Orientador: Alberto Vazquez Saa / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Matemática, Estatística e Computação Científica / Made available in DSpace on 2018-08-20T03:54:09Z (GMT). No. of bitstreams: 1 Leal_Isabel_M.pdf: 984828 bytes, checksum: b0a33558ae8b5683163892248364a85b (MD5) Previous issue date: 2012 / Resumo: Nesta dissertação, fazemos uma revisão da literatura existente sobre vórtices em superfícies de curvatura constante, dando especial atenção às questões de integrabilidade e não integrabilidade. Além disso, apresentamos alguns resultados originais sobre o movimento de vórtices no plano hiperbólico que indicam um possível caminho para demonstrar a não integrabilidade de um sistema de quatro vórtices nessa superfície / Abstract: In this thesis, we review the existing literature on vortices on surfaces of constant curvature, giving special attention to the issues of integrability and non-integrability. In addition, we present some original results on the motion of vortices on the hyperbolic plane that indicate a possible way to demonstrate the non-integrability of a system of four vortices on that surface / Mestrado / Matematica / Mestre em Matemática

Orientador : Reginaldo Palazzo Junior / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Eletrica e de Computação / Made available in DSpace on 2018-08-01T22:04:54Z (GMT). No. of bitstreams: 1 Cavalcante_RodrigoGusmao_M.pdf: 2715046 bytes, checksum: c156a4685480bb31389a41287e7f804e (MD5) Previous issue date: 2002 / Mestrado

L’hélium, deuxième élément le plus abondant de l’univers après l’hydrogène (He/H ~ 1/10), n’a étonnamment jamais été observé sous une autre forme que celle d'atomes neutres ou ionisés dans le milieu interstellaire (MIS). L’hélium étant un gaz noble peu réactif, sa non-observation au sein d’un édifice moléculaire neutre est compréhensible mais cela est plus surprenant pour des espèces chargées positivement comme HeH+, [HeH3]+ ou CHe2+. La première partie de cette thèse a pour but de proposer des raisons chimiques à cette non-observation à l’aide de calculs de chimie quantique de haut niveau (CASPT2) couplés à des calculs d’association radiative. Au vu des résultats sur les mécanismes de destruction de HeH+, nous suggérons une zone du MIS où il serait envisageable de le détecter.La seconde partie de ce travail porte sur la possibilité de détection de variations temporelles des constantes fondamentales de la physique. En 1999, Webb et al., après analyse de la lumière issue de quasars lointains, affirmèrent que la constante de structure fine α pouvait avoir été plus faible par le passé. Aucune étude postérieure ne vint confirmer ce résultat. Il était donc important de déterminer théoriquement dans quelle mesure une telle variation affecterait le spectre électronique de petites molécules primordiales afin d’en évaluer la détectabilité par les instruments actuels. Nous avons pour cela mis au point un protocole ab initio qui évalue le décalage spectral induit par une variation d’α. Les calculs (niveau MRCI) montrent qu’une variation d’α de l’ordre de grandeur de ce que Webb et al. auraient détecté induirait des déplacements de raies non décelables par les télescopes actuels. / Despite Helium is the second most abundant element in the Universe (He/H ~ 1/10), it has never been observed in any other forms than that of an atom or an ion in the InterStellar Medium (ISM). Since He is a noble gas, its non-observation as part of neutral molecular systems is understandable, but it is quite surprising for positively charged species like HeH+, [HeH3]+ or CHe2+. The first part of this study aims at finding a chemical reason for such a non-observation and in particular for the three ions mentioned above. For that purpose, we have computed high level quality (CASPT2) energy hyper-surfaces and performed radiative association calculations. Finally, we are able to suggest a region of the ISM where the detection of HeH+ might be achieved.The second part of this work deals with the possibility that the fundamental constants could be time-dependent. In 1999, Webb et al., analyzing the quasar emissions, claimed that the fine structure constant α could have been smaller in the past, but this result has not been confirmed. Thus it seemed necessary to determine theoretically how much such a variation could affect the electronic spectra of some primordial molecules in order to determine whether such variations might be detectable or not with the current observational instrumentation. For that purpose, we have developed an ab initio protocol to evaluate the shift induced by a variation of α. High level quantum chemistry calculations (MRCI) show that a variation of α of the same order of magnitude than that reported by Webb et al., would induce shifts that are not detectable by the current telescopes.

Nous étudions les conséquences cosmologiques des anomalies de Weyl qui émergent de la renormalisation des opérateurs composés des champs, y compris la métrique. Ces anomalies sont codifiées dans les habillements gravitationnels des opérateurs dans une action effective quantique non-locale. Nous obtenons les équations d'évolution qui découlent de cette action et nous en cherchons des solutions cosmologiques. Par simplicité on se limite à la gravité d'Einstein-Hilbert avec une constante cosmologique. Nous initions par considérer la gravité en deux dimensions, où la théorie de Liouville nous permet de calculer l'habillement gravitationnel de la constant cosmologique. Avec une formulation invariante de Weyl, nous déterminons l'action effective et le tenseur de moment correspondant, qui deviennent non-locaux. Les anomalies de Weyl modifient le tenseur entier, pas seulement sa trace, et nous trouvons une énergie du vide qui décline avec le temps et un ralentissement de l'expansion de de Sitter à une de quasi-de Sitter. En quatre dimensions, motivés par nos résultats en deux dimensions, nous paramétrisons l'action effective avec des habillements gravitationnels générales. Dans le cas des dimensions anormales constantes, le tenseur de moment conduit encore à une énergie du vide qui décline et une expansion de quasi-de Sitter de roulement lent. Les dimensions anormales sont calculables à priori dans une certaine théorie microscopique avec des méthodes semi-classiques. Même si les dimensions anormales sont petites en théorie des perturbations, leur contribution intégrée le long des plusieurs e-folds pourrait mener à des effets significatifs pendant la cosmologie primordiale. / In this thesis we study the cosmological consequences of Weyl anomalies arising from the renormalization of composite operators of the fundamental fields, including the metric. These anomalies are encoded in the gravitational dressings of the operators in a non-local quantum effective action. We derive the evolution equations that follow from this action and look for cosmological solutions. For simplicity, we focus on Einstein-Hilbert gravity with a cosmological constant. We first consider two-dimensional gravity, where Liouville theory allows us to compute the gravitational dressing of the cosmological constant operator. Using a Weyl-invariant formulation, we determine the gauge-invariant but non-local effective action, and compute the corresponding non-local momentum tensor. The Weyl anomalies modify the full quantum momentum tensor, not only its trace, and hence lead to interesting effects in the cosmological dynamics. In particular, we find a decaying vacuum energy and a slow-down of the de Sitter expansion. In four dimensions, motivated by our results in two dimensions, we parametrize the effective action with scale-dependent gravitational dressings, and compute the general evolution equations. In the approximation of constant anomalous dimensions, the momentum tensor leads to a decaying vacuum energy and a slow-roll quasi-de Sitter expansion, just as in two dimensions. The anomalous dimensions are in principle computable in a given microscopic theory using semiclassical methods. Even though the anomalous dimensions are small in perturbation theory, their integrated effect over several e-folds could add up to something significant during primordial cosmology.

L’objectif de cette thèse était d’étudier suivant deux approches la dégradation des polydiméthylsiloxanes. L’approche expérimentale a permis d’étudier les mécanismes de rupture de chaîne et les phénomènes de réticulation du polymère lorsque ce dernier est soumis à des conditions de thermo-oxydation ou de photo-oxydation comparables à celles du vieillissement naturel. La seconde partie propose de modéliser les résultats expérimentaux par un modèle cinétique issu des calculs ab initio. L’exploitation in vitro de la dégradation du polymère a permis de mettre en évidence la formation de monoxyde de carbone et de dioxyde de carbone, ceux-ci jouant le rôle de révélateurs de rupture de liaison Si-CH3. Toutefois le comportement des PDMS sur des temps de dégradation plus importants montre clairement la formation d’oligomères cycliques par dépolymérisation de la chaîne macromoléculaire. Parallèlement la photo-oxydation de ces polymères entraîne la formation de réseaux multidimensionnels qui traduisent des phénomènes de réticulation avec formation d’acide formique. Cette étude a permis de montrer que la dégradation des PDMS, dans des conditions de vieillissement naturel, procède de deux mécanismes antagonistes, l’un favorisant la réticulation du polymère et le second sa dépolymérisation. La seconde partie de ce travail s’intéresse aux mécanismes de formation des oligomères cycliques observés expérimentalement lors de la dégradation des PDMS. Des réponses précises ont pu être amenées grâce à une analyse théorique détaillée de la constante de cyclisation de ces polymères. Cette étude nous a permis de montrer le rôle essentiel du couplage des rotateurs internes dans le calcul de la constante de cyclisation en fonction de la taille des cycles obtenus. Nos résultats théoriques reproduisent avec exactitude l’évolution de la courbe de la constante de cyclisation observée expérimentalement pour des cycles de taille inférieure à 20 motifs, à savoir un maximum global pour des cycles constitués de quatre motifs et un minimum local pour des cycles à dix motifs. Nous avons démontré que l’origine de l’évolution oscillatoire de la constante de cyclisation traduisait le changement de caractère de certains degrés de liberté entre des vibrations pures (petits cycles) et des rotations empêchées (cycles de plus grande taille). / This work aimed at investigating the degradation pathways of polydimethylsiloxanes through two perspectives. The experimental approach studied bond scission and cross-linking degradation mechanisms when the polymer is exposed to thermo- or photo-oxidation conditions that are similar to that of the natural ageing. In the second part, the experimental results are modeled with a theoretical kinetic model, based on ab initio calculations.The in-vitro study of the polymer degradation showed that formation of carbon monoxide and carbon dioxide were by-products of Si-CH3 bond scissions. However, the degradation of PDMS for longer time periods showed clearly the formation of cyclic oligomers obtained through depolymerization of the macromolecule. In parallel, the photo-oxidation conditions yielded the formation of multidimensional cross-linked networks and formation of formic acid. This study showed that in the natural conditions, the degradation of PDMS proceeded through two opposite mechanisms, one that produced cross-linked networks while in the other, depolymerization was favored. In the second part, we investigated the mechanisms of the formation of cyclic oligomers that were observed experimentally during the degradation of the polymer. A detailed theoretical model was built in order to reproduce the dependence of the experimental cyclization constant with cycle size. This study showed the key role of the coupling in the treatment of hindered rotors. Our theoretical results reproduced accurately the oscillatory behavior of the cyclization constant for cycle sizes less than 20-mers, namely the global maximum for the 4-unit cyclic oligomers, and the local minimum for cycle sizes of 10 units. We have also shown that the origin of the oscillatory behavior of the cyclization constant revealed that some degrees of freedom underwent specific character transformation between a pure vibration for small cycles and hindered rotation for larger ring sizes.

Orientador: Claudio Francisco Tormena / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-14T14:30:02Z (GMT). No. of bitstreams: 1 Santos_FranciscoPaulodos_D.pdf: 15350887 bytes, checksum: 67e192401b6f5d14d6d2568ea89baff1 (MD5) Previous issue date: 2009 / Resumo: A tese está estruturada da seguinte forma. Primeiro uma parte introdutória relatando o efeito das interações hiperconjugativas na constante de acoplamento JXY e uma discussao sobre a as principais metodologias para a determinação de constantes de acoplamento a JXY a longa distância. Nesta primeira parte o leitor e introduzido nos tópicos básicos desta tese. Seguindo o corpo da tese contém os resultados e discussão. Primeiro apresentamos as metodologias para determinação das constantes de acoplamento JCH com enfase para o experimento de HSQMBC e para os experimentos de estado de spin seletivo (HSQC-TOCSY-IPAP e HSQC-TOCSY-IPAP-triplamente editado). Posteriormente apresentamos uma racionalização para a diferença entre os acoplamentos JC4H1 e JC1H4 da 3-exo-2-norbornanona (X = Cl, Br, SCH3). Mostramos que ambos os acoplamentos JC1H e JC4H14 deveriam apresentar uma redução de seus valores, devido as interações hiperconjugativas sC1-C7p*C2=O e sC1-C7s*C2=O que retiram densidade eletrônica do caminho a três ligações.Entretanto, observamos que a existência de uma terceira interação sC3-C4s*C2-O recupera parte da densidade eletrônica do acoplamento JC4H1 através de um caminho adicional a quatro ligações fazendo com que o acoplamento JC4H1 seja maior. Este caminho a quatro ligações é similar ao observado em sistemas homoalílicos, sendo que a principal diferença é a natureza do orbital antiligante, que para nossos sistemas é um orbital do tipo s, enquanto para os homoalílicos é do tipo p. / Abstract: In the introduction, it is presented a discussion about the effect of hyperconjugative interactions on coupling constants and a discussion about some methodologies for the measurement of long range heteronuclear coupling constants. JCH, with special emphasis on HSQMBC experiments and the spin state selective methodologies (HSQC-TOCSY-IPAP and HSQC-TOCSY-IPAP-triple editing). After that, a rationalization of the known difference between the JC4H1 and JC1H4 coupling constant transmitted mainly through the 7-bridge in norbornanone is presented in terms of the effects of hyperconjugative interactions involving the carbonyl group. Theoretical and experimental JC4H couplings were carried out for 3-endo- and 3-exo-X-2-norbornanone (X = Cl, Br, SCH3) and for exo- and endo-2- norbornanes derivatives. The hyperconjugative interactions were studied with the Natural Bond Orbital (NBO) analyses. It was observed that interactions involving the carbonyl p*C2=O and s*C2=O antibonding orbitals produce a decrease of threebond contribution for o both JC4H1 and JC1H4 couplings.However, the latter antibonding orbital also undergoes a strong sC3-C4s*C2=O interaction, which defines an additional coupling pathway for JC4H1 but not for JC1H4 .This pathway is similar to that known for homoallylic couplings, being the only difference the nature of the intermediate antibonding orbital, i.e. for JC4H1 is of s-type, while in homoallylic couplings is of p-type. / Doutorado / Quimica Organica / Doutor em Ciências

Tomando a América Latina como área de estudio, en el presente trabajo se analizan los patrones de cambio institucional en un entorno institucional débil; es decir, en un contexto en el que las reglas de juego son inestables y/o aplicadas de manera desigual. Tomando como punto de partida el trabajo de Kathleen Thelen y sus colaboradores, sostenemos que el cambio institucional en América Latina rara vez se aproxima a los modelos del llamado equilibrio interrumpido y a los modos de cambio gradual. En su lugar, el cambio usualmente toma la forma de un remplazo o sustitución constante, en el cual las instituciones repetidamente atraviesan una transformación abrupta y total. En la primera parte, el artículo examina las condiciones que conllevan a patrones de remplazo constante; posteriormente, el artículo presta atención a la  relación entre el enforcement y el cambio institucional. Se sostiene que el non- enforcement puede ser una fuente importante de estabilidad institucional, y que el aumento o reducción del enforcement puede, en sí mismo, ser un modo importante de cambio institucional.

The article solves the riddle of the fine structure constants with the help of the Planck units, derives its physical meaning and shows the consequences.:Abstract Introduction What is the fine structure constant? Consequence from the existence of the fine structure constant.

Cette thèse s'inscrit dans l'étude des sous-variétés minimales et à courbure moyenne constante et de l'influence de la géométrie de la variété ambiante sur les solutions de ce problème.Dans le premier chapitre, en suivant les idées de F. Almgren, on propose une généralisation de la notion d'hypersurface de courbure moyenne constante à toutes codimensions. En dimension n-k on définie les sous-variétés à courbure moyenne constante comme les points critiques de la fonctionnelle de k-volume des bords des variétés minimales de dimension k+1. On prouve l'existence dans une variété riemannienne compacte de dimension n de sous-variétés à courbure moyenne constante de codimension n-k pour tout k < n qui sont des perturbations des sphères géodésiques de petit volume.Dans le deuxième chapitre, on s'intéresse aux surfaces minimales à bords libres dans la boule unité de l'espace euclidien de dimension 3, c'est-à-dire aux surfaces minimales plongées dans la boule unité dont le bord rencontre la sphère unité orthogonalement. On démontre l'existence de deux famille géométriquement distinctes de telles surfaces qui sont indexées par un entier n assez grand, qui représente le nombre de composantes connexes du bord de ces surfaces. Nous donnons en particulier une deuxième preuve d'un résultat de A. Fraser et R. Schoen concernant l'existence de telles surfaces.Un des résultats fondamentaux de la théorie des surfaces à courbure moyenne constante est le théorème de Hopf qui affirme que les seules sphères topologiques à courbure moyenne constante dans l'espace euclidien de dimension 3 sont les sphères rondes. Dans le troisième chapitre, on propose une construction dans une variété riemannienne de dimension 3 d'une famille de sphères topologiques à courbure moyenne constante qui ne sont pas convexes et dont la courbure moyenne est très grande. / The subject of this thesis is the study of minimal and constant mean curvature submanifolds and of the influence of the geometry of the ambient manifold on the solutions of this problem.In the first chapter, following the ideas of F. Almgren, we propose a generalization of the notion of hypersurface with constant mean curvature to all codimensions. In codimension n-k we define constant mean curvature submanifolds as the critical points of the functional of the k - dimensional volume of the boundaries of k+1 - dimensional minimal submanifolds. We prove the existence in compact n-dimensional manifolds of n-k codimensional submanifolds with constant mean curvature for all k<n which are perturbations of geodesic spheres of small volume.In the second chapter, we consider free boundary minimal surfaces in the unit ball of the three dimensional Euclidean space, i.e. minimal surfaces embedded in the unit ball and which meet the unit sphere orthogonally. We prove the existence of two geometrically distinct families of such surfaces parametrized by an integer n large enough, which represents the number of the boundary components. In particular, we give an independent proof of the result of A. Fraser and R. Schoen concerning the existence of such surfaces.One of the fundamental results of the theory of constant mean curvature surfaces is the Hopf's theorem which asserts that the only topological spheres with constant mean curvature in the Euclidean 3-space are round spheres. In the third chapter, we propose a construction in a three dimensional Riemannian manifold of a family of nonconvex topological spheres with large constant mean curvature.

A formação dos monoalquil carbonatos (MACs) em meio aquoso - produzidos pela reação de um álcool e bicarbonato foi investigada por eletroforese capilar (CE) com detecção condutométrica sem contato (C4D). Foram estudadas ao todo 29 substâncias, das quais 25 apresentaram formação de adutos aniônicos monocarregados e 2 delas, adutos aniônicos com dupla carga. A eletroforese capilar proporcionou a obtenção de medidas de propriedades físico-químicas. Através do tempo de migração, foram obtidos mobilidade, coeficiente de difusão e raio iônico hidratado. Para os n-álcoois de 1 a 5 átomos de carbono, os adutos apresentaram raio iônico hidratado entre 216 pm e 310 pm. Os MACs têm raio iônico proporcional ao do álcool gerador, sendo sistematicamente maiores devidos à anexação do grupo carbonato. Quando comparado a ácidos carboxílicos de cadeia carbônica similar, os MACs possuem menor raio iônico hidratado. A obtenção dos valores da cinética de formação e hidrólise foi possível pela utilização de dupla detecção condutométrica, a qual permitia determinar a concentração do MAC em dois momentos diferentes ao longo da coluna. Devido à impossibilidade de uma calibração direta - já que os sais de MACs se decompõem em água - foi introduzida uma nova técnica de calibração que dispensa o uso de uma solução padrão do analito em favor de uma com espécie de mobilidade similar. As constantes cinética e termodinâmica foram comparadas com aquelas disponíveis na literatura, mostrando boa concordância, como no caso dos adutos para o metanol e etanol (a 25 ºC em meio aquoso), cujos valores da constante termodinâmica sugeridos pela literatura são de 3,57 e 1,80, respectivamente, enquanto que os valores calculados em nosso trabalho são de 4,2 e 2,3, a 25ºC. De forma similar ao ácido carbônico, os ácidos alquilcarbônicos (ACAs) se decompõem em meio ácido, o que dificulta a determinação da verdadeira constante de dissociação. Ainda assim, estudos em pH de 3 a 9, permitiram estimar os valores de pKa dos ácidos derivados de metanol, etanol e propanol como estando algo abaixo de 4, o que estaria em acordo com o valor de 3,6 do ácido carbônico. A formação de MACs também foi observada para dióis, como o etileno glicol e polióis, como o glicerol e manitol. Foi também possível observar, por eletroforese capilar, a formação de adutos aniônicos monovalentes para açúcares, tais como a sacarose, glicose e frutose. Por fim, a pesquisa revelou a possibilidade da formação de adutos com dupla carga - os bis(carbonatos) - para alguns dióis: o 1,4-butanodiol e o 1,6-hexanodiol. Esta é a primeira vez que estas espécies foram observadas. Estes resultados sugerem a formação de adutos aniônicos para várias outras classes de compostos, as quais possuam a hidroxila na cadeia carbônica. Embora, em meio predominantemente aquoso, estas espécies não estejam em alta concentração, trata-se de um novo conjunto de espécies a serem consideradas quando se trabalha em condições propícias. / The formation of monoalkyl carbonates (MACs) in aqueous medium - resulting from an alcohol and bicarbonate - was investigated by using capillary electrophoresis with capacitively coupled contactless conductivity detection (C4D). Twenty nine substances were studied. The mono-charged anionic adducts were observed for 25 of them and double-charged species were observed for 2. Capillary electrophoresis allowed us to obtain some physical-chemical properties. The migration time was used to calculate the ionic mobility, coefficient of diffusion, and hydrodynamic radius. The radii ranged from 216 to 310 pm for the adducts formed from the n-alcohols of 1 to 5 carbon atoms, respectively. The MACs have radii proportional to the size of the alcohol, being systematically greater because of the attached carbonate group. When compared to carboxylic acids of similar carbonic chain, the MACs have smaller radii. The calculation of the kinetic constants was possible due to the double C4D detection, which allows quantitation of the MAC at two different moments along the capillary. Due to the decomposition of the MAC salt in water, a direct quantitation was not possible. Thus an indirect calibration approach was introduced, where the analyte is substituted by a stable species of similar mobility. Good agreement was obtained between the kinetic and thermodynamic constants obtained by this method and those ones available in literature. For instance, the methanol and ethanol adducts were 4.2 and 2.3 (at 25 ºC), respectively, while the literature\'s values are 3.57 and 1.80. Similarly to carbonic acid, the alkyl carbonic acids (ACAs) decompose in acid medium, which impairs the determination of the dissociation constant. Even so, studies from pH between 3 and 9 allowed us to estimate that the pKa values of the adducts for methanol, ethanol, and propanol are somewhat below 4, which is in agreement with the value 3.6 for the carbonic acid. MACs were also observed for diols and polyols as well as for sugars. Finally, double-charged species bis(carbonates) were formed with 1,4-butanediol and 1,6-hexanediol. This is the first time that these species are reported. Although the concentrations of these species are not high in an aqueous medium, they form a new set of substance to be considered in aqueous solution when the conditions are favorable.