<p>Clusters are finite ensembles of atoms or molecules with sizes in the nanometer regime (<i>i.e.</i> nanoparticles). This thesis present results on the geometric and electronic structure of homogeneous and heterogeneous combinations of atoms and molecules. The systems have been studied with synchrotron radiation and valence, core and Auger electron spectroscopic techniques.</p><p>The first theme of the thesis is that of mixed clusters. It is shown that by varying the cluster production technique both structures that are close to that predicted by equilibrium considerations can be attained as well as far from equilibrium structures.</p><p>Electronic processes following ionization constitute the second theme. The post-collision interaction phenomenon, energy exchange between the photo- and the Auger electrons, is shown to be different in clusters of argon, krypton and xenon. A model is proposed that takes polarization screening in the final state into account. This result is of general character and should be applicable to the analysis of core level photoelectron and Auger electron spectra of insulating and semi-conducting bulk materials as well.</p><p>Interatomic Coloumbic Decay is a process that can occur in the condensed phases of weakly bonded systems. Results on the time-scale of the process in Ne clusters and mixed Ar/Ne clusters are herein discussed, as well observations of resonant contributions to the process. In analogy to Auger <i>vis-à-vis</i> Resonant Auger it is found that to the ICD process there is a corresponding Resonant ICD process possible. This has later been observed in other systems and by theoretical calculations as well in subsequent works by other groups.</p><p>Delocalization of dicationic valence final states in the hydrogen bonded ammonia clusters and aqueous ammonia has also been investigated by Auger electron spectroscopy. With those results it was possible to assign a previously observed feature in the Auger electron spectrum of solid ammonia.</p>

Clusters are finite ensembles of atoms or molecules with sizes in the nanometer regime (i.e. nanoparticles). This thesis present results on the geometric and electronic structure of homogeneous and heterogeneous combinations of atoms and molecules. The systems have been studied with synchrotron radiation and valence, core and Auger electron spectroscopic techniques. The first theme of the thesis is that of mixed clusters. It is shown that by varying the cluster production technique both structures that are close to that predicted by equilibrium considerations can be attained as well as far from equilibrium structures. Electronic processes following ionization constitute the second theme. The post-collision interaction phenomenon, energy exchange between the photo- and the Auger electrons, is shown to be different in clusters of argon, krypton and xenon. A model is proposed that takes polarization screening in the final state into account. This result is of general character and should be applicable to the analysis of core level photoelectron and Auger electron spectra of insulating and semi-conducting bulk materials as well. Interatomic Coloumbic Decay is a process that can occur in the condensed phases of weakly bonded systems. Results on the time-scale of the process in Ne clusters and mixed Ar/Ne clusters are herein discussed, as well observations of resonant contributions to the process. In analogy to Auger vis-à-vis Resonant Auger it is found that to the ICD process there is a corresponding Resonant ICD process possible. This has later been observed in other systems and by theoretical calculations as well in subsequent works by other groups. Delocalization of dicationic valence final states in the hydrogen bonded ammonia clusters and aqueous ammonia has also been investigated by Auger electron spectroscopy. With those results it was possible to assign a previously observed feature in the Auger electron spectrum of solid ammonia.

Aqueous solutions were studied using photoelectron and Auger spectroscopy, based on synchrotron radiation and a liquid micro-jet setup. By varying the photon energy in photoelectron spectra, we depth profiled an aqueous tetrabutylammonium iodide (TBAI) solution. Assuming uniform angular emission from the core levels, we found that the TBA+ ions were oriented at the surface with the hydrophobic butyl arms sticking into the liquid. We investigated the association between ions and their neighbors in aqueous solutions by studying the electronic decay after core ionization. The (2p)−1 decay of solvated K+ and Ca2+ ions was studied. The main features in the investigated decay spectra corresponded to two-hole final states localized on the ions. The spectra also showed additional features, related to delocalized two-hole final states with vacancies on a cation and a neighboring water molecule. These two processes compete, and by comparing relative intensities and using the known rate for the localized decay, we determined the time-scale for the delocalized process for the two ions. We compared to delocalized electronic decay processes in Na+, Mg2+, and Al3+, and found that they were slower in K+ and Ca2+, due to different internal decay mechanisms of the ions, as well as external differences in the ion-solute distances and interactions. In the O 1s Auger spectra of aqueous metal halide solutions, we observed features related to delocalized two-hole final states with vacancies on a water molecule and a neighboring solvated anion. The relative intensity of these feature indicated that the strength of the interaction between the halide ions and water correlated with ionic size. The delocalized decay was also used to investigate contact ion pair formation in high concentrated potassium halide solutions, but no concrete evidence of contact ion pairs was observed. / Felaktigt tryckt som Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 726

Nuclear fuel performance is highly affected by the behaviour of fission gases, particularly<p>at elevated burnups, where large amounts of gas are produced and can<p>potentially be released. The importance of fission gas release was the motivation<p>for large efforts, both experimentally and theoretically, in order to increase our<p>understanding of the different steps of the process, and to continuously improve<p>our models.<p>Extensions to higher burnups, together with the growing interest in novel types<p>of fuels such as inert matrix fuels envisaged for the transmutation of minor actinides,<p>make that one is still looking for a permanently better modelling, based<p>on a physical understanding and description of all stages of the release mechanism.<p>Computer simulations are nowadays envisaged in order to provide a better<p>description and understanding of atomic-scale processes such as diffusion, but even<p>in order to gain insight on specific processes that are inaccessible by experimental<p>means, such as the fuel behaviour during thermal spikes.<p>In the present work simulation techniques based on empirical potentials have<p>been used, focusing in a first stage on pure uranium dioxide. The behaviour of<p>point defects was at the core of this part, but also the estimation of elastic and<p>melting properties.<p>Then, in a second stage, the study has been extended to the behaviour of helium<p>and xenon. For helium, the diffusion in different domains of stoichiometry<p>was considered. The simulations enabled to determine the diffusion coefficient and<p>the migration mechanism, using both molecular dynamics and static calculation<p>techniques. Xenon behaviour has been investigated with the additional intention<p>to model the behaviour of small intragranular bubbles, particularly their interaction<p>with thermal spikes accompanying the recoil of fission fragments. For that<p>purpose, a simplified description of these events has been proposed, which opens<p>perspectives for further work.<p>/<p>Les performances du combustible nucléaire sont fortement affectées par le comportement<p>des gaz de fission, et ce particulièrement lorsqu’un taux d’épuisement<p>élevé est atteint, puisque d’importantes quantités de gaz sont alors produites<p>et peuvent potentiellement être relâchées. Les enjeux, entre autre économiques,<p>liés au relâchement de gaz de fission ont donné lieu à d’importants efforts, tant<p>sur le plan expérimental que théorique, afin d’accroître notre compréhension des<p>différentes étapes du processus, et d’améliorer sans cesse les mod`eles. Les extensions<p>à des taux d’épuisements encore plus élevés ainsi que l’intérêt croissant pour<p>de nouveaux types de combustible tels que les matrices inertes, envisages en vue<p>de la transmutation des actinides mineures, font qu’à l’heure actuelle, le besoin<p>permanent d’une meilleure modélisation, basée sur une compréhension et une description<p>physique des différentes étapes du processus de relâchement de gaz de<p>fission, est toujours de mise.<p>Les simulations par ordinateur ont ainsi été considérée comme un nouvel angle<p>de recherche sur les processus élémentaires se produisant à l’échelle atomique, à la<p>fois afin d’obtenir une meilleure compréhension de processus tels que la diffusion<p>atomique ;mais aussi afin d’avoir accès à certains processus qui ne sont pas observables<p>par des voies expérimentales, tels que la le comportement du combustible<p>lors de pointes thermiques.<p>Dans ce travail, deux techniques, basées sur l’utilisation de potentiels interatomiques<p>empiriques, ont permis d’étudier le dioxyde d’uranium, dans un premier<p>temps en l’absence d’impuretés. Cette partie était principalement centrée sur le<p>comportement des défauts ponctuels, mais a aussi concerné différentes propriétés<p>élastiques, ainsi que le processus de fusion du composé.<p>Ensuite l’étude a été étendue aux comportements de l’hélium de du xénon. Pour<p>ce qui a trait à l’hélium, la diffusion dans différents domaines de stoechiométrie<p>a été considérée. Les simulations ont permis de déterminer le coefficient de diffusion<p>ainsi que le mécanisme de migration lui-même. Quant au xénon, outre les<p>propriétés de diffusion, l’intention fut de se diriger vers la modélisation des petites<p>bulles intragranulaires, et plus précisément vers leur interaction avec les pointes<p>thermiques, créées lors du recul des fragments de fission. Une description simplifiée de ce processus a été proposée, qui offre de nouvelles perspectives dans ce<p>domaine.<p><p> / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

Une approche donnant de meilleurs résultats pour les potentiels interatomiques en apprentissage-machine à la volée est proposée en comparant trois approches pour la recherche de processus activés par la technique d'activation-relaxation. Tout d'abord, nous discutons de l'intérêt et des enjeux de l'utilisation des potentiels en apprentissage-machine et justifions l'utilisation de l'apprentissage à la volée pour la recherche de processus activés. Cela nous mène à présenter la forme générale des potentiels en apprentissage-machine, quelques modèles via leurs descripteurs de configuration atomique, paramètres et hyperparamètres ainsi que la méthode de l'apprentissage à la volée. Ensuite, nous présentons les méthodes d'exploration utilisées et les détails d'intégration du potentiel à la volée. Enfin, nous menons une étude comparative des trois approches pour un système de Si et de SiGe avec diffusion de lacune. La méthodologie proposée de potentiel de haute précision permet d'étendre la gamme de problèmes pouvant être étudiés par la technique d'activation-relaxation. / An approach giving better results for on-the-fly machine learning interatomic potential proposed by comparing three approaches for exploration of activated processes by the activationrelaxation technique. We first discuss the interest and challenges of on-the-fly machine learning potential and justify the use of on-the-fly learning for the search for activated processes. This leads us to present the general form of machine learning potentials and some models via their atomic configuration descriptors, parameters and hyperparameters as well as the on-the-fly learning method. Then, the exploration methods used are defined and the details of the integration of the potential are presented. Finally, a study is conducted comparing the three approaches for a Si and SiGe system with vacancy diffusion. The proposed methodology of high-precision potential allows to extend the range of possible problems to be studied by the activation-relaxation technique.