Durant ma thèse, j'ai étudié cinq molécules d'intérêt astrophysique et atmosphérique en utilisant la spectroscopie à haute résolution dans les régions spectrales microonde, millimétrique et infrarouge lointain. Il s'agit du thioformate de méthyleCH3SCH(O), de sulfure de diméthyle (CH3)2S, de méthacroléine CH3C(CHO)CH2, d'acétate de vinyle CH3C(O)OCHCH2 et d'acétate de butadiènyle CH3C(O)O(CH)3CH2. Tous les spectres de ces molécules étudiées possèdent comme point en commun un mouvement de grande amplitude de rotation interne de un ou deux groupes méthyles CH3 qui aboutit à un dédoublement des raies. Ainsi, une modélisation spectrale spécifique pour chaque molécule est nécessaire afin de reproduire leurs spectres à la précision expérimentale et déterminer un ensemble de paramètres spectroscopiques à trés haute précision.Les molécules de thioformate de méthyle et de sulfure de diméthyle sont potentiellement détectables dans le milieu interstellaire (MIS) étant donné qu'elles sont les analogues soufrés du formiate de méthyle CH3OCH(O) et du diméthyle éther (CH3)2O, deux molécules relativement abondantes dans le MIS. Nous avons effectué pour la première fois une étude spectroscopique complète au laboratoire pour ces molécules, étude qui est indispensable pour fournir aux astrophysiciens des listes de fréquences et d'intensités de raies qui leur permettront dans le futur de détecter ces espèces et d'exploiter les spectres observés dans le MIS avec les radiotélescopes au sol et/ou embarqués. La méthacroléine est l'un des composés de l'oxydation des isoprènes émis dans la troposphère et elle joue un rôle important dans la chimie de l'atmosphère terrestre. Notre travail dans le domaine microonde a permis de mieux comprendre sa structure moléculaire et sa stabilité.Enfin, deux molécules d'esters carboxyliques ont été étudiées pendant ma thèse dans les régions spectrales des microondes comprises entre 2 et 40 GHz. J'ai complété l'étude du spectre microonde de l'acétate de vinyle CH3COOCHCH2 et j'ai étudié pour la première fois le spectre de deux isomères d'acétate de butadiènyle CH3COO (CH)3CH2. Outre que la validation des calculs de chimie quantiques effectués, cette étude a permis une meilleure compréhension de l'évolution des valeurs de barrières de potentielles entravant la rotation interne en fonction de la structure chimique. / During my thesis, I studied five molecules of astrophysical and atmospheric interest using high-resolution spectroscopy in the spectral regions of microwave, millimeterwave and far infrared. These molecules are methyl thioformate CH3SCH(O), dimethyl sulfide(CH3)2S, methacrolein CH3C(CHO)CH2, vinyl acetate CH3C(O)OCHCH2 and butadienylacetate CH3C(O)O(CH)3CH2. All of their spectra have in common a large amplitude motion,the internal rotation of the methyl group(s) CH3 leading to a splitting of the lines. Then, iused a specific theoretical modeling for each molecule in order to reproduce their spectra at experimental accuracy and to determine a set of spectroscopic parameters with very highprecision.Methyl thioformate and dimethyl sulfide are potentially detectable in the interstellar medium(MIS) as they represent the sulfur analogues of methyl formate CH3OCH(O) and dimethylether (CH3)2O, two molecules relatively abundant in the MIS. I performed a complete spectroscopic study in laboratory in order to provide astrophysicists with lists of frequencies and intensities of lines, which enable them to exploit the observed spectra in the MIS.Methacrolein is one of the compounds of the oxidation of isoprene emitted in the troposphereand plays an important role in the chemistry of the earth's atmosphere. Our studies in themicrowave range enables us to better determine its molecular structure which is useful inorder to better understand its stability. Finally, two ester molecules have been studied in the microwave spectral regions between2 and 40 GHz. The study of the microwave spectrum of vinyl acetate CH3COOCHCH2 is completed and the spectrum of two isomers of butadienyl acetate CH3COO(CH)3CH2 is studied for the first time.In addition to the validation of quantum chemistry calculations, this study allowed a better under standing of the evolution of potential barrier values du to internal rotation as a function of chemical structure.

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A busca de uma melhor compreensão dos ciclos químicos que ocorrem na atmosfera de Titan, um dos satélites naturais de Saturno, tem posto em relevância a importância de reações químicas envolvendo nitrogênio atômico e hidrocarbonetos, principalmente o radical metila. Além desta ênfase astroquìmica, essa reação tem também um papel importante no estudo da decomposição de metano em plasma pós-descarga de nitrogênio e no entendimento de processos de combustão. Neste trabalho, dando continuidade a estudos teóricos envolvendo reações de espécies atômicas com hidrocarbonetos realizados por este grupo e utilizando o estado da arte em termos de cálculos de estrutura eletrônica, realizou-se uma ampla investigação da superfície tripleto de energia potencial 3[H3, C, N] com ênfase nos aspectos estruturais, energéticos e espectroscópicos dos pontos estacionários e na cinética global da reação. Nesta superfície de energia potencial, foram caracterizados 7 pontos estacionários, sendo 3 estados de transição e 4 mínimos. No melhor nível de cálculo, CCSD(T)/CBS, o mínimo global corresponde à formação do radical metilnitreno, 71,01 kcal/mol mais estável do que o canal de entrada N(4S) + CH3 (2A2\"). Entretanto, via caminhos distintos, a reação prossegue formando H2CN + H como o principal produto, resultado esse que não confirma uma suposição anterior de que HCN seria o produto principal. No aspecto cinético, verificou-se que a etapa determinante da reação é regida pelo canal de entrada bimolecular, sem barreira, e que o valor para a constante de velocidade global, na melhor descrição deste trabalho, de 1,93 x 10-10 cm3 molécula?1 s-1, é bem superior à de estudo teórico anterior. Além da boa concordância com dados experimentais, nossos resultados também mostram um aumento da constante de velocidade com a temperatura, o que não foi previsto nesse estudo anterior. / The search for a better understanding of chemical cycles in Titan´s atmosphere, one of Saturn´s largest natural satellite, has emphasized the importance of chemical reactions between atomic nitrogen and hydrocarbons, especially methyl radical. Besides this astrochemical relevance, this reaction also plays a key role in the study of methane decomposition in after-glow nitrogen plasma, and in combustion processes. In this work, as another step towards theoretical studies of reactions involving atomic species with hydrocarbons carried out by this group, and using state-of-the-art electronic structure calculations, a wide investigation of the triplet potential energy surface 3[H3, C, N] was made with emphasis on structural, energetic, and spectroscopic aspects of the stationary points, and on the global kinetic description of the reaction. In this potential energy surface, 7 stationary points were characterized: 3 transition states and 4 minima. In our best description, CCSD(T)/CBS, the global minimum corresponds to the formation of the methylnitrene radical, 71.01 kcal/mol more stable than the entrance channel N(4S) + CH3 (2A2\"). However, by different paths, the reaction proceeds leading to the formation of H2CN + H as the major product, a result that does not confirm a previous supposition that HCN would be the major product. Kinetically, we have shown that the rate determining step is the barrierless bimolecular collision of CH3 and N(4S), and that the global rate constant, in the best estimate of this work, 1.93 x 10-10 cm3 molecule-1 s-1, is well superior to that of a previous theoretical study. Besides the good agreement with the experimental data, our results also show an increase of the rate constant with the temperature, a result not predicted by that previous study.

A busca de uma melhor compreensão dos ciclos químicos que ocorrem na atmosfera de Titan, um dos satélites naturais de Saturno, tem posto em relevância a importância de reações químicas envolvendo nitrogênio atômico e hidrocarbonetos, principalmente o radical metila. Além desta ênfase astroquìmica, essa reação tem também um papel importante no estudo da decomposição de metano em plasma pós-descarga de nitrogênio e no entendimento de processos de combustão. Neste trabalho, dando continuidade a estudos teóricos envolvendo reações de espécies atômicas com hidrocarbonetos realizados por este grupo e utilizando o estado da arte em termos de cálculos de estrutura eletrônica, realizou-se uma ampla investigação da superfície tripleto de energia potencial 3[H3, C, N] com ênfase nos aspectos estruturais, energéticos e espectroscópicos dos pontos estacionários e na cinética global da reação. Nesta superfície de energia potencial, foram caracterizados 7 pontos estacionários, sendo 3 estados de transição e 4 mínimos. No melhor nível de cálculo, CCSD(T)/CBS, o mínimo global corresponde à formação do radical metilnitreno, 71,01 kcal/mol mais estável do que o canal de entrada N(4S) + CH3 (2A2\"). Entretanto, via caminhos distintos, a reação prossegue formando H2CN + H como o principal produto, resultado esse que não confirma uma suposição anterior de que HCN seria o produto principal. No aspecto cinético, verificou-se que a etapa determinante da reação é regida pelo canal de entrada bimolecular, sem barreira, e que o valor para a constante de velocidade global, na melhor descrição deste trabalho, de 1,93 x 10-10 cm3 molécula?1 s-1, é bem superior à de estudo teórico anterior. Além da boa concordância com dados experimentais, nossos resultados também mostram um aumento da constante de velocidade com a temperatura, o que não foi previsto nesse estudo anterior. / The search for a better understanding of chemical cycles in Titan´s atmosphere, one of Saturn´s largest natural satellite, has emphasized the importance of chemical reactions between atomic nitrogen and hydrocarbons, especially methyl radical. Besides this astrochemical relevance, this reaction also plays a key role in the study of methane decomposition in after-glow nitrogen plasma, and in combustion processes. In this work, as another step towards theoretical studies of reactions involving atomic species with hydrocarbons carried out by this group, and using state-of-the-art electronic structure calculations, a wide investigation of the triplet potential energy surface 3[H3, C, N] was made with emphasis on structural, energetic, and spectroscopic aspects of the stationary points, and on the global kinetic description of the reaction. In this potential energy surface, 7 stationary points were characterized: 3 transition states and 4 minima. In our best description, CCSD(T)/CBS, the global minimum corresponds to the formation of the methylnitrene radical, 71.01 kcal/mol more stable than the entrance channel N(4S) + CH3 (2A2\"). However, by different paths, the reaction proceeds leading to the formation of H2CN + H as the major product, a result that does not confirm a previous supposition that HCN would be the major product. Kinetically, we have shown that the rate determining step is the barrierless bimolecular collision of CH3 and N(4S), and that the global rate constant, in the best estimate of this work, 1.93 x 10-10 cm3 molecule-1 s-1, is well superior to that of a previous theoretical study. Besides the good agreement with the experimental data, our results also show an increase of the rate constant with the temperature, a result not predicted by that previous study.

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Yes / The complexes [RuCp*(PP)Cl] (Cp* = C5Me5; [1], PP = dppm; [4], PP = Xantphos), [RuCp#(PP)Cl] (Cp# = C5Me4(CH2)5OH; [2], PP = dppm; [5], PP = Xantphos) and [RuCp*(dppm)(CH3CN)][SbF6] [3] were synthesized and evaluated in vitro as anticancer agents. Compounds 1–3 gave nanomolar IC50 values against normoxic A2780 and HT-29 cell lines, and were also tested against hypoxic HT-29 cells, maintaining their high activity. Complex 3 yielded an IC50 value of 0.55 ± 0.03 μM under a 0.1% O2 concentration.

The possibility of using methylamines instead of ammonia as a nitrogen precursor for the CVD of nitrides is studied using quantum chemical computations of reaction energies: reaction electronic energy (Δ𝑟𝐸𝑒𝑙𝑒𝑐) reaction enthalpy (Δ𝑟𝐻) and reaction free energy (Δ𝑟𝐺). The reaction energies were calculated for three types of reactions: Uni- and bimolecular decomposition to more reactive nitrogen species, adduct forming with trimethylgallium (TMG) and trimethylaluminum (TMA) followed by a release of methane or ethane and surface adsorption to gallium nitride for both the unreacted ammonia or methylamines or the decomposition products. The calculations for the reaction entropy and free energy were made at both STP and CVD conditions (300°C-1300°C and 50 mbar). The ab inito Gaussian 4 (G4) theory were used for the calculations of the decomposition and adduct reactions while the surface adsorptions were calculated using the Density Functional Theory method B3LYP. From the reactions energies it can be concluded that the decomposition was facilitated by the increasing number of methyl groups on the nitrogen. The adducts with mono- and dimethylamine were more favorable than ammonia and trimethylamine. 𝑁𝐻2 was found to be most readily to adsorb to 𝐺𝑎𝑁 while the undecomposed ammonia and methylamines was not willingly to adsorb.