Le présent travail concerne l’avancement des approximations de l’énergie d’échange- corrélation (XC) de la théorie fonctionnelle de la densité (DFT) de Kohn-Sham (KS) basée sur l’approche du facteur de corrélation (CF). Le travail est organisé en trois parties où chaque partie est construite sur des modèles et méthodes précédents. La première partie du travail introduit une nouvelle condition physique à travers la déri- vation du développement en série du quatrième ordre du trou d’échange exact. La dérivation détaillée des formules requises est suivie d’une analyse approfondie qui montre que le terme de quatrième ordre peut ajouter des informations supplémentaires importantes qui sont par- ticulièrement pertinentes pour les molécules par rapport aux atomes. Sur la base de ces résultats, nous explorons les fonctionnelles d’échange qui dépendent du terme de quatrième ordre de l’expansion du trou d’échange. Nous constatons également que les développements d’ensembles de base gaussiens, fréquemment utilisés dans les codes de structure électronique, donnent des représentations insatisfaisantes du terme de quatrième ordre. La deuxième partie de ce travail porte sur la mise en œuvre de nouvelles versions du modèle CF initial [J. P. Precechtelova, H. Bahmann, M. Kaupp et M. Ernzerhof, J. Chem. Phys. 143, 144102 (2015)] dans lequel le trou XC est approximé. Étant donné que diverses contraintes satisfaites par le trou XC sont connues, des approximations peuvent être conçues pour éviter en grande partie des ajustements empiriques. Dans l’approche CF, le trou XC est écrit comme le produit d’un trou d’échange multiplié par un facteur de corrélation. Une contrainte importante satisfaite par le modèle CF est qu’il reproduit correctement l’éner- gie d’échange exacte dans la limite de haute densité. Ceci est réalisé en utilisant l’énergie d’échange exacte par particule comme variable d’entrée, c’est-à-dire que le modèle CF s’ap- puie sur l’échange exact. Des variations du modèle CF initial sont proposées qui assurent que la réponse exacte est obtenue dans la limite homogène. De plus, nous appliquons une correction à la profondeur du trou XC qui est conçue pour capturer une forte corrélation. Les fonctions d’échange-corrélation qui s’appuient sur un échange exact, comme les hybrides, échouent souvent pour les systèmes qui présentent une corrélation électronique importante. Malgré ce fait et malgré la réduction de l’empirisme à un seul paramètre dans CF, des énergies d’atomisation précises sont obtenues pour des composés de métaux de transition fortement corrélés. Le modèle CF montre des résultats significativement supérieurs aux fonctionnelles populaires comme Perdew-Burke-Ernzerhof (PBE), PBE hybride et Tao-Perdew-Staroverov- Scuseria (TPSS). La troisième partie du travail s’appuie sur les modèles CF précédents développés dans notre groupe et aborde l’erreur d’auto-interaction à un électron et introduit un modèle de facteur de corrélation modifié où f C (r, u) est construit tel qu’il se réduit à un dans les régions à un électron d’un système à plusieurs électrons. Ce trou XC avec une correction d’auto- interaction est ensuite utilisé pour générer la fonctionnelle énergie XC correspondante. La nouvelle fonctionnelle est évaluée en l’implémentant dans un programme KS et en calculant diverses propriétés moléculaires. Nous constatons que, dans l’ensemble, une amélioration significative est obtenue par rapport aux versions précédentes du modèle de facteur de cor- rélation. / The present work is concerned with the advancement of approximations to the exchangecorrelation (XC) energy of Kohn-Sham (KS) density functional theory (DFT) based on the correlation factor (CF) approach. The work is organized in three parts where each part is build upon previous models and methods. The first part of the work introduces a new physical condition through the derivation of the fourth-order series expansion of the exact exchange hole. The detailed derivation of the required formulas is followed by a thorough analysis that shows that the fourth-order term can add important additional information that is particularly relevant for molecules compared to atoms. Drawing on these findings, we explore exchange functionals that depend on the fourth-order term of the expansion of the exchange hole. We also find that Gaussian basis set expansions, frequently used in electronic structure codes, result in unsatisfactory representations of the fourth-order term. The second part of this work addresses the implementation of new versions of the initial CF model [J. P. Precechtelova, H. Bahmann, M. Kaupp, and M. Ernzerhof, J. Chem. Phys. 143, 144102 (2015)] in which the XC hole is approximated. Since various constraints satisfied by the XC hole are known, approximations to it can be designed which largely avoid empirical adjustments. In the CF approach, the XC-hole is written as a product of an exchange hole times a correlation factor. An important constraint satisfied by the CF model is that it correctly reproduces the exact exchange energy in the high density limit. This is achieved by employing the exact exchange-energy per particle as an input variable, i.e., the CF model builds on exact exchange. Variations of the initial CF model are proposed which ensure that the exact answer is obtained in the homogeneous limit. Furthermore, we apply a correction to the depth of the XC-hole that is designed to capture strong correlation. Exchangecorrelation functionals that build on exact exchange, such as hybrids, often fail for systems that exhibit sizeable electron correlation. Despite this fact and despite the reduction of empiricism to a single parameter within CF, accurate atomization energies are obtained for strongly-correlated transition metal compounds. The CF model significantly improves upon widely used functionals such as Perdew-Burke-Ernzerhof (PBE), PBE hybrid, and Tao-Perdew-Staroverov-Scuseria (TPSS) density functionals. The third part of the work builds on the previous CF models developed in our group and addresses the one-electron, self-interaction error and introduces a modified correlation factor model where fC(r, u) is constructed such that it reduces identically to one in oneelectron regions of a many-electron system. This self-interaction corrected XC-hole is then used to generate the corresponding XC-energy functional. The new functional is assessed by implementing it into a KS program and by calculating various molecular properties. We find that, overall, a significant improvement is obtained compared to previous versions of the correlation factor model.

Panoramic Sham is sunset and sunrise, a walk through a field of wildflowers or a day in the forest. It is that moment when a light breeze tousles your hair and chirping birds reaffirm vitality. Panoramic Sham is also a heap of outdated home goods that once transformed our living rooms into artificial habitats. I reimagine decommissioned domestic goods as a way to confront trends of mass-production, habits of consumption and to explore systems of artifice, authenticity, and the consumer haze perpetuated by contemporary American society. Comprised of synthetic materials and manufactured to impersonate nature, these 20th century cast-offs provide an abundant cycle of cultural and generational refuse.

Made available in DSpace on 2016-04-28T19:59:21Z (GMT). No. of bitstreams: 1 Aline Aparecida de Souza Gomes.pdf: 297002 bytes, checksum: 2b39f2eec846156044b2cf82c8ed7261 (MD5) Previous issue date: 2010-04-26 / Secretaria da Educação do Estado de São Paulo / Situated in the field of literature and Literary criticism, the objective of this research is to investigate the characteristics of the play O Santo e a Porca (1957) THE saint and the sow (1957) , by Ariano Suassuna, seeking to highlight the elements that represent his artistic-literary aspect. The study starts relying on the basis used and recreated by the author on an attempt to enlight the elements of popular northern culture. For that, on Chapter I Miscellanea of traditions : we reflect about a mythical-dramatic speech, o Romanceiro the Romancer, the actors/singers, the correlation author-actors-public, sham and the irony. After that, we work on Chapter II The frame of the fabling in The Saint and the Sow , the scene as reinvention of reality, Caroba s treacherous dialog and the disconnections between word, scene and action, using them related to the treason to life. On Chapter III The theatre of the nonsense on the Saint and the Sow s storyline : we think about the theme variations provoked by the imaginary, the reinvention of the common based on the sintatic-semantics mismatch and the revelation of the meaning of life that reaches the northeastern men through the storyline. We take as support Mikhail Bakhtin that helped us comprehend the popular culture on Middle Ages and on the Renaissance; Vladimir Propp who gave basis on the comic feature. Henri Bergson was also used to help in the Teoria do Riso and Idelette Muzart Santos, researcher, that helped us analyze the universality of the Suassunian Theatre , among others. The methodology in use was marked by the inductive-deductive and descriptive-analytic procedures, contributing to the recognizing and interpretation of the presence of indicators of the intertextuality of the form and the theatre storyline s speech of The Saint and the Sow , and to score the novelty marks of his literary creation in a new scenario: the universal / Situada na área da Literatura e Crítica Literária, esta pesquisa tem como objetivo investigar as características peculiares à peça O santo e a porca (1957), de Ariano Suassuna, buscando dar relevância aos elementos que lhe conferem o cunho artístico-literário. O estudo parte, primeiramente, das fontes utilizadas e recriadas pelo autor na tentativa de valorizar os elementos da cultura popular nordestina. Para isso, no capítulo I Miscelâneas de Tradições : refletimos sobre a narrativa míticodramática, o Romanceiro, os atores/cantadores, a correlação autor-atores-público, a farsa e a ironia. Na sequência, trabalhamos no capítulo II A Moldura da Efabulação em O santo e a porca , a questão da cena como reinvenção da realidade, o diálogo traiçoeiro de Caroba e as desconexões entre a palavra, a cena e a ação, correlacionando-as com a traição à vida. No capítulo III O Teatro do absurdo no enredo de O santo e a porca refletimos sobre as variações temáticas provocadas pelo imaginário, a reinvenção do popular com base nos desencontros sintático-semânticos e a revelação do sentido da vida que se desprende do enredo e atinge o homem nordestino. Tomamos como suporte o teórico Mikhail Bakhtin que nos auxiliou a compreender a questão da cultura popular na Idade Média e no Renascimento; Vladimir Propp que nos fundamentou com a questão do cômico. Também nos servimos de Henri Bergson com a teoria do riso e Idelette Muzart Santos, estudiosa e pesquisadora, que nos ajudou a refletir sobre a universalidade do teatro suassuniano, dentre outros. A metodologia em uso caracterizou-se pelo procedimento indutivo-dedutivo e descritivo-analítico, contribuindo para o reconhecimento e interpretação da presença dos indicadores na intertextualidade da forma e da linguagem do roteiro teatral de O santo e a porca, e para se alcançar as marcas da novidade de sua criação literária em novo cenário, o universal

Made available in DSpace on 2016-04-26T20:24:02Z (GMT). No. of bitstreams: 1 Nicole Najjar Prado de Oliveira.pdf: 35223176 bytes, checksum: ce90c5dd883866cdfa47c54df03dc0d7 (MD5) Previous issue date: 2015-11-24 / The purpose of this study is to present the conclusion regarding the analysis of the a sample of Administrative Board of Tax Appeals CARF case laws involving tax planning, focused on the identification of the grounds of these decisions. In the first part, constitutional institutes concerning to the matter were carefully explored, with a special highlight for the lawfulness, tipicity and fiscal capacity principles. In addition, it was also subject to our review the defects of the legal transactions, since the majority of CARF decisions relies on them to disregard the acts conducted by taxpayers. From the empirical research, it was noted certain common qualities related to the sample of decisions under analysis, which revealed that transactions that imply on tax saving, structured through indirect legal acts, and performed within a short period of time and between related parties are likely significant characteristics at CARF s trials. Besides that, it called our attention the magnitude of influence that the so called business purpose has on the judgment process by CARF´s judges. The results suggest that, despite the discrepancy regarding the qualification of the illicit act (sham, fraud, abuse of rights, etc...), transactions with similar characteristics tend to have the same outcome when it comes to decision reasoning. In fact, the study supports that there is hegemony of use of the sham institute to base the disregard of acts, mostly on the grounds of lack of business purpose to justify the practice by taxpayers. At last, we critically analyzed the reasoning of such decisions based on pre-juridical criteria. We stressed our opinion that the assessment of the tax law should not depend on external factors, such as the time taken between the transactions, their parties or even the existence of such a subjective concept as business purpose, in breach of lawfulness and tipicity principles / Neste trabalho, apresentamos as conclusões da pesquisa jurisprudencial realizada junto ao Conselho Administrativo de Recursos Fiscais CARF, em casos envolvendo planejamento tributário, com o enfoque de identificar a fundamentação dessas decisões. Como ponto de partida, analisamos cuidadosamente os institutos constitucionais afetos à matéria, sendo especialmente destacados os princípios da legalidade, tipicidade e capacidade contributiva. Neste contexto, também foi objeto de estudo os vícios dos negócios jurídicos e institutos correlatos, já que a maioria das decisões do CARF os utiliza como fundamento para possibilitar a desconsideração de atos praticados pelos contribuintes. Neste contexto, da pesquisa empírica, pudemos notar a existência de certas características presentes nas decisões dos casos selecionados, que nos fizeram concluir que operações que impliquem economia de tributos, alcançadas por meio de negócios jurídicos indiretos, compostas por atos encadeados em curto espaço de tempo e realizados entre partes relacionadas são algumas das propriedades relevantes nos julgamentos da matéria pelo CARF. Além disso, nos chamou a atenção a magnitude de influência que o chamado propósito negocial tem sobre a tomada de decisão pelos julgadores do CARF. Foi possível notarmos que, a despeito de eventual discrepância com relação à tipificação do ilícito (simulação, fraude, abuso de direito e etc...), operações com características semelhantes tendem a ter suas decisões fundamentadas da mesma forma. Em realidade, o que pudemos concluir foi a hegemonia da utilização do instituto da simulação para embasar a desconsideração dos atos praticados, na maioria dos casos, sob o argumento de não haver propósito negocial apto a justificar a conduta realizada pelos contribuintes. Por fim, analisamos criticamente a fundamentação dessas decisões em critérios préjurídicos. Enfatizamos nossa opinião de que a incidência da norma jurídica tributária não deve depender de fatores externos ao Direito, tais como o tempo decorrido entre as operações, as partes que a realizaram ou até mesmo a existência ou não de conceito tão subjetivo como é o propósito negocial, sob pena de macularmos o princípio da legalidade e da tipicidade

This thesis concerns quadratic response properties and their application to properties in Jablonski diagrams such as resonant two-photon absorption and excited state absorption. Our main interest lies in optical power limiting applications, and in this context, molecules containing heavy metal atoms prove superior. Therefore, we are interested in how relativity affects these properties, and in order to assess this, a four-component relativistic framework is adopted. To properly address the molecular properties of interest, both relativistic effects and electron correlation need to be accounted for. These two properties are not additive, and, therefore, correlation needs to be incorporated into the four-component framework. We present the implementation of quadratic response properties at the four-component density functional level of theory. For second-harmonic generation, we have, with numerical examples, demonstrated that correlation and relativity are indeed not additive and that the inclusion of noncollinear magnetization is of little importance. We report that both electron correlation as well as relativity strongly affect results for second-harmonic generation. For example, relativity alone reduces the µβ-response signal by 62% and 75% for meta- and ortho-bromobenzene, respectively, and enhances the same response by 17% and 21% for meta- and ortho-iodobenzene, respectively. In the four-component framework, we present the implementations of single and double residues of the quadratic response function, which allows for the evaluation of resonant two-photon absorption cross sections and excited state properties. Using these tools, we discuss different levels of approximation to the relativistic Hamiltonian and we demonstrate that for two-photon absorption, a proper treatment of relativistic effects qualitatively alters the spectrum. For example, already for an element as light as neon, significant differences are seen between the relativistic and nonrelativistic spectra as triplet transitions acquire substantial absorption cross sections in the former case. Finally, quantum mechanics in conjunction with electrodynamics is applied to determine clamping levels in macroscopic samples. The microscopic properties of the optically active chromophores are determined by response theory, and then, electrodynamics is used to describe the interactions between the chromophores and incident laser pulses. Using this approach a series of molecules have been investigated and their performances have been compared and ranked in order to find novel materials for optical power limiting applications.

The structures of AgSin (n = 1 ¡V 16) clusters are investigated using first-principles calculations. Our studies suggest that AgSin clusters with n = 7, 10, and 15 are relatively stable isomers and that these clusters prefer to be exohedral rather than endohedral. Moreover, doping leaves the inner core structure of the clusters largely intact. Additionally, the plot of fragmentation energies as a function of silicon atoms shows that the AgSin are favored to dissociate into one Ag atom and Sin clusters. Alternative pathways exist for n > 7 (except n = 11 and 16) in which the AgSin cluster dissociates into a stable Si7 and a smaller fragment AgSin􀀀7. The AgSi11 and AgSi16 cluster dissociates into a stable Si10 and a small fragment AgSi. Lastly, our analysis indicates that doping of Ag atom significantly decreases the gaps between the highest occupied molecular orbital and the lowest unoccupied molecular orbital for n > 7.

The structures of AuSin (n = 1 - 16) clusters are investigated systematically using first-principles calculations. The lowest energy isomers exhibit preference toward exohedral rather than endohedral structure. Our studies suggest that AuSin clusters with n = 5 and 10 are relatively stable isomers. We found no significant alteration in the cluster¡¦s inner core structure for sizes n= 6, 7, 10, 11, 12, 14, and 15 even in the presence of doping. Moreover, analysis of fragmentation energies is presented in detail. Our studies further indicate that doping of Au atom significantly decreases the gaps between the highest occupied molecular orbital and the lowest unoccupied molecular orbital for n > 7. Additionally, we report on similar results obtained for CuSin (n = 1 - 16) and AgSin (n = 14, 15, and 16) and compared them with those on AuSin clusters. Next, the low energy isomers for certain sizes of CuSin (n = 10 -16 ) clusters are selected for further optimizations using Gaussian 03 package. We found that for CuSin (n = 12 - 16 ), the endohedral isomers have lower energies than their exohedral counterparts, consistent with a recent study by Janssens et al. [15] in which a similar trend was observed.

No description available.

No description available.

Embora os direitos de Propriedade Intelectual (PI) sejam supostamente instituídos de forma a fomentar a inovação e o bem-estar em longo prazo, seu uso pode ensejar comportamentos oportunistas e abusivos como os Artigos 8.2 e 40 do TRIPS expressamente admitem. Sempre que tal tipo de comportamento afetar a concorrência em determinado mercado excluindo concorrentes, impondo barreiras à entrada, prejudicando consumidores por meio de aumento de preços ou redução da oferta o Direito de Concorrência será chamado a intervir. Considerando tais questões, o objetivo desse trabalho é identificar um quadro de trabalho brasileiro para tratar de questões envolvendo questões de Direito de Concorrência relacionadas à Propriedade Intelectual. O autor buscou delinear os conceitos de uso abusivo de direitos de Propriedade Intelectual, Dominação de Mercado por meio de uso da Propriedade Intelectual e de abuso de posição dominante, considerando o novo quadro regulatório introduzido pela Lei 12.259/2001. / While intellectual property (IP) rights are usually claimed to be designed to foster innovation and welfare in the long run, their use may give rise to opportunistic, abusive behavior - as Articles 8.2 and 40 of TRIPS openly admit. Whenever such sort of behavior affects competition in a given market - whether by dislodging competitors, imposing barriers to entry, harming costumers, raising prices or reducing output - competition law is called to intervene. Considering these issues, the purpose of this paper is to identify a Brazilian legal framework for dealing with IP related competition issues. The author sought to draw the legal concepts of abusive of IP rights, market domination and abuse of dominant position considering the new regulatory framework introduced by Law 12.259/2011.