In this thesis, we use first-principles methods to study a class of systems known as strongly correlated materials in which exceptionally strong electron-electron repulsion in the d or f electron shell can lead to intriguing physical properties. The focus is on transition metal oxide and phosphate intercalation materials such as LiₓCoO₂ and LiₓFePO₄, which are employed as the positive electrode in rechargeable Li ion batteries. We also study the transition metal dichalcogenide system VS₂ as a candidate for strong correlation physics with analogous features to the cuprate high-temperature superconductors. Density functional theory (DFT), the standard theory of materials science which can be viewed as an effective single-electron theory, often breaks down for strongly correlated materials. In this thesis, we augment DFT with a more sophisticated many-electron approach known as dynamical mean-field theory (DMFT). We use the resultant DFT+DMFT approach with the numerically exact continuous-time quantum Monte Carlo solver to explore the physics of the materials studied here and probe compositional phase stability and related observables within DFT+DMFT for the first time. The elementary but efficient Hartree-Fock solver for the DMFT equations (i.e., DFT+U) is also utilized in order to cleanly separate the role of dynamical correlations and to better understand the respective methods. With these ab initio methods, we predict the compositional phase stability, average intercalation voltage, Li order-disorder transition temperature, structural phase stability, phonons, magnetic properties, and other important characteristics of strongly correlated materials. At the DFT+U level of theory, electronic correlations destabilize the intermediate-x compounds of cathode materials via enhanced ordering of the endmember d orbitals. DFT+U is qualitatively consistent with experiments for phase stable LixCoO₂, phase separating LiₓFePO₄, and phase stable LiₓCoPO₄. In Li₁/₂CoO₂, which is not charge ordered in experiments, the charge ordering predicted by DFT+U primarily stems from the approximate interaction, is necessary to qualitatively capture the phase stability, and erroneously predicts an insulating state and an overestimated Li order-disorder transition temperature. DFT+DMFT calculations describe LiCoO₂ as a band insulator with appreciable correlations within the Eg states and CoO₂ as a moderately correlated Fermi liquid; for both these systems we find evidence for appreciable charge and spin fluctuations. Dynamical correlations substantially dampen changes in the number of d electrons per site and the total energy as compared to DFT+U, which alters the predicted battery voltage between the two methods. We find that our DFT+DMFT results underestimate the average intercalation voltage for LiₓCoO₂ and discuss possible reasons for the discrepancy. In monolayer VS₂, a combination of crystal field splitting and direct V-V hopping leads to an isolated low-energy band for the trigonal prismatic phase within non-spin-polarized DFT. Ferromagnetism spin splits this band within spin DFT and leads to a S=1/2 ferromagnetic Stoner insulator. DFT+U opens this gap and leads to Mott insulating behavior, though for sufficiently high U an octahedral phase becomes favored. Using the known charge density wave of this octahedral phase, we assess the validity of DFT and DFT+U in this class of materials. If realized, trigonal prismatic VS₂ could be experimentally probed in an unprecedented fashion due to its monolayer nature.

Strongly correlated materials are an important class of materials for research in condensed matter physics. Other than ordinary solid-state physical systems, which can be well described and analyzed by the energy band theory, the electron-electron correlation effects in strongly correlated materials are far more significant. So it is necessary to develop theories and methods that are beyond the energy band theory to describe their rich and varied behaviors. Not only are there electron-electron correlations, typically the multiple degrees of freedom in strongly correlated materials, such as charge distribution, orbital occupancies, spin orientations, and lattice structure exhibit cooperative or competitive behaviors, giving rise to rich phase diagrams and sensitive or non-perturbative responses to changes in external parameters such as temperature, strain, electromagnetic fields, etc. This thesis is divided into two parts. In the first part, we use the density functional theory (DFT) plus U correction, i.e., the DFT+U method, to calculate the equilibrium and nonequilibrium phase transitions of LuNiO3 and VO2. The effect of adding U is manifested in both materials as the change of band structure in response to the change of orbital occupancies of electrons, i.e., the soft band effect. This effect bring about competitions of electrons between different orbitals by lowering the occupied orbitals and raising the empty orbitals in energy, giving rise to multiple metastable states. In the second part, we study the dynamic mean field theory (DMFT) as a beyond band-theory method. This is a Green's function based theory for open quantum systems. By selecting one lattice site of an interacting lattice model as an open system, the other lattice sites as the environment are equivalently replaced by a set of non-interaction orbitals according to the hybridization function, so the whole system is transformed into an Anderson impurity model. We studied how to use the density matrix renormalization group (DMRG) method to perform real-time evolutions of the Anderson impurity model to study the non-equilibrium dynamics of a strongly correlated lattice system. We begin in Chapter 1 with an introduction to strongly correlated materials, density functional theory (DFT) and dynamical mean-field theory (DMFT). The Kohn-Sham density functional theory and its plus U correction are discussed in detail. We also demonstrate how the DMFT reduces the lattice sites other than the impurity site as a set of non-interacting bath orbitals. Then in Chapters 2 and 3, we show material-related studies of LuNiO3 as an example of rare-earth nickelates under substrate strain, and VO2 as an example of a narrow-gap Mott insulator in a pump-probe experiment. These are two types of strongly correlated materials with localized 3d orbitals (for Ni and V). We use the DFT+U method to calculate their band structures and study the structural phase transitions in LuNiO3 and metal-insulator transitions in both materials. The competition between the charge-ordered and Jahn-Teller distorted phases of LuNiO3 is studied at various substrate lattice constants within DFT+U. A Landau energy function is constructed based on group theory to understand the competition of various distortion modes of the NiO6 octahedra. VO2 is known for its metal-insulator transition at 68 degree C, above which temperature it's a metal and below which it's an insulator with a doubled unit cell. For VO2 in a pump-probe experiment, a metastable metal phase was found to exist in the crystal structure of the equilibrium insulating phase. Our work is to understand this novel metastable phase from a soft-band picture. We also use quantum Boltzmann equation to justify the prethermalization of electrons over the lifetime of the metastable metal, so that the photoinduced transition can be understood in a hot electron picture. Finally, in Chapters 4 and 5, we show a focused study of building a real-time solver for the Anderson impurity model out of equilibrium using the density matrix renormalization group (DMRG) method, towards the goal of building an impurity solver for nonequilibrium dynamical mean-field theory (DMFT). We study both the quenched and driven single-impurity Anderson models (SIAM) in real time, evolving the wave function written in a form with 4 matrix product states (MPS) in DMRG. For the quenched model, we find that the computational cost is polynomial time if the bath orbitals in the MPSs are ordered in energy. The same energy-ordering scheme works for the driven model in the short driving period regime in which the Floquet-Magnus expansion converges. In the long-period regime, we find that the computational time grows exponentially with the physical time, or the number of periods reached. The computational cost reduces in the long run when the bath orbitals are quasi-energy ordered, which is discussed in further detail in the thesis.

Insulin resistance and type 2 diabetes are pathogenetically linked to increased risk of cardiovascular disease. While insulin resistance is defined by a dysregulation in hepatic insulin signaling, it is unclear how this impairment relates to the development of cardiovascular disease. Recently, there has been evidence showing that in insulin resistant individuals, cardiovascular disease is associated with a defect in reverse cholesterol transport – the cardioprotective process by which excess cholesterol is removed from the periphery, and returned to the liver for biliary excretion. Reverse cholesterol transport is facilitated by high-density lipoprotein (HDL) metabolism. Thus, malfunction in HDL turnover during reverse cholesterol transport may contribute to the buildup of atherosclerotic plaques, and subsequent cardiovascular disease in insulin resistant individuals. In this thesis, we seek to establish a better understanding of HDL metabolism and reverse cholesterol transport, as they relate to key transcription factors that mediate hepatic insulin signaling, namely the insulin-repressible forkhead transcription factors, FoxO1, FoxO3, and FoxO4 (FoxOs). We demonstrate that mice with liver-specific triple FoxO knockout (L-FoxO1,3,4) have increased HDL-cholesterol (HDL-C), associated with decreased expression of HDL-C clearance factors, scavenger receptor class B type I (SR-BI) and hepatic lipase, and defective selective uptake of HDL-cholesteryl ester by the liver. As such, we uncover a novel mechanism by which HDL-mediated reverse cholesterol transport to the liver is regulated by the hepatic insulin-->FoxO signaling pathway.

O Método das Densidades de Força (MDF), proposto primeiramente por Linkwitz (1971) e depois por Scheck (1974), é uma alternativa conveniente para encontrar configurações de redes de cabos e membranas, uma vez que fornece geometrias viáveis com uma única análise linear de equilíbrio. O Método das Densidades de Força Natural (MDFN) é uma extensão do MDF para busca de formas de estruturas de membranas, que preserva a linearidade do método original e supera suas dificuldades em lidar com malhas irregulares. Foi primeiramente sugerido por Pauletti em 2006, baseado no elemento triangular de membrana introduzido por Argyris em 1974. O Método tem sido aplicado com sucesso em vários projetos. O MDFN original requer o uso de malhas compostas exclusivamente por elementos triangulares. Esta dissertação apresenta uma extensão do método para elementos quadrangulares, considerando um elemento composto por quatro subelementos triangulares. Mesmo que a ideia básica seja muito simples, algumas dificuldades surgem do fato de que nesta abordagem, o elemento de quatro nós pode não conter todos os nós em um mesmo plano, especialmente no caso de superfícies anticlásticas, sendo que não existe um campo de tensões bem definido para o interior do elemento. O trabalho compara alguns resultados obtidos com malhas exclusivamente triangulares, como requerido pelo método original, com os resultados obtidos com o elemento quadrangular proposto, discutindo a forma de combinar as tensões dos subelementos triangulares para originar as tensões atuantes no elemento quadrangular. Os modelos obtidos no MDFN são inseridos no programa Ansys, e os resultados são comparados para analisar a viabilidade da solução proposta e dos resultados obtidos por meio desta. / The Force Density Method (FDM), first proposed by Linkwitz(1971) and after by Scheck(1974), is a convenient alternative for finding configurations of cable nets and membranes, since it provides viable geometries in a single linear equilibrium analysis. The Natural Force Density Method (NFDM) is an extension of the FDM to the shape finding of membrane structures, which preserves the linearity of the original method and overcomes the difficulties of the original method to deal with irregular meshes. It was first suggested by Pauletti in 2006, based on a triangular membrane element introduced by Argyris in 1974. The method has been successfully applied to several design cases. The original NFDM required the use of meshes composed exclusively of triangular elements. This text presents an extension of the method to quadrangular elements, considering an equivalent assemblage of flat triangular elements. Even if the basic idea is very simple, some difficulties arise from the fact that in this approach, the quadrangular element can have a non-flat configuration, especially in the anticlastic shape, and there is not a know stress field into the interior of the element. The text compares several results obtained with fully triangulated meshes, as required by the original NFDM, to those obtained with the proposed quadrangular element, discussing the different strategies that have been explored to map stresses from the internal triangular mesh to the four nodes of the element. The models obtained in the NFDM are inserted in software Ansys and the results compared to approve the solution and the results obtained.

Les buts de cette thèse étaient d’explorer les effets de la composition corporelle, de la surcharge pondérale et d’un programme d'entraînement pluridisciplinaire en endurance sur le contenu minéral osseux (CMO) et la densité minérale osseuse (DMO) chez les adolescents. Au total 4 études ont été menées. La première étude avait comme but d’explorer la contribution relative de la masse maigre et de la masse grasse aux valeurs de DMO chez 35 filles et 65 garçons français. Celle-ci a montré que la masse grasse est un déterminant positif de la DMO chez les filles mais pas chez les garçons. En effet, la masse maigre était le meilleur déterminant de la DMO chez les garçons. La deuxième et la troisième étude avaient comme objectif d’étudier les effets de la surcharge pondérale sur le CMO et la DMO du corps entier, du rachis lombaire et de la hanche chez des adolescentes libanaises. Ces 2 études ont montré que la surcharge pondérale est accompagnée d’une augmentation des valeurs absolues de CMO et de DMO. Cependant, après ajustement par le poids, ces différences disparaissent. Dès lors, ces études suggèrent que la DMO des filles en surcharge pondérale soit bien adaptée à l’excès de poids. La quatrième étude a étudié les effets de 12 semaines d’entraînement en endurance sur le CMO et la DMO chez des adolescentes obèses, en surpoids et normo-pondérées. Cette étude a montré une augmentation des valeurs de DMO dans les 3 groupes alors que le CMO n’a augmenté que dans le groupe obèse. Cette étude confirme le rôle positif de l’exercice physique sur la DMO chez les adolescentes obèses et non obèses. / The aims of this thesis were to explore the effects of body composition, overweight and of an endurance training program on bone mineral content (BMC) and bone mineral density (BMD) in adolescents. 4 studies were undertaken to achieve this goal. The first study explored the relative importance of lean and fat mass on BMD in a group of adolescent girls and boys. This study showed that fat mass is a positive determinant of BMD in girls but not in boys. In fact, lean mass was the best positive determinant of BMD in boys. The studies 2 and 3 aimed at studying the effects of overweight on whole-body, lumbar spine and hip BMD in Lebanese adolescent girls. These studies showed that the crude values of BMC and BMD were higher in overweight girls compared to controls. However, there were no differences in BMC or BMD between the two groups after adjusting for weight. Therefore, these studies suggest that the BMD of the overweight girls adapts to the increased body weight. The last study explored the effects of 12 weeks of endurance training on BMC and BMD in obese, overweight and normal-weighted sedentary adolescent girls. The BMD increased in the three groups. However, the whole-body BMC increased only in the obese group. This study confirmed the positive effects of physical exercise on BMD in obese and non-obese adolescent girls.

Chan Sze-ki. / Thesis submitted in: December 2004. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references (leaves 73-76). / Abstracts in English and Chinese. / ABSTRACT (English Version) --- p.iii / ABSTRACT (Chinese Version) --- p.iv / ACKNOWLEDGEMENTS --- p.v / TABLE OF CONTENTS --- p.vi / LIST OF TABLES --- p.viii / LIST OF FIGURES --- p.xi / Chapter CHAPTER 1 --- INTRODUCTION / Chapter 1.1. --- Structure of Deoxyribonucleic acid (DNA) / Chapter 1.1.1. --- Configuration and Conformation of Deoxyribonucleic acid (DNA) --- p.1 / Chapter 1.1.2. --- Torsion Angle --- p.2 / Chapter 1.1.3. --- Base Pairing --- p.5 / Chapter 1.2. --- DNA Damage --- p.6 / Chapter 1.3. --- The Objective of this Project --- p.11 / Chapter CHAPTER 2 --- theory and Computational Details / Chapter 2.1. --- Computational Theory / Chapter 2.1.1. --- Density Functional Theory (DFT) --- p.12 / Chapter 2.1.2. --- Closed-shell and Open-shell Determinantal Wavefunctions --- p.13 / Chapter 2.1.3. --- Calculation Method --- p.13 / Chapter 2.1.4. --- Basis Set Details --- p.14 / Chapter 2.2. --- Ionization Potential and Electron Affinity --- p.15 / Chapter 2.3. --- Charge Distribution --- p.16 / Chapter 2.4. --- Molecular Orbital --- p.16 / Chapter 2.5. --- Computation Details in this Project / Chapter 2.5.1. --- Calculation Method --- p.17 / Chapter 2.5.2. --- Studied Model --- p.17 / Chapter CHPATER 3 --- Results and Discussion / Chapter 3.1. --- Neutral State / Chapter 3.1.1. --- Bond Length --- p.19 / Chapter 3.1.2. --- Torsion Angle of DNA backbone --- p.19 / Chapter 3.1.3. --- Sugar Ring Puckering Mode --- p.25 / Chapter 3.1.4. --- Natural Population Analysis (NAP) --- p.28 / Chapter 3.1.5. --- Molecular Orbitals --- p.31 / Chapter 3.2. --- Cationic State / Chapter 3.2.1. --- Ionization Potential --- p.33 / Chapter 3.2.2. --- Bond Length --- p.34 / Chapter 3.2.3. --- Backbone Torsion Angles --- p.38 / Chapter 3.2.4. --- Puckering Mode of Sugar Ring --- p.40 / Chapter 3.2.5. --- Charge Distribution --- p.43 / Chapter 3.2.6. --- Molecular Orbitals --- p.43 / Chapter 3.2.7. --- Summary --- p.47 / Chapter 3.3. --- Anionic State / Chapter 3.3.1. --- Ionization Potential --- p.51 / Chapter 3.3.2. --- Bond Lengths --- p.52 / Chapter 3.3.3. --- Torsion Angles of Backbone --- p.54 / Chapter 3.3.4. --- Sugar Ring Puckering Mode --- p.54 / Chapter 3.3.5. --- Charge Distribution --- p.58 / Chapter 3.3.6. --- Molecular Orbital --- p.63 / Chapter 3.3.7. --- Summary --- p.66 / Chapter CHAPTER 4 --- CONCLUSION AND FUTURE WORK / Chapter 4.1. --- Conclusion --- p.68 / Chapter 4.2. --- Future Work --- p.71 / REFERENCE --- p.73

Doctor of Philosophy / Department of Chemical Engineering / Bin Liu / In the course of mitigating our dependence on fossil energy, it has become an urgent issue to develop unconventional and innovative technologies based on renewable energy utilization for fuels and chemicals production. Due to the lack of fundamental understanding of catalytic behaviors of the novel chemical compounds involved, the task to design and engineer effective catalytic systems is extremely challenging and time-consuming. One central challenge is that an intricate balance among catalytic reactivity, selectivity, durability, and affordability must be achieved pertinent to any successful design. In this dissertation, density functional theory (DFT), coupled with modeling techniques derived from DFT, is employed to gain insights into molecular interactions between elusive intermediates and targeted functional catalytic materials for novel electrochemical and heterogeneous catalytic processes. Two case studies, i.e., electroreduction of furfural and step-catalysis for cyclic ammonia production, will be discussed to demonstrate the capability and utility of DFT-based theoretical modeling toolkits and strategies. Transition metal cathodes such as silver, lead, and nickel were evaluated for furfuryl alcohol and 2-methylfuran production through detailed DFT modeling. Investigation of the molecular mechanisms revealed that two intermediates, mh6 and mh7 from mono-hydrogenation of furfural, are the key intermediates that will determine the product formation activities and selectivities. Nickel breaks the trends from other metals as DFT calculations suggested the 2-methylfuran formation pathway is most likely different from other cathodes. In this work, the Brønsted–Evans–Polanyi relationship, derived from DFT energy barrier calculations, has been found to be particularly reliable and computationally efficient for C-O bond activation trend predictions. To obtain the solvation effect on the adsorptions of biomass-derived compounds (e.g., furfural and glycerol), influence of explicit solvent was probed using periodic DFT calculations. The adsorptions of glycerol and its dehydrogenation intermediates at the water-platinum surface were understood via various water–adsorbate, water–water, and water–metal interactions. Interestingly, the bond-order-based scaling relationship established in solvent-free environment is found to remain valid based on our explicit solvent models. In the second case study, step-catalysis that relies on manganese’s ability to dissociate molecular nitrogen and as a nitrogen carrier emerges as an alternative route for ammonia production to the conventional Haber-Bosch process. In this collaborative project, DFT was used as the primary tool to produce the mechanistic understanding of NH3 formation via hydrogen reduction on various manganese nitride systems (e.g., Mn4N and Mn2N). Both nickel and iron dopants have the potential to facilitate NH3 formation. A broader consideration of a wide range of nitride configurations revealed a rather complex pattern. Materials screening strategies, supported by linear scaling relationships, suggested the linear correlations between NHx (x=0, 1, 2) species must be broken in the development of optimal step catalysis materials. These fundamental findings are expected to significantly guide and accelerate the experimental material design. Overall, molecular modeling based on DFT has clearly demonstrated its remarkable value beyond just a validation tool. More importantly, its unique predictive power should be prized as an avenue for scientific advance through the fundamental knowledge in novel catalysts design.

Yim Wai-leung. / "September 2002." / Thesis (Ph.D.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references (p. 117-123). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. Ann Arbor, MI : ProQuest Information and Learning Company, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese.

Au Yuen-yee. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2001. / Includes bibliographical references (leaves 140-152). / Abstracts in English and Chinese. / Abstract --- p.iii / Acknowledgements --- p.v / Chapter Chapter One: --- General Background and Introduction --- p.1 / Chapter 1 -1 --- Introduction --- p.1 / Chapter 1-2 --- Three-Bond Coupling Constants (3J) --- p.1 / Chapter 1-2-1 --- Development of the Karplus Equation --- p.1 / Chapter 1-2-2 --- Application of3J in the Conformational Analysis of Nucleic Acid --- p.4 / Chapter 1-2-3 --- Problem of Accuracy for3 J Measurement --- p.7 / Chapter 1-3 --- Two-Bond Coupling Constants (2J) --- p.7 / Chapter 1-3-1 --- The Use of the Projection Method --- p.7 / Chapter 1-3-2 --- 2J Coupling Constant Involving Hydrogen Bonds --- p.8 / Chapter 1-4 --- One-Bond Coupling Constants (1J) --- p.10 / Chapter 1-5 --- Conclusion --- p.11 / Chapter Chapter Two: --- Experimental Section / Chapter 2-1 --- Introduction --- p.12 / Chapter 2-2 --- Heteronuclear Multiple-Quantum Coherence (HMQC) Experiment --- p.12 / Chapter 2-3 --- Experimental Section --- p.15 / Chapter 2-3-1 --- Sample Preparation --- p.15 / Chapter 2-3-2 --- NMR Spectroscopy --- p.16 / Chapter Chapter Three: --- Theory of Nuclear Spin-Spin Coupling Constants --- p.18 / Chapter 3-1 --- Introduction --- p.18 / Chapter 3-2 --- Application of Finite Perturbation Theory on Nuclear Spin-Spin Coupling --- p.18 / Chapter 3-3 --- Methodology --- p.22 / Chapter Chapter Four: --- DFT and NMR Study of1JCH Coupling Constants --- p.28 / Chapter 4-1 --- Introduction --- p.28 / Chapter 4-2 --- Nomenclature and Definition of Structural Parametersin DNA and RNA --- p.28 / Chapter 4-2-1 --- "Nomenclature, Symbols and Atomic Numbering Schemes" --- p.28 / Chapter 4-2-2 --- Definition of Torsion Angles and their Rangesin Nucleotides --- p.31 / Chapter 4-2-3 --- Description of the Furanose Ring --- p.31 / Chapter 4-3 --- Results and Discussion --- p.37 / Chapter 4-3-1 --- Basis Set Effect --- p.37 / Chapter 4-3-2 --- Relative Conformational Energy Profiles --- p.37 / Chapter 4-3-3 --- Comparison of the Dependence of 1JCH Coupling Constants on Conformational Changes With and Without the DNA Backbone --- p.40 / Chapter 4-3-4 --- Effect of Backbone 3'- and 5'-Phosphate --- p.42 / Chapter 4-3-5 --- Effect of Glycosidic Torsion Anglex --- p.49 / Chapter 4-3-6 --- Effect of Ring Conformation with Fixed Glycosidic Torsion Anglex --- p.52 / Chapter 4-3-7 --- Effect of Torsion Angle α --- p.52 / Chapter 4-3-8 --- Effect of Torsion Angle β --- p.53 / Chapter 4-3-9 --- Effect of Torsion Angle γ --- p.56 / Chapter 4-3-10 --- Effect of Torsion Angle ε --- p.59 / Chapter 4-3-11 --- Effect of Torsion Angle ζ --- p.61 / Chapter 4-3-12 --- Effect of Base Pairing --- p.65 / Chapter 4-3-13 --- Effect of Base Stacking from the (n-1) and (n+1) Base --- p.65 / Chapter 4-3-14 --- Comparison of Experimental and Theoretical Data --- p.68 / Chapter 4-4 --- Conclusion --- p.74 / Chapter Chapter Five: --- DFT Study of 2JCH and 3JCH Coupling Constants --- p.79 / Chapter 5-1 --- Introduction --- p.79 / Chapter 5-2 --- Results and Discussion on 2JCH Coupling Constants --- p.79 / Chapter 5-2-1 --- Effect of Backbone 3'- and 5'-Phosphate --- p.79 / Chapter 5-2-2 --- Effect of Ring Conformation with Fixed Glycosidic Torsion Anglex --- p.82 / Chapter 5-2-3 --- Effect of Glycosidic Torsion Anglex --- p.87 / Chapter 5-2-4 --- Effect of Torsion Angleγ --- p.87 / Chapter 5-2-5 --- Effect of Torsion Angle ε --- p.90 / Chapter 5-2-6 --- Effect of Base Pairing --- p.90 / Chapter 5-2-7 --- Effect of Base Stacking from the (n-1) and (n+1) Base --- p.90 / Chapter 5-3 --- Results and Discussion on 3JCH Coupling Constants --- p.95 / Chapter 5-3-1 --- Effect of Backbone 3'- and 5'-Phosphate --- p.95 / Chapter 5-3-2 --- Effect of Ring Conformation with Fixed Glycosidic Torsion Anglex --- p.95 / Chapter 5-3-3 --- "Effect of Different Torsion Angles (X,α,β,γ,ε,and ζ)" --- p.100 / Chapter 5-3-4 --- Effect of Base Pairing --- p.100 / Chapter 5-3-5 --- Effect of Base Stacking from the (n-1) and (n+1) Base --- p.105 / Chapter 5-4 --- Conclusion --- p.105 / Chapter Chapter Six: --- Conclusion --- p.111 / Appendix A Product Operator Formalism on HMQC Pulse Scheme --- p.113 / Appendix B Finite Perturbation Theory --- p.115 / Appendix C Supplementary Figures of Chapter Four --- p.118 / Appendix D Some of the NMR Spectra --- p.134 / References --- p.140

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O presente estudo trás informações acerca da comunidade de anfíbios anuros do folhiço nas florestas que compõem a região da Serra das Torres, sul do Espírito Santo, sudeste do Brasil. Foram utilizados métodos de parcelas 4 x 4 m para obter os primeiros dados de sazonalidade na composição, massa e densidade no estado do Espírito Santo. Amostragens de campo foram realizadas durante as estações seca e de chuvas, no período de junho de 2009 a dezembro de 2010. Foram registrados 348 indivíduos com média de 1,0 0,1 ind/parcela, em 14 espécies associadas ao folhiço do chão da floresta. As curvas de rarefação e do coletor apresentaram assíntotas tendendo a estabilizarem. A densidade de anuros na área estudada foi de 6,59 ind/100 m e a biomassa total 413,9 g. Brachycephalus didactylus foi a espécie com maior densidade (3,8 ind/100 m) e a maior abundância (100 indivíduos ou 40,6% da comunidade geral), entretanto, apresentou biomassa relativamente baixa (16,8 g) quando comparada às demais espécies como Haddadus binotatus (239,6 g ou 57,2% da biomassa total da comunidade). Não foi registrada nenhuma variação sazonal em relação à densidade ou biomassa na comunidade. A umidade relativa do ar e a profundidade do folhiço foram fatores ambientais significativos para a abundância de indivíduos, enquanto a temperatura e a presença de rochas ou árvores no interior das parcelas não foram importantes na estruturação da comunidade daquela área. Este estudo aumenta a distribuição geográfica de Brachycephalus didactylus, Zachaenus parvulus, Physalaemus crombiei, Ischnocnema cf. bolbodactyla, Ischnocnema gr. lactea e Leptodactylus cf. bokermanni. / We studied the leaf-litter frog community of the forests of Serra das Torres, southern Espírito Santo, southeastern Brazil. We used methods 4 x 4 m plots for the first data on seasonality in the composition, mass and density in the state of Espirito Santo. We field sampling during the dry and rainy season, from June 2009 to December 2010. We recorded 348 individuals with an average of 1.0 0.1 ind / plot, and 14 species associated with leaf litter on the forest floor. Rarefaction curves and the collector had asymptotes tended to stabilize. The density of frogs in the study area was 6.59 ind/100 m and total biomass 413.9 g. Brachycephalus didactylus was the species with the highest density (3.8 ind/100 m) and greater abundance (100 individuals or 40.6% of the general community), however, had relatively low biomass (16.8 g) when compared to other species as Haddadus binotatus (239.6 g or 57.2% of the total biomass of the community). We register no seasonal variation in relation to the density or biomass in the community. The relative humidity and leaf litter depth environmental factors were significant for abundance, while the temperature and the presence of rocks or trees within the plots were not important in structuring the community in that area. This study adds to the geographic distribution of Brachycephalus didactylus, Zachaenus parvulus, Physalaemus crombiei, Ischnocnema cf. bolbodactyla, Ischnocnema gr. lactea and Leptodactylus cf. bokermanni.