In the present thesis the electronic properties of two organic molecules were studied by means of density functional theory (DFT) in connection to their possible applications in organic photovoltaics and molecular spintronics respectively. The first analysed system is the C60 derivative PCBM extensively used in polymer solar cells for the charge separation process. Since fullerenes have been shown to undergo modifications as a result of light exposure, investigating their electronic structure is the first step in elucidating the photodegradation process. The electronic excitations from core levels to unoccupied molecular orbitals reveal not only the empty level structure of the molecule, but provide additional information related to the chemical bonds involving a specific atom type. In this way, they represent a means of determining the chemical changes that the molecule might withstand. The electronic transitions from carbon 1s core levels to unoccupied states are explained for the unmodified PCBM by a joint theoretical (DFT) and experimental study using the near edge x-ray absorption fine structure (NEXAFS) spectroscopy. The second investigated system is the transition metal phthalocyanine with a manganese atom as the metal center. Manganese phthalocyanine (MnPc) is a single molecular magnet in which the spin switch process can be triggered by various methods. It has been shown, for instance, that the adsorption of hydrogen to the Mn center changes the spin state of the molecule from 3/2 to 1. More interestingly, the process is reversible and can be controlled, opening up the possibility of using MnPc as a quantum bit in magnetic memory devices. Up to this date, the d orbital occupation in MnPc has been under a long debate, both theoretical and experimental studies revealing different configurations. In this thesis the electronic structure of the phthalocyanine is thoroughly analysed by means of DFT and the calculated results are compared to photoelectron spectroscopy measurements. The combination of theoretical and experimental tools reveals that in gas phase at high temepratures the molecule exhibits a mixed electronic configuration. In this light, the possible control of the specific electronic state of the central metal represents an interesting prospect for molecular spintronics.

Interest in the variation of fundamental constants has recently been stimulated by claims that the fine structure constant, α, was smaller in the past. Physicists are investigating whether α is currently varying using a number of methods including atomic clock experiments and quasar absorption spectra. To date atomic clock experiments have not reached the same level of precision as the quasar results but the precision to which transition frequencies are being measured is increasing dramatically and very soon atomic clock experiments based on Earth will be able to rival or surpass the quasar results. In order to relate the change in transition frequencies to a variation of α accurate calculations of relativistic effects in atoms and their dependence upon α are needed. Other effects, such as the small shift of transition frequencies due to blackbody radiation also need to be accounted for. In this thesis we perform accurate calculations of the dependence of transition frequencies in two-valence-electron atoms and ions on a variation of α. The relativistic Hartree-Fock method is used with many-body perturbation theory and configuration interaction methods to calculate transition frequencies. We also consider transitions with an enhanced sensitivity to α variation. In particular, narrow lines that correspond to atomic transitions between close lying, long-lived atomic states of different configurations. The small transition frequency, coupled with differences in the electron structure ensures a strong enhancement of the relative frequency change compared to a possible change in α . We also show that using the modified form of the Dirac Hamiltonian, as suggested by Bekenstein, does not affect the analysis of the quasar data pertaining to a measurement of α variation, nor does it affect atomic clock experiments. Finally we have performed calculations of the size of the frequency shift induced by a static electric field on the clock transition frequencies of the hyperfine splitting in Y b+, Rb, Cs, Ba+, and Hg+. The calculations are used to find the frequency shifts due to blackbody radiation which are needed for accurate frequency measurements and improvements of the limits on variation of α. Our result for Cs [??v/=E2 = -2:26(2) x 10-10Hz/(V/m)2] is in good agreement with early measurements and ab initio calculations. We present arguments against recent claims that the actual value might be smaller. The difference (~ 10%) is due to the continuum spectrum in the sum over intermediate states.

Thesis (Ph. D.)--University of Washington, 1999. / Vita. Includes bibliographical references (p. [151]-156).

Submitted by MAICON CARLONE DA SILVA null (maicon.carlone@gmail.com) on 2017-05-23T16:56:49Z No. of bitstreams: 1 Dissertação - Maicon Carlone da Silva .pdf: 5898245 bytes, checksum: dcaea8b738bb0b5c8699c89bc40d8b7a (MD5) / Approved for entry into archive by Luiz Galeffi (luizgaleffi@gmail.com) on 2017-05-23T18:30:12Z (GMT) No. of bitstreams: 1 silva_mc_me_bauru.pdf: 5898245 bytes, checksum: dcaea8b738bb0b5c8699c89bc40d8b7a (MD5) / Made available in DSpace on 2017-05-23T18:30:12Z (GMT). No. of bitstreams: 1 silva_mc_me_bauru.pdf: 5898245 bytes, checksum: dcaea8b738bb0b5c8699c89bc40d8b7a (MD5) Previous issue date: 2017-04-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Compostos do tipo Ca1-xRxB6 (onde R representa o elemento de terra rara) tem sido estudados durantes os últimos anos principalmente no que se refere as suas características magnéticas e de transporte, porem elas ainda são controversas. Em particular a técnica de Ressonância Magnética tem sido usada para estudar compostos de Ca1-xEuxB6 (EPR) para diversas concentrações de Eu, o qual sugere a existência de uma transição metal isolante quando mudamos a concentração de Eu. Neste trabalho deveremos analisar teoricamente os espectros experimentais deste composto, em função da concentração deste elemento de terra rara. Os espectros de EPR foram simulados usando o modelo de Plefka para diversos valores de concentração x em Ca1-xEuxB6 monocristalino, isto é, 7%, 10%, 15%, 30%, 60% e 100%, visando elucidar a evolução das fases isolantes e semimetálicas, além do colapso do espectro com o aumento da concentração da impureza magnética. Tendo em vista que formas de linha simétricas são características de matrizes isolantes e assimétricas de matrizes metálicas, focaremos o nosso estudo na assimetria dos espectros de EPR. Para procurar pelo conjunto de parâmetros que melhor ajusta o espectro teórico ao experimental utilizamos o método de Simulated Annealing (SA), onde minimizamos a diferencia média quadrática entre os espectros. Ao longo deste trabalho foram reproduzidos as principais características dos espectros experimentais. Também obtivemos parâmetros importantes como o de Campo Cristalino, valor de g, parâmetros de troca da interação Eu-Eu e o parâmetro de assimetria do espectro de absorção. Conseguimos mostrar que ao aumentar a concentração o espectro evolui de uma forma Lorentziana para Dysoniana, mostrando a existência da transição metal-isolante. / Compounds of the type Ca1-xRxB6 (where R represents the element of rare earth) have been studied during the last years mainly as regards their magnetic and transport characteristics, but they are still controversial. In particular the Magnetic Resonance technique has been used to study compounds of Ca1-xEuxB6 (EPR) for several concentrations of Eu, which suggests the existence of an insulating metal transition when we change the concentration of Eu. In this work we will theoretically analyze the spectra Experimental results of this compound, depending on the concentration of this element of rare earth. In the present case, the EPR fine structure spectra were simulated using the Plefka model for various values of concentration (x) in monocrystalline Ca1-xEuxB6, that is, 7%, 10%, 15%, 30%, 60% and 100%, aiming to elucidate the evolution of the insulating and semi-metallic phases, besides the collapse of the spectrum with the increase of the concentration of magnetic impurities. Considering that symmetrical line shapes are characteristic of insulating and asymmetric matrices of metal matrices, we will focus our study on the asymmetry of RPE spectra. To find for the set of parameters that best adjusts the theoretical spectrum to the experimental, we used the Simulated Annealing (SA) method, where we minimize the mean square difference between the spectra. Throughout this work the main characteristics of the experimental spectra were reproduced. We also obtained important parameters such as the Crystalline Field, g value, Eu-Eu interaction exchange parameters and the asymmetry parameter of the absorption spectrum. We show that by increasing the concentration the spectrum evolves from a Lorentzian to Dysonian form, showing the existence of the metal-insulating transition.

Observamos neste trabalho o processo de mudança de estrutura fina em colisões entre átomos de 85Rb resfriados e aprisionados em uma armadilha magneto-óptica. Medimos, através da fotoionização de fragmentos atômicos gerados nessas colisões, as taxas segundo as quais os átomos deixam a armadilha induzidos por esse processo colisional. Realizamos estudos das taxas de perda com relação a intensidade do laser de aprisionamento e com a freqüência, utilizando para isso a técnica de catálise. Nossos resultados indicam que a contribuição do processo de mudança de estrutura fina para a taxa de perdas total não é dominante. Constatamos que a estrutura hiperfina desempenha um papel importante na dinâmica colisional e na determinação dos valores das taxas. Interpretamos nossos resultados através de um modelo semi-clássico, sendo que este foi incapaz de explicar todos os efeitos observados. Propusemos algumas explicações qualitativas para as discrepâncias observadas. Acreditamos que nossos resultados devam servir de estímulo para novos trabalhos teóricos nesta área. / We report the observation of trap-loss collisional rates due to fine structure changing collisions between cold and trapped 85Rb atoms. We have measured, by photoionization of the atomic fragments in 5P1/2 state originated in these collisions, the rates through the atoms leave the trap induced by this loss mechanism. We carried out experiments to determine the rate dependence with the intensity of the trapping laser, and with the frequency, using the catalisys technique. We also measured the contribution of this process to the total trap-loss rate and determined that fine structure changing is not the dominant loss mechanism. It was also observed that the hyperfine structure plays an important role in the rate behavior. We compared our results with those given by a semiclassical theoretical approach, the Gallagher-Pritchard model, and some disagreements were observed. We proposed some arguments to explain these discrepancies. We believe that such results should stimulate theoretical work on this field.

No description available.

This thesis addresses the issue of the time variability of the fine structure constant, alpha. Recent claims of a varying alpha are set against the established standards of quantum electrodynamical theory and experiments. A study of the feasibility of extracting data on the time dependence of alpha using particles in Penning traps is compared to the results obtained by existing methods, including those using astrophysical data and those obtained in atomic clock experiments. Suggestions are made on the nature of trapped particles and the trapping fields.

No description available.

No description available.

<p>In this thesis, the importance of temporal fine structure (TFS) in speech perception is investigated. It is well accepted that TFS is important for sound localization and pitch perception, while envelope (ENV) is primarily responsible for speech perception. Recently, a significant contribution of TFS in speech perception has been suggested. This was linked to the improved ability of normal-hearing subjects to understand speech in fluctuating-power background noise as compared to hearing-impaired people. However, the accuracy of this claim is questionable since TFS and ENV are correlated and one can recover ENV to some extent if provided with TFS-only speech. In this work, we quantify the relative advantages of TFS and the possible influence of recovered ENV on speech recognition scores. We used a computational model for the cat auditory periphery, which was modified to match the available data for human cochlear tuning. The output of the model was analyzed by the spectro-temporal modulation index (STMI) metric to predict speech intelligibility. A speech recognition experiment was conducted on five normal-hearing subjects and the STMI predictions were mapped to intelligibility using a specially constructed mapping function. The TFS role was quantified by examining the TFS intelligibility scores and the corresponding intelligibility predictions from ENV recovery. Our results show that although ENV recovery has some influence on the intelligibility results, it cannot account for the total reported intelligibility.</p> / Doctor of Philosophy (PhD)