data above 3 K. The application of a magnetic field reduces the energy gap between the singlet and the triplet of the dimer and the crossover between these levels is observed at 6 T. The field induced phase emerges precisely at this crossover suggesting the occurrence of a Bose-Einstein condensation of triplets states.