Dissertations / Theses on the topic 'Dipolar'

Orientador: Marcelo Knobel
Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin
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Resumo: Nesta dissertação de mestrado são apresentados resultados do efeito do campo dipolar magnético em conjuntos formados por fios e microfios ferromagnéticos amorfos de composição Fe77,5Sil2,5B15. Devido à estrutura de domínios peculiar destes fios magnéticos, eles podem ser, em princípio, aproximados a dipolos magnéticos, permitido a análise destes campos magnetostáticos nestas estruturas macroscópicas. Os estudos foram realizados em conjuntos de fios colocados lado a lado. As curvas de magnetização foram medidas variando-se o número de elementos. Além disso, no caso de dois fios, medidas em função da separação entre os dois elementos foram realizadas. Estas medidas magnéticas foram feitas empregando um magnetômetro desenvolvido durante o projeto e também utilizado um magnetômetro SQUID. Os resultados são explicados considerando o campo dipolar gerado por cada fio do conjunto, que altera os valores do campo de inversão da magnetização e faz com que platôs sejam observados nas curvas de magnetização. Os efeitos do campo dipolar também foram observados em medidas de magnetoimpedância, onde a presença do fio rico em Fe desloca as curvas de magnetoimpedância de um fio amorfo base Co, de modo análogo a um campo bias
Abstract: The results of the magnetic dipolar field in an array of amorphous ferromagnetic wires and microwires of composition Fe77,5Si12,5B15 are presented in this dissertation. Due to their peculiar domain structure, in principle, they can be approximated to magnetic dipoles, a11owing the analysis of the magnetostatic field among these macroscopic entities. The studies were carried out in arrays of wires placed side by side. The magnetic loops were measured changing the number of elements. Moreover, in the case of two parallel wires, measurements as function of the distance between the wires were performed. The magnetic measurements were carried out in an inductive magnetometer developed during this project and a1so using a SQUID magnetometer. The results are explained considering the dipolar field created by each wire in the array. The dipolar field changes the reversal field of the wires, a11owing the appearance of plateaus during the demagnetization. The effects of the dipolar field were also observed in magnetoimpedance measurements when a Fe-rich wire in placed near an amorphous Co-based wire, its presence dislocates the Co-based wire magnetoimpedance curves, ana1ogously as a bias field
Mestrado
Física
Mestre em Física

Cette thèse couvre l'auto-assemblage de particules dipolaires (magnétiques/électriques). Ces systèmes sont abondants en physique de la matière condensée (molécules et nanoparticules magnétiques, particules colloïdales magnétiques, bactérie magnétotactique, etc.). Sur un plan fondamental, ils représentent un défi important en raison de l'anisotropie et de la longue portée de l'interaction de paire. Le principal objectif de ce travail de recherche est de prédire les microstructures de ces systèmes en tenant compte de façon adéquate de l'interaction complexe dipôle-dipôle ainsi que des effets stériques et ceux dus à un éventuel confinement. Comprendre et revisiter les interactions de filaments dipolaires tels que des aiguilles et des chaînes faites de billes dipolaires est une première étape importante de cette thèse. En effet, les chaînes sont les constituants élémentaires de nombreux systèmes dipolaires, notamment sous l'effet d'un champ magnétique extérieur appliqué. Ensuite, l'agrégation colonnaire des chaînes dipolaires est examinée, ce qui conduit aussi naturellement à l'étude des cristaux dipolaires massifs où une nouvelle phase est découverte. Le cas plus générique des chaînes hélicoïdales est discuté en considérant les situations limites que sont les chaînes linéaires droites et en zigzag. L'association des chaînes dipolaires, dans le cas bidimensionnel, forme des rubans, puis une monocouche avec un réseau hexagonal. La réponse non triviale d'un tel réseau à un champ magnétique perpendiculaire imposé est aussi étudiée. Il est démontré qu'un réseau rhombique peut être induit de cette façon. Finalement, la sédimentation de particules paramagnétiques dans une monocouche inclinée en présence d'un champ magnétique est explorée via une étude mêlant expériences, théorie et simulations. L'ordre induit par gravité s'avère être une voie prometteuse pour l'élaboration contrôlée de réseaux bidimensionnels
This thesis covers the self-assembly of dipolar (magnetic/dielectric) particles. These systems are abundant in condensed matter physics (magnetic molecules and nanoparticles, magnetic colloidal particles, magnetotactic bacteria, etc). They also represent a fundamental challenge owing to the both long range and anisotropic nature of the pair interaction. The main objective of this research work is to predict the microstructures of these systems by properly handling the intricate dipole-dipole interaction combined with steric and possibly confinement effects. Understanding and revisiting the interaction of dipolar filaments such as needles or chains made up of dipolar beads is a first important achievement in this thesis. Indeed, the chains are the fundamental building blocks of many dipolar systems especially under applied external magnetic field. Then, the columnar aggregation of dipolar chains is investigated which naturally leads to the study of the bulk dipolar crystals. A new phase is discovered there. The more generic case of helical chains is discussed by considering limiting situations such as straight linear chains and zigzag chains. The association of dipolar chains in two-dimensions forms ribbons then a monolayer with triangular lattice symmetry. The interesting response of such a layer to an imposed perpendicular magnetic is addressed as well. It is demonstrated that rhombicity can be induced that way. Finally, sedimenting paramagnetic particles in a tilted monolayer in presence of a magnetic field are investigated by experiments, theory and simulations. The gravity-mediated ordering is found to be a promising route to elaborate tailored two-dimensional patterns

Tese (doutorado) - Universidade Federal de Santa Catarina, Centro de Ciências Físicas e Matemáticas, Programa de Pós-graduação em Física, Florianópolis, 2010
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Nesta Tese estudamos o efeito do acoplamento dipolar nas propriedades magnéticas de dois tipos de sistemas. O primeiro deles consiste de duas pequenas partículas cujos spins estão acoplados ferromagneticamente. Cada partícula é descrita por uma estrutura bidimensional finita de spins interagindo através da hamiltoniana de Ising, ou por uma rede finita em duas ou três dimensões de spins interagindo através da hamiltoniana de Heisenberg com spins clássicos. Em ambas as situações temos um spin central rodeado por um número variável de camadas magnéticas. O acoplamento entre spins dentro de cada partícula é ferromagnético, e consideramos uma interação dipolar apenas entre as partículas. Nós investigamos o sistema bidimensional de spins de Ising através da aproximação de campo médio e simulações de Monte Carlo. A interação dipolar é calculada de duas maneiras diferentes. Em uma delas, assumimos que a interação dipolar ocorra entre momentos magnéticos efetivos localizados nos centros das partículas, e na outra, computamos diretamente as interações entre todos os pares de spins, um em cada partícula. Mostramos que a diferença entre os valores da energia dipolar calculada pelos dois métodos é descrita por uma lei de potência do tipo d5, onde d é a distância entre os centros das partículas. Calculamos a magnetização e a susceptibilidade em função da temperatura, do número de camadas e da distância entre os centros de partículas. Mostramos que a temperatura crítica aumenta com o número de spins em cada partícula, e isso é mais notável nos cálculos realizados através da aproximação de campo médio que nas simulações de Monte Carlo. O segundo problema estudado nesta Tese consiste de um conjunto de partículas de monodomínio. Este sistema é investigado através de simulações de Monte Carlo em três redes diferentes. Consideramos uma rede cúbica simples, uma rede cúbica de face centrada e uma estrutura tipo líquido. As partículas são acoplados pela interação dipolar de longo alcance e apresentam uma anisotropia uniaxial, cuja magnitude é escolhida a partir de uma distribuição de Gauss e cujos eixos de fácil magnetização estão orientados aleatoriamente no espaço tridimensional. Determinamos a temperatura de bloqueio e as curvas de histerese em função da razão entre as magnitudes da interação dipolar e da anisotropia uniaxial. Mostramos que a remanência e o campo coercivo dependem fortemente da estrutura considerada. Estes resultados são comparados com aqueles obtidos para um sistema de partículas não interagentes.

Esta tesis es un trabajo teórico, en el que estudiamos la física de los átomos dipolares bosónicos ultrafríos en retículos ópticos. Éstos gases consisten de átomos o moléculas bosónicas, enfriados bajo la temperatura de degeneración cuántica, típicamente del orden de nK. En éstas condiciones, en una trampa armónica tridimensional (3D), los bosones que interaccionan débilmente condensan y forman un Condensado de Bose Einstein (BEC). Cuando se carga un BEC en un retículo óptico producido por ondas estacionarias de luz láser, se producen nuevos fenómenos físicos. Estos sistemas entonces realizan modelos de tipo Hubbard y pueden ser llevados a regimenes fuertemente correlacionados.

En 1989, M. Fisher et. al. predecían que el modelo de Bose-Hubbard homogéneo (BH) presenta la transición de fase cuántica Superfluid-Mott insulator (SF-MI). En 2002, la transición entre éstas dos fases fue observada experimentalmente por primera vez en el grupo de T. Esslinger e I. Bloch. La realización experimental de un BEC dipolar de cromo en el grupo de T. Pfau, y los progresos recientes en las técnicas de enfriamiento y atrapamiento de moléculas dipolares en los grupos de D. Jin e J. Ye, han abierto el camino hacia los gases cuánticos ultra-fríos dominados por la interacción dipolar. La evolución natural, y el reto de hoy en día por parte experimental, es de cargar BEC dipolares en retículos ópticos y estudiar los gases dipolares fuertemente correlacionados.

Antes de éste trabajo de doctorado, estudios sobre modelos de BH con interacciones extendidas a los primeros vecinos mostraron la evidencia de nuevas fases cuánticas, como el supersólido (SS) y la fase checkerboard (CB). Debido al carácter de largo alcance de la interacción dipolo-dipolo, que decae con la potencia cúbica inversa de la distancia, es necesario incluir más de un primer vecino para obtener una descripción fiel y cuantitativa de los sistemas dipolares. De hecho, al incluir más vecinos se permiten y se estabilizan aún más nuevas fases.

En esta tesis estudiamos modelos de BH con interacciones dipolares, investigando más allá del estado fundamental. Estudiamos un retículo bidimensional (2D) donde los dipolos están polarizados en dirección perpendicular al plano 2D, dando lugar a una interacción dipolar repulsiva e isotrópica. Utilizamos aproximaciones de campo-medio y un ansatz Gutzwiller, que son suficientemente correctos y adecuados para describir este sistema. Encontramos que los gases dipolares en 2D presentan una multitud de estados metaestables de tipo MI, que compiten con el estado fundamental, de modo parecido a sistemas desordenados. Estudiamos en detalle el destino de estos estados metaestables: como pueden ser preparados de manera controlada, como pueden ser detectados, cual es su tiempo de vida debido al tunnelling, y cual es su rol en los procesos de enfriamiento. Además, encontramos que el estado fundamental está caracterizado por estados MI de tipo checkerboard con coeficiente de ocupación n fraccionario (numero medio de partículas por sitio) que depende del cut-off utilizado en el radio de alcance de la interacción. Confirmamos esta predicción estudiando el mismo sistema con métodos Quantum Monte Carlo (worm algorithm). En este caso no utilizamos ningún cut-off en el radio de alcance de la interacción, y encontramos pruebas de una "Devil's staircase" en el estado fundamental, i.e. donde las fases MI aparecen en todos los n racionales del retículo subyacente. Encontramos además, regiones de los parámetros donde el estado fundamental es supersólido, obtenido drogando los sólidos con partículas o con agujeros.

En este trabajo, investigamos también como cambia la estructura precedente en 3D. Nos focalizamos en el retículo 3D más sencillo compuesto de dos planos 2D, en el cual los dipolos están polarizados perpendicularmente a los planos; la interacción dipolar es entonces repulsiva por partículas del mismo plano, mientras es atractiva por partículas en el mismo sitio de dos planos diferentes. En cambio suprimimos el tunnelling entre los planos, lo cual hace el sistema equivalente a una mezcla bosónica en un retículo 2D. Nuestros cálculos muestran que las partículas se juntan en parejas, y demostramos la existencia de la nueva fase cuántica Pair Super Solid (PSS).

Actualmente estamos estudiando un retículo 2D donde los dipolos están libres de apuntar en ambas direcciones perpendicularmente al plano, lo cual resulta en una interacción a primeros vecinos repulsiva (atractiva) por dipolos alineados (anti-alineados). Encontramos regiones de parámetros donde el estado fundamental es ferromagnético u anti-ferromagnético, y encontramos pruebas de la existencia de la fase cuántica Counterflow Super Solid (CSS).
Las nuestras predicciones tienen directas consecuencias experimentales, y esperamos que vengan pronto controladas en experimentos con gases dipolares atómicos y moleculares ultra-fríos.
This thesis is a theoretical work, in which we study the physics of ultra-cold dipolar bosonic gases in optical lattices. Such gases consist of bosonic atoms or molecules, cooled below the quantum degeneracy temperature, typically in the nK range. In such conditions, in a three-dimensional (3D) harmonic trap, weakly interacting bosons condense and form a Bose-Einstein Condensate (BEC). When a BEC is loaded into an optical lattice produced by standing waves of laser light, new kinds of physical phenomena occur.

These systems realize then Hubbard-type models and can be brought to a strongly correlated regime. In 1989, M. Fisher et. al. predicted that the homogeneous Bose-Hubbard model (BH) exhibits the Superfluid-Mott insulator (SF-MI) quantum phase transition. In 2002 the transition between these two phases were observed experimentally for the first time in the group of T. Esslinger and I. Bloch. The experimental realisation of a dipolar BEC of Chromium by the group of T. Pfau, and the recent progresses in trapping and cooling of dipolar molecules by the groups of D. Jin and J. Ye, have opened the path towards ultra-cold quantum gases with dominant dipole interactions. A natural evolution and present challenge, on the experimental side is then to load dipolar BECs into optical lattices and study strongly correlated ultracold dipolar lattice gases.

Before this PhD work, studies of BH models with interactions extended to nearest neighbours had pointed out that novel quantum phases, like supersolid (SS) and checkerboard phases (CB) are expected. Due to the long-range character of the dipole-dipole interaction, which decays as the inverse cubic power of the distance, it is necessary to include more than one nearest neighbour to have a faithful quantitative description of dipolar systems. In fact, longer-range interactions tend to allow for and stabilize more novel phases.

In this thesis we study BH models with dipolar interactions, going beyond the ground state search. We consider a two-dimensional (2D) lattice where the dipoles are polarized perpendicularly to the 2D plane, resulting in an isotropic repulsive interaction. We use the mean-field approximations and a Gutzwiller ansatz which are quite accurate and suitable to describe this system. We find that dipolar bosonic gas in 2D exhibits a multitude of insulating metastable states, often competing with the ground state, similarly as in a disordered system. We study in detail the fate of these metastable states: how can they be prepared on demand, how they can be detected, what is their lifetime due to tunnelling, and what is their role in various cooling schemes. Moreover, we find that the ground state is characterized by insulating checkerboard-like states with fractional filling factors v(average number of particles per site) that depend on the cut-off used for the interaction range. We confirm this prediction by studying the same system with Quantum Monte Carlo methods (the worm algorithm). In this case no cut-off is used, and we find evidence for a Devil's staircase in the ground state, i.e. where insulating phases appear at all rational of the underlying lattice. We also find regions of parameters where the ground state is a supersolid, obtained by doping the solids either with particles or vacancies.

In this work, we also investigate how the previous scenario changes in 3D. We focus on the simplest 3D lattice composed of two 2D layers in which the dipoles are polarized perpendicularly to the planes; the dipolar interaction is then repulsive for particles laying on the same plane, while it is attractive for particles at the same lattice site on different layers. Instead we consider inter-layer tunnelling to be suppressed, which makes the system analogous to a bosonic mixture in a 2D lattice. Our calculations show that particles pair into composites, and demonstrate the existence of the novel Pair Super Solid (PSS) quantum phase.
Currently we are studying a 2D lattice where the dipoles are free to point in both directions perpendicularly to the plane, which results in a nearest neighbour repulsive (attractive) interaction for aligned (antialigned) dipoles. We find regions of parameters where the ground state is ferromagnetic or antiferromagnetic, and find evidences for the existence of a Counterflow Super Solid (CSS) quantum phase.
Our predictions have direct experimental consequences, and we hope that they will be soon checked in experiments with ultracold dipolar atomic and molecular gases.

Inelastic collisions between dipolar molecules, assumed to be trapped in a static electric field at cold (> 10−3K) temperatures, are investigated and compared with elastic collisions. For molecules with a Λ-doublet energy-level structure, a dipole moment arises because of the existence of two nearly degenerate states of opposite parity, and the collision of two such dipoles can be solved entirely analytically in the energy range of interest. Cross sections and rate constants are found to satisfy simple, universal formulas. In contrast, for molecules in a Σ electronic ground state, the static electric field induces a dipole moment in one of three rotational sublevels. Collisions between two rotor dipoles are calculated numerically; the results scale simply with molecule mass, rotational constant, dipole moment, and field strength. It might be expected that any particles interacting only under the influence of the dipole-dipole interaction would show similar behavior; however, the most important and general result of this research is that at cold temperatures inelastic rate constants and cross sections for dipoles depend strongly upon the internal structure of the molecules. The most prominent difference between the Λ-doublet and rotor molecules is variation of the inelastic cross section with applied field strength. For Λ-doublet dipoles, cross sections decrease with increasing field strength. For rotor dipoles, cross sections increase proportionally with the square of field strength. Furthermore, the rate constants of the two types of molecules depend very differently on the angular orientations of the dipoles in the electric field.

Neste trabalho investigamos os efeitos das interações na expansão de um condensado de átomos de Rb. Dois problemas são abordados: o efeito de temperatura finita e as alterações introduzidas pela interação dipolar. No primeiro caso, dados experimentais não puderam ser explicados por meio da aproximação de Thomas-Fermi (TF) no regime de T = 0. Num condensado de cerca de 1 - 2 x 105 átomos condensados, o desvio da aproximação de TF ocorreu pelo fato de termos desconsiderado a interação dos átomos térmicos com os do condensado. Elaboramos um modelo teórico, baseado em modelos existentes de temperatura finita, o qual explicou relativamente bem os nossos resultados experimentais. No segundo problema atacado, foi analisada a variação na expansão do gás condensado quando a interação dipolar é incluída no sistema. Ambos os problemas mostram aspectos importantes da expansão de gases quânticos.
In this study we investigated the effects of interactions on the expansion of a condensate of Rb atoms. Two problems are addressed: the effect of finite temperature and the changes introduced by the dipolar interaction. In the first case, experimental data could not be explained by the Thomas-Fermi (TF) approach in the T = 0 regime. In a condensate of about 1 - 2 x 105 condensed atoms, the deviation of TF approach was due to the fact that we disregarded the interaction of thermal atoms those of the condensate. We developed a theoretical model, based on existing models of finite temperature, which explained relatively well our experimental results. In the second problem considered, we analyzed the variation in the expansion of the condensate gas when the dipolar interaction is included in the system. Both problems show important aspects of the expansion of quantum gases.

The project was concerned with investigating the synthesis of novel enantiomerically pure heterocyclic compounds of various ring size via an intramolecular 1,3-dipolar cycloaddition reaction. The thesis begins with a general introduction to asymmetric synthesis and to 1,3-dipolar cycloadditions in chapters 1 and 2. The synthetic work described in the remaining chapters utilized the chiral template approach. Cheap readily available materials, namely aspartic acid and glucose, were used as building blocks to form suitable nitrile oxide or nitrone (1,3-dipoles) precursors for the 1,3-dipolar cycloaddition reaction. These precursors needed to contain a vinyl ether functionality (dihydrofuran or dihydropyran) for the regioselectivity of the intramolecular cycloaddition. [chemical formula] The synthetic route to pyrrolidines from aspartic acid was not successful due to the inability to alkylate the various derivatives of 3(S)-amino-y-butyrolactone. The synthesis of nitrile oxide and nitrone precursors for the six and eight membered heterocyclic system was unsuccessful whereas the synthesis of the precursors for the five and seven membered heterocyclic systems was successful. The nitrone precursor for the seven membered ring system did not cyclise possibly due to the extra rigidity which had been introduced into the molecule, whereas the nitrile oxide and nitrone precursors to the five membered ring system cyclised to form respectively a Delta2-isoxazoline and an isoxazolidine as single stereoisomers. The cleavage of the Delta2-isoxazoline and isoxazolidine produced was further investigated. It was found that the cycloadducts exhibited extra stability which was believed to be due to the oxygen in the adjoining ring. The Delta2-isoxazoline could not be cleaved under a range of conditions but the isoxazolidine was successfully cleaved and modified to form a functionalised tetrahydrofuran. An alternative synthesis of pyrrolidines was carried out, starting from glucose. A 3-aminoglucose derivative was prepared which underwent further reactions to give a nitrone which cyclised to an isoxazolidine as a potential precursor to functionalised pyrrolidines. A brief preliminary study of the cleavage of this system was unsuccessful. The final chapter gives details of the experimental procedures used.

This Ph.D. thesis has been concerned with the reinvestigation and improvement of the intermolecular 1,3-dipolar cycloaddition strategy using isoxazoles, towards the 3-acyltetramic acids (3-acylpyrrrolidine-2,4-diones) and also the investigation and development of the corresponding intramolecular strategy. A second generation of the intermolecular route was developed previously within our group and we have synthesised a variety of pyrroloisoxazoles, the 'masked' tetramic acids. We have modified and improved both the isoxazole formations and the peptide coupling reactions; we have further developed the chain extension at the isoxazole C-5 (tetramic acid C-3) substituent, testing the aldol-type reaction with some aromatic aldehydes and extending it to aliphatic aldehydes. We have demonstrated the condensation method using a strong base and hydroxyl adducts were obtained. Dehydration has been undertaken to yield the alkenyl C-5 side-chain. Development of the desmethyllaccarin, a derivative of the natural product laccarin, has also been attempted via the intermolecular route. A potential intramolecular route has the reversed sequence from the intermolecular route, by using the N-acylation product produced from an amino acid for the formation of a nitrile oxide and hence our building block pyrroloisoxazole by intramolecular dipolar cycloaddition. We have generated a nitro ketoester compound from the amino acid and investigation on the synthesis of the pyrroloisoxazole has been undertaken.

Cette thèse porte sur la cristallisation bidimensionnelle de particules dipolaires. La première partie concerne les systèmes à un composant. L’idée d’utiliser des matériaux granulaires secs comme substituts de suspensions colloïdales mouillées y est exploitée pour aborder le phénomène de cristallisation. Des systèmes granulaires athermaux bidimensionnels sont alors exposés à un bruit mécanique extérieur conduisant à un mouvement de type brownien des grains. En utilisant des interactions interparticulaires répulsives via un champ magnétique externe imposé, on montre que la microstructure observée dans les suspensions colloïdales peut être retrouvée quantitativement à l’échelle macroscopique. A cette fin, des expériences sur des granulaires (réalisées au laboratoire GRASP à Liège) et sur des systèmes colloïdaux constitués de particules magnétiques ainsi que des simulations numériques sont effectuées et comparées. Un excellent accord pour toute la gamme de couplage dipolaire est obtenu pour les fonctions de distribution de paires ainsi que pour les fonctions de corrélation orientationnelles. Cette découverte ouvre de nouvelles possibilités pour explorer efficacement et aisément les transitions de phase, la cristallisation, la nucléation, etc. dans des géométries confinées. Le second volet de cette thèse concerne les systèmes à deux composants. Des mélanges binaires constitués de particules pourvues de moments dipolaires similaires sont examinés. En utilisant des simulations Monte Carlo, une analyse structurale détaillée basée sur les fonctions de distribution de paires partielles et les clichés de microstructures est présentée pour un couplage dipolaire fort. Pour une composition équimolaire, la coexistence entre des super-réseaux triangulaires avec une stoechiométrie AB2 et A2B est mise en évidence, où A(B) dénote les grands (faibles) moments dipolaires. Ce résultat est en très bonne adéquation avec les prédictions théoriques à température nulle
This thesis deals with two-dimensional crystallization of dipolar particles. The first part of the manuscript treats one component systems. There, the idea of using excited dry granular media as substitutes of wet colloidal suspensions is exploited to tackle the problem of crystallization. Athermal two-dimensional granular systems are exposed to external mechanical noise leading to Brownian-like motion. Using tunable repulsive interparticle interaction via an external imposed magnetic field, it is shown that the same microstructure as that observed in colloidal suspensions can be quantitatively recovered at a macroscopic scale. To that end, experiments on granular (realized by the GRASP group in Liège) and colloidal systems made up of magnetized particles as well as computer simulations are performed and compared. Excellent agreement throughout the range of the dipolar coupling is found for the pair distribution as well as the bond-orientational correlation functions. This finding opens new ways to efficiently and very conveniently explore phase transitions, crystallization, nucleation, etc in confined geometries. The second part of this thesis addresses two component systems. Binary mixtures made up of particles carrying similar dipole moments are investigated. Using Monte Carlo simulations, a detailed structural analysis based on partial pair distribution functions and microstructure snapshots is presented for high dipolar coupling. At equimolar composition, the relevance of the coexistence of triangular superlattices with stoichiometry AB2 and A2B is revealed, with A(B) standing for the large(small) dipole moments. This finding is in excellent qualitative agreement with the zero temperature theoretical predictions

Dans ce mémoire nous présentons plusieurs études expérimentales des propriétés magnétiques d’un condensat de Bose-Einstein de Chrome chargé dans un réseau 3D, en nous focalisant sur les effets associés aux interactions dipolaires. Nous montrons que dans un réseau 3D, la relaxation dipolaire est un processus résonant du fait de la réduction de la densité d’états orbitaux accessibles. Les résonances sont observées à des champs magnétiques Bres tels que l’énergie Zeeman relâchée soit égale à l’énergie nécessaire à exciter les atomes dans une bande d’énergie supérieure du réseau. Nous pouvons inhiber ce processus en appliquant un champ différent de Bres. L’analyse des résonances a permis de sonder la structure de bande 3D du réseau, ainsi que la mise en évidence de l’effet des interactions entre atomes. Nous avons étudié la dynamique d’échange de spin dans un réseau 3D. Nous présentons en particulier la première observation d’échange de spin entre atomes localisés dans des sites séparés. Ces études permettent une exploration nouvelle du magnétisme en réseau. En variant la profondeur du réseau, nous étudions ces effets dans le régime superfluide, bien décrit par une théorie de champ moyen, et dans le régime fortement corrélé, dont la description théorique est difficile. Enfin, nous étudions l’évolution de deux spins géants interagissant par interaction dipolaire. Le condensat initialement divisé en deux, les atomes des deux nuages sont préparés dans des états de spin opposés formant ainsi deux spins géants ±3xN. Nous montrons que toute dynamique de spin est énergétiquement inhibée pour de grands spins ce qui est bien reproduit par une théorie classique
This Thesis reports on several experimental studies of magnetic properties of a Chromium Bose-Einsteincondensate loaded into a 3D optical lattice, focusing on the effects induced by dipolar interactions.We show that in a 3D lattice dipolar relaxation is a resonant process due to the reduction of the density ofaccessible orbital states. These resonances are observed for magnetic fields Bres such that the Zeeman energyreleased matches an excitation towards higher-energy bands of the lattice. We can thus inhibit those processes byapplying a field different from Bres. Analyses of the resonances allowed us to probe the lattice 3D band structureas well as to demonstrate the effects of local interactions between atoms.We study spin exchange dynamics in a 3D lattice. We especially observed for the first time spin exchangebetween atoms localized in different lattice sites mediated by dipolar interactions. These studies are the firststep toward a new exploration of magnetism in lattice. Varying the depth of the lattice we study these effects inthe superfluid regime, well described by mean filed theories, as well as in the strongly correlated regime, whosetheoretical description is still challenging.Finally, we study the evolution dynamics of two giant spins interacting through dipolar interactions. Thecondensate being initially splitted in half, atoms from the two clouds are prepared in opposite spin states thusproducing two giant spins ±3×N. We show that any spin dynamics is energetically inhibited for large spinswhich is well accounted for by a classical theory

A microscopic description of the many-body properties of anisotropic homogeneous gases of bosonic dipoles in two dimensions is presented and discussed. By changing the polarization angle with respect to the plane, we study the impact of the anisotropy, present in the dipole-dipole interaction on different physical quantities. We restrict the analysis to the range of polarization angles where the interaction is always repulsive, although the strength of the repulsion can be strongly dependent on the orientation with respect to the polarization field. We present a study of the zero energy two-body problem which allows us to find the scattering length of the interaction and to build a suitable Jastrow many-body wave function that will be used as a trial wave function for Monte Carlo simulations of the bulk two-dimensional system of bosonic dipoles. In the first part of this work we have studied the low-density dipolar Bose gas and we find that the anisotropy has an almost negligible impact on the ground state properties of the many-body system in the universal regime where the scattering length governs the physics of the system. We also show that scaling in the gas parameter persists in the dipolar case up to values where other isotropic interactions with the same scattering length yield different predictions. We also evaluate the excitation spectrum of the dipolar Bose gas in the context of the Feynman approximation and compare the results obtained with the Bogoliubov ones. As expected, we find that these two approximations agree at very low densities, while they start to deviate from each other as the density increases. When the density of the system is increased we find that the behavior of the system depends on the value of the polarization angle of the dipolar moments of the system. At large densities and moderate values of the polarization angle the system undergoes a first-order quantum phase transition from a gas and a crystal phase. We also find that the anisotropy of the dipole-dipole potential causes an elongation of the crystalline lattice of the system in the direction where the interaction is stronger. At large polarization angles and moderate densities the system undergoes a second-order quantum phase transition from a gas to a stripe phase. Interestingly, the critical exponents of this second order transition are nearly independent of the tilting angle and are compatible with the 3D Ising and 3D XY model universality classes within the statistical uncertainty of our simulations. Finally, at high densities and large tilting angles the system shows a first order phase transition between the crystal and stripe phases. The slope of this transition curve is extremely large indicating that, due to the anisotropy of the interaction, the crystal phase of the system is no longer stable if the dipole - dipole potential is highly anisotropic. We consider the ground state of a bilayer system of dipolar bosons, which is a configuration consisting in the continement of the particles in two paralel planes by means of a trapping potential. We consider the simplest situation where dipole moments are oriented by an external field in the direction perpendicular to the parallel planes. Quantum Monte Carlo methods are used to calculate the ground-state energy, the one-body and two-body density matrix as a function of the separation between layers. We find that by decreasing the interlayer distance for fixed value of the strength of the dipolar interaction, the behavior of all the physical observables studied are compatible with the existence of a second order phase transition modulated by the inter-layer distance. In this sense, the results presented in this work are in good agreement with some previous studies of dipolar gases in a bilayer setup
En este trabajo presentamos una descripción de las propiedades de los gases homogéneos de dipolos bosónicos en dos dimensiones. Cambiando el ángulo de polarización respecto a la perpendicular al plano donde las partículas están confinadas estudiamos el impacto de la anisotropía de la interacción dipolar en diferentes magnitudes físicas. El análisis se restringe al rango de ángulos de polarización en que la interacción es repulsiva aunque la intensidad pueda depender fuertemente de la orientación respecto a la dirección de polarización. El análisis del problema a dos cuerpos a energía cero nos permite evaluar la longitud de difusión de la interacción y construir una función de onda de tipo Jastrow para el sistema de muchos cuerpos. Esta función de onda será usada como función de prueba para las simulaciones Monte Carlo del sistema homogéneo de dipolos bosónicos en dos dimensiones. En la primera parte de la tesis hemos estudiado el gas de Bose dipolar en el régimen de bajas densidades, observando que el impacto de la anisotropía es negligible en las propiedades macroscópicas en el regimen donde la longitud de difusión gobierna la física del sistema. Hemos comprobado también que el escalado en el parámetro de gas persiste en el caso dipolar hasta valores donde otras interacciones isótropas con la misma longitud de difusión llevan a distintas predicciones. Hemos evaluado el espectro de excitaciones elementales del gas de Bose dipolar en el contexto de la aproximación de Feynman, comparando los resultados con los obtenidos mediante la aproximación de Bogoliubov. Como cabría esperar, las dos aproximaciones coinciden a bajas densidades y se alejan progresivamente al aumentar la densidad. Al aumentar la densidad del sistema vemos que el comportamiento del gas depende del valor del ángulo de polarización de los momentos dipolares. A altas densidades y valores moderados del ángulo de polarización el sistema experimenta una transición de fase de primer orden pasando de una fase gaseosa a una cristalina. Hemos observado también que la anisotropía de la interacción dipolar causa una elongación de la red cristalina en la dirección de interacción más intensa. Para valores elevados del ángulo de polarización y densidades moderadas el sistema muestra transición de fase, esta vez de segundo orden, en la que el sistema pasa de la fase gaseosa a una fase de bandas. Los exponentes críticos de esta transición de fase son independientes del ángulo de polarización y, dentro de los errores estadísticos de las simulaciones, son compatibles con las clases de universalidad del modelo de Ising y XY en tres dimensiones. Finalmente, a altas densidades y valores grandes del ángulo de polarización el sistema muestra otra transición de fase de primer orden entre la fase cristalina y la fase de bandas. La pendiente de esta curva de transición es extremadamente grande indicando que, debido a la anisotropía de la interacción, la fase cristalina deja de ser estable si el potencial de interacción dipolo-dipolo es muy anisótropo. En la última parte de la tesis estudiamos el estado fundamental de un sistema bicapa de dipolos bosónicos, que es una configuración en la que se confinan las partículas en dos planos paralelos mediante un potencial externo. Consideramos la situación más simple en la que los momentos dipolares están orientados por un campo externo en la dirección perpendicular a los planos. Hemos evaluado la energía del estado fundamental y las matrices densidad a uno y dos cuerpos en función de la distancia entre capas usando métodos Monte Carlo. Hemos encontrado que disminuyendo la distancia entre planos para un valor fijo de la intensidad de la interacción, el comportamiento de todos los observables estudiados es compatible con la existencia de una transición de fase de segundo orden modulada por la distancia entre capas. En este sentido, los resultados obtenidos en este trabajo muestran buen acuerdo con estudios previos de este sistema.

This thesis describes advances in novel (3+2) dipolar cycloadditions of pyridinium ylides, their reactions with electrophilic alkenes afford tetrahydroindolizines which can possess alkaloid-like scaffolds. Pyridinium ylides have been shown to be highly reactive intermediates that are able to rapidly generate molecular complexity with excellent regio and diastereoselectivity. Chapter one reports an introduction on the chemistry of pyridinium ylides and introduces spirocyclic indolizidine containing natural products which could conceivably be synthesised through (3+2) dipolar cycloadditions. The results and discussion section is divided into three chapters: Chapter two describes the synthesis of indoxyl dipolarophiles including a novel approach towards the synthesis of 2-alkenylindol-3-ones. Details of the reactions of these dipolarophiles with pyridinium ylides to afford spirocyclic indoxyl cycloadducts follow. Subsequent modification of the 1,2-dihydropyridine moiety in the resulting cycloadducts is also demonstrated; Chapter three describes the investigation towards an asymmetric (3+2) dipolar cycloaddition, using pyridinium ylides generated by the in situ decomposition of diazo compounds with transition metal catalysts; Finally, chapter four describes attempts to synthesise spirocyclic indoxyl compounds which are structurally related to the opioid mitragynine pseudoindoxyl. Initially this is investigated via the methodology developed in chapter two, then subsequently using a magnesium iodide promoted ring expansion of a cyclopropane.

Thesis (Ph.D.)--Boston University PLEASE NOTE: Boston University Libraries did not receive an Authorization To Manage form for this thesis or dissertation. It is therefore not openly accessible, though it may be available by request. If you are the author or principal advisor of this work and would like to request open access for it, please contact us at open-help@bu.edu. Thank you.
The 1,3 dipolar photocycloaddition reaction between 3-hydroxy-4',5,7-trimethoxyflavone (3-HTMF) and methyl cinnamate is investigated in this work. Since its inception in 2004 [JACS, 124, 13260 (2004)], this reaction remains at the forefront in the synthetic design of the rocaglamide natural products. The reaction is multi-faceted in that it involves multiple excited states and is contingent upon excited state intramolecular proton transfer (ESIPT) in 3-HTMF. Given the complexity of the reaction, there remain many questions regarding the underlying mechanism. Consequently, throughout this work we investigate the mechanism of the reaction along with a number of other properties that directly influence it. To investigate the photocycloaddition reaction, we began by studying the effects of different solvent environments on the ESIPT reaction in 3-hydroxyfiavone since this underlying reaction is sensitive to the solvent environment and directly influences the cycloaddition. To study the ESIPT reaction, we developed a parallel multi-level genetic program to fit accurate empirical valence bond (EVB) potentials to ab initio data. We found that simulations with our EVB potentials accurately reproduced experimentally determined reaction rates, fluorescence spectra, and vibrational frequency spectra in all solvents. Furthermore, we found that the ultrafast ESIPT process results from a combination of ballistic transfer and intramolecular vibrational redistribution. To investigate the cycloaddition reaction mechanism, we utilized the string method to obtain minimum energy paths on the ab initio potential. These calculations demonstrated that the reaction can proceed through formation of an exciplex in the S1 state, followed by a non-adiabatic transition to the ground state. In addition, we investigated the enantioselective catalysis of the reaction using α,α,α',α'-tetraaryl-1,3-dioxolan-4,5-dimethanol alcohol (TADDOL). We found that TADDOL lowered the energy barrier by 10-12 kcal/mol through stabilizing hydrogen bond interactions. Using temperature accelerated molecular dynamics, we obtained the potential of mean force (PMF) associated with 3-HTMF attacking the TADDOL/methyl cinnamate complex. We found that the exo reaction is inhibited through steric interactions with the aryl substituents on TADDOL. Furthermore, we found that the exo configuration breaks the intramolecular hydrogen bond in TADDOL, which stabilizes the individual reactants apart from each other. The role of the T1 state is also discussed.

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Estrelas de nêutrons se manifestam como diferentes tipos de classes de fontes astrofísicas, que estão associadas a distintas fenomenologias. Aqui focaremos nossas atenções aos magnetares (ou estrelas de nêutrons altamente magnetizadas) que estão associados aos Soft Gamma Repeaters e os Anomalous X-ray pulsars. O campo magnético na superfície desses objetos atingem valores maiores que 1015G. No âmbito de campos magnéticos tão intensos, efeitos relativísticos começam a serem determinantes para a definição da estrutura desses objetos e somos tentados a nos questionarmos de que forma esses campos magnéticos tão intensos modificam a estrutura e a evolução dessas estrelas. Neste trabalho realizaremos um estudo a respeitos de duas soluções das equações de Einstein-Maxwell (a solução de Bonnor que é uma solução analítica e a solução completa das equações de Einstein-Maxwell encontrada por métodos numéricos) e que descrevem o espaço-tempo exterior a um objeto compacto massivo e com campo magnético dipolar. Para isto revisaremos estas duas soluções e em seguida descreveremos as equações das geodésicas geradas por tais soluções. Nossos estudos mostram que, apesar da solução de Bonnor não satisfazer as equações de Maxwell, as órbitas geradas por esta solução são as mesmas descritas pela solução numérica. Também mostraremos que a inserção de campos magnéticos que assumem valores de até 1017G no centro da estrela não modificam tanto as órbitas das partículas massivas e dos fótons descritas ao redor dessa estrela, e assim a utilização da solução de Schwarzschild para a descrição das órbitas ao redor desse objeto é uma aproximação razoável.
Neutron stars manifest themselves as different classes of astrophysical sources that are associated to distinct phenomenology. Here we focus ours attention on magnetars (or strongly magnetized neutron stars) that are associated to Soft Gamma Repeaters and Anomalous Xray Pulsars. The magnetic field on surface these objects, reaches values greater than 1015. Under intense magnetic fields, relativistic effects begin to be decisive for the definition of the structure and evolution of these objects and are tempted to question ourselves how these strengths fields affect the structure of these stars. In this work we will conduct a study to respect the two solutions of Einstein-Maxwell’s equations (the Bonnor solution which is an analytical solution and a complete solution of the Einstein -Maxwell equations found by numerical methods) that have been found in the literature which describe the spacetime exterior a massive compact object wich possess a magnetic field that a character dipole. For this we revised this two solutions, and then describe the geodesic equations generated by such solutions. Our studies show that, despite the Bonnor solution does not satisfy Maxwell’s equations, the orbits generated by this solution are the same as described by numerical solution. Also show that the inclusion of magnetic fields that assumes values of up to 1017G in the center of the star does not modify the orbits of the massive particles and the photons which are described around this star, and so the use of Schwarzschild solution for the description of the orbits around this object is a reasonable approximation.

Dans le cadre de cette thèse, j’ai étudié le refroidissement et le piégeage d’un gaz d’atomes de dysprosium dans des potentiels lumineux. Cet atome lanthanide possède dans son état électronique fondamental un moment magnétique très élevé, permettant l’exploration du domaine des gaz dipolaires ultrafroids. Ce caractère dipolaire enrichit la gamme des phénomènes physiques réalisés expérimentalement, en tirant avantage de la nature anisotrope et à longue-portée de l’interaction entre dipôles magnétiques. De plus, grâce à sa structure électronique riche, le Dysprosium offre la possibilité de créer un fort couplage entre le spin atomique et des champs lumineux, tout en gardant un taux de chauffage faible par rapport au cas usuel des atomes alcalins. Ceci ouvre la voie vers l’implémentation de champs de jauge artificiels, qui suscitent un vif intérêt dans le domaine des atomes froids dans un contexte de simulation quantique. Ce travail de thèse consiste en l’étude des mécanismes d’interactions dans un gaz de Dysprosium ultrafroid, allant des collisions assistées par la lumière à la relaxation dipolaire en passant par le refroidissement par évaporation. J’expose également la réalisation expérimentale d’un champ magnétique effectif en utilisant un déplacement lumineux dépendant du spin, permettant de contrôler optiquement la force des interactions atomiques au moyen d’une résonance de Feshbach
In this thesis, I present the study of the laser trapping and cooling of a Dysprosium atomic gas. This latter belong to the lanthanide family, it exhibits a large angular momentum in its electronic ground state, making it a suitable candidate for investigating dipolar quantum gases. These systems present a major interest as they can lead to the observation of novel quantum phenomena thanks to the anisotropic and long-range character of the interaction between magnetic dipoles. Moreover, Dysprosium has a rich electronic structure offering the possibility to implement strong light-spin coupling with a reduced heating with respect to alkali species, which paves the way toward the realization of synthetic gauge fields.In this work, I present the experimental investigation of different interaction mechanisms occurring in an ultracold gas of Dysprosium, ranging from light-assisted collisions to dipolar relaxation and evaporative cooling. I expose also the experimental realization of an effective magnetic field, using spin-dependent light-shift, allowing optical control over atomic interactions by means of Feshbach resonances

Realizamos a caracterização elétrica de alexandrita (BeAl2O4:Cr3+), formas sintética e natural, através de medidas de Corrente de Despolarização Termicamente Estimulada (CDTE). Obtivemos evidências conclusivas do fenômeno de relaxação dipolar em ambos os tipos de amostra, e que as cwas experimentais devem ser ajustadas por urna distribuição contínua dos parârnetros de relaxação. Para a amostra sintética a banda de CDTE está centralizada em tomo de 179K e para as naturais em 187 a 195K. Utilizando o método de Havriliak-Negarni são necessárias duas distribuições continuas de Ea e ▨ para ajustar as curvas experimentais, sendo que uma delas, em torno de 177 K, com Ea ≅ 0,56 e ▨ ≅ 1,2x10-14s sente em ambos os tipos de amostras. As bandas de CDTE são atribuídas a dipolos do tipo impureza-vacância de oxigênio ou a deformação local da estrutura causada pela diferença de raio iônico entre os íons Cr3+ (0,615 Å) e A13+(0,535 Å). Também realizamos medidas de CDTE fotoinduzidas, onde as amostras são irradiadas com um laser sintonizado em comprimentos de onda entre 3373 e 676,4nm. Verificamos que as bandas de CDTE podem ser \"destruídas\" ou \"criadas\" com a incidência de luz com diferentes condições iniciais de polarização. Para ajudar a interpretação dos resultados de CDTE nós usamos outras técnicas de caracterização, tais como Absorção Óptica, Luminescência, Difração de Raios X e micro análises de EDX e WDX. Todas estas técnicas foram também aplicadas às amostras naturais após tratamentos térmicos consecutivos
We have done electrical characterization of natural and synthet ic alexandrite (BeAl2O4:Cr3+), usimg the thermally stimulated depolarization current (TSDC) technique. We have obtained conclusive evidences of dipole relaxation in both kinds of samples. Besides, the experimental data must be fitted by a continuous distribution of relaxation parameters. For the synthetic sample, TSDC band has a peak about 179K and for natural samples, TSDC bands have peaks about 187K at 195K. Using Havriliak-Negami method, we need two continuous distributions of activation energy (Ea) and relaxation time constant (▨) to fit experimental data. One of these two curves, centered at 177K, is present for both kinds of sarnples and has Ea ≅ 0,56 e ▨ ≅ 1,2x10-14s. T SDC bands are attributed to impurity-oxygen vacancy dipoles or local structure deforrnation caused by the dserence between ionic radius of Cr3+ (0,615 Å) and A13+(0,535 Å) ions. We have also carried out photo-induced TSDC, where sarnples are irradiated with a tunable laser with wavelength fiom 337.5nm to 676.5nm. We have observed that TSDC bands rnay be destroyed or created with illumination fiom daerent polarization conditions. To help the interpretation of TSDC results we have used other techniques of characterization such as optical absorption, luminescence, X-ray difliaction, besides EDX and WDX rnicroanalyses. All of these techniques were also applied to natural samples afier consecutive annealing

Entre la amplia variedad de materiales nanocristalinos ferromagnéticos existe un pequeño grupo que presenta un comportamiento histerético muy particular: el ciclo de histéresis está desplazado en el eje horizontal y su silueta es asimétrica. Normalmente, la ruptura de la simetría del ciclo de histéresis se ha observado en materiales que tienen anisotropía de canje, sin embargo el comportamiento histerético anómalo a que nos referimos aquí presenta unas características que claramente lo diferencian de éste.En el presente trabajo de tesis se ha analizado la relación entre la nanocristalización de la aleación Co66 Fe4 Mo2Si16B12 y su histéresis magnética. Se ha hecho un estudio experimental para relacionar la microestructura en volumen y superficie de muestras tratadas térmicamente con el fenómeno del ciclo de histéresis desplazado. El origen de este desplazamiento se ha atribuido a la interacción dipolar entre las fases magnéticamente blanda (matriz amorfa) y dura (cristales embebidos en la matriz amorfa). Basándonos en este modelo se han simulado numéricamente la forma de los ciclos y la evolución de sus principales características con los campos aplicados, el tiempo y la temperatura.Mediante medidas de magnetometría de par en muestras con elevada fracción nanocristalina se han estimado las constantes de anisotropía de los nanocristales existentes en las muestras. Se constata además el comportamiento anómalo del par en las muestras con bajo grado de nanocristalización.

DE LA TESI:

L'exposició dels estudis realitzats segueix el següent esquema:

- En el primer capítol es calcula el moment dipolar de la molècula d'àcid malònic lliure i amb ell el valor de l'efecte dioxà en la mesura experimental d'aquesta propietat. Per a portar a cap aquest càlcul hom ha estudiat les possibilitats que ofereixen els diversos mètodes d'estudi de propietats de molècules no rígides, per a acabar proposant-ne un de més adequat al tipus de molècules que ens ocupen.

S'efectua, també, el càlcul del moment dipolar dels àcids succínic, glutàric i adípic mitjançant un dels mètodes que podriem anomenar pobres. I, prèviament a tot càlcul, s'analitza el concepte de molècula no rígida i es justifica la necessitat de conèixer propietats com el valor mig del moment dipolar per a obtenir informació estructural de la mateixa molècula.

- En el segon capítol es planteja l'estudi del líquid dioxà pur mitjançant simulació Monte Carlo, des de l'anàlisi del potencial d'interacció més adequat fins a la definició del sistema simulador passant per la descripció de les tècniques a tenir en compte en la construcció del programa d'ordinador. Aquests càlculs són un pas previ a la simulació de la dissolució malònic-dioxà, i els resultats que s'hi obtenen són una referència per a saber si el model que es construeix està ben encaminat o no, a la vegada que tenen interès en si mateixos com a font d'informació sobre el comportament del líquid dioxà.

- Finalment, en el tercer capítol, s'empren la simulació de la dissolució diluida d'àcid malònic en dioxà, per a averiguar si aquest canvia l'equilibri conformacional del diàcid. Es planteja la problemàtica característica d'aquest tipus de simulació, la seva resolució, el nou potencial malònic-dioxà a incorporar en el procés de càlcul, i s'efectúa l'estudi per a dos sistemes simuladors diferents. Els resultats, allà mateix analitzats, són significatius.

En aquest procés, repartit en tres capítols, hom pot observar la repetició d'un mateix esquema teòric: l'estudi de la dinàmica d'un sistema de partícules en interacció. La dinàmica intramolecular dels diàcids pot ser vista, com la d'un sistema de partícules (àtoms) que es mouen sota unes forces de tipus enllaçant i no enllaçant.

En la simulació del líquid dioxà les partícules del sistema són les molècules, les quals interaccionen entre si d'acord a unes forces intermoleculars. En analitzar la influencia del líquid dioxà sobre l'equilibri conformacional de l'àcid malònic es produeix un contacte entre els dos sistemes descrits anteriorment. Depèn de la importància de les forces que s'estableixin entre les particules-molécules del sistema-dissolució per a que les partícules-àtoms del sistema-molecula vegin afectada la seva dinàmica.

En conjunt, tres estudis que poden ser vistos independentment però que estan íntimament relacionats, no només pel fet de basar-se sobre un esquema teòric similar sinó també per formar part d'un treball global que intenta subministrar noves dades sobre el comportament de la matèria a nivell molecular, tant en estat gasós com en l'encara poc conegut estat líquid.

This thesis contains a study of ultracold paramagnetic atoms or polar molecules characterized by a long-range anisotropic dipolar interaction. We particularly focus on two aspects of ultracold dipolar gases. In the first problem the ground state properties of dipolar Bose-Einstein condensates (BEC) are investigated. This problem has gained importance due to recent experimental advances in achieving a condensate of Chromium atoms and ongoing research to produce quantum degenerate polar molecules. In the second problem, we consider possible applications of ultracold polar molecules to rotation sensing and interferometry. First, we concentrate on the interplay between the trapping geometry and dipole-dipole interaction for a polarized dipolar bosonic condensate. As the dipole-dipole interaction is attractive along the polarized direction, the lowest energy state of the BEC is always a collapsed state. However by applying a trapping potential along the polarization direction it is possible to achieve a metastable dipolar BEC. By numerically solving the Gross-Pitaevskii equation, we show that below a critical interaction strength, a metastable state exists depending on the trapping geometry. We also show that a novel feature of dipolar BEC is the appearance of different structural metastable ground states for certain combinations of trapping geometry and particle number. Next, by mixing in single component fermions we show that dipolar BEC can be stabilized against collapse in pancake shaped or cylindrical traps. We also show that the excitation spectrum of the BEC may have a minimum for non-zero momentum, termed a “roton minimum”. This minimum leads to a transition to stable or metastable density-wave states depending on the density of the bosons and boson-fermion interaction strength. In the second problem, we study a proposal for a large-angle coherent beam splitter for polar molecules. By taking into account the effect of a quasi-static external electric field on the rotational levels of the polarized molecules we show that it is possible to coherently split a stationary cloud of molecules into two counter-propagating components. We then investigate the effect of longitudinal acceleration on the transverse motion of the particles, assuming that the longitudinal motion of the molecules can be approximated classically by a wave packet with some mean velocity while the transverse motion is governed by quantum mechanics. We propose a particular time-dependent shape of acceleration to minimize the excitations in the transverse motion. Our theory is also applicable to the general case of particles moving along a circular guide with time-dependent longitudinal velocity. In addition, we include the effects of velocity fluctuations due to noise in the accelerating field.

The studies presented in this work are aimed towards a better understanding of the fundamental physics of the electrode/organic molecule interface in both the ground and excited state manifolds. Systematic investigations of single systems using two-photon photoemission (TPPE) and ultraviolet photoelectron spectroscopy (UPS) were undertaken in order to assess the evolution of the electronic structure and molecular organization at the interface. The adsorbate molecule vanadyl naphthalocyanine (VONc) was used whose properties are well-suited to this purpose. Interfacial electronic states of thin films of VONc were studied with two different substrates: highly ordered pyrolytic graphite (HOPG) and Au(111).The substrate of HOPG is a surface which does not possess reactive dangling bonds and the electron density close to the Fermi edge is very low, permitting high resolution spectroscopic band analysis of VONc and revealing subtle changes to the electronic structure. From interfacial studies of this weakly interacting substrate/ adsorbate system, it is shown in this work that molecular electronic levels in both the ground and excited state manifolds can shift independently of the vacuum level. Further, electron transfer between close lying electron donor and acceptor energy levels may be influenced by energy level shifts caused by depolarization effects as a function of dipole density.The VONc/Au(111) interface is investigated in order to examine energy level alignment in a system with the additional complexity of molecule/substrate interactions. The electron rich Au(111) surface leads to a strong interface dipole upon addition of VONc. Joint experimental and computational data is presented showing that the underlying cause of this interface dipole is Pauli repulsion. Additionally, investigations of energy level alignment in the excited state manifold are presented and the possibility of quantum interference is discussed.The interfacial electronic structure is quite different among these two model systems. The interfacial alignment observed in the HOPG/VONc system was largely due to depolarization of the intrinsic molecular dipole as a function of density, whereas the Au(111)/VONc interface is dominated by interfacial Pauli repulsion interactions.

The cycloaddition of benzonitrile oxide to 2-alkoxy-5,6- dihyclro-2H-pyrans was investigated with particular interest in the factors affecting the regio- and stereoselectivity of the reaction. The 2-methoxy analogue showed weak activity and little selectivity. The isolated products consisted of two by-products, three 1:1 cycloadducts and three 2:1 cycloadducts. The -butoxy analogue afforded only two cycloadducts. Both arose from attack anti to the bulky alkoxy substituent. Addition of benzonitrile oxide and Q,j-dipheny1njtrone to a bridged pyran, 6,8-dioxabicyclo[3 .2. l]oct-3-ene, showed similar selectivity and much enhanced reactivity. Levoglucosenone, a chiral bicyclic enone showed excellent reactivity and selectivity in reaction with benzonitrile oxide. Two cycloadducts were isolated in a ratio of ca. 100:1 and a combined yield of 71%; the major adduct having added from the face anti to the methyleneoxy bridge. This isoxazoline was investigated further in reactions involving reduction of the carbonyl group, acetal formation and nucleophilic addition of nitromethane. Levoglucosenone was also shown to be a reactive dipolarophjle to other 1,3-dipoles such as nitrones, a nitrile imine and a carbohydrate nitrile oxide. The chemistry of some of these adducts was also investigated. Finally, the Michael addition of nitromethane to levoglucosenone was investigated under many different conditions and with different basic catalysts. The aim was to synthesise levoglucosenone with a primary nitro substituent to use as a nitrile oxide precursor. The series of reactions afforded 8 identifiable products, none of which was the desired Michael adduct.