Les évolutions rapides du marché des composants électroniques font apparaître de nombreux challenges pour la conception et la fabrication de ces derniers. Lorsque ces éléments deviennent plus petits, leur comportement se complexifie à mesure que de nouveaux phénomènes, liés aux effets d'interférence, entrent en jeu. Comprendre ces derniers nécessite le développement d'outils théoriques avancés. Dans ce contexte cette thèse est consacrée au transport électronique quantique dans des systèmes multi-terminaux. Dans la première partie on développe un formalisme général, utilisant les fonctions de Green de Keldysh, pour le transport électronique quantique dans des systèmes multi-terminaux en présence de perturbations oscillantes. Nous sommes capable d'exprimer toute obervable AC en termes de fonctions de Green à l'équilibre et des self-énergies des contacts. Ceci fait de notre formalisme un outil pratique pour toute une variété de perturbations à fréquence finie. Dans la seconde partie on présente l'idée d'induction d'un fort couplage spin-orbite dans le graphène en déposant à sa surface un certain type d'atomes lourds. Le graphène devient alors un isolant topologique. Nous avons ensuite étudié l'évolution de la phase topologique avec un champ magnétique externe. Une transition entre la phase de Hall quantique et la phase de Hall quantique de spin a été identifiée dans le même système en variant seulement la position du niveau de Fermi. Nous avons montré qu'une hétérojonction entre ces deux phases donnait lieu à un nouveau type d'état chiral à l'interface. / Rapidly changing market of electronic devices sets up a lot of challenges for the manufacturing and design technologies. When electronic circuit elements get smaller, the device behavior becomes increasingly complicated as new physical phenomena due to quantum interference effects come into play. Understanding of the latter necessitates development of advanced theoretical tools. In this thesis we investigate quantum electron transport in multiterminal devices. In the first part making use of the Keldysh Green's functions we develop a general framework for electron quantum transport in multi-terminal systems in the presence of oscillating fields. We are able to express any AC observable in terms of stationary Green's functions and leads self-energies, which makes our formalism a practical numerical tool for a variety of possible finite-frequency perturbations. In the second part we investigate theoretically a proposal to induce strong spin-orbital coupling in graphene by functionalizing its surface with certain type of heavy adatoms. In this case graphene becomes a topological insulator. Then we investigate the evolution of this topological phase in external magnetic field. We were able to see a unique transition between quantum Hall and quantum spin Hall phases in the same system by only varying the position of the Fermi level. A heterojunction between these two phases was shown to give rise to a new type of a chiral state at the interface between the latter.

Les débris spatiaux sont devenus une menace considérable pour la viabilité des satellites opérationnels en orbite basse. Afin de pouvoir éviter des collisions accidentelles, des systèmes de surveillance de l'espace existent mais sont limités en performances de détection pour les objets de petite taille (diamètre inférieur à 10cm), ce qui pousse à l'étude de nouvelles solutions. Cette thèse a pour objectif d'appuyer la faisabilité d'un système radar au sol utilisant un champ de veille étroit pour le catalogage de petits débris en orbite basse. Un tel système fournirait en effet des observations dites « isolées », c'est-à-dire qu'une orbite n'est pas immédiatement déductible de chacune d'entre elles. Le grand nombre combinaisons nécessaires est alors prohibitif en termes de temps de calcul pour la résolution de ce problème de pistage. Nous proposons dans ces travaux une nouvelle méthode pour initialiser les pistes, c'est-à-dire associer des observations isolées avec une faible ambiguïté et en déduire des orbites précises. Les pistes ainsi obtenues sont combinées et filtrées grâce à un algorithme de pistage multicible que nous avons adapté aux particularités du problème. Avec un taux de couverture de plus de 80 % obtenu en temps réel sur 3 jours pour des scénarios de 500 à 800 objets en plus d'un fort taux de fausses alarmes, les performances de la méthode proposée tendent à prouver la faisabilité du système envisagé. Afin d'extrapoler les résultats obtenus à de plus fortes densités d'observations, nous proposons un modèle de complexité combinatoire calibré sur les performances de l'algorithme aux faibles densités. L'apport d'un second capteur identique est également étudié et met en évidence un point de compromis entre réactivité et complexité combinatoire, ce qui offre un degré de liberté supplémentaire dans la conception d'un tel système. / Space debris have become a significant threat to the viability of operational satellites in Low-Earth-Orbit. In order to avoid accidental collisions, space surveillance systems exist but their detection performance is limited for the small debris (less than 10cm). New solutions are then at study. This thesis aims at supporting the feasibility of a ground-based radar sensor with a narrow-fence type field of regard for the cataloging of the small space debris. Such a system would produce “isolated” observations, that is to say that an orbit is not directly available from each one of them. The large number of potential combinations is then computationally prohibitive for solving this tracking problem. In this work, we propose a new method for track initiation, i.e. associating isolated observations with little ambiguity and deduce accurate orbits. The obtained set of tracks are combined and filtered using an multitarget tracking algorithm that we have adapted to the peculiarities of the problem. With a coverage rate of more than 80% in real-time on 3 days for 500 to 800-objects scenarios in addition of a high false alarm rate, the performance of the proposed method supports the feasibility of the considered system. Aiming at extrapolating the obtained results to higher observation densities, we propose a combinatorial complexity model calibrated with the algorithm performance for low detection densities. The contribution of a second identical sensor is also assessed and reveals a possible trade-off between reactivity and combinatorial complexity, which offers an additional degree of freedom in the design of such a system.

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-06-22T12:43:46Z No. of bitstreams: 0 / Made available in DSpace on 2016-06-22T12:43:46Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Le Centre Galactique abrite en son cœur un objet compact de plusieurs millions de masses solaires. L'hypothèse faite à l'heure actuelle est que cet objet serait un trou noir supermassif décrit par la relativité générale. L'instrument de seconde génération du Very Large Telescope Interferometer, GRAVITY, va permettre d'apporter des réponses quant à la réelle nature de cet objet. Grâce à sa précision astrométrique de 10 microsecondes d'angle, il va pouvoir sonder l'espace-temps en champ fort via l'observation des étoiles et du gaz situés à proximité de l'objet central.Au cours de ma thèse j'ai mis au point un modèle permettant de simuler les observations d'orbites d'étoiles de GRAVITY, l'objectif étant d'extraire à l'aide de celui-ci les paramètres fondamentaux du candidat trou noir central ainsi que les effets relativistes. Pour cela, j'ai utilisé le code de tracé de rayons GYOTO développé à l'Observatoire de Paris. Ce code permet de calculer des trajectoires d'étoiles et de photons obtenues en présence d'un objet compact. Il est alors possible de simuler les positions apparentes d'étoiles en orbite autour du Centre Galactique en calculant leur image relativiste.J'ai d'abord validé le calcul des trajectoires des photons effectué dans GYOTO. Grâce à des tests effectués en déflexion faible et forte, j'ai pu démontrer que GYOTO était hautement satisfaisant pour simuler les observations GRAVITY. En effet, j'ai montré que l'erreur sur le calcul des géodésiques de genre lumière était inférieure à environ 10^-2 microseconde d'angle, et cela même pour de grandes distances d'intégration.Je me suis ensuite intéressée à l'étude d'une étoile appelée S2 qui a contribué à fortement contraindre la masse de l'objet central. Sa proximité au Centre Galactique fait d'elle une cible idéale pour sonder l'espace-temps en champ fort. En particulier, j'ai estimé quels étaient les temps minimaux d'observation nécessaires pour détecter des effets relativistes à l'aide de mesures astrométriques et spectroscopiques obtenues sur l'étoile S2. Pour cela, j'ai mis en place plusieurs modèles d'orbites prenant en compte chacun un certain nombre d'effets relativistes. Le modèle le plus précis est obtenu en relativité générale complète avec le code GYOTO. Néanmoins, puisque l'étoile S2 est suffisamment éloignée de l'objet compact, ce modèle néglige certains effets de lentilles gravitationnelles telles que les images secondaires et l'amplification des images primaires. Par ailleurs, je me suis également intéressée à la contraindre du moment cinétique du candidat trou noir central avec cette étoile. En particulier, j'ai déterminé, grâce au modèle le plus précis mis en place ici, qu'il était possible de contraindre la norme et la direction du moment cinétique avec une incertitude d'environ 0,1 et 20 degrés, respectivement, et cela en considérant des observations obtenues sur trois périodes de S2 et des précisions de 10 microsecondes d'angle et 10 km/s.En vue de la possible détection d'étoiles plus proches du Centre Galactique par GRAVITY, j'ai développé un modèle prenant en compte les effets de lentilles négligés dans le modèle précédent. Néanmoins, afin de minimiser le temps de calcul demandé par celui-ci, j'ai déterminé une zone de l'espace dans laquelle il était tout de même possible d'utiliser ce dernier.Enfin, j'ai étudié l'influence de corps du Système Solaire sur les mesures astrométriques de GRAVITY, c'est-à-dire sur la séparation angulaire entre deux sources du Centre Galactique. Cette étude a montré que ces mesures différentielles n'étaient déviées que de quelques microsecondes d'angle par la perturbation gravitationnelle engendrée par le Soleil. Cependant, celles-ci sont modifiées de plusieurs centaines de microsecondes d'angle par l'effet d'aberration induit par le mouvement de la Terre par rapport aux sources du Centre Galactique. Il sera donc nécessaire de prendre en compte cet effet lors de l'interprétation des données obtenues par GRAVITY. / Decades of studies have demonstrated the presence of a compact object of several million solar masses at the center of the Galaxy. Nowadays, the assumption is that this compact object is probably a supermassive black hole described by general relativity. The second generation instrument at the Very Large Telescope Interferometer, GRAVITY, is expected to better constrain the nature of this central object. By using its astrometric accuracy of about 10 microarcseconds, it will probe spacetime in strong gravitational fields by observing stars and gas located near the compact object.During my PhD I have developed a stellar-orbit model in order to interpret the future GRAVITY observations. By using this model it will be possible to extract the central black hole candidate parameters and relativistic effects. To implement the model, I used the ray-tracing code GYOTO developed at Observatoire de Paris. This code allows computing star and photon trajectories obtained in the vicinity of a compact object. It is thus possible to simulate apparent positions of stars orbiting the Galactic Center by computing relativistic images.My work started by validating the photon trajectories computed in GYOTO. By doing tests in both weak- and strong-deflection limits, I have shown that the GYOTO code is highly qualified to simulate GRAVITY observations. Indeed, the error made on the photon trajectories is inferior to 10^-2 microarcsecond, even when integrating over large distances.Then, I was interested in studying a star called S2 that contributed to importantly constrain the mass of the central object. This star is the second closest star to the Galactic Center and has an orbital period of about 16 years. Nowadays, we do not know whether closer-in stars will be discovered by GRAVITY. It is thus important to extract as much information as possible from this star. In particular, I have estimated the minimal observation times needed to detect relativistic effects by using astrometric and spectroscopic measurements of S2. To do so, I have developed different stellar-orbit models taking into account a certain number of relativistic effects. The more accurate model is obtained by using the ray-tracing code GYOTO and considering all relativistic effects. However, as the S2 star is sufficiently far from the compact object, this model neglects certain gravitational lensing effects such as the secondary images and the primary images amplification. Besides, I was also interested in the possibility of constraining the angular momentum of the central black hole candidate with the S2 star. In particular, I have shown that with a model which does not use ray-tracing, the norm and the direction of the angular momentum can be constrained with an uncertainty of about 0.1 and 20 degrees, respectively, by using observations obtained during three periods of S2 and with accuracies reaching 10 microarseconds and 10 km/s.Since closer-in stars could be detected by GRAVITY, I have developed a more accurate stellar-orbit model taking into account the lensing effects neglected in the previous model. However, in order to minimize the computing time required by this model, I determined a volume in which it is possible to neglect both the secondary images and the primary images amplification.Finally, I have studied the impact of different components of the Solar System on astrometric positions measured by GRAVITY. This study has shown that those measurements are deviated by an amount of a few microarcseconds by the gravitational perturbation generated by the Sun. However, those apparent positions are shifted by several hundred microarcseconds by the aberration effect due to the movement of the Earth with respect to the Galactic Center. It is thus necessary to take into account this effect in future interpretations of GRAVITY observations.

Soit (X, μ) un espace de probabilité standard et Γ un groupe dénombrable agissant sur X de manière à préserver la mesure de probabilité (p.m.p.). La partition de l’espace X en orbites induite par l’action de Γ est entièrement encodée par le groupe plein de l’action, constitué de l’ensemble des bijections boréliennes de l’espace qui agissent par permutation sur chaque orbite. Plus précisément, le théorème de reconstruction de H. Dye stipule que deux actions p.m.p. sont orbitalement équivalentes (i.e. induisent la même partition à une bijection p.m.p. près) si et seulement si leurs groupes pleins sont isomorphes.Le sujet de cette thèse est grandement motivé par ce théorème de reconstruction, puisqu’il s’agit de voir comment des invariants d’équivalence orbitale, qui portent donc sur la partition de l’espace en orbites, se traduisent en des propriétés algébriques ou topologiques du groupe plein associé.Le résultat majeur porte sur le rang topologique des groupes pleins, c’est-à-dire le nombre minimum d’éléments nécessaires pour engendrer un sous-groupe dense. Il se trouve être fortement relié a un invariant fondamental d’équivalence orbitale : le coût. Plus précisément, nous avons montré que le rang topologique était, dans le cas ergodique, égal à la partie entière du coût de l’action plus un. Le cas non ergodique a également été étudié, et on a obtenu des résultats complémentaires sur la généricité de l’ensemble des générateurs topologiques.Enfin, on a caractérisé les actions dont toutes les orbites sont infinies : ce sont exac- tement celles dont le groupe plein n’admet aucun morphisme non trivial à valeurs dans Z/2Z. / Let (X,μ) be a standard probability space and Γ a countable group acting on X in a measure preserving way. The partition of the space X into Γ-orbits is entirely encoded by the full group of the action, consisting of all the Borel bijections of X which act by permutation on every orbit. To be more precise, Dye’s reconstruction theorem states that two measure preserving actions are orbit equivalent (i.e. they induce the same partition up to a measure preserving bijection of (X, μ)) if and only if their full groups are isomorphic.The reconstruction theorem is the main motivation for this thesis, in which we try to understand how exactly orbit equivalence invariants of measure preserving actions translate into algebraic or topological properties of the associated full group.The main result deals with the topological rank of full groups, that is the minimal number of elements needed to generate a dense subgroup. It happens to be deeply linked to a fundamental invariant of orbit equivalence : the cost. To be more precise, we have shown that the topological rank is, in the ergodic case, equal to the integer part of the cost of the action plus one. The non-ergodic case was also treated, and we obtained some genericity results for the set of topological generators.We also obtained a characterization of the measure preserving actions having only infinite orbits : these are the ones whose full group has non nontrivial morphism into Z/2Z.

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-06-22T12:43:46Z No. of bitstreams: 0 / Made available in DSpace on 2016-06-22T12:43:46Z (GMT). No. of bitstreams: 0 / Neste trabalho foi estabelecido um sistema padrão primário para raios X de energias baixas (10 kV a 50 kV), utilizando uma câmara de ionização de ar livre de cilindros concêntricos da marca Victoreen (modelo 481-5) no Laboratório de Calibração de Instrumentos (LCI) do Instituto de Pesquisas Energéticas e Nucleares (IPEN/CNEN-SP). Para isso foi desenvolvido um novo protocolo de alinhamento da câmara de ionização no sistema de radiação e foi feita uma modificação no suporte dos micrômetros utilizados para o movimento dos cilindros internos. Os resultados obtidos nos testes de estabilidade e de caracterização ficaram dentro dos limites estabelecidos pelas normas IEC 61674 e IEC 60731. Foram determinados também os fatores de correção para atenuação de fótons no ar, transmissão e espalhamento no diafragma, espalhamento e fluorescência, e recombinação iônica. Esses valores foram comparados com os valores obtidos pelo laboratório padrão primário alemão,Physikalisch-Technische Bundesanstalt (PTB), mostrando boa concordância. Por último, foi determinado o valor absoluto da grandeza taxa de kerma no ar para as qualidades padronizadas de mamografia de feixes diretos WMV28 e WMV35 e feixes atenuados WMH28 e WMH35; os resultados são compatíveis, com diferença máxima de 3,8% com os valores obtidos utilizando o sistema padrão secundário do LCI. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Retrusão do terço médio da face é característica das disostoses sindrômicas. Falta de projeção e deficiência estrutural podem ser responsáveis pelo fenômeno, mas estes nunca foram avaliados adequadamente tridimensionalmente. O objetivo deste estudo é analisar a interface entre a base do crânio e a face, o volume dos ossos do terço médio da face e o volume e estrutura dos componentes da órbita, para fornecer uma compreensão da etiopatogenia da deficiência do terço médio da face e da dismorfologia ocular. Crianças com tomografia computadorizada, na ausência de qualquer intervenção cirúrgica, foram incluídas. As informações demográficas foram obtidas para três grupos (Apert, Crouzon, Controle). As tomografias computadorizadas foram digitalizadas e analisadas usando o software Materialise (Surgicase CMF (TM)). Dados craniométricas relativos ao terço médio da face, esfenóide e da órbita foram recolhido. Avaliação volumétrica do terço médio da face e órbita foi tabulada. A análise estatística foi realizada utilizando T-teste. Para a análise da retrusão do terço médio da face, trinta e seis tomografias foram incluídas (Controle n = 17, Crouzon / Apert n = 19). Todas as crianças estavam no período de dentição mista. A fossa anterior craniana é mais curta e mais larga em Crouzon/Apert versus Controles. Os ângulos da base do crânio medidos não foram estatisticamente diferentes entre os grupos. Crouzon/Apert mostrou ângulos mais obtusos entre as maiores asas do esfenóide, e mais obtusos entre as placas pterigóides. O ângulo formado pelo nasion-sela-fissura pterigomaxilar foi mais obtuso no grupo Crouzon e Apert comparado aos Controles. Não houve diferença volumétrica da maxila, zigoma e esfenóide comparando Crouzon/Apert aos Controles. Para a análise da dismorfologia orbital, trinta e uma tomografias computadorizadas foram incluídas (Controle n = 12, n = 9 Crouzon, Apert n = 10). A média de idade do grupo Apert foi de 5,31 ± 5 anos, Crouzon foi 5,77 ± 2,7 anos e Controle foi de 6,4 ± 3,6 anos (p = 0,6). O grupo de Crouzon era composto por 5 meninos e 4 meninas, o grupo de Apert continha 4 meninos e 6 meninas e o grupo Controle tinha 6 meninos e 6 meninas (p > 0,7). O comprimento da órbita óssea é 12% menor em Apert (p = 0,004) e 17% menor no grupo Crouzon quando comparado ao grupo Controle (p < 0,0001). A altura da órbita é 14% maior no grupo de Apert (p <0,0001) e 7% maior no grupo Crouzon quando comparados com os Controles (p = 0,03). A largura da órbita não é estatisticamente diferente no Crouzon ou grupo Apert quando comparados aos Controles (p = 0,1). O volume da órbita óssea é 21% menor nas crianças Apert (p = 0,0006) e 23% menor em Crouzon quando comparados aos Controles (p = 0,003). A projeção do globo é 99% maior em Apert e 119% maior em Crouzon quando comparados aos Controles (ambos p < 0,0001). Volume projetado fora da órbita é 179% maior em ambos Crouzon e Apert grupo quando comparados aos Controles (ambos p < 0,0001). O volume do globo ocular é 15% maior em Apert (p = 0,008) e 36% maior no grupo Crouzon quando comparado com o grupo Controle (p < 0,0001). O volume da porção do globo ocular dentro da órbita é 27% menor em Apert (p = 0,03). O grupo Crouzon não apresentou diferença estatística em relação ao grupo Controle para essa variável(p = 0,47). O volume da periórbita é 18% menor em Apert (p = 0,027) e 27% menor em Crouzon (p = 0,039), quando comparado com o grupo Controle (p = 0,001). O volume total dos tecidos moles (globo mais periórbita) em ambos os grupos Apert e Crouzon não foi estatisticamente diferente de Controles. Em suma, retrusão do terço médio da face em pacientes com Crouzon e Apert é associado com deformidade do esfenóide, que consiste na retrusão das placas pterigóides, causando alargamento e deformidade maxilar amplo, sugerindo crescimento diminuição inferior e anteriormente. Não há deficiência volumétrica dos ossos do terço médio da face nos grupos Crouzon e Apert comparado com Controles. Além disso, a dismorfologia ocular está relacionada com um encurtamento da órbita óssea associado com diminuição do volume orbital, aumento do volume do globo e diminuição do volume de periórbita. Apesar desses pacientes apresentarem volume normal do conteúdo da orbita, os conteúdos são alteradas, e da órbita óssea é mais curta e tem menos volume, o que não se encaixa na descrição clássica de exoftalmia ou exorbitismo / Midface retrusion is the hallmark of the syndromic dysotoses. Lack of forward projection and structural deficiency could be responsible, but neither has been adequately 3-dimensionally assessed. The purpose of this study is to examine cranial base interface and midface volume to provide understanding of the etiopathogenesis of midface deficiency. Children with CT scans in the absence of any surgical intervention were included. Demographic information was recorded for three groups (Apert, Crouzon, Control). CTs were digitized and manipulated using Materialise software (Surgicase CMF(TM)). Craniometric data relating to the midface, sphenoid and orbit was collected. Volumetric assessment of the midface and orbit were tabulated. Statistical analysis was performed using T-test. For the midface retrusion analysis, thirty-six CT scans were included (Control n=17, Crouzon/Apert n=19). All children were in the early mixed dentition. The anterior cranial fossa proved to be shorter and wider in Crouzon/Apert versus controls. The cranial base angles measured were not statistically different across the groups. Crouzon/Apert group showed angles more obtuse between the greater wings of the sphenoid, and more obtuse between the pterygoid plates. Nasion-sella-pterygomaxillary fissure angle was more obtuse in Crouzon/Apert. There was no volumetric difference in the maxilla, zygoma, and sphenoid comparing Crouzon/Apert to controls. For the orbital dysmorphology analysis, thirty-one CT scans were included (Control n=12, Crouzon n=9, Apert n=10). The mean age of the Apert group was 5.31 ± 5 years, Crouzon was 5.77 ± 2.7 years and Control was 6.4 ± 3.6 years (p=0.6). The Crouzon group consisted of 5 boys and 4 girls, the Apert group had 4 boys and 6 girls and the Control group had 6 boys and 6 girls (p > 0.7). The bony orbit length was 12% shorter in Apert (p=0.004) and 17% shorter in the Crouzon group when compared to controls (p < 0.0001). Orbital height was 14% higher in the Apert group (p < 0.0001) and 7% higher in the Crouzon group when compared to controls (p=0.03). Orbital width was not statistically different in either Crouzon or Apert group when compared to controls (p=0.1). The bony orbital volume was 21% smaller in the Apert children (p=0.0006) and 23% smaller in Crouzon when compared to controls (p=0.003). The globe projection was 99% larger in Apert and 119% larger in Crouzon groups when compared to controls (both p < 0.0001). Volume projected outside the orbit was increased over 179% in both Crouzon and Apert group when compared to Controls (both p < 0.0001). Globe volume was 15% larger in Apert (p=0.008) and 36% larger in Crouzon group when compared to Controls (p < 0.0001). Globe volume inside the orbit was 27% smaller in Apert (p=0.03) and the Crouzon group presented no statistical difference when compared to Controls (p=0.47). Periorbita volume was 18% less in Apert (p=0.027) and 27% less in Crouzon (p=0.039) group when compared to Controls (p=0.001). Total soft tissue volume (globe plus periorbita) in both Apert and Crouzon groups was not statistically different from Controls. In summary, midface retrusion in Crouzon and Apert is associated with altered sphenoid morphology consisting of widened and retruded pterygoid plates, with a flatter and wider maxilla, suggesting diminished growth inferiorly and anteriorly. There is no volumetric deficiency in Crouzon/Apert versus controls. Orbital dysmorphology is associated with altered sphenoid morphology, shortened bony orbit with diminished orbital volume, increased globe volume and decreased volume of periorbita. Despite normal volume of the overall orbital contents, the contents are altered, and the bony orbit is shorter and holds less volume, which does not fit the classic description of either exophthalmos or exorbitism

Submitted by Franciele Moreira (francielemoreyra@gmail.com) on 2017-12-27T12:48:10Z No. of bitstreams: 2 Tese - Pablo Vandré Jacob Furlan - 2017.pdf: 3620430 bytes, checksum: 7275b5a734d392f78e2829268555ec68 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2017-12-28T09:41:38Z (GMT) No. of bitstreams: 2 Tese - Pablo Vandré Jacob Furlan - 2017.pdf: 3620430 bytes, checksum: 7275b5a734d392f78e2829268555ec68 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-12-28T09:41:38Z (GMT). No. of bitstreams: 2 Tese - Pablo Vandré Jacob Furlan - 2017.pdf: 3620430 bytes, checksum: 7275b5a734d392f78e2829268555ec68 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-11-27 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In this work, we establish a new method to calculate the index of curves in a neighborhood of a boundary and we show that the index of a trajectory of a vector field which intersects the boundary at two points is 1/2. Using this method we extended the index definition for discontinuous vector fields with a regular transition manifold and we calculate the index for closed curves that intersect the variety of transition = f−1(0), where f is a differentiable function, and is the union of the regions tangency, sewing, sliding and escaping. We also show that the index for solutions of the discontinuous vector field that are −closed of type 1 and intersect the boundary at 2-point is equal to 1. We also establish an index theory for discontinuous vector fields when the transition manifold is not regular in a point and we show that the index is given by the calculation in its regular regions and add ±1/2, depending on the dynamics at the non-regular point. We apply the theory of index developed in this work and we give quotas for the indices of continuous vector field and for polynomial vector fields on two zones. Finally, we demonstrate a version of the Poincaré-Hopf Theorem for discontinuous vector fields in compact manifolds. / Neste trabalho estabelecemos um novo método para calcular o índice de curvas numa vizinhança do bordo e mostramos que o índice de uma trajetória de um campo vetorial a qual intersecta o bordo em dois pontos é 12 . Utilizando este método estendemos a definição do índice para campos vetoriais descontínuos com variedade de transição regular e calculamos o índice para curvas fechadas que intersectam a variedade de transição = f−1(0), onde f é uma função diferenciável, e é a união das regiões de tangência, de deslize, escape ou costura. Mostramos também que o índice para soluções do campo vetorial descontínuo que são −fechadas do tipo 1 e intersectam o bordo em 2 pontos é igual a 1. Estabelecemos também uma teoria do índice para campos vetoriais descontínuos quando a variedade de transição não é regular em um ponto e mostramos que o índice é dado pelo cálculo em suas regiões regulares e somar ±1 2 , a depender da dinâmica no ponto não regular. Aplicamos a teoria do índice desenvolvida neste trabalho e damos cotas para índices de campos vetoriais contínuos e para campos vetoriais polinomiais por partes. Finalmente, demostramos uma versão do Teorema de Poincaré-Hopf para campos vetoriais descontínuos em variedades compactas.

Les travaux théoriques réalisés dans le cadre de la thèse nous ont permis d’étudier en détail, sur la base de méthodes DFT, TD-DFT et ab initio les propriétés structurales, électroniques et spectroscopiques de deux classes de molécules, les composés carbonyles hydrures des métaux de transition de la 1re et 3me rangée (Mn, Re) et les complexes cyclométalants phenyl pyridine de l’iridium. L’accent a été mis plus particulièrement sur les effets de couplage spin-orbite sur les spectres d’absorption électronique de ces molécules. La quantification de ces effets a permis de montrer que seuls les spectres électroniques des complexes possédant un centre métallique de la 3me rangée des métaux de transition (Re, Ir) étaient modifiés par la correction spin-orbite en perturbation. Le caractère des états, MC ou MLCT, la proximité des états singulets et triplets sont les facteurs qui influencent fortement l’interaction spinorbite entre états excités. Un effet remarquable observé pour le complexe du rhenium est le décalage important du spectre d’absorption vers le rouge du à l’éclatement de l’état triplet le plus bas. Dans ce cas l’effet de couplage spinorbite doit être pris en compte pour obtenir un spectre plus proche de l’expérience. Un effet spin-orbite déjà observé sur d’autres systèmes est l’augmentation de de la densité d’états par éclatement des états triplets et la diminuation des force d’oscillateur qui se répartissent sur ces états pour aboutir à des spectres d’absorption électronique plus étendus et moins intenses. L’étude menée sur les complexes d’iridium pour lesquels les spectres expérimentaux sont particulièrement mal résolus, montre un accord remarquable entre ceux-ci est les spectres d’absorption théoriques TD-DFT. Cependant les effets de fonctionnelle peuvent jouer un rôle important sur la qualité des spectres. Pour ces molécules les calculs ab initio n’ont pu aboutir au-delà du niveau CASSCF. Les états excités sont très délocalisés dans ces molécules et il est difficile de décrire au même niveau d’approximation les différents types d’états MLCT, LLCT, MC, LMCT... Dans la plupart des cas les fonctionnelles B3LYP et PW91 donnent des résultats satisfaisants pour les complexes d’iridium. Les éclatements spin-orbite des états électroniques triplets peuvent être supérieurs à 1500 cm-1 dans les complexes possédant un centre métallique de la 3me rangée des métaux de transition. / The theoretical work of the thesis have allowed us to study in detail, on the basis of DFT methods, TD-DFT and ab initio structural, electronic and spectroscopic properties of two classes of molecules, carbonyl compounds, hydrides transition metals of the 1st and 3rd row (Mn, Re) and complex cyclométalants phenyl pyridine iridium. The focus was specifically on the effects of spin-orbit coupling on the electronic absorption spectra of these molecules. The quantification of these effects showed that only electronic spectra of the complexes with a metal center of the 3rd row transition metals (Re, Ir) were modified by correcting spin-orbit perturbation. The character states, MC or MLCT, the proximity of singlet and triplet states are the factors that strongly influence the spin-orbit interaction between excited states. A remarkable effect observed for the rhenium complex is the large shift of the absorption spectrum to the red of the bursting of the lowest triplet state. In this case the effect of spin-orbit coupling must be taken into account to get closer to the experience spectrum. A spin-orbit effects already observed on other systems is to increase the density of states per burst and triplet states as decreasing the oscillator strength which fall on these statements lead to absorption spectra electronic broader and less intense. The study of the iridium complexes for which experimental spectra are particularly poorly resolved, shows a remarkable agreement between them is the theoretical absorption spectra of TDDFT. However, the functional effects can play an important role in the quality of the spectra. For these molecules ab initio calculations do not reach beyond the CASSCF level. The excited states are delocalized in these molecules and it is difficult to describe the same level of approximation the different types of states MLCT, LLCT, MC, LMCT ... In mostcases the functional B3LYP and PW91 give satisfactory results for the iridium complexes. The spin-orbit explosions electronic triplet states may be higher than 1500 cm-1 in complex with metal center 3rd row transition metals.

La molécule SO2 est connue depuis longtemps dans la pour son spectre d'absorption compliqué résultant de forts couplages entre les états électroniques impliqués. Cette longue histoire a récemment été complétée par de nouvelles études spectroscopiques résolues en temps; la spectroscopie de photoémission (TRPES) et la génération d'harmoniques d'ordre élevé. De nouvelles questions ont ainsi émergées, concernant le rôle des différents états électroniques excités, les différents couplages et leur temps caractéristiques. Pour répondre à ces questions, nous avons considéré, dans un premier temps, l'état électronique fondamental et les deux premiers états singulets excités. Ceux-ci interagissent par l'intermédiaire de couplage non-adiabatic, conduisant à la complexité du spectre d'absorption. Nos résultats se sont avérés particulièrement précis, en particulier pour la description des bandes de Cléments, donnant lieu à leur première description et interprétation théorique. Le couplage spin-orbite et les états triplets ont été introduits dans la description du système et l'analyse de la dynamique a permis de comprendre les différents mécanismes de conversion intersystème. Trois résultats majeurs sont obtenus, (i) le rôle prédominant d'un état 3B2, (ii) la présence d'interférences quantiques lors du processus et (iii) une nouvelle interprétation de la bande dite " interdite ", émanant des état triplets. Les spectroscopies TRPES et HHG ont été utilisées pour sonder la dynamique moléculaire dans ces états. Grâce à des simulations ab-initio nous montrons que la méthode TRPES permet l'étude la dynamique pour tous les états alors que la HHG n'est sensible qu'à la conversion intersystème. / The SO2 molecule is long known in the literature for its complex UV absorption spectrum, which is caused by a variety of strong couplings between the electronic states involved. This long and rich history was augmented recently by new time-dependent spectroscopic methods, namely, Time-Resolved Photoelectron Spectroscopy (TRPES) and High-order Harmonic Generation (HHG). Additional open questions emerged immediately, e.g., what was the role of the different known electronic states, which were the relevant couplings and also the timescales of the different relevant processes.To resolve these issues theoretically, we start by considering the electronic ground state and the two lowest singlet excited states. The latter interact through non-adiabatic couplings leading to a complex photoabsorption spectrum. Our results were accurate, especially concerning the Clements bands, and provide a comprehensive description of the photoabsorption spectrum. When including the spin-orbit coupling, relevant for the weak long-wavelength absorption system, the three-states model turns into a 12 coupled-states system. Analysis of the different couplings gives insight into the different mechanisms of the intersystem crossing. Three main points are shown: (i) the preponderant role of a 3B2 state, (ii) the possibility of quantum interferences during the process and (iii) a new interpretation of the forbidden band.The TRPES and the HHG spectroscopies have been used to probe the time-dependent dynamics in all these states. With the aid of first-principles simulations we show that the TRPES method is sensitive to the dynamics in the manifold, while HHG is sensitive only to the intersystem crossing.