Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-05-26T11:59:53Z No. of bitstreams: 1 larissalavoratolima.pdf: 7961540 bytes, checksum: 62acce4548a060da77b38e930d2e8807 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-05-26T13:14:37Z (GMT) No. of bitstreams: 1 larissalavoratolima.pdf: 7961540 bytes, checksum: 62acce4548a060da77b38e930d2e8807 (MD5) / Made available in DSpace on 2017-05-26T13:14:37Z (GMT). No. of bitstreams: 1 larissalavoratolima.pdf: 7961540 bytes, checksum: 62acce4548a060da77b38e930d2e8807 (MD5) Previous issue date: 2017-02-22 / As redes metalorgânicas (ou MOF, do inglês Metal-Organic Frameworks) pertencem à classe dos polímeros de coordenação (ou CP, do inglês coordination polymers) e exibem características como porosidade e cristalinidade. Em particular, as MOF bidimensionais têm despertado o interesse no desenvolvimento de uma nova geração de dispositivos ópticos e eletrônicos. A capacidade de formação de filmes finos de algumas dessas MOF as tornam materiais mais atraentes. A MOF bidimensional estudada neste trabalho foi a rede {[Zn(2,5-pdc)(H2O)2].H2O}n (2,5­-pdc = 2,5-piridinodicarboxilato), ZnPDC2D. A MOF 2D foi sintetizada e caracterizada por diferentes técnicas experimentais e também foi estudada por simulação computacional. O modelo do ZnPDC2D foi otimizado por dois métodos (PBE e PBE-­D2), os quais descreveram bem os parâmetros estruturais. A partir do modelo do ZnPDC2D, foi elaborada uma proposta para o processo de desidratação e assim, sugerindo a formação de três novas fases (d1-­ZnPDC2D, d2-­ZnPDC2D e d3-ZnPDC2D). A temperatura em que o ZnPDC2D sofre amorfização foi determinada através da medida de difração de raios X com aumento de temperatura in situ e pôde­se inferir que a fase amorfa sofre uma transformação reversível após ser exposta ao ambiente. A termodinâmica da primeira etapa da desidratação mostra que o funcional PBE é mais adequado para descrever a espontaneidade da reação. Espera­se obter as estruturas por meio de análises de difração de raios X por policritais e refinamento pelo método de Rietveld. O trabalho também reporta a simulação da energia de formação do monofilme pelos métodos PBE e PBE-D2. As análises de propriedades eletrônicas para todas as estruturas citadas foram executadas e discutidas conforme os processos e mudanças envolvidas. / Metal-organic frameworks (MOFs) belong to the class of coordination polymers (CPs) and exhibit properties such as porosity and crystallinity. In particular, two­dimensional MOFs have attracted interest in the development of a new generation of optical and electronic devices. The possibility of thin film formation of some of these MOFs makes them more attractive materials. The two­dimensional MOF studied in this work was the network {[Zn(2,5-pdc)(H2O)2].H2O}n (2,5-pdc = 2,5-pyridinedicarboxylate), ZnPDC2D. The MOF 2D was synthesized and characterized by different experimental techniques and was also studied by computer simulation. Two optimized ZnPDC2D structures were obtained by distinct methods (PBE and PBE­-D2) with a good description of their parameters. The structure obtained from the simulation of the dehydration process suggest the formation of three new phases (d1-ZnPDC2D, d2-ZnPDC2D and d3-ZnPDC2D). The temperature at which ZnPDC2D undergoes amorphization was determined by X­ray podwer diffraction measurement with in situ temperature rise and it could be inferred that the amorphous phase undergoes a reversible transformation after being exposed to the environment. The thermodynamics of the first stage of dehydration shows that the PBE functional is adequate to describe the spontaneity of the reaction. The structures are expected to be obtained by X­ray podwer diffraction analysis and refinement by the Rietveld method. Thise work also reports the simulation of the monofilm by the PBE and PBE-D2 methods. The analyses of electronic properties for all th cited structures were performed and discussed according to the processes and changes involved.

The thesis deals with the preparation, characterization and, in particular, with the switching properties of phase-change material (PCM) thin films. The films were deposited using the Pulsed Laser Deposition (PLD) technique. Phase transformations in these films were triggered by means of thermal annealing, laser pulses, and electrical pulses. The five major physical aspects structure transformation, crystallization kinetics, topography, optical properties, and electrical properties have been investigated using XRD, TEM, SEM, AFM, DSC, UV-Vis spectroscopy, a custom-made nanosecond UV laser pump-probe system, in situ resistance measurements, and conductive-AFM. The systematic investigation of the ex situ thermally induced crystallization process of pure stoichiometric GeTe films and O-incorporating GeTe films provides detailed information on structure transformation, topography, crystallization kinetics, optical reflectivity and electrical resistivity. The results reveal a significant improvement of the thermal stability in PCM application for data storage. With the aim of reducing the switching energy consumption and to enhance the optical reflectivity contrast by improving the quality of the produced films, the growth of the GeTe films with simultaneous in situ thermal treatment was investigated with respect to optimizing the film growth conditions, e.g. growth temperature, substrate type. For the investigation of the fast phase transformation process, GeTe films were irradiated by ns UV laser pulses, tailoring various parameters such as pulse number, laser fluence, pulse repetition rate, and film thickness. Additionally, the investigation focused on the comparison of crystallization of GST thin films induced by either nano- or femtosecond single laser pulse irradiation, used to attain a high data transfer rate and to improve the understanding of the mechanisms of fast phase transformation. Non-volatile optical multilevel switching in GeTe phase-change films was identified to be feasible and accurately controllable at a timescale of nanoseconds, which is promising for high speed and high storage density of optical memory devices. Moreover, correlating the dynamics of the optical switching process and the structural information demonstrated not only exactly how fast phase change processes take place, but also, importantly, allowed the determination of the rapid kinetics of phase transformation on the microscopic scale. In the next step, a new general concept for the combination of PCRAM and ReRAM was developed. Bipolar electrical switching of PCM memory cells at the nanoscale can be achieved and improvements of the performance in terms of RESET/SET operation voltage, On/Off resistance ratio and cycling endurance are demonstrated. The original underlying mechanism was verified by the Poole-Frenkel conduction model. The polarity-dependent resistance switching processes can be visualized simultaneously by topography and current images. The local microstructure on the nanoscale of such memory cells and the corresponding local chemical composition were correlated. The gained results contribute to meeting the key challenges of the current understanding and of the development of PCMs for data storage applications, covering thin film preparation, thermal stability, signal-to-noise ratio, switching energy, data transfer rate, storage density, and scalability.

1 ABSTRACT The work deals with the infiltration process and the emphyteutic law evidence in the Čáslav province in the Middle ages. This area can be delimitated with the range of the Iron Mountains from the north, and then with the river Sázava from the south. Several significant territorial suzerains (authorities) acted here such as Vilémov monastery, Sedlec monastery and Želivka monastery, especially significant was the colonization activity of the Lichtenberk family which was developing in the area from the half of the 13th century. The Lichtenberks came to the area from north-western Bohemia, from the contact area of the Czech state, where their relatively early-ripening emphyteutic contracts are documented, and infiltration of early forms of the German law is presumed in general. This medieval law, sometimes designated as "stable and firm" in written sources, was brought from the area of present western Europe (also form the Netherlands) by new settlers, colonists who were bringing with them excluding new knowledge of landscape cultivation (drainage, forest transformation into fields) also juridical habits, which were used to adjust legislative relations while establishing villages. They were not only farmers, but they were also other specialists, mainly miners who brought with them technologies of...

Submitted by Luciene Torres de Mello Pereira (lutmp@fgvmail.br) on 2017-06-11T04:16:24Z No. of bitstreams: 1 Tese_Luciene.pdf: 1961088 bytes, checksum: 1e99bd46d1a1ec6aa2c3b353a6c76a0f (MD5) / Approved for entry into archive by Maria Almeida (maria.socorro@fgv.br) on 2017-06-23T12:39:36Z (GMT) No. of bitstreams: 1 Tese_Luciene.pdf: 1961088 bytes, checksum: 1e99bd46d1a1ec6aa2c3b353a6c76a0f (MD5) / Made available in DSpace on 2017-06-23T12:40:06Z (GMT). No. of bitstreams: 1 Tese_Luciene.pdf: 1961088 bytes, checksum: 1e99bd46d1a1ec6aa2c3b353a6c76a0f (MD5) Previous issue date: 2016-12-20 / This thesis contains three chapters. The first chapter studies the emergence of slums as a common feature in a country's path towards urbanization, structural transformation and development. Based on salient micro and macro evidence of Brazilian labor, housing and education markets, we construct a simple model to examine the conditions for slums to emerge. We then use the model to examine whether slums are barriers or stepping stones for lower skilled households and for the development of the country as a whole. We calibrate our model to explore the dynamic interaction between skill formation, income inequality and structural transformation with the rise (and potential fall) of slums in Brazil. We then conduct policy counterfactuals. For instance, we find that cracking down on slums could slow down the acquisition of human capital, the growth of cities (outside slums) and non-agricultural employment. The impact of reducing housing barriers to entry into cities is also explored. The second chapter studies the impact of education and fertility in structural transformation and growth. In the model there are three sectors, agriculture, manufacturing and services. Parents choose optimally the number of children and their skill. Educational policy has two dimensions, it may or may not allow child labor and it subsidizes education expenditures. The model is calibrated to South Korea and Brazil, and is able to reproduce some key stylized facts observed between 1960 and 2005 in these economies, such as the low (high) productivity of services in Brazil (South Korea) which is shown to be a function of human capital and very important in explaining its stagnation (growth) after 1980. We also analyze how different government policies towards education and child labor implemented in these countries affected individuals' decisions toward education and the growth trajectory of each economy. The third chapter investigates how the positive assortative mating in the marriage market contributes to income inequality across households in Brazil. To adress this question, we analyze samples of hundreds of thousands of households from the Brazilian Census Bureau for the period 1970 to 2010. The positive assortative mating in a first moment does not affect negatively income inequality. However, from some counterfactual exercises, we show that the improvement in income distribution during this period could have been even better if the trend in the marriage market had not ocurred. / Esta tese contém três capítulos. O primeiro aborda o surgimento e o desenvolvimento de favelas como uma característica comum à trajetória das economias em direção ao desenvolvimento e à urbanização. Com base em evidências micro e macroeconômicas do mercado de trabalho, de habitação e de educação no Brasil, nós construímos um modelo simples para examinar as condições para a emergência de favelas. E então, o usamos para avaliar se as favelas são barreiras ou etapas intermediárias ao desenvolvimento econômico. Nós calibramos o modelo com o objetivo de explorar a interação dinâmica entre a formação de habilidades, a desigualdade de renda e a transformação estrutural, tendo como pano de fundo o surgimento e o desenvolvimento de favelas no Brasil. Com isso, desenvolvemos políticas contrafactuais. Primeiro, mostramos que a proibição de formação de favelas poderia retardar o processo de transformação estrutural, a aquisição de capital humano pelos indivíduos e o crescimento das cidades. O efeito de uma redução nas barreiras de entrada ao mercado de habitação nas cidades também é explorado. O segundo capítulo estuda o impacto de educação e fertilidade no processo de transformação estrutural e crescimento. No modelo, há três setores: agricultura, manufatura e serviços. Os indivíduos escolhem otimamente o número de filhos e a habilidade deles. A política educacional apresenta duas dimensões: a proibição ou não de trabalho infantil na economia e o subsídio aos gastos com educação. O modelo é calibrado para a Coreia do Sul e o Brasil e ele é capaz de reproduzir alguns fatos estilizados centrais observados entre 1960 e 2005, tais como: a baixa (alta) produtividade do setor de serviços no Brasil (na Coreia do Sul), que é função do capital humano e que explica a estagnação (crescimento) após os anos 1980. Nós também analisamos como diferentes políticas governamentais no âmbito de educação e trabalho infantil afetam a decisão dos indivíduos de acumulação de capital e a trajetória de crescimento de cada economia. O terceiro capítulo investiga a evolução do mercado de casamento e o seu impacto na distribuição de renda no Brasil. A partir da análise de dados dos censos demográficos de 1970 a 2010, encontramos evidências de que as pessoas estão cada vez mais se casando com parceiros de características semelhantes, ao longo dos anos. O aumento do número de casamentos seletivos, a princípio, não é capaz de afetar negativamente a desigualdade de renda. No entanto, quando realizamos alguns exercícios conrafactuais, é possível perceber que a melhora na distribuição de renda, ocorrida nesse período, poderia ter sido ainda maior caso essa tendência no mercado de casamento não tivesse ocorrido.

Made available in DSpace on 2016-06-02T20:13:16Z (GMT). No. of bitstreams: 1 DissRFC.pdf: 2011180 bytes, checksum: 61c7f3194a9fcfd0de4ff44748fc2269 (MD5) Previous issue date: 2002-02-07 / Financiadora de Estudos e Projetos / This dissertation aims to discuss the theoretical sources taken by Jürgen Habermas to legitimate his concept of public sphere (Öffentlichkeit). The study also presents alternative interpretive perspectives to the one assumed by Habermas in The Structural Transformation of the Public Sphere (Strukturwandel der Öffentlichkeit). / Esta dissertação objetiva discutir as fontes teóricas tomadas por Jürgen Habermas para legitimar seu conceito de esfera pública (Öffentlichkeit). O estudo também apresenta perspectivas interpretativas alternativas àquela assumida por Habermas em Mudança Estrutural da Esfera Pública (Strukturwandel der Öffentlichkeit).

The past few decades have witnessed an almost exponential increase in interest in the field of metal organic frameworks (MOFs), which can be evidenced from the large number of scientific articles being published routinely in this area. The MOFs are crystalline hybrid materials built via the judicial use of inorganic metal ions and organic linkers, thereby bridging the gap between purely inorganic and organic materials. The structural versatility and the potential tunability of the MOFs imparts unique physicochemical and thermomechanical properties, which have rendered them immensely useful in the branches of chemistry, material science, physics, biology, nanotechnology, medicine as well as environmental engineering. The MOFs have been shown to be promising as materials for gas storage and separation, sensors, ferroelectric and non-linear optical materials, magnetism, catalysis, drug delivery etc and researchers have been devising strategies to utilize the MOFs to tackle a number of global challenges of the twenty-first century. A survey of the literature reveals that the linear organic linkers, 1,4- benzenedicarboxylic acid (BDC) and 4,4’-biphenyldicarboxylic acid (BPDC), have been the organic linkers of choice for the construction of stable, porous and multifunctional MOFs. The aim of this thesis has been to monitor the effect that the presence of a functional group in between the benzene rings of the BPDC would have on the overall structures and the properties of the MOFs. Thus, as part of the investigations, the preparation of the MOF compounds using 4,4’-sulfonyldibenzoic acid (SDBA) and 4,4’- azodibenzoic acid (ABA) have been accomplished. Along with the conventional hydrothermal and solvothermal synthetic techniques, the liquid-liquid biphasic reaction method was also utilized for the synthesis of some of the compounds. The structures of the compounds were ascertained from single crystal X-ray diffraction technique. Proton conductivity studies were performed on Mn based porous MOFs using AC impedance spectroscopy. The ferroelectric behavior in a Co based porous MOF was established using dielectric and polarization vs electric field measurements. The labile nature of the lattice solvent molecules was established utilizing single crystal X-ray diffraction studies and water sorption experiments. In addition, the site selective substitution in a homometallic MOF and the subsequent conversion to a mixed-metal spinel oxide upon thermal decomposition, have also been studied. Chapter 1 of the thesis is a brief overview of the metal organic framework compounds and summarizes the various important structures that have been reported in literature and the interesting properties that they exhibit. In chapter 2, the proton conductivity behavior, solvent mediated single crystal to single crystal (SCSC) and related structural transformations in a family of Mn and Co based porous MOFs with SDBA have been presented. Also presented are the results of the site selective substitution of Mn by Co in a homometallic Mn based MOF and it’s subsequent decomposition to CoMn2O4 spinel oxide nanoparticles. In chapter 3, the syntheses, structures and the magnetic properties of the pentanuclear Mn5 based MOF compounds with SDBA have been presented. The role of the time and the temperature in the formation of the compounds has also been presented. In chapter 4, the dehydration/rehydration mediated switchable room temperature ferroelectric behavior, the single crystal to single crystal solvent exchange studies and selective gas sorption behavior in an anionic Co based MOF with SDBA has been discussed. In chapter 5, the use of the liquid-liquid biphasic synthetic route in the formation of Zn and Cd based MOFs with ABA has been discussed. Structural transformations between the one dimensional Zn based compounds and the heterogeneous catalytic studies using the Cd based compounds have also been presented.

Cette thèse s’articule autour de trois chapitres indépendants qui s’inscrivent dans les champs de la macroéconomie, de l’économie monétaire et de la finance internationale. Dans le premier chapitre, je construis un modèle néo-keynesien d’équilibre général sous incertitude pour examiner les implications de la production domestique des ménages pour la politique monétaire. Le modèle proposé permet de reconcilier deux faits empiriques majeurs: la forte sensibilité du produit intérieur brut aux chocs monétaires (obtenue à partir des modèles VAR), et le faible degré de rigidité nominale observé dans les micro-données. Le deuxième chapitre étudie le role de la transformation structurelle (réallocation de la main d’oeuvre entre secteurs) sur la volatilité de la production aggregée dans un panel de pays. Le troisième chapitre quant à lui met en exergue l’importance de la cartographie des échanges commerciaux pour le choix entre un régime de change fixe et l’arrimage à un panier de devises. "Household Production, Services and Monetary Policy" (Chapitre 1) part de l’observation selon laquelle les ménages peuvent produire à domicile des substituts aux services marchands, contrairement aux biens non durables qu’ils acquièrent presque exclusivement sur le marché. Dans ce contexte, ils procèdent à d’importants arbitrages entre produire les services à domicile ou les acquerir sur le marché, dépendamment des changements dans leur revenu. Pour examiner les implications de tels arbitrages (qui s’avèrent être importants dans les micro-données) le secteur domestique est introduit dans un modèle néo-keyenesien d’équilibre général sous incertitude à deux secteurs (le secteur des biens non durables et le secteur des services) autrement standard. Je montre que les firmes du secteur des services sont moins enclin à changer leurs prix du fait que les ménages ont l’option de produire soit même des services substituts. Ceci se traduit par la présence d’un terme endogène supplémentaire qui déplace la courbe de Phillips dans ce secteur. Ce terme croit avec le degré de substituabilité qui existe entre les services produits à domicile et ceux acquis sur le marché. Cet accroissement de la rigidité nominale amplifie la sensibilité de la production réelle aux chocs monétaires, notamment dans le secteur des services, ce qui est compatible avec l’évidence VAR selon laquelle les services de consommation sont plus sensibles aux variations de taux d’intérêt que les biens non durables. "Structural Transformation and the Volatility of Aggregate Output: A Cross-country Analysis" (Chapitre 2) est basée sur l’évidence empirique d’une relation négative entre la part de la main d’oeuvre allouée au secteur des services et la volatilité de la production aggrégée, même lorsque je contrôle pour les facteurs tels que le développement du secteur financier. Ce resultat aggregé est la conséquence des développements sectoriels: la productivité de la main d’oeuvre est beaucoup plus volatile dans l’agriculture et les industries manufacturières que dans les services. La production aggregée deviendrait donc mécaniquement moins volatile au fur et à mesure que la main d’oeuvre se déplace de l’agriculture et de la manufacture vers les services. Pour évaluer cette hypothèse, je calibre un modèle de transformation structurelle à l’économie américaine, que j’utilise ensuite pour générer l’allocation sectorielle de la main d’oeuvre dans l’agriculture, l’industrie et les services pour les autres pays de l’OCDE. Dans une analyse contre-factuelle, le modèle est utlisé pour restreindre la mobilité de la main d’oeuvre entre secteurs de façon endogène. Les calculs montrent alors que le déplacement de la main d’oeuvre vers le secteur des services réduit en effet la volatilité de la production aggregée. "Exchange Rate Volatility under Alternative Peg Regimes: Do Trade Patterns Matter?" (Chapitre 3) est une contribution à la litterature économique qui s’interesse au choix entre divers regimes de change. J’utilise les données mensuelles de taux de change bilatéraux et de commerce extérieur entre 1980 et 2010 pour les pays membre de l’Union Economique et Monétaire Ouest Africaine (UEMOA). La monnaie de ces pays (le franc CFA) est arrimée au franc Francais depuis le milieu des années 40 et à l’euro depuis son introduction en 1999. Au moment de l’arrimage initial, la France était le principal partenaire commercial des pays de l’UEMOA. Depuis lors, et plus encore au cours des dix dernières années, la cartographie des échanges de l’union a significativement changé en faveur des pays du groupe des BICs, notamment la Chine. Je montre dans ce chapitre que l’arrimage à un panier de devises aurait induit une volatilité moins pronnoncée du taux de change effectif nominal du franc CFA au cours de la décennie écoulée, comparé à la parité fixe actuelle. Ce chapitre, cependant, n’aborde pas la question de taux de change optimal pour les pays de l’UEMOA, un aspect qui serait intéressant pour une recherche future. / This thesis includes three independent essays in the fields of macroeconomics, monetary economics and international finance. In the first essay, I build a new Keynesian DSGE model to examine the implications for monetary policy of household production. The proposed theory helps reconcile the relatively strong response of output to monetary policy shocks as suggested by VAR-based evidence and the low degree of price rigidity found in micro data. The second essay analyzes the role of structural transformation (the reallocation of labor across sectors overtime) in shaping the volatility of aggregate output across countries. Finally, the third essay illustrates the importance of trade patterns in choosing between a single currency peg and a peg to a composite basket of currencies. “Household Production, Services and Monetary Policy” (Chapter 1) builds on the observation that consumer services (unlike consumer nondurable) have close substitutes at home. Households may therefore switch between consuming home and market service as the real wage (the opportunity cost of working at home) changes. To study the implications of this arbitrage for monetary policy, I embed a household sector into an otherwise standard two-sector (a nondurable good sector and a service sector) new Keynesian DSGE model. The fact that households are able to produce services at home makes service sector’s firms more reluctant to change their price. This translates into an extra endogenous shift term in the new Keynesian Phillips that is increasing with the extent of substitutability between home and market services. This increased nominal rigidity endogenously amplifies the output response to monetary policy shock, especially in the service sector, which is consistent with VAR-based evidence in the paper that consumer services are more interest-rate sensitive than consumer nondurables. “Structural Transformation and the Volatility of Aggregate Output: A Cross-country Analysis” (Chapter 2) is based on the evidence of a negative relationship between the employment share of the service sector and the volatility of aggregate output, which I obtain after controlling for several factors (including the level of financial development). This aggregate result is driven by sectoral labor productivity differentials: Labor productivity is substantially more volatile in agriculture and manufacturing than in services. Aggregate output would therefore become mechanically more stable as labor shifts away from agriculture and manufacturing, and toward the service sector. To quantify this conjecture, I first calibrate a model of structural transformation (secular reallocation of labor across sectors) to the U.S. economy, which I use to match the time path of labor shares in agriculture, manufacturing and services across OECD countries. The model is subsequently used to conduct a set of counterfactual experiments in which labor is endogenously constrained from moving across sectors. Computations suggest that the shift of labor toward the services sector is indeed volatility-reducing. “Exchange Rate Volatility under Alternative Peg: Do Trade Patterns Matter?” (Chapter 3) is a contribution to the literature on the choice of exchange rate regimes. I use monthly bilateral exchange rate and external trade data from 1980 to 2010 for the member countries of the Western African and Monetary Union (WAEMU). These countries have their common currency (the CFA franc) pegged to the French franc since the mid-40s and to the euro since its introduction in 1999. At the time of the initial peg arrangement, France accounted for most of the external trade of WAEMU countries. Since then, and more notably since the early 2000s, the trade patterns of these countries shifted briskly away from France and other Euro area countries and towards the BICs (China in particular). The chapter finds that a peg to a composite basket of currencies would have led to a less volatile effective exchange rate over the last decade compare to the current hard peg. This chapter, however, does not derive an optimal exchange rate for WAEMU countries, which is an important area for further research.

Cette thèse s’articule autour de trois chapitres indépendants qui s’inscrivent dans les champs de la macroéconomie, de l’économie monétaire et de la finance internationale. Dans le premier chapitre, je construis un modèle néo-keynesien d’équilibre général sous incertitude pour examiner les implications de la production domestique des ménages pour la politique monétaire. Le modèle proposé permet de reconcilier deux faits empiriques majeurs: la forte sensibilité du produit intérieur brut aux chocs monétaires (obtenue à partir des modèles VAR), et le faible degré de rigidité nominale observé dans les micro-données. Le deuxième chapitre étudie le role de la transformation structurelle (réallocation de la main d’oeuvre entre secteurs) sur la volatilité de la production aggregée dans un panel de pays. Le troisième chapitre quant à lui met en exergue l’importance de la cartographie des échanges commerciaux pour le choix entre un régime de change fixe et l’arrimage à un panier de devises. "Household Production, Services and Monetary Policy" (Chapitre 1) part de l’observation selon laquelle les ménages peuvent produire à domicile des substituts aux services marchands, contrairement aux biens non durables qu’ils acquièrent presque exclusivement sur le marché. Dans ce contexte, ils procèdent à d’importants arbitrages entre produire les services à domicile ou les acquerir sur le marché, dépendamment des changements dans leur revenu. Pour examiner les implications de tels arbitrages (qui s’avèrent être importants dans les micro-données) le secteur domestique est introduit dans un modèle néo-keyenesien d’équilibre général sous incertitude à deux secteurs (le secteur des biens non durables et le secteur des services) autrement standard. Je montre que les firmes du secteur des services sont moins enclin à changer leurs prix du fait que les ménages ont l’option de produire soit même des services substituts. Ceci se traduit par la présence d’un terme endogène supplémentaire qui déplace la courbe de Phillips dans ce secteur. Ce terme croit avec le degré de substituabilité qui existe entre les services produits à domicile et ceux acquis sur le marché. Cet accroissement de la rigidité nominale amplifie la sensibilité de la production réelle aux chocs monétaires, notamment dans le secteur des services, ce qui est compatible avec l’évidence VAR selon laquelle les services de consommation sont plus sensibles aux variations de taux d’intérêt que les biens non durables. "Structural Transformation and the Volatility of Aggregate Output: A Cross-country Analysis" (Chapitre 2) est basée sur l’évidence empirique d’une relation négative entre la part de la main d’oeuvre allouée au secteur des services et la volatilité de la production aggrégée, même lorsque je contrôle pour les facteurs tels que le développement du secteur financier. Ce resultat aggregé est la conséquence des développements sectoriels: la productivité de la main d’oeuvre est beaucoup plus volatile dans l’agriculture et les industries manufacturières que dans les services. La production aggregée deviendrait donc mécaniquement moins volatile au fur et à mesure que la main d’oeuvre se déplace de l’agriculture et de la manufacture vers les services. Pour évaluer cette hypothèse, je calibre un modèle de transformation structurelle à l’économie américaine, que j’utilise ensuite pour générer l’allocation sectorielle de la main d’oeuvre dans l’agriculture, l’industrie et les services pour les autres pays de l’OCDE. Dans une analyse contre-factuelle, le modèle est utlisé pour restreindre la mobilité de la main d’oeuvre entre secteurs de façon endogène. Les calculs montrent alors que le déplacement de la main d’oeuvre vers le secteur des services réduit en effet la volatilité de la production aggregée. "Exchange Rate Volatility under Alternative Peg Regimes: Do Trade Patterns Matter?" (Chapitre 3) est une contribution à la litterature économique qui s’interesse au choix entre divers regimes de change. J’utilise les données mensuelles de taux de change bilatéraux et de commerce extérieur entre 1980 et 2010 pour les pays membre de l’Union Economique et Monétaire Ouest Africaine (UEMOA). La monnaie de ces pays (le franc CFA) est arrimée au franc Francais depuis le milieu des années 40 et à l’euro depuis son introduction en 1999. Au moment de l’arrimage initial, la France était le principal partenaire commercial des pays de l’UEMOA. Depuis lors, et plus encore au cours des dix dernières années, la cartographie des échanges de l’union a significativement changé en faveur des pays du groupe des BICs, notamment la Chine. Je montre dans ce chapitre que l’arrimage à un panier de devises aurait induit une volatilité moins pronnoncée du taux de change effectif nominal du franc CFA au cours de la décennie écoulée, comparé à la parité fixe actuelle. Ce chapitre, cependant, n’aborde pas la question de taux de change optimal pour les pays de l’UEMOA, un aspect qui serait intéressant pour une recherche future. / This thesis includes three independent essays in the fields of macroeconomics, monetary economics and international finance. In the first essay, I build a new Keynesian DSGE model to examine the implications for monetary policy of household production. The proposed theory helps reconcile the relatively strong response of output to monetary policy shocks as suggested by VAR-based evidence and the low degree of price rigidity found in micro data. The second essay analyzes the role of structural transformation (the reallocation of labor across sectors overtime) in shaping the volatility of aggregate output across countries. Finally, the third essay illustrates the importance of trade patterns in choosing between a single currency peg and a peg to a composite basket of currencies. “Household Production, Services and Monetary Policy” (Chapter 1) builds on the observation that consumer services (unlike consumer nondurable) have close substitutes at home. Households may therefore switch between consuming home and market service as the real wage (the opportunity cost of working at home) changes. To study the implications of this arbitrage for monetary policy, I embed a household sector into an otherwise standard two-sector (a nondurable good sector and a service sector) new Keynesian DSGE model. The fact that households are able to produce services at home makes service sector’s firms more reluctant to change their price. This translates into an extra endogenous shift term in the new Keynesian Phillips that is increasing with the extent of substitutability between home and market services. This increased nominal rigidity endogenously amplifies the output response to monetary policy shock, especially in the service sector, which is consistent with VAR-based evidence in the paper that consumer services are more interest-rate sensitive than consumer nondurables. “Structural Transformation and the Volatility of Aggregate Output: A Cross-country Analysis” (Chapter 2) is based on the evidence of a negative relationship between the employment share of the service sector and the volatility of aggregate output, which I obtain after controlling for several factors (including the level of financial development). This aggregate result is driven by sectoral labor productivity differentials: Labor productivity is substantially more volatile in agriculture and manufacturing than in services. Aggregate output would therefore become mechanically more stable as labor shifts away from agriculture and manufacturing, and toward the service sector. To quantify this conjecture, I first calibrate a model of structural transformation (secular reallocation of labor across sectors) to the U.S. economy, which I use to match the time path of labor shares in agriculture, manufacturing and services across OECD countries. The model is subsequently used to conduct a set of counterfactual experiments in which labor is endogenously constrained from moving across sectors. Computations suggest that the shift of labor toward the services sector is indeed volatility-reducing. “Exchange Rate Volatility under Alternative Peg: Do Trade Patterns Matter?” (Chapter 3) is a contribution to the literature on the choice of exchange rate regimes. I use monthly bilateral exchange rate and external trade data from 1980 to 2010 for the member countries of the Western African and Monetary Union (WAEMU). These countries have their common currency (the CFA franc) pegged to the French franc since the mid-40s and to the euro since its introduction in 1999. At the time of the initial peg arrangement, France accounted for most of the external trade of WAEMU countries. Since then, and more notably since the early 2000s, the trade patterns of these countries shifted briskly away from France and other Euro area countries and towards the BICs (China in particular). The chapter finds that a peg to a composite basket of currencies would have led to a less volatile effective exchange rate over the last decade compare to the current hard peg. This chapter, however, does not derive an optimal exchange rate for WAEMU countries, which is an important area for further research.

Cette thèse vise à étudier les liens entre les investissements publics, le mode definancement et la croissance économique, tout en mettant en exergue le rôle des conditionsstructurelles. Premièrement, dans un scenario d’amélioration des conditions structurelles(mesurées par l’efficience et la capacité d'absorption de l’économie) comparé à un scenario debase, nous montrons que le potentiel de croissance est supérieur comparé au scenario de base. Parconséquent, la stabilisation de la dette ne nécessite pas des ajustements budgétaires douloureux.Deuxièmement, à travers un scénario d'investissement agressif sur la base d’emprunts nonconcessionnelsen anticipation des revenus futurs du pétrole, nous constatons l’occurrence decontraintes liées à la capacité d'absorption et partant l’effet adverse du syndrome hollandais sur lacroissance du PIB hors pétrole. En outre, des réformes structurelles qui résorberaient lescontraintes liées à l’inefficience et à la capacité d'absorption se traduiraient par une augmentationimportante et durable du capital public. Cela entrainerait une croissance supplémentaire du PIBhors pétrole. Troisièmement, nous montrons que les délais d’exécution peuvent contrer l’effetclassique selon lequel une augmentation de l’investissement public entraine un effet richessenégatif dans le long terme. Aussi, une productivité élevée de l’investissement public peutsubstantiellement créer un effet richesse positif dans le long terme, stimuler la production etpermettre à la consommation et à l’investissement privé de baisser moins. Finalement, noussimulons l’impact des dépenses publiques d’éducation sur la pauvreté au Burkina Faso en utilisant2 mécanismes d’ajustement fiscal : la taxe directe et la taxe indirecte. Les simulations montrentqu’une augmentation uniforme de 40 pourcent des dépenses publiques dans l’éducation primairefiancée par les deux mécanismes de financement améliore non seulement le bien-être maiségalement entraine une baisse de la pauvreté chez tous les types de ménage. Toutefois, lefinancement par la taxe indirecte conduit à un résultat inférieur comparé au financement par lataxe directe. / This dissertation seeks to study the public investment-financing-growth linkages whileeliciting the role of structural economic conditions. First, through an alternative scenario ofimproved structural economic conditions (efficiency and absorptive capacity) and comparing witha baseline scenario, we find that the growth potential is higher than the baseline. Consequently,stabilizing debt does not require painful fiscal consolidation. Second, through an aggressiveinvestment scaling-up scenario that builds on commercial borrowing in anticipation of future oilrevenue, we find that the economy is subject to absorptive capacity constraints and ultimately toDutch disease effects that affect negatively the non-oil GDP growth in the short run. Moreover,we find that structural reforms that address absorptive capacity constraints and inefficienciestranslate into sizable and sustainable increase in public capital. This in turn has a positive spillovereffect in terms of additional growth in the non-resource GDP. Third, we find that implementationdelays can offset the standard negative wealth effect from an increase in government investmentspending in the long run. Also, high-yielding public investment can substantially create positivewealth effect in the long run, raise output and enable private consumption and investment to fallless. Finally, we simulate a 40-percent across-the-board increase in public spending for primaryeducation, financed by an increase in taxes on household income and indirect taxes. We find thatthe two financing mechanisms, not only leads to an increase in the welfare but also to a decline inthe incidence of poverty for all household types. However, the indirect tax-based financing leadsto smaller outcomes compared to the income tax-based financing.

The thesis involves computer simulation and theoretical studies of dynamics of water under confinement and structural transformation in different complex systems. Based on the systems and phenomena of interest, the work has been classified in to three major parts: I. Dynamics of water under confinement II. Dynamics of water in presence of amphiphilic solutes III. Structural transformation in complex systems The three parts have further been divided into nine chapters. Brief chapter wise outline of the thesis is discussed below. Part I deals with the dynamics of water in confined systems. In Chapter I.1, we provide a brief introduction of water dynamics inc on fined systems. We also give a brief outline of relevant experimental and theoretical techniques used to study the water dynamics under confinement. Chapter I.2 describes a model based analytical study of dynamical correlation in confined systems. Here, we introduce a novel one dimensional Ising model to investigate the propagation and annihilation of dynamical correlations in confined systems and to understand the intriguing shortening of the orientational relaxation time that has been reported for small sized reverse micelles (RMs).In our model, the two spins located at the two end cells are oriented in the opposite directions to mimic the surface effects present in the real systems. These produce opposing polarizations which propagate from the surface to the center, thus producing bulk like condition at the center. This model can be solved analytically for short chains. For long chains, we solve the model numerically with Glauber spin flip dynamics (and also with Metropolis single-spin flip Monte Carlo algorithm).We show that the model satisfactorily reproduces many of the features observed in experiments. Due to the destructive interference among correlations that propagate from the surface to the core, one of the rotational relaxation time components decays faster than the bulk. In general, the relaxation of spins is non-exponential due to the interplay between various interactions. In the limit of strong coupling between the spins or in the limit of low temperature, the nature of the relaxation of spins undergoes a change with the emergence of homogeneous dynamics, where the decay is predominantly exponential. In Chapter I.3, layer-wise distance dependent orientation relaxation of water confined in reverse micelle s(RM)is studied using theoretical and computational tools. We use both a newly constructed spins on a ring (SOR) Ising-type model with modified Shore-Zwanzig rotational dynamics and atomistic simulations with explicit water. Our study explores the size effect of RMs and the role of intermolecular correlations, compromised by the presence of a highly polar surface, on the distance (from the surface) dependence of water relaxation. The SOR model can capture some aspects of distance dependent orientation relaxation, such as acceleration of orientation relaxation at intermediate layers. In atomistic simulations, layer-wise decomposition of hydrogen bond (H-bond) formation pattern clearly reveal that the H-bond arrangement of water at a certain distance away from the surface can remain frustrated due to interaction with the polar surface head groups. We show that this layer-wise analysis also reveals the presence of a non-monotonic, slow relaxation component which can be attributed to the frustration effect and is accentuated in small to intermediate size RMs. For larger RMs, the long-time component decreases monotonically from the interface to the interior of the RMs with slowest relaxation observed at the interface. In ChapterI.4, we present theoretical two dimensional infrared spectroscopic (2D-IR) studies of water confined within RMs of various sizes. Here we focus again mainly on the altered dynamics of confined water by performing a layer-wise decomposition of water. We aim to quantify the relative contributions to the calculated 2D-IR spectra by water molecules located in different layers. The spectra of 0-1 transition clearly show substantial elongation along the diagonal, due to in homogeneous broadening and incomplete spectral diffusion, in the surface water layer of different size of RMs studied in this work. Our study reveals that the motion of the surface water molecules is sub-diffusive, establishing the constrained nature of their dynamics. This is further supported by the two peak nature of the angular analogue of the van Hove correlation function. With increasing system size the motion of water molecules becomes more diffusive in nature and the structural diffusion is observed to be almost completed in the central layer of larger RMs. Comparisons between experiment and simulation help establishing the correspondence between the spectral decomposition available in experimental 2D-IR with the spatial decomposition of simulated 2D-IR. Simulations also allow a quantitative exploration of the relative role of water, sodium ions and sulfonate head groups in irrational dephasing. Interestingly, the negative cross correlation between forces on oxygen and hydrogen of O-H bond in bulk water significantly decreases in the surface layer of different RMs. This negative cross correlation gradually increases in the central layer with increasing size of the RMs and this is found to be partly responsible for the faster relaxation rate of water in the central layer. Part II consists of two chapters and focuses on the dynamics of water in presence of amphiphilic solutes. In Chapter II.1, we present a brief introduction of water – DMSO binary mixture and various anomalous properties of the same. In Chapter II.2, we present theoretical IR study of water dynamics in water–DMSO binary mixtures of different compositions. We show that with increasing DMSO concentration, the IR absorption peak maxima show the presence of structural transformation in similar concentration range, observed in earlier studies. Analysis of H-bonded network near hydrophilic and hydrophobic part of DMSO also suggests that average number of hydrogen bonds near the hydrophobic parts possess maxima at the same concentration range. We also show that with increasing DMSO concentration water dynamics becomes very slow. This has been supported by the diagonal elongation of the 2D-IR spectra and also the slow decay of frequency fluctuation correlation n function (FFCF) and the orientation time correlation function (OTCF). The decoupling of the OTCF establishes that water-DMSOH-bond is much stronger than that of water-water. The last part (Part III) consists of three chapters that deal with structural transformation in various complex systems. In Chapter III.1, we introduce polydisperse systems and present existing theoretical, computer simulation and experimental studies. It also contains the importance and diversity of polydisperse system in nature. In Chapter III.2, we present computer simulation study of melting of polydisperse Lennard-Jones (LJ) system with Gaussian polydispersity in size. The phase diagram reproduces the existence of an early temperature in variant terminal polydispersity (δt0.11), with no signature of re-entrant melting. The absence of re-entrant melting can be attributed to the influence of attractive part of the potential on melting. We find that at terminal polydispersity the fractional density change approaches zero that seems to arise from vanishingly small compressibility of the disordered phase. At constant temperature and volume fraction system undergoes a sharp transition from crystalline solid to disordered state with increasing polydispersity. This has been quantified by second and third order rotational invariant bond orientational orders as well as by the average inherent structure energy. The translational order parameter also indicates similar structural change The free energy calculation further supports the nature of the transition. The third order bond orientational order shows that with increasing polydispersity, local cluster favors more icosahedral-like arrangements and thus the system loses its crystalline symmetry. In Chapter III.3, we present study of phase transition and effect of confinement on it in SOR model. This system is similar to our SOR model discussed in Chapter I.3. The spins execute continuous rotation under a modified XY Hamiltonian. In order to understand the nature of phase transition in such confined spin systems we have performed extensive Monte Carlo simulations. The system size dependence of Binders cumulant, specific heat, order parameter and finite size scaling of order parameter universally suggest the existence of a phase transition. The absence of hysteresis and Scaling of Binders energy cumulant minimum confirm the continuous nature of the transition. The finite size scaling analyses give rise to the mean field nature of the transition. Plausible applications of the proposed model in modeling dipolar liquids in confined systems are also discussed. In Appendix A, we discuss a preliminary study of front propagation in a non-equilibrium system. The model system analogous to the super cooled liquid shows non-Avrami domain growth during rejuvenation. The origin of the non-Avrami nature of the domain growth and the presence of cross over are also discussed. In Appendix B, we discuss umbrella a sampling technique and WHAM analysis which is used in ChapterIII.2 to get the free energy of polydisperse LJ system.