The absorption lines found in the spectra of distant quasars provide a unique method of probing the physical conditions in the universe at early epochs. This thesis describes a study of the Lyman alpha forest absorption systems seen in the spectra of high redshift QSOs. The Anglo-Australian Telescope has been used to obtain high resolution spectra of several bright QSOs. Considerable effort has gone into developing statistical techniques for profile fitting to the data to objectively and reliably extract the parameters associated with each absorbing cloud. The distribution functions for these are given and discussed. Particular attention has been paid to the clustering properties of the Lyman alpha clouds and it is found that they are weakly (but significantly) clustered on small velocity scales. Possible interpretations of this result are discussed. One especially interesting aspect of QSO absorption systems concerns the potential for measuring, or obtaining limits on, the deuterium to hydrogen abundance at high redshifts. A knowledge of this quantity is important for constraining cosmological models and can also help us to understand the chemical evolution of light elements in galaxies. A series of numerical simulations has been carried out to explore the potential for such measurements and an absorption system has been analysed to obtain an upper limit to D/H at z = 3.

Damped Lyman α systems (DLAs) are useful probes of the chemical enrichment of the universe as they provide accurate abundance measurements of many chemical species. Using a sample of 30 DLAs (with large metal column densities) observed with the High Resolution Echelle Spectrometer on the Keck I telescope, the abundances of several elements (i.e. iron, zinc, chromium, silicon, sulphur, phosphorus, manganese, and boron) are derived and presented. A comparison is drawn between the abundances from these metal-rich DLAs with literature samples encompassing the largest compilation of high resolution observations of other DLAs, and stars from the Milky Way and its satellite galaxies to understand the astrophysical nature of DLAs. Furthermore, the first ever extragalactic study of boron is presented. Using the sample of 30 metal-rich DLAs, two 3σ detections and one near detection 2.97σ) were found. From the comparison of [B/O] and, for the first time, [B/S], with studies in the Milky Way, there appears to be an excess of boron relative to its parent nucleus (oxygen) in these three DLA systems, suggesting that there may be a higher cosmic ray flux in DLAs than in the Milky Way. / Graduate / 0606

Damped Lyman α systems (DLAs) are useful probes of the chemical enrichment of the universe as they provide accurate abundance measurements of many chemical species. Using a sample of 30 DLAs (with large metal column densities) observed with the High Resolution Echelle Spectrometer on the Keck I telescope, the abundances of several elements (i.e. iron, zinc, chromium, silicon, sulphur, phosphorus, manganese, and boron) are derived and presented. A comparison is drawn between the abundances from these metal-rich DLAs with literature samples encompassing the largest compilation of high resolution observations of other DLAs, and stars from the Milky Way and its satellite galaxies to understand the astrophysical nature of DLAs. Furthermore, the first ever extragalactic study of boron is presented. Using the sample of 30 metal-rich DLAs, two 3σ detections and one near detection 2.97σ) were found. From the comparison of [B/O] and, for the first time, [B/S], with studies in the Milky Way, there appears to be an excess of boron relative to its parent nucleus (oxygen) in these three DLA systems, suggesting that there may be a higher cosmic ray flux in DLAs than in the Milky Way. / Graduate / 0606

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Oxygen in single crystalline antimony triselenide (Sb₂Se₃) is addressed by infrared (IR) absorption spectroscopy. Measurements conducted on Sb₂Se₃ samples doped—during growth, post-growth annealing in the O₂ ambient, or by O ion implantation—with ¹⁶O reveal an IR absorption line at 527 cm⁻¹ (10 K). Substitution of ¹⁶O by ¹⁸O “red”-shifts the signal down to 500 cm⁻¹ based on which the line is assigned to a local vibrational mode of an isolated oxygen defect. Annealing of O-enriched samples in hydrogen atmosphere at temperatures above 380 °C results in the suppression of the 527-cm⁻¹ line and concurrent appearance of the signals due to hydroxyl groups, suggesting formation of oxygen-hydrogen complexes. The configuration of the 527-cm⁻¹ oxygen center is discussed.

L’étude du transfert radiatif dans les gaz (atmosphères planétaires, chambres de combustion, etc.) se heurte à deux principales difficultés : les hétérogénéités et la dépendance spectrale des propriétés radiatives du milieu d’intérêt. Les travaux présentés dans ce manuscrit proposent, au travers d’une approche statistique du rayonnement, une solution à ces deux limites qui ne nécessite aucune approximation de modèle physique ou numérique. Cette approche conduira au développement d’algorithmes de Monte-Carlo considérés à l’heure actuelle comme méthodes de référence dans la communauté du transfert radiatif. La difficulté liée aux hétérogénéités du milieu participant sera traitée par une technique empruntée à d’autres disciplines de la physique du transport : les algorithmes à collisions nulles. Leur application au rayonnement consiste à ajouter arbitrairement aux évènements d’absorption et de diffusion, un troisième type de collision n’ayant aucun effet sur le transport de photons : les collisions nulles. Ainsi, le coefficient d’extinction résultant de ces trois types de collision pourra être assumé comme homogène. Ensuite, il sera montré comment cette même technique lève un second verrou permettant de repenser de façon statistique l’idée de coefficient d’absorption. Cela ouvrira la voie à des algorithmes de Monte-Carlo qui estiment directement une observable radiative à partir de paramètres de transitions répertoriés dans des bases de données spectroscopiques, sans avoir à précalculer rigoureusement le coefficient d’absorption. / Two major challenges are encountered when studying radiative transfer in gases (e.g. combustion chambers or planetary atmospheres): heterogeneity and spectral dependence of radiative properties. The work introduced in this manuscript, addresses this problem through a statistical approach of radiation that requires no model or numerical approximation. This approach leads to the development of Monte-Carlo methods, currently considered as reference solutions in the community of radiative transfer. The difficulty related to heterogeneity is handled by a technique borrowed from other fields of transport physics: null-collision algorithms. Their application to radiation consists in adding to the events of absorption and scattering a third arbitrary type of collision that has no effect on the photon transport. Thus, the extinction coefficient resulting from these three types of collisions can be assumed to be homogeneous. Then, it is shown how this very same technique opens the door to rethinking statistically the concept of absorption coefficient. This leads to Monte-Carlo algorithms that directly estimate radiative observables from transition parameters indexed in molecular spectroscopic databases, without the need of rigorously precomputing absorption coefficients.

Fundação de Amparo a Pesquisa do Estado de Minas Gerais / In this work we made a theoretical study of absorption line-shape of poly (pphenylene vinylene) (PPV). The model was applied in films processed by techniques: spin-coating (SC), layer-by-layer (LbL), and Langmuir-Blodgett (LB). The probability of electronic transitions was calculated based on the molecular model of excitons, Franck-Condon states, Gaussian distribution of non-entangled chains with conjugate degree n, semi-empirical parameterization of energy gap, electric dipole moment, and electron-vibrational mode coupling. Based on the approach of the energy gap functional dependence 1/n, the inclusion of the non-homogeneity energy dispersion 1/n2 is essential to obtain good experimental data agreement, mainly, where the absorption spectra display peaks width of about 65 meV. For unresolved absorption spectra, such as those observed for a large number of conjugated polymers processed via spin-coating technique, for example, the non-homogeneity energy dispersion parameterization is not significant. We develop a model to describe the possible chemical reactions of conversion of poly(xylyliden tetrahydrothiophenium chloride) (PTHT) monomers to PPV monomers and PPV monomers in others monomers of different degrees of conjugation. The dependence 1/n of the functional energy gap was compared with experimental data oligomers and calculations optimized geometry by Density Functional Theory (DFT). Effects of exciton confinement were considered in the transition dipole moment functional. Simulations to calculate the oscillator strength of the absorption spectra in PPV oligomers indicate that the HOMO-LUMO state prevails over other excited states. Results obtained from the use of the distribution of the random walk are as good as those achieved by the use of Gaussian distribution of conjugated segments in simulations of absorption spectra of the PPV. The use of transition dipole moment functional, which includes the effect of exciton confinement together with the distribution of the random walk provide good results in adjustments theoretical absorption spectra of PPV with more consistent physical parameters. / Nesse trabalho fizemos um estudo teórico da forma de linha de absorção do poli(p-fenileno vinileno) (PPV). O modelo foi aplicado em filmes processados pelas técnicas: spin-coating (SC), layer-by-layer (LbL) e Langmuir-Blodgett (LB). A probabilidade de transição eletrônica foi calculada com base no modelo do exciton molecular, estados de Franck-Condon, distribuição Gaussiana de cadeias não emaranhadas com grau de conjugação n, parametrização semi-empírica do gap de energia, do momento de dipolo elétrico e do acoplamento eletrônico vibracional. Baseamos na aproximação do funcional do gap de energia de dependência 1/n, a inclusão da dispersão de energia não homogênea 1/n2, que é essencial para se obter uma boa concordância com os dados experimentais, principalmente em casos, onde o espectro de absorção apresenta picos com largura de aproximadamente 65 meV. Em espectros de filmes pouco definidos, tais como os processados pela técnica spin-coating, a dispersão de energia não homogênea não é significativa. Desenvolvemos um modelo para descrever as possíveis reações químicas de conversão de monômeros de poli- (cloreto de xilideno tetrahidrotiofeno) (PTHT) em PPV e de monômeros de PPV em outros de diferentes graus de conjugação. A dependência 1/n do funcional do gap de energia foi comparada com dados experimentais de oligômeros de PPV e cálculos otimizados da geometria pela Teoria do Funcional da Densidade (DFT). Efeitos de confinamento de exciton foram considerados no funcional do momento de dipolo de transição eletrônica. Simulações feitas para calcular a força de oscilador no espectro de absorção em oligômeros de PPV indicam que o estado HOMO-LUMO prevalece sobre outros estados excitados. Resultados obtidos pelo uso da distribuição do passeio aleatório são tão bons quanto aos realizados pelo uso da distribuição Gaussiana de segmentos conjugados em simulações de espectros de absorção do PPV. O uso do funcional do momento de dipolo de transição, que inclui efeito de confinamento de excitons, junto com a distribuição do passeio aleatório propiciam bons resultados nos ajustes teóricos de espectros de absorção do PPV com parâmetros físicos mais consistentes. / Doutor em Física

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