Orientador: Rogério Custodio / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-25T11:52:57Z (GMT). No. of bitstreams: 1 Pereira_DouglasHenrique_D.pdf: 3749609 bytes, checksum: b3ed317231247b116e3bdb8974c60c94 (MD5) Previous issue date: 2014 / Resumo: Este trabalho desenvolveu e aplicou métodos de química quântica, mais especificamente a teoria Gaussian 3, nos estudos de propriedades eletrônicas e estruturais de átomos e molécula e encontra-se dividido em 5 capítulos. No capítulo 1 são apresentados os resultados da implementação de pseudopotencial na teoria G3 para 446 reções envolvendo moléculas contendo átomos do 1º, 2º e 3° período representativo da tabela periódica, método denominado G3CEP. O método G3CEP foi aplicado para cálculos de entalpias de formação, energias de atomização e ionização, afinidade eletrônica e de prótons. A implementação final apresentou um desvio absoluto médio total de 1,29 kcal mol-1 para o G3CEP e 1,16 kcal mol-1 para o método G3. Outro aspecto importante associado ao uso do método G3CEP é a redução do tempo de CPU. Em geral, a redução no tempo de CPU varia entre 7-60%, dependendo do tamanho da molécula e dos tipos de átomos presentes na estrutura. O capítulo 2 mostra a aplicação do método G3CEP juntamente com o método original G3, no estudo de 43 barreiras rotacionais internas. Neste estudo procurou-se analisar a precisão dos métodos, bem como entender os efeitos estereoeletrônicos responsáveis pelas conformações mais estáveis. A comparação dos resultados demonstra que os cálculos G3 e G3CEP são mais precisos do que os cálculos MP4 ou cálculos incluindo a energia do ponto zero em relação aos dados experimentais. Considerando o tamanho das moléculas estudadas, uma redução de 32 % no tempo de CPU foi obtida com a utilização do método G3CEP. No capítulo 3 foram aplicados três métodos de alta precisão, os quais são: método Gaussian-3 (G3), Monte Carlo Quântico de Difusão (MCQD) e Coupled Cluster (CCSD(T)/aug-cc-pVQZ) para os cálculos de potenciais de ionização sucessivos e os conjuntos testes estudados foram os três primeiros períodos da tabela periódica [H-Ar]. O método CCSD(T) apresentou melhor precisão nos resultados para as ionizações do 1° e 2° período, seguido do G3 e por fim o MCQD. Para o 3º período o método MCQD é o mais preciso, seguido dos métodos G3 e CCSD(T). Analisando-se os três períodos juntos, o método MCQD juntamente com o método G3 mostraram resultados similares para o potencial de ionização com um desvio absoluto médio de 1,44 eV. O capítulo 4 mostra os resultados da implementação de pseudopotencial na teoria G3(MP2). Este trabalho vem dando continuidade a teoria desenvolvida no capítulo 1, embora agora, utilizando uma versão de ordem reduzida a qual elimina os cálculos em nível MP4 reduzindo assim a demanda computacional. Os resultados mostram um desvio absoluto médio total de 1,67 kcal mol-1 para o G3CEP(MP2) e 1,47 kcal mol-1 para o método G3(MP2) com uma redução computacional de 10-40 %. Por final, o capítulo 5 traz a aplicação do método G3CEP(MP2) e G3(MP2) no estudo da preferencia endo/exo de reações de Diels-Alder. A reação do anidrido maleico e ciclopentadieno apresentou uma menor energia de ativação para o aduto endo em relação ao aduto exo para ambas as metodologias empregadas. Os parâmetros de avaliação termodinâmicos apontam para o produto exo com o método G3(MP2) e para o produto endo utilizando o método G3CEP(MP2). A reação de acrilonitrila com o ciclo-hexadieno mostrou que a preferencia exo é observado tanto pelo controle cinético como pelo termodinâmico para as metodologias empregadas / Abstract: Abstract This study developed and applied methods of quantum chemistry, specifically the Gaussian 3 theory in studies of electronic and structural properties of atoms and molecule and is divided into five chapters: In Chapter 1, related to the development of methods, the results of the implementation of pseudopotential in the G3 theory for 446 atoms and molecules containing the 1st, 2nd and 3rd representative period of the periodic table, method referred to as G3CEP are presented. The G3CEP method was applied to calculations of enthalpies of formation, atomization and ionization energy, electron and protons affinity. The final implementation presented a total mean absolute deviation of 1.29 kcal mol-1 for G3CEP and 1.16 kcal mol-1 for G3 method. Another important aspect associated with the use of G3CEP is the reduction of CPU time. In general CPU time has been reduced from 7% to 60% depending on the size of the molecule and type of atom present in the structure. Chapter 2 shows the application of the G3CEP method together with the original G3, in the study of 43 internal rotational barriers. This study sought to analyze the accuracy of the methods as well as to understand the stereoelectronic effects responsible for the most stable conformations. The comparison of the results shows that the G3 calculations and G3CEP are more accurate than MP4 calculations or calculations including zero point energy in relation to the experimental data. Considering the size of the molecules studied, a 32% reduction in CPU time was obtained using the G3CEP method. In Chapter 3, three methods of high accuracy were applied. They are: Gaussian-3 theory (G3), Diffusion Quantum Monte Carlo (DQMC) and Coupled Cluster (CCSD(T)/aug-cc-pVQZ) for calculations of successive ionization potentials and test sets studied were the first three periods of the periodic table [H-Ar]. The CCSD(T) method showed better accuracy in the results for the ionization of the 1st and 2nd period, followed by G3 and finally DQMC. For the 3rd period the DQMC method is the most accurate, followed by G3 and CCSD(T). Analyzing the three periods together, the DQMC with the G3 methods showed similar results for the ionization potential with a mean absolute deviation of 1.44 eV. Chapter 4 shows the results of the implementation of pseudopotential in the G3(MP2) theory. This work is continuing the theory developed in Chapter 1, although now using a reduced-order version which eliminates the calculations at MP4, thereby, reducing the computational demand. The results show a total mean absolute deviation of 1.67 kcal mol-1 for G3CEP(MP2) and 1.47 kcal mol-1 for G3(MP2) with a reduced computational of 9-40%. By the end, chapter 5 brings the application of methods G3CEP(MP2) and G3(MP2) in the study of preference endo/exo of Diels-Alder reaction. The reaction of maleic anhydride and cyclopentadiene showed lower activation energy for the endo adduct compared to the exo adduct for both methodologies. The evaluation of the thermodynamic parameters indicate the exo product for the G3(MP2) method, and for the endo product using the G3CEP(MP2) method. The reaction of acrylonitrile with cyclohexadiene showed that the exopreference is observed by both the thermodynamic and kinetic controls to the methodologies applied / Doutorado / Físico-Química / Doutor em Ciências

Le rotomoulage réactif est un procédé de fabrication de pièces creuses en polymère où la synthèse du matériau intervient pendant la mise en œuvre. Cette méthode présente plusieurs avantages comparée à la méthode traditionnelle utilisant des poudres thermoplastiques : réduction du temps de cycle, utilisation possible de matériaux techniques, et baisse de la consommation d'énergie et du coût des matières premières. Cependant le rotomoulage réactif est plus complexe à mettre en œuvre car la polymérisation provoque un changement important et rapide de la viscosité. Une des solutions pour optimiser ce procédé est de simuler l'écoulement du système réactif pendant la mise en œuvre.Pour ce travail nous avons utilisé un polyuréthane thermodurcissable. Des analyses thermiques et rhéologiques ont permis d'étudier les phénomènes de gélification et de vitrification du matériau et le diagramme Temps-Température-Transformation a été établi. Le comportement rhéocinétique du système a également été modélisé.Le procédé a été simulé en utilisant un code de calcul basé sur la méthode « Smoothed Particle Hydrodynamics » (SPH). Ce code a été développé par notre équipe et plusieurs améliorations ont été apportées au cours de cette étude. Pour effectuer des simulations plus réalistes en utilisant un plus grand nombre de particules, la première amélioration a consisté à accélérer la résolution des calculs. Ensuite l'évolution de la viscosité a été prise en compte grâce à l'utilisation d'un modèle rhéocinétique et une nouvelle condition limite a été développée pour simuler l'adhésion du polymère sur la paroi du moule. Les modifications nécessaires à la simulation d'écoulements 3D ont également été apportées au code SPH. / Reactive rotational molding is a process to manufacture hollow plastic parts where synthesis occurs during the shaping. This method has several advantages compared to traditional rotomolding using thermoplastic powders: shorter cycle time, possible use of high performance materials, and decrease of energy consumption and raw materials costs. However reactive rotational molding is more complex to implement mainly because of the important and quick change of viscosity occurring during polymerization. One of the solutions to optimize this process is to simulate the reactive system flow during processing.In this work we used thermoset polyurethane as reactive system. Thanks to thermal and rheological analysis, gelation and vitrification phenomena were studied and Time-Temperature-Transformation diagram was established. Material chemiorheological behavior was also modeled.The process has been simulated using a solver based on Smoothed Particle Hydrodynamics (SPH) method. This solver was developed in our research team and several improvements have been added during this study. To be able to simulate realistic flows with a high number of particles, the first improvement was to accelerate the resolution of calculations. Then the change of viscosity has been taken into account using a chemiorheological model and a new boundary condition was developed to simulate adhesion of polymer on the mold wall. To be able to simulate 3D flows, the needed modifications have been also added to the SPH solver.

Fundação de Amparo a Pesquisa no Estado do Rio Grande do Sul / The Exchange Bias (EB) phenomenon consists of an interfacial exchange coupling between a ferromagnetic (FM) material and an antiferromagnetic (AFM) one and has as the main characteristics the rise of a unidirectional anisotropy and a rotational hysteresis (HR) in torque curves. In this work we have investigated the behavior of the magnetic behavior of systems presenting EB through magnetization curves, anisotropic magnetorresistance (AMR)and torque magnetometry. We have grown films, via magnetron sputtering, of NiFe/FeMn (bilayers) with different thickness of the FM layer and film structures of NiFe/IrMn/Ta with different repetitions of the basic s tructure. From the X-ray diffraction and reflectivity we have determined the preferential crystallographic growth direction, the thickness and the grain size of the studied samples. It was implemented at the Magnetism and Magnetic Materials Laboratory (LMMM) an apparatus to measure the AMR in two configurations: resistance as a function of the applied field angle and resistance as function of the field applied in a particular angle direction. To adjust the magnetization and AMR data we have used a phenomenological model for EB considering four energy terms: Zeeman, uniaxial, unidirectional and magnetostatic. The AMR curves have shown an asymmetry around 180º when measured at field smaller than the Bias one. According to the used model used, such asymmetry can be caused either by a misalignment between the anisotropy axes (uniaxial and unidirectional) or by a misalignment between the measurement current direction easy magnetization axis of the sample. It was not observed in the multilayers an increase on the uniaxial anisotropy dispersion with increasing on the trilayers number, as expected. In order to fit average torque curves, we have used an equation with two harmonic terms. The resulting parameters allow us to study the field evolution of the harmonic amplitudes Kθ e K2θ. In the multilayer system as higher total energy is, higher is the energy losses by HR. In bilayers system, the HR energy losses still increases even above the saturation field. Such behavior was associated to the configuration of interfacial spins and suggests the need of an additional contribution to total energy of the magnetic system. / O fenômeno de Exchange Bias (EB) consiste de um acoplamento de troca interfacial entre um material ferromagnético (FM) e um material antiferromagnético (AFM) e tem como características principais o surgimento de uma anisotropia unidirecional e a histerese rotacional (HR) em curvas de torque. Neste trabalho investigamos o comportamento de sistemas magnéticos com EB através de curvas de magnetização, magnetorresistência anisotrópica (AMR) e magnetometria de torque. Foram crescidos filmes via magnetron sputtering, de NiFe/FeMn (bicamadas) variando a espessura da camada de NiFe e filmes de NiFe/IrMn/Ta com diferentes números de repetições dessa estrutura básica (multicamadas). A partir da difração e refletividade de raios-X determinamos a direção preferencial de crescimento cristalográfico, espessura e o tamanho de grão das amostras estudadas. Foi implementado no Laboratório de Magnetismo e Materiais Magnéticos (LMMM) um aparato experimental para medidas de AMR: resistência em função do ângulo do campo aplicado e resistência em função do campo aplicado para um determinado ângulo escolhido. Para o ajuste aos dados das curvas de magnetização e AMR é apresentado um modelo fenomenológico para EB considerando quatro termos de energia: Zeeman, uniaxial, unidirecional e magnetostático. As curvas de AMR apresentam uma assimetria em torno de 180º quando medidas em valores de campo menores que o campo de Bias. De acordo com o modelo utilizado, tal assimetria pode ser causada por um desalinhamento entre os eixos de anisotropia (uniaxial e unidirecional) ou por um desalinhamento entre a direção da corrente de medida e o eixo fácil de magnetização da amostra. Não foi observado um aumento na dispersão da anisotropia uniaxial com o aumento das repetições das tricamadas, conforme esperado. Para o ajuste das curvas de torque médio utilizamos uma equação com dois termos harmônicos. Os parâmetros resultantes do ajuste das curvas de torque permitiram estudar a evolução das componentes harmônicas Kθ e K2θ. Nas multicamadas quanto maior a energia associada ao torque médio maiores são as perdas de energia por HR. Já nas bicamadas, as perdas de energia por HR aumentam mesmo acima do campo de saturação. Tal comportamento foi associado à configuração de spins interfaciais e sugere a necessidade de uma contribuição adicional para a energia total do sistema magnético.

Rotational falls, or somersault falls, have led to serious and fatal injuries during the cross-country phase of Eventing competitions. Research to improve the safety of the sport began in 2000 after five fatal injuries occurred in the 1999 Eventing season. These efforts led to safety devices such as air jackets, improved helmets, and frangible/deformable fences. The focus of this thesis is to develop a more complete understanding of the horse-fence interaction as the approach motion transitions to a rotational fall. To achieve this, a large distribution of inertial properties was compiled through the development of a cylinder-based inertia approximation and a citizen science effort to gather equine geometrical measurements through a survey distributed by the United States Eventing Association (USEA). Furthermore, fundamental kinematic properties of the horse and rider were gathered from the literature. These distributions were used to conduct a Monte Carlo analysis to examine if the approach conditions of the horse and rider would result in a transition to a rotational fall upon horse-fence contact. Through the analysis the sensitivity of the main control parameters was explored to determine the dominant variables in the transition.

A centrifugal compressor is a mechanical machine with purpose to convert kineticenergy from a rotating impeller wheel into the fluid medium by compressingit. One application involves supplying boost air pressure to downsized internalcombustion engines (ICE). This allows, for a given combustion chamber volume,more oxygen to the combustion process, which is key for an elevated energeticefficiency and reducing emissions. However, the centrifugal compressor is limitedat off-design operating conditions by the inception of flow instabilities causingrotating stall and/or surge. These instabilities appear at low flow rates andtypically leads to large vibrations and stress levels. Such instabilities affectthe operating life-time of the machine and are associated with significant noiselevels.The flow in centrifugal compressors is complex due to the presence of a widerange of temporal- and spatial-scales and flow instabilities. The success fromconverting basic technology into a working design depends on understandingthe flow instabilities at off-design operating conditions, which limit significantlythe performance of the compressor. Therefore, the thesis aims to elucidate theunderlying flow mechanisms leading to rotating stall and/or surge by means ofnumerical analysis. Such knowledge may allow improved centrifugal compressordesigns enabling them to operate more silent over a broader operating range.Centrifugal compressors may have complex shapes with a rotating partthat generate turbulent flow separation, shear-layers and wakes. These flowfeatures must be assessed if one wants to understand the interactions among theflow structures at different locations within the compressor. For high fidelityprediction of the complex flow field, the Large Eddy Simulation (LES) approachis employed, which enables capturing relevant flow-driven instabilities underoff-design conditions. The LES solution sensitivity to the grid resolution usedand to the time-step employed has been assessed. Available experimentaldata in terms of compressor performance parameters, time-averaged velocity,pressure data (time-averaged and spectra) were used for validation purposes.LES produces a substantial amount of temporal and spatial flow data. Thisnecessitates efficient post-processing and introduction of statistical averagingin order to extract useful information from the instantaneous chaotic data. Inthe thesis, flow mode decomposition techniques and statistical methods, suchas Fourier spectra analysis, Dynamic Mode Decomposition (DMD), ProperOrthogonal Decomposition (POD) and two-point correlations, respectively, areemployed. These methods allow quantifying large coherent flow structures atvfrequencies of interest. Among the main findings a dominant mode was foundassociated with surge, which is categorized as a filling and emptying processof the system as a whole. The computed LES data suggest that it is causedby substantial periodic oscillation of the impeller blade incidence flow angleleading to complete system flow reversal. The rotating stall flow mode occurringprior to surge and co-existing with it, was also captured. It shows rotating flowfeatures upstream of the impeller as well as in the diffuser. / <p>QC 20171117</p>

Ce travail de recherche est une contribution à l'étude de la propagation d'ondes élastiques dans les milieux granulaires. L'objectif principal est d'analyser deux aspects particuliers qui influencent la propagation, d'une part le degré de liberté en rotation des grains et d'autre part les non-linéarités de contact. Dans le cadre de ce travail, des structures granulaires périodiques et unidimensionnelles sont étudiées.L'apport principal de ce travail est la mise en évidence expérimentale et la modélisation d'ondes de rotation pures dans une chaîne granulaire composée de billes magnétiques. Le point de départ de la modélisation est la description du contact en torsion entre deux sphères jusqu'au premier ordre de non-linéarité. Pour un moment de torsion oscillant, il est montré un comportement de type purement hystérétique quadratique. Généralement, cette non-linéarité coexiste avec d'autres types de non-linéarités (quadratique, clappement, ...) et certains de ses effets n'ont jamais été observés. Pour la première fois, la distorsion d'ondes impulsionnelles par une non-linéarité hystérétique est mise en évidence et modélisée.D'autres effets liés à la dispersion et aux non-linéarités de contact dans une chaîne diatomique sont étudiés théoriquement et expérimentalement. En particulier, la génération de l'harmonique 2 des ondes de compression présente une richesse intéressante selon leur caractère propagatif, fortement dispersif ou évanescent.Outre les apports fondamentaux, les résultats obtenus peuvent trouver des applications dans le domaine du contrôle des ondes : filtres acoustiques dépendant de l'amplitude, convertisseurs de fréquences, rectificateurs et diodes acoustiques, ... . / This research is a contribution to the study of the propagation of elastic waves in granular media. The main purpose is to analyze two particular aspects that influence the propagation, first the rotation motion of grain and other nonlinearities of contact. As part of this work, the periodic one-dimensional granular structure is studied. The main contribution of this work is the experimental demonstration and modeling purely rotational wave in a granular chain composed of magnetic beads. The starting point of modeling is the description of the pure shear coupling at the contact between two spheres excited in torsion up to the first order of nonlinearity. For a oscillating torque, pure nonlinear quadratic hysteretic behaviour is shown. Generally, this nonlinearity coexists with other types of nonlinearities (quadratic, clapping, ...) and some of its effects have not been observed. For the first time, the transformation of pulse profile in a medium with pure hysteretic quadratic nonlinearity, essentially different from the distortion by classical nonlinearities, is reported.Other effects related to the dispersion and nonlinearity of contact in a diatomic chain are studied theoretically and experimentally. In particular, the generation of the 2nd harmonic wave compression presents an interesting behaviour according to their propagating nature, highly dispersive or evanescent. Apart from the fundamental interests, the results may find applications in the field of wave control: amplitude dependent filtering devices, rectifiers, actuating devices, acoustic diodes, ... .

The nature of interactions within a molecule, i.e. chemical bonding, is well understood today. However, our understanding about intermolecular interactions, which has great relevance in nature, is still evolving. Historically there are two types of intermolecular interactions, van der Waals interaction and hydrogen bonding. However, there has been an upsurge of interest in the halogen bonding and lithium bonding during the last decade. The main emphasis of our research is to understand these interactions in detail, in particular non-conventional hydrogen bond acceptors. In this work, weakly bound complexes are studied using Pulsed Nozzle Fourier Transform Microwave Spectrometer, which has been fabricated in our laboratory and various theoretical methods. FTMW spectroscopy in the supersonic beam provides accurate structural information about the near-equilibrium geometry of small dimers and trimers in isolation. The home-built Pulsed Nozzle Microwave spectrometer, having a spectral range of 2-26.5 GHz has been used to record the microwave spectrum of these complexes. The spectrometer consists of a Fabry-Perot cavity, electronic circuit and pumps. Fabry-Perot cavity is the interaction zone of the molecules and radiation. The electronic circuit is used for the polarization and detection of the signal. Mechanical and diffusion pumps are used to maintain the vacuum inside the cavity. The gas molecules of interest are then mixed with a carrier gas and pulsed supersonically inside the cavity through a nozzle of 0.8 mm diameter. The emission from the complexes formed during the expansion is detected by super-heterodyne detection technique and then Fourier transformed. The first chapter of the thesis gives a brief introduction to intermolecular interactions, hydrogen bonding, halogen bonding, lithium bonding and molecular 2 of clusters. The chapter also includes a brief introduction to rotational spectroscopy. The second chapter of the thesis discusses the experimental and theoretical methods. It includes a detailed discussion of the mechanical and electrical parts of the spectrometer and the software used, which is developed in Labview 7.1. The various theoretical methods (ab initio and DFT) and the basis sets are discussed along with Atoms In Molecules Theory and the criteria used to characterize hydrogen bond. In the third chapter, to understand the ability of saturated hydrocarbons to act as hydrogen bond donor and acceptor, interaction of CH4 with H2S is studied using rotational spectroscopy as well as theoretical methods such as ab initio and Atoms In Molecules theory. Three progressions were obtained for the CH4•••H2S complex using microwave spectroscopy. The progressions were independently fitted to a linear top Hamiltonian. Absence of J10 transition in Progression II confirms the presence of higher internal angular momentum state, m=1. This also confirms the internal rotation of the monomers in the complex. Progressions II and III have negative centrifugal distortion constants. Hence both the states are from some excited internal rotation/torsional motion with strong vibrational-rotational coupling. The moment of inertia obtained from the experimental rotational constant confirms the structure in which sulphur of H2S is close to CH4. This also supports the structure in which CH4 is the hydrogen bond donor, if such an interaction is present. AIM analysis and the potential energy barrier for internal rotation show orientational preference and hence hydrogen bonding. The ab initio results show that CH4•••HSH interaction is more favorable than CH3H•••SH2. Ab initio and AIM studies also gave a structure where there is direct interaction between C and S. This is interesting since the electronegativities of C and S are comparable. Experimentally obtained negative distortion constants for the other two states, confirm excited state rotational-vibrational coupling. The experimental data give a floppy structure having internal rotation. In the fourth chapter the complex chosen for investigation is benzene-ethylene. Experiments in condensed phase and theoretical works show evidence of - stacking in benzene dimer, but there is no gas phase spectroscopic evidence available for the same. The lack of permanent dipole moment in the -stacked geometry of benzene dimer is the hindrance in the experimental observation of the same using microwave spectroscopy. Substitution of one of the benzene with ethylene in the -stacked structure will result in a complex having permanent dipole moment. C6H6 C2H4 complex can have, in addition to -stacking, C-H/interaction. There could be a competition between C6H6 and C2H4, either of which can act as H-bond donor. Experiments show the evidence of C-H/interaction, where C2H4 is the hydrogen bond donor. To ascertain hydrogen bond interaction AIM analysis has been carried out. The results show C-H/interaction, where one of the C2H4 hydrogen interacts with the benzene. Even though the aim was to get the -stacked geometry, it could not be obtained. However theory and AIM supports the formation of -stacked complex. In the fifth chapter using theoretical methods the ability of radicals as acceptor of hydrogen, lithium and chlorine bonds are examined with CF3 radical as the model system. As hydrogen bonds are highly sensitive to the environment, the effect of substitution of hydrogen by fluorine is also analyzed. It is found that, even though CH3 and CF3 radicals are topologically different, they interact in a similar fashion. AIM analysis of CF3HY satisfies all the eight criteria proposed by Koch and Popelier for hydrogen bonding. Here the hydrogen bond formed is charge transfer assisted. The interaction energies of the complexes are inversely proportional to the dipole moment of hydrogen bond donors and are proportional to the charge transfer occurring in the complex. Interaction energies from ab initio calculations confirm complexation of CF3 radical with LiY(Y=F, Cl, Br) and ClF. AIM analysis of CF3LiY and CF3ClF complexes show a bond critical point between Li/Cl and the C of CF3 and the condition of mutual penetration is also met. In CF3LiY complexes the interaction energies and charge transferred are directly proportional to the dipole moment of the Li bond donor. In the sixth chapter in order to extend the concept of non-conventional hydrogen bond acceptors to transition metals, complexes of Fe (Fe(CO)5) with HX (X=F,Cl,Br) have been studied theoretically. DFT calculations show that the structure in which the hydrogen of HX interacting with Fe through the sixth co-ordination site is a stable geometry. AIM analysis shows the presence of a bond critical point between the iron and the hydrogen of HX and hence bond formation. Q obtained from NBO analysis shows that there is charge transfer from the organometallic system to the hydrogen bond donor. However the interaction energies of the complexes are proportional to the dipole moment of hydrogen bond donors and are inversely proportional to the charge transfer for these complexes. H-bonding leads to the stabilization of square pyramidal geometry. ‘Hydrogen bond radius’ of iron has also been defined. Studies on the interaction of Fe(CO)5 with ClF and ClH showed that Fe can also act as a chlorine bond acceptor. Seventh chapter provides the overall conclusion and also discusses future direction.

O presente trabalho teve como objetivo avaliar o desempenho de novilhas da raça Nelore, suplementadas com níveis de proteína bruta em pastagem de capimbraquiarão (Brachiaria brizantha cv. Marandu), no período de transição água-seca. O experimento foi conduzido na Faculdade de Zootecnia e Engenharia de Alimentos - FZEA/USP em Pirassununga-SP. Utilizou-se quatro tratamentos: Controle (CTRL) sendo sal mineral; Suplemento com 20% de proteína bruta (20%); suplemento com 40% de proteína bruta (BC 40%), sendo esses de baixo consumo e suplemento 40% de proteína bruta de alto consumo (AC 40%). O ciclo de pastejo foi de 35 dias, sendo sete dias de ocupação e 28 dias de descanso. O delineamento experimental foi em blocos completos casualizados com 4 repetições.Foram utilizadas 96 novilhas da raça Nelore com peso médio inicial de 316 kg e cerca de 18 meses de idade, num período experimental de 105 dias, tendo início em 09 de abril e término em 27 de agosto de 2008, considerado período de transição água-seca. Para o ganho de peso médio diário, não houve diferença estatística entre os tratamentos AC 40% e BC 20% (p<0,05), sendo o GPD de 0,470 e 0,369 gramas/dia, respectivamente, enquanto que para os tratamentos CTRL, 20% e BC 40%, não houve diferença estatística (P>0,05), sendo osGPD de 0,336, 0,369 e 0,353 gramas/dia, respectivamente. A utilização de suplementos protéicos no desempenho de novilhas teve desempenhos satisfatórios no período de transição água-seca, porém, para a recomendação da utilização, recomenda-se realizar uma análise econômica, pois somente assim, garantirá qual será o melhor tratamento para o período. / The aim of this study was to evaluate the performance of Nelore heifers supplemented with crude protein levels in pasture of Brachiaria grass (Brachiaria brizantha cv. Marandu), during the transition period of wet-dry seasons. The experiment was conducted at the Faculty of Animal Science and Food Engineering - FZEA / USP in Pirassununga-SP. It was used four treatments: Control (CTRL) being mineral salt, supplement with 20% of crude protein (20%) supplement with 40% of crude protein (BC 40%), as low consumption and with crude protein of 40% as high consumption (AC 40%). The grazing cycle was 35 days, seven days of occupation and 28 days of interval. A randomized complete block design, with 4 repetitions was utilized. It was used 96 Nelore heifers with an average weight of 316 kg and around 18 months, in a probationary period of 105 days, starting on 09 April and ending in August 27, 2008, considered the transitional period of wet-dry seasons. For the average daily gain, there was no statistical difference between treatments AC 40% and 20% (p<0,05), being GPD of 0.470 and 0.369 grams/day, respectively, while for the treatments CTRL, 20% and BC 40%, there was no statistical difference (P>0,05), being GPD of 0.336, 0.369 and 0.353 grams/day, respectively. The use of crude protein supplements on performance of heifers had performed satisfactorily during the transition period of wet-dry seasons however, to recommend the use, it is suggest to perform an economic analysis, for only thus ensure the best treatment for the period.

The chemical complexity of the interstellar medium and combustion environments pose a challenge to the scientific community seeking to provide a molecular understanding of their combustion. More refined spectroscopic tools and methodologies must be developed to selectively detect and characterize the widening array of fuel and interstellar species. The direct relationship between molecular structure and rotational frequencies makes rotational spectroscopy highly structural specific; therefore, it offers a powerful means of characterizing polar molecules. However, rotational spectra usually contain transitions from multiple components with multiple conformations as well as other dynamical properties interleaved with one another, making the assignment of the spectra very challenging. This thesis describes experimental work using broadband microwave spectroscopy and vacuum ultraviolet time-of-flight mass spectrometry to address a number of challenging problems in the spectroscopy of gas complex mixtures.<div><br></div><div>In the first part of my work, we report details of the design and operation of a single apparatus that combines Chirped-Pulse Fourier Transform Microwave spectroscopy (CP-FTMW) with VUV photoionization Time-of-Flight Mass Spectrometry (VUV TOFMS). The supersonic expansion used for cooling samples is interrogated first by passing through the region between two microwave horns capable of broadband excitation and detection in the 2-18 GHz frequency region of the microwave. After passing through this region, the expansion is skimmed to form a molecular beam, before being probed with 118 nm (10.5 eV) single-photon VUV photoionization in a linear time-of-flight mass spectrometer. The two detection schemes are powerfully complementary to one another. CP-FTMW detects all components with significant permanent dipole moments. Rotational transitions provide high-resolution structural data. VUV TOFMS provides a gentle and general method for ionizing all components of a gas phase mixture with ionization thresholds below 10.5 eV, providing their molecular formulae. The advantages, complementarity, and limitations of the combined methods are illustrated through results on two gas-phase mixtures made up of (i) three furanic compounds, two of which are structural isomers of one another, and (ii) the effluent from a flash pyrolysis source with <i>o-</i>guaiacol as precursor. <br></div><div><br></div><div>The broadband spectrum of 3-phenylpropionitrile was recorded under jet-cooled conditions over the 8-18 GHz region. A novel multi-resonance technique called strong field coherence breaking (SFCB) was implemented to record conformer-specific microwave spectra. This technique involves sweeping the broadband chirp followed by selectively choosing a set of single frequencies pulses to yield a set of rotational transitions that belong to a single entity in the gas-phase mixture, aiding assignment greatly. Transitions belonging to anti and gauche conformers were identified and assigned and accurate experimental rotational constants were determined to provide insight on the molecular structure. Experimental rotational transitions provided relative abundances in the supersonic expansion. A modified line picking scheme was developed in the process to modulate more transitions and improve the overall efficiency of the SFCB multiple selective excitation technique.<br></div><div><br></div><div>The rotational spectrum of 2-hexanone was recorded over the 8-18 GHz region using a CPFTMW spectrometer. SFCB was utilized to selectively modulate the intensities of rotational transitions belonging to the two lowest energy conformers of 2-hexanone, aiding the assignment. In addition, the SFCB method was applied for the first time to selectively identify rotational transitions built off the two lowest energy hindered methyl rotor states of each conformer, 0a₁ and 1e. Since these two states have rotational energy levels with different nuclear spin symmetries, their intensities could be selectively modulated by the resonant monochromatic pulses used in the SFCB method. The difference spectra, final fit and structural parameters are discussed for the three assigned conformers of 2-hexanone.<br></div><div><br></div><div>Developing new experimental techniques that allow for species identification and quantification in the high-temperature environment of reacting flows is a continuing challenge in combustion research. Here, we combine broadband chirped-pulse microwave (rotational) spectroscopy with an atmospheric-pressure jet-stirred reactor as a novel method to identify key reactive intermediates in low-temperature and ozone-assisted oxidation processes. In these experiments, the gas sample, after being withdrawn from reactive dimethyl ether/O₂/Ar, dimethoxy methane/O₂/Ar, and ethylene/O₂/O₃/Ar mixtures, expands via a supersonic expansion into the high vacuum of a microwave spectrometer, where the rotationally cold ensemble of polar molecules is excited with short MW radiation frequency ramps (chirps). The response of the molecular ensemble is detected in the time domain and after a Fourier transformation, the spectral composition of the transient emission is obtained in the frequency domain. The observed rotational frequencies are uniquely correlated to molecular structures and allow for an unambiguous identification of the sampled species. Detection and identification of intermediates such as formaldehyde, methyl formate, formic acid, formic acid anhydride, and the primary ethylene ozonide via literature-known rotational frequencies are evidence for the superb identification capabilities of broadband chirped-pulse microwave spectroscopy. Strong-field coherence breaking is employed to identify and assign transitions due to a specific component. The observation of van der Waals complexes provides an opportunity to detect combustion intermediates and products that are impossible to detect by rotational spectroscopy as isolated molecules. <br></div><div><br></div><div>Lastly, preliminary data on important combustion precursors is studied including pentanal, <i>trans-</i>2-pentenal and <i>o-,m- </i>and <i>p</i>-vinylanisole. The rotational spectrum of these five molecules is recorded from the 8-18 GHz region under jet-cooled conditions. For pentanal and <i>trans-</i>2-pentenal, SFCB was utilized to dissect the broadband spectrum, identifying the four and two lowest energy structures, respectively. The structural parameters and finals fits are provided. <br></div>

Shallowly embedded column base connections with unreinforced block out concrete are a common method of connecting steel columns to their foundation. There has been little research done to accurately quantify the effects of this block out concrete on the connection strength and rigidity, and therefore there is nothing to aid the practicing engineer in accounting for this in structural analysis. Due to this lack of understanding, engineers have typically ignored the effects of shallow block out concrete in their analysis, presumably leading to a conservative design. Recent research has attempted to fill this gap in understanding. Several methods have been proposed that seek to quantify the effects of shallow block out concrete on a column base connection. Barnwell proposed a model that predicts the strength of a connection. Both Jones and Tryon used numerical modeling to predict the rotational stiffness of the connection. An experimental study was carried out to investigate the validity of these proposed models. A total of 8 test specimens were created at 2/3 scale with varying column sizes, connection details, and embedment depths. The columns were loaded laterally and cyclically at increasing displacements until the connection failed. The results show that the strength model proposed by Barnwell is reasonable and appropriate, and when applied to this series of physical tests produce predictions that have an observed/predicted ratio of between 0.95 to 1.39. The results also show that methods for estimating the rotational stiffness of the connection at the top of the block out concrete, as proposed by Jones and Tryon also produce reasonable values that had observed/predicted ratios of between 0.93 to 1.47. An alternative model for determining a design value for the rotational stiffness of a shallowly embedded column base plate is also proposed. When the embedment depth to column depth ratio is greater than 1.22, the connection is sufficiently rigid and at small deflections (less than 1% story drift) may be accurately modelled with infinite rotational stiffness (a "fixed" connection) at the base of the column.