Quantum spin liquids (QSLs) are strongly correlated systems displaying fascinating phenomena like long-range entanglement and fractionalized excitations. The research on these states has since its beginning followed trends generated by the synthesis of new compounds and the construction of new theoretical tools. In coherence with this history, a manifold of new results about QSLs were established during the past decade due to studies on the integrable Kitaev model on the honeycomb lattice. This j = 1/2 model displays bond-dependent and anisotropic exchanges that are essential to stabilize its QSL ground state with Majorana fermion excitations and emergent Z2 gauge field. Even more interestingly, this model is relevant to understand the magnetism of a certain class of 4/5d5 Mott insulators with specific lattice constraints, t2g orbital degeneracy and strong spin-orbit coupling (SOC). This mechanism defining these so-called Kitaev materials can be applied to similar compounds based on transition metal ions in different electronic configurations. In this thesis, I investigate minimal models for two types of 4/5d1 Mott insulators: the ones on the ordered double perovskite structure (ODP) and the ones isostructural to the Kitaev materials. Their effective models generically show bond-dependent and anisotropic interactions involving multipoles of an effective j = 3/2 angular momentum. Such degrees of freedom are conveniently written in terms of pseudospin s and pseudo-orbital τ operators resembling spin and orbital operators of Kugel-Khomskii models with twofold orbital degeneracy. Despite their anisotropy, the two realistic models display continuous global symmetries in the limit of vanishing Hund\'s coupling enhancing quantum fluctuations and possibly stabilizing a QSL phase. Parton mean-field theory was used to propose fermionic QSLs that will be called quantum spin-orbital liquids (QSOLs) due their dependence with s and τ. On ODPs, I studied a chiral QSOL with Majorana fermion excitations and a gapless spectrum characterized by nodal lines along the edges of the Brillouin zone. These nodal lines are topological defects of a non-Abelian Berry connection and the system exhibits dispersing surface states. Several experimental responses of the chiral QSOL within the mean-field approximation are compared with the experimental data available for the spin liquid candidate Ba2YMoO6. Moreover, based on a symmetry analysis, I discuss the operators involved in resonant inelastic X-ray scattering (RIXS) amplitudes for 4/5d1 Mott insulators and show that the RIXS cross sections allow one to selectively probe pseudospin and pseudo-orbital degrees of freedom. For the chiral spin-orbital liquid in particular, these cross sections provide information about the spectrum for different flavors of Majorana fermions. The model for materials isostructural to the Kitaev materials has an emergent SU(4) symmetry that is made explicit by means of a Klein transformation on pseudospin degrees of freedom. The model is known to stabilize a QSOL on the honeycomb lattice and instigated the investigation of QSOLs on a generalization of this lattice to three dimensions. Parton mean-field theory was used once again to propose the liquid states, and a variational Monte Carlo (VMC) method was used to compute the energies of the projected wave functions. The numerical results show that the lowest-energy QSOL corresponds to a zero-flux state with a Fermi surface of four-color fermionic partons. Further VMC computations also revealed that this state is stable against formation of plaquette ordering (tetramerization). The energy of this QSOL is highly competitive even when Hund\'s coupling induced perturbations are included, as shown by comparison with simple ordered states. Extensions and perspectives for future work are discussed in the end of this thesis. / Líquidos de spin quânticos (QSLs) são sistemas fortemente correlacionados que apresentam fenômenos fascinantes como emaranhamento de longo alcance e excitações fracionárias. A pesquisa a respeito destes estados seguiu tendências geradas pela síntese de novos compostos e construção de novas técnicas teóricas desde seu princípio. Coerentemente com essa história, uma variedade de novos resultados a respeito de líquidos de spin foram estabelecidos na última década graças a estudos feitos sobre o modelo integrável de Kitaev na rede colmeia. Este modelo de spins j = 1/2 apresenta interações de troca anisotrópicas e direcionalmente dependentes que são essenciais para estabilizar um estado fundamental do tipo QSL com férmions de Majorana e campo de gauge Z2 emergente. Ainda mais interessante, este modelo é relevante para se entender o magnetismo de uma certa classe de isolantes de Mott baseados em metais de transição na configuração 4/5d5 em redes específicas, degenerescência orbital t2g e acoplamento spin-órbita forte (SOC). Esse mecanismo que define os chamados materiais do tipo Kitaev podem ser aplicados a compostos baseados em metais de transição em configurações eletrônicas diferentes. Nesta tese, eu investigo modelos mínimos para dois tipos de isolantes de Mott do tipo 4/5d1: os que se apresentam na estrutura perovskita dupla ordenada (ODP) e os isostruturais aos materiais do tipo Kitaev. Seus modelos efetivos genericamente apresentam interações multipolares anisotrópicas e direcionalmente dependentes de um momento angular efetivo j = 3/2. Estes graus de liberdade são convenientemente escritos em termos de operadores de pseudospin s e pseudo-orbital τ semelhantes a operadores de spin e orbital de modelos do tipo Kugel-Khomskii com orbitais duplamente degenerados. A despeito da anisotropia, esses dois modelos realísticos apresentam simetrias globais contínuas no limite de acoplamento de Hund nulo que incrementam flutuações quânticas e possivelmente estabilizam uma fase do tipo QSL. A teoria de campo médio com partons foi usada para propor QSLs fermiônicos que serão chamados de líquidos spin-orbitais quânticos (QSOLs) devido à dependência deles com s e τ. Em ODPs, eu estudei um líquido de spin quiral com excitações do tipo férmion de Majorana e um espectro sem gap caracterizado por linhas nodais ao longo das arestas da zona de Brillouin. Essas linhas nodais são defeitos topológicos de uma conexão de Berry não-abeliana e o sistema apresenta estados de superfície dispersivos. Várias respostas experimentais foram calculadas para o QSOL quiral dentro da aproximação de campo médio e comparadas com os dados experimentais disponíveis para o candidato a líquido de spin Ba2YMoO6. Além disso, baseado em uma análise de simetria, discuto os operadores envolvidos nas amplitudes de espalhamento de raios-x ressonante para isolantes de Mott na configuração 4/5d1 e mostro que seções de choque de RIXS permitem estudar seletivamente os graus de liberdade de pseudospins e pseudo-orbitais. Para o caso particular do líquido spin-orbital quiral, essas seções de choque nos fornecem informações sobre o espectro de diferentes sabores de férmions de Majorana. Esse modelo possui uma simetria SU(4) emergente que é tornada explícita através de uma transformações de Klein nos graus de liberdade de pseudospin. Sabe-se que este modelo estabiliza um QSOL na rede colmeia, o que instigou uma investigação de QSOLs na generalização desta rede em três dimensões. A teoria de campo médio com partons foi usada novamente para propor estes líquidos quânticos, e o método de Monte Carlo Variacional (VMC) foi usado para calcular as energias das funções de onda projetadas. Os resultados numéricos mostraram que o QSOL de menor energia corresponde a um estado de fluxo-zero com superfície de Fermi envolvendo partons fermiônicos de quatro cores. Cálculos adicionais com VMC também demonstraram que este estado é estável à formação de ordem de plaquetas (tetramerização). A energia deste QSOL é altamente competitiva mesmo quando perturbações induzidas pelo acoplamento de Hund são incluídas, o que é mostrado através da comparação com estados ordenados simples. Extensões e perspectivas para trabalhos futuros são discutidas no final desta tese.

Error characteristics associated with satellite-derived precipitation products are important for atmospheric and hydrological model data assimilation, forecasting, and climate diagnostic applications. This information also aids in the refinement of physical assumptions within algorithms by identifying geographical regions and seasons where existing algorithm physics may be incorrect or incomplete. Examination of relative errors between independent estimates derived from satellite microwave data is particularly important over regions with limited surface-based equipments for measuring rain rate such as the global oceans and tropical continents. In this context, analysis of microwave based satellite datasets from the Tropical Rainfall Measuring Mission (TRMM) enables to not only provide information regarding the inherent uncertainty within the current TRMM products, but also serves as an opportunity to prototype error characterization methodologies for the TRMM follow-on program, the Global Precipitation Measurement (GPM) . Most of the TRMM uncertainty evaluation studies focus on the accuracy of rainfall accumulated over time (e.g., season/year). Evaluation of instantaneous rainfall intensities from TRMM orbital data products is relatively rare. These instantaneous products are known to potentially cause large uncertainties during real time flood forecasting studies at the watershed scale. This is more so over land regions, where the highly varying land surface emissivity offers a myriad of complications, hindering accurate rainfall estimation. The error components of orbital data products also tend to interact nonlinearly with hydrologic modeling uncertainty. Keeping these in mind, the present thesis fosters the development of uncertainty analysis using instantaneous satellite orbital data products (latest version 7 of 1B11, 2A25, 2A23, 2B31, 2A12) derived from the passive and active microwave sensors onboard TRMM satellite, namely TRMM Microwave Imager (TMI) and precipitation radar (PR). The study utilizes 11 years of orbital data from 2002 to 2012 over the Indian subcontinent and examines the influence of various error sources on the convective and stratiform precipitation types. Two approaches are taken up to examine uncertainty. While the first approach analyses independent contribution of error from these orbital data products, the second approach examines their combined effect. Based on the first approach, analysis conducted over the land regions of Mahanadi basin, India investigates three sources of uncertainty in detail. These include 1) errors due to improper delineation of rainfall signature within microwave footprint (rain/no rain classification), 2) uncertainty offered by the transfer function linking rainfall with TMI low frequency channels and 3) sampling errors owing to the narrow swath and infrequent visits of TRMM sensors. The second approach is hinged on evaluating the performance of rainfall estimates from each of these orbital data products by accumulating them within a spatial domain and using error decomposition methodologies. Microwave radiometers have taken unprecedented satellite images of earth’s weather, proving to be a valuable tool for quantitative estimation of precipitation from space. However, as mentioned earlier, with the widespread acceptance of microwave based precipitation products, it has also been recognized that they contain large uncertainties. One such source of uncertainty is contributed by improper detection of rainfall signature within radiometer footprints. To date, the most-advanced passive microwave retrieval algorithms make use of databases constructed by cloud or numerical weather model simulations that associate calculated microwave brightness temperature to physically plausible sample rain events. Delineation of rainfall signature from microwave footprints, also known as rain/norain classification (RNC) is an essential step without which the succeeding retrieval technique (using the database) gets corrupted easily. Although tremendous advances have been made to catapult RNC algorithms from simple empirical relations formulated for computational expedience to elaborate computer intensive schemes which effectively discriminate rainfall, a number of challenges remain to be addressed. Most of the algorithms that are globally developed for land, ocean and coastal regions may not perform well for regional catchments of small areal extent. Motivated by this fact, the present work develops a regional rainfall detection algorithm based on scattering index methodology for the land regions of study area. Performance evaluation of this algorithm, developed using low frequency channels (of 19 GHz, 22 GHz), are statistically tested for individual case study events during 2011 and 2012 Indian summer monsoonal months. Contingency table statistics and performance diagram show superior performance of the algorithm for land regions of the study region with accurate rain detection observed in 95% of the case studies. However, an important limitation of this approach is comparatively poor detection of low intensity stratiform rainfall. The second source of uncertainty which is addressed by the present thesis, involves prediction of overland rainfall using TMI low frequency channels. Land, being a radiometrically warm and highly variable background, offers a myriad of complications for overland rain retrieval using microwave radiometer (like TMI). Hence, land rainfall algorithms of TRMM TMI have traditionally incorporated empirical relations of microwave brightness temperature (Tb) with rain rate, rather than relying on physically based radiative transfer modeling of rainfall (as implemented in TMI ocean algorithm). In the present study, sensitivity analysis is conducted using spearman rank correlation coefficient as the indicator, to estimate the best combination of TMI low frequency channels that are highly sensitive to near surface rainfall rate (NSR) from PR. Results indicate that, the TMI channel combinations not only contain information about rainfall wherein liquid water drops are the dominant hydrometeors, but also aids in surface noise reduction over a predominantly vegetative land surface background. Further, the variations of rainfall signature in these channel combinations were seldom assessed properly due to their inherent uncertainties and highly non linear relationship with rainfall. Copula theory is a powerful tool to characterize dependency between complex hydrological variables as well as aid in uncertainty modeling by ensemble generation. Hence, this work proposes a regional model using Archimedean copulas, to study dependency of TMI channel combinations with respect to precipitation, over the land regions of Mahanadi basin, India, using version 7 orbital data from TMI and PR. Studies conducted for different rainfall regimes over the study area show suitability of Clayton and Gumbel copula for modeling convective and stratiform rainfall types for majority of the intraseasonal months. Further, large ensembles of TMI Tb (from the highly sensitive TMI channel combination) were generated conditional on various quantiles (25th, 50th, 75th, 95th) of both convective and stratiform rainfall types. Comparatively greater ambiguity was observed in modeling extreme values of convective rain type. Finally, the efficiency of the proposed model was tested by comparing the results with traditionally employed linear and quadratic models. Results reveal superior performance of the proposed copula based technique. Another persistent source of uncertainty inherent in low earth orbiting satellites like TRMM arise due to sampling errors of non negligible proportions owing to the narrow swath of satellite sensors coupled with a lack of continuous coverage due to infrequent satellite visits. This study investigates sampling uncertainty of seasonal rainfall estimates from PR, based on 11 years of PR 2A25 data product over the Indian subcontinent. A statistical bootstrap technique is employed to estimate the relative sampling errors using the PR data themselves. Results verify power law scaling characteristics of relative sampling errors with respect to space time scale of measurement. Sampling uncertainty estimates for mean seasonal rainfall was found to exhibit seasonal variations. To give a practical demonstration of the implications of bootstrap technique, PR relative sampling errors over the sub tropical river basin of Mahanadi, India were examined. Results revealed that bootstrap technique incurred relative sampling errors of <30% (for 20 grid), <35% (for 10 grid), <40% (for 0.50 grid) and <50% (for 0.250 grid). With respect to rainfall type, overall sampling uncertainty was found to be dominated by sampling uncertainty due to stratiform rainfall over the basin. In order to study the effect of sampling type on relative sampling uncertainty, the study compares the resulting error estimates with those obtained from latin hypercube sampling. Based on this study, it may be concluded that bootstrap approach can be successfully used for ascertaining relative sampling errors offered by TRMM-like satellites over gauged or ungauged basins lacking in in-situ validation data. One of the important goals of TRMM Ground Validation Program has been to estimate the random and systematic uncertainty associated with TRMM rainfall estimates. Disentangling uncertainty in seasonal rainfall offered by independent observations of TMI and PR enables to identify errors and inconsistencies in the measurements by these instruments. Motivated by this thought, the present work examines the spatial error structure of daily precipitation derived from the version 7 TRMM instantaneous orbital data products through comparison with the APHRODITE data over a subtropical region namely Mahanadi river basin of the Indian subcontinent for the seasonal rainfall of 6 years from June 2002 to September 2007. The instantaneous products examined include TMI and PR data products of 2A12, 2A25 and 2B31 (combined data from PR and TMI). The spatial distribution of uncertainty from these data products was quantified based on the performance metrics derived from the contingency table. For the seasonal daily precipitation over 10x10 grids, the data product of 2A12 showed greater skill in detecting and quantifying the volume of rainfall when compared with 2A25 and 2B31 data products. Error characterization using various error models revealed that random errors from multiplicative error models were homoscedastic and that they better represented rainfall estimates from 2A12 algorithm. Error decomposition technique, performed to disentangle systematic and random errors, testified that the multiplicative error model representing rainfall from 2A12 algorithm, successfully estimated a greater percentage of systematic error than 2A25 or 2B31 algorithms. Results indicate that even though the radiometer derived 2A12 is known to suffer from many sources of uncertainties, spatial and temporal analysis over the case study region testifies that the 2A12 rainfall estimates are in a very good agreement with the reference estimates for the data period considered. These findings clearly document that proper characterization of error structure offered by TMI and PR has wider implications in decision making, prior to incorporating the resulting orbital products for basin scale hydrologic modeling. The current missions of GPM envision a constellation of microwave sensors that can provide instantaneous products with a relatively negligible sampling error at daily or higher time scales. This study due to its simplicity and physical approach offers the ideal basis for future improvements in uncertainty modeling in precipitation.

Les interférences quantiques apparaissant lors de la superposition cohérente d'états quantiques de la matière sont à l'origine de la compréhension et du contrôle de nombreux processus élémentaires. Dans cette thèse, deux problèmes distincts, qui ont pour origine de tels effets, sont discutés avec leurs applications potentielles : 1. Diffraction électronique induite par Laser (LIED) et imagerie des orbitales moléculaires ; 2. Effets collectifs dans des vapeurs denses et transparence électromagnétique induite par interaction dipôle-dipôle (DIET). La première partie de cette thèse traite du mécanisme de recollision dans des molécules linéaires simples lorsque le système est exposé à un champ laser infrarouge de forte intensité. Cette interaction provoque une ionisation tunnel du système moléculaire, conduisant à la création d'un paquet d'ondes électronique dans le continuum. Ce paquet d'ondes suit une trajectoire oscillante, dirigée par le champ laser. Cela provoque une collision avec l'ion parent qui lui a donné naissance. Ce processus de diffraction peut être de nature inélastique, engendrant la génération d'harmoniques d'ordre élevé (HHG) ou l'ionisation double non-séquentielle, ou de nature élastique, processus que l'on appelle généralement « diffraction électronique induite par laser ». La LIED porte des informations sur la molécule et sur l'état initial à partir duquel les électrons sont arrachés sous forme de motifs de diffraction formés en raison de l'interférence entre différentes voies de diffraction. Dans ce projet, une méthode est développée pour l'imagerie des orbitales moléculaires, reposant sur des spectres de photo-électrons obtenus par LIED. Cette méthode est basée sur le fait que la fonction d'ondes du continuum conserve la mémoire de l'objet à partir duquel elle a été diffractée. Un modèle analytique basé sur l'approximation de champ fort (SFA) est développé pour des molécules simples linéaires et appliqué aux orbitales moléculaires HOMO et HOMO-1 du dioxyde de carbone. L'interprétation et l'extraction des informations orbitalaires imprimées dans les spectres de photo-électrons sont présentées en détail. Par ailleurs, nous estimons que ce type d'approche pourrait être étendu à l'imagerie de la dynamique électro-nucléaire de tels systèmes. La deuxième partie de cette thèse traite des effets collectifs dans des vapeurs atomiques ou moléculaires denses. L'action de la lumière sur ces gaz crée des dipôles induits qui oscillent et produisent des ondes électromagnétiques secondaires. Lorsque les particules constitutives du gaz sont assez proches, ces ondes secondaires peuvent coupler les dipôles induits entre-eux, et lorsque cette corrélation devient prépondérante la réponse du gaz devient une réponse collective. Ceci conduit à des effets spécifiques pour de tels systèmes, comme l'effet Dicke, la superradiance, et les décalages spectraux de Lorentz-Lorenz ou de Lamb. A cette liste d'effets collectifs, nous avons ajouté un effet de transparence induite dans l'échantillon. Cet effet collectif a été appelé « transparence électromagnétique induite par interaction dipôle-dipôle ». La nature collective de l'excitation du gaz dense réduit la vitesse de groupe de la lumière transmise à quelques dizaines de mètre par seconde, créant ainsi une lumière dite « lente ». Ces effets sont démontrés pour les transitions D1 du 85Rb et d'autres applications potentielles sont également discutées. / Quantum interference, coherent superposition of quantum states, are widely used for the understanding and engineering of the quantum world. In this thesis, two distinct problems that are rooted in quantum interference are discussed with their potential applications: 1. Laser induced electron diffraction (LIED) and molecular orbital imaging, 2. Collective effects in dense vapors and dipole induced electromagnetic transparency (DIET). The first part deals with the recollision mechanism in molecules when the system is exposed to high intensity infrared laser fields. The interaction with the intense field will tunnel ionize the system, creating an electron wave packet in the continuum. This wave packet follows an oscillatory trajectory driven by the laser field. This results in a collision with the parent ion from which the wave packet was formed. This scattering process can end up in different channels including either inelastic scattering resulting in high harmonic generation (HHG) and non-sequential double ionization, or elastic scattering often called laser induced electron diffraction. LIED carries information about the molecule and about the initial state from which the electron was born as diffraction patterns formed due to the interference between different diffraction pathways. In this project, a method is developed for imaging molecular orbitals relying on scattered photoelectron spectra obtained via LIED. It is based on the fact that the scattering wave function keeps the memory of the object from which it has been scattered. An analytical model based on the strong field approximation (SFA) is developed for linear molecules and applied to the HOMO and HOMO-1 molecular orbitals of carbon dioxide. Extraction of orbital information imprinted in the photoelectron spectra is presented in detail. It is anticipated that it could be extended to image the electro-nuclear dynamics of such systems. The second part of the thesis deals with collective effects in dense atomic or molecular vapors. The action of light on the vapor samples creates dipoles which oscillate and produce secondary electro-magnetic waves. When the constituent particles are close enough and exposed to a common exciting field, the induced dipoles can affect one another, setting up a correlation which forbids them from responding independently towards the external field. The result is a cooperative response leading to effects unique to such systems which include Dicke narrowing, superradiance, Lorentz-Lorenz and Lamb shifts. To this list of collective effects, one more candidate has been added, which is revealed during this study: an induced transparency in the sample. This transparency, induced by dipole-dipole interactions, is named “dipole-induced electromagnetic transparency”. The collective nature of the dense vapor excitation reduces the group velocity of the transmitted light to a few tens of meter per second resulting in 'slow' light. These effects are demonstrated for the D1 transitions of 85Rb and other potential applications are also discussed.

The thesis is dealing with the investigation of charge and orbital order and their behaviour under external pressure. Therefore, a new pressure cell has been developed which allows the observation of superlattice reflections corresponding to the order phenomena under pressure using scattering of high-energy synchrotron radiation. The maximum pressure that can be reached is 1.25 GPa. Until today there has been no possibility to conduct such studies of charge and orbital order superlattice reflections under pressure using x-ray scattering. The intensities of the reflections of the single crystalline samples are quite weak compared to fundamental peaks. Therefore the measurements are strongly affected by the absorption of the radiation in the pressure cell itself. Further difficulties result from the facts that low temperatures are needed and the sample has to be oriented in reciprocal space after being mounted into the cell. Therefore, the design of a compact clamp-type piston pressure cell was chosen here. The cell is made from a copper-beryllium alloy with the wall thickness reduced in the height of the sample volume. This allows the usage inside a closed-cycle cryostat mounted on a three-axis-diffractometer. Absorption effects are minimized due to the combination of reduced wall thickness and the usage of high energy synchrotron radiation (E = 100 keV at the beamline BW5 at HASYLAB/DESY). The new experimental technique was established and used for a study of two representatives of the transition metal oxide compounds, i.e. doped cuprates and manganites, which belong to the class of strongly correlated electron systems. The 1/8-doped cuprate La_{2-x}Ba_{x}CuO_{4} reveals an ordered state at low temperatures. Inside the CuO_{2} planes a combined order of charge stripes and antiferromagnetic spin stripes is observed. The ordering results from the interaction between charge, spin and lattice degrees of freedom. Here the lattice degrees of freedom play a major role. Particularly, a structural transition from an orthorhombic to a tetragonal symmetry is prerequisite for the observation of the ordered state. The cell constructed in this work allows a more exact analysis of the coupling between the crystal lattice and the formation of the charge and spin ordered phase. The manganite system Pr_{0.7}(Ca_{0.9}Sr_{0.1})_{0.3}MnO_{3} shows a strong magnetoresistive effect, called colossal magnetoresistance (CMR). In this system, several ordered phases can be found, which exhibit charge, spin and - since the orbital degree of freedom is also present in the manganites - additionally orbital ordering phenomena. In particular, an antiferromagnetically spin ordered insulating phase, which is connected to a charge- and orbital ordered state competes with a ferromagnetic metallic phase. This competition leads to a phase separation, which determines the properties of the sample. Both phases are strongly coupled to the lattice degrees of freedom, so that application of external pressure drastically affects the interplay between the different phases and allows a detailed study of the relation between the charge and orbital ordered phase and the crystal structure. / Die vorliegende Arbeit befaßt sich mit dem Studium der Ordnungszustände von Ladungen und Orbitalen und deren Beeinflußung durch externen Druck. Als experimentelle Neuentwicklung wurde dafür eine Druckzelle entworfen, mit deren Hilfe die Beobachtung der jeweiligen Ordnungsphänomene unter Druck mittels der Streuung hochenergetischer Synchtrotronstrahlung möglich ist. Die Zelle erlaubt die Messung der orbitalen und Ladungsüberstrukturreflexe, welche aus den geordneten Zuständen resultieren, in einem Druckbereich bis 1.25 GPa. Die experimentelle Herausforderung ergibt sich hierbei aus der Tatsache, dass die Überstrukturreflexe im Vergleich zu den fundamentalen Reflexen der einkristallinen Proben sehr schwach sind und zusätzlich durch die Absorption im Mantelmaterial der Druckzelle stark beeinträchtigt werden. Darüber hinaus soll die Zelle bei tiefen Temperaturen einsetzbar und die Probe auch innerhalb der Zelle im reziproken Raum orientierbar sein. Bei dem hier realisierten Ansatz wurde für das Design daher der Typ einer kompakten Klemmdruckzelle aus einer Kupfer-Beryllium-Legierung gewählt, deren Zellwände im Bereich des Probenvolumens reduziert wurden. Dadurch ist der Einsatz der Zelle im Inneren eines Closed-Cycle-Kryostaten auf einem Einkristall-Diffraktometer möglich. Aufgrund der geringen Wandstärke der Zelle und der Nutzung von hochenergetischer Röntgenstrahlung (E = 100 keV am Messplatz BW5 des HASYLAB/DESY) werden Absorptionseffekte minimiert. Die neue Messmethode wurde im Rahmen der Arbeit etabliert und zur Untersuchung zweier wichtiger Übergangsmetalloxidverbindungen (dotierte Kuprate, Manganate), die zur Klasse der stark korrelierten Elektronensysteme gehören, eingesetzt. Das 1/8-dotierte Kupratsystem La_{2-x}Ba_{x}CuO_{4}, weist bei tiefen Temperaturen einen statisch geordneten Zustand auf. Innerhalb der CuO_{2}-Schichten des Kristalls ergibt sich eine Ordnung, bei der sich Streifen lokalisierter Löcher und antiferromagnetische Bereiche abwechseln. Ursache dieses Zustands ist das Wechselspiel von Ladungen, Spins und strukturellen Freiheitsgraden. Dabei spielen letztere eine herausgehobene Rolle. So ist insbesondere ein struktureller Übergang von einer orthorhombischen zu einer tetragonalen Phase Voraussetzung für die Beobachtung der Ordnung. Die in dieser Arbeit aufgebaute Druckzelle erlaubt eine genauere Analyse des Zusammenhangs zwischen Struktur des Kristalls und der Ausbildung der ladungs- und spingeordneten Phase. Das Manganatsystem Pr_{0.7}(Ca_{0.9}Sr_{0.1})_{0.3}MnO_{3}, zeichnet sich durch einen sehr starken magnetoresistiven Effekt aus, der auch als kolossaler Magnetowiderstand (CMR) bezeichnet wird. Auch hier kann bei tiefen Temperaturen eine geordnete Phase beobachtet werden. Allerdings spielt in diesem System zusätzlich der orbitale Freiheitsgrad der Elektronen eine entscheidende Rolle, so dass sich eine kombinierte Ladungs- und Orbitalordnung ergibt. Diese Phase, die isolierend und zusätzlich antiferromagnetisch geordnet ist, steht im direkten Wettbewerb zu einer ferromagnetischen Phase. Aus dieser Konkurrenz ergibt sich eine Tendenz zur Phasenseparation, deren Effekte die Eigenschaften des Kristalls dominieren. Da beide Phasen stark an die strukturellen Freiheitsgrade gekoppelt sind, läßt sich das Gleichgewicht zwischen ihnen durch externen Druck beeinflussen und die Abhängigkeit der ladungs- und orbitalgeordneten Phase von den strukturellen Eigenschaften des Kristalls im Detail untersuchen.

<div>The orbits of interest for potential missions are stable or nearly stable to maintain long term presence for conducting scientific studies and to reduce the possibility of rapid departure. Near Rectilinear Halo Orbits (NRHOs) offer such stable or nearly stable orbits that are defined as part of the L1 and L2 halo orbit families in the circular restricted three-body problem. Within the Earth-Moon regime, the L1 and L2 NRHOs are proposed as long horizon trajectories for cislunar exploration missions, including NASA's upcoming Gateway mission. These stable or nearly stable orbits do not possess well-distinguished unstable and stable manifold structures. As a consequence, existing tools for stationkeeping and transfer trajectory design that exploit such underlying manifold structures are not reliable for orbits that are linearly stable. The current investigation focuses on leveraging stretching direction as an alternative for visualizing the flow of perturbations in the neighborhood of a reference trajectory. The information supplemented by the stretching directions are utilized to investigate the impact of maneuvers for two contrasting applications; the stationkeeping problem, where the goal is to maintain a spacecraft near a reference trajectory for a long period of time, and the transfer trajectory design application, where rapid departure and/or insertion is of concern.</div><div><br></div><div>Particularly, for the stationkeeping problem, a spacecraft incurs continuous deviations due to unmodeled forces and orbit determination errors in the complex multi-body dynamical regime. The flow dynamics in the region, using stretching directions, are utilized to identify appropriate maneuver and target locations to support a long lasting presence for the spacecraft near the desired path. The investigation reflects the impact of various factors on maneuver cost and boundedness. For orbits that are particularly sensitive to epoch time and possess distinct characteristics in the higher-fidelity ephemeris model compared to their CR3BP counterpart, an additional feedback control is applied for appropriate phasing. The effect of constraining maneuvers in a particular direction is also investigated for the 9:2 synodic resonant southern L2 NRHO, the current baseline for the Gateway mission. The stationkeeping strategy is applied to a range of L1 and L2 NRHOs, and validated in the higher-fidelity ephemeris model.</div><div><br></div><div>For missions with potential human presence, a rapid transfer between orbits of interest is a priority. The magnitude of the state variations along the maximum stretching direction is expected to grow rapidly and, therefore, offers information to depart from the orbit. Similarly, the maximum stretching in reverse time, enables arrival with a minimal maneuver magnitude. The impact of maneuvers in such sensitive directions is investigated. Further, enabling transfer design options to connect between two stable orbits. The transfer design strategy developed in this investigation is not restricted to a particular orbit but applicable to a broad range of stable and nearly stable orbits in the cislunar space, including the Distant Retrograde Orbit (DROs) and the Low Lunar Orbits (LLO) that are considered for potential missions. Examples for transfers linking a southern and a northern NRHO, a southern NRHO to a planar DRO, and a southern NRHO to a planar LLO are demonstrated.</div>

The thesis deals with the employment of direct forms of presentation in the genre of hard news. The texts for the analysis were excerpted from the main British broadsheet newspapers. The classification of forms of presentation is based on Semino and Short (2004) and focuses on their deictic and syntactic properties, interpreted in terms of the pragmatic concepts of perspective, faithfulness claims and the role of the reported and reporting speaker. Attention is paid to various direct forms, including direct speech, free direct speech and combined forms, i.e. non-direct forms appearing with a partial direct quote. The thesis draws heavily on the work by White (1998), whose approach to genre is informed by the ideas proposed by the Sydney School and Systemic Functional Linguistics. Hard news is characterised by the orbital generic structure, consisting of the nucleus and a number of specifying satellites (White 1998). The occurrence of direct and combined forms of presentation is explained by their deictic, syntactic and pragmatic properties, the generic role and characteristic features of the nucleus and individual satellites, and the overall function of hard news. The function of hard news and forms of presentation is also discussed in terms of the more general concepts of heteroglossia, dialogue...

Cette thèse traite de l'évitement de collision entre un engin spatial opérationnel, appelé objet primaire, et un débris orbital, dit secondaire. Ces travaux concernent aussi bien la question de l'estimation du risque pour une paire d'objets sphériques que celle du calcul d'un plan de manoeuvres d'évitement pour le primaire. Pour ce qui est du premier point, sous certaines hypothèses, la probabilité de collision s'exprime comme l'intégrale d'une fonction gaussienne sur une boule euclidienne, en dimension deux ou trois. On en propose ici une nouvelle méthode de calcul, basée sur les théories de la transformée de Laplace et des fonctions holonomes. En ce qui concerne le calcul de manoeuvres de propulsion, différentes méthodes sont développées en fonction du modèle considéré. En toute généralité, le problème peut être formulé dans le cadre de l'optimisation sous contrainte probabiliste et s'avère difficile à résoudre. Dans le cas d'un mouvement considéré comme relatif rectiligne, l'approche par scénarios se prête bien au problème et permet d'obtenir des solutions admissibles. Concernant les rapprochements lents, une linéarisation de la dynamique des objets et un recouvrement polyédral de l'objet combiné sont à la base de la construction d'un problème de substitution. Deux approches sont proposées pour sa résolution : une première directe et une seconde par sélection du risque. Enfin, la question du calcul de manoeuvres de proximité en consommation optimale et temps fixé, sans contrainte d'évitement, est abordée. Par l'intermédiaire de la théorie du vecteur efficacité, la solution analytique est obtenue pour la partie hors-plan de la dynamique képlérienne linéarisée. / This thesis is about collision avoidance for a pair of spherical orbiting objects. The primary object - the operational satellite - is active in the sense that it can use its thrusters to change its trajectory, while the secondary object is a space debris that cannot be controlled in any way. Onground radars or other means allow to foresee a conjunction involving an operational space craft,leading in the production of a collision alert. The latter contains statistical data on the position and velocity of the two objects, enabling for the construction of a probabilistic collision model.The work is divided in two parts : the computation of collision probabilities and the design of maneuvers to lower the collision risk. In the first part, two kinds of probabilities - that can be written as integrals of a Gaussian distribution over an Euclidean ball in 2 and 3 dimensions -are expanded in convergent power series with positive terms. It is done using the theories of Laplace transform and Definite functions. In the second part, the question of collision avoidance is formulated as a chance-constrained optimization problem. Depending on the collision model, namely short or long-term encounters, it is respectively tackled via the scenario approach or relaxed using polyhedral collision sets. For the latter, two methods are proposed. The first one directly tackles the joint chance constraints while the second uses another relaxation called risk selection to obtain a mixed-integer program. Additionaly, the solution to the problem of fixed-time fuel minimizing out-of-plane proximity maneuvers is derived. This optimal control problem is solved via the primer vector theory.

<p>In this thesis, we present novel computational methods and frameworks to address the challenges associated with the determination of free energy profiles for condensed-phase chemical reactions using combined quantum mechanical and molecular mechanical (QM/MM) approaches. We focus on overcoming issues related to force matching, molecular polarizability, and convergence of free energy profiles. First, we introduce a method called Reaction Path-Force Matching in Collective Variables (RP-FM-CV) that efficiently carries out ab initio QM/MM free energy simulations through mean force fitting. This method provides accurate and robust simulations of solution-phase chemical reactions by significantly reducing deviations on the collective variables forces, thereby bringing simulated free energy profiles closer to experimental and benchmark AI/MM results. Second, we explore the role of pairwise repulsive correcting potentials in generating converged free energy profiles for chemical reactions using QM/MM simulations. We develop a free energy correcting model that sheds light on the behavior of repulsive pairwise potentials with large force deviations in collective variables. Our findings contribute to a deeper understanding of force matching models, paving the way for more accurate predictions of free energy profiles in chemical reactions. Next, we address the underpolarization problem in semiempirical (SE) molecular orbital methods by introducing a hybrid framework called doubly polarized QM/MM (dp-QM/MM). This framework improves the response property of SE/MM methods through high-level molecular polarizability fitting using machine learning (ML)-derived corrective polarizabilities, referred to as chaperone polarizabilities. We demonstrate the effectiveness of the dp-QM/MM method in simulating the Menshutkin reaction in water, showing that ML chaperones significantly reduce the error in solute molecular polarizability, bringing simulated free energy profiles closer to experimental results. In summary, this thesis presents a series of novel methods and frameworks that improve the accuracy and reliability of free energy profile estimations in condensed-phase chemical reactions using QM/MM simulations. By addressing the challenges of force matching, molecular polarizability, and convergence, these advancements have the potential to impact various fields, including computational chemistry, materials science, and drug design.</p>

Indiana University-Purdue University Indianapolis (IUPUI) / In this thesis, we present novel computational methods and frameworks to address the challenges associated with the determination of free energy profiles for condensed-phase chemical reactions using combined quantum mechanical and molecular mechanical (QM/MM) approaches. We focus on overcoming issues related to force matching, molecular polarizability, and convergence of free energy profiles. First, we introduce a method called Reaction Path-Force Matching in Collective Variables (RP-FM-CV) that efficiently carries out ab initio QM/MM free energy simulations through mean force fitting. This method provides accurate and robust simulations of solution-phase chemical reactions by significantly reducing deviations on the collective variables forces, thereby bringing simulated free energy profiles closer to experimental and benchmark AI/MM results. Second, we explore the role of pairwise repulsive correcting potentials in generating converged free energy profiles for chemical reactions using QM/MM simulations. We develop a free energy correcting model that sheds light on the behavior of repulsive pairwise potentials with large force deviations in collective variables. Our findings contribute to a deeper understanding of force matching models, paving the way for more accurate predictions of free energy profiles in chemical reactions. Next, we address the underpolarization problem in semiempirical (SE) molecular orbital methods by introducing a hybrid framework called doubly polarized QM/MM (dp-QM/MM). This framework improves the response property of SE/MM methods through high-level molecular polarizability fitting using machine learning (ML)-derived corrective polarizabilities, referred to as chaperone polarizabilities. We demonstrate the effectiveness of the dp-QM/MM method in simulating the Menshutkin reaction in water, showing that ML chaperones significantly reduce the error in solute molecular polarizability, bringing simulated free energy profiles closer to experimental results. In summary, this thesis presents a series of novel methods and frameworks that improve the accuracy and reliability of free energy profile estimations in condensed-phase chemical reactions using QM/MM simulations. By addressing the challenges of force matching, molecular polarizability, and convergence, these advancements have the potential to impact various fields, including computational chemistry, materials science, and drug design.

The Canadian Nanosatellite Advanced Propulsion System is a liquefied cold-gas thruster system that provides propulsive capabilities to CanX-4/-5, the Canadian Advanced Nanospace eXperiment 4 and 5. With a launch date of early 2014, CanX-4/-5's primary mission objective is to demonstrate precise autonomous formation flight of nanosatellites in low Earth orbit. The high-level CanX-4/-5 mission and system architecture is described. The final design and assembly of the propulsion system is presented along with the lessons learned. A high-level test plan provides a roadmap of the testing required to qualify the propulsion system for flight. The setup and execution of these tests, as well as the analyses of the results found therein, are discussed in detail.