Noncovalent intermolecular interactions, widely found in molecular clusters and bio-molecules, play a key role in many important processes, such as phase changes, folding of proteins and molecular recognition. However, accurate calculation of interaction energies is a very difficult task because the interactions are normally very weak. Rigorous expressions for the electrostatic and polarization interaction energies between two molecules A and B, in term of the electronic densities, have been programmed: (see formula in document). Z is atomic charge, ρ0 is the electron density of the isolated molecule and Δρind is the electron density change of the molecule caused by polarization. With some approximations, procedures for electrostatic and polarization energy calculations were developed that involve numerical integration. Electrostatic and polarization energies for several bimolecular systems, some of which are hydrogen bonded, were calculated and the results were compared to other theoretical and experimental data. A second method for the computing of intermolecular interaction energies has also been developed. It involves a “supermolecule” calculation for the entire system, followed by a partitioning of the overall electric density into the two interacting components and then application of eq. (1) to find the interaction energy. In this approach, according to Feynman’s explanation to intermolecular interactions, all contributions are treated in a unified manner. The advantages of this method are that it avoids treating the supersystem and subsystems separately and no basis set superposition error (BSSE) correction is needed. Interaction energies for several hydrogen-bonded systems are calculated by this method. Compared with the result from experiment and high level ab initio calculation, the results are quite reliable.

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Orientador: Antonio Carlos Dias Ângelo / Resumo: Com o intuito de ampliar as fontes de energia por meio de dispositivos eletroquímicos, as células a combustível, o desenvolvimento de eletrocatalisadores que sejam eficientes para a oxidação de combustíveis orgânicos, torna-se primordial. Porém, sabe-se que a eletrocátalise das reações de oxidação de combustíveis orgânicos é certamente, influenciada pelas características geométricas e eletrônicas do material anódico. O presente trabalho estudou a influência do ambiente químico do sítio de adsorção de PtSn sobre a atividade eletroquímica, frente à reação de oxidação de álcoois (etanol, etilenoglicol e glicerol) em meio alcalino. As nanopartículas de PtSn/C foram preparadas sob a configuração de intermetálico ordenado, liga metálica e core-shell suportados em carbono de alta área superficial e caracterizadas por Difração de Raios X, Energia Dispersiva de Raios X, Microscopia Eletrônica de Transmissão e Espectroscopia de Absorção de Raios X. Além disso, os materiais foram avaliados frente à reação de oxidação dos combustíveis pelas técnicas de voltametria cíclica e cronoamperometria. A partir dos resultados foram confirmadas a obtenção das estruturas cristalinas desejadas, na estequiometria 1:1, sendo ainda possível, verificar que o core-shell formado apresentou a configuração Sn@PtSn. O tamanho encontrado para os diferentes eletrocatalisadores PtSn/C, intermetálico ordenado e liga, foram de aproximadamente 2 nm, enquanto que para o core-shell foi o dobro. O material Sn@PtSn apr... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The development of efficient and stable electrocatalysts for organic fuels oxidation reaction is a crucial issue to the application of environmentally friendly electrochemical devices as fuel cells. The electrocatalysis of organic fuels oxidation reactions is surely influenced by the geometric and electronic properties of the anode materials. This work presents the investigation on the influence of the chemical environment around the adsorption surface site in PtSn materials on the alcohols electrooxidation in alkaline medium. PtSn/C nanoparticles were synthesized in three distinct configurations: ordinary alloy, ordered intermetallic and core-shell structure anchored in high surface area carbon support. The obtained materials were characterized by X Ray Diffraction, X Ray Energy Dispersive, Transmission Electron Microscopy and X Ray Absorption Spectroscopy. Furthermore, the synthesized materials were studied as anode materials towards the electrochemical oxidation of organic fuels in alkaline medium by means of the cyclic voltammetry and chornoamperometry techniques. The analysis of the collected data confirmed the aimed geometric structures and the core-shell material Sn@PtSn (ordered), in an atomic ratio 1:1 Pt to Sn. Alloy and ordered intermetallic were found to have about 2 nm diameter of the particle size while Sn@PtSn core-shell was found the double of the size. Core-shell material presented the best performance as used as anode for the electrooxidation of the ethanol,... (Complete abstract click electronic access below) / Doutor

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L'étude et analyse dans l'espace réel de la densité électronique en mettant l'accent sur la liaison chimique, se déroule grâce à deux nouveaux techniques: les domaines de probabilité maximale (MPDs) et les orbitales naturelles adaptatives (NAdOs). D'un côté, la méthode MPD permet l'optimisation d'une région de l'espace qui maximise la probabilité de trouver un nombre entier et exact d'électrons. Donc, un domaine de probabilité maximale est la région qui maximise cette probabilité. De cette manière on engendre une division de l'espace en régions avec un sens physique claire. Avec la méthode MPD, une connexion entre la mécanique quantique et la structure de Lewis classique est établie. Ainsi, les domaines obtenus peuvent être associés aux liaisons, paires libres et coeurs. De l'autre côté, les NAdOs récupèrent et généralisent le concept des "domain averaged Fermi holes" (DAFHs), introduit par R. Ponec. Le développement de les orbitales naturelles adaptatives est basé sur des objets largement connues comme matrices densité réduites. L'utilisation conjointe de ces matrices, en particulier leurs parties qui ne peuvent pas être exprimées en termes d'ordre inférieur (densités cumulantes) avec les divisions de l'espace réel, permet de définir une hiérarchie d'indices de liaison chimique entre plusieurs fragments de l'espace. En plus, l'étude de la corrélation électronique à travers de les NAdOs est facilement accessible. / The study and analysis of the electronic density in real space, in particular the chemical bond, is carried out through two new techniques: maximum probability domains (MPDs) and natural adaptive orbitals (NAdOs).On one hand, the MPD method allows for an optimization of a spatial region in order to maximize the probability of finding a given and exact number of electrons. Thus, a maximum probability domain is a region of space maximizing such probability. In this way, it is possible to generate a space partitioning in several regions with a clear physical interpretation.With the MPD method, a connection between Quantum Mechanics and the classical Lewis’ picture may be established. MPD regions may be associated to bonds, lone pairs and cores.On the other hand, NAdOs recover and generalize the domain averaged Fermi hole (DAFH) concept,introduced by R. Ponec. The development of natural adaptive orbitals is based on widely known objects, called reduced density matrices. The combination of theses matrices, especially withthose parts that can not be expressed in terms of lower order (cumulant densities) with divisions of the real space, allows to define a hierarchy of chemical bond indices between several fragments of space. In addition, the study of electronic correlation through NAdOs is easily accesible.

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Le radar haute fréquence (HF : 3 MHz à 30 MHz) à mode hybride est une solution prometteuse pour assurer la surveillance permanente, jusqu'à 2000 km, de zones maritimes et terrestres. Ce mode est une combinaison des modes de fonctionnement des radars à onde de ciel et à ondes de surface. Lorsque l'intégration du signal est effectuée sur une cible lente, les instabilités ionosphériques affectent les images Doppler-distance. Pour rendre compte de ce phénomène en simulation, un module logiciel basé sur des modèles probabilistes du fouillis ionosphérique a été développé dans le but de simuler le comportement spatial et temporel de l'ionosphère dans le traitement radar. La version finale de ce module est basée sur le profil de densité électronique de Booker, aléatoirement modifié en espace à partir de la fonction de densité spectrale de puissance de Shkarofsky. L'aspect temporel a été aussi pris en compte dans le traitement radar en appliquant aux chemins de phase aléatoires ainsi générés un filtrage passe-bas en prenant en considération les variations du TEC (Contenu Électronique Total). La sensibilité des étalements en décalage Doppler et en distance aux paramètres de la densité spectrale de puissance et à la valeur de la fréquence de coupure du filtre passe-bas, a également été étudiée. Enfin, les images synthétisées ont été comparées aux images réelles obtenues à partir d'un radar HF situé dans le Sud de la France. / High-frequency (HF: 3 MHz to 30 MHz) hybrid mode radar is a promising solution for continuous monitoring of sea and land areas up to 2000 km. This mode is a combination of the modes of operation of the sky wave and surface wave radars. When signal processing is performed on a slow target, the ionospheric irregularities degrade the Doppler-distance images. To take this phenomenon into account in simulation, a software module based on probabilistic models of the ionospheric clutter has been developed with the aim of simulating the spatial and temporal behavior of the ionosphere in radar processing.The final version of this module is based on Booker's electron density profile, randomly modified in space from the Shkarofsky power spectral density function. The temporal aspect has also been taken into account in the radar processing by applying to the random phase paths thus generated a low-pass filtering taking into consideration the TEC (Total Electron Content) variation. The sensitivity of the Doppler shift and distance spreading to the parameters of the power spectral density and the cut-off frequency of the low-pass filter has also been studied. Finally, the synthesized images have been compared with the actual images obtained from an HF radar located in the South of France.

La théorie de la fonctionnelle de la densité (DFT) est une reformulation du problème quantique à N corps où l'énergie de l'état fondamental est exprimée sous la forme d'une fonction de la densité électronique. Dans l'approche de Kohn-Sham de la DFT, seule l'énergie dite d'échange-corrélation décrivant la partie non classique de l'interaction électron-électron nécessite d'être approchée comme une fonctionnelle de la densité. Dans le cadre de la thèse nous nous intéressons à une approximation visant à améliorer la précision et qui consiste à combiner de façon rigoureuse une approximation de type " fonctionnelle de la densité " avec un calcul explicite de type " fonction d'onde " à l'aide d'une décomposition de l'interaction électron-électron coulombienne. L'objectif est de disposer de méthodes améliorant la précision de la DFT actuelle avec un effort de calcul restant compétitif. Ce travail de thèse se décompose en trois études distinctes. Une première étude a consisté a étendre l'analyse de la convergence en base à la séparation de portée qui a permit de mettre en évidence une convergence exponentielle pour l'énergie de corrélation MP2 de longue portée. Dans un second temps nous nous sommes intéressés à une approximation auto-cohérente des fonctionnelles double-hybride utilisant la méthode des potentiels-effectifs-optimisés. Finalement la troisième étude propose une analyse de l'approximation adiabatique semi-locale du noyau d'échange et de corrélation de courte portée dans le cadre de la TDDFT avec séparation de portée dans son formalisme de réponse linéaire. / The theory of the functional of the density ( DFT) is a reformulation of the quantum problem in N body where the energy of the fundamental state is expressed under the shape of a function(office) of the electronic density. In the approach of Kohn-Sham of the DFT, only the said energy of exchange-correlation describing the not classic part(party) of the interaction electron-electron requires to be approached as a functional of the density. Within the framework of the thesis(theory) we are interested in an approximation to improve the precision and which consists in combining(organizing) in a rigorous way an approximation of type(chap) " functional of the density " with an explicit calculation of type(chap) " function(office) of wave " by means of a decomposition of the interaction electron-electron coulombienne. The objective is to have methods.

Submitted by Angela Maria de Oliveira (amolivei@uepg.br) on 2018-06-06T14:39:52Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Tech, Lohane.pdf: 2007649 bytes, checksum: ed3cf3b82a08ab6680c21d8be8071469 (MD5) / Made available in DSpace on 2018-06-06T14:39:52Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Tech, Lohane.pdf: 2007649 bytes, checksum: ed3cf3b82a08ab6680c21d8be8071469 (MD5) Previous issue date: 2018-02-26 / No presente trabalho foram analisadas 25 solos com diversas texturas, do estado do Paraná Brasil. Com o intuito de avaliar os parâmetros de interação da radiação com os solos, as amostras foram submetidas a análise semi-quantitativa por fluorescência de raios X (FRX) por dispersão de energia a fim de se obter os teores dos óxidos que compunham o solo. Dois tamanhos de partículas foram analisados, sendo eles: diâmetro de 45 μm, que é o padrão recomendado pelo fabricante do equipamento de FRX, e diâmetro de 2-1 mm. O teor dos óxidos, o coeficiente de atenuação de massa (⁄), a seção de choque molecular (), a seção de choque atômica (), a seção de choque eletrônica (), o número atômico efetivo () e a densidade eletrônica (), foram analisadas para os 25 solos para os dois tamanhos de partículas. Os resultados mostraram diferenças nos teores de óxidos dos solos entre um tamanho de agregado e outro, constatando mudanças nas porcentagens do óxidos de Al2O3, SiO2 e Fe2O3. Como consequência, houve alteração nos valores dos outros parâmetros analisados, as seções de choque, o número atômico efetivo e a densidade eletrônica. A seção de choque molecular e a densidade eletrônica mostrou dependência com o teor dos óxidos Al2O3 e SiO2, que são encontrados em maior porcentagem nos solos arenosos e nos solos com textura franco, para os dois tamanhos de agregados. A seção de choque atômica mostrou dependência com o número total de unidades de fórmulas moleculares presentes na composição do solo. Já os parâmetros restantes, coeficiente de atenuação de massa, seção de choque eletrônica e número atômico efetivo mostraram dependência com o óxido Fe2O3, que é encontrado em maior teor nas amostras com textura mais argilosa, para os dois tamanhos de agregados. Desta forma, observou-se dependência da textura e do tamanho de partículas ambas com a composição química elementar porque no primeiro caso, diferentes texturas são relacionadas a composição mineral e elementar nos diferentes solos e a segunda devido a conformação dos agregados nos dois conjuntos analisados. / This study analysed 25 soil samples from the State of Paraná, Brazil, with different textures. Aiming at evaluating the parameters of radiation interaction with the matter, the samples were submitted to the semi-quantitative analysis using energy dispersive X-ray (XRF) fluorescence, to obtain the content of oxides contained in the soil mixture. Two particle sizes were analysed, being: the 45 μm, wich is the standard required by the manufacturer of the X-ray fluorescence equipment, and the 2-1mm. The oxide content, mass attenuation coefficient (⁄), molecular cross section (), atomic cross section (), electronic cross section (), effective atomic number () and the electronic density () were analysed in the 25 samples and for the two particle sizes. The results showed differences in the soil oxide content between one aggregate size and the other, revealing changes in the percentage of the Al2O3, SiO2 and Fe2O3 oxides. With the difference observed, there was change in the values of other parameters under analysis, the cross sections, the effective atomic number and the electronic density. The molecular cross section and the effective electronic density showed dependence on the content of Al2O3 and SiO2 oxides, which were found in higher percentages in sandy and loam soils, for both aggregate sizes. The atomic cross section was seen to present dependence on the total number of molecular formula units contained in the soil composition. While the remaining parameters, mass attenuation coefficient, electronic cross sections and the effective atomic number showed dependence on the Fe2O3 oxide, whose higher contents were found in the clay textured samples, for both aggregate sizes. In this way, it was observed texture and size dependency, both with the elementary chemical composition because in the first case, different textures are related to elementary and mineral composition in the different soils and the second due to the conformation of the aggregated in both analyzed arrays.

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