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Under the title 'Angle Resolved Photoelectron Spectroscopy Study of Small Molecules', the thesis discussed the following aspects: Processes after the interaction of photons with atoms or molecules, including photoscattering, photoexcitation and fluorescence, photoabsorption, photodissociation and photoionization; Concepts of photoionization and photoelectron spectroscopy, including ionization potentials, photoionization cross sections, photoelectron angular distributions, shape resonances and autoionization; Theory of photoionization and photoelectron angular distributions, including central field approximation, Hartree-Fock calculations and multichannnel quantum defect theory; Apparatus for an angle resolved high resolution photoelectron experiment, including the synchrotron radiation source at Daresbury Laboratory, UK and an angle resolved electron spectrometer system from NIST/ANL, USA; The experiment on <i>CO</i>₂ at Daresbury Laboratory, including electron spectrometer calibrations, experimental procedures and data processing; Results and discussion, including results for the photoionization cross sections of the <i>CO</i>^+₂<i>X</i>^{2 Π_h} state, vibrational branching ratios and asymmetry parameters for the synmmetric stretch vibrations (000) to (500) in the <i>CO</i>^+₂<i>X</i>^{2 Π_h} state in the photon wavelength region of 687 - 790AA with a resolution of about 0.1AA, analysis of photoelectron spectra taken at the Tanaka-Ogawa resonances and result for the Franck-Condon factors for transitions from the autoionizing states to different vibrational levels of the molecule.

Orientador: Aguinaldo Robinson de Souza / Banca: Ourides Santim Filho / Banca: Marcelo Carbone Carneiro / Resumo: Este trabalho procurou identificar como estudantes do Ensino Médio se apropriam de conceitos e elaboram determinados modelos inseridos em Cinética Química, especificamente o modelo cinético de colisão de partículas numa reação (Teoria das Colisões). Esta análise e as reflexõe que a seguiram foram baseadas principalmente nos estudos realizados por Piaget (1975, 1975b, 1977), Piaget & Inhelder (1975, 1977), Jun (2000) e Fischbein (1975). Utilizamos como documentos as transcrições das entrevistas (pré e pós-testes) realizadas individualmente com cada aluno. Inicialmente os estudantes foram entrevistados (pré-testes) com o intuito de identificar a familiaridade com a noção de evento probabilístico ou aleatório. Numa segunda etapa (pós-testes) esse conhecimento (ou a ausência parcial/total dele) foi posto à prova numa tentativa de estabelecer relações com um conteúdo específico da Química (Teoria das Colisões). Os resultados obtidos apontam para grandes discrepâncias entre o modelo cinético de colisões elaborado pelos estudantes e o cientificamente aceito. / Abstract: The purpose of this work is to contribute for Science teaching making analysis and reflections on the way high school students appropriate the concepts and models related to Chemical Kinetics, mainly particles collisions' kinetics model in chemical reaction (Collision Theory Model). This investigation was based on Piaget and Inhelder' studies (1975), and also on Piaget (1975, 1977), Jun (2000), and Fischbein (1975) works, which have studied the connection between the young students and the probabilistic thinking. The analysis of the document evidences had the aim to evaluate if the students would be able to achieve generalization and develop concepts about Probability Theory. In the second part these concepts or its partial/total lacks were linked with chemical kinetics in attempt to establish relationships between correct explanation of collision kinetic model and the students' failure models. The obtained result points to great misconceptions related to the correct and scientific model and the student's. / Mestre

Made available in DSpace on 2014-06-11T19:24:49Z (GMT). No. of bitstreams: 0 Previous issue date: 2007-03-30Bitstream added on 2014-06-13T20:13:11Z : No. of bitstreams: 1 cirino_mm_me_bauru.pdf: 7880513 bytes, checksum: 90db4c500722605231950129993ca3de (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Este trabalho procurou identificar como estudantes do Ensino Médio se apropriam de conceitos e elaboram determinados modelos inseridos em Cinética Química, especificamente o modelo cinético de colisão de partículas numa reação (Teoria das Colisões). Esta análise e as reflexõe que a seguiram foram baseadas principalmente nos estudos realizados por Piaget (1975, 1975b, 1977), Piaget & Inhelder (1975, 1977), Jun (2000) e Fischbein (1975). Utilizamos como documentos as transcrições das entrevistas (pré e pós-testes) realizadas individualmente com cada aluno. Inicialmente os estudantes foram entrevistados (pré-testes) com o intuito de identificar a familiaridade com a noção de evento probabilístico ou aleatório. Numa segunda etapa (pós-testes) esse conhecimento (ou a ausência parcial/total dele) foi posto à prova numa tentativa de estabelecer relações com um conteúdo específico da Química (Teoria das Colisões). Os resultados obtidos apontam para grandes discrepâncias entre o modelo cinético de colisões elaborado pelos estudantes e o cientificamente aceito. / The purpose of this work is to contribute for Science teaching making analysis and reflections on the way high school students appropriate the concepts and models related to Chemical Kinetics, mainly particles collisions' kinetics model in chemical reaction (Collision Theory Model). This investigation was based on Piaget and Inhelder' studies (1975), and also on Piaget (1975, 1977), Jun (2000), and Fischbein (1975) works, which have studied the connection between the young students and the probabilistic thinking. The analysis of the document evidences had the aim to evaluate if the students would be able to achieve generalization and develop concepts about Probability Theory. In the second part these concepts or its partial/total lacks were linked with chemical kinetics in attempt to establish relationships between correct explanation of collision kinetic model and the students' failure models. The obtained result points to great misconceptions related to the correct and scientific model and the student's.

Room-temperature chemisorption of hexacyclic aromatic hydrocarbons on the 2x1, sputtered, oxidized and H-terminated Si(100) surfaces, as well as those upon post treatments of hydrogenation, oxidization and electron irradiation have been investigated by using thermal desorption spectrometry (TDS), Auger electron spectroscopy (AES) and low energy electron diffraction (LEED). This work focuses on the effects of the functional groups (phenyl, methyl, vinyl, heteroatom, and H atom) in the chemisorbed aromatic hydrocarbons (benzene, toluene, xylene isomers, styrene and pyridine) on organic functionalization of the Si(100) surface, particularly on such surface processes as cycloaddition, dative adsorption, hydrogen abstraction, desorption, dissociation, diffusion, and condensation polymerization. Unlike the earlier notion that hydrogen evolution in the hydrocarbon/Si(100) systems is the result of hydrocarbon dissociation (into smaller hydrocarbon fragments and H atoms) on the surface, condensation polymerization of the adsorbed aromatic hydrocarbons is proposed in the present work, in order to explain the higher-temperature hydrogen evolution feature in the toluene/Si(100) system. This hypothesis is supported by our TDS results for other hydrocarbon adsorbates, especially in the pyridine/Si(100) system where electron-induced condensation polymerization has been observed at room temperature. The improved techniques in the TDS experiments developed in the present work have enabled us to observe condensation polymerization and the effect of H on the surface processes (via surface reconstruction) on Si(100) for the first time. New analysis methods have also been developed to determine the adsorption coverage from the AES data, and this work has not only improved the accuracy of the elemental-coverage evaluation, but also provided a means to estimate the rate and the order of chemisorption. By using the density functional theory with the Gaussian 98 program, the adsorption geometries and the corresponding adsorption energies of various adsorption phases have been calculated. These computational results have provided useful insights into the chemisorption structures on the Si(100) surface. The present work also presents the development of three kinetics models for hydrogen evolution in the aforementioned aromatic-hydrocarbon systems on Si(100). Based on a modified collision theory with consideration of diffusion, these theoretical models have proven to be quite successful in simulating the observed TDS profiles and in estimating the kinetic parameters for the analysis of condensation polymerization in 2-dimensional diffusion systems. The present work illustrates that TDS experiments can be used effectively with quantum computation and theoretical kinetics modelling to elucidate the intricate nature of organosilicon surface chemistry.

A mecânica quântica apresenta assimetria por reversão temporal. Podemos entender que a origem de tal assimetria é a forma como a medida é feita na mecânica quântica descrita usualmente. Em 1964, Aharonov, Bergmann e Lebowitz propõem a pós-seleção, instrumento capaz de torná-la simétrica no tempo, bem como argumentam a validade física de tal. Aqui é discutida uma outra saída, utilizando Teorias Probabilístico-Operacionais. Encontra-se uma forma mais geral do Teorema de Wigner. Além disso, se aplica esse novo formalismo, que vale em espaços de Hilbert de dimensão finita, no experimento de medida fraca descrito por Aharonov, Albert e Vaidman em 1988, em que preparamos um estado térmico dentro de uma caixa, estudamos seu comportamento e realizamos a reversão temporal do mesmo, confirmando que a probabilidade se mantém invariante sob tal transformação de simetria. / Quantum mechanics presents a time-reversal asymmetry. We see the origin of such asymmetry is the way how we make measurements in the usually described quantum mechanics. In 1964, Aharonov, Bergmann and Lebowitz propose the post-selection, a tool able to make it time symmetric, as well as argues such physical validity of this tool. Here, we discuss another exit, using operational-probabilistic theories. We find a more general form of Wigner´s Theorem. Moreover, we apply this new formalism, true in finite-dimensional Hilbert spaces, in Aharonov, Albert and Vaidman 1988 weak measure described experiment, in which we prepare a thermal state inside a box, study its behaviour and perform the time reversal of it, confirming that the probability is invariant under such symmetry transformation.

Un réseau optique, créé par des lasers, permet de piéger des atomes refroidis à ultra-basse température. Il permet d'obtenir une contrainte comme s'il s'agissait d'un cristal idéal (un cristal sans agitation thermique). Je décris les états des particules dans un potentiel périodique (un réseau optique) à l'aide d'ondes de probabilité (physique quantique) stationnaires (théorie indépendante du temps). Le caractère ondulatoire de la matière est exacerbé à très basse température et donne lieu à des phénomènes d'interférence et de résonance particuliers. / An optical lattice, created by lasers, can trap atoms cooled to ultra-low temperatures. It provides a constraint as if it were a perfect crystal (a crystal without thermal agitation). I describe the states of particles in a periodic potential (optical network) using probability waves (quantum physics) stationary (independent theory of time). The wave nature of the material is exacerbated at very low temperatures and gives rise to interference phenomena and individual resonance.

Room-temperature chemisorption of hexacyclic aromatic hydrocarbons on the 2x1, sputtered, oxidized and H-terminated Si(100) surfaces, as well as those upon post treatments of hydrogenation, oxidization and electron irradiation have been investigated by using thermal desorption spectrometry (TDS), Auger electron spectroscopy (AES) and low energy electron diffraction (LEED). This work focuses on the effects of the functional groups (phenyl, methyl, vinyl, heteroatom, and H atom) in the chemisorbed aromatic hydrocarbons (benzene, toluene, xylene isomers, styrene and pyridine) on organic functionalization of the Si(100) surface, particularly on such surface processes as cycloaddition, dative adsorption, hydrogen abstraction, desorption, dissociation, diffusion, and condensation polymerization. Unlike the earlier notion that hydrogen evolution in the hydrocarbon/Si(100) systems is the result of hydrocarbon dissociation (into smaller hydrocarbon fragments and H atoms) on the surface, condensation polymerization of the adsorbed aromatic hydrocarbons is proposed in the present work, in order to explain the higher-temperature hydrogen evolution feature in the toluene/Si(100) system. This hypothesis is supported by our TDS results for other hydrocarbon adsorbates, especially in the pyridine/Si(100) system where electron-induced condensation polymerization has been observed at room temperature. The improved techniques in the TDS experiments developed in the present work have enabled us to observe condensation polymerization and the effect of H on the surface processes (via surface reconstruction) on Si(100) for the first time. New analysis methods have also been developed to determine the adsorption coverage from the AES data, and this work has not only improved the accuracy of the elemental-coverage evaluation, but also provided a means to estimate the rate and the order of chemisorption. By using the density functional theory with the Gaussian 98 program, the adsorption geometries and the corresponding adsorption energies of various adsorption phases have been calculated. These computational results have provided useful insights into the chemisorption structures on the Si(100) surface. The present work also presents the development of three kinetics models for hydrogen evolution in the aforementioned aromatic-hydrocarbon systems on Si(100). Based on a modified collision theory with consideration of diffusion, these theoretical models have proven to be quite successful in simulating the observed TDS profiles and in estimating the kinetic parameters for the analysis of condensation polymerization in 2-dimensional diffusion systems. The present work illustrates that TDS experiments can be used effectively with quantum computation and theoretical kinetics modelling to elucidate the intricate nature of organosilicon surface chemistry.