This thesis describes and develops two experimental techniques, Time Resolved Photoelectron Spectroscopy (TRPES), and Time Resolved Coincidence Imaging Spectroscopy (TRCIS), to study ultrafast gas phase chemical dynamics. We use TRPES to investigate the effects of methyl substitution on the electronic dynamics of the simple alpha, beta-enones acrolein, crotonaldehyde, methylvinylketone, and methacrolein following excitation to the S2 state. We determine that following excitation, the molecules move rapidly away from the Franck-Condon region reaching a conical intersection promoting relaxation to the S1 state. Once on the S1 surface, the trajectories access another conical intersection leading them to the ground state. Only small variations between molecules are seen in their S2 decay times. However, the position of methyl group substitution greatly affects the relaxation rate from the S1 surface. Ab initio calculations used to compare the geometries, energies, and topographies of the S1/S0 conical intersections of the molecules are not able to explain the variations in relaxation behaviour. We propose a model that uses dynamical factors of specific motions in the molecules to explain the differing nonadiabatic S1/S0 crossing rates. The second part of this thesis examines the issues involved with design and construction of a Coincidence Imaging Spectrometer. This type of spectrometer measures the 3-dimensional velocities of both photoelectrons and photoions generated from probing of laser induced photodissociation reactions. Importantly, the photoelectrons and photoions are measured in coincidence from single molecules, enabling measurements such as recoil frame photoelectron angular distributions and correlated photoelectron/photoion energy maps, inaccessible using existing techniques. How to optimize the spectrometer resolution through design, tuning, and calibration is discussed. The power of TRCIS is demonstrated with the investigation of the photodissociation dynamics of the NO dimer. TRPES experiments first identified a sequential kinetic model following 209nm excitation resulting in NO(X) (ground state) and NO(A) (excited state) products. Using TRCIS, it was possible to measure time resolved vibrational energy distributions of the products, indicating the extent of vibrational energy redistribution within the dimers prior to dissociation. Recoil frame photoelectron angular distributions and theoretical support allow identification of a previously disputed intermediate on the dissociation pathway. / Thesis (Ph.D, Chemistry) -- Queen's University, 2007-04-01 10:12:39.968

La présente recherche traite des constructions participiales en –ing de l’anglais contemporain. Elle s’appuie sur un corpus de plus de 1700 occurrences de participiales issues de romans et d’articles de journaux, ainsi que sur le British National Corpus et le Corpus of Contemporary American English. Les participiales ont pour caractéristique majeure ne pas expliciter les liens syntaxiques et sémantiques qui les unissent à la proposition dont elles dépendent. Pour expliquer les fondements linguistiques de cette propriété, la recherche établit une typologie détaillée des participiales, étudie les relations qu’elles entretiennent avec leur sujet, ainsi que la nature de l’incidence et de la prédication qui les caractérisent, et détaille les interprétations sémantiques qu’elles peuvent recevoir. Elle montre que la valeur sémantique basique des participiales est la circonstance concomitante, soit un simple lien établi entre deux procès qui forment une unité dans l’esprit de l’énonciateur. Ce sont les traits spécifiques du co- et du contexte qui peuvent modifier cette valeur basique pour déboucher sur l’interprétation finale, adverbiale ou adjectivale, de la participiale. La recherche propose, dans le cadre de la psychosystématique de Gustave Guillaume, des hypothèses susceptibles d’expliquer le comportement syntaxique et sémantique des participiales ; elle montre qu’il est directement lié au sens du participe présent, dont il est postulé que l’incidence est interne et qu’il code la simultanéité et l’imperfectif dans tous ses emplois. / This research deals with –ing participle clauses in contemporary English. It is based on a corpus totalling over 1,700 participle clauses collected from novels and newspaper articles, and it also relies on data from electronic corpora – the British National Corpus and the Corpus of Contemporary American English. The main characteristic of –ing participle clauses is that they lack an explicit syntactic and semantic link to their superordinate clause: to shed light on the linguistic phenomena accounting for this specificity, the research establishes a detailed typology of –ing clauses, studies their relationship to their subjects, investigates the specific nature of their incidence and predication, and provides a detailed analysis of their semantic indeterminacy. It shows that their basic semantic value is one of attendant circumstance – a mere link between two events or states that form a unit in the speaker’s mind. The characteristics of the co- and context may alter this basic value to give the clause its final (adjectival or adverbial) meaning. The research puts forward hypotheses to account for the syntactic and semantic characteristics of –ing participle clauses within the framework of Gustave Guillaume’s psychosystematic theory: it shows the syntactic and semantic behaviour of –ing clauses can be directly traced back to the meaning of the –ing participle, which, it is hypothesised, has an internal incidence and expresses simultaneity and imperfectivity in all of its uses.

Made available in DSpace on 2016-06-02T20:27:40Z (GMT). No. of bitstreams: 1 4629.pdf: 1448309 bytes, checksum: c6f5e451b1247c565791c643df7dc7d5 (MD5) Previous issue date: 2012-10-23 / Financiadora de Estudos e Projetos / This thesis was developed in two parts. Firstly, we consider a pair of fiber-preserving maps f1, f2 : M → M in a fiber bundle with base S1 and fiber Klein bottle. Using an algebraic system of equations we found in what situations the minimal coincidence set over S1 of the pair (f1, f2) is empty. In the second part, motivated by this problem, we consider a fiber-preserving map f : M → M in a fiber bundle with base S1 and fiber torus. Using the one-parameter fixed point theory we studied the minimal fixed point set over S1 of the map f. In some fiber bundle we classified completely this sets. / Esta tese foi desenvolvida em duas partes. Inicialmente, consideramos um par de aplicações que preserva fibra, f1, f2 : M → M, em um fibrado com base S1 e fibra garrafa de Klein. Utilizando-se de um sistema algébrico de equações, descobrimos em que situações o conjunto minimal de coincidências sobre S1 do par (f1, f2) é vazio. Na segunda parte, motivado por esse problema, consideramos uma aplicação que preserva fibra, f : M → M, em um fibrado com base S1 e fibra toro. Usando a teoria algébrica de ponto fixo a 1-parâmetro estudamos o conjunto minimal dos pontos fixos sobre S1 da aplicação f. Em alguns fibrados foi possível obter uma classificação completa desses conjuntos.

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Made available in DSpace on 2015-05-15T11:46:01Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 1921576 bytes, checksum: 089bb16dfc8ec52a2ca6e0e4fea4e360 (MD5) Previous issue date: 2011-07-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In this work, we present some properties of the class of multiple summing multilinear operators. We summarize the theory with the aim of showing in details recent results such as coincidence results, inclusion results and results involving cotype. / No presente trabalho, estudamos algumas propriedades dos operadores multilineares múltiplo somantes. Fazemos um resumo da teoria com o objetivo de apresentar com detalhes resultados recentes de coincidência, inclusão e resultados envolvendo cotipo.