This thesis concerns the development and study of Ru-based water oxidation catalysts (WOCs) which are the essential components for solar energy conversion to fuels. The first chapter gives a general introduction about the field of homogenous water oxidation catalysis, including the catalytic mechanisms and the catalytic activities of some selected WOCs as well as the concerns of catalyst design. The second chapter describes a family of mononuclear Ru complexes [Ru(pdc)L3] (H2pdc = 2,6-pyridinedicarboxylic acid; L = pyridyl ligands) towards water oxidation. The negatively charged pdc2− dramatically lowers the oxidation potentials of Ru complexes, accelerates the ligand exchange process and enhances the catalytic activity towards water oxidation. A Ru aqua species [Ru(pdc)L2(OH2)] was proposed as the real catalyst. The third chapter describes the analogues of [Ru(terpy)L3]2+ (terpy = 2,2′:6′,2′′-terpyridine). Through the structural tailor, the ligand effect on the electrochemical and catalytic properties of these Ru complexes was studied. Mechanistic studies suggested that these Ru-N6 complexes were pre-catalysts and the Ru-aqua species were the real WOCs. The forth chapter describes a family of fast WOCs [Ru(bda)L2] (H2bda = 2,2′-bipyridine-6,6′-dicarboxylic acid). Catalytic mechanisms were thoroughly investigated by electrochemical, kinetic and theoretical studies. The main contributions of this work to the field of water oxidation are (i) the recorded high reaction rate of 469 s−1; (ii) the involvement of seven-coordinate Ru species in the catalytic cycles; (iii) the O-O bond formation pathway via direct coupling of two Ru=O units and (iv) non-covalent effects boosting up the reaction rate. The fifth chapter is about visible light-driven water oxidation using a three component system including a WOC, a photosensitizer and a sacrificial electron acceptor. Light-driven water oxidation was successfully demonstrated using our Ru-based catalysts. / QC 20110922

Thesis (Ph.D.)--University of Nebraska-Lincoln, 2007. / Title from title screen (site viewed July 22, 2008). PDF text: viii, 127 p. : ill. (some col.) ; 2 Mb. UMI publication number: AAT 3296996. Includes bibliographical references. Also available in microfilm and microfiche formats.

Cette thèse présente la recherche d'un boson de Higgs chargé (H+) qui serait produit dans les collisions proton-proton à des énergies de 7 TeV$ et 8 TeV, en utilisant les données recueillies par l'expérience ATLAS au LHC (Large Hadron Collider). Plusieurs canaux de recherche sont utilisés, présentant la caractéristique commune de contenir au moins un lepton chargé (électron ou muon) énergétique, ce qui réduit efficacement le bruit de fond contenant des jets, tout en permettant un déclenchement efficace du détecteur.Ici le boson de Higgs chargé se désintègre en un lepton tau et un neutrino, ce qui conduit à des états finaux avec deux leptons chargés, ou bien un lepton chargé et un tau hadronique. Une source importante de taus mal identifiés provient de quarks et de gluons, par l'intermédiaire des jets hadroniques qu'ils initient. Plusieurs méthodes ont été développées pour estimer ce bruit de fond, l'une d'elles étant basée directement sur les données. Des processus avec des bosons de Higgs chargés dont la masse est soit en dessous soit au-dessus de celle du quark top sont considérés. Avec l'ensemble de données recueillies à une énergie de 8 TeV, correspondant à une luminosité intégrée de 20,3/fb, des limites avec un taux de confiance de 95% sont placées sur le rapport de branchement Br(t -> bH+)*Br(H+ -> tau nu) entre 1,1 et 0,3% pour des masses du boson de Higgs chargé entre 80 GeV et 160 GeV, et sur la section efficace de production du boson de Higgs chargé en association avec un quark top entre 0,53 et 0,04 pb, pour un boson de Higgs chargé ayant cette fois une masse comprise entre 180 GeV et 1 TeV. / This thesis presents searches for a charged Higgs boson (H+) in proton-proton collisions with center-of-mass energies of 7 TeV and 8 TeV, using data collected by the ATLAS experiment at the CERN Large Hadron Collider. Multiple search channels are used with a common characteristic of at least one charged lepton (electron or muon) that effectively reduces the multi-jet background and is used for efficient triggering.Charged Higgs bosons decaying to a tau lepton and a neutrino are searched for using final states with two charged leptons or one charged lepton and a hadronically decaying tau. A significant background originates from quark- and gluon-initiated jets that may be misidentified as hadronic tau decays. Methods to estimate this background are developed, including a largely data-driven matrix method. Signal processes with a charged Higgs boson mass below or above that of the top quark are considered. With the dataset collected at a center-of-mass energy of 8 TeV, corresponding to an integrated luminosity of 20.3/fb, upper limits at 95% confidence level are placed on the branching fraction Br(t -> bH+)*Br(H+ -> tau nu) in the range 1.1-0.3% for charged Higgs boson masses between 80 GeV and 160 GeV, and on the top-quark associated charged Higgs boson production cross section in the range 0.53-0.04 pb for charged Higgs boson masses between 180 GeV and 1 TeV.

xxvi, 199 p. : ill. (some col.) A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / The abundance of B mesons at B factories opens the door to the search in rare decays for physics outside of the Standard Model. Flavor-changing neutral current transitions proceed only via higher order in the Standard Model, resulting in a b [arrow right] s³y branching fraction of about 3 x 10 -4 , but hypothesized particles could alter the rate significantly. Decays of B mesons that proceed via this electroweak penguin diagram are an interesting example of flavor-changing neutral currents, due to the large number of accessible final states with observables that are sensitive to new processes. This dissertation describes the analyses of such decays B - [arrow right] p ³, B - [arrow right] £ 0 p ³, B - [arrow right] p and B - [arrow right] p using about 350 million B meson pairs recorded by the BABAR detector in the years 2001 through 2006. In addition to the decay rate, the distribution of the invariant mass of the baryon pair is presented, using a method for statistical unfolding. The analysis is the first of these decays at the BABAR experiment and lays the groundwork for future analyses of the branching fractions and angular correlations of b [arrow right] s decays containing A hyperons and other baryons at BABAR or higher luminosity B factories. / Adviser: James E. Brau

xii, 107 p. : ill. (some col.) A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / Non-muscle myosin II generates contractile forces for processes such as cytokinesis, motility, and polarity. Contractility requires assembly of myosin molecules into bipolar mini-filaments through electrostatic interactions between coiled-coil tail domains of the heavy chains. Analyses of myosin II from various organisms have revealed "assembly domains" within the C-terminal portion of the tail domain that mediate filament formation. However, it has been unclear precisely how assembly domains interact with one another, or otherwise contribute to tail-tail interactions, to form the bipolar mini-filament structure. To understand tail domain interactions, we first identified a 90-residue region (1849-1940) of the Drosophila non-muscle myosin II tail domain that was necessary and sufficient for filament formation, using salt-dependent solubility and a novel fluorescence energy transfer assay. We identified residues within this "assembly domain" that were critical for filament assembly by analyzing the effect of point mutations. We found that single point mutations in specific positively charged regions completely disrupt filament assembly. Surprisingly, none of the negatively charged regions within the assembly domain are required for assembly. Most of the mutations in positively charged residues that disrupted filament assembly clustered within a 15-residue segment (1880-1894) that appears to form a critical interaction surface. Using this information, along with known geometrical constraints and electrostatic calculations, we constructed a structural model of the bipolar mini-filament. This model features one favored anti-parallel tail overlap and multiple slightly less stable alternative overlaps. The ability of the positive segment to interact with multiple negative regions explains the lack of required negatively charged residues in the assembly domain. To our knowledge, this structural model of the non- muscle myosin II bipolar filament is consistent with all physical observations and provides a framework for understanding the detailed mechanism by which this fundamental cellular structure is generated. This dissertation contains previously published and unpublished co-authored material. / Committee in charge: Tom Stevens, Chairperson, Chemistry; Kenneth Prehoda, Advisor, Chemistry; J. Andrew Berglund, Member, Chemistry; Christopher Doe, Member, Biology; Karen Guillemin, Outside Member, Biology

En 2012, les expériences ATLAS et CMS ont annoncé la découverte d’un nouvelle particule compatible avec le boson de Higgs prévu par le modèle standard. Cette particule a été postulée dans les années 1960. Elle explique comment les particules fondamentales obtiennent leurmasse. Cependant, la plupart des modèles allant au-delà du modèle standard prédisent l'existence de bosons de Higgs chargés. Les propriétés de telles particules, par exemple sa masse et son couplage aux autres particules, ne sont pas précisément prédites par la théorie, mais constituent un espace deparamètres qui doit être exploré. Des recherches de bosons de Higgs chargés ont été effectuée avant le LHC, cependant l'extension en énergie réalisée par le LHC a permis d'explorer un domaine plus large en masse. Dans ce travail nous avons cherché un boson chargé de Higgs se décomposant en une paire de quarks t et b. Aucun écart par rapport au modèle standard n'a été observé dans les données recueillies jusqu’en 2016, nous pouvons en déduire deslimites supérieures sur le taux de production d’un boson chargé de Higgs.Ces limites peuvent alors être utilisées pour exclure des parties de l’espacedes paramètres.Le LHC sera mis à niveau vers 2025 pour augmenter sa luminosité (le nombre de collisions par seconde et par cm2). Les protons sont accélérés par paquets. Ainsi, la luminosité peut être augmentée en injectant plus de protons par paquet, mais aussi en focalisant les paquets (réduisant leur taille transverse) au point de collision. Cela signifie que le taux auquel nouspouvons espérer produire des événements rares augmentera, mais aussique le taux de bruit de fond correspondant à l'empilement (le nombre de collisionsmoles de protons par croisement) augmentera. Le taux de croisement de paquets au LHCest trop élevé pour pouvoir lire et stocker toutes les don-nées produites. Ainsi nous devons utiliser un système de déclenchement quisélectionne rapidement les événements intéressants à enregistrer. Le système de déclenchementactuel n'est pas adapté au taux élevé d’empilement attendu pour la phase à hauteluminosité (HL) du LHC. Il doit donc être améliorée.Une façon de le faire est d'utiliser les informations du détecteur internequi fournit des informations sur les trajectoires de particules chargées.En utilisant des algorithmes qui peuvent être mis en œuvre dans l'électronique,un déclenchement de premier niveau sur les traces peut être rendu assez rapide pour fonctionnerdans la courte latence requise au HL-LHC. Le détecteur interne fournitdes points d’espace, des mesures des trajectoires des particules à des intervalles différents où sont installés des pistes de silicium. La quantité dedonnées du trajectomètre est trop grande, aussi effectuer des calculs sur toutes les combinaisons de points spatiaux prendrait trop de temps. Par conséquent, undéclenchement interne de premier niveau doit pouvoir sélectionner un sous-ensemble de pointsspatiaux sur lesquels effectuer le calcul. Dans cette thèse, nous avons exploré l’idée d’utiliser les régions d'intérêt fournies par le système de déclenchement d’électrons et de muonspour sélectionner une partie du volume du détecteur interne, puis de sélectionner lespoints d’espace qui correspondent aux modèles attendus des traces à haute énergie. Il a été démontré que c’est une option viable pour réduire les taux de bruit de fond tout en gardant une efficacitéélevée pour les événements que nous voulons garder, même dansdes conditions élevées d’empilement. / In 2012 the ATLAS and CMS experiments announced the discoveryof a new particle, a Higgs boson. This particle was hypothesized in the1960’s and explains how fundamental particles get their mass. However, amodel with a single Higgs boson is still not able to explain the aforemen-tioned cosmological observations. An electrically charged Higgs boson isa feature of many suggested extensions of the current model, includingsupersymmetry. The properties of such a particle, e.g. its mass and howit interacts with other particles are not fixed by theory but forms a pa-rameter space in which we must look for it. Searches for charged Higgsbosons have been performed prior to the LHC, but with the new energyscale of the LHC, the experiments have been able to look for heavier par-ticles. In this work we searched for a charged Higgs boson decaying intothe heaviest two quarks, a top and bottom pair. No deviations from thestandard model were found in the data gathered up until 2016, and hencewe can set upper limits on the production rate of a charged Higgs boson.These limits can then be used to exclude parts of the parameter space.The LHC will be upgraded around 2025 to increase the luminosity,that is the intensity of the proton beams. Protons are not acceleratedone by one at the LHC but in bunches. The luminosity can be increasedby using more protons per bunch but also by squeezing the bunches to besmaller at the point of collision. This means that the rate at which we canhope to produce rare events will increase but also that the backgroundrates and so called pile-up, the number of proton collisions per bunchcrossing, will increase. The rate of bunch crossings at the LHC is muchtoo high for ATLAS to be able to readout and store all data for eachevent, instead we use triggers that select events which look interesting.The current triggers are not suited for the high rates and pile-up of theHigh Luminosity (HL) LHC after the upgrade and must thus be improved.A way to do this is to use the information from the tracking detector thatprovides information on the trajectories of charged particles. By usingalgorithms that can be implemented in hardware a track trigger can bemade fast enough to work within the short latency required at the HL-LHC. The tracking detector provides space points, measurements of theparticle trajectories at different intervals, to which a track can be fitted.The amount of data from the tracker is very large, and performing trackfits on all the combinations of the space point would take too much time.Therefore a track trigger must be able to select a subset of space points onwhich to perform the track fit. For this thesis we have explored the idea ofusing standalone electron and muon triggers to select a part of the trackervolume, and then select space points that match precomputed patternsthat correspond to high energy particles. It has been shown that this isa viable option to reduce background rates while keeping high efficiencyfor the events we want to keep, even in high pile-up conditions.

L’expérience ATLAS (A Toroidal LHC Apparatus), collaboration de plus de 3000 scientifiques dans le monde, mène des recherches auprès du grand collisionneur de hadron (LHC). Celui-ci a produit des collisions de faisceaux de protons à une énergie dans le centre de masse de 7 TeV en 2011 et 8 TeV en 2012, période appelée Run1 et représentant 20.3 fb−1 de luminosité intégrée, puis en 2015 et 2016 à 13 TeV pour le Run 2 avec 36.1 fb−1. Le détecteur généraliste ATLAS a un riche potentiel de mesures précises du Modèle Standard (SM) et de recherche de phénomènes de nouvel physique. Deux analyses de physiques sont ici présentées. La première consiste à rechercher dans les données Run 1 la production de tri-bosons, W±W±W∓, se désintégrant totalement ou partiellement en leptons et à étudier le couplage de jauge quartique anormal (aQGC). Le nombre d’événements observés est en accord avec les prédictions du SM. La limite supérieure observée à 95% CL sur la section efficace W±W±W∓ SM est de 730 fb avec une limite attendue de 560 fb en l’absence de production W±W±W∓. La deuxième analyse présentée est la recherche du boson de Higgs doublement chargé effectuée sur les données du Run 2. Ce boson est prédit par un modèle qui prolonge le SM pour permettre des neutrinos massif. Ce modèle introduit plusieurs bosons de Higgs dont l'un est le H±±. Le cas où ce dernier se désintègre en bosons W avec un état final à deux leptons de même charge est plus particulièrement étudié. Le bruit de fond total estimé est en accord avec les données et aucun excès significatif n’est observé. Des limites supérieures sont déduites et le modèle considéré est exclus à 95% CL pour MH±± < 220 GeV. / The ATLAS (A Toroidal LHC Apparatus) experiment, a collaboration of more than 3,000 scientists worldwide, is conducting research at the Large Hadron Collider (LHC). It produced proton beam collisions at an energy in the center of mass of 7 TeV in 2011 and 8 TeV in 2012, period called Run1 and representing 20.3 fb-1 of integrated luminosity, then in 2015 and 2016 at 13 TeV for Run 2 with 36.1 fb-1. The ATLAS general purpose detector has a rich potential for accurate Standard Model (SM) measurements and the search for new physics phenomena. Two physics analyzes are presented here. The first is to search the Run 1 data for tri-bosons production, W ± W ± W∓, totally or partially decayed into leptons and to study abnormal quartic gauge coupling (aQGC). The number of observed events is consistent with the SM predictions. The observed upper limit at 95% CL on the W ± W ± W∓ SM cross section is 730 fb with an expected limit of 560 fb in the absence of W ± W ± W∓ production. The second analysis presented is the search for the doubly charged Higgs boson carried out on the Run 2 data. This boson is predicted by a model that extends the SM to allow massive neutrinos. This model introduces several Higgs bosons, one of which is the H ±±. The case where this latter decays in bosons W with a final state with two leptons of the same charge is more particularly studied. The estimated total background is in agreement with the data and no significant excess is observed. Upper limits are deduced and the model considered is excluded at 95% CL for MH ±± <220 GeV.

Ce travail aborde le sujet des d efauts charg es dans le silicium. Jusqu' a pr esent, les d efauts charg es ont principalement et e etudi es en conditions p eriodiques (PBC). En e et, l'approche PBC est parfaite pour simuler unsolide in ni. Mais, comme je le montre dans ce chapitre, elle apporte aussi des artefacts. En particulier dans le traitement de l' electrostatique, o u des traitements math ematiques important doivent ^etre utilis es pour supprimer les interactions non d esir ees entre r epliques. Notre approche vise a simuler correctement un d efaut charg e, tout en conservant de bonne propri et es pourle mat eriau massif. Elle consiste a simuler le d efaut dans un nano-agr egat. Le traitement de l' electrostatique est correct dans un nano-agr egat et les r esultats obtenus peuvent ^etre extrapol es au mat eriau massif, comme il est montr e dans ce chapitre. Les perspectives de cette m ethode sont aussi abord ees ici. / In this work we have studied Si clusters with point defects in various charged states. Point defects in semiconductors affects the electronic structure of the material introducing new energy levels and consequently new modes of transport.Detailed study of the point defects have been undertaken in various approaches. The most common practice is to usesuper-cell calculations under the framework of Density Functional Theory with Periodic Boundary Conditions (PBC). Inthis formalism there are a lot of factors like defect-defect interactions, image charge interactions, that are to be correctedfor to achieve the " artefact-free" results. In this study we have used Free Boundary Conditions with nano-clusters of Sipassivated with Hydrogen at the surface. Previous works have undertaken in detail the geometrical effects in the nanoclusters. But a complete picture of the electrostatics and its effect on the energy states demand a complete study. Hence inour calculations we take another approach, devoid of the correction factors for cases with PBC, and produce an alternativeway to calculate the formation energy of the defects. We have described the formation and stability of the defects invarious charged states and provided with a detailed analysis of the properties pertaining to the nano-scale size. Finallymigration parameters are provided with respect to the charge states of the defects. Our results are also compared with thePBC calculations with critical discussions.

Made available in DSpace on 2014-10-09T12:48:40Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:57Z (GMT). No. of bitstreams: 1 09020.pdf: 3988111 bytes, checksum: 2604028ac5be423a7b85b745a959fb86 (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

O gás de Bose carregado foi estudado em duas e três dimensões, sendo que no caso bidimensional foram considerados dois tipos distintos de interação: l/r e ln(r). Aplicamos a esses sistemas o método do campo auto-consistente que leva em consideração a interação de curto alcance entre os bosons através de uma correção de campo local. Por meio de cálculos numéricos auto-consistentes determinamos o fator de estrutura S(&#8594k) em um amplo intervalo de densidades. A partir de S(&#8594k) obtivemos a função de correlação dos pares, a energia do estado fundamental que é essencialmente a energia de correlação, a pressão do gás e o espectro de excitações elementares. Calculamos ainda a densidade de blindagem induzida por uma impureza carregada fixada no gás. No limite de altas densidades nossos cálculos reproduzem os resultados da teoria de perturbação de Bogoliubov. Na região de densidades intermediárias em que os sistemas são fortemente correlacionados nossos resultados apresentam uma boa concordância com cálculos baseados na aproximação de HNC e no método de Monte Carlo. Nossos resultados são em várias situações confrontados com os de RPA demonstrando que o método que utilizamos é muito mais adequado para tratar o sistema. Os sistemas bidimensionais mostraram-se mais correlacionados que o tridimensional, sendo que o gás com interação l/r é mais correlacionado que o logarítmico a altas densidades, mas na região de densidades baixas essa situação se inverte. Finalmente calculamos as funções termodinâmicas dos sistemas bi e tridimensionais a temperaturas finitas próximas do zero absoluto baseando-nos nos espectros de excitação do gás a temperatura zero. / The two and three-dimensional charged Bose gas have been studied. In the bidimensional case two different types of interaction were considered: l/r and ln(r).We have applied to these systems the self-consistent-field method, which takes into account the short range correlations between the bosons through a local-field correction. By using self-consistent numerical calculations we determinate the structure factor S(&#8594k) in a wide range of densities. From S(&#8594k) we obtained the pair-correlation function, the ground-state energy, the pressure of the gas and the spectrum of elementary excitations. In addition we calculated the screening density induced by a fixed charged impurity. In the high-density limit our calculations reproduce the results given by Bogoliubov\'s perturbation theory. In the intermediate-density region, corresponding to the strongly coupled systems, our results are in very good agreement with calculations based on HNC approximation as well as Monte Carlo method. Our results are compared in several situations with RPA results showing that the self-consistent method is much more accurate. The two-dimensional systems showed to be more correlated than the three-dimensional one; the gas with interaction l/r is also more correlated than the logarithmic one at high densities, but it begins to be less correlated than this one in the low-density region. Finally we calculated the thermodynamic functions of the two and three-dimensional systems at finite temperatures near absolute zero, based upon the gas excitation spectra at zero temperature.