Frustrated magnets realize exotic forms of quantum matter beyond conventional order. Due to a lack of controlled and unbiased methods to study frustration in three dimensions, many questions remain unanswered. While most established numerical techniques have limited applicability, approaches based on cluster expansions are promising alternatives. By design, they do not suffer from dimensionality or frustration and generate reliable insights into the thermodynamic limit without any restriction in the parameter space. This thesis makes significant methodological progress in controlled numerical approaches tailored to study frustration in three dimensions. It covers (i) an automatic detection algorithm for symmetries in generic clusters, (ii) a general approach to the numerical linked cluster algorithm to study finite - and zero - temperature properties, and (iii) an expansion method based on the linked cluster theorem to obtain a suitable dressing for valence-bond crystals. In particular, we study one of the archetypal problems of frustrated magnetism in three dimensions: the pyrochlore Heisenberg antiferromagnet. For the first time, we are able to unbiasedly resolve its thermodynamic quantities to a temperature far beyond the scale on which the Schottky anomaly occurs. The broad applicability of the numerical linked cluster algorithm allows for the systematic investigation of different spin-liquid candidate materials such as the Cerium-based pyrochlores Ce₂Zr₂O₇ and Ce₂Sn₂O₇. Despite a similar chemical composition, the algorithm finds fundamental differences in their quantum mechanical nature by constraining their microscopic exchange parameters. Zero temperature properties are even less accessible: Neither the nature of the ground state nor an estimate of its energy are known for the pyrochlore antiferromagnet. Large-scale density matrix renormalization group calculations pushed to three dimensions provide the first reliable estimate of its ground-state energy and yield robust evidence for a spontaneous inversion symmetry breaking manifesting itself as an energy density difference on the tetrahedral sublattice. The symmetry-breaking tendency of the model is further observed in the presence of an external magnetic field where similar calculations suggest a stable 1/2-magnetization plateau. Continuing the investigation of low-energy states, we propose a new family - exponentially numerous in the linear system size - of valence-bond crystals as potential ground states. Understanding the stability of the previously overlooked family of states suggests a remarkable change of perspective on frustration with a focus on unfrustrated motifs. In sum, these discoveries present significant progress towards resolving long-standing questions regarding the nature of the ground state of the quantum pyrochlore S=1/2 antiferromagnet. / Frustrierte Magnete realisieren exotische Formen von Quantenmaterie, welche gewöhnliche Ordnungen übersteigen. Viele etablierte numerische Methoden versagen bei Frustration in drei Dimensionen, da sie entweder nicht anwendbar sind, unkontrolliert sind oder bestimmte Zustände vorziehen. Clusteralgorithmen bilden eine vielversprechende Alternative. Sie erfahren keine Einschränkung durch die Dimensionalität oder die Frustration des Problems und erlauben daher zuverlässige Einblicke in den thermodynamischen Limes. Diese Arbeit präsentiert methodische Fortschritte von kontrollierbaren Ansätzen, welche auf frustrierte Systeme in drei Dimensionen zugeschnitten sind. Sie beinhaltet (i) die Entwicklung eines Algorithmus zur automatischen Detektion räumlicher Symmetrien für allgemeine Cluster, (ii) einen allgemeinen Zugang zum 'numerical linked cluster algorithm'', um Eigenschaften bei endlicher Temperatur und dem absoluten Nullpunkt zu studieren und (iii) einen Clusteralgorithmus zur Optimierung des Zustands eines 'valence-bond' Kristalls. Die methodischen Fortschritte dieser Arbeit tragen zur Lösung eines archetypischen Problems von frustriertem Magnetismus in drei Dimensionen bei: dem Pyrochlor Heisenberg Antiferromagnet. Sie erlauben zuverlässige Einblicke in die Thermodynamik bis hin zu nicht-trivialen Temperaturen weit unter der Schottky-Anomalie. Die weiten Anwendungsmöglichkeiten des Clusteralgorithmus macht die systematische Untersuchung von Spinflüssigkeitskandidaten, wie die auf Cer basierenden Pyrochlore Ce₂Zr₂O₇ und Ce₂Sn₂O₇, möglich. Trotz einer ähnlichen chemischen Komposition, findet der Algorithmus fundamentale Unterschiede in ihrer quantenmechanischen Struktur. Frustration in drei Dimensionen ist am absoluten Nullpunkt ähnlich unzugänglich wie bei endlicher Temperatur und weder der Grundzustand, noch Schätzungen der Grundzustandsenergie des Pyrochlor Antiferromagneten sind bekannt. Groß angelegte Dichtematrixrenomierungsgruppenrechnungen in drei Dimensionen ermöglichen erstmals eine verlässliche Schätzung der Energie und finden eine spontan gebrochene Inversionssymmetrie, welche durch einen Unterschied in der Energiedichte auf dem tetraedrischen Untergitter ausgedrückt ist. Die Tendenz, die Symmetrie des Systems zu brechen, ist auch in der Präsenz eines externen magnetischen Feldes zu beobachten. Rechnungen deuten die Stabilität des 1/2-Magnetisierungsplateaus an. Einen signifikanten Beitrag zum Verständnis des Heisenberg-Models auf dem Pyrochlor wird durch eine Familie von potentiellen Grundzuständen geleistet, welche als harte Hexagone im Gitter visualisiert werden können. Ihre Anzahl skaliert exponentiell in der linearen Systemgröße und ihre niedrige Energie eröffnet eine neue Sichtweise auf frustrierte Magnete, welche den Fokus auf unfrustrierte Geometrien lenkt. Im Widerspruch zu der prominenten Spinflüssigkeitsannahme deuten die Ergebnisse dieser Arbeit auf Ordnung im Pyrochlor Antiferromagneten hin.

This thesis explores systems that exhibit strong coupling between an optical cavity field and a many-particle system. To treat the drive and dissipative nature of the cavity on the same footing as the dynamics of the many-particle system, we use a non-equilibrium field theoretic approach. The first system considered is an ultracold bosonic gas trapped inside a cavity. The dispersive coupling between the cavity field and the atoms' motion leads to the formation of a polariton. We show how a modulation of the pump laser on the energy scale of the transverse cavity mode splitting can be used to create effective interactions between different cavity modes. This effective interaction results in the polariton acquiring a multimode nature, exemplified by avoided crossings in the cavity spectrum. As the laser power is increased, the polariton softens and at a critical power becomes unstable. This instability signals the transition into a superradiant state. If the multimode polariton contains a cavity mode with an effective negative detuning, then the transition does not happen through a mode softening but at a finite frequency. To investigate this, classical non-linear equations are constructed from the action and from these we derive the critical couplings and frequencies. It is shown how the superradiant transition happening at a finite frequency is a consequence of a competition between the negatively and the positively detuned cavity modes making up the polariton. The finite-frequency transition is found to be equivalent to a Hopf bifurcation and leads to the emergence of limit cycles. Our analysis shows that the system can exhibit both bistabilities and evolution constricted to a two-torus. We end the investigation by showing how interactions among the atoms combined with the emerging limit cycle open new phonon scattering channels. The second system considered in the thesis is inspired by the recent experiments on gated Transition-metal dichalcogenides (TMD) monolayers inside cavities. An exciton within the TMD can couple strongly to the cavity and, due to the electronic gating, also interact strongly with the conduction electrons. To treat the strong interactions of the excitons with both cavity and electrons, we solve the coupled equations for the correlation functions non-perturbatively within a ladder approximation. The strong interactions give rise to new quasiparticles known as polaron-polaritons. By driving the system through the cavity, we show how the competition between electron-induced momentum relaxation and cavity loss leads to the accumulation of polaritons at a small but finite momentum, which is accompanied by significant decrease of the polariton linewidth Due to the hybrid nature of the polaron-polariton, we show that this behavior can by qualitatively modified by changing the cavity detuning.

We study the low-temperature physics arising in models of a strongly correlated, tunnel-coupled double quantum dot (DQD), particularly the two-impurity Anderson model (2AIM) and the two-impurity Kondo model (2IKM), employing a combination of physical arguments and the Numerical Renormalisation Group. These models exhibit a rich range of Kondo physics. In the regime with essentially one electron on each dot, there is a competition between the Kondo effect and the interdot exchange interaction. This competition gives rise to a quantum phase transition (QPT) between local singlet and Kondo singlet phases in the 2IKM, which becomes a continuous crossover in the 2AIM as a result of the interlead charge transfer present. The 2IKM is known to exhibit two-channel Kondo (2CK) physics at the QPT, and we investigate whether this is also the case for the 2AIM at the crossover. We find that while in principle 2CK physics can be observed in the 2AIM, extremely low temperatures are required, such that it is unlikely that 2CK physics will be observed in an experimental DQD system in the near future. We have studied the effect of a magnetic field on the 2AIM and the 2IKM, finding that both the zero-field QPT in the 2IKM and the zero-field crossover in the 2AIM, persist to finite field. This presents the possibility of observing 2CK physics in an experimental DQD at finite field, but we find that the temperatures required to do so are extremely low. We show that longer even-numbered chains of spins also exhibit QPTs at finite field, and argue that a 2N-spin chain should undergo N QPTs as field is increased (starting deep in the local singlet phase at zero field). We have also carried out a joint theoretical-experimental study of a carbon nanotube based DQD, in collaboration with Dr. Mark Buitelaar et al. The agreement between experimental and theoretical results is good, and the experiments are able to access the crossover present in the 2AIM at finite field. Furthermore, the experiments show the wide range of physics exhibited by DQD systems, and illustrate the utility of such systems in probing correlated electron physics.

This thesis presents a collection of four papers published in peer-reviewed scientific journals plus a manuscript yet to be submitted, all of them in the field of low temperature physics and quantum fluids. Each of these works reports a step forward in the ever-developing theoretical description of helium systems by means of density functional theory. The first two papers deal with questions related to the groundstate description of helium complexes around atomic impurities. We have computed such structure and determined its effect on the dipole absorption spectrum of Na in (3)He—(4)He clusters and of Mg in the homogeneous, isotopically mixed liquid. We have also explored the limits of density functional calculations for a small number of helium atoms interacting with a linear carbonyl sulfide (OCS) molecule. To this end we have implemented a Kohn-Sham scheme for 3He and computed the structure of OCS@3HeN clusters for N up to 40. The next three papers deal with the real-time description of dynamical processes in helium systems of experimental interest. We present an efficient and quantitatively accurate procedure to compute dynamical processes, namely the dynamics of an excited electron bubble and of an excited silver impurity, following a time-dependent density functional theory (TDDFT) for helium coupled to the appropiate dynamics of impurities. In the case of the electron bubble, we have related the experimental disappearance of 1P bubbles at high pressures with the existence of a nonradiative de-excitation path involving the bubble splitting about 20 picoseconds after the excitation. In the case of the desorption of a silver atom from a He drop, our dynamical calculations predict a range of velocities for the ejected impurity consistent with the experimental velocity distribution, which can be taken as indirect evidence of the superfluidity of helium nanodroplets. / En esta tesis se presenta una colección de cuatro artículos publicados y un manuscrito aún no publicado, todos ellos en el campo de la física de bajas temperaturas y fluidos cuánticos. Cada uno de ellos reporta un paso adelante en la descripción teórica de los sistemas de helio por medio de la teoría del funcional de la densidad. Los primeros dos artículos están clasificados como “estructura" ya que tratan cuestiones relacionadas con la descripción del estado fundamental de complejos de helio dopados con impurezas atómicas. En ellos hemos calculado la estructura y determinado su efecto sobre el espectro de absorción dipolar del Na en agregados de (3)He-(4)He y del Mg en el líquido homogéneo e isotópicamente mezclado. Para el caso de Na en gotas se ha encontrado que, a pesar de necesitar una gran cantidad de (3)He para que la capa exterior de la gota sature, el espectro de la impureza es muy insensible a la composición isotópica y rápidamente satura al valor que toma en las gotas de (3)He puras. Para Mg en el líquido mezclado, la presencia de (3)He induce cambios en el espectro mucho más pequeños que su anchura característica, por lo que se ha encontrado que el efecto general de la composición isotópica de la mezcla en la espectroscopia es mínima. Hemos explorado también los límites del funcional de la densidad para un número pequeño de átomos de helio interactuando con una molécula lineal de sulfuro de carbonilo (OCS). Para ello hemos implementado un esquema de Kohn-Sham para el (3)He y hemos obtenido la estructura de agregados OCS@(3)He(N) para un número de átomos “N” hasta 40. Hemos comparado los resultados de los agregados de (4)He con el mismo número de átomos y hemos encontrado que la alta anisotrop_á de la molécula de OCS magni_ca los efectos de las diferentes estadísticas de cada isótopo. Nuestra estimación de los momentos de inercia de estos agregados es consistente con la interpretación de los datos experimentales que sugieren una estructura de 11 átomos de helio rotando solidariamente con la molécula de OCS. Los siguientes tres trabajos, clasificados como “dinámica", describen la evolución temporal de ciertos procesos de interés experimental en los sistemas de helio. Mientras que las publicaciones sobre la estructura completan una línea de trabajo bien establecida, las de esta sección abren un nuevo frente de exploración teórica sobre los procesos dinámicos con resolución de picosegundos. En ellos se presenta un procedimiento eficiente para describirlos cuantitativamente mediante una teoría del funcional de la densidad dependiente del tiempo (TDDFT, por sus siglas en inglés) para el helio, acoplado a la dinámica adecuada para la impureza. Cuál es la dinámica “adecuada" depende de las propiedades de la impureza: para la burbuja electrónica 1P se puede utilizar una descripción puramente mecanocuántica del electrón en una aproximación adiabática, mientras que para la burbuja 2P la aproximación adiabática no es aplicable y se deben acoplar las evoluciones en tiempo real del helio y del electrón. Para una impureza masiva como la Ag una descripción clásica de su movimiento es suficiente, pero el efecto de spin-órbita es lo suficientemente importante como para que el estado electrónico del átomo deba tenerse en cuenta en la dinámica como un grado de libertad cuantizado . En el caso de las burbujas electrónicas, hemos relacionado la desaparición de las burbujas 1P a altas presiones con la existencia de un camino de relajación no-radiativo que causa la rotura de la burbuja en dos mitades casi esféricas tras haber transcurrido unos 20 picosegundos desde su excitación. Hemos sido capaces de establecer esta relación gracias a que nuestro cálculo predice la “fisión" de la burbuja solo para presiones superiores a 1 bar, que es el mismo umbral observado experimentalmente para la desaparición de las burbujas 1P. Teniendo en cuenta que aumentar la presión en 1 bar aumenta la densidad de saturación del líquido en poco más de un 1 %, la exactitud de este resultado indica que TDDFT contiene la física relevante para describir este tipo de procesos y tiene capacidad de predicción cuantitativa. También hemos encontrado un marcado cambio en el comportamiento del espectro de absorción con resolución temporal de la burbuja 1P dependiendo de si ésta fisiona o no, es decir, dependiendo de la presión del líquido. La observación experimental de este cambio y su determinación podrá completar la información obtenida en los experimentos de cavitación y fotoconductividad. En el caso de la desorción de un átomo de plata tras su fotoexcitación en el interior de una gota de He, nuestros cálculos dinámicos predicen un rango de velocidades para la impureza consistente con la distribución de velocidades experimental. Esta velocidad es el resultado de cuánta energía transfiere la impureza a la gota, lo cual depende de los modos de excitación disponibles para dicha transferencia. Nuestra descripción del líquido solo permite excitaciones colectivas tales como ondas de densidad u oscilaciones de superficie, por lo que la compatibilidad de nuestros resultados con los datos experimentales se puede tomar como una evidencia indirecta de la superfluidez de las nanogotas de helio. Adicionalmente hemos descartado la nucleación vórtices como un posible canal de transferencia de energía en gotas nanoscópicas al no haberlos generado en nuestros cálculos.

A system with two magnetic molecules embedded in a junction between non-magnetic leads was studied. In this system electrons tunnel from the localized energy level in region one to the localized energy level in region two generating a flow of electric charge through the quantum dot system. The current density and thus the conductance changes depending on the molecular spin moment. In this work we studied molecules with either spin "up" or spin "down" and with symmetric coupling strengths. The results indicate that the coupling strength between energy level and molecule together with the tunneling rate through the insulating layer play a major role when switching from parallel to anti-parallel molecular spin, for a specific combination of the coupling strength and tunneling rate we could observe a decrease in the current by 99.7% in the non-gated system and 99.4% in the gated system.

Dans cette thèse, nous avons étudié expérimentalement les propriétés physiques des fermions ultra-froids grâce à une machine conçue pour refroidir un mélange fermionique de 6Li et 40K. Après une courte description concernant la construction de l'expérience et quelques améliorations que j'ai implémentées pendant ma thèse (telles que la désorption atomique par lumière ultraviolette dans le 2D-MOT), l'exposé se concentre sur deux observations principales de l'origine fermionique des gaz de potassium et de lithium.La première partie présente la quasithermalization du 6Li dans un potentiel quadrupolaire, créé par un piège magnétique. Malgré l'absence de collisions dans un gaz fermionique polarisé en dessous d'une température donnée, nous observons une redistribution d'énergie dans l'ensemble statistique après une excitation dans le piège linéaire. Une étude expérimentale détaillée ainsi qu'une analyse théorique du phénomène sont présentées. De plus, une transformation canonique de l'hamiltonien du système permet la description de particules sans masses dans un piège harmonique. Les résultats expérimentaux du système réel (gaz 6Li dans un potentiel quadrupolaire) sont donc réinterprétés pour décrire ces particules non massiques, difficiles à observer. Un développement supplémentaire de notre système expérimental permet également la réalisation d'un couplage spin-orbite non-abélien dans le gaz fermionique sans interactions.Dans la deuxième partie, on décrit la réalisation d'un gaz dégénéré de 40K à l'aide du refroidissement évaporatif. Une succession d'étapes d'évaporation, utilisant différentes technologies de piégeage, nous permet d'obtenir 1.5e5 atomes dans l'état fondamental à une température de 62nK, température équivalente à 17% de la température de Fermi. / In this thesis we investigate experimentally the physics of a cold fermionic mixture consisting of 6Li and 40K. After a short description of the experimental apparatus and of a few technical particularities implemented during my PhD, for example the light-induced atomic desorption in the 2D-MOT by UV-light, we focus on two main observations of the fermionic nature of the gas.The first part describes the quasithermalization of 6Li in a magnetic quadrupole potential. Even though collisions are absent in a spin-polarized fermionic gas below a given temperature, the statistical ensemble undergoes energy redistribution after an excitation within the linear potential. We present an extensive experimental study as well as a comprehensive theoretical analysis. Moreover, the studied Hamiltonian can be canonically mapped onto a system of massless, harmonically trapped particles and the previously developed results are re-interpreted in order to describe this experimentally inaccessible system. A further development of the realized experiment allows even for the implementation of spin-orbit coupling in a gas of non-interacting fermions.In the second part, we describe the evaporative cooling of 40K to quantum degeneracy. Through different evaporative cooling stages we reach with a final number of 1.5e5 atoms in the ground-state a temperature of 62nK, which corresponds to 17% of the Fermi temperature.

Ma thèse de doctorat était consacrée à l'étude des systèmes quantiques à plusieurs corps dissipatifs et pilotés. Ces systèmes représentent des plateformes naturelles pour explorer des questions fondamentales sur la matière dans des conditions de non-équilibre, tout en ayant un impact potentiel sur les technologies quantiques émergentes. Dans cette thèse, nous discutons d'une décomposition spectrale de fonctions de Green de systèmes ouverts markoviens, que nous appliquons à un modèle d'oscillateur quantique de van der Pol. Nous soulignons qu’une propriété de signe des fonctions spectrales des systèmes d’équilibre ne s’imposait pas dans le cas de systèmes ouverts, ce qui produisait une surprenante "densité d’états négative", avec des conséquences physiques directes. Nous étudions ensuite la transition de phase entre une phase normale et une phase superfluide dans un système prototype de bosons dissipatifs forcés sur un réseau. Cette transition est caractérisée par une criticité à fréquence finie correspondant à la rupture spontanée de l'invariance par translation dans le temps, qui n’a pas d’analogue dans des systèmes à l’équilibre. Nous discutons le diagramme de phase en champ moyen d'une phase isolante de Mott stabilisée par dissipation, potentiellement pertinente pour des expériences en cours. Nos résultats suggèrent qu'il existe un compromis entre la fidélité de la phase stationnaire à un isolant de Mott et la robustesse d'une telle phase à taux de saut fini. Enfin, nous présentons des développements concernant la théorie du champ moyen dynamique (DMFT) pour l’étude des systèmes à plusieurs corps dissipatifs et forcés. Nous introduisons DMFT dans le contexte des modèles dissipatifs et forcés et nous développons une méthode pour résoudre le problème auxiliaire d'une impureté couplée simultanément à un environnement markovien et à un environnement non-markovien. À titre de test, nous appliquons cette nouvelle méthode à un modèle simple d’impureté fermionique. / My PhD was devoted to the study of driven-dissipative quantum many-body systems. These systems represent natural platforms to explore fundamental questions about matter under non-equilibrium conditions, having at the same time a potential impact on emerging quantum technologies. In this thesis, we discuss a spectral decomposition of single-particle Green functions of Markovian open systems, that we applied to a model of a quantum van der Pol oscillator. We point out that a sign property of spectral functions of equilibrium systems doesn't hold in the case of open systems, resulting in a surprising ``negative density of states", with direct physical consequences. We study the phase transition between a normal and a superfluid phase in a prototype system of driven-dissipative bosons on a lattice. This transition is characterized by a finite-frequency criticality corresponding to the spontaneous break of time-translational invariance, which has no analog in equilibrium systems. Later, we discuss the mean-field phase diagram of a Mott insulating phase stabilized by dissipation, which is potentially relevant for ongoing experiments. Our results suggest that there is a trade off between the fidelity of the stationary phase to a Mott insulator and robustness of such a phase at finite hopping. Finally, we present some developments towards using dynamical mean field theory (DMFT) for studying driven-dissipative lattice systems. We introduce DMFT in the context of driven-dissipative models and developed a method to solve the auxiliary problem of a single impurity, coupled simultaneously to a Markovian and a non-Markovian environment. As a test, we applied this novel method to a simple model of a fermionic, single-mode impurity.

Le sujet de cette thèse est la théorie à partir des premiers principes de la structure électronique de matériaux présentant de fortes corrélations électroniques. D’importants progrès ont été faits dans ce domaine grâce aux implémentations modernes de Théorie de la Fonctionelle de Densité (DFT). Néanmoins, la méthode DFT a certaines limitations. D’une part, elle est faite pour décrire les propriétés de l’état fondamental mais pas des états excités des matériaux, bien que ces derniers soient également importants. D’autre part, les approximations de la fonctionnelle employées en pratique réduisent la validité de la DFT, conceptuellement exacte : en particulier elles décrivent mal les matériaux aux effets de corrélations les plus importants.Depuis les années 1990, différentes théoriques quantiques à N corps ont été utilisées pour améliorer ou compléter les simulations à base de DFT. Une des plus importantes est la Théorie du Champ Moyen Dynamique (DMFT), dans laquelle un modèle sur réseau est relié de manière auto-cohérente à un modèle plus simple d’impureté, ce qui donne de bons résultats à condition que les corrélations soient principalement locales. Nous présentons brièvement ces théories dans la première partie de cette thèse. Les progrès récents de la DMFT visent, entre autres, à mieux décrire les effets non-locaux, à comprendre les propriétés hors équilibre et à décrire de vrais matériaux plutôt que des modèles.Afin d’utiliser la DMFT pour décrire de vrais matériaux, il faut partir d’un calcul de structure électronique traitant tous les électrons au même niveau, puis appliquer une correction traitant les effets à N corps sur un sous-espace de basse énergie d’orbitales autour niveau de Fermi. La définition cohérente d’un tel sous-espace nécessite de tenir compte de la dynamique des électrons en-dehors de cet espace. Ces derniers, par exemple, réduisent la répulsion de Coulomb entre électrons dans le sous-espace. Néanmoins, combiner la DFT et la DMFT n’est pas aisé car les deux n’agissent pas sur la même observable. Dans la deuxième partie de cette thèse, nous étudions les modèles de basses énergies, comme la technique échange écranté + DMFT récemment proposée. Nous analysons l’importance de l’échange non-local et des interactions de Coulomb retardées, et illustrons cette théorie en l’appliquant aux états semi-cœur dans les métaux d10 Zn et Cd.Dans la dernière partie, nous utilisons ces méthodes pour étudier trois matériaux corrélés importants d’un point de vue technologique. Dans un premier temps, nous nous intéressons à la physique des mono-lacunes dans la phase paramagnétique du fer. De façon surprenante pour un défaut aussi simple, son énergie de formation n’a toujours pas été obtenue de manière cohérente par la théorie et l’expérience. Nous démontrons que cela est dû à de subtils effets de corrélations autour de la lacune dans la phase paramagnétique à haute température : cette phase est plus fortement corrélée que la phase ferromagnétique, où des calculs de DFT ont été faits.Dans un deuxième temps, nous étudions la transition métal-isolant dans la phase métastable VO2 B. Nous montrons que cette transition ressemble à celle entre la phase conventionnelle rutile et la phase M2 de VO2, mettant en jeu à la fois des liaisons covalentes dans les dimères et une transition de Mott sur les atomes V restants. Nous étudions également l’effet de lacunes d’oxygène sur la structure électronique de VO2.Enfin, nous proposons une technique au-delà de la DFT pour calculer le champ cristallin dans les oxydes et alliages de terres rares. Bien que l’amplitude de ce champ soit faible pour les orbitales localisées 4f des lanthanides, il est crucial pour leur caractère d’aimant permanent. En modifiant l’approximation Hubbard I pour résoudre les équations de DMFT, nous évitons une erreur d’auto-interaction faible en valeur absolue mais physiquement importante, démontrant l’importance de modèles de basse énergie correctement définis. / The topic of this thesis is the first-principles theory of the electronic structure of materials with strong electronic correlations. Tremendous progress has been made in this field thanks to modern implementations of Density Functional Theory (DFT). However, the DFT framework has some limits. First, it is designed to predict ground state but not excited state properties of materials, even though the latter may be just as important for many applications. Second, the approximate functionals used in actual calculations have more limited validity than conceptually exact DFT: in particular, they are not able to describe those materials where many-electron effects are most important.Since the 1990's, different many-body theories have been used to improve or complement DFT calculations of materials. One of the most significant non-perturbative methods is Dynamical Mean-Field Theory (DMFT), where a lattice model is self-consistently mapped onto an impurity model, producing good results if correlations are mostly local. We briefly review these methods in the first part of this thesis. Recent developments on DMFT and its extensions were aimed at better describing non-local effects, understanding out-of-equilibrium properties or describing real materials rather than model systems, among others. Here, we focus on the latter aspect.In order to describe real materials with DMFT, one typically needs to start with an electronic structure calculation that treats all the electrons of the system on the same footing, and apply a many-body correction on a well-chosen subspace of orbitals near the Fermi level. Defining such a low-energy subspace consistently requires to integrate out the motion of the electrons outside this subspace. Taking this into account correctly is crucial: it is, for instance, the screening by electrons outside the subspace strongly reduces the Coulomb interaction between electrons within the subspace. Yet it is a complex task, not least because DFT and DMFT are working on different observables. In the second part of this thesis, we discuss low-energy models in the context of the recently proposed Screened Exchange + DMFT scheme. In particular, we study the importance of non-local exchange and dynamically-screened Coulomb interactions. We illustrate this by discussing semi-core states in the d10 metals Zn and Cd.In the third and last part, we use the methods described above to study the electronic structure of three fundamentally and technologically important correlated materials. First, we discuss the physics of point defects in the paramagnetic phase of bcc Fe, more precisely the simplest of them: the monovacancy. Surprisingly for such a simple point defect, its formation energy had not yet been reported consistently from calculations and experiments. We show that this is due to subtle but nevertheless important correlation effects around the vacancy in the high-temperature paramagnetic phase, which is significantly more strongly correlated than the ferromagnetic phase where DFT calculations had been done.Second, we study the metal-insulator phase transition in the metastable VO2 B phase. We show that this transition is similar to that between the conventional rutile and M2 VO2 phases, involving both bonding physics in the dimer and an atom-selective Mott transition on the remaining V atoms. Motivated by recent calculations on SrVO3, we study the possible effect of oxygen vacancies on the electronic structure of VO2.Finally, we propose a scheme beyond DFT for calculating the crystal field splittings in rare earth intermetallics or oxides. While the magnitude of this splitting for the localized 4f shell of lanthanides does not typically exceed a few hundred Kelvin, it is crucial for their hard-magnetic properties. Using a modified Hubbard I approximation as DMFT solver, we avoid a nominally small but important self-interaction error, stressing again the importance of carefully tailored low-energy models.

In this doctoral thesis, we theoretically investigate the propagation of sound waves in dilute Bose gases, in both the collisionless and hydrodynamic regimes. The study of sound wave is a topic of high relevance for the understanding of dynamical properties of any fluid, classical or quantum, and further provides insightful information about the equation of state of the system. In our work, we focus in particular on the two-dimensional (2D) Bose gas, in which the sound wave is predicted to give useful information about the nature of the superfluid phase transition. Recently, experimental measurement of sound wave in a uniform 2D Bose gas has become available, and we show that the measured data are quantitatively well explained by our collisionless theory. Finally, we study the mixtures of weakly interacting Bose gases, by developing a beyond mean-field theory, which includes the effects of thermal and quantum fluctuations in both the density and spin channels. Our new theory allows for the investigation of sound dynamics, as well as the fundamental problem of phase- separation.

Many problems in applied mathematics and physics are formulated most naturally in terms of matrices, and can be solved by computing functions of these matrices. For example, in quantum mechanics, the coherent dynamics of physical systems is described by the matrix exponential of their Hamiltonian. In state of the art experiments, one can now observe such unitary evolution of many-body systems, which is of fundamental interest in the study of many-body quantum phenomena. On the other hand the theoretical simulation of such non-equilibrium many-body dynamics is very challenging. In this thesis, we develop a symbolic approach to matrix functions and quantum dynamics based on a novel algebraic structure we identify for sets of walks on graphs. We begin by establishing the graph theoretic equivalent to the fundamental theorem of arithmetic: all the walks on any finite digraph uniquely factorise into products of prime elements. These are the simple paths and simple cycles, walks forbidden from visiting any vertex more than once. We give an algorithm that efficiently factorises individual walks and obtain a recursive formula to factorise sets of walks. This yields a universal continued fraction representation for the formal series of all walks on digraphs. It only involves simple paths and simple cycles and is thus called a path-sum. In the second part, we recast matrix functions into path-sums. We present explicit results for a matrix raised to a complex power, the matrix exponential, matrix inverse, and matrix logarithm. We introduce generalised matrix powers which extend desirable properties of the Drazin inverse to all powers of a matrix. In the third part, we derive an intermediary form of path-sum, called walk-sum, relying solely on physical considerations. Walk-sum describes the dynamics of a quantum system as resulting from the coherent superposition of its histories, a discrete analogue to the Feynman path-integrals. Using walk-sum we simulate the dynamics of quantum random walks and of Rydberg-excited Mott insulators. Using path-sum, we demonstrate many-body Anderson localisation in an interacting disordered spin system. We give two observable signatures of this phenomenon: localisation of the system magnetisation and of the linear magnetic response function. Lastly we return to the study of sets of walks. We show that one can construct as many representations of series of walks as there are ways to define a walk product such that the factorisation of a walk always exist and is unique. Illustrating this result we briefly present three further methods to evaluate functions of matrices. Regardless of the method used, we show that graphs are uniquely characterised, up to an isomorphism, by the prime walks they sustain.