Since the development of the understanding that the electron distribution within a molecule is chiefly responsible for its properties and behavior, factors influencing this charge distribution have been of interest to scientists. The chemical reactivity of a molecule, the physical properties, and to a large extent, structure and geometry, are all functions of the electron distribution. This study examines the issue of electronic structure from two points of view, each of them focussing on a specific component within the molecules studied. In the present work, the effects of the highly polar carbonyl group on spectroscopic parameters and physical behavior are investigated. An additional area of study is the effect of fluorine substitution on the energy levels of some halogenated ethylenes. The specific parameters examined are the ionization potentials, the absorption frequencies, and the energies of a class of excited states known as molecular Rydberg states. It was during the study of these halogenated ethylenes that the observations leading to the carbonyl compound investigations were made, so that the two areas examined are connected both experimentally and chemically.

The past three decades have seen extraordinary progress in the manipulation of neutral atoms with laser light, to the point where it is now routine to trap and cool both individual atoms and entire atomic clouds to temperatures of only a few tens of nanoKelvin in a controlled and repeatable fashion. In this thesis we study several applications of Rydberg atoms - atoms with an electron in a highly excited state - within such ultracold atomic systems. Due to their highly-excited electron, Rydberg atoms have a number of exaggerated properties: in addition to being physically large, they have long radiative lifetimes, and interact strongly both with one another and with applied external fields. Rydberg atoms consequently find many interesting applications within ultracold atomic physics. We begin this thesis by analysing the way in which a rubidium atom prepared in an excited Rydberg state decays to the ground state. Using quantum defect theory to model the wavefunction of the excited electron, we compute branching ratios for the various decay channels that lead out of the Rydberg states of rubidium. By using these results to carry out detailed simulations of the radiative cascade process, we show that the dynamics of spontaneous emission from Rydberg states cannot be adequately described by a truncated atomic level structure. We then investigate the stability of ultra-large diatomic molecules formed by pairs of Rydberg atoms. Using quantum defect theory to model the electronic wavefunctions, we apply molecular integral techniques to calculate the equilibrium distance and binding energy of these molecular Rydberg states. Our results indicate that these Ryberg macro-dimers are predicted to show a potential minimum, with equilibrium distances of up to several hundred nanometres. In the second half of this thesis, we present a new method of symbolically evaluating functions of matrices. This method, which we term the method of path-sums, has applications to the simulation of strongly-correlated many-body Rydberg systems, and is based on the combination of a mapping between matrix multiplications and walks on weighted directed graphs with a universal result on the structure of such walks. After presenting and proving this universal graph theoretic result, we develop the path-sum approach to matrix functions. We discuss the application of path-sums to the simulation of strongly-correlated many-body quantum systems, and indicate future directions for the method.

Made available in DSpace on 2014-06-12T18:02:18Z (GMT). No. of bitstreams: 2 arquivo2372_1.pdf: 8696396 bytes, checksum: e6b2bbf30b6a6d612f05e9365db67ee7 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2009 / Universidade Federal de Pernambuco / Neste trabalho, observamos evidências da interação de longo alcance entre átomos de Rydberg usando um processo não linear, a geração de segundo harmônico (SHG), em um vapor contendo alta densidade de átomos de rubídio.O sinal de segundo harmônico, ressonante por dois fótons, é observado a partir de estados altamente excitados, s , p e d, onde a assinatura da interação de longo alcance aparece como um alargamento espectral assimétrico para o lado de baixas energias das linhas de ressonância. Esta assimetria é comparada com cálculos teóricos das curvas de potencial assintóticas para os pares de átomos interagentes, mostrando uma boa concordância dos resultados experimentais com as previsões teóricas. Para estados de Rydberg nd, com número quântico principal n≈13, um estudo detalhado da dependência do alargamento com a intensidade do laser de excitação e para diferentes densidades atômicas foi realizado. A observação de uma fraca dependência da intensidade do sinal com a densidade atômica sugere uma supressão da excitação coerente, e/ou a participação de outros processos de decaimento. Para os estados de Rydberg np, com n≈12 , observamos um comportamento distinto para o dubleto de estrutura fina, P 1/2 e P 3/2. Enquanto as linhas P 3/2 apresentam um alargamento assimétrico e uma fraca dependência com a densidade atômica, semelhante ao observado para as linhas nd, as linhas P 1/2, permanecem estreitas e apresentam uma dependência diferenciada com a densidade atômica. Nossos experimentos, usando vapor de Rb com alta densidade atômica e um processo não linear coerente, podem ser vistos como proposta de uma técnica não destrutiva para investigar interação de longo alcance e suas possíveis aplicações em informação quântica

Made available in DSpace on 2014-06-12T18:06:15Z (GMT). No. of bitstreams: 2 arquivo8043_1.pdf: 3446816 bytes, checksum: 55377eb04f6b857ed5c4dc178a6d3491 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2002 / Estudamos efeitos ópticos não-lineares em vapores alcalinos, quando níveis de Rydberg estão envolvidos como estados intermediários, quase ressonantes, em processos como: mistura de quatro ondas (MQO), absorção de dois fótons, geração de soma (SF) e diferença de freqüência (DF). Analisamos um processo de MQO, com transições de dois fótons envolvendo níveis de Rydberg do átomo de rubídio, e observamos franjas de interferência no sinal não linear. Neste estudo, mostramos que é possível ter um controle coerente sobre os múltiplos caminhos quânticos acessíveis ao sistema atômico, explorando a dependência do sinal não linear com a polarização dos feixes incidentes. Medimos a visibilidade das franjas observadas e obtivemos valores de 100% para o contraste da interferência, na ressonância de dois fótons com um nível de Rydberg. Os resultados experimentais apresentam um bom acordo com cálculos teóricos, baseados no formalismo da matriz densidade aplicado a um sistema atômico de quatro níveis. A distribuição de população para um átomo de quatro níveis foi calculada no regime estacionário, resolvendo as equações da matriz densidade em ordens superiores nos campos incidentes. Mostramos que uma interferência entre os caminhos quânticos de excitação de um estado atômico pode levar ao cancelamento ou ao aumento da população desse nível, dependendo das polarizações dos lasers incidentes. Estudamos também efeitos transientes, resolvendo a equação de Schrödinger dependente do tempo para um sistema de três níveis na configuração V, e previmos a ocorrência de oscilações de Rabi de dois fótons, e batimentos quânticos nas populações do sistema atômico. Finalmente, medimos pela primeira vez a geração da DF em uma amostra de rubídio em alta densidade, através de um processo proibido por dipolo elétrico, envolvendo níveis de Rydberg. Utilizando o modelo do campo elétrico estático, induzido por fotoionização, como um mecanismo de quebra de simetria, desenvolvemos cálculos teóricos que permitiram prever a forma espacial do sinal não linear gerado, e comparar com os resultados existentes na literatura para a geração de segundo harmônico em vapores atômicos

Die Arbeit beschäftigt sich mit der Dynamik von Gasen aus hoch angeregten Atomen. Es wird sowohl die Erzeugung von Rydberggasen, als auch ihre Dynamik nach der Laser-Anregung betrachtet. Zur Beschreibung des Anregungsprozesses wird ein quasi-klassischer Zugang verwendet. Er basiert auf der adiabatischen Eliminierung von Kohärenzen aus der vollen Quanten-Beschreibung und führt auf eine klassische Mastergleichung. Diese Näherung ist gerade für typische experimentelle Situationen durchführbar. Die klassische Mastergleichung kann durch ein simples Monte-Carlo-Verfahren für Systeme aus zehntausenden von Teilchen unter voller Berücksichtigung der Rydberg-Rydberg-Wechselwirkung gelöst werden. Mit Hilfe des Monte-Carlo-Verfahrens wird die Anregung von Rydbergatomen in einem ultrakalten Gas untersucht. Die in Experimenten gefundene Anregungsblockade wird durch die Methode gut beschrieben. Bei der Anregung von Rydbergatomen aus einem optischen Gitter wird sogar eine Anregungsverstärkung - eine Antiblockade - vorhergesagt. Die Antiblockade in einem Gitter erlaubt eine Charakterisierung räumlicher Korrelationen der Rydbergatome allein durch die Messung ihrer Dichte. Sie ist robust gegenüber Gitterfehlstellen und sollte mit heutigen experimentellen Techniken nachweisbar sein. Für die Anregung im ungeordneten Gas wird gezeigt, dass sich die räumlichen Korrelationen der Rydbergatome indirekt in den Momenten der Häufigkeitsverteilung angeregter Atome widerspiegeln. Durch die Untersuchung der Fluktuationen in der Zahl angeregter Atome lassen sich die Unterschiede in den Paarkorrelationsfunktionen bei Blockade und Antiblockade im Gas messen. Ein Vergleich mit experimentellen Daten zeigt eine qualitativ gute Übereinstimmung. Für die Dynamik des Rydberggases nach dem Abschalten der Anregungslaser ist der Fall besonders interessant, dass Atome in unterschiedlichen Rydbergzuständen resonant ihre Anregungsenergie austauschen können. In der Arbeit wird argumentiert, dass sich der räumliche Transfer von Anregungsenergie in Rydbergsystemen ohne störende Umgebungseinflüsse gezielt untersuchen lässt. Mit Hilfe der Frenkelschen Exziton-Theorie wird der Energietransfer entlang einer eindimensionalen Anordnung von Rydbergatomen untersucht. Zusätzlich wird dargelegt, dass die exzitonische Anregung auch mechanische Kräfte auf die Rydbergatome induziert. Diese werden mit Hilfe einer quanten-klassischen Methode analysiert. Der Zusammenhang der auftretenden Kräfte mit den Symmetrien der exzitonischen Eigenfunktionen wird aufgezeigt. In einer eindimensionalen Anordnung von Rydbergatomen wird ein adiabatischer Energietransfer vorhergesagt, der an die Bewegung der Atome gebunden ist. Er läuft vollständig auf einer einzigen adiabatischen Potentialfläche ab. Dieser Transport ist langsam genug, um mit heutigen experimentellen Methoden im Prinzip orts- und zeitaufgelöst abgebildet zu werden.

No description available.

The coupling of light to ensembles of strongly interacting Rydberg atoms via electromagnetically induced transparency (EIT) has emerged as a particularly promising approach towards quantum nonlinear optics, allowing freely propagating photons to acquire long-ranged effective interactions of unprecedented strength. This thesis explores different photon interaction mechanisms enabled by this general approach, and examines how these can be utilized for various different practical applications. Considering dissipative photon interactions, we first examine the effect of blockade-induced photon scattering on the spatial coherence of collective Rydberg excitations stored in an atomic medium, and how this influences the efficiency of photon storage and retrieval. Based on this developed understanding, we examine the performance of single-photon switching capabilities enabled by dissipative scattering and establish optimized switching protocols over a range of parameters. We then generalize this to consider the many-body decoherence of multiple stored excitations. Here we identify a correlated coherence protection mechanism in which photon scattering from one excitation can preserve the spatial coherence of all others in the medium, and consider the utility of this effect for implementing robust single-photon subtraction. We then outline a new approach towards coherent quantum nonlinear optics via Rydberg-EIT, in which the emergent photon interaction features intrinsically suppressed photon losses. The underlying idea exploits Rydberg blockade to modify rather than break EIT conditions for multiple photons in close proximity, the effect of which alters the underlying dispersion relation of light propagation in a coherent fashion. We devise a specific implementation of this general mechanism fostering a reflective optical nonlinearity and discuss how this can enable efficient single-photon routing with a multitude of unique practical applications.

Strong resonant dipole-dipole interactions in flexible Rydberg aggregates enable the formation of excitons, many-body states which collectively share excitation between atoms. Exciting the most energetic exciton of a linear Rydberg chain whose outer two atoms on one end are closely spaced causes the initiation of an exciton pulse for which electronic excitation and diatomic proximity propagate directed through the chain. The emerging transport of excitation is largely adiabatic and is enabled by the interplay between atomic motion and dynamical variation of the exciton. Here, we demonstrate the coherent splitting of such pulses into two modes, which induce strongly different atomic motion, leading to clear signatures of nonadiabatic effects in atomic density profiles. The mechanism exploits local nonadiabatic effects at a conical intersection, turning them from a decoherence source into an asset. The conical intersection is a consequence of the exciton pulses moving along a linear Rydberg chain and approaching an additional linear, perpendicularly aligned Rydberg chain. The intersection provides a sensitive knob controlling the propagation direction and coherence properties of exciton pulses. We demonstrate that this scenario can be exploited as an exciton switch, controlling direction and coherence properties of the joint pulse on the second of the chains. Initially, we demonstrate the pulse splitting on planar aggregates with atomic motion one-dimensionally constrained and employing isotropic interactions. Subsequently, we confirm the splitting mechanism for a fully realistic scenario in which all spatial restrictions are removed and the full anisotropy of the dipole-dipole interactions is taken into account. Our results enable the experimental observation of non-adiabatic electronic dynamics and entanglement transport with Rydberg atoms. The conical intersection crossings are clearly evident, both in atomic mean position information and excited state spectra of the Rydberg system. This suggests flexible Rydberg aggregates as a test-bench for quantum chemical effects in experiments on much inflated length scales. The fundamental ideas discussed here have general implications for excitons on a dynamic network.

Cette thèse porte sur l’étude des interactions dipôle-dipôle entre des atomes de Rydberg froids formés au sein d'un jet supersonique, en particulier sur l'étude des transitions Landau-Zener autour d'une résonance de Förster dans des sytèmes de paires d'atomes de Rydberg. L'adiabaticité de la transition dépend de la distance entre les atomes de la paire et est contrôlée par l'application d'un champ électrique homogène dépendant du temps. L'étude des processus binaires, non collisionnels et dont l'efficacité est contrôlé par l'expérimentateur, permet de sonder l'environnement de chaque atome et constitue une mesure de la distribution de plus proches voisins. Nous en déduisons une méthode originale de mesure directe et précise de la densité d'un gaz de Rydberg. Cette méthode ne nécessite ni la connaissance du nombre d'atomes de Rydberg ni celle du volume du gaz. Après un passage adiabatique de paire, les atomes de Rydberg constituant cette paire se trouvent dans un état intriqué. Nous proposons une méthode pour prouver leur intrication, fondée sur la mesure de la fluctuation quantique au cours d'oscillations de Rabi entre des états de paire. / This thesis deals with the study of dipole-dipole interaction between Rydberg atoms, in particular of Landau-Zener transitions around a Förster resonance for Rydberg atoms pairs. The adiabaticity of the transition depends of the interatomic distance and is controlled by a time-dependant electric field. The adiabatic transition efficiency is the control knob to probe the nearest neighbour distribution. We infer a new and original method to measure the density of a gas very accurately by probing the nearest neighbour distibution in the gas, which depends parametrically on its density. Such adiabatic transitions should leave the pair of Rydberg atoms in an entangled state. We investigated how quantum fluctuations could reveal the atom entanglement, in two-atom Rabi oscillation measurements.

Au cours de cette thèse, la physique des systèmes en interaction à été étudié expérimentalement à partir de gaz froids d'atomes de Rydberg. Les atomes de Rydberg sont des atomes dans un état fortement excités et ils ont la propriété d'interagir fortement du fait d'interactions électrostatiques à longue portée. Le premier résultat majeur de cette thèse est l'observation expérimentale d'un processus à quatre corps. Ce processus consiste en l'échange d'énergie interne entre quatre atomes de Rydberg induit par leurs interactions mutuelles. Il a été possible, en plus de son observation expérimentale, de décrire théoriquement ce processus, au niveau quantique. L'excitation par laser des gaz d'atomes de Rydberg en forte interaction a aussi été étudiée durant cette thèse. Cette situation donne lieu à de très intéressants comportements à N-corps. Ce sujet d'intérêt fondamental pourrait aussi amener à d'éventuelles applications pour la réalisation de simulateurs quantiques ou de sources de lumière non classiques. Un second résultat majeur de cette thèse est l'observation expérimentale d'une statistique fortement sub-poissonienne, i.e corrélée de l'excitation Rydberg. Ce résultat confirme le caractère à N-corps de tels systèmes. Le troisième résultat majeur de cette thèse est le développement d'un modèle théorique pour l'excitation par laser des gaz d'atomes de Rydberg en forte interaction. En utilisant les états quantiques dit états collectifs de Dicke, il a été possible de mettre au jour de nouveaux mécanismes liés au comportement à N-corps de ces sytèmes atomiques en forte interaction. / Uring this thesis, the Physics of interacting systems has been investigated experimentally using Cold Rydberg gases. Rydberg atoms are highly excited atoms and have the property to interact together through long-range electrostatic interactions.The first highlight of this thesis is the direct experimental observation of a 4-body process. This process consists in the exchange of internal energy between 4 Rydbergs atoms due to their mutual interactions. In addition to its observation, it has been possible to describ this process theoretically at a quantum level.The laser excitation of strongly interacting Rydberg gases has been also investigated during this thesis. In this regime, the interactions between Rydberg atoms give rise to very interesting many-body behaviors. In addition to fundamental interest, such systems could be used to realyze quantum simulators or non-classical light sources.A second highlight of this thesis is the experimental observation of a highly sub-poissonian, i.e correlated, excitation statistics. This result confirms the many-body character of the investigated system.The third highlight of this thesis is the development of a theoretical model to describ the laser excitation of strongly interacting Rydberg gases. Using the so-called Dicke collective states it has been possible to point out new mechanismes related to the many-body character of strongly atomic interacting systems.