Darmstadt, Techn. Universiẗat, Diss., 2000. / Dateiformat: tar.gz, Dateien im PDF-Format.

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

L'isoprène est le composé organique volatil biogénique le plus émis à l'échelle de la planète. Il a été montré récemment que, malgré ses faibles rendements de production d'aérosols organiques secondaires (AOS), il pouvait contribuer de manière significative à la matière organique particulaire totale atmosphérique du fait de sa forte émission à l'échelle globale. L'AOS est reconnu pour présenter plusieurs impacts sur l'environnement, et notamment, sur le climat. Cependant, ses processus de formation, et notamment ceux ayant lieu via les gouttelettes nuageuses (voie potentiellement importante) restent encore mal connus. L'objectif de ce travail a été d'étudier la formation d'AOS issus de la photooxydation de l'isoprène (ou de la méthacroléine, un de ses produits d'oxydation majeurs) en conditions sèches ainsi qu'en présence de nuage. La chimie se produisant dans les phases gazeuse, particulaire et aqueuse ; et les échanges ayant lieu entre ces phases ont ainsi été investigués via une approche multiphasique originale dans la chambre de simulation atmosphérique CESAM. Une caractérisation des phases gazeuse et particulaire durant la photooxydation de l'isoprène en absence d'hydrométéores a, dans un premier temps, été effectuée. Les rendements de production d'AOS présents dans la littérature montrent une dispersion générale, les rendements obtenus lors des expériences sont cependant en bon accord avec les valeurs basses présentées dans la littérature. Cette caractérisation en conditions sèches a été complétée par la modélisation 0D des résultats. Les désaccords entre les données mesurées et les simulations issues des modèles explicite et détaillé sont importants et une inadéquation des codes chimiques à la chimie de l'isoprène ne peut être écartée. Pour la première fois en chambre de simulation, des protocoles destinés à étudier la photochimie en phase nuageuse ont été développés. Une méthodologie spécifique permettant de générer des nuages de durée de vie suffisante pour permettre l'établissement de réactions en phase aqueuse a ainsi été mise en place. L'influence de cycles d'évapo-condensation nuageux sur la photooxydation de l'isoprène, ou de ses produits d'oxydation, a ensuite été investiguée. Cette étude a permis de mettre en évidence l'existence d'un impact de la génération de nuage sur les phases gazeuse et particulaire, suggérant fortement l'existence d'une production très significative d'AOS issus de la photooxydation de l'isoprène via les gouttelettes nuageuses / Isoprene is the most abundant volatile organic compound in global scale. Despite its low secondary organic aerosol (SOA) yields, it has been recently shown that isoprene can significantly contribute to total particulate organic mass due to its large emissions. SOA are known to have various impacts on the environment, especially on climate. However, lacks in the comprehension of the SOA formation pathways, particularly via cloud droplets, are still important. The aim of the present work is to study SOA formation from isoprene (or methacrolein, one of isoprene major oxidation products) photooxidation, in dry condition, as well as in the presence of cloud. The chemistry occurring in the gaseous, particulate and aqueous phases, and the exchange between these phases were investigated through an original multiphase approach in the CESAM simulation chamber. Gaseous and particulate phases during isoprene photooxidation without hydrometeor were first characterized. While the SOA yields in the literature exhibit a general dispersion, the SOA yields obtained during the experiments are consistent with the lowest values found in the literature. This characterization in dry condition was completed by a simulation approach using a 0D photochemical box model. SOA yields obtained from explicit and detailed models show important disagreement with those measured: an incompatibility of the chemical codes with the isoprene chemistry cannot be dismissed. For the first time, protocols have been developed to study photochemistry in cloud phase in a simulation chamber. A specific methodology allowing the production of a cloud with an important lifetime was set up. The impact of cloud evapo-condensation cycles on the photooxidation of isoprene and its oxidation products was finally investigated. The impact of the cloud generation on the gaseous and particulate phases has been highlighted, suggesting a significant production of SOA from isoprene photooxidation by interactions with cloud droplets

A tall tower flux measurement setup was established in metropolitan Houston, Texas, to measure trace gas fluxes from both anthropogenic and biogenic emission sources in the urban surface layer. We describe a new relaxed eddy accumulation system combined with a dual-channel gas chromatography - flame ionization detection used for volatile organic compound (VOC) flux measurements in the urban area, focusing on the results of selected anthropogenic VOCs, including benzene, toluene, ethylbenzene and xylenes (BTEX), and biogenic VOCs including isoprene and its oxidation products, methacrolein (MACR) and methyl vinyl ketone (MVK). We present diurnal variations of concentrations and fluxes of BTEX, and isoprene and its oxidation products during summer time (May 22 - July 22, 2008) and winter time (January 1 - February 28). The measured BTEX values exhibited diurnal cycles with a morning peak during weekdays related to rush-hour traffic and additional workday daytime flux maxima for toluene and xylenes in summer time. However, in winter time there was no additional workday daytime peaks due mainly to the different flux footprints between the two seasons. A comparison with different EPA National Emission Inventories (NEI) with our summer time flux data suggests potential underestimates in the NEI by a factor of 3 to 5. The mixing ratios and fluxes of isoprene, MACR and MVK were measured during the same time period in summer 2008. The presented results show that the isoprene was affected by both tail-pipe emission sources during the morning rush hours and biogenic emission sources in daytime. The observed daytime mixing ratios of isoprene were much lower than over forested areas, caused by a comparatively low density of isoprene emitters in the tower's footprint area. The average daytime isoprene flux agreed well with emission rates predicted by a temperature and light only emission model (Guenther et al., 1993). Our investigation of isoprene's oxidation products MACR and MVK showed that both anthropogenic and biogenic emission sources exist for MACR, while MVK was strongly dominated by a biogenic source, likely the isoprene oxidation between the emission and sampling points.

Cette étude se focalise sur les impacts de la réactivité en phase aqueuse de la méthacroléïne et de la méthyl vinyl cétone sur la formation des nouveaux aérosols organiques secondaires (AOS), et les impacts de la réactivité en phase aqueuse sur le vieillissement des AOS formés par l’isoprène, α-pinène et 1,3,5-triméthylbenzène en phase gazeuse. Les études de la réactivité en phase aqueuse ont été étudiées vis-à-vis des radicaux OH. Dans le but d’identifier et quantifier les produits d’oxydation des différents précurseurs d’intérêt, les échantillons en phase aqueuse ont été analysés par différents systèmes analytiques. Les résultats montrent clairement la formation de petits composés primaires et secondaires qui ont été expliqués par les mécanismes réactionnels. On a observé également la formation de composés à haute masse moléculaire par rapport à leurs précurseurs. Ces produits ont été supposés être très peu volatils et pourraient induire la formation des AOS lors de l’évaporation de l’eau. Leur capacité à former des AOS a été montrée expérimentalement par les expériences de nébulisation des solutions aqueuses à différents temps de réaction. Les résultats montrent qu’au moins une part de ces produits à haute masse moléculaire reste en phase particulaire lors de l’évaporation de l’eau, et contribue à la formation des AOS. L’ensemble de ces résultats met en évidence le fait que la réactivité en phase aqueuse atmosphérique peut induire des effets importants sur la formation et le vieillissement des AOS atmosphériques, qui peut induire une modification des propriétés physico-chimiques des aérosols. / This work focused on the impacts of aqueous phase OH-oxidation of methacrolein, methyl vinyl ketone on the SOA formation, and impacts of aqueous phase OH-oxidation on aging of SOA that are formed by isoprene, -pinene and 1,3,5-trimethylbenzene in gas phase. The chemical characterization of aqueous phase was performed by different analytical techniques. The results show the formation of small primary and secondary reaction products that were explained by suitable chemical reaction mechanisms. The formation of oligomers with high molecular mass (compared with their precursors) has also been observed during the OH-oxidation. These oligomers might be low volatile compounds that induce the formation of SOA during water evaporation. Their capacity to form SOA was experimentally demonstrated by nebulizing the aqueous phase solution at different reaction times. The results show that at least a part of oligomers remains in the particle phase during water evaporation, and contributes to the SOA formation. All of these results highlight that aqueous phase reactivity could induce important effects on the formation and aging of atmospheric SOA, which can induce modification of physico-chemical properties of SOA.