Semiconductors absorb photos with energy greater than their band gap energy may induce electron-hole pairs. In semiconductor physics, increasing charge carrier improves the electric conductivity of semiconductor. The following methodology was taken to investigate the electric conductivity and the electron hole pairs affected performance of a dye sensitized solar cell. I applied 3 specific monochromatic light (365nm, 405nm and 437nm, respectively.) mixed with xenon light and normal xenon light separately illuminating on dye sensitized solar cells. At the assumption of the normalized photon to current conversion efficiency of solar cell illuminated by 437nm monochromatic light is 100%, the normalized photon to current conversion efficiency of the solar cell illuminated by 365nm monochromatic light was only 28%, however, that illuminated by 365nm monochromatic light mixed xenon light raised to 58%. The more intense mixed light produced more excited electrons than only 365nm monochromatic light. The holes generated by 365nm monochromatic light is easier to be captured by the electrons in the more intense mixed xenon light irradiation results in higher photon to current conversion efficiency. The output of photocurrent of the dye sensitized solar cell irradiated by 365nm ultraviolet light mixed xenon light was enhanced most significantly by 6.53% compared with that by normal xenon light irradiation.

Submitted by Maike Costa (maiksebas@gmail.com) on 2016-05-05T13:15:05Z No. of bitstreams: 1 arquivo total.pdf: 2975630 bytes, checksum: b2593e52b5f5a204312589a9ac8406b6 (MD5) / Made available in DSpace on 2016-05-05T13:15:05Z (GMT). No. of bitstreams: 1 arquivo total.pdf: 2975630 bytes, checksum: b2593e52b5f5a204312589a9ac8406b6 (MD5) Previous issue date: 2015-08-11 / The main objective of this study is to elucidate the cooperative effect caused by the formation of dimers of carboxylic acids, R-COOH, with R= -H, -CH3 e –OH, by the formation of two intermolecular hydrogen bonds. In order to complement the study of cooperative effect, changes in structural, electronic, vibrational and topological of the species involved due to the intermolecular interaction were analyzed. The quantum-computational methods employed were MP2 and DFT/B3LYP, both together with the base 6-311++G(d,p). The QTAIM and NBO methods were used to assess the topology of the electron density and the greatest contribution to the orbital intermolecular interaction, respectively. The results showed no significant differences between the two methods correlated, leading us to suggest the use of DFT / B3LYP method to study similar systems to the investigated here due to their lower computational requirements. The increment values in bond length of the proton donor group are enhanced in dimers R = -CH3 in both calculating levels. The values of intermolecular bond length in dimers R = -OH were the smallest observed in both MP2 and DFT / B3LYP methods. The carboxylic acids dimers with R = -CH3 were the most stabilized by the formation of hydrogen bonds. Regarded to the harmonic effect redshift stretching mode of proton donating groups to carboxylic acids, they were well pronounced and could be observed in all dimers. The new vibrational modes were also pronounced, emphasizing the stretch of the intermolecular bond method. From the studies employing QTAIM was possible to obtain the values of the electron density and the Laplacian of the electron density and evaluate these parameters at critical points in OH bond and intermolecular hydrogen bond, demonstrating the formation of hydrogen dimers. With studies employing the NBO method were evaluated pair of orbital occupancy variations not shared electrons of oxygen (proton donor) and the interaction energy of the orbital involved in intermolecular hydrogen bond. / O principal objetivo do presente trabalho é elucidar o efeito cooperativo ocasionado pela formação de dímeros de ácidos carboxílicos, R-COOH, com R= -H, -CH3 e –OH, pela formação de duas ligações de hidrogênio intermoleculares. Em complemento ao estudo do efeito cooperativo, mudanças nas propriedades estruturais, eletrônicas, vibracionais e topológicas das espécies envolvidas devido à interação intermolecular foram avaliadas. Os métodos quântico-computacionais empregados foram MP2 e DFT/B3LYP, ambos com o conjunto de base 6-311++G(d,p). Os métodos QTAIM e NBO foram empregados para avaliar a topologia da densidade eletrônica e os orbitais de maior contribuição para a interação intermolecular, respectivamente. Os resultados não mostraram diferenças significativas entre os dois métodos correlacionados empregados, nos levando a sugerir o emprego do método DFT/B3LYP para estudos de sistemas semelhantes aos investigados aqui, devido a menor demanda computacional desses. Os valores de incremento no comprimento de ligação do grupo doador de próton são mais acentuados nos dímeros com R= -CH3, em ambos os níveis de cálculo. Os valores de comprimento de ligação intermolecular nos dímeros com R= -OH são os menores observados, em ambos os métodos MP2 e DFT/B3LYP. Os dímeros dos ácidos carboxílicos com R= -CH3 foram os mais estabilizados pela formação das ligações de hidrogênio. Com respeito ao efeito redshift para o modo de estiramento harmônico dos grupos doadores de próton nos ácidos carboxílicos, estes foram bem acentuados, podendo ser observados em todos os dímeros. Foram ainda destacados os novos modos vibracionais, dando ênfase ao modo de estiramento da ligação intermolecular. Dos estudos empregando a QTAIM foi possível obter os valores da densidade eletrônica e do Laplaciano da densidade eletrônica e avaliar os valores desses parâmetros nos pontos críticos de ligação em O-H e na ligação de hidrogênio intermolecular, comprovando dessa forma a formação dos dímeros de hidrogênio. Com os estudos empregando o método NBO foram avaliadas as variações de ocupação do orbital do par de elétrons não compartilhado do oxigênio (doador de próton) e a energia de interação dos orbitais envolvidos na ligação de hidrogênio intermolecular.

Un axe de recherche particulièrement développé en chimie organométallique moderneconcerne la recherche d’agents chimiothérapeutiques alternatifs au cisplatine dans lestraitements contre le cancer. Dans ce domaine, plusieurs stratégies ont été développées depuisplusieurs dizaines d’années, parmi lesquelles nous pouvons citer la multinucléarité, consistanten la création d’édifices polymétalliques. L’objectif de la première partie de ce manuscrits’inscrit dans cette thématique, par la conception, l’obtention et l’étude des propriétésbiologiques de complexes hétérobimétalliques "early-late" (Ti-Ru, Ti-Au, Ti-Pt, Ti-Os, Ti-Rh, Ti-Ir) et "late-late" (Pt-Au). Un deuxième concept développé au cours de ce manuscritconsiste en la génération de nouvelles espèces théranostiques, par association au sein d’unmême complexe d’un fragment métallique à activité thérapeutique et d’une sonde fluorescentepermettant de visualiser le trajet et les cibles biologiques de ce premier. Dans ce cadre, deuxséries parallèles de complexes bimétalliques ont été synthétisées à partir des squelettesRu(bipy)32+ et Ru(bipy)2(dipy)2+ dont les propriétés de luminescence ont été largementdécrites et utilisées pour diverses applications. Ces composés bimétalliques ont pu fairel’objet de mesures sur les deux fronts, à savoir leur activité cytotoxique envers des lignéescellulaires cancéreuses et leurs propriétés photophysiques. / A research theme especially developed in modern organometallic chemistry deals withnew chemotherapeutic agents as alternatives to cisplatin for the treatments against cancer. Inthis area, several strategies have been considered since decades, among which one can citemultinuclearity, meaning the creation of polymetallic structures. The objective of the first partof this manuscript deals with this theme, with the design, synthesis and study of the biologicalproperties of "early-late" hetero-bimetallic complexes (Ti-Ru, Ti-Au, Ti-Pt, Ti-Os, Ti-Rh, Ti-Ir) and "late-late" (Pt-Au). A second concept developed in this thesis consists in thegeneration of new theranostic agents by association inside a same unit of a metal fragmentwith therapeutic activity, and of a fluorescent probe allowing the visualization of thebiological targets. In this field, two parallel series of bimetallic compounds have beenobtained based on the skeletons Ru(bipy)32+ and Ru(bipy)2(dipy)2+, whose luminescenceproperties have been widely described and used for several applications. These bimetalliccomplexes have been tested both for their cytotoxic activity against cancer cells lines andtheir photophysical properties.

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.

In der vorliegenden Arbeit wurden facettierte Nanolegierungen aus Gold und Palladium in der Größenordnung von 1 – 3 nm synthetisiert und charakterisiert. Die Synthese erfolgte in sphärischen Polyelektrolytbürsten (SPB), welche als Stabilisatorsystem fungierten. Die Strukturaufklärung erfolgte mittels hochauflösender Transmissionselektronenmikroskopie (HR-TEM) und Extended X-ray Absorption Fine Structure (EXAFS) Spektroskopie. Die Nanolegierungen wurden als Katalysatoren zur Reduktion von 4-Nitrophenol verwendet, wobei eine gesteigerte katalytische Aktivität, im Vergleich zu monometallischen Nanopartikeln, beobachtet wurde. Im HR-TEM wurden auf den Kanten der Metallkristalle Oberflächendefekte in Form von Stufen sichtbar, wobei eine Korrelation der Oberflächendefekte zur katalytischen Aktivität hergestellt wurde. Durch EXAFS-Analysen konnte nachgewiesen werden, dass eine Zusammensetzung von 75 mol-% Gold und 25 mol-% Palladium annähernd eine statistische Mischung aufweist. Mit steigendem Palladiumgehalt wurde eine leichte Anreicherung von Palladium an der Oberfläche der Partikel, sowie nichtmetallisches Palladium der Oxidationsstufe 2+ gefunden. Diese unterschiedliche Anordnung der Elemente für verschiedene Zusammensetzungen korreliert ebenfalls mit der katalytischen Aktivität. Ferner konnte eine Kontraktion des Netzebenenabstands für kleine Partikel mittels EXAFS nachgewiesen werden. Bei der Verwendung als Katalysatoren wurde eine zeitliche Reaktionsverzögerung festgestellt, welche auf die Oberflächenrestrukturierung der Metallnanopartikel hinweist. Zusätzlich konnte durch den Vergleich von SPB stabilisierten und stabilisatorfreien Goldnanopartikeln festgestellt werden, dass das SPB System die katalytische Aktivität nicht signifikant beeinträchtigt. / In this work facetted gold-palladium nanoalloys have been synthesized and characterized in the range of 1 – 3 nm. The spherical polyelectrolyte brushes (SPB) have been used during synthesis and for stabilization of the nanoparticles. Structural analyses have been done by high resolution transmission electron microscopy (HR-TEM) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The nanoalloys have been used as catalysts for the reaction of 4-nitrophenol, where an enhanced catalytic activity has been found compared to monometallic nanoparticles. Surface defects are visible by steps at the edge of the metallic crystal where a correlation of these surface defects and the catalytic activity has been found. By EXAFS spectroscopy an almost statistic mixture for a composition of 75 mol-% gold and 25 mol-% palladium, slight enrichment of palladium at the surface of the particle, and the presence of nonmetallic palladium with an oxidation number of 2+ has been observed. This different atomistic arrangement correlates with the catalytic activity as well. In addition, a contraction of the lattice parameter has been observed for small particles by EXAFS measurements. Using the nanoalloys as catalyst, a delay time for the reaction has been found which indicates a restructuring of the surface of the metal nanoparticles. By comparison of SPB stabilized and support-free gold nanoparticles no significant influence of the SPB system on the catalytic activity has been observed.