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A minimum-norm method has been developed for solving the coupled integro-differential equations describing the scattering of positrons by one-electron targets in which the rearrangement channels for positronium formation have been explicitly included. The minimum-norm method, applied to this application for the first time in this thesis, is an enhancement of a previously reported least-squares method which has enabled the extension to a significantly larger basis consisting of up to 26 states on the direct centre, including pseudostates, and 3 states on the positronium. The method has been applied here to e+-H and e+-He+ scattering; cross-sections have been produced for the latter over a range of energies up to 250 eV. The basis was found to be large enough to produce smooth cross sections and little evidence of pseudoresonance structure was found. The results are the first converged cross sections to be calculated for e+-He+ scattering using the coupled channel approximation. Results for e+-H scattering compare well with the work of other authors. A highly efficient parallel code was developed for solving the largest coupling cases. The results prove the minimum-norm approach to be an accurate and reliable method for large-scale coupled channel calculations involving rearrangement collisions. Also in this thesis, the capture of slow antiprotons by atomic hydrogen and positronium has been simulated by the Classical Trajectory Monte Carlo (CTMC) method. Statistically accurate cross sections for protonium and antihydrogen formation have been obtained and the energy dependence of the process established. Antihydrogen formation from antiproton collisions with positronium in the presence of a laser has also been simulated with the CTMC method and the effects of laser polarisation, frequency and intensity studied. Enhancements of the antihydrogen formation cross section were observed and it is suggested that more sophisticated calculations should be undertaken

This thesis presents an experimental study of non-thermal atmospheric pressure gas plasmas in presence of liquid as an efficient source of transient and reactive species to initiate chemical reactions necessary for many important applications. Two types of liquid-containing plasmas are considered: discharges formed between a needle electrode and a liquid electrode, and plasma jets formed in a water vapour flow mixed in helium or argon gas. Two plasma modes (the pulsed and the continuous mode) are observed in the needle-to-liquid plasma. A comparative study of the needle-to-liquid plasma in the continuous mode with DC and AC excitations reveals that the plasmas are glow discharges, and AC excited plasmas have the highest energy efficiency. A study of helium/water vapour plasma jet shows that “plasma bullets” are formed even with water vapour in the gas mixture, but become quenched when the moist helium flow rate is above 300sccm (~1800ppm water concentration). Moderate amount of water vapour (~250ppm water concentration) is beneficial for active species production mainly due to the high electron density. Hydrogen peroxide production in saline solution with three different plasma sources is investigated due to the importance of H2O2 in several important applications. Long lifetime of H2O2 in the liquid after plasma treatment indicates an exciting possibility of plasma pharmacy.

Inert gases in metals can occur due to ion implantation, from a plasma in a magnetron device or as a result of being by-products of nuclear reactions. Mainly because of the nuclear applications, the properties of the inert gases, helium, argon and xenon in the body centred cubic (bcc) iron crystal are examined theoretically using a combination of molecular dynamics, static energy minimisation and long time scale techniques using empirical potential functions. The same techniques are also used to investigate argon and xenon in aluminium. The primary interest of the work occurred because of He produced in nuclear fission and its effect on the structural materials of a fission reactor. This structure is modelled with perfectly crystalline bcc Fe. In bcc iron, helium is shown to diffuse rapidly forming small bubbles over picosecond time scales, which reach a certain optimum size. In the initial phase of He accumulation, Fe interstitials are ejected. This occurs instantaneously for bubbles containing 5 He atoms and as the more He accumulates, more Fe interstitials are ejected. The most energetically favourable He to vacancy ratios at 0 K, vary from 1 : 1 for 5 vacancies up to about 4 : 1 for larger numbers of vacancies. An existing He bubble can be enlarged by a nearby collision cascade through the ejection of Fe interstitials, allowing more He to be trapped. Ar and Xe in bcc Fe prefer to be substitutional rather than interstitial and there are large barriers to be overcome for the inert gas atoms to diffuse from a substitutional site. Bubbles that form can again be enlarged by the presence of a nearby collision cascade or at very high temperatures. In this case the most energetically favourable vacancy ratios in the bubbles is 1: 1 for Ar and from 0.6: 1 to 0.8: 1 for Xe. For Ar and Xe, bubble formation is more likely as a direct result of radiation or radiation enhanced diffusion rather than diffusion from a substitutional site. Ar in aluminium is also studied. Ar atoms in fcc Al prefer to be substitutional rather than interstitial and evolution into substitutional occurs over picosecond time scales at room temperature. Bubble formation can occur more easily than in bcc iron, mainly because the barriers for vacancy diffusion are much lower but the time scales for bubble accumulation are much longer than those for He. A vacancy assisted mechanism is found which allows Ar to diffuse through the lattice. Finally some preliminary results on the energetics of different geometrical structures of larger Xe bubbles in Al are investigated since experiment has indicated that these can become facetted.

La photo-dissociation d'une molécule comme CH3I dans l'agrégat d'hélium présente un grand intérêt pour comprendre la recombinaison et la solvatation des photo-fragments après la dissociation dans un liquide quantique. Après la recombinaison certaines structures de D@Hen(D= Ar^+, I^q, q= -1, 0, +1, +2) montrent les stabilités particulières avec les nombres magiques bien définis. Notre but ultime est d'étudier théoriquement la dynamique de la photo-dissociation de CH3I dans les agrégats d'hélium et de comparer avec les résultats expérimentaux disponibles dans la littérature. Notre recherche préliminaire est motivée par les données disponibles sur les espèces de couche ouverte comme D@Hen (D= Ar^+, Mg^+) et commence par un test sur notre modèle potentiel analytique pour les systèmes D@Hen à plusieurs corps. Notre modèle inclut les énergies électrostatique classique et quantique de dispersion,et également les énergies de charge/dipôle induit et de dipôle induit/dipôle induit dans le cas où le dopant D est ionique. La représentation analytique de l'interaction D-He est obtenue en fittant les fonctions ayant une forme asymptotique physiquement correcte aux résultats de calculs ab initio corrélés de haut niveau pour la molécule D-He. La matrice "Diatomices-in-Molecules" (DIM) de notre modèle potentiel à plusieurs corps est construite pour les situations avec l'anisotropie électronique et le couplage spin-orbite (SOC) pour l'atome lourd D est inclus dans la base de couplage du type s-l pour l'atome D. Les structures et les énergies de cohésion de systèmes D@Hen sont étudiées en fonction de la taille du système n par la méthode MonteCarlo quantique de diffusion (DMC).De nouvelles sous-routines pour évaluer le potentiel D-He ont été programmées pour le programme DMC existant et une fonction d'essai améliorée a été appliquée dans le calcul DMC / The photo-dissociation of molecule like CH3I inside helium droplet presents great interest for the understanding of recombination and salvation of photo-fragments after dissociation inside a quantum liquid. After recombination certain structures of D@Hen(D= Ar^+, I^q, q=-1,0,+1,+2))show particular stabilities with well defined magic numbers. Our ultimate goal is to theoretically study the dynamics of the photo-dissociation of CH3I inside helium clusters and to compare with experimental results available for this process in the literature. Our initial research is motivated by the available information on open shell species like D@Hen (D= Ar^+, Mg^+)and begins by an examination of our analytical potential model for many body systems D@Hen. Our model includes the classical electrostatic and the quantum dispersion energies and also the charge-induced dipole and induced dipole-induced dipole interaction energies in the case of ionic D^q. The analytic representation of the D-He interaction is obtained by fitting functions with the physically correct asymptotic form to the results of high level correlated ab initio calculations for D-He. Diatomics-in-Molecules (DIM) matrices of our many body potential model are constructed for situations with electronic anisotropy and spin-orbit coupling for heavy atom D is included in the basis of the s-l coupling pattern of the doping atom D. The structures and cohesive energies of the D@Hen systems are computed as a function of system size n by the diffusion quantum Monte Carlo method (DMC).New subroutines for the potential evaluation have been programmed for the existing DMC program and an improved type of trial wave function has been implemented

A energia não adiabática do estado fundamental para o átomo de hélio é obtida com o formalismo adiabático hiperesférico (HAA). Curvas de potencial, acoplamentos não adiabáticos e funções de canal são calculados por um procedimento numericamente exato baseado em uma expansão analítica das funções de canal. As equações radiais acopladas são resolvidas por técnicas usuais. A convergência do procedimento é investigada conforme os acoplamentos não adiabáticos são sistematicamente introduzidos. Com a inclusão, pela primeira vez, de onze curvas de potencial e funções de canal obtém-se uma energia para o estado fundamental que difere do melhor cálculo variacional por 0.1 partes por milhão. As forças de oscilador para as transições discretas do hélio na \"length-form\" e \"acceleration-form\" também são calculadas. Concluímos que o HAA não está mais obstruído pela falta de uma prescrição para se obter funções de onda de precisão arbitrária para sistemas coulombianos. / The nonadiabatic ground state for the helium atom is obtained with the hyperspherical adiabatic approach (HAA). Potential curves, nonadiabatic couplings, and channel functions are calculated by a numerically exact procedure based on the analytical expansion of the channel functions. The coupled radial equations are solved by standard techniques. The convergence of the procedure is investigated as nonadiabatic couplings are systematically introduced. The inclusion, for the first time, of eleven potential curves and channel functions gives a groundstate energy that differs from the best variational calculation by 0.1 parts per million. The oscillator strength for the discrete helium transitions in the length-form and acceleration-form are also presented. We conclude that the HAA is no longer hampered by the lack of prescription for the obtainment of arbitrary precision wave functions for Coulombic systems.

Cette thèse est consacrée à l’étude des bulles d’hélium dans le silicium. Dans un premier temps, des simulations atomistiques de type dynamique moléculaire (DM) ont été réalisées afin d’étudier les propriétés physiques d’une bulle nanométrique : densité et pression d’hélium en fonction du diamètre de la bulle et de la quantité d’hélium initialement introduite dans la bulle. Nos calculs ont montré que la déformation plastique de la matrice ne permettait pas de dépasser une valeur de densité d’hélium nettement inférieure aux résultats expérimentaux. En modélisant un système plus réaliste, un excellent accord avec les mesures expérimentales a été retrouvé. Nous avons aussi montré que le choix du potentiel interatomique était capital afin de modéliser des bulles sous fortes pressions. En outre, nos résultats ont montré que la loi de Laplace-Young n’était pas adaptée pour prédire la pression dans les bulles d’hélium dans du silicium. Enfin, l’étude de l’état de l’hélium dans la bulle indique que l’hélium peut être sous forme solide à 300 K, du fait des pressions élevées. Dans un second temps, une approche de type dynamique d’amas (DA) a été employée afin de comprendre les premiers stades d’évolution des bulles. Nous avons construit un modèle applicable à la DA à l’aide d’un grand nombre de calculs DM. Une étude paramétrique a ensuite été réalisée. Ceci nous a permis d’étudier les mécanismes de croissance des bulles, en prenant en compte l’influence de l’hélium et la présence ou non d’une source continue de défauts. / This thesis is devoted to the study of helium bubbles in silicon. First, molecular dynamics (MD) simulations were performed in order to study the physical properties of a nanobubble: helium density and pressure as a function of the bubble diameter and of the initial helium quantity introduced in the bubble. A maximum value of the helium density in the bubble is reached due to the plastic deformation of the matrix; this value is significantly lower than the experimental results. By modelling a more realistic system, an excellent agreement with the experimental measurements is found. Moreover, the choice of the interatomic potential is essential to model the properties of bubbles under high pressure. Further, the Laplace-Young law is not appropriate to predict the pressure in helium bubbles in silicon. In addition, the investigation of the helium configuration in the bubble indicates that helium can be in the solid state at 300 K. In a second part, a cluster dynamics (CD) approach was employed to understand the early stages of bubble evolution. A helium in silicon interaction model to be used in CD was built by means of a large number of MD calculations. A parametric study was then performed taking into account the influence of helium and the presence or not of a continuous source of defects and allowing for the study of the mechanisms of bubble growth.

Soluções não-adiabáticas em coordenadas hiperesférica para sistemas coulombianos de três corpos são apresentadas. Energias altamente precisas para o estado fundamental do hélio são obtidas, pela primeira vez, no método adiabática hiperesferico (HAA). Com a inclusão de somente três curvas de potencial e os correspondentes acoplamentos, precisão de partes por milhão foram obtidas. Concluímos que o HAA, usado exaustivamente para descrever semi-quantitativamente sistemas atômicos e moleculares, não está mais obstruído pela falata de prescrição para se obter funções de onda de precisão arbritária para sitemas coulombianos. / Non-adiabatic solutions for the Coulombic three-body systems in hyperspherical coordinates are presented. Highly accurated energies for the helium ground state are obtained, by the first time, in the hyperspherical adiabatic approach (HAA). With the inclusion of only three potential curves and the corresponding couplings, precision of parts per million have been achieved. We conclude that the HAA, exhaustively used to describe semi-quantitatively both molecular and atomic systems, is no longer more hampered by the lack of prescription for the obtainment of arbitrary precision wave functions for Coulombic systems.

Les thématiques abordées dans ce mémoire illustrent deux spécificités des gaz ultrafroids d'Hélium métastable : la possibilité de comparer les résultats expérimentaux à des évaluations théoriques précises (niveaux d'énergie, potentiels d'interaction) et une méthode de détection originale fournie par les ionisations Penning. Nous présentons la construction et la caractérisation d'un nouveau piège magnétique offrant un large accès optique et permettant ainsi de combiner la production d'un condensat de Bose-Einstein et son chargement in situ dans un réseau optique 3D. Les fondements théoriques des expériences prévues dans ces potentiels optiques sont ensuite détaillés. Dans un piège dipolaire croisé, l'influence du champ magnétique, devenu un paramètre libre, sur les taux de collisions Penning peut être mesurée et comparée à une nouvelle évaluation théorique. Concernant l'Hélium dans des réseaux optiques, deux sujets sont développés : l'effet du confinement sur les collisions inélastiques Penning (réseau 1D), ainsi que la modélisation des pertes Penning dans un modèle de Bose-Hubbard dissipatif (réseau 3D). Enfin, nous présentons la première mesure directe de la transition dipolaire magnétique 23S1 vers 23P2, liant les familles singulet et triplet de l'Helium 4. Cette expérience de spectroscopie, réalisée en collaboration avec le groupe de W. Vassen (LaserLab - Amsterdam), allie le domaine des atomes froids aux techniques des peignes de fréquences, afin d'obtenir une précision de 5 kHz.

<p>This thesis addresses the investigation of doubly excited <i>2l´nl</i> states in helium atoms and double core excitations in solid lithium compounds.</p><p>Measurements on <i>He</i> are made in field free environments and under the influence of electric and magnetic fields, using synchrotron based inelastic photon scattering. Cross sections for scattering to singly excited final states are directly determined and compared to theoretical results and are found to be in excellent agreement. Radiative and spin-orbit effects are quantified and are shown to play an important role in the overall characterization of highly excited <i>He </i>states below the <i>N =2</i> threshold. A dramatic electric field dependence is also observed in the flourecence yield already for relatively weak fields. This signal increase, induced by electric as well as magnetic fields, is interpreted in terms of mixing with states of higher fluorescence branching ratios.</p><p>Double core excitations at the lithium site in solid lithium compounds are investigated using resonant inelastic x-ray scattering (RIXS). The lithium halides <i>LiF, LiCl, LiBr</i> and <i>LiI </i>are studied as well as the molecular compounds <i>Li</i><i>2</i><i>O, Li</i><i>2</i><i>CO</i><i>3</i> and <i>LiBF</i><i>4</i>. States with one, as well as both, of the excited electrons localized at the site of the bare lithium nucleus are identified, and transitions which involve additional band excitations are observed. A strong influence of the chemical surrounding is found, and it is discussed in terms of the ionic character of the chemical bond.</p>