This thesis presents applications of near infrared diode lasers to high resolution spectroscopy of transient radical species. Firstly, time resolved near infrared laser gain versus absorption is utilised in Chapter 2 to determine the I∗ quantum yield following ultraviolet photolysis of iodobenzene and its fluorinated analogues. The experimental method is first confirmed by comparison with literature values of the quantum yield for iodomethane photolysis, returning a quantum yield of Φ(I∗) = 0.71 ± 0.04 in good agreement with the literature, before being applied to determine the I∗ quantum yield following 248 nm and 266 nm photolysis of iodobenzene (Φ(I^∗) = 0.28 ± 0.04) and pentafluoroiodobenzene (Φ(I^∗) = 0.32 ± 0.05). The I^∗ quantum yields for 4-fluoroiodobenzene, 2,4-difluoroiodobenzene and 3,5-difluoroiodobenzene are also reported in order to determine the effect of selective fluorination on the dynamics of the photodissociation process. This work complements velocity-map ion imaging studies and spin-orbit resolved ab initio calculations of the ultraviolet photolysis of these compounds. Chapter 3 details the development of a narrow-bandwidth tunable continuous wave ultraviolet radiation source, through sum frequency mixing of tunable near infrared diode lasers with a fixed frequency, high powered, solid state laser. The application of the UV radiation source to spectroscopy of the A¹A₂ − X¹A₁ electronic band of formaldehyde is explored, where absolute absorption cross sections are determined for rotational transitions within the 220410 and 220430 vibronic bands. The sub-Doppler resolution has allowed refinement of the rotational constants for the slowly predissociating excited state of the 2²₀4³₀ vibronic band. The lifetimes of several rotational levels is determined to be in the range 0.74 ns to 1.46 ns. In Chapter 4 the UV radiation source developed in Chapter 3 is applied to the A ²Σ⁺ − X ²Π electronic band of the OH radical. Firstly, this source is utilised to probe a continuous supply of hydroxyl radicals using cavity-enhanced absorption spectroscopy and wavelength modulation spectroscopy. Pressure induced broadening parameters for the Q₁(2) rotational transition for He, Ne, Ar and N₂ buffer gases are also measured. Following the successful application of this source to probe a continuous OH source at atmospheric pressure, the UV spectrometer is used to probe OH radicals from nitric acid photolysis at 193 nm, where the nascent speed distribution and Doppler lineshape is shown to be in excellent agreement with the literature. Time resolved absorption spectroscopy of the nascent OH fragment also returns a translational relaxation constant of k_trans = (3.85±1.06)×10⁻¹⁰cm³molecule⁻¹s⁻¹, which is in good agreement with literature values. These preliminary results indicate the potential of this narrow-bandwidth tunable UV source as an absorption-spectroscopy-based probe of nascent Doppler profiles. Chapter 5 presents the application of frequency-modulated radiation from a near infrared diode laser as a probe of the angular momentum polarisation of the nascent CN fragments, produced by 266 nm photolysis of ICN. These CN fragments are probed in the high rotational states of both the ground and first excited vibrational level on the A ²Π − X ²Σ⁺ electronic transition; in particular these constitute the first measurements of alignment and orientation in the first excited vibrational level at this photolysis wavelength. The alignment parameters reported for both vibrational levels are comparable, indicating that the incoherent dynamics contributing to their formation are the same. In contrast, the orientation of the v = 1 CN fragment is shown to be of opposite sign to that of v = 0 at this photolysis wavelength, although the absolute differences in their orientation parameters are similar to that observed for photolysis at 248 nm. This observation is consistent with coherent orientation arising from phase differences between wavepackets propagating on multiple excited potential energy surfaces.

Ce travail de thèse a pour objectif d'étudier les propriétés des molécules de métaux alcalins M2+ immergées dans des agrégats de néon, par le biais de simulations numériques. Nous développons une approche globale dans laquelle la détermination de la structure électronique se réduit à un problème à un électron. Ce dernier évolue dans un potentiel modélisé par des pseudo-potentiels semi-locaux à cœur polarisable. Nous les avons paramétrés après avoir calculé les courbes de potentiel des dimères MNe et M+Ne de manière ab initio. Nous effectuons une dynamique moléculaire classique, en y incorporant un traitement des couplages non-adiabatiques grâce à un algorithme de saut de surface. Nous avons trouvé les géométries d'équilibre des systèmes M2+Nen jusqu'à la première couche de solvatation de la molécule. Nous en avons déduit les propriétés statiques de ces systèmes en examinant les énergies de liaison, les distances d'équilibre, et les spectres optiques d'absorption. Nous avons ensuite étudié la dynamique de ces systèmes placés initialement sur un état excité. Nous avons établi que le taux de photodissociation dépend fortement du nombre d'atomes de néon et de l'ordre des transitions électroniques. Nous avons observé un effet de cage pour les systèmes Li2+Nen à partir de 18 atomes de néon. Nous avons également effectué des analyses sur la distribution des fragments produits, sur les états moléculaires stabilisés, et sur la localisation de la charge dans les systèmes asymétriques.

Les hydrocarbures forment l'ossature de la chimie interstellaire en phase gazeuse. Pour autant, la distribution et l'abondance de ces espèces ne sont connues que dans une poignée d'objets. Après avoir introduit quelques notions d'astrochimie, nous nous intéressons dans la deuxième partie de cette thèse à l'étude des hydrocarbures dans les nuages sombres. Nous montrons d'abord -- à l'issue d'un travail consacré au nuage TMC-1 -- que le rapport d'abondance des isomères cyclique et linéaire de la molécule C3H2 dépend de la fraction électronique dans le gaz et pourrait donc être utilisé comme sonde de cette quantité. Nous soulignons aussi que les molécules C6H et l-C3H2, rarement observées jusqu'ici, sont communes dans les nuages sombres. Nous montrons enfin que les hydrocarbures sont présents dans l'enveloppe du nuage L134N et que leurs abondances correspondent à celles d'une chimie riche en carbone. La troisième partie est consacrée à l'observation d'hydrocarbures dans trois régions de photodissociation, dont la nébuleuse de la Tête de cheval. Les cartes que nous avons réalisées montrent que les hydrocarbures sont présents en abondance dans les zones soumises au champ ultraviolet. En outre, leur émission est spatialement corrélée à celle des PAH. Nous remarquons que les modèles de chimie en phase gazeuse échouent à reproduire ces propriétés puis soulignons que la photoérosion des PAH -- non prise en compte actuellement -- semble pouvoir former des hydrocarbures à un taux suffisant pour réconcilier modèles et observations.

<p>The main focus of this thesis is the investigation of the dissociation dynamics of aryl halides using femtosecond pump-probe spectroscopy. In the monohalogenated aryl halides, iodo-, bromo- and chlorobenzene, the rate of dissociation following excitation at 266 nm in the gas phase increased with increasing mass of the halogen atom. This process was assigned to predissociation of the initially excited singlet (π, π*) state via a repulsive triplet (n, σ*) state due to spin-orbit interaction. In addition to the predissociative mechanism, a direct dissociation channel was observed in iodobenzene. The rate of the predissociation in bromobenzene was found to be faster in the condensed phase than in the gas phase, which can be explained by solvent-induced symmetry perturbations. <i>Ab initio</i> calculations of the potential energy surfaces of the ground state and several low lying excited states in bromobenzene have been performed in order to verify the suggested mechanism. Substituting one of the hydrogen atoms in bromobenzene affected the predissociation rate significantly. In o-, m- and p-dibromobenzene the predissociation rate increased with decreasing distance between the bromine atoms in accordance with an increased spin-orbit interaction introduced by the bromine substituent. The fastest predissociation rate was observed in 1,3,5-tribromobenzene. With chlorine and fluorine substitution, inductive and conjugative effects were found to be of importance. In the o- and m-isomers of the dihalogenated aryl halides, an additional faster dissociation channel was observed. Guided by <i>ab initio</i> calculations of the potential energy surfaces in the dibromobenzene isomers, we ascribed the fast dissociation pathway to predissociation of an initially excited triplet state. Upon methyl group substitution in bromobenzene, the decreased lifetime of the initially excited state was attributed to an incresaed density of coupled states.</p><p>Another system which has been studied in the condensed phase is diiodomethane. Using Car-Parrinello molecular dynamics simulations we observed a prompt dissociation and subsequent recombination to the isomer, iso-diiodomethane, in acetonitrile solution.</p><p>Vibrational wavepacket dynamics in the C (¹Σ⁺) state of NaK were studied using a direct ionization probing scheme. A simple analytical expression for the pump-probe signal was developed in order to see what factors that govern direct ionization of the vibrational wavepacket. Our experimental data was consistent with a photoionization transition dipole moment that varies with internuclear distance.</p>

The main focus of this thesis is the investigation of the dissociation dynamics of aryl halides using femtosecond pump-probe spectroscopy. In the monohalogenated aryl halides, iodo-, bromo- and chlorobenzene, the rate of dissociation following excitation at 266 nm in the gas phase increased with increasing mass of the halogen atom. This process was assigned to predissociation of the initially excited singlet (π, π*) state via a repulsive triplet (n, σ*) state due to spin-orbit interaction. In addition to the predissociative mechanism, a direct dissociation channel was observed in iodobenzene. The rate of the predissociation in bromobenzene was found to be faster in the condensed phase than in the gas phase, which can be explained by solvent-induced symmetry perturbations. Ab initio calculations of the potential energy surfaces of the ground state and several low lying excited states in bromobenzene have been performed in order to verify the suggested mechanism. Substituting one of the hydrogen atoms in bromobenzene affected the predissociation rate significantly. In o-, m- and p-dibromobenzene the predissociation rate increased with decreasing distance between the bromine atoms in accordance with an increased spin-orbit interaction introduced by the bromine substituent. The fastest predissociation rate was observed in 1,3,5-tribromobenzene. With chlorine and fluorine substitution, inductive and conjugative effects were found to be of importance. In the o- and m-isomers of the dihalogenated aryl halides, an additional faster dissociation channel was observed. Guided by ab initio calculations of the potential energy surfaces in the dibromobenzene isomers, we ascribed the fast dissociation pathway to predissociation of an initially excited triplet state. Upon methyl group substitution in bromobenzene, the decreased lifetime of the initially excited state was attributed to an incresaed density of coupled states. Another system which has been studied in the condensed phase is diiodomethane. Using Car-Parrinello molecular dynamics simulations we observed a prompt dissociation and subsequent recombination to the isomer, iso-diiodomethane, in acetonitrile solution. Vibrational wavepacket dynamics in the C (1Σ+) state of NaK were studied using a direct ionization probing scheme. A simple analytical expression for the pump-probe signal was developed in order to see what factors that govern direct ionization of the vibrational wavepacket. Our experimental data was consistent with a photoionization transition dipole moment that varies with internuclear distance.

La Méthode de la Trajectoire Adiabatique Contrainte est développée dans le but de résoudre globalementl'équation de Schrödinger. Cette méthode utilise le formalisme de Floquet et une décomposition de Fourier pourdécrire les dépendances temporelles. Elle transforme ainsi un problème dynamique en un problème aux valeurspropres partiel dans un espace de Hilbert étendu au temps. Cette manipulation requiert l'application decontraintes sur les conditions initiales de l'état propre de Floquet recherché. Les contraintes sont appliquées parl'intermédiaire d'un opérateur absorbant artificiel. Cet algorithme est adapté à la description de systèmes dirigéspar des hamiltoniens dépendant explicitement du temps. Il ne souffre pas de l'accumulation d'erreurs au cours dutemps puisqu'il fournit une solution globale ; les erreurs éventuelles proviennent de la non-complétude des basesfinies utilisées pour la description moléculaire ou temporelle et de l'imperfection du potentiel absorbant dépendantdu temps nécessaire pour fixer les conditions initiales. Une forme générale de potentiel absorbant a étédéveloppée pour être en mesure d'intégrer un problème avec une condition initiale quelconque. Des argumentsrelatifs au suivi adiabatique dans le cas de Hamiltoniens non-hermitiens sont également présentés. Nous insistonssur le rôle des facteurs de phase géométrique. Les méthodes développées sont appliquées à des systèmesatomiques ou moléculaires soumis à des impulsions laser intenses, en relation avec la problématique du contrôlemoléculaire. Nous considérons plusieurs exemples : modèles d'atomes à deux ou trois niveaux, ion moléculairehydrogène et molécules froides de sodium.

The Multidisciplinary University Research Initiative (MURI) research at Texas A and M University is concerned with the experimental characterization of non-thermal and non-chemical equilibrium systems in hypersonic (Mach greater than 5) flowfields using experimental diagnostics, and is an interdisciplinary collaboration between the Chemistry and Aerospace Engineering departments. Hypersonic flight conditions often lead to non-thermochemical equilibrium (NTE) state of air, where the timescale of reaching a single (equilibrium) Boltzmann temperature is much longer than the timescale of the flow, meaning that certain molecular modes such as vibrational modes, may be much more excited than the translational or rotational modes of the molecule leading to thermal-nonequilibrium. A nontrivial amount of energy is therefore contained within the vibrational mode, and this energy cascades into the flow as thermal energy, affecting flow properties through the process of various vibrational-vibrational (V-V) and vibrational-translational (V-T) energy exchanges between the flow species. The research is a fundamental experimental study of these NTE systems and involves the application of advanced laser and optical diagnostics towards hypersonic flowfields. The research is broken down into two main categories: the application and adaptation of existing laser and optical techniques towards characterization of NTE, and the development of new molecular tagging velocimetry techniques which have been demonstrated in an NTE flowfield, but may be extended towards a variety of flowfields.

Deux modèles sont développés afin d'interpréter la physico-chimie des ions organométalliques en phase gazeuse.<br /><br /> Les surfaces de potentiel associées à la réactivité sont modélisées dans le cadre de la théorie des hamiltoniens effectifs, et l'on s'intéresse plus particulièrement à l'addition oxydante d'un ion LnM+ sur une liaison H-H. L'idée est de bâtir un hamiltonien effectif associé aux électrons actifs, c'est-à-dire à l'insertion de M+ dans la liaison H-H, puis d'utiliser une approche de type champ de ligands pour traiter l'effet des ligands spectateurs (Ln). L'originalité de l'approche réside surtout dans la construction du hamiltonien effectif associé à M+ + H-H. Il est bâti à partir de potentiels à deux corps associés à M+-H et H-H, dérivés de calculs ab initio sur les états électroniques de valence de ces fragments. En utilisant une correction appropriée pour les termes à trois corps, notre modèle localise correctement les points stationnaires de M+ + H2, et la précision sur leurs énergies relatives est de l'ordre de 20 kJ/mol.<br /><br /> La seconde partie porte sur le développement d'un modèle cinétique pour interpréter l'efficacité de fragmentation d'ion induite par une absorption multiphotonique infrarouge en phase gazeuse, phénomène exploité pour obtenir le spectre IR d'ions formés en spectrométrie de masse. Les paramètres de notre modèle sont associés à la focalisation et à la structure temporelle du laser, ainsi qu'à la trajectoire et aux paramètres physico-chimiques des ions. La très bonne simulation de plusieurs expériences permet de mieux comprendre les phénomènes observés et constituera un guide précieux pour les prochaines campagnes d'expériences.

Many anticancer therapies are based on the interaction of small molecule drugs with nucleic acids, particularly DNA. Electrospray ionization tandem mass spectrometry has established itself as an irreplaceable tool for the characterization of DNA adducts produced by alkylating agents, carcinogens, and antitumor drugs, in addition to the characterization of nucleic acid post-transcriptional modifications. ESI-MS was used to assess the non-covalent binding of a novel series of intercalating anthrapyrazoles to duplexes containing different sequences. Relative binding affinities paralleled the shift in melting point of the DNA duplexes measured from a previous study. Upon collisionally induced dissociation of the duplex/anthrapyrazole complexes, different binding strengths were discerned based on the fragmentation patterns. In addition, the interactions of a new series of sulfur-containing acridine ligands, some that functioned as alklyating mustards, with duplex DNA were also evaluated. Non-covalent and covalent binding of each ligand was determined, and the site of adduction (G > A) was revealed for the covalent modifications. The distribution of cross-linked products and mono-adducts by psoralen analogs was also monitored by both LC-UV and IRMPD-MS methods. Reactions at 5’-TA sites were favored over 5’-AT sites. The sites of interstrand cross-linking were determined by fragmentation of the duplex/psoralen complexes by infrared multiphoton dissociation (IRMPD). Ultraviolet photodissociation (UVPD) at 193 nm caused efficient charge reduction of deprotonated oligodeoxynucleotides via electron detachment. Subsequent CID of the charge-reduced oligodeoxynucleotides formed upon electron detachment, in a net process called electron photodetachment dissociation (EPD), resulted in a diverse array of abundant sequence ions which allowed the modification site(s) of three modified oligodeoxynucleotides to be pinpointed to a more specific location than by conventional CID. Electron transfer dissociation (ETD) caused efficient charge reduction of multi-protonated oligonucleotides. Subsequent CAD of the charge-reduced oligonucleotides formed upon electron transfer, in a net process termed electron transfer collision activated dissociation (ETcaD), resulted in rich backbone fragmentation, with a marked decrease in the abundance of base loss ions and internal fragments. ETcaD of an oligonucleotide duplex resulted in specific backbone cleavages, with conservation of weaker non-covalent bonds. In addition, IRMPD and UVPD were used to activate charge-reduced oligonucleotides formed upon electron transfer. ET-IRMPD afforded tunable characterization of the modified DNA and RNA, allowing for modified bases to be directly analyzed. ET-UVPD promoted higher energy backbone fragmentation pathways and created the most diverse MS/MS spectra. The numerous products generated by the hybrid MS/MS techniques (ETcaD, ET-IRMPD, and ET-UVPD) resulted in specific and extensive backbone cleavages which allowed for the modification sites of multiple oligonucleotides to be pinpointed. / text

La théorie de la dynamique des processus chimiques élementaires cherche à décrire quantitativement les collisions réactives à l'échelle atomique. Les mouvements des noyaux étant extrêmement difficiles à traiter dans le formalisme quantique, les tomes sont souvent considérés comme des objets classiques. Cepandant, les effets purement quantiques jouent un rôle majeur dans certaines situations, alors que la description classique les néglige. Cette thèse apporte de nouvelles perspectives sur l'inclusion, dans le formalisme clasique, de forts effets quantiques, à savoir la quantification des mouvements internes des réactifs et produits.