Neste trabalho, a estrutura local e média de nanopartículas foi estudada utilizando-se métodos de espalhamento e difração de raios X. Os métodos utilizados foram: Análise da Função de Distribuição de Pares Atômicos (Atomic Pair Distribution Function Analysis, em inglês) para o estudo do ordenamento estrutural de curto alcance, Refinamento de Rietveld e Modelamento Total do Perfil de Difração de Pó para o estudo do ordenamento médio. Os materiais estudados foram: nanopartículas de KY3F10 dopadas com Tb, nanocubos núcleo-camada (core-shell, em inglês) de FeO-Fe3O4 e nanopartículas de ferritas de Mn-Zn. O trabalho teve como objetivo demonstrar como os métodos mencionados podem ser utilizados de forma complementar para fornecer informações de curto, médio e longo alcance usando-se dados de espalhamento e difração de raios X. Neste trabalho, ressalta-se a importância de cada método no estudo da estrutura cristalina e demonstra avanço e desenvolvimento de metodologias para a sua aplicação. / In this work, local and average structure of nanoparticles were studied using X-ray scattering and diffraction methods. The methods used were: Atomic Pair Distribution Function Analysis to study the short-range ordering, Rietveld refinement and Whole Powder Pattern Modelling to study the long-range ordering. The studied materials were: Tb-doped KY3F10 nanoparticles, core-shell FeO-Fe3O4 nanocubes and Mn-Zn ferrite nanoparticles. The objective of this work was to demonstrate how the methods mentioned can be used in a complementary way to provide short, average and long range information about the structure using X-ray scattering and diffraction data. The importance of each method to study the crystalline structure is highlighted demonstrating progress and development of methodologies for its application.

Dünne Filme aus konjugierten Molekülen werden vermehrt in der organischen Optoelektronik, Bio-Sensorik und Oberflächenmodifikationen eingesetzt. Jedoch steckt das nanoskopische Verständnis von elementaren Prozessen bzgl. des molekularen Wachstums, der Film-Stabilität und thermisch-mechanischer Eigenschaften noch in den Kinderschuhen. Im ersten Teil dieser Arbeit nutzen wir Echtzeit in situ spekulare und diffuse Röntgenstreuung in Kombination mit Kinetik-Monte-Carlo Simulationen, um die Nukleation und das Multilagen-Wachstum von C60 zu studieren. Wir quantifizieren einen konsistenten Satz von Energieparametern, die die Oberflächenprozesse während des Wachstums beschreiben: eine effektive Ehrlich-Schwoebel Barriere von EES = 110 meV, eine Oberflächendiffusions-Barriere von ED = 540 meV und die Bindungsenergie von EB = 130 meV. Durch die Analyse der Teilchendynamiken finden wir, dass die laterale Diffusion ähnlich derer von Kolloiden ist, jedoch weist die Stufenkanten-Diffusion eine atom-ähnlichen Schwoebel-Barriere auf. Außerdem haben wir für die erste Monolage ein thermisch-aktiviertes Dewetting nach dem Wachstum von C60 auf Mica mit einer effektiven Aktivierungsbarriere von (0.33 ± 0.14) eV für die Aufwärts-Diffusion beobachtet. Im zweiten Teil der Arbeit untersuchen wir die thermomechanischen Eigenschaften der supra-molekularen Anordnung von dem organischen Halbleiter PTCDI-C8. Temperaturabhängige GIXD-Experimente decken einen außergewöhnlich großen positiven und negativen thermischen Expansionskoeffizienten der Kristallstruktur auf. Die Moleküle vollführen kooperative rotierende Bewegungen als Reaktion auf die Temperaturänderung, die zu dieser anomalen thermischen Expansion führen. Unsere Beschreibung der Bewegungen einzelner adsorbierter Moleküle während des Wachstums und der kooperativen Bewegungen einzelner Moleküle in supra-molekularen Ensembles auf der molekularen Skala wird die weitere Arbeit auf dem Weg zu funktionalen molekularen dünnen Filmen beleben. / Thin films of conjugated molecules are increasingly used in organic optoelectronics, biosensing and surface modification. However, nanoscopic understanding of elementary processes regarding the molecular film growth, the stability of these films and regarding the thermal and mechanical properties of supra-molecular assemblies are in its infancy. In the first part of this thesis we use real-time in situ specular and diffuse X-ray scattering in combination with kinetic Monte Carlo simulations to study C60 nucleation and multilayer growth. We quantify a consistent set of energy parameters, which describe the surface processes during growth, yielding an effective Ehrlich-Schwoebel barrier of EES = 110 meV, a surface diffusion barrier of ED = 540 meV and a binding energy of EB = 130 meV. Analysing the particle-resolved dynamics, we find that the lateral diffusion is similar to colloids, but step-edge crossing is characterized by an atom-like Schwoebel barrier. Furthermore, a thermally-activated post-growth dewetting for C60 on mica has been observed for the first monolayer with an effective activation barrier for upward interlayer transport of (0.33 ± 0.14) eV. In the second part we investigate the thermomechanical properties of the supra-molecular assembly of the organic semiconductor PTCDI-C8. Temperature-dependent Grazing Incidence X-ray Diffraction (GIXD) experiments reveal extraordinary large positive and, surprisingly, negative thermal expansion coefficients of the thin film crystal structure. The molecules perform temperature-controlled cooperative rotational motions leading to the change of the molecular crystal structure at different temperatures. We hope that our molecular scale picture of the movement of single ad-molecules during growth and the cooperative motions of single molecules in supra-molecular ensembles will stimulate further work towards the optimized, rational design of functional molecular thin films and nanomaterials.

Neste trabalho, a estrutura local e média de nanopartículas foi estudada utilizando-se métodos de espalhamento e difração de raios X. Os métodos utilizados foram: Análise da Função de Distribuição de Pares Atômicos (Atomic Pair Distribution Function Analysis, em inglês) para o estudo do ordenamento estrutural de curto alcance, Refinamento de Rietveld e Modelamento Total do Perfil de Difração de Pó para o estudo do ordenamento médio. Os materiais estudados foram: nanopartículas de KY3F10 dopadas com Tb, nanocubos núcleo-camada (core-shell, em inglês) de FeO-Fe3O4 e nanopartículas de ferritas de Mn-Zn. O trabalho teve como objetivo demonstrar como os métodos mencionados podem ser utilizados de forma complementar para fornecer informações de curto, médio e longo alcance usando-se dados de espalhamento e difração de raios X. Neste trabalho, ressalta-se a importância de cada método no estudo da estrutura cristalina e demonstra avanço e desenvolvimento de metodologias para a sua aplicação. / In this work, local and average structure of nanoparticles were studied using X-ray scattering and diffraction methods. The methods used were: Atomic Pair Distribution Function Analysis to study the short-range ordering, Rietveld refinement and Whole Powder Pattern Modelling to study the long-range ordering. The studied materials were: Tb-doped KY3F10 nanoparticles, core-shell FeO-Fe3O4 nanocubes and Mn-Zn ferrite nanoparticles. The objective of this work was to demonstrate how the methods mentioned can be used in a complementary way to provide short, average and long range information about the structure using X-ray scattering and diffraction data. The importance of each method to study the crystalline structure is highlighted demonstrating progress and development of methodologies for its application.

Dans le travail actuel, nous avons entrepris une étude structurale des monocristaux de polystyrène-polyoxyde d'éthylène (PS-b-PEO) pour élucider l'influence de la conformation du bloc de PS sur la cristallisation à partir d'une solution diluée. Nous avons également étudié le comportement des monocristaux lors d'une chauffe. Il est à noter que l'intérêt dans ces systèmes a été récemment réapparu en vue d'utilisation des monocristaux de copolymères pour générer des brosses amorphes uniformes. Lors de la cristallisation du PEO le bloc amorphe, c. à d. le PS, est rejeté du cristal et s'accumule donc sur des surfaces basales des lamelles cristallines. Puisque l'épaisseur cristalline qui résulte d'un processus de cristallisation isotherme a une valeur bien définie, la densité de greffage de PS en est aussi. Ainsi en changeant l'épaisseur du cristal nous pouvons générer des brosses de PS ayant des densités de greffage très variées. Dans notre étude, nous avons employé une combinaison des techniques d'analyse qui sont opérationnelles dans l'espace directe et réciproque telles que l'AFM et le SAXS/WAXS. Les expériences AFM ont été réalisées sur des monocristaux isolés tandis que les mesures SAXS/WAXS ont été faites sur des gâteux de monocristaux orientés qui ont été préparés par sédimentation lente à partir d'une solution diluée. L'interprétation des résultants SAXS se base sur le modèle à deux phases où les épaisseurs des régions cristallines (Lc) et amorphes (La) peuvent être déterminées en suivant les approches conventionnelles de la fonction de corrélation ou la fonction de distribution des interfaces. / In the present work, we have undertaken a structural study of PS-b-PEO single crystals to elucidate the influence of the state of the PS block on crystallization from dilute solution and on subsequent thermal annealing at elevated temperature. It is noteworthy that the interest in these systems has been recently renewed in the perspective of using them as a model of grafted amorphous brushes with variable grafting density. Indeed, during crystallization of PEO, the amorphous block, i.e. PS, is rejected from the crystal accumulating on its basal surfaces. Since the crystal thickness formed during isothermal crystallization is a sharply selected value, the grafting density of the resulting PS brush is also well defined. Therefore by varying the crystal thickness one can obtain the PS brushes with grafting density varying in a broad range.In our study, a combination of reciprocal and direct-space techniques such as SAXS/WAXS and AFM was employed. While AFM experiments were performed on isolated single crystals, the SAXS investigation was carried out on oriented mats of single crystals slowly sedimented from the "mother" solution. In this case, the one-dimensional two-phase system model was used for the data interpretation where the thickness of the amorphous (La) and crystalline (Lc) layers are conventionally determined following the correlation fonction and interface distribution fonction approaches.

Die Kristallisation ist ein wichtiger Teilprozess bei der industriellen Herstellung vieler Materialien und Medikamente. Es ist jedoch ein vielschichtiger, physikalischer Vorgang, der noch nicht vollständig aufgeklärt ist. Der Schwerpunkt dieser Arbeit liegt auf der Kristallisation von organischen, polymorphen Verbindungen aus unterschiedlichen Lösungsmitteln. Die Kristallisationsstudien wurden in einem akustischen Levitator mit Klimakammer, der den Einfluss von Temperatur, Feuchtigkeit und festen Oberflächen steuert, durchgeführt. Verschiedene analytische in-situ-Methoden und deren Kopplung kamen für die Analyse der Kristallisationsabläufe zum Einsatz. Als Unterstützung für die Interpretation der beobachteten Phänomene wurden unter äquivalenten Bedingungen Moleküldynamik-Simulationen vorgenommen. Die Kristallisation der Modellverbindungen zeigte verschiedene spezifische Kristallisationspfade, die nicht dem klassischen Kristallisationsmodell entsprachen. Zunächst verdampfte das Lösungsmittel, was mit einer Konzentrationszunahme der Lösung und der Ausbildung von charakteristischen amorphen Phasen (Polyamorphismus) einherging, und schließlich trat die Kristallisation ein. Durch die oberflächenfreie Kristallisation wurde ausschließlich nur ein Polymorph ein- und derselben Verbindung als Kristallisationsprodukt isoliert. Die gezielte Wahl der Ausgangskonzentration und eines Lösungsmittels ermöglichte die Steuerung des Kristallisationsverlaufs hin zu einer gewünschten Kristallstruktur des untersuchten Materials. Die Ergebnisse dieser Arbeit unterstützen das Verständnis über den komplexen Ablauf des Kristallisationsvorgangs, gleichzeitig zeigen sie weitere Ansätze auf, die Kristallisation zu untersuchen. Die neuen Erkenntnisse sind hilfreich bei der Optimierung der Herstellungsprozesse verschiedener Materialien. / Crystallization is a complex process, which is used in different processes in the industrial production of various materials. The limited understanding about its fundamental mechanisms challenges the control of crystallization and influences the quality of the materials. The research of this work concentrates on the crystallization studies of organic model systems (active pharmaceutical ingredients) from different organic solvents in an acoustic levitator. This specific sample environment regulates the influence that solid surfaces, temperature, and humidity have on the crystallization process. The investigations were performed with in situ analytical techniques and theoretical simulations to gain a comprehensive insight into processes, occurring intermediates, and required reaction conditions. The results show that the model systems follow specific crystallization pathways different than those predicted by the classical nucleation theory. The crystallization proceeded via the evaporation of the solvent and the formation of characteristic amorphous phases (polyamorphism) into one crystalline structure of the compound. The targeted choice of the solvent and the concentration enabled the guidance of the pathways, therefore, resulting in the isolation of one desired crystalline structure. The findings are of great interest and they help explain the crystallization mechanisms on a molecular level, which is a fundamental contribution for the optimization of manufacturing processes.

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.

Isotactic polypropylene (iPP), as one of the most versatile commodity thermoplastic polymers, is a polymorphic material having several crystal modifications, among which the β-form exhibits higher performance including excellent impact strength and improved elongation at break.Up to now, the effective and convenient way to prepare the iPP with high content of β-phase has been successfully achieved by addition of certain β-nucleating agent. Since the coexistence of β-nucleating agent and flow (shear flow, extensional flow or mixed), which usually exists in common industrial processing, makes the crystallization process more complex, their combined effect on the structure evolution of polymers, especially in the early stage of crystallization is still not well understood. The mechanical properties of iPP depend strongly on its crystallinity, crystal orientation and morphology determined by the conditions during preparation. On the other hand, the mechanical properties of polymers can also be modulated by deformation processing, which is directly related to the deformation-induced structure transition. However, the transition mechanism of different crystal forms and structure-property correlation still remain unclear. In this thesis, time-resolved synchrotron X-ray scattering was firstly used for the in-situ study of the structural and morphological developments of β-nucleated iPP during shear-induced crystallization. It was found that the crystallization process was strongly influenced by the concentration of β-nucleating agent, shear rate and shear temperature. Then extension-induced crystallization was investigated by a novel melt draw experiment, where a different crystallization mechanism compared to the shear-induced crystallization was found. Subsequently, β-nucleated iPP samples with different thermomechanical histories were scanned by synchrotron X-ray microbeam to construct their overall morphological distributions, including distributions of crystallinity, lamellar thickness, orientation, etc. Finally, these morphology-identified samples were investigated by in-situ synchrotron X-ray measurements coupled with mechanical testing to follow the structure evolution during deformation at elevated temperature. It was found that the deformation behaviour of β-nucleated iPP was closely associated with its initial morphology, its subsequent variation during stretching as well as the stretching conditions including the stretching rate and stretching temperature. The current study would not only contribute to the development of crystallization and deformation theory but also be beneficial for the material design.

Owing to their versatile orbital character with both local and highly dispersive degrees of freedom, transition metal oxides span the range of ionic, covalent and metallic bonding. They exhibit a vast diversity of electronic phenomena such as high dielectric, piezoelectric, pyroelectric, ferroelectric, magnetic, multiferroic, catalytic, redox, and superconductive properties. The nature of these properties arises from sensitive details in the electronic structure, e.g. orbital mixing and orbital hybridization, due to non-stoichiometry, atomic displacements, broken symmetries etc., and their coupling with external perturbations. In the work presented here, these variations of the electronic structure of crystals due to structural and electronic defects have been investigated, exemplarily for the quasi-binary system SrO - SrTiO3 - TiO2. A number of binary and ternary structures have been studied, both experimentally as well as by means of electronic modeling. The applied methods comprise Resonant X-ray Scattering techniques like Diffraction Anomalous Fine Structure, Anisotropy of Anomalous Scattering and X-ray Absorption Fine Structure, and simultaneously extensive electronic calculations by means of Density Functional Theory and Finite Difference Method Near-Edge Structure to gain a thorough physical understanding of the underlying processes, interactions and dynamics. It is analyzed in detail how compositional variations, e.g. manifesting as oxygen vacancies or ordered stacking faults, alter the short-range order and affect the electronic structure, and how the severe changes in mechanical, optical, electrical as well as electrochemical properties evolve. Various symmetry-property relations have been concluded and interpreted on the basis of these modifications in electronic structure for the orbital structure in rutile TiO2, for distorted TiO6 octahedra and related switching mechanisms of the Ti valence, for elasticity and resistivity in strontium titanate, and for surface relaxations in Ruddlesden-Popper phases. Highlights of the thesis include in particular the methodical development regarding Resonant X-Ray Diffraction, such as the first use of partially forbidden reflections to get the complete phase information not only of the tensorial structure factor but of each individual atomic scattering tensor for a whole spectrum of energies, as well as the determination of orbital degrees of freedom and details of the partial local density of states from these tensors. On the material side, the most prominent results are the identification of the migration-induced field-stabilized polar phase and the exergonic redox behavior in SrTiO3 caused by defect migration and defect separation.

The majority of structural studies on DNA have been carried out using fibre diffraction, while studies of its dynamics and thermal behaviour have been mainly performed in solution. When the DNA double helix is heated, it exhibits local separation of the two strands that grow in size with temperature and lead to their complete separation. This work has investigated various aspects of this phenomenon. The experiments reported in this thesis were carried out on films of oriented fibres of DNA prepared with the Wet Spinning Apparatus. Thus, sample preparation and characterisation are essential parts of the research. The structures of two forms of DNA, A and B, have been explored as a function of relative humidity at fixed ionic conditions. A method to eliminate traces of ever-present B-form contamination in A-form samples was established. The high orientation of the DNA molecules within the samples allowed us to investigate dynamical fluctuations and the melting transition of DNA using neutron scattering, which can provide the spatial information crucial to understand a phase transition, probing the static correlation length along the molecule as a function of temperature. The transition has been investigated for A and B-forms in order to understand its dependence on molecular configuration.Furthermore, after the first melting, denatured DNA films show typical glass behaviour. Their thermal relaxation has been explored using calorimetry.Neutron and X-ray inelastic scattering (INS and IXS) were used in the past to measure longitudinal phonons in fibre DNA, and the results shown disagreement. Recent INS measurements supported with phonon simulations have been crucial to understand the different dispersion curves reported to date. Experiments using INS and IXS have been carried out to continue with this investigation. Attempts to observe the transverse fluctuations associated to the thermal denaturing of DNA, never experimentally investigated before, have been made.

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.