<p>The recent state of art in the magnetic resonance area putsforward the electron paramagnetic resonance, EPR, and nuclearmagnetic resonance, NMR, experiments on prominent positions forinvestigations of molecular and electronic structure. A mostdifficult aspect of such experiments is usually the properinterpretation of data obtained from high-resolution spectra,that, however, at the same time opens a great challenge forpure theoretical methods to interpret the spectral features.This thesis constitutes an effort in this respect, as itpresents and discusses calculations of EPR and NMR parametersof paramagnetic molecules. The calculations are based on newmethodology for determination of properties of paramagneticmolecules in the framework of the density functional theory,which has been developed in our laboratory.</p><p>Paramagnetic molecules are, in some sense, very special. Thepresence of unpaired electrons essentially modifies theirspectra. The experimental determination of the magneticresonance parameters of such molecules is, especially in theNMR case, quite complicated and requires special techniques ofspectral detection. The significant efforts put into suchexperiments are completely justi fied though by the importantroles of paramagnetic species playing in many areas, such as,for example, molecular magnets, active centers in biologicalsystems, and defects in inorganic conductive materials.</p><p>The first two papers of this thesis deal with thetheoretical determination of NMR parameters, such as thenuclear shielding tensors and the chemical shifts, inparamagnetic nitroxides that form core units in molecularmagnets. The developed methodology aimed to realize highaccuracy in the calculations in order to achieve successfulapplications for the mentioned systems. Theeffects of hydrogenbonding are also described in that context. Our theory forevaluation of nuclear shielding tensors in paramagneticmolecules is consistent up to the second order in the finestructure constant and considers orbital, fully isotropicdipolar, and isotropic contact contributions to the shieldingtensor.</p><p>The next three projects concern electron paramagneticresonance. The wellknown EPR parameters, such as the g-tensorsand the hyperfine coupling constants are explored. Calculationsof electronic g-tensors were carried out in the framework of aspin-restricted open-shell Kohn-Sham method combined with thelinear response theory recently developed in our laboratory.The spincontamination problem is then automatically avoided.The solvent effects, described by the polarizable continuummodel, are also considered. For calculations of the hyperfinecoupling constants a so-called restricted-unrestricted approachhas been developed in the context of density functional theory.Comparison of experimentally and theoretically determinedparameters shows that qualitative mutual agreement of the twosets of data can be easily achieved by employing the proposedformalisms.</p>

Submitted by Bruna Alves Ferraz (bruna.alves.ferraz@gmail.com) on 2018-01-12T12:56:17Z No. of bitstreams: 1 Dissertacao_BrunaAF.pdf: 1135818 bytes, checksum: 02e01c1ac05f20f13657b40ed7d959fe (MD5) / Rejected by Adriana Aparecida Puerta null (dripuerta@rc.unesp.br), reason: Prezada Bruna Alves Ferraz, Solicitamos que realize uma nova submissão seguindo as orientações abaixo: - Capa - Faltou a capa no documento enviado. Este item é elemento obrigatório de acordo com as normas de trabalhos do seu Programa de Pós Graduação e deve vir antes da Página de rosto. Agradecemos a compreensão e aguardamos o envio do novo arquivo. Atenciosamente, Biblioteca Campus Rio Claro Repositório Institucional UNESP on 2018-01-12T16:18:28Z (GMT) / Submitted by Bruna Alves Ferraz (bruna.alves.ferraz@gmail.com) on 2018-01-15T18:07:31Z No. of bitstreams: 1 Bruna Alves Ferraz.pdf: 1341591 bytes, checksum: 6e9837abd2a00d05c9ba70d843b7c4c2 (MD5) / Approved for entry into archive by Adriana Aparecida Puerta null (dripuerta@rc.unesp.br) on 2018-01-15T18:18:13Z (GMT) No. of bitstreams: 1 ferraz_ba_me_rcla.pdf: 1265910 bytes, checksum: 9b0bcbf17772b4ac87b8058427405948 (MD5) / Made available in DSpace on 2018-01-15T18:18:13Z (GMT). No. of bitstreams: 1 ferraz_ba_me_rcla.pdf: 1265910 bytes, checksum: 9b0bcbf17772b4ac87b8058427405948 (MD5) Previous issue date: 2017-12-19 / Neste trabalho discutiremos alguns métodos clássicos para otimização irrestrita, a saber o Método de Cauchy e o Método de Newton, e analisaremos a convergência desses métodos. Veremos que o Método de Cauchy, que faz a cada iteração uma busca unidirecional na direção de máxima descida, ou seja, na direção oposta ao gradiente, tem convergência linear. O método de Newton, por outro lado, minimiza, em cada iteração, a aproximação quadrática da função objetivo. Nos métodos de busca unidirecional é preciso minimizar uma função a partir de um certo ponto, segundo uma direção dada, que é a direção de busca. Por essa razão, estudaremos o Método da Seção Áurea, que fornece uma minimização exata de uma função real de uma variável real. / In this work we will discuss some classic methods for unrestricted optimization, namely the Cauchy Method and Newton’s Method, and we will analyze the convergence of those methods. We will see that the Cauchy Method, that realizes on each iteration a unidirectional search in the direction of maximum descent, that is, in the direction opposite to the gradient, has linear convergence. The Newton Method, on the other hand, minimizes, in each iteration, the quadratic approximation of the objective function. In unidirectional search methods, one must minimize a function from a certain point in a given direction, which is the search direction. For that reason, we will study the Golden Section Method, which provides the exact minimization of a real function of a real variable.

Orientador: Maria Aparecida Diniz Ehrhardt / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Matematica, Estatistica e Computação Cientifica / Made available in DSpace on 2018-08-11T11:26:07Z (GMT). No. of bitstreams: 1 Rincao_Thiago_M.pdf: 860262 bytes, checksum: ba41e2489a44afc63f51092ba2434970 (MD5) Previous issue date: 2008 / Resumo: Neste trabalho, tratamos de problemas de minimização irrestrita. Estudamos as condições de otimalidade para este tipo de problema, bem como os métodos clássicos para sua resolução, tais como: o método do Gradiente, de Newton e os Quase-Newton. Abordamos também procedimentos de busca linear e de região de confiança, conhecidos como estratégias de globalização. No entanto, nosso principal interesse está voltado a métodos de minimização que não fazem uso das derivadas da função objetivo. Neste sentido, enfocamos um método de minimização irrestrita, sem derivadas, baseado em interpolação quadrática, proposto por M. J. D. Powell, que está implementado no software NEWOUA. Com o objetivo de avaliar o desempenho computacional do algoritmo realizamos vários experimentos numéricos / Abstract: In this work, we are interested in unconstrained minimization problems. We study the optimality conditions for this kind of problem, and the classical methods for its resolution, such as: the Gradient method, Newton and Quasi- Newton methods. We also consider line search and trust region techniques, which are known as globalization strategies. However, our main interest is the study of derivative-free minimization methods. In this sense, we consider a derivative-free unconstrained minimization approach, based on quadratic interpolation, proposed by M. J. D. Powell, which is implemented in the software NEWUOA. In order to analyze the performance of the algorithm, we present several numerical experiments / Mestrado / Otimização / Mestre em Matemática Aplicada

This study investigated the perceptions of the beneficiaries of a learner transport programme in the Idutywa District of the Eastern Cape. Learner transport in South Africa continues to be a challenge, especially for those in the rural areas. The Statistics South Africa General Household Survey (2016:14) reported that more than two thirds (69.8%) of learners walked to school and 83.6% of these learners needed 30 minutes or less to get to school. Many learners in the rural areas still walk long distances to access schools due to poor infrastructure and the limited number of easily accessible schools. To understand the beneficiaries’ perceptions, a qualitative case study of a secondary school in the rural Eastern Cape village was designed. Data was collected through 47 face-to-face interviews with learners, teachers, parents, a principal as well as through a telephone interview with a government official. Additionally, observations were undertaken to gather supplementary data focusing on the geography of the village as well as the arrival and departure times of the school transport. The study draws on a social policy framework to make sense of the study findings. Through a thematic analysis of the data, themes such as spaces of operation, learners’ travelling experiences, schooling barriers as well as unintended consequences of the learner transport programme were arrived at. Although the transport provided much needed relief, findings indicate that learners still walk to school if the transport does not pick them up as scheduled and they often do not have money for public transport. They also got to school late when they had to walk to school, there is a shortage in the number of vehicles assigned to transport them, learners also missed extra lessons due to the pick-up and departure times of the transport and there is occasional conflict amongst the learners using the learner transport. The study concludes that there needs to be an increased provision of the government learner transport, work needs to be done regarding the implementation of the Learner Transport Policy, as well as the management of the programme in rural villages such as the one that the study focused on in Eastern Cape. / Sociology / MSocSci / Unrestricted

The recent state of art in the magnetic resonance area putsforward the electron paramagnetic resonance, EPR, and nuclearmagnetic resonance, NMR, experiments on prominent positions forinvestigations of molecular and electronic structure. A mostdifficult aspect of such experiments is usually the properinterpretation of data obtained from high-resolution spectra,that, however, at the same time opens a great challenge forpure theoretical methods to interpret the spectral features.This thesis constitutes an effort in this respect, as itpresents and discusses calculations of EPR and NMR parametersof paramagnetic molecules. The calculations are based on newmethodology for determination of properties of paramagneticmolecules in the framework of the density functional theory,which has been developed in our laboratory. Paramagnetic molecules are, in some sense, very special. Thepresence of unpaired electrons essentially modifies theirspectra. The experimental determination of the magneticresonance parameters of such molecules is, especially in theNMR case, quite complicated and requires special techniques ofspectral detection. The significant efforts put into suchexperiments are completely justi fied though by the importantroles of paramagnetic species playing in many areas, such as,for example, molecular magnets, active centers in biologicalsystems, and defects in inorganic conductive materials. The first two papers of this thesis deal with thetheoretical determination of NMR parameters, such as thenuclear shielding tensors and the chemical shifts, inparamagnetic nitroxides that form core units in molecularmagnets. The developed methodology aimed to realize highaccuracy in the calculations in order to achieve successfulapplications for the mentioned systems. Theeffects of hydrogenbonding are also described in that context. Our theory forevaluation of nuclear shielding tensors in paramagneticmolecules is consistent up to the second order in the finestructure constant and considers orbital, fully isotropicdipolar, and isotropic contact contributions to the shieldingtensor. The next three projects concern electron paramagneticresonance. The wellknown EPR parameters, such as the g-tensorsand the hyperfine coupling constants are explored. Calculationsof electronic g-tensors were carried out in the framework of aspin-restricted open-shell Kohn-Sham method combined with thelinear response theory recently developed in our laboratory.The spincontamination problem is then automatically avoided.The solvent effects, described by the polarizable continuummodel, are also considered. For calculations of the hyperfinecoupling constants a so-called restricted-unrestricted approachhas been developed in the context of density functional theory.Comparison of experimentally and theoretically determinedparameters shows that qualitative mutual agreement of the twosets of data can be easily achieved by employing the proposedformalisms.

Many observers are concerned about the ramifications of the policy regulation in Nigeria that allows public servants to accept gifts without restriction on the basis of culture. The purpose of this qualitative case study was to better understand this cultural practice and its implications for the integrity of public servants. Using Mettler and SoRelle's conceptualization of policy feedback theory, the research questions focused on the perceptions of leaders of civic organizations on this cultural practice in relation to the integrity of public servants in a particular region of Nigeria. Data were collected from 10 purposely selected leaders of civic organizations using open-ended, semi-structured interview protocols, and other publicly available documents. The data were subjected to an inductive coding procedure followed by thematic analysis. Findings suggested that the perceptions of the cultural practice of unrestricted giftgiving in the public service were negative and unethical. Consequently, the findings suggested an amendment to the relevant sections of Nigerian Constitution to provide for a restricted monetary value of gifts allowable in the public service. The implications for positive social change include discussing how policy makers and practitioners may be able to act on the study findings to bring about ethical, effective, and efficient public service in Nigeria.

No description available.

Experimental methods based on the magnetic resonance phenomenon belong to the most widely used experimental techniques for investigations of molecular and electronic structure. The difficulty with such experiments, usually a proper interpretation of data obtained from high-resolution spectra, opens new challenges for pure theoretical methods. One of these methods is density functional theory (DFT), that now has an advanced position among a whole variety of computational techniques. This thesis constitutes an effort in this respect, as it presents theory and discusses calculations of electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) parameters of paramagnetic molecules. It is known that the experimental determination of the magnetic resonance parameters of such molecules, especially in the case of NMR, is quite complicated and requires special techniques of spectral detection. On the other hand, paramagnetics play an important role in many areas, such as molecular magnets, active centers in biological systems, and defects in inorganic conductive materials. Therefore, they have spurred great interest among experimentalists, motivating us to facilitate the interpretation of spectral data through theoretical calculations. This thesis describes new methodologies for the determination of magnetic properties of paramagnetic molecules in the framework of DFT, which have been developed in our laboratory, and their applications in calculations of a wide range of molecular systems. The first two papers of this thesis deal with the theoretical determination of NMRparameters, such as nuclear shielding tensors and chemical shifts, in paramagnetic nitroxides that form core units in molecular magnets. The developed methodology is aimed to realize a high calculational accuracy for these systems. The effects of hydrogen bonding are also described in that context. Our theory for the evaluation of nuclear shielding tensors in paramagnetic molecules is consistent up to second order in the fine structure constant and considers orbital, fully anisotropic dipolar, and isotropic contact contributions to the shielding tensor. The next projects concern electron paramagnetic resonance. The well-known EPR parameters, such as the g-tensors and the hyperfine coupling constants are explored. Calculations of electronic g-tensors were carried out in the framework of a spin-restricted open-shell Kohn-Sham method combined with the linear response theory recently developed in our laboratory and allowing us to avoid by definition the spin-contamination problem. The inclusion of solvent effects, described by the polarizable continuum model, extends the possibility to treat molecular systems often investigated in solution. For calculations of the hyperfine coupling constants a so-called restricted-unrestricted approach to account for the spin polarization effect has been developed in the context of DFT. To examine the validity of the approximations implicit in this scheme, the neglect ii of singlet operators, a generalized RU methodology was implemented, which includes a fully unrestricted treatment with both singlet and triplet operators. The small magnitude of the changes in hyperfine coupling constants confirms the validity of the original scheme. / QC 20100923

China entered the WTO, which has the meaning stands for globalization and contact with world economic, also means that China¡¦s market is open to foreign country. After China joined WTO, media industry used to be constrained by China central government also need to face the unrestricted trend gradually. What will be the effect when media industry interacted with the unrestricted trend, foreign investment and market competition? And what is the attitude that China will have when foreign and international companies enter media industry (liberalism and western culture entering China), which also deserves our attention. Therefore, my research engage in the theory, international rules and the practice of China to study the media industry market opening after China joined WTO. The research will divide into two directions based on economic of globalization. First, the related rules of media industry in the international economic and trade organization (WTO) came with economic globalization and the real practice after China joined WTO. Second , I will talk about the rising of transnation media group. And how American transnation media group giant disposition in China ? Above is my major research directions. The research would talk about the GATS of WTO regarding the opening rules of media market , the negotiation between China and America base on the WTO frame and the contents that China promises to open the market ,the how China would modify their domestic laws to response the changes after WTO and how China think about their media industry strategy and media core value to further talk about the changes of China internal media market. Furthermore, I would mention the investment and disposition of American transnation media group based on their business profit to further understand the current situation about those American company entered China, and I also take two famous international group as an example, they are, VIACOM and TIME WARNER , base on these two company¡¦s real operation to check the China¡¦s practice and control about transnation media groups to fully investigate how much China unrestricted media industry after attending WTO.

Orientador: Vera Lucia da Rocha Lopes / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Matematica, Estatistica e Computação Cientifica / Made available in DSpace on 2018-08-12T04:23:12Z (GMT). No. of bitstreams: 1 JimenezUrrea_Liliana_M.pdf: 3576733 bytes, checksum: 0e211564f3f081c060195cfa21aa4135 (MD5) Previous issue date: 2008 / Resumo: Neste trabalho apresentamos métodos de minimização irrestrita, de uma função objetivo F de várias variáveis, que não fazem uso nem do gradiente da função objetivo - métodos derivative-free, nem de aproximações do mesmo. Nosso objetivo básico foi estudar e comparar o desempenho de métodos desse tipo propostos por M. J. D. Powell, que consistem em aproximar a função F por funções quadráticas - modelos quadráticos - e minimizar tal aproximação em regiões de confiança. Além do algoritmo de Powell de 2002 - UOBYQA - são testados: uma variante dele, na qual utilizamos a escolha de alguns parâmetros, por nós estabelecida, e também a nova versão de NEWUOA, proposta por Powell em 2006. Todos os testes foram realizados com problemas da coleção de Hock-Schittkowski. São comparados os resultados numéricos obtidos pelos métodos de Powell: entre eles mesmos e também entre eles e um método de busca padrão de autoria de Virginia Torczon, o qual define, em cada iteração, um conjunto padrão de direções de busca a partir do ponto atual, procurando melhores valores para F. / Abstract: In this work we study numerical methods to solve problems of nonlinear programming without constraints, which do not make use, neither of the gradient of the objective function, nor of approaches to it. A method that consists on the approximation of the function F by a quadractic model, due to Powell (2002), UOBYQA, and a variant of this method were implemented. A new version of the NEWUOA, introduced by Powell in 2006, was also implemented. Besides the Powell algorithm, commentaries of the implementations are done. Numerical tests of such implementations with problems of the Hock-Schittkowski collection, are made at the end of the work. There are also comparisons of the Powell methods among themselves, and also a comparison among the Powell methods with a pattern search method, which looks for the improvement of the value of the objective function throughout a set of directions, depending on the current point. Such a method is due to Virginia Torczon. / Mestrado / Otimização / Mestre em Matemática Aplicada