Ab Initio Quantum Chemical Studies on Neutral-Radical Reactions of Ethynyl (C2H) and Cyano (CN) with Unsaturated Hydrocarbons

An Ab Initio/RRKM study of the reaction mechanism and product branching ratios of neutral-radical ethynyl (C2H) and cyano (CN) radical species with unsaturated hydrocarbons is performed. The reactions studied apply to cold conditions such as planetary atmospheres including Titan, the Interstellar Medium (ISM), icy bodies and molecular clouds. The reactions of C2H and CN additions to gaseous unsaturated hydrocarbons are an active area of study. NASA’s Cassini/Huygens mission found a high concentration of C2H and CN from photolysis of ethyne (C2H2) and hydrogen cyanide (HCN), respectively, in the organic haze layers of the atmosphere of Titan. The reactions involved in the atmospheric chemistry of Titan lead to a vast array of larger, more complex intermediates and products and may also serve as a chemical model of Earth’s primordial atmospheric conditions. The C2H and CN additions are rapid and exothermic, and often occur barrierlessly to various carbon sites of unsaturated hydrocarbons. The reaction mechanism is proposed on the basis of the resulting potential energy surface (PES) that includes all the possible intermediates and transition states that can occur, and all the products that lie on the surface. The B3LYP/6-311g(d,p) level of theory is employed to determine optimized electronic structures, moments of inertia, vibrational frequencies, and zero-point energy. They are followed by single point higher-level CCSD(T)/cc-vtz calculations, including extrapolations to complete basis sets (CBS) of the reactants and products. A microcanonical RRKM study predicts single-collision (zero-pressure limit) rate constants of all reaction paths on the potential energy surface, which is then used to compute the branching ratios of the products that result. These theoretical calculations are conducted either jointly or in parallel to experimental work to elucidate the chemical composition of Titan’s atmosphere, the ISM, and cold celestial bodies.

Resolución 091 del 22 de julio de 2013: Por la cual se resuelve un recurso de reposición

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Optimization of the power electronics system associated with ocean wave electric generators

The present thesis is focused on wave energy, which is a particular kind of ocean energy, and is based on the activity carried out during the EU project SEA TITAN. The main scope of this work is the design of a power electronic section for an innovative wave energy extraction system based on a switched-reluctance machine. In the first chapter, the general features of marine wave energy harvesting are treated. The concept of Wave Energy Converter (WEC) is introduced as well as the mathematical description of the waves, their characterization and measurement, the WEC classification, the operating principles and the standardization framework. Also, detailed considerations on the environmental impact are presented. The SEA TITAN project is briefly described. The second chapter is dedicated to the technical issues of the SEA TITAN project, such as the operating principle, the performance optimization carried out in the project, the main innovations as well as interesting demonstrations on the behavior of the generator and its control. In the third chapter, the power electronics converters of SEA TITAN are described, and the design choices, procedures and calculations are shown, with a further insight into the application given by analyzing the MATLAB Simulink model of the system and its control scheme. Experimental tests are reported in the fourth chapter, with graphs and illustrations of the power electronic apparatus interfaced with the real machine. Finally, the conclusion in the fifth chapter offers a global overview of the project and opens further development pathways.

Estimation of the satellite ephemerides of Saturn using optical navigation pictures of Cassini

The goal of this dissertation thesis is the estimation of the Saturnian satellites ephemerides using optical data of Cassini. In the first part we describe the software employed for the reduction of the images showing its main features and the accuracy that can be achieved comparing the results with published astrometry. Afterwards we describe the orbit determination problem (ODP) with particular focus on the weights selection for the estimation process. The third chapter describes the dynamical model used and the sources of potential errors in the residuals. The model have been validated trying to replicate JPL's published ephemerides SAT365, SAT375, SAT389 and SAT409. The final part investigates the residuals and the estimated ephemerides with particular focus on the giant moon Titan, the only in the solar system with an atmosphere other than the Earth. No astrometry have been retrieved in literature of Titan using optical observables, thus this represents one of the first investigations of the giant.