O desenvolvimento desta tese foi direcionado ao estudo da química iônica, em fase gasosa, de alguns compostos organo-metálicos, como: Ge(OEt)4, Ti(i-Pro)4, BU3SnOMe, GeE4, GeMe4, SiMe4 e Me6Si2NH. Foram abordados vários aspectos da química iônica destes compostos desde o estudo dos seus processos de fragmentação, a reatividade de cátions e ânions derivados destes compostos, a fotodisssociação de espécies hipervalentes formadas a partir de reações de adição, e por último foram obtidos dados sobre a afinidade protônica de ânions derivados de germânio. Além disto, foram promovidas outras investigações experimentais destinadas á obtenção de informações sobre a estrutura de espécies hipervalentes e a análise de substâncias químicas desconhecidas contendo átomos de Ge. Os resultados obtidos em algumas investigações são conclusivos, e por isto em alguns casos não foi criada uma seção voltada exclusivamente para as conclusões. Mesmo assim, algumas observações podem ser destacadas. De modo geral, os alcóxidos metálicos reagem com íon fluoreto através de reações de adição-eliminação formando complexos pentacoordenados, que no caso dos derivados de germânio e titânio, absorvem radiação infravermelha de um laser de CO2, e por absorção multifotônica promovem sucessivos processos de eliminação de espécies neutras simples. O mesmo comportamento não é observado nas alquilas metálicas. Os cátions derivados destes compostos são poderosos ácidos de Lewis, e sofrem reações de adição-eliminação com diversos substratos neutros, do tipo base de Lewis. O mais surpreendente foi à observação de reações de abstração de ligantes como CH3- por alguns destes cátions, e a subseqüente formação, em alguns casos, de espécies formadas através de reações de troca de ligantes. A afinidade protônica de alguns ânions formados através da fotodissociação de espécies hipervalentes, derivadas de germânio, foi obtida por meio de reações de abstração de prótons com substratos de afinidade protônica conhecida. Foi possível caracterizar a acidez dos ácidos conjugados destes ánions como sendo próxima a das mercaptanas. / The present thesis describes the study of the gas-phase ion chemistry of a number of organometallic compounds such as Ge(OEt)4, Ti(i-Pro)4, BU3SnOMe, GeE4, GeMe4, SiMe4 and Me6Si2NH. Several aspects of the ion chemistry of these compounds were investigated including fragmentation processes in their mass spectra, reactivity of cations and anions obtained from these compounds by electron ionization, photodissociation of hypervalent species formed by nucleophilic addition, and the proton affinity of a number of germanium-containing anions. Additional experimental investigations were carried out to characterize the structure of hypervalent studies and to explore analytical applications of unknown germanium-containing substrates. The results in several cases are sufficiently conclusive such that a general section of conclusions was considered unnecessary. For example, the metal alkoxides studied in this work react with fluoride ion in the gas-phase by an addition-elimination mechanism that initially results in the formation of a pentacoordinated species. The germanium and titanium pentacoordinated species absorb readily infrared radiation from a CO2 laser and undergo successive elimination of sim pie neturals by sequential mutiphoton absorption. This behavior is not observed for the metal alkyls. Cations derived from these compounds are powerful Lewis acids and are capable of promoting addition-elimination reactions with several neutral substrates that can act as Lewis bases. The most surprising reactions have been the abstraction of methide (formally a CH3- ion) by some of these cations followed, in the case of some Si- and Ge-containing ions, by a ligand exchange reaction. The proton affinity of Ge-containing anions obtained from the photodissociation of hypervalent precursors was established using the bracketing technique by studying the proton abstraction reaction with a number of substrates of well-known proton affinities. The absolute values derived for the proton affinities of these species, and the corresponding gas-phase acidities of the conjugate acids are close to the values of similar mercaptans.

<p>Crude oil is a mixture of hydrocarbons so complex that it is predicted to comprise as many compounds as there are genes in the human genome. Developing methods to not only recover crude oil from the ground but also to convert crude oil into desirable products is challenging due to its complex nature. Thus, the petroleum industry relies heavily on analytical techniques to characterize the oil in reservoirs prior to enhanced oil recovery efforts and to evaluate the chemical compositions of their crude oil based products. Mass spectrometry (MS) is the only analytical technique that has the potential to provide elemental composition as well as structural information for the individual compounds that comprise petroleum samples. The continuous development of ionization techniques and mass analyzers, and other instrumentation advances, have primed mass spectrometry as the go-to analytical technique for providing solutions to problems faced by the petroleum industry. The research discussed in this dissertation can be divided into three parts: developing novel mass spectrometry-based methods to characterize mixtures of saturated hydrocarbons in petroleum products (Chapters 3 and 5), exploring the cause of fragmentation of saturated hydrocarbons upon atmospheric pressure chemical ionization to improve the analysis of samples containing these compounds (Chapter 4), and developing a better understanding of the chemical composition of crude oil that tightly binds to reservoir surfaces to improve chemically enhanced oil recovery (Chapter 6). </p>

Mass-selected infrared multiple photon spectroscopy (IRMPD), Fourier transform ion cyclotron resonance (FT-ICR) kinetic experiments, RRKM and electronic structure calculations have been performed in order to propose a complex mechanism involving the formation of the proton-bound dimer of water (H5O2+) from 1,1,3,3-tetrafluorodimethyl ether. It has been found that the reaction is facilitated by a series of sequential exothermic bimolecular ion-molecule reactions. Evidence for the dominant mechanistic pathway involving the reaction of CF2H-O=CHF+, an ion of m/z 99, with water is presented. The primary channel occurs via nucleophilic attack of water on the ion of m/z 99 (CF2H-O=CHF+), to lose formyl fluoride and yield protonated difluoromethanol (m/z 69). Association of a second water molecule with protonated difluoromethanol generates a reactive intermediate which decomposes via a 1,4-elimination to release hydrogen fluoride and yield the proton-bound dimer of water and formyl fluoride (m/z 67). The 1,4-elimination of hydrogen fluoride is found to be strongly supported by the results of both RRKM theory and electronic structure calculations. Lastly, the elimination of formyl fluoride occurs by the association of a third water molecule to produce H5O2+ (m/z 37). The most probable isomeric forms of the ions with m/z 99 and 69 were found using IRMPD spectroscopy and electronic structure theory calculations. Thermochemical information for reactant, transition and product species was obtained using MP2/aug-cc-pVQZ//MP2(full)/6-31G(d) level of theory. Ionic hydrogen bond (IHB) interactions, resulting from the association of ammonia and two of the protonated methylxanthine derivatives, caffeine and theophylline, have been characterized using mass-selected IRMPD and electronic structure calculations at the MP2/aug-cc-pVTZ//B3LYP/6-311+G(d,p) level of theory. It was found that the formation of a proton-bound dimer (PBD) of caffeine and ammonia was elusive under the experimental conditions. The low binding energy of the caffeine and ammonia PBD is responsible for the perceived difficulty in obtaining an IRMPD spectrum. The IRMPD spectrum of the PBD of theophylline and ammonia was obtained and revealed bidentate IHB formation within the complex, which greatly increased the binding energy relative to the most stable isomer of the PBD of caffeine and ammonia. The IRMPD spectra of the protonated forms of caffeine and theophylline have also obtained. The spectrum of protonated caffeine showed the dominant existence of a single isomer, whereas the spectrum of protonated theophylline showed a mixture of isomers. The mixture of isomers of protonated theophylline resulted as a consequence of proton-transport catalysis (PTC) occurring within the PBD of theophylline and ammonia. All calculated harmonic spectra have been produced at the B3LYP/6-311+G(d,p) level of theory with fundamental frequencies scaled by 0.9679; calculated anharmonic spectra have also been provided at the same level of theory and were found to greatly improve the match with the IRMPD spectra obtained in all cases. Ionic hydrogen bond (IHB) interactions, resulting from the association of caffeine and theophylline with their protonated counterparts, forming proton-bound homodimers, have been characterized using mass-selected IRMPD and electronic structure calculations at the MP2/6-311+G(2d,2p)//B3LYP/6-311+G(d,p) level of theory. It is found that the IRMPD spectra of the proton-bound homodimers of caffeine and theophylline are complicated resulting from the existence of several pairs of enantiomers separated by a narrow range of relative Gibbs free energies (298 K) of 15.6 and 18.2 kJ mol-1, respectively. The IRMPD spectrum of the proton-bound homodimer of theophylline is dominated by a unique isomer facilitated by formation of a bidentate IHB. Formation of this interaction lowers the relative Gibbs free energy of the ion to 9.75 kJ mol-1 below that of the most favourable pair of enantiomers. The IRMPD spectrum of the PBD of caffeine is complicated by the existence of at least two pairs of enantiomers with the strong likelihood of the spectral contributions of a third pair existing. The most favourable enantiomeric pair involves the formation of a O-H+⋯O IHB. However, verification of a pair of enantiomeric PBDs containing a N-H+⋯O IHB is also observed in the IRMPD spectrum of the PBD of caffeine due to the presence of three free carbonyl stretching modes located at 1731, 1751 and 1785 cm-1. The mass-selected IRMPD spectra of the sodium cation-bound dimers (SCBD) of caffeine and theophylline also have been obtained. Both the mass-selected IRMPD spectra and electronic structure calculations predict the most likely structure of the SCBDs of caffeine and theophylline to form by an efficient O⋯Na+⋯O interaction between C=O functional groups possessed by each monomer. The frequencies of the C=O-Na+ stretch are found to be nearly identical in the IRMPD spectra for both of the SCBDs of caffeine and theophylline at 1644 and 1646 cm-1, respectively. However, the degenerate free C=O symmetric and asymmetric stretches for the SCBDs of caffeine and theophylline found at 1732 and 1758 cm^(-1), respectively, demonstrating a red-shift for caffeine possibly linked to a steric interaction absent in theophylline. Free rotation about the O⋯Na+⋯O bond is found to greatly decrease the complexity of the IRMPD spectra of the SCBDs of caffeine and theophylline and demonstrates excellent agreement between the IRMPD and calculated spectra. Electronic structure calculations have been done at the MP2(full)/aug-cc-pCVTZ/6-311+G(2d,2p)//B3LYP/6-311+G(d,p) level of theory using the aug-cc-pCVTZ basis set for Na+ and all Na+-interacting heterotatoms, and the 6-311+G(2d,2p) basis set for all non-interacting atoms within the SCBDs, in order to provide accurate electronic energies. Currently, installation and implementation of a pulsed electrospray high pressure ion source mated to an existing high pressure mass spectrometer (HPMS) is underway. The new ion source will greatly increase the range of possibilities for the study of ion-molecule reactions in the McMahon laboratory. One of the unique features of the new design is the incorporation of a gas-tight electrospray interface, allowing for more possibilities than only the study of cluster-ion equilibria involving hydration (H2On⋯S+), where S+ is an ion produced by electrospray. Other small prototypical biological molecules such as amines and thiols can be used without concern for the toxicity of these species. Another unique design feature allows electrosprayed ions to associate with neutral solvent species in an electric field free reaction chamber (RC). This ensures that values of equilibrium constants determined are truly representative of ions in states of thermochemical equilibrium. The existing HPMS in the McMahon laboratory is limited to the study of small volatile organic molecules. The new ion source will permit the exploration of systems involving non-volatile species, doubly charged ions and many biologically relevant molecules such as amino acids, peptides, nucleobases and carbohydrates.

Mass-selected infrared multiple photon spectroscopy (IRMPD), Fourier transform ion cyclotron resonance (FT-ICR) kinetic experiments, RRKM and electronic structure calculations have been performed in order to propose a complex mechanism involving the formation of the proton-bound dimer of water (H5O2+) from 1,1,3,3-tetrafluorodimethyl ether. It has been found that the reaction is facilitated by a series of sequential exothermic bimolecular ion-molecule reactions. Evidence for the dominant mechanistic pathway involving the reaction of CF2H-O=CHF+, an ion of m/z 99, with water is presented. The primary channel occurs via nucleophilic attack of water on the ion of m/z 99 (CF2H-O=CHF+), to lose formyl fluoride and yield protonated difluoromethanol (m/z 69). Association of a second water molecule with protonated difluoromethanol generates a reactive intermediate which decomposes via a 1,4-elimination to release hydrogen fluoride and yield the proton-bound dimer of water and formyl fluoride (m/z 67). The 1,4-elimination of hydrogen fluoride is found to be strongly supported by the results of both RRKM theory and electronic structure calculations. Lastly, the elimination of formyl fluoride occurs by the association of a third water molecule to produce H5O2+ (m/z 37). The most probable isomeric forms of the ions with m/z 99 and 69 were found using IRMPD spectroscopy and electronic structure theory calculations. Thermochemical information for reactant, transition and product species was obtained using MP2/aug-cc-pVQZ//MP2(full)/6-31G(d) level of theory. Ionic hydrogen bond (IHB) interactions, resulting from the association of ammonia and two of the protonated methylxanthine derivatives, caffeine and theophylline, have been characterized using mass-selected IRMPD and electronic structure calculations at the MP2/aug-cc-pVTZ//B3LYP/6-311+G(d,p) level of theory. It was found that the formation of a proton-bound dimer (PBD) of caffeine and ammonia was elusive under the experimental conditions. The low binding energy of the caffeine and ammonia PBD is responsible for the perceived difficulty in obtaining an IRMPD spectrum. The IRMPD spectrum of the PBD of theophylline and ammonia was obtained and revealed bidentate IHB formation within the complex, which greatly increased the binding energy relative to the most stable isomer of the PBD of caffeine and ammonia. The IRMPD spectra of the protonated forms of caffeine and theophylline have also obtained. The spectrum of protonated caffeine showed the dominant existence of a single isomer, whereas the spectrum of protonated theophylline showed a mixture of isomers. The mixture of isomers of protonated theophylline resulted as a consequence of proton-transport catalysis (PTC) occurring within the PBD of theophylline and ammonia. All calculated harmonic spectra have been produced at the B3LYP/6-311+G(d,p) level of theory with fundamental frequencies scaled by 0.9679; calculated anharmonic spectra have also been provided at the same level of theory and were found to greatly improve the match with the IRMPD spectra obtained in all cases. Ionic hydrogen bond (IHB) interactions, resulting from the association of caffeine and theophylline with their protonated counterparts, forming proton-bound homodimers, have been characterized using mass-selected IRMPD and electronic structure calculations at the MP2/6-311+G(2d,2p)//B3LYP/6-311+G(d,p) level of theory. It is found that the IRMPD spectra of the proton-bound homodimers of caffeine and theophylline are complicated resulting from the existence of several pairs of enantiomers separated by a narrow range of relative Gibbs free energies (298 K) of 15.6 and 18.2 kJ mol-1, respectively. The IRMPD spectrum of the proton-bound homodimer of theophylline is dominated by a unique isomer facilitated by formation of a bidentate IHB. Formation of this interaction lowers the relative Gibbs free energy of the ion to 9.75 kJ mol-1 below that of the most favourable pair of enantiomers. The IRMPD spectrum of the PBD of caffeine is complicated by the existence of at least two pairs of enantiomers with the strong likelihood of the spectral contributions of a third pair existing. The most favourable enantiomeric pair involves the formation of a O-H+⋯O IHB. However, verification of a pair of enantiomeric PBDs containing a N-H+⋯O IHB is also observed in the IRMPD spectrum of the PBD of caffeine due to the presence of three free carbonyl stretching modes located at 1731, 1751 and 1785 cm-1. The mass-selected IRMPD spectra of the sodium cation-bound dimers (SCBD) of caffeine and theophylline also have been obtained. Both the mass-selected IRMPD spectra and electronic structure calculations predict the most likely structure of the SCBDs of caffeine and theophylline to form by an efficient O⋯Na+⋯O interaction between C=O functional groups possessed by each monomer. The frequencies of the C=O-Na+ stretch are found to be nearly identical in the IRMPD spectra for both of the SCBDs of caffeine and theophylline at 1644 and 1646 cm-1, respectively. However, the degenerate free C=O symmetric and asymmetric stretches for the SCBDs of caffeine and theophylline found at 1732 and 1758 cm^(-1), respectively, demonstrating a red-shift for caffeine possibly linked to a steric interaction absent in theophylline. Free rotation about the O⋯Na+⋯O bond is found to greatly decrease the complexity of the IRMPD spectra of the SCBDs of caffeine and theophylline and demonstrates excellent agreement between the IRMPD and calculated spectra. Electronic structure calculations have been done at the MP2(full)/aug-cc-pCVTZ/6-311+G(2d,2p)//B3LYP/6-311+G(d,p) level of theory using the aug-cc-pCVTZ basis set for Na+ and all Na+-interacting heterotatoms, and the 6-311+G(2d,2p) basis set for all non-interacting atoms within the SCBDs, in order to provide accurate electronic energies. Currently, installation and implementation of a pulsed electrospray high pressure ion source mated to an existing high pressure mass spectrometer (HPMS) is underway. The new ion source will greatly increase the range of possibilities for the study of ion-molecule reactions in the McMahon laboratory. One of the unique features of the new design is the incorporation of a gas-tight electrospray interface, allowing for more possibilities than only the study of cluster-ion equilibria involving hydration (H2On⋯S+), where S+ is an ion produced by electrospray. Other small prototypical biological molecules such as amines and thiols can be used without concern for the toxicity of these species. Another unique design feature allows electrosprayed ions to associate with neutral solvent species in an electric field free reaction chamber (RC). This ensures that values of equilibrium constants determined are truly representative of ions in states of thermochemical equilibrium. The existing HPMS in the McMahon laboratory is limited to the study of small volatile organic molecules. The new ion source will permit the exploration of systems involving non-volatile species, doubly charged ions and many biologically relevant molecules such as amino acids, peptides, nucleobases and carbohydrates.

Hydrocarbons, in particular polycyclic aromatic hydrocarbons (PAHs), have been long discussed to be carriers of interstellar infrared (IR) emission and ultraviolet (UV) absorption features. Yet, their origin in dense phases of the interstellar medium (ISM), such as molecular clouds, remains unclear. In this work, growth mechanisms based on ion-molecule reactions between cationic PAHs/hydrocarbons and methyne (CH) were investigated. The reaction type and the precursor were derived and selected from known chemical and physical properties of the ISM. These chemical reactions were characterised by calculating branching ratios (based on cross sections) and capture rate coefficients, minimum reaction paths, reaction enthalpies, thermal equilibrium constants, and microcanonic isomerisation and radiative deactivation rate coefficients. In order to cope with the variety of reaction parameters, a hierarchic workflow scheme was set up. First, the reaction potential energy surface was sampled by molecular dynamics simulations. Then, minimum energy paths of the most probable reaction channels were investigated. Finally, molecular and kinetic properties of stationary points were calculated. The quantum chemical level of theory was increased at each step from DFTB (tight-binding density-functional), to DFT, and finally to post-Hartree-Fock methods. Results on CH based hydrocarbon growth showed the transition from non-cyclic hydrocarbons to cyclic and aromatic structures and from cyclic to polycyclic aromatic hydrocarbons. Additionally, the reactive collisions between hydrocarbons and CH were found to produce sufficient energy for isomerisation and fragmentation processes even at ultra low temperatures. In all, the results indicate that methyne might be a proper precursor for the formation of large interstellar PAHs. / Kohlenwasserstoffe, insbesondere polyzyklische Kohlenwasserstoffe (engl. PAHs), werden seit einigen Jahren als Mitverursacher interstellar IR-Emissions- und UV-Absorptionsbanden angesehen und diskutiert. Dabei ist die Herkunft dieser Moleküle in den dichten Phasen des interstellaren Mediums (ISM) aber noch nicht aufgeklärt. In dieser Arbeit wurden daher die Bildungsmechanismen, welche auf Ion-Molekül-Reaktionen zwischen kationischen PAHs und Kohlenwasserstoffen und dem Molekül CH beruhen, untersucht. Sowohl der Reaktionstyp als auch der Präkursor wurden anhand von bekannten physikalischen und chemischen Eigenschaften des ISM abgeleitet und ausgewählt. Die Analyse der chemischen Reaktionen basierte auf Berechnungen zur Produktzusammensetzung und Einfangsratenkoeffizienten (welche wiederum aus berechneten Reaktionsquerschnitten hervorgingen) Minimumenergiepfade (MEP), Reaktionsenthalpien, thermische Gleichgewichtskonstanten und mikrokanonische Isomerisierungs- und Strahlungsdeaktivierungs-Ratenkoeffizienten. Um der Vielzahl an Reaktionsparameter gerecht zu werden, wurden die Berechnungsmethoden entsprechend eines hierarischen Fließschemas kombiniert. Hierzu wurden zuerst durch Molekulardynamik-Simulationen die Reaktionspotentialenergieflächen abgerastert. Auf der nächsten Stufe wurden statistisch bedeutsame Reaktionskanäle bezüglich ihrer Minimumenergiepfade untersucht. Den Abschluss bildete die Berechnung molekularer und kinetischer Charakteristika stationärer Punkte auf einem MEP. Entsprechend dieses Schemas wurde die quantenchemische Genauigkeit auf jeder Stufe von approximativer DFT über DFT zu post-Hartree-Fock verändert. Die Ergebnisse des CH-basierten Kohlenwasserstoffwachstums zeigten einen Übergang von nichtzyklischen zu zyklischen and aromatischen Strukturen, sowie von zyklischen zu polyzyklischen Kohlenwasserstoffen. Außerdem zeigte sich, dass reaktive Kollisionen zwischen Kohlenwasserstoffen und CH auch bei Tiefsttemperaturen immer ausreichend Energie für Isomerisierungs- und Fragmentationsprozesse liefert. Die Ergebnisse dieser Arbeit lassen den Schluss zu, dass CH ein geeigneter Präkursor für die Bildung großer interstellarer PAH ist.

Hydrocarbons, in particular polycyclic aromatic hydrocarbons (PAHs), have been long discussed to be carriers of interstellar infrared (IR) emission and ultraviolet (UV) absorption features. Yet, their origin in dense phases of the interstellar medium (ISM), such as molecular clouds, remains unclear. In this work, growth mechanisms based on ion-molecule reactions between cationic PAHs/hydrocarbons and methyne (CH) were investigated. The reaction type and the precursor were derived and selected from known chemical and physical properties of the ISM. These chemical reactions were characterised by calculating branching ratios (based on cross sections) and capture rate coefficients, minimum reaction paths, reaction enthalpies, thermal equilibrium constants, and microcanonic isomerisation and radiative deactivation rate coefficients. In order to cope with the variety of reaction parameters, a hierarchic workflow scheme was set up. First, the reaction potential energy surface was sampled by molecular dynamics simulations. Then, minimum energy paths of the most probable reaction channels were investigated. Finally, molecular and kinetic properties of stationary points were calculated. The quantum chemical level of theory was increased at each step from DFTB (tight-binding density-functional), to DFT, and finally to post-Hartree-Fock methods. Results on CH based hydrocarbon growth showed the transition from non-cyclic hydrocarbons to cyclic and aromatic structures and from cyclic to polycyclic aromatic hydrocarbons. Additionally, the reactive collisions between hydrocarbons and CH were found to produce sufficient energy for isomerisation and fragmentation processes even at ultra low temperatures. In all, the results indicate that methyne might be a proper precursor for the formation of large interstellar PAHs. / Kohlenwasserstoffe, insbesondere polyzyklische Kohlenwasserstoffe (engl. PAHs), werden seit einigen Jahren als Mitverursacher interstellar IR-Emissions- und UV-Absorptionsbanden angesehen und diskutiert. Dabei ist die Herkunft dieser Moleküle in den dichten Phasen des interstellaren Mediums (ISM) aber noch nicht aufgeklärt. In dieser Arbeit wurden daher die Bildungsmechanismen, welche auf Ion-Molekül-Reaktionen zwischen kationischen PAHs und Kohlenwasserstoffen und dem Molekül CH beruhen, untersucht. Sowohl der Reaktionstyp als auch der Präkursor wurden anhand von bekannten physikalischen und chemischen Eigenschaften des ISM abgeleitet und ausgewählt. Die Analyse der chemischen Reaktionen basierte auf Berechnungen zur Produktzusammensetzung und Einfangsratenkoeffizienten (welche wiederum aus berechneten Reaktionsquerschnitten hervorgingen) Minimumenergiepfade (MEP), Reaktionsenthalpien, thermische Gleichgewichtskonstanten und mikrokanonische Isomerisierungs- und Strahlungsdeaktivierungs-Ratenkoeffizienten. Um der Vielzahl an Reaktionsparameter gerecht zu werden, wurden die Berechnungsmethoden entsprechend eines hierarischen Fließschemas kombiniert. Hierzu wurden zuerst durch Molekulardynamik-Simulationen die Reaktionspotentialenergieflächen abgerastert. Auf der nächsten Stufe wurden statistisch bedeutsame Reaktionskanäle bezüglich ihrer Minimumenergiepfade untersucht. Den Abschluss bildete die Berechnung molekularer und kinetischer Charakteristika stationärer Punkte auf einem MEP. Entsprechend dieses Schemas wurde die quantenchemische Genauigkeit auf jeder Stufe von approximativer DFT über DFT zu post-Hartree-Fock verändert. Die Ergebnisse des CH-basierten Kohlenwasserstoffwachstums zeigten einen Übergang von nichtzyklischen zu zyklischen and aromatischen Strukturen, sowie von zyklischen zu polyzyklischen Kohlenwasserstoffen. Außerdem zeigte sich, dass reaktive Kollisionen zwischen Kohlenwasserstoffen und CH auch bei Tiefsttemperaturen immer ausreichend Energie für Isomerisierungs- und Fragmentationsprozesse liefert. Die Ergebnisse dieser Arbeit lassen den Schluss zu, dass CH ein geeigneter Präkursor für die Bildung großer interstellarer PAH ist.

<p dir="ltr">Tandem mass spectrometry (MSⁿ) has become the most widely used analytical technique for the chemical characterization of unknown organic compounds in complex mixtures. It has led to the development of a large number of mass spectrometers with different mass analyzers as well as a wide array of ionization methods. This technique can be coupled with a diverse range of chromatography methods, such as gas chromatography (GC) and high-performance liquid chromatography (HPLC). Some of the primary strengths of MS include its great sensitivity, its versatility to seamlessly integrate with various chromatography techniques and its flexibility in the sense of access to different mass analyzers and different ionization methods. During MS experiments, analytes are evaporated and ionized and the resulting ions are separated based on their mass-to-charge (<i>m/z</i>) ratios and then detected. On the other hand, MSⁿ experiments involve isolating a specific ion of interest from all other ions and subjecting them to reactions such as collision-activated dissociation (CAD) or ion-molecule reactions. These reactions generate product ions that can be used to obtain structural information for the analyte. In addition, MSⁿ experiments can be used to generate and study the chemical properties of reaction intermediates, such as oxenium cations. </p><p dir="ltr">The mass spectrometer and the ionization source used to perform the research discussed in this thesis are described in Chapter 2. After this, the development of experiments involving ion-molecule reactions accompanied by collision-activated dissociation in a linear quadrupole ion trap is discussed, with the goals of differentiating the aziridine functionality from structurally related functional groups, such as the amino group and identifying aromatic aldehyde functionalities in protonated oxygen-containing monofunctional analytes. The integration of machine learning with mass spectral data has become an increasingly prevalent and valuable way to interpret data faster and more accurately without human bias than conventional manual approaches. Chapter 5 discusses combining machine learning-guided automated HPLC analysis coupled with MSⁿ experiments based on diagnostic ion-molecule reactions for the structural elucidation of unknown compounds. Finally, experimental and computational studies on the gas-phase reactivity of quinoline-based ground-state singlet oxenium cations are discussed.</p>

Ce travail a pour motivation de fournir des données expérimentales importantes pour l'interprétation de la chimie des ionosphère planétaires, en particulier pour le plus grand satellite de Saturne, Titan. On s'intéresse spécifiquement à la réactivité des espèces ioniques excitées. Cette thèse porte, d'une part, sur des expériences de préparation des cations (CH3+ et CF3+) sélectionnés en énergie interne par photoionisation VUV d'espèces neutres, et d'autre part, sur des réactions de cations sélectionnés en énergie interne avec des molécules, O+ avec CH4 et N+(3P) avec C3H4, C3H6 et C3H8.L'étude de la préparation des cations CH3+ et CF3+ sélectionnés dans des niveaux vibrationnels a été réalisée par la technique de coïncidence TPEPICO et du rayonnement VUV synchrotron à SOLEIL. Un spectromètre de type PFI-ZEKE qui permet d'atteindre une résolution de 0.84 cm-1 a été construit pour la réalisation d'études complémentaires avec le rayonnement laser VUV du Centre Laser de l'Université Paris Sud (CLUPS), à Orsay en France.Les expériences pour la détermination de l'influence de l'excitation du cation O+ (2S,2D,2P) sur sa réactivité avec le méthane ont été réalisées par les techniques de coïncidence TPEPICO et de guides d'ions. Elles ont été réalisées sur la ligne de rayonnement VUV DESIRS du synchrotron SOLEIL. Les études pour déterminer la constante de vitesse et les rapports de branchement entre produits des réactions de N+(3P) avec C3H4, C3H6 et C3H8 ont été réalisées par l'utilisation de la technique SIFT sur un montage de type commercial de petite taille à l'Institut de Physico-Chimie J. Heyrovský à Prague, en République Tchèque. / This work has the motivation to provide experimental data relevant to the interpretation of the chemistry of planetary ionospheres, particularly for the largest satellite of Saturn, Titan. Here we have a particular interest in studying the reactivity of excited ionic species. The first part of this work concerns the production of CH3+ and CF3+ state selected cations by VUV photoionization of neutral species and the second part, the reactions of state selected cations with molecules: O+ with methane and N+(3P) with C3H4, C3H6 and C3H8.The study of the preparation of the CH3+ and CF3+ cations in selected vibrational levels was performed by using the TPEPICO coincidence technique and VUV radiation at the french synchrotron, SOLEIL. A PFI-ZEKE spectrometer, that allowed us to obtain a resolution down to 0.84 cm-1, was constructed to conduct additional studies involving laser VUV radiation at the Laser Center of the University Paris Sud XI, at Orsay in France.Experiments to determine the influence of the O+ (2S,2D,2P) cation excitation on its reaction with methane were performed using the TPEPICO coincidence and the guide ion beam technique. These experiments were performed on the VUV DESIRS beamline at the synchrotron SOLEIL. Rate constants and products branching ratio for the reacion of N+(3P) with C3H4, C3H6 and C3H8 were measured with the SIFT technique in a small commercial apparatus at the Institute of Physical Chemistry J. Heyrovský in Prague, Czech Republic. / Este trabalho tem como motivação fornecer dados experimentais importantes para a interpretação da química de ionosferas planetárias, em particular para o maior Satélite de Saturno, Titan. Aqui temos o interesse específico pelo estudo de reatividades de espécies iônicas excitadas. Uma parte deste trabalho consistiu de experiências de preparação de cátions (CH3+ e CF3+) selecionados em energia interna via a fotoionização VUV de espécies neutras e de reações de cátions selecionados em massa e energia interna com moléculas (O+ com metano e N+(3P) com C3H4, C3H6 e C3H8).O estudo de preparação dos cátions CH3+ e CF3+ selecionados energia interna (vibracional) foi realizado pela utilização da técnica de coincidência TPEPICO com a radiação VUV do síncrotron SOLEIL. Um espectrômetro do tipo PFI-ZEKE que nos permite obter uma resolução de até 0.84 cm-1 foi construído para a realização de estudos complementares envolvendo a radiação VUV laser do Centro de Laser da Universidade Paris Sud XI, em Orsay na França.Experiências para determinar a influência da excitação do cátion O+ (2S,2D,2P) na produção de íons devido a sua reação com o metano foram realizadas com a utilização da técnica de coincidência TPEPICO e da técnica de guia de íons. Estes experimentos foram realizados na linha de radiação VUV DESIRS do síncrotron SOLEIL. Estudos de determinação de constantes de velocidade e dos produtos formados da reação N+(3P) com C3H4, C3H6 e C3H8 foram realizados a partir da utilização da técnica SIFT em uma montagem do tipo comercial de pequeno porte no Instituto de Físico-Química J. Heyrovský em Praga, na República Checa.