This work presents a study of the thermal evaporation and stability of pyrene (C 16 H 10) n clusters. Thermal evaporation rates of positively charged mass-selected clusters are measured for sizes in the range n=3-40 pyrene units. The experimental setup consists of a gas aggregation source, a thermalization chamber and a time of flight mass spectrometer. A microcanonical Phase Space Theory (PST) simulation is used to determine the dissociation energies of pyrene clusters by fitting the experimental breakdown curves. Calculations using the Density Functional based Tight Binding combined with Configuration Interaction (CI-DFTB) model and a hierarchical optimization scheme are also performed in the range n=2-7 to determine the harmonic frequencies and a theoretical estimation of the dissociation energies. The frequencies are used in the calculations of the density of states needed in the PST simulations, assuming an extrapolation scheme for clusters larger than 7 units. Using the PST model with a minimal set of adjustable parameters, we obtain good fits of the experimental breakdown curves over the full studied size range. The approximations inherent to the PST simulation and the influence of the used parameters are carefully estimated. The derived dissociation energies show significant variations over the studied size range. Compared to neutral clusters, significantly higher values of the dissociation energies are obtained for the smaller sizes and attributed to charge resonance in line with CI-DFTB calculations.

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Research into a novel type of compact bushing is being conducted through the HVIV (High Voltage holding In Vacuum) partnership between CEA-Cadarache 1 , GeePs-Centralesupélec 4 , LPGP 3 and LCAR 2. The bushing aims to concentrate the high electric field inside its interior, rather than in the vacuum tank. Hence the field emission current is also concentrated inside the bushing and it can be attempted to suppress this so-called dark current by conditioning the internal surfaces and by adding gas. LCAR have performed theoretical quantum mechanical studies of electron field emission and the role of adsorbates in changing the work function. LPGP studied the ionization of gas due to field emission current and the behavior of micro particles exposed to emissive electron current in the vacuum gap under high electric fields. Experiments at Geeps have clarified the role of surface conditioning in reducing the dark current. Geeps also found that adding low pressure nitrogen gas to the vacuum is much more effective than helium in reducing the field emission. An interesting observation is the growth of carbon structures after exposure of an electrode to the electric field. Finally, IRFM have performed experiments on a single stage test bushing that features a 36 cm high porcelain insulator and two cylindrical electrode surfaces in vacuum or low-pressure gas. Using 0.1 Pa N 2 gas, the voltage holding exceeded 185 kV over a 40 mm "vacuum" gap without dark current. Above this voltage, exterior breakdowns occurred over the insulator, which was in air. The project will finish with the fabrication of a 2-stage compact bushing, capable to withstand 400 kV.

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A collision-induced dissociation study of hydrated protonated uracil (H 2 O) n=1-15 UH + clusters is reported. The mass-selected clusters collide with water molecules and rare gases at a controlled center of mass collision energy. From these measurements, absolute fragmentation cross sections and branching ratios are extracted as a function of the uracil hydration. For small clusters, up to n = 4, we observe that only neutral water molecules are evaporated upon collisions, whereas for larger clusters neutral uracil is also evaporated: this transition in the nature of the evaporation products is interpreted considering the lowest-energy isomers of each species that are obtained from a combination of density-functional based tight-binding (DFTB) and MP2 calculations. The simulations show that in (H 2 O) 1-4 UH + the proton is located on the uracil molecule or on a water molecule strongly bound to uracil whereas, in larger clusters, the proton is bound to water molecules far from uracil. This correlation between the structure of the low-energy isomers and the experimental fragmentation channel suggests that dissociation may occur in a very short time after collisions, so that energy has not enough time to be redistributed among all degrees of freedom and the ground-state geometry of the parent cluster partly determines the nature of the favored fragmentation channels. Of course, thermal dissociations originating from long lived, thus thermalized, collision complexes cannot be ruled out but they are not expected to play the major role since experimental results can be satisfactorily accounted for by assuming that the fragmentation processes are mainly impulsive. 2

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We present the design of a versatile gas aggregation source that allows producing molecular beams of charged clusters containing a controlled amount of chosen impurities. Several examples of clusters production using this source characterized by time of flight mass spectrometry are presented here. We demonstrate the source ability to produce homogeneous clusters, such as pure protonated water and alcohol clusters, as well as inhomogeneous ones such as water clusters containing a few units of uracil, glycine, sulfuric acid or pyrene.

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Le dispositif expérimental original développé à Toulouse permet de contrôler les collisions entre un agrégat chargé, libre, thermalisé, sélectionné en masse et des molécules. Il permet d'étudier l'attachement de la molécule sur l'agrégat ou la fragmentation induite par collision. Afin de mieux comprendre les processus d'attachement d'une molécule sur un agrégat, nous avons mesuré les sections efficaces d'attachement de molécules d'alcool, méthanol et éthanol, sur des agrégats d'alcool. Nous avons pu observer un comportement similaire aux agrégats d'eau, c'est à dire des sections efficaces d'attachement inférieures à la section efficace géométrique aux petites tailles qui tendent vers cette section géométrique quand la taille augmente. Ce comportement avait été attribué pour l'eau à un effet dynamique. Ce modèle dynamique peut être étendu avec un bon accord qualitatif aux agrégats d'alcools. Les processus d'attachement et de fragmentation nous permettent de réaliser des expériences de nanocalorimétrie. Nous avons pu déterminer les capacités calorifiques et les températures de transition de phase dans des agrégats d'eau protonés (H2O)nH+, qui viennent compléter les mesures effectuées sur les agrégats déprotonés (H2O)n-1OH-. La nature de la transition est discutée. Un troisième volet de cette thèse concerne la fragmentation induite par collision de molécules d'intérêt biologique : l'uracile protoné, isolé ou hydraté. Nous avons observé les différentes voies de fragmentation de l'uracile protoné. L'influence du nombre de molécules d'eau hydratant la molécule d'uracile sur le spectre de fragmentation est liée à l'affinité protonique des constituants et à la structure de l'agrégat.

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Absolute attachment cross sections of single molecules M (M = water, ethanol, or methanol) onto positively charged mass-selected clusters XnH+ (X = water, ethanol, or methanol) were measured for cluster sizes ranging from tens to hundreds of molecules and center-of-mass collision energies varying from 0.1 to ∼1 eV. The attachment cross sections, which converge as expected toward geometrical cross sections at large cluster sizes, are systematically and noticeably lower than geometrical cross sections at small sizes. Attachment cross sections depend barely on the nature of the reactants. Homogeneous attachment reactions XnH+ + X → Xn+1H+ can be accounted for by a dynamical collisional model, in which the intermolecular interactions between the target cluster and the impinging molecule can be neglected. Dynamical arguments account satisfactorily for size and energy dependences of attachment cross sections and also for their variation from one element to another. It is thus suggested that either the attachment probabilities are likely to be more governed by the capacity of clusters to absorb collision energy rather than by cluster/molecule intermolecular interactions, or it indicates that the strength of these interactions does not differ noticeably among the hydrogen-bonded systems investigated. However, for inhomogeneous reactions of the form XnH+ + Y → XnYH+ (X, Y = water, ethanol, methanol), although the global size dependences are qualitatively reproduced, the variations of attachment cross sections with the nature on the impinging molecule are not satisfactorily accounted for within the simple empirical model proposed for homogeneous reactions.

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An experimental nanocalorimetric study of mass selected protonated (H2O)nH+ and deprotonated (H2O)n−1OH− water clusters is reported in the size range n = 20-118. Water cluster's heat capacities exhibit a change of slope at size dependent temperatures varying from 90 to 140 K, which is ascribed to phase or structural transition. For both anionic and cationic species, these transition temperatures strongly vary at small sizes, with higher amplitude for protonated than for deprotonated clusters, and change more smoothly above roughly n ≈ 35. There is a correlation between bonding energies and transition temperatures, which is split in two components for protonated clusters while only one component is observed for deprotonated clusters. These features are tentatively interpreted in terms of structural properties of water clusters.

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Angle-resolved photoelectron spectra, resulting from the strong-field ionization of atoms or molecules, carry a rich amount of information on ionization pathways, electron dynamics, and the target structure. We have investigated angle-resolved photoelectron spectra arising from the nonresonant ionization of xenon Rydberg atoms in the multiphoton regime, using intense midinfrared radiation from a free-electron laser. The experimental data reveal a rich oscillatory structure in the low-order above-threshold ionization region. By performing quantum-mechanical and semiclassical calculations, the observed oscillations could be well reproduced and explained by both a multiphoton absorption picture as by a model invoking electron wave-packet interferences. Furthermore, we demonstrate that the shape and orientation of the initial Rydberg state leaves its own fingerprint on the final angular distribution.

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Heat capacities of mass selected deprotonated water clusters (H2O)n−1OH− have been measured in the size range n = 48-118, as a function of temperature. We have found that they undergo a melting-like transition in the range 110-130 K. The transition temperature is size dependent with a strong correlation with the dissociation energy around the shell closure at n = 55.

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