Yes / This paper aims to investigate the mean velocities and turbulence characteristics, which include Reynolds shear stresses (RSS) and turbulent intensities, in order to study temporal and spatial flow patterns around a complex three square-piers group. Measurements have been performed by acoustic Doppler velocimeter (ADV) to identify turbulence flow structures alteration and vortices formation in longitudinal, transverse, and vertical directions. In total, 164 locations around the bridge piers have been measured, while each location consists of no lesser than 15 vertical depth ADV data point measurements. To investigate the flow turbulence, critical locations have been observed from high vortex-influenced regions. The impacted mean velocity profiles have been compared to that at the unaffected region to study the flow alteration caused by piers group. The result reveals that the log-law layer near wall has been enhanced by the installation of pier. Furthermore, as identified from the most critical locations of turbulent structures across different measurement rows, the accelerated flow will result in lower observed turbulent structures. Although flow after each pier has been influenced by strong reversal velocities, vortices have managed to form at near wake. Analysis has been divided into inner and outer flow regions (IFR and OFR) based on flow depth to enhance the understanding of how bridge piers contribute to the development of flow turbulence. / Shuyan Zang acknowledges the support of Chinese National Natural Science Foundation (Grant No. 22308222) to this study.

Telomeres are the outermost parts of linear chromosomes. They consist of tandemly repeated non-coding short nucleotide sequences (TTAGGG in all vertebrates), in humans spanning over the last 2 to 15 kilobase pairs of the chromosome. Due to the end-replication problem, telomeres shorten with each cellular division. A critically short telomere will trigger the cell to enter a state of cellular senescence or to apoptose. The rate of telomere shortening can be accelerated by factors such as oxidative stress and inflammation. Taken together, this contributed to making telomere length a candidate biomarker of health and aging. Studies have shown that leukocyte telomere length progressively shortens with age, and that it independent of age is associated with age-related morbidity, lifestyle factors, and mortality. This thesis was aimed at exploring the relationships of leukocyte telomere length with various functional and structural attributes of the brain. In Paper I, telomere length was shown to be longer among non-demented carriers of the apolipoprotein E (APOE) ε4 allele, a well-established risk factor for Alzheimer’s disease. However, the rate of telomere shortening was greater among the ε4 carriers, possibly due to the higher levels of oxidative stress and inflammation associated with this allele. Furthermore, performance on episodic memory tests was inversely related to telomere length among ε4 carriers. The results may contribute to a better understanding of the pathophysiology related to the APOE ε4 allele. The volume of the hippocampus, a structure in the brain critical for episodic memory function, was in Paper II found to be inversely related to telomere length among non-demented APOE ε3/ε3 carriers. No correlation between hippocampal volume and telomere length was discernible among ε4 carriers, but they fit the pattern exhibited by the ε3/ε3 carriers as they tended to have smaller hippocampi and longer telomere length compared with the ε3/ε3 carriers. The results are possibly explained by a low proliferative activity among subjects with smaller hippocampi, which might also explain the inverse association between telomere length and episodic memory performance in Paper I. In Paper III, we describe results corroborating earlier findings of shorter telomere length among individuals suffering from depression. Moreover, we found that the shorter telomere length among the patients to a large extent could be linked to a hypocortisolemic state; a state which has been associated with chronic stress. The findings corroborate the link between telomere length and stress, and underline the role of stress in depressive illness. Two prominent manifestations of the aging brain are atrophy and white matter hyperintensities. In Paper IV, we report that white matter hyperintensities and cerebral subcortical atrophy were associated with shorter telomere length in aged non-demented individuals. Cortical atrophy was not associated with telomere length. Inflammation may be the underlying cause of the associations, as it is linked to telomere attrition, subcortical atrophy, and white matter hyperintensities. Taken together, these results show that leukocyte telomere length has the potential of being used as a biomarker for structural and functional attributes of the brain. Furthermore, the findings can provide new insights into mechanisms of disease and aging of the brain

Submitted by Claudia Rocha (claudia.rocha@udesc.br) on 2017-12-05T12:41:21Z No. of bitstreams: 1 PGCS15MA124.pdf: 1312847 bytes, checksum: 750d88452b24e573464fff88790dbef6 (MD5) / Made available in DSpace on 2017-12-05T12:41:21Z (GMT). No. of bitstreams: 1 PGCS15MA124.pdf: 1312847 bytes, checksum: 750d88452b24e573464fff88790dbef6 (MD5) Previous issue date: 2015-05-15 / The soil organic matter (SOM) is formed by a set of chemical compounds which have different decomposition rates and products of these processes result as the main source of sulfur, phosphorus and nitrogen into the soil. Because of its great importance to the ground, it is of utmost importance to quantify MOS content. Its composition consists of carbon (C), hydrogen (H), oxygen (O), nitrogen (N), phosphorus (P) and sulfur (S), among others, it is difficult to determine its content. Most analytical techniques measure only carbon and estimate the MOS by a conversion factor. The study aimed to develop an analytical method for quantification of soil organic matter by means of a colorimetric method based on image analysis. The proposed method used the carbon oxidation process of Walkley-Black methodology and the resulting solutions were inserted into spectrophotometer cells for a smart phone equipped with a digital camera with a CCD detector (charge coupled device) register the images. These were treated with ImageJ software and the image of each solution has been selected from an area in which 100x100p were extracted RGB intensities (Red, Green and Blue colors, designs, especially for 8-bit data). We analyzed the RGB values and its relations with the MOS concentrations, resulting that the RED channel showed the best relationship with the organic matter content. The data were modeled by a linear regression (ARED = 0.1222 MOS - 0.1621; R² = 0.9934 and p <0.05) and it was possible to build a model that relates the color intensity with concentration. The proposed method showed accuracy of approximately 71% using a standard soil sample (LUFA Speyer - type 2.2), similar to the result obtained with the method currently used (Walkley-Black) which was 74% / A matéria orgânica do solo (MOS) é formada por um conjunto de compostos químicos que possuem diferentes taxas de decomposição, e os produtos desses processos resultam como fontes principais de enxofre, fósforo e nitrogênio para o solo. Devido a sua grande importância para o solo, é de extrema importância a quantificação do teor da MOS. Como a sua composição consiste em carbono (C), hidrogênio (H), oxigênio (O), nitrogênio (N), fósforo (P) e enxofre (S), dentre outros, torna-se difícil a determinação do seu teor. A maioria das técnicas analíticas mensuram apenas carbono e estimam a MOS por um fator de conversão. A pesquisa teve por objetivo o desenvolvimento de uma metodologia analítica para quantificação de matéria orgânica do solo por meio de um método colorimétrico baseado em análise de imagens. O método proposto utilizou o processo de oxidação de carbono da metodologia Walkley-Black e as soluções resultantes foram inseridas em celas espectrofotométricas para que um smartphone equipado com uma câmera digital, com um detector CCD (charge coupled device), registre as imagens. Estas foram tratadas com o software ImageJ e na imagem de cada solução foi selecionado uma área de 100x100p no qual extraíram-se as intensidades RGB (Red, Green e Blue, modelos de cores, especialmente para dados de 8 bits). Analisou-se os valores RGB e suas relações com as concentrações de MOS, resultando que o canal RED apresentou a melhor relação com o teor de matéria orgânica. Os dados foram modelados por meio de uma regressão linear (ARED = 0,1222 MOS – 0,1621; R² = 0,9934 e p < 0,05) e assim foi possível a construção de um modelo que relaciona a intensidade de cor com a concentração. O método prposto apresentou exatidão de aproximadamente 71% usando uma amostra de solo padronizada (LUFA Speyer – tipo 2.2), similar ao resultado obtido com o método usado atualmente (Walkley-Black) que foi de 74%

Orientador: Roy Edward Bruns / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-15T20:17:10Z (GMT). No. of bitstreams: 1 Meneses_HelenGraciCoelhode_M.pdf: 636858 bytes, checksum: 800e3602970307826daad0f0170d7220 (MD5) Previous issue date: 2010 / Resumo: Neste trabalho investigamos se o método QCISD e o conjunto de base de cc-pVTZ apresentariam resultados mais próximos das intensidades experimentais no infravermelho do que as obtidas dos cálculos usando o método MP2 e a função de base 6-311++G(3d,3p) para os hidrocarbonetos. Nos níveis com o método QCISD o erro rms foi de 4,7 km/mol para as duas bases enquanto que no nível MP2/6-311++G(3d,3p) foi de 7,6 km/mol e para o nível MP2/cc-pVTZ 9,0 km/mol. Foi observado que para as intensidades o efeito do método é maior que o efeito da base e que o efeito de interação método base, em geral, é muito pequeno. Também foi avaliado, através de um planejamento fatorial, se os parâmetros CCFDF (Charge-Charge Flux-Dipole Flux) dependem sensivelmente do método e da base utilizados no cálculo. Para as contribuições de carga, fluxo de carga e fluxo de dipolo para as derivadas médias do momento dipolar em termos de coordenadas cartesianas, de um modo geral, a base tem efeitos maiores do que o método e o efeito de interação entre método e base é muito pequeno. Entretanto, para a derivada total o efeito do método é maior do que o da base, o que é consistente com os resultados para as intensidades. Os cálculos foram feitos para moléculas de metano (CH4), etano (C2H6), eteno (C2H4), etino (C2H2), aleno (C3H4), propino (C3H4) e ciclo-propano (C3H6) / Abstract: The QCISD quantum method and cc-pVTZ basis set were investigated relative to the second order Möller-Plesset level and 6-311G++(3d,3p) basis set for calculating accurate infrared vibrational intensities of fundamental bands of the hydrocarbons. The QCISD results for both basis sets had root mean square errors of 4.7 km mol whereas at the Möller-Plesset level, the 6-311++G(3d,3p) basis set provided a 7.6 km mol error and the cc-pVTZ basis, a 9.0 km mol error. The effects of changing the quantum method on the intensities were larger than the effects of changing basis sets. Furthermore their interaction effects were small. Also by means of a factorial design, the sensitivities of charge - charge flux ¿ dipole flux (CCFDF) parameters to quantum level and basis set changes were evaluated. The basis set change provoked a larger effect on the charge, charge flux and dipole flux contributions to the mean dipole moment derivative than did the change in quantum level. On the other hand, the total mean dipole moment derivative is more sensitive to changes in the quantum method than the basis set, consistent with the finding for the intensities. Calculations were carried out on methane (CH4), ethane (C2H6), ethylene (C2H4), acetylene (C2H2), allene (C3H4), propene (C3H4 ) and cyclkopropane (C3H6) / Mestrado / Físico-Química / Mestre em Química

Orientador: Roy Edward Bruns / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-23T23:59:20Z (GMT). No. of bitstreams: 1 Pitoli_AndrewCorreiaLacerda_M.pdf: 2077655 bytes, checksum: 32c10438ae1b1f0a2497289009934861 (MD5) Previous issue date: 2013 / Resumo: Nesta dissertação de mestrado investigaram-se as partições atômicas, uma abordagem inovadora e complementar ao modelo QTAIM/CCFDF, da derivada do momento dipolar molecular e das intensidades no infravermelho. O nível de teoria QCISD/6-311++G(d,p) foi escolhido para realização dos cálculos por apresentar o menor erro rms associado ao menor custo computacional, quando comparamos os resultados obtidos experimentalmente e diretamente da função de onda para a derivada média do momento dipolar, ±0,0187e, de nove moléculas diatômicas: CO, HBr, HCl, HF, LiH, LiF, LiCl, NaF e NaCl. Os resultados calculados para a derivada média do momento dipolar, a anisotropia atômica, o quadrado da carga efetiva, o momento dipolar molecular e sua derivada, quando comparados os valores calculados aos experimentais, ratificaram a qualidade da função de onda obtida e comprovou a eficácia da teoria QTAIM na descrição de propriedades moleculares. A partição atômica da derivada do momento dipolar molecular durante a vibração mostrou, segundo um modelo simples, que, para as diatômicas em geral, a polarização da nuvem eletrônica se dá em direção ao átomo mais eletronegativo na molécula, como observado pelo termo de transferência de carga, entretanto, a nuvem eletrônica tende a acomodar-se na região internuclear nas imediações do núcleo mais eletronegativo, como observado pelo sentido das variações dos dipolos atômicos. Avaliando as partições atômicas das intensidades no infravermelho, observou-se a importância do fator mecânico relacionado à massa reduzida do sistema, para as moléculas diatômicas em estudo, onde a contribuição do átomo de hidrogênio à intensidade no infravermelho é predominante nas moléculas que o contém. As partições atômicas da intensidade no infravermelho da banda característica do grupo carbonil, na série de fluorocloroaldeídos em estudo, revelou que a soma das contribuições atômicas do carbono, oxigênio e a interação de dois núcleos C,O é predominante na descrição do valor da banda. Ainda segundo o modelo de partições atômicas, observou-se que a contribuição dos átomos de carbono à soma das intensidades no infravermelho na série dos fluorocloroaldeídos e dos fluoroclorometanos é correlacionada positivamente à média de eletronegatividade de seus substituintes, enquanto o comportamento oposto é observado para a série dos oxissulfetos de carbono. Por fim, uma comparação entre o modelo de partições atômicas e o modelo de eletronegatividade de Barros Neto & Bruns revelou que, embora os dois modelos partam de quantidades físicas diferentes, os resultados previstos pelos modelos e obtidos experimentalmente estão em acordo menor que dois porcento entre os erros rms dos desvios relativos percentuais de ambos os modelos / Abstract: In this dissertation we investigated atomic partitions, an innovative and complementary approach to the QTAIM/CCFDF model, of the molecular dipole moment derivative and infrared intensities. Calculations were carried at the QCISD/6-311++G(d,p) level of theory due to its reasonable computational cost and its lower rms error,± 0.0187 e, on comparing mean moment dipole derivative results obtained experimentally with those calculated directly from the wave functions of nine diatomic molecules: CO, HBr, HCl, HF, LiH, LiF, LiCl, NaF and NaCl. The calculated results for the mean moment dipole derivative, atomic anisotropy, square of the effective charge, the molecular dipole moment and its derivative, on comparison with the experimental values, ratified the quality of the wave function obtained and proved the QTAIM theory efficacy in the description of molecular properties. The atomic partitions of the molecular dipole moment derivative during vibration revealed that, according to a simple model, for the diatomic molecules in general, the electron density accumulates in the direction of the more electronegative atom in the molecule, as observed by the charge transfer term. However, the electron cloud tends to polarize in the opposite direction as noted by the direction of changes in atomic dipoles. Evaluating the atomic partitions of the infrared intensities, we observed the importance of mechanical factors related to the system mass for the diatomic molecules under study, as the contribution of the hydrogen atom to the infrared intensity is predominant in molecules containing it. For the fluorine and chlorine substituted aldehydes under study, the atomic partitions of the carbonyl characteristic absorption intensity revealed that the sum of the carbon and oxygen atomic contributions and their interaction term is predominant in the description of the band value. Regarding the atomic partitions model, it was observed that the carbon atoms atomic contributions to the intensity sum are positively correlated to the average electronegativity of its substituents for both the fluorine and chlorine substituted aldehydes and methanes, while the opposite behavior is observed for the oxide sulfide substituted carbons. Finally, a comparison between the atomic partitions model and the electronegativity model of Barros Neto & Bruns revealed that, although both models are based on different physical phenomena, the results predicted by both models and experimental data are in agreement with less than two percent deviation between the rms errors of the relative percentage deviations of both models / Mestrado / Físico-Química / Mestre em Química

Orientador: Roy Edward Bruns / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-22T08:17:00Z (GMT). No. of bitstreams: 1 Richter_WagnerEduardo_M.pdf: 2307688 bytes, checksum: 6bea76734d3591eb0c48a2fb4a4c7c53 (MD5) Previous issue date: 2013 / Resumo: Nesta dissertação de mestrado foram estudadas as estruturas eletrônicas do trifluoreto e tricloreto de boro através da metodologia QTAIM/CCFDF. O critério de qualidade dos resultados foi o erro médio quadrático para a soma das intensidades fundamentais, sendo o conjunto de base 6-31G(2d,2p) (nos níveis MP2 e QCISD) o que obteve melhor performance para o BF3, gerando erros inferiores a 20 km.mol nos dois casos. Para o BCl3 isso infelizmente não pode ser feito, pois os dados teóricos disponíveis põe em dúvida a validade das medidas experimentais. Após uma análise estatística de diversos níveis de teoria, viu-se que os melhores níveis para o BF3 poderiam funcionar para o BCl3 também. As cargas QTAIM calculadas seguiram o esperado, com maior magnitude nos atomos do BF3 frente aos do BCl3 (para o boro, 2,48e versus 2,02e), fruto da maior diferença de eletronegatividade entre boro e fluor. Estas magnitudes foram tamanhas que é até possível interpretar a ligação B.F como sendo iônica. As intensidades fundamentais, obtidas da função de onda, foram reproduzidas com boa precisão para o BF3 e para as bandas Q2 e Q4 do BCl3, e a concordância destas com as respectivas CCFDF foi quase perfeita, comprovando a robustez da integração feita pelo programa MORPHY. As contribuições CCFDF para os modos normais ressaltaram o caráter altamente polar das ligações, com cargas de fluxo zero sempre preponderantes, em maior grau no BF3. Por outro lado, as contribuições CCFDF para a derivada média do momento dipolar de cada átomo apresentaram termos dinâmicos bastante significativos para todos os átomos em ambas as moléculas, resultado interpretado como possível evidência de uma retrodoação na molécula BF3 e inexistente na molécula BCl3. Esta hipótese foi testada com uso dos Orbitais Naturais de Ligação, sendo que por meio dela ficou claro que a retrodoação no BF3 existe e é bastante intensa (55 kcal.molpor ligação), além dos motivos de sua ausência no BCl3. De fato, a doação X ¿¿B parece existir nas duas moléculas, mas envolve orbitais diferentes nas duas, fazendo com que o ciclo doação-retrodoação seja completo apenas no BF3, fator este que tem influência direta na acidez de Lewis destas moléculas. Como os parâmetros QTAIM, bem como as contribuições CCFDF para os modos normais, apontam para estruturas predominantemente iônicas, e sendo a retrodoação um fenômeno conceitualmente covalente, foi dada uma interpretação alternativa baseada em estruturas de ressonância para o BF3, reunindo ambos os comportamentos dentro de uma única proposta / Abstract: In this master's dissertation the electronic structures of boron trifluoride and trichoride were analyzed trough the QTAIM/CCFDF model. The quality criterion for the results was the root mean square error for the sum of the fundamental intensities, and Pople's 6-31G(2d,2p) basis set was chosen due to its best performance. The errors with both MP2 and QCISD correlation methods were less than 20km.mol for BF3. Unfortunately, the theoretical data put in doubt the validity of the experimental measurements for BCl3. It was necessary to carry out a statistical analysis to determine the best level of theory, and the conclusion was that the same levels of theory for BF3 would work for BCl3. The QTAIM charges calculated at these levels show no surprises, with a greater magnitude for the atoms that compose BF3 than BCl3 (2.48e vs. 2.02e for boron, with MP2), due to the large electronegativity difference between boron and fluorine. Moreover, the charges on boron and fluorine in BF3 were so large that it is possible to classify the B.F bond as ionic. The infrared intensities were determined with good precision for BF3 and for the Q2 and Q4 bands of BCl3. The agreement between the wave function intensities and the CCFDF ones is almost perfect, attesting to the robustness of the MORPHY98 integration algorithm. The CCFDF contributions to the normal modes highlighted the extension of the polarization attributed to the B.F bond, with zero flux charges always having greater values than the dynamical terms, mainly in BF3. Furthermore, the CCFDF contributions to the mean dipole moment derivatives of each atom show a different pattern, with significant values for at least one dynamical contribution for all the atoms in both molecules. This result supports the hypothesis of a back-donation mechanism in the BF3 molecule, nonexistent in the BCl3 molecule. This hypothesis was tested with Natural Bond Orbital calculations, from which one can conclude that back-donation really exists in BF3, with great influence on the bond energy (55 kcal.mol per bond), whereas this possibility is excluded for BCl3. Indeed X ¿¿B donation is predicted to exist in both molecules, but involves different orbitals in each one with the cycle only being completed in BF3. This fact has a direct impact on their Lewis acidities. Since the QTAIM parameters, like the CCFDF contributions, point to predominantly ionic bonds, and the back-donation mechanism is a purely covalent concept, an alternative interpretation was given based on resonance structures for BF3, merging both ionic and covalent observations in a unique model / Mestrado / Físico-Química / Mestre em Química

Yes / This study presents results from a vegetation-induced flow experimental study which investigates 3-D turbulence structure profiles, including Reynolds stress, turbulence intensity and bursting analysis of open channel flow. Different vegetation densities have been built between the adjacent vegetations, and the flow measurements are taken using acoustic Doppler velocimeter (ADV) at the locations within and downstream of the vegetation panel. Three different tests are conducted, where the first test has compact vegetations, while the second and the third tests have open spaces created by one and two empty vegetation slots within the vegetated field. Observation reveals that over 10% of eddies size is generated within the vegetated zone of compact vegetations as compared with the fewer vegetations. Significant turbulence structures variation is also observed at the points in the non-vegetated row. The findings from burst-cycle analysis show that the sweep and outward interaction events are dominant, where they further increase away from the bed. The effect of vegetation on the turbulent burst cycle is mostly obvious up to approximately two-third of vegetation height where this phenomenon is also observed for most other turbulent structure. / The full text will be available at the end of the publisher's embargo period: 1st Feb 2025

L'interaction d'un plasma avec une impulsion laser-intense suscite de plus en plus d'intérêt du fait des progrès en matière de technologie laser d'outils numériques. La réaction du rayonnement affecte la dynamique des électrons, celle du rayonnement synchrotron, ainsi que celle des ions via le champ de séparation de charge, pour des intensités laser supérieures à 10puissance22 W/CM2. les équations cinétiques régissant le transport de particules à ultra-haute intensité ont été obtenues. La réaction du rayonnement implique la contraction du volum de l'epace des phases des électrons A l'aide de simulations numériques nous avons démontré la forte rétro-action que les effets collectifs induisent sur le rayonnement synchrotron généré par les électons accélérés. L'importance des effets collectifs dépend fortement de la masse des ions et de l'épaisseur du plasma considéré. Ces effets pourraient être vérifiés expérimentalement avec des cibles cryogéniques d'hydrogène. / Résumé en anglais

This thesis falls within the field of high resolution Fourier transform spectroscopy of gas phase molecules in the far to near infrared ranges. It is focused on quantitative aspects of gas phase spectroscopy: absolute line intensity measurements. Both stable and unstable molecules, of atmospheric interest, are investigated. With this work, we aim to provide the reference spectroscopic information needed to analyze spectra of planetary atmospheres and improve our understanding of the physical chemistry of these environments. We studied two molecules of atmospheric interest: the 13C16O2 isotopologue of carbon dioxide, which is a stable molecule, and the H16O79Br and H16O81Br isotopologues of hypobromous acid which are short-lived unstable molecules. The work carried out in the 2 and 1.6 µm regions of 13C16O2 falls in the framework of highly precise remote sensing of carbon dioxide in the Earth’s atmosphere, needing more and more accurate reference spectroscopic information. We measured 872 absolute line intensities corresponding to 317 different lines in seven vibration-rotation bands of 13C16O2. These measurements, together with measurements performed in the Laboratoire de Spectrométrie Physique (Université Joseph Fourier, Grenoble, France) led to the improvement of the theoretical description of the spectrum of carbon dioxide, performed in the Laboratory of Theoretical Spectroscopy, (Institute of Atmospheric Optics, Tomsk, Russia). This study is preceeded by a preliminary work on the main isotopologue of carbon dioxide, 12C16O2 in the same spectral regions, aimed to determine the best suited line profile to model the observed line shapes of 13C16O2. HOBr exists only in equilibrium with its decomposition products, like Br2O and H2O. Quantitative spectroscopy on such an unstable molecule therefore implied the use of a specific method to determine the concentration of HOBr in the studied gas sample. Simultaneously, Tunable Diode Laser (TDL) infrared spectra of some lines of the nu2 band and a far infrared Fourier transform spectrum of pure rotation lines of HOBr were recorded. The measured intensities of pure rotation lines together with the permanent electric dipole moment of the molecule were used to determine the partial pressure of HOBr, thus allowing absolute intensities of the lines probed by the TDL to be determined. These infrared absolute line intensities were then used to “calibrate” the relative line intensities in the nu2 band, measured in a Fourier transform spectrum recorded separately. Cette thèse s’inscrit dans le cadre de la spectroscopie è haute résolution de molécules en phase gazeuse dans l’infrarouge proche à lointain. Ce travail se concentre sur les aspects quantitatifs de la spectroscopie en phase gazeuse: la mesure d’intensités absolues. Des molécules d’interêt atmosphérique stables et instables ont été étudiées. Le but de ce travail est de fournir des informations spectroscopiques de référence utiles à l’analyse de spectres d’atmosphères planétaires et, ainsi, améliorer notre compréhension de la physico-chimie de ces environnements. Nous avons étudié deux molécules d’interêt atmosphérique: l’isotopologue 13C16O2 du dioxyde de carbone, qui est une molécule stable, et les isotopologues H16O79Br et H16O81Br de l’acide hypobromeux qui sont des molécules instables. Le travail effectué sur les régions spectrales à 2 et 1.6 µm de 13C16O2 s’inscrit dans le cadre des mesures à distance à très haute précision du dioxyde de carbone présent dans l’atmosphère terrestre. Nous avons mesuré 872 intensités absolues correspondant à 317 raies d’absorption dans sept bandes de vibration-rotation de 13C16O2. Ces mesures, ainsi que celles réalisées au Laboratoire de Spectrométrie Physique (Université Joseph Fourier, Grenoble, France) ont abouti à l’amélioration de la description théorique du spectre du dioxyde de carbone, réalisée au Laboratory of Theoretical Spectroscopy (Institute of Atmospheric Optics, Tomsk, Russie). Cette étude est précédée par un travail préliminaire sur l’isotopologue principal du dioxyde de carbone, 12C16O2 dans les mêmes régions spectrales, visant à déterminer le profil de raie le plus adapté pour modéliser les profils observés de 13C16O2. HOBr existe uniquement en équilibre avec ses produits de décomposition tels que Br2O and H2O. Effectuer des mesures quantitatives pour ce type de molécule instable implique dès lors l’utilisation d’une technique spécifique afin de déterminer la pression partielle de HOBr. Un spectre infrarouge en Diode Laser Accordable (DLA) de quelques raies de la bande nu2 de HOBr et un spectre infrarouge lointain en transformée de Fourier d’un même échantillon gazeux ont été enregistrés simultanément. Les intensités mesurées de raies de rotation pure combinées au moment dipolaire électrique permanent de la molécule ont été utilisées pour déterminer la pression partielle de HOBr, nous permettant ainsi de déterminer les intensités absolues des raies mesurées à l’aide de la DLA. Ces intensit´es absolues ont ensuite été utilisées pour “calibrer” les intensités relatives des raies de la bande nu2, mesurées dans un spectre à transformée de Fourier enregistré séparément.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / Emission line intensities from ionized nebulae are an important information source about this objects. There are many data on line intensities emitted from supernova remnants scattered in the literature. However, these data can be more efficiently used if avaliable in the form of an electronic data base. Based on this, it was made a catalog of emission line intensities of supernova remnants with data obtained from the literature, including lines in the spectral range of 900Å to 100 mm. About 300 supernova remnants and more than 25 000 emission line intensities were cataloged, including adittional information associated to the objects and the observations. As a demonstration of the aplicability of this catalog, diagnostic diagrams were made with emission line intensities from supernova remnants and from HII regions, using the line ratios [O III] l5007/Hb, [N II] l6583/Ha, [O II] l3727/Hb, [S II] (l6716+l6730)/Ha and [O I] l6300/Ha. Besides these traditional diagrams, the large amount of data in the catalog allowed the construction of others diagrams using relatively weak lines, rarely measured. The diagrams were effective for the classification and discrimination of these classes of objects. It was also verified the values of the ratios [O III] l5007/l4959 and [N II] l6584/l6548, which returned results in agreement with some others published. Moreover, considering the ultraviolet spectroscopy advances in recent decades, it is presented an history of the instrumentation and its performance evolution, regarding some topics that show the importance of the studies about the ultraviolet spectra of supernova remnants. Finally, a list of all ultraviolet emission lines already measured in supernova remnants until 2010 was made, and compared with a similar list created in 1996. It was found that many new lines were detected and some multiplets became resolved since then. Each one of the 142 lines was identified by its wavelength, the ion and parameters of the transition that generates it. This table may be used as a reference for identifying emission lines in supernova remnants in future studies. / As intensidades de linhas de emissão de nebulosas ionizadas constituem uma importante fonte de informação sobre esses objetos. São numerosos os dados que podem ser encontrados em diferentes artigos da literatura referentes a intensidades de linhas emitidas por remanescentes de supernovas. Porém, esses dados podem ser mais eficientemente utilizados se disponibilizados em conjunto e de maneira organizada, ou seja, na forma de um catálogo. Com base nisso, foi construído um catálogo de intensidades de linhas de emissão de remanescentes de supernovas com dados extraídos da literatura, incluindo linhas no intervalo espectral de 900 Å até 100 mm. Cerca de 300 remanescentes de supernovas e mais de 25 000 intensidades de linhas de emissão foram catalogadas, incluindo informações adicionais associadas ao objeto e à observação. Como demonstração de aplicação do catálogo, foram construídos diagramas de diagnóstico com intensidades de linhas de emissão de remanescentes de supernovas e de regiões HII, utilizando as razões de intensidades de linhas [O III] l5007/Hb, [N II] l6583/Ha, [O II] l3727/Hb, [S II] (l6716+l6730)/Ha e [O I] l6300/Ha. Além desses diagramas tradicionais, a grande quantidade de dados do catálogo permitiu construir novos diagramas utilizando linhas relativamente fracas, raramente medidas. Os diagramas mostraram-se eficientes para a classificação e distinção dessas classes de objetos. Também verificou-se os valores das razões [O III] l5007/l4959 e [N II] l6584/l6548, retornando valores em concordância com outros publicados. Por fim, considerando os avanços na espectroscopia ultravioleta das últimas décadas, apresenta-se um histórico da instrumentação utilizada e da evolução de sua performance, considerando também alguns tópicos que mostram a importância dos estudos espectroscópicos na faixa do ultravioleta em remanescentes de supernovas. Construiu-se uma lista com todas as linhas de emissão do ultravioleta já medidas em remanescentes de supernovas até o ano de 2010, fazendo-se um comparativo com as linhas medidas até o ano de 1996. Verificouse que várias novas linhas foram detectadas e que alguns multipletos passaram a ser resolvidos. Essas 142 linhas são identificadas pelo seu comprimento de onda, pelo íon e por parâmetros das transições que as geram, e são listados os remanescentes de supernovas em que cada linha foi medida. Essa tabela pode ser utilizada como referência na identificação das linhas em futuros estudos de remanescentes de supernovas.