Dual-broadband and dual-pump nanosecond CARS experiments were performed to investigate the pure rotational transitions of the nitric oxide molecule. The former experiment was initially utilized to determine the pure rotational structure while the latter focused on polarization suppression of the pure rotational transitions of nitric oxide. A polarization calculation and analysis were conducted on the rotational and vibrational transitions of nitrogen, and the pure rotational transitions of nitric oxide were subjected to a similar polarization scheme. The electronic transitions that arise due to the spin-split nature of nitric oxide ground electronic energy levels were suppressed by the polarization scheme in a similar manner to the rotational S branch transitions. Results have been compared with a spectral simulation developed by Dr. Lucht, and the theory is partially presented. Comparison between simulation and experimental data yielded favorable agreement for the pure rotational transitions of nitric oxide.

Ce travail présente l’optimisation d’un système de spectroscopie Raman résolue en temps dédiée aux très hautes températures. Ce dispositif répond au besoin sans cesse croissant d’étudier en temps réels les transformations de phases et des cinétiques de réactions dans des environnements extrêmes. Ce dispositif a été validé dans des conditions d’usages sur des oxydes (Gd₂O3, Y₂O3, ZrO₂ , ZrSiO4 et CeO₂) et des nitrures (h-BN). Le potentiel du système a permis de lever les principaux verrous technologiques et instrumentaux qui limitent l’utilisation de la spectroscopie Raman à haute température. Les trois principaux faits marquants qui illustrent le caractère innovant de ce travail sont les suivants : Le premier correspond au nouveau record mondial d’analyse Raman à haute température à travers l’acquisition du mode E₂g de h-BN jusqu’à 2700°C. La comparaison des performances des deux voies Pockels et ICCD montrent que la voie Pockels est plus performante que l’ICCD, mais plus délicate de mise en oeuvre. Le second fait marquant concerne les autres applications du Raman résolu en temps, comme pour séparer la contribution de la diffusion Raman et de la luminescence. La dernière application quant à elle présente l’étude de la dépendance temporelle comparée des diffusions Raman résonnante et non résonante. Le Raman résonnant se déclenche systématiquement avant le non résonnant. Plus généralement, l’intérêt des méthodes Raman résolues en temps ouvre de nouveaux champs d’application dans la caractérisation de matériaux en condition extrêmes, éventuellement in situ : aéronautique, réfractaire ; sidérurgie, nucléaire, etc… / This work presents the optimization of a time-resolved Raman spectroscopy device dedicated to very high temperatures. This device meets the ever-increasing need to study in real time phase transformations and reaction kinetics in extreme environments. This device has been validated under working conditions on oxides (Gd₂O3, Y₂O3, ZrO₂ , ZrSiO4 et CeO₂) and nitrides (h-BN). The potentialities of the device have enabled the main technological and instrumental locks that limit the use of high temperature Raman spectroscopy to be removed. The three main highlights illustrating the innovative nature of this work are as follows. The first corresponds to the new world record for high temperature Raman analysis through the acquisition of the E₂g mode of h-BN up to 2700°C.A comparison of the performance of the two Pockels and ICCD channels shows that the Pockels channel is more efficient than the ICCD, but more difficult to implement. The second important fact concerns the other applications of time-resolved Raman, as to separate the contribution of Raman scattering and luminescence. The last application presents the study of the comparative time dependence of resonant and non-resonant Raman scattering. The resonant Raman is triggered systematically before the non-resonant. More generally, the interest of time-resolved Raman methods opens new fields of application in the characterization of materials in extreme conditions, possibly in situ: aeronautics, refractories, steel industry, nuclear, etc....

De part ses nombreuses applications scientifiques et sociétales comme la radiographie protonique ou encore la protonthérapie, l’accélération d’ions par laser suscite un grand intérêt. Cette thèse s’inscrit dans ce cadre et présente une étude de l’interaction d’une impulsion laser d’intensité relativiste avec un plasma de densité modérée. Dans ce régime, le plasma est transparent à l’onde laser et les électrons oscillent à des vitesses relativistes dans le champ de l’onde incidente. Ces conditions sont favorables à un transfert efficace de l’énergie laser vers le plasma, et donc sont intéressantes pour l’accélération d’ions par laser. Ce régime permet également la création de solitons électromagnétiques et acoustiques dont les mécanismes de formation et les propriétés nécessitent une meilleur compréhension. Nous réalisons une étude détaillée de simulations Particle-In-Cell (réalisées avec le code OCEAN) de l’interaction d’une impulsion laser intense avec un plasma sous dense. Nous montrons que la diffusion Raman stimulée (SRS) dans le régime relativiste est le principal processus responsable de l’absorption de l’énergie laser par le plasma et qu’il est, en outre, très efficace puisqu’il permet de transférer près de 70 % de l’énergie de l’impulsion laser aux électrons. Cette instabilité apparaît dans des plasmas dont la densité est nettement supérieure à la densité quart-critique du fait de la diminution de la fréquence plasma électronique et se développe sur des temps très courts. Il permet ainsi un chauffage homogène des électrons tout le long de la propagation de l’impulsion laser à travers le plasma. Ces électrons participent à la détente du plasma, et créent sur ses bords raids un champ électrostatique permettant l’accélération des ions. Ces derniers gagnent 30 % de l’énergie laser initiale. Nous avons aussi développé un modèle simple qui permet de prédire et donc d’optimiser le taux de rétro-diffusion du plasma du fait du développement de l’instabilité SRS. Nous nous intéressons également à la séquence des processus permettant la formation des cavités électromagnétiques. Cette analyse souligne le rôle joué par l’instabilité modulationnelle ou de Benjamin-Feir sur le front de l’impulsion laser qui est divisée en un train de plusieurs solitons électromagnétiques. À l’aide d’une étude détaillée, nous montrons que ces solitons excitent des ondes plasmas dans leur sillage en se propageant dans le plasma, perdent de l’énergie et finissent par être piégés. Ils forment également des dépressions (cavités) des densités électroniques et ioniques du plasma. Ces cavités sont des pièges pour les champs électromagnétiques rayonnés par le plasma (par exemple du fait de l’instabilité SRS) et survivent grâce à un équilibre entre la pression de radiation des champs piégés et les pressions cinétiques électroniques à leurs bords. Ces cavités absorbent une part importante de l’énergie laser mais elles n’en conservent qu’une partie sous forme d’énergie électromagnétique piégée. Le reste de l’énergie permet l’expansion de la cavité, la génération de solitons acoustiques supersoniques et l’accélération de particules. / The laser-accelerated ions draw an increasing interest due to their potential applications and to their unique properties. This manuscript presents a study of the interaction between a relativistic intense laser pulse and a low density plasma. In this regime, the plasma is transparent to the laser pulse and electrons oscillate with relativistic velocities in the field of the incident wave. These conditions make the transfer of the laser pulse energy to the plasma efficient, and therefore are interesting for the ion acceleration. This regime generates also electromagnetic and acoustic solitons whose formation mechanisms and properties need to be better understood. We carry out a detailed analysis of Particle-In-Cell simulations (performed with the code OCEAN) of interaction of an intense laser pulse with a low density plasma.We show that the stimulated Raman scattering (SRS) is the main mechanism responsible for the absorption of laser energy in plasma. This process is very efficient : it leads to the transfer of 70 % of the laser pulse energy to electrons. This instability occurs in plasmas with a density larger than the quarter critical one due to the decrease of the electron plasma frequency and develops in a very short time scale. It leads to an homogeneous electron heating all along the distance of propagation of the laser pulse through the plasma. The ions are efficiently accelerated at the plasma edges and can get nearly 30%of the initial laser energy. This study is accompanied by a simple analytical model which is able to predict and so optimize the laser backscattering fraction due to the development of the SRS instability. We also present a sequence of stages which lead to the formation of electromagnetic cavities. This analysis highlights the role of the modulationnal or Benjamin-Feir instability in the front of the laser pulse, which is split in a train of electromagnetic solitons. Our detailed study shows that these solitons excite plasmas waves in their wake, lose energy and are finally trapped in the plasma. They lead to the formation of density depressions (cavities) which may trap the electromagnetic fields produced in the plasma (by the SRS instability, for example). These structures may survive for a long time thanks to an equilibrium of the trapped field radiation pressure and the electronic kinetic pressure at their borders. These cavities absorb an significant part of the laser energy but only a part of it is trapped inside. The remaining part is invested in the cavity expansion, generation of acoustic solitons and acceleration of charged particles.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Neste trabalho apresentamos uma investigaÃÃo dos compostos RVO4 (onde R = Sm, Ho, Yb e Lu) e La1-xCexPO4 (onde x = 0,00, 0,04, 0,16, 0,22, 0,32 e 1,00) atravÃs da tÃcnica de espalhamento Raman. Medidas de espalhamento Raman polarizadas foram realizadas nos compostos RVO4 para obter uma descriÃÃo dos fÃnons a temperatura ambiente melhor do que aquelas publicadas anteriormente na literatura. Observamos que a freqÃÃncia da maioria dos fÃnons aumenta com o aumento do nÃmero atÃmico (Z) de R. Este comportamento resulta da contraÃÃo da rede quando R vai de La atà Lu. Por outro lado, devido Ãs dimensÃes e forma dos compostos La1-xCexPO4, medidas de espalhamento Raman nÃo-polarizadas foram usadas para obter seus espectros de fÃnons a temperatura ambiente. Nenhuma mudanÃa apreciÃvel foi observada, indicando que a rede do composto LaPO4 nÃo sofre modificaÃÃes considerÃveis por causa da dopagem de Ce. Contudo alguns fÃnons extras ou adicionais foram observados. A origem desses modos advÃm, provavelmente, da ativaÃÃo de modos infravermelho causadas por quebras de regras de simetria. / In this work we present a Raman investigation of RVO4 (where R = Sm, Ho, Yb and Lu) and La1-xCexPO4 (where x = 0,00, 0,04, 0,16, 0,22, 0,32 and 1,00) compounds. Polarized Raman scattering measurements were carried out in the RVO4 compounds to obtain a better description of the room temperature phonons than those previously reported in literature. We observe that the frequencies of most of phonons increase with increasing atomic number (Z) of R. This behavior results from the lattice contraction when R goes from La to Lu. On the other hand, due to their dimensions and shape, unpolarized Raman scattering was used to investigate the room temperature phonon spectra of La1-xCexPO4 compounds. No appreciable changes were observed, indicating that the LaPO4 lattice is not substantially modified by Ce doping. However, some extra or additional phonons were observed. The origin of these modes comes probably from the activation of infrared modes due to the breakdown of symmetry rules.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / FundaÃÃo Cearense de Apoio ao Desenvolvimento Cientifico e TecnolÃgico / No presente trabalho foram realizadas medidas de espalhamento Raman polarizado em cristais de L-metionina e de DL-alanina (dois aminoÃcidos) e em diversas amostras de nanotubos de carbono de parede simples (SWNT). As medidas de espalhamento Raman em cristais de L-metionina foram realizadas no intervalo espectral entre 50 cm-1 e 3100 cm-1 desde a temperatura ambiente atà a temperatura de 17 K. No intervalo de temperatura estudado a estrutura da L-metionina manteve-se estÃvel. à temperatura ambiente tambÃm foram realizadas medidas Raman em altas pressÃes hidrostÃticas. A mÃxima pressÃo atingida foi de 4,7 GPa e diversas modificaÃÃes nos modos associados Ãs unidades CO2, NH3, CC, CS, CH, CH2 e CH3 sugerem que a L-metionina sofre um transiÃÃo estrutural de fase em torno de 2,1 GPa com histerese de aproximadamente 0,8 GPa. No cristal de DL-alanina foram realizadas medidas de espalhamento Raman no intervalo de temperatura de 15 K a 295 K. Embora nenhuma mudanÃa significativa tenha sido observada neste intervalo de temperatura, os resultados sÃo importantes para se entender o comportamento de uma molÃcula fundamental na constituiÃÃo das proteÃnas. Medidas de espalhamento Raman em SWNTâs foram realizadas em amostras preparadas pela tÃcnica de arco voltÃico, utilizando-se vÃrios catalisadores metÃlicos. As amostras foram divididas em duas sÃries: A primeira com os catalisadores à base de MnNiCo e a segunda à base de FeNiCo. Em ambas as sÃries observou-se que a inserÃÃo de CÃrio (Ce) foi responsÃvel por tornar a distribuiÃÃo de diÃmetros do subconjunto ressonante com a energia 2,41 eV mais estreita. AlÃm disso, o mÃximo da distribuiÃÃo à deslocado para o azul, provavelmente em conseqÃÃncia da seleÃÃo de tubos de menor diÃmetro dentro do subconjunto estudado. A inserÃÃo de ZircÃnio (Zr) à segunda sÃrie nÃo trouxe mudanÃas significativas. Foram realizadas medidas de espalhamento Raman em funÃÃo da pressÃo hidrostÃtica em uma amostra comercial de SWNT. Como fluido transmissor foram utilizadas soluÃÃes de dois surfactantes: o dodecil sulfato de sÃdio (SDS) e o Ãcido plurÃnico F127 (F127). Devido à baixa relaÃÃo sinal-ruÃdo, nÃo foi possÃvel estudar o comportamento dos modos de respiraÃÃo radial (RBM), mas pela descontinuidade do grÃfico da freqÃÃncia em funÃÃo da pressÃo dos modos tangenciais em aproximadamente 2 GPa à provÃvel que os nanotubos sofram uma transiÃÃo de fase estrutural nessa pressÃo, com deformaÃÃo da seÃÃo circular dos tubos como predito por estudos teÃricos. Dois conjuntos de amostras contendo diferentes nÃveis de inserÃÃo de lÃtio tambÃm foram estudados por espectroscopia Raman. Cada conjunto era formado por uma amostra sem lÃtio, uma com lÃtio e a terceira com inserÃÃo parcial de lÃtio (obtida pela lavagem da amostra que contÃm lÃtio). Nos dois conjuntos a inserÃÃo foi eficiente, contudo o mecanismo de inserÃÃo à diferente de uma sÃrie para outra. Na primeira sÃrie o catalisador utilizado para a inserÃÃo de lÃtio foi LiNi0,5Co0,5O2. Com este composto o lÃtio à intercalado intersticialmente e pode ser removido quase que completamente pela lavagem da amostra. Jà na segunda sÃrie o composto utilizado foi LiCO3/NiO/CoO o que fez com que o lÃtio fosse intercalado dentro dos tubos de modo a nÃo ser removido pela lavagem da amostra. / This work describes polarized Raman scattering measurements in L-methionine and in DL-alanine (two amino acids) crystals and in several samples of single-walled carbon nanotubes (SWNT). In L-methionine crystal the Raman spectra were obtained from 17 K to 295 K in the spectral range from 50 cm-1 to 3100 cm-1, but no indication of a phase transition was observed. At room temperature, Raman scattering measurements were also performed for pressure up to 5 GPa. Several changes observed in the spectra were interpreted as due to structural phase transition undergone by L-methionine crystal at ~ 2.1 GPa. The results for decompression show that the phase transition is reversible with a hysteresis of ~ 0.8 GPa. In DL-alanine crystal the Raman spectra were obtained at temperatures from 15 K to 295 K over the spectral range 50 cm-1 - 3100 cm-1. No evidence of structural phase transition was found in this range of temperature, although information about diverse modes of the crystal were furnished. Samples of SWNTâs studied were prepared with metallic catalysts using the arc voltaic method. MnNiCo was the main compound of the first series and FeNiCo, the main compound of the second. In both sets it was observed that Cerium (Ce) insertion induces in the sub-set, probed with the 2.41 eV excitation energy, a narrowing of the diameter distribution favoring the tubes with smaller diameter. The Raman scattering measurements in a commercial sample of SWNTâs show a discontinuity at about 2 GPa. The discontinuity was represented by a changing in the slope of the frequency versus pressure for tangential modes. The measurement was performed twice, using two different solutions of surfactants, sodium dodecil sulfate (SDS) and plurocic acid F127 (F127), and the results were similar. The anomaly was interpreted as due to the deformation of the tubes as predicted theoretically. Two sets of three samples of SWNTâs containing different levels of lithium insertion were also analyzed by Raman spectroscopy. Each set of sample was formed by a sample with lithium, a sample without lithium and a sample with partial insertion of lithium. The results show that the lithium is efficiently intercalated with both lithium containing compound (LiCO3/NiO/CoO and LiNi0.5Co0.5O2), but the mechanism of intercalation differs from one to the other. The intercalation is unstable when lithium is intercalated interstitially (LiNi0.5Co0.5O2) and it can be removed almost completely by washing the sample, but if the lithium is intercalated inside the tubes (LiCO3/NiO/CoO) it can not be removed by the same process.

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-06-06T20:07:41Z No. of bitstreams: 1 RaffaelPinto.pdf: 7905766 bytes, checksum: 7f7997961e840698d9d936cdea00b602 (MD5) / Made available in DSpace on 2017-06-06T20:07:41Z (GMT). No. of bitstreams: 1 RaffaelPinto.pdf: 7905766 bytes, checksum: 7f7997961e840698d9d936cdea00b602 (MD5) Previous issue date: 2008-05-21 / Fundação de Amparo à Pesquisa e ao Desenvolvimento Científico e Tecnológico do Maranhão (FAPEMA) / In this work have been investigated the dielectric and vibrational properties of the ORMOSIL membranes based on PDMS and TEOS doped with MDS using the Di erential Scanning Calorimetry (DSC), impedance, Raman and infrareds spectroscopy technics. Such membranes are hybrid organic-inorganic materials with potential application in PEMFC (Proton Exchange Membrane Fuel Cell) and were doped with concentrations 0%(Pure Membrane), 5%, 10%, 20% e 30% of MDS. The thermal measurements were performed in the range from room temperature and 550 oC. The results showed that, after the MDS inclusion, the membranes absorb water. Besides, then thermal stability of the membranes decreased with the MDS inclusion. The dielectrics measurements were performed in temperature range of 313K-373K. The results showed that room temperature conductivity increases linearly with the frequency, until 353K, suggesting a hopping conduction and leaving this linear behavior above 353K. Besides, it was observed that conductivity doesn't increases linearly with MDS concentration, but increases until maximal value for 20% MDS concentration and decreases again for 30% MDS concentration de ning a synergetic e ect, which probably is associate with con gurational arrange of microcristallites MDS. Another feature of that membranes is a relaxation process visible in the electrical module graphics which appear just in doped membranes, being however, due to the MDS. The vibrational properties of hybrids membranes were obtained through Raman scattering and infrared. The results con rmed the presence of Si¡O¡Si, Si¡C, Si¡OH, C2H5, Si¡CH3, CH3, CH2, C¡H, S=O and S¡O groups. Where the S=O and S¡O groups are presents just in MDS compound. Consequently, their respective peaks appear only in the doped membrane spectra. / Neste trabalho foram investigadas as propriedades térmicas, dielétricas e vibracionais das membranas de ORMOSIL baseadas em PDMS e TEOS dopadas com MDS através das técnicas de calorimetria diferencial de varredura, espectroscopias de impedância, Raman e infravermelho. Essas membranas são materiais híbridos orgânico-inorgânico com grande potencialidade de aplicação em células combustíveis do tipo PEM (Proton Exchange Membrane) e foram dopadas nas concentrações de 0%(Pura), 5%, 10%, 20% e 30% de MDS. As medidas térmicas foram realizadas entre a temperatura ambiente e 500 oC e mostraram que as membranas passam a absorver água quando o MDS é inserido. Mostraram também que as membranas têm sua estabilidade térmica reduzida quando o MDS é inserido. As medidas dielétricas foram realizadas no intervalo de temperatura entre 40 e 100oC. Os resultados mostraram que a condutividade à temperatura ambiente aumenta de maneira praticamente linear com a freqüência, mantendo-se assim até 80±C sugerindo uma condução por hopping e deixando de ter esse comportamento linear para temperaturas acima de 80±C. Observou-se também que a condutividade não aumenta linearmente com a concentração de MDS, mas atinge um valor máximo para a membrana com 20% de MDS e diminui novamente para a membrana com 30% de MDS caracterizando assim um efeito sinergético, que provavelmente está associado ao arranjo configuracional dos microcristalitos do MDS. Uma outra característica interessante dessas membranas, é um processo de relaxação visível nos grá cos do módulo elétrico o qual consta apenas nas membranas dopadas, sendo portanto, característico do MDS. As propriedades vibracionais desses materiais híbridos foram determinadas através de medidas do espalhamento Raman. Os resultados da espectroscopia Raman e infravermelho confirmaram a presença dos grupos Si¡O¡Si, Si¡C, Si¡OH, C2H5, Si¡CH3, CH3, CH2, C¡H, S=O e S¡O. Onde estes dois últimos estão presentes somente no MDS e, por essa razão, seus respectivos picos só se apresentaram no espectro das membranas dopadas.

Die Suche nach neuen Materialien von technischem Interesse hat in den letzten Jahren neue Antriebe zu der Untersuchung organischer Verbindungen gegeben. Organische Substanzen haben viele Vorteile wie z.B. die Möglichkeit, ihre Eigenschaften durch verschiedene chemische und physikalische Techniken im Herstellung-Prozess für ein bestimmtes Ziel zu modifizieren. Oxadiazolverbindungen sind interessant aufgrund ihrer Nutzung als Material für Licht emittierende Dioden und Scintillatoren. <br /> <br /> Die physikalischen Eigenschaften eines Festkörpers hängen von seiner Struktur ab. Unterschiedliche Strukturen entwickeln unterschiedliche intra- und intermolekülare Wechselwirkungen. Eine ausgezeichnete Weise, um sowohl die intra- als auch die intermolekularen Wechselwirkungen eines bestimmtes Stoffes zu beeinflussen, ohne seine chemischen Charakteristiken zu ändern, ist die Verwendung von hohem Druck. <br /> <br /> Wir haben den Einfluss von hohem Druck und hoher Temperatur auf die super-molekulare Struktur einiger Oxadiazolverbindungen im kristallinem Zustand untersucht. Aus diesen Untersuchungsergebnissen wurde eine Zustandsgleichung für diese Kristalle bestimmt. Überdies wurden die spektroskopischen Eigenschaften dieser Materialien unter hohem Druck charakterisiert. / In recent years the search for new materials of technological interest has given new impulses to the study of organic compounds. Organic substances possess a great number of advantages such as the possibility to adjust their properties for a given purpose by different chemical and physical techniques in the preparation process. Oxadiazole derivatives are interesting due to their use as material for light emitting diodes (LED) as well as scintillators. <br /> <br /> The physical properties of a solid depend on its structure. Different structures induce different intra- and intermolecular interactions. An advantageous method to modify the intra- as well as the intermolecular interactions of a given substance is the application of high pressure. Furthermore, using this method the chemical features of the compound are not influenced.<br /> <br /> We have investigated the influence of high pressure and high temperature on the super-molecular structure of several oxadiazole derivatives in crystalline state. From the results of this investigation an equation of state for these crystals was determined. Furthermore, the spectroscopical features of these materials under high pressure were characterized.

The three dimensional Monte Carlo radiation transport model McArtim is extended to account for the simulation of the propagation of polarized radiation and the inelastic rotational Raman scattering which is the cause of the so called Ring effect. From the achieved and now sufficient precision of the calculated Ring effect new opportunities in optical absorption spectroscopy arise. In the calculation the method of importance sampling (IS) is applied. Thereby one obtains from an ensemble of Monte Carlo photon trajectories an intensity accounting for the elastic aerosol particle-, Cabannes- and the inelastic rotational Raman scattering (RRS) and simultaneously an intensity, for which Rayleigh scattering is treated as an elastic scattering process. By combining both intensities one obtains the so called filling-in (FI, which quantifies the filling-in of Fraunhofer lines) as a measure for the strength of the Ring effect with the same relative precision as the intensities. The validation of the polarized radiometric quantities and the Ring effect is made by comparison with partially published results of other radiation transport models. Furthermore the concept of discretisation of the optical domain into grid cells is extended by making grid cells arbitrarily joining into so called clusters, i.e. grid cell aggregates. Therewith the program is able to calculate derivatives of radiometrically or spectroscopically accessible quantities, namely the intensities at certain locations in the atmospheric radiation field and the light path integrals of trace gas concentrations associated thereto, i.e. the product of the DOAS (differential optical absorption spectroscopy) method, with respect to optical properties of aerosols and gases in connected spatial regions. The first and second order derivatives are validated through so called self-consistency tests. These derivatives allow the inversion of three dimensional tracegas and aerosol concentration profiles and pave the way down to 3D optical scattered light tomography. If such tomographic inversion scheme is based solely on spectral intensitites the available second order derivatives allows the consideration of the curvature in the cost function and therefore allows implementation of efficient optimisation algorithms. The influence of the instrument function on the spectra is analysed in order to mathematically assess the potential of DOAS to a sufficient degree. It turns out that the detailed knowledge of the instrument function is required for an advanced spectral analysis. Concludingly the mathematical separability of narrow band signatures of absorption and the Ring effect from the relatively broad band influence of the elastic scattering processes on the spectra is demonstrated which corresponds exactly to the DOAS principle. In that procedure the differential signal is obtained by approximately 4 orders of magnitude faster then by the separate modelling with and without narrow band structures. Thereby the fusion of the separated steps DOAS spectral analysis and subsequent radiation transport modeling becomes computationally feasible.

Les lasers à fibres à modes bloqués font partie des rares systèmes qui permettent de réaliser une variété de fonctions optiques élaborées, au moyen de peu de composants optiques. La gestion de la dispersion apporte à ce type de lasers une variété de comportements, qui est si riche que la cartographie complète et l’analyse détaillée des états stables deviennent difficilement réalisable lorsqu’on utilise les outils conventionnels basés sur les équations de propagation du champ intra-cavité. Dans cette thèse nous montrons que l’adjonction de la technique des coordonnées collectives aux outils théoriques conventionnels, permet de résoudre au moins en partie le problème de la complexité et l’extrême diversité des états stables des cavités gérées en dispersion. En particulier, nous proposons l’ACCD (approche des coordonnées collectives dynamiques), comme un outil théorique permettant de réaliser des gains de performance substantiels dans des opérations de recherche et caractérisation des états stables du laser. D’autre part, le recours à l’approche des cordonnées collectives nous permet de mettre en évidence des effets majeurs induits par certains phénomènes qui étaient jusqu’à présent largement sous-estimés. Notamment, nous mettons en évidence des modifications majeures desdomaines respectifs des différents états stables du laser, qui surviennent lorsqu’on change la bande passant de la fitre. D’autre part, en considérant une cavité où la largeur spectrale du champ lumineux (3.12 THz) est d’un ordre de grandeur plus petite que la largeur de la bande du gain Raman, nous mettons en lumière des effets remarquables de la diffusion Raman sur les phénomènes d’hystérésis. / Mode-locked fiber laser are among the few systems that allow to achieve a variety of elaborate optical functions, by means of few optical components. The use of dispersion management brings to this type of lasers a variety of behaviors, which is so rich that the complete mapping and detailed analysis of the stable states becomes impractical when conventional tools based on the intra-cavity field propagation equations, are used. In this thesis we show that the addition of the technique ofcollective coordinates to the conventional theoretical tools, allows to solve at least in part the problem of complexity and diversity of the stable states of the cavity. In particular, we propose the DCCA (dynamical collective coordinate approach), as a theoretical tool to achieve substantial performance gains in search and characterization of stable states of the laser. Furthermore, the use of the collective coordinated approach allows us to highlight major effects induced by certain phenomena that were until now largely underestimated. In particular, we highlight major changes in the respective areas ofthe different stable states of the laser, which occur when changing the width of the band-pass filter BPF. Furthermore, considering a cavity where the spectral width of the light field (3.12 THz) is an order of magnitude smaller than the bandwidth of the Raman gain, we highlight remarkable effects of Raman scattering on hysteresis phenomena.

LIMA JÚNIOR, José Alves de. Espectroscopia Raman dos Aminoácidos L - metionina e DL - alanina e de Nanotubos de Carbono. 2008. 214 f. Tese (Doutorado) - Programa de Pós-Graduação em Física, Centro de Ciências, Departamento de Física, Universidade Federal do Ceará, Fortaleza, 2008. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2014-05-13T22:56:00Z No. of bitstreams: 1 2008_tese_jalimajúnior.pdf: 3662330 bytes, checksum: ad8b8ed63bf2df476f4e050aae5f5d70 (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2014-05-14T18:26:53Z (GMT) No. of bitstreams: 1 2008_tese_jalimajúnior.pdf: 3662330 bytes, checksum: ad8b8ed63bf2df476f4e050aae5f5d70 (MD5) / Made available in DSpace on 2014-05-14T18:26:53Z (GMT). No. of bitstreams: 1 2008_tese_jalimajúnior.pdf: 3662330 bytes, checksum: ad8b8ed63bf2df476f4e050aae5f5d70 (MD5) Previous issue date: 2008 / This work describes polarized Raman scattering measurements in L-methionine and in DL-alanine (two amino acids) crystals and in several samples of single-walled carbon nanotubes (SWNT). In L-methionine crystal the Raman spectra were obtained from 17 K to 295 K in the spectral range from 50 cm-1 to 3100 cm-1, but no indication of a phase transition was observed. At room temperature, Raman scattering measurements were also performed for pressure up to 5 GPa. Several changes observed in the spectra were interpreted as due to structural phase transition undergone by L-methionine crystal at ~ 2.1 GPa. The results for decompression show that the phase transition is reversible with a hysteresis of ~ 0.8 GPa. In DL-alanine crystal the Raman spectra were obtained at temperatures from 15 K to 295 K over the spectral range 50 cm-1 - 3100 cm-1. No evidence of structural phase transition was found in this range of temperature, although information about diverse modes of the crystal were furnished. Samples of SWNT’s studied were prepared with metallic catalysts using the arc voltaic method. MnNiCo was the main compound of the first series and FeNiCo, the main compound of the second. In both sets it was observed that Cerium (Ce) insertion induces in the sub-set, probed with the 2.41 eV excitation energy, a narrowing of the diameter distribution favoring the tubes with smaller diameter. The Raman scattering measurements in a commercial sample of SWNT’s show a discontinuity at about 2 GPa. The discontinuity was represented by a changing in the slope of the frequency versus pressure for tangential modes. The measurement was performed twice, using two different solutions of surfactants, sodium dodecil sulfate (SDS) and plurocic acid F127 (F127), and the results were similar. The anomaly was interpreted as due to the deformation of the tubes as predicted theoretically. Two sets of three samples of SWNT’s containing different levels of lithium insertion were also analyzed by Raman spectroscopy. Each set of sample was formed by a sample with lithium, a sample without lithium and a sample with partial insertion of lithium. The results show that the lithium is efficiently intercalated with both lithium containing compound (LiCO3/NiO/CoO and LiNi0.5Co0.5O2), but the mechanism of intercalation differs from one to the other. The intercalation is unstable when lithium is intercalated interstitially (LiNi0.5Co0.5O2) and it can be removed almost completely by washing the sample, but if the lithium is intercalated inside the tubes (LiCO3/NiO/CoO) it can not be removed by the same process. / No presente trabalho foram realizadas medidas de espalhamento Raman polarizado em cristais de L-metionina e de DL-alanina (dois aminoácidos) e em diversas amostras de nanotubos de carbono de parede simples (SWNT). As medidas de espalhamento Raman em cristais de L-metionina foram realizadas no intervalo espectral entre 50 cm-1 e 3100 cm-1 desde a temperatura ambiente até a temperatura de 17 K. No intervalo de temperatura estudado a estrutura da L-metionina manteve-se estável. À temperatura ambiente também foram realizadas medidas Raman em altas pressões hidrostáticas. A máxima pressão atingida foi de 4,7 GPa e diversas modificações nos modos associados às unidades CO2, NH3, CC, CS, CH, CH2 e CH3 sugerem que a L-metionina sofre um transição estrutural de fase em torno de 2,1 GPa com histerese de aproximadamente 0,8 GPa. No cristal de DL-alanina foram realizadas medidas de espalhamento Raman no intervalo de temperatura de 15 K a 295 K. Embora nenhuma mudança significativa tenha sido observada neste intervalo de temperatura, os resultados são importantes para se entender o comportamento de uma molécula fundamental na constituição das proteínas. Medidas de espalhamento Raman em SWNT’s foram realizadas em amostras preparadas pela técnica de arco voltáico, utilizando-se vários catalisadores metálicos. As amostras foram divididas em duas séries: A primeira com os catalisadores à base de MnNiCo e a segunda à base de FeNiCo. Em ambas as séries observou-se que a inserção de Cério (Ce) foi responsável por tornar a distribuição de diâmetros do subconjunto ressonante com a energia 2,41 eV mais estreita. Além disso, o máximo da distribuição é deslocado para o azul, provavelmente em conseqüência da seleção de tubos de menor diâmetro dentro do subconjunto estudado. A inserção de Zircônio (Zr) à segunda série não trouxe mudanças significativas. Foram realizadas medidas de espalhamento Raman em função da pressão hidrostática em uma amostra comercial de SWNT. Como fluido transmissor foram utilizadas soluções de dois surfactantes: o dodecil sulfato de sódio (SDS) e o ácido plurônico F127 (F127). Devido à baixa relação sinal-ruído, não foi possível estudar o comportamento dos modos de respiração radial (RBM), mas pela descontinuidade do gráfico da freqüência em função da pressão dos modos tangenciais em aproximadamente 2 GPa é provável que os nanotubos sofram uma transição de fase estrutural nessa pressão, com deformação da seção circular dos tubos como predito por estudos teóricos. Dois conjuntos de amostras contendo diferentes níveis de inserção de lítio também foram estudados por espectroscopia Raman. Cada conjunto era formado por uma amostra sem lítio, uma com lítio e a terceira com inserção parcial de lítio (obtida pela lavagem da amostra que contém lítio). Nos dois conjuntos a inserção foi eficiente, contudo o mecanismo de inserção é diferente de uma série para outra. Na primeira série o catalisador utilizado para a inserção de lítio foi LiNi0,5Co0,5O2. Com este composto o lítio é intercalado intersticialmente e pode ser removido quase que completamente pela lavagem da amostra. Já na segunda série o composto utilizado foi LiCO3/NiO/CoO o que fez com que o lítio fosse intercalado dentro dos tubos de modo a não ser removido pela lavagem da amostra.