A new numerical analysis method, dispersion vs. absorption plots (DISPA), has been developed for ESR. This method may be used for semi-quantitative line-shape studies and is useful both as a diagnostic and analytical tool. In addition it provides a method of automatic phasing for magnetic resonance spectra. Numerous examples of its applications, both simulated and experimental are presented, with emphasis on spin-probe studies. The digital acquisition and processing methods used for these studies are also briefly discussed. ESR and NMR relaxation time studies of the bis(dialkyl-N-carbodithioate) metal(II) class of spin-probes have been performed. The T₁,'s of ¹³C and ²H enriched nickel complex were measured by NMR. The line-widths of ⁶³Cu complex were measured by ESR and analysed by Redfield theory. The two sets of results were combined to give the principal elements of the rotational diffusion tensor for the pyrollidine derivative in toluene. This is the first time that ESR and NMR studies have been combined to measure a diffusion tensor. A general strategy for this approach is presented. ESR data from previous work has been re-analysed in the light of the new results. The analysis shows that the commonly used assumption of isotropic diffusion is extremely misleading. / Science, Faculty of / Chemistry, Department of / Graduate

High resolution solar spectra are routinely recorded since more than two decades by the University of Liège at the International Scientific Station of the Jungfraujoch (Swiss Alps, 46.5°N, 8.0°E, 3580 m asl) with Fourier Transform Infrared (FTIR) spectrometers. Over the last years, major improvements have been implemented in the algorithms used to retrieve the abundances of atmospheric constituents accessible to the FTIR technique. Now, in addition to total column, information on the vertical distribution of the target gas is often available, allowing producing partial column data sets. We take advantage of these improvements to generate and characterize long-term total and partial columns time series of some important inorganic fluorinated trace gases deduced from FTIR measurements performed at Jungfraujoch. First, our investigations on hydrogen fluoride (HF) indicate that the adoption of a Galatry line shape model for this species significantly improves the fitting quality of the retrievals. The sensitivity of our FTIR measurements to HF inversions in three distinct regions that range from the low to the high stratosphere is confirmed thanks to products derived from two satellites and from two numerical models. We further demonstrate that the HF seasonal variations that occur in the low stratosphere are mainly responsible for the seasonal cycle observed in our HF total column time series. We have also developed an original multi-spectrum multi-window retrieval strategy allowing to derive, for the first time, some information on the vertical distribution of carbonyl fluoride (COF2) from ground-based FTIR measurements. After comparison with model data, our COF2 and HF FTIR datasets are combined to assess the atmospheric inorganic fluorine burden Fy. A trend analysis of our HF, COF2 and Fy time series is then performed for four different time periods spanning the 1985-2010 time interval. While we observe a recent stabilization for HF, corresponding COF2 data show a significant rise, after a period of significant reduction in its accumulation rate. This is probably ascribable to the combination of the decrease of its main source gas CFC-12 with the increase of the substitute product HCFC-22. However, this increase in the COF2 rate of change does not significantly impact the Fy trend, which is essentially driven by the change in HF. In addition, we show that the partitioning between the two major fluorine reservoirs HF and COF2 has not changed since the beginning of this century. Together, they account for around 95% of total inorganic fluorine in the atmosphere. Finally, we study the long-term evolution of carbon tetrafluoride (CF4), for the first time from ground-based FTIR measurements. The trend analysis of our time series indicates a slowing, initiated during the nineties, in the CF4 growth rate despite the fact that the absolute loading of this compound is still increasing. Our linear accumulation rates are consistent with those deduced from space or surface measurements.

xvi, 280 p. : ill. A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / Doppler-limited, steady-state, linear absorption spectra of 127 I 2 (diatomic iodine) near 675 nm were recorded with an internally-referenced wavelength modulation spectrometer, built around a free-running diode laser using phase-sensitive detection, and capable of exceeding the signal-to-noise limit imposed by the 12-bit data acquisition system. Observed I 2 lines were accounted for by published spectroscopic constants. Pressure broadening and pressure shift coefficients were determined respectively from the line-widths and line-center shifts as a function of buffer gas pressure, which were determined from nonlinear regression analysis of observed line shapes against a Gaussian-Lorentzian convolution line shape model. This model included a linear superposition of the I 2 hyperfine structure based on changes in the nuclear electric quadrupole coupling constant. Room temperature (292 K) values of these coefficients were determined for six unblended I 2 lines in the region 14,817.95 to 14,819.45 cm -1 for each of the following buffer gases: the atoms He, Ne, Ar, Kr, and Xe; and the molecules H 2 , D 2 , N 2 , CO 2 , N 2 O, air, and H 2 O. These coefficients were also determined at one additional temperature (388 K) for He and CO 2 , and at two additional temperatures (348 and 388 K) for Ar. Elastic collision cross-sections were determined for all pressure broadening coefficients in this region. Room temperature values of these coefficients were also determined for several low- J I 2 lines in the region 14,946.17 to 14,850.29 cm -1 for Ar. A line shape model, obtained from a first-order perturbation solution of the time-dependent Schrödinger equation for randomly occurring interactions between a two-level system and a buffer gas treated as step-function potentials, reveals a relationship between the ratio of pressure broadening to pressure shift coefficients and a change in the wave function phase-factor, interpreted as reflecting the "cause and effect" of state-changing events in the microscopic domain. Collision cross-sections determined from this model are interpreted as reflecting the inelastic nature of collision-induced state-changing events. A steady-state kinetic model for the two-level system compatible with the Beer-Lambert law reveals thermodynamic constraints on the ensemble-average state-changing rates and collision cross-sections, and leads to the proposal of a relationship between observed asymmetric line shapes and irreversibility in the microscopic domain. / Committee in charge: David Herrick, Chairperson, Chemistry; John Hardwick, Advisor, Chemistry; Jeffrey Cina, Member, Chemistry; David Tyler, Member, Chemistry; Michael Raymer, Outside Member, Physics

Magnetic Resonance Spectroscopy (MRS) and Spectroscopic Imaging (MRSI) play an emerging role in clinical assessment, providing in vivo estimation of disease markers while being non-invasive and applicable to a large range of tissues. However, static magnetic field inhomogeneity, as well as eddy currents in the acquisition hardware, cause important distortions in the lineshape of acquired NMR spectra, possibly inducing significant bias in the estimation of metabolite concentrations. In the post-acquisition stage, this is classically handled through the use of pre-processing methods to correct the dataset lineshape, or through the introduction of more complex analytical model functions. This thesis concentrates on handling arbitrary lineshape distortions in the case of quantitation methods that use a metabolite basis-set as prior knowledge. Current approaches are assessed, and a novel approach is proposed, based on adapting the basis-set lineshape to the measured signal.Assuming a common lineshape to all spectral components, a new method is derived and implemented, featuring time domain local regression (LOWESS) filtering. Validation is performed on synthetic signals as well as on in vitro phantom data. Finally, a completely new approach to MRS quantitation is proposed, centred on the use of the compact spectral support of the estimated common lineshape. The new metabolite estimators are tested alone, as well as coupled with the more common residual-sum-of-squares MLE estimator, significantly reducing quantitation bias for high signal-to-noise ratio data.

La Spectroscopie et l'Imagerie Spectroscopique de Résonance Magnétique (ISRM) jouent un rôle émergent parmi les outils cliniques, en donnant accès, d'une manière complètement non-invasive, aux concentrations des métabolites in vivo. Néanmoins, les inhomogénéités du champ magnétique, ainsi que les courants de Foucault, produisent des distorsions significatives de la forme de raie des spectres, induisant des conséquences importantes en termes de biais lors de l'estimation des concentrations. Lors des traitements post-acquisition, cela est habituellement traité à l'aide des méthodes de pré-traitement, ou bien par l'introduction de fonctions analytiques plus complexes. Cette thèse se concentre sur la prise en compte de distorsions arbitraires de la forme de raie, dans le cas des méthodes qui utilisent une base de métabolites comme connaissance a priori. L'état de l'art est évalué, et une nouvelle approche est proposée, fondée sur l'adaptation de l'amortissement de la base des métabolites au signal acquis. La forme de raie présumée commune à tous les métabolites est estimée et filtrée à l'aide de la méthode LOWESS. L'approche est validée sur des signaux simulés, ainsi que sur des données acquises in vitro. Finalement, une deuxième approche novatrice est proposée, fondée sur l'utilisation des propriétés spectrales de la forme de raie commune. Le nouvel estimateur est testé seul, mais aussi associé avec l'estimateur classique de maximum de vraisemblance, démontrant une réduction significative du biais dans le cas des signaux à haut rapport signal-sur-bruit. / Magnetic Resonance Spectroscopy (MRS) and Spectroscopic Imaging (MRSI) play an emerging role in clinical assessment, providing in vivo estimation of disease markers while being non-invasive and applicable to a large range of tissues. However, static magnetic field inhomogeneity, as well as eddy currents in the acquisition hardware, cause important distortions in the lineshape of acquired NMR spectra, possibly inducing significant bias in the estimation of metabolite concentrations. In the post-acquisition stage, this is classically handled through the use of pre-processing methods to correct the dataset lineshape, or through the introduction of more complex analytical model functions. This thesis concentrates on handling arbitrary lineshape distortions in the case of quantitation methods that use a metabolite basis-set as prior knowledge. Current approaches are assessed, and a novel approach is proposed, based on adapting the basis-set lineshape to the measured signal.Assuming a common lineshape to all spectral components, a new method is derived and implemented, featuring time domain local regression (LOWESS) filtering. Validation is performed on synthetic signals as well as on in vitro phantom data. Finally, a completely new approach to MRS quantitation is proposed, centred on the use of the compact spectral support of the estimated common lineshape. The new metabolite estimators are tested alone, as well as coupled with the more common residual-sum-of-squares MLE estimator, significantly reducing quantitation bias for high signal-to-noise ratio data.

Spatially-resolved measurements of flame temperature have been demonstrated with diode lasers for the first time. The technique is based on the use of blue diode lasers to perform laser-induced fluorescence on indium atoms seeded to the flame. Temperature measurements have been carried out in laminar flames both by the two-line atomic fluorescence technique, and also by a novel line-shape thermometry method that requires the use of only a single diode laser. The first part of this work involved the development of blue extended cavity diode lasers with favourable tuning properties. Two custom-designed extended cavity diode lasers (ECDL) have been built, emitting at wavelengths of around 410 nm and 451 nm respectively. These devices are capable of mode-hop free tuning over ranges greater than 90 GHz. The performance of these devices exceeds that of commercially available systems and a patent application has been filed. High resolution fluorescence spectroscopy has been performed on both the 52P1/2→62S1/2 and 52P3/2→62S1/2 transitions of indium atoms seeded at trace quantities into atmospheric pressure flames. In both cases, the spectra obtained show excellent agreement with a theoretical fit based on the individual hyperfine components of the transition. The two ECDLs have been used to build a sensor for the measurement of temperature in combustion systems. It is much simpler, more compact, less expensive, and more versatile than any previously existing device. The two lasers were used sequentially to probe indium atoms seeded to the flame. The ratio of the resulting fluorescence signals is related to the relative populations in the two sub-levels of the spin-orbit split ground state of indium, and thus to the temperature. Temperature measurements have been successfully performed in a laminar flame and the data thus obtained do not need to be corrected by any ‘calibration constant’. This novel thermometry technique offers a robust alternative to traditional methods involving bulky high power lasers. A further development has been made by demonstrating a fluorescence line-shape thermometry technique requiring only a single diode laser excitation source. Progress has been made towards the goal of rapid temperature measurements appropriate to the study of turbulent flames. This involved the development of a simple technique for actively locking the wavelength of the blue diode laser to a resonance line of the tellurium molecule. A high-speed thermometry system would work by rapidly switching between the two locked laser beams using an optical modulator.

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