Research Doctorate - Doctor of Philosophy (PhD) / Helium has the highest ionization energy of any species and is as a consequence difficult to detect by conventional means. On the other hand, it is the ideal surface probe, having no net charge or spin, a low mass and a short de Broglie wavelength. Therefore, there exists a strong incentive to develop a microscopy technique based on helium atom scattering. The purpose of this thesis is to investigate in detail how an efficient helium detector might be developed using the phenomenon of field ionization, an ionization method that relies on quantum mechanical tunneling rather than the more conventional electron impact ionization techniques. In particular, the work focusses on the potential use of a novel nanomaterial, carbon nanotubes, as the source of the high electric fields required for field ionization detection. In Chapter 1 we review the history of field ionization research and the properties and synthesis methods for carbon nanotubes. Chapter 2 describes the experimental apparatus and procedures used for the present research, and Chapter 3 introduces the theoretical framework and background for field ionization. In Chapter 4, the prototypical field ionization system is considered from a detector viewpoint. The work demonstrates that existing theory is not sufficiently quantitative for describing a field ionization detector and therefore a semi-empirical theory is advanced for that purpose. Chapter 5 considers the problem of nanotube field enhancement in detail using computational methods, leading to a complete description of the maximum field enhancement of a nanotube array based on the four fundamental array parameters. Efforts to synthesize carbon nanotubes in the Newcastle plasma-enhanced chemical vapor deposition system are described in Chapter 6. Several procedures are developed for reproducible growth of nanotube films and the chemical vapor deposition system is characterized with single parameter studies. Chapter 7 presents the results of electron field emission and helium field ionization experiments carried out using the grown nanotube films. We demonstrate for the first time the field ionization of helium using a planar film of carbon nanotubes. Finally, we conclude the investigation of field ionization detection in Chapter 8 with a discussion on how such a detection method integrates into a helium microscope and in particular we detail the design and initial calculations for the planned Newcastle helium microscope.

The field of noble gas mass spectrometry is a rapidly developing one. There is a sustained requirement for continuous development of instrumentation in order to allow researchers to answer critical questions facing their respective fields. Within planetary science, the question of whether our solar system is 'typical', has been a driving force behind many lines of research. This project sought to build upon the strong instrumental base of the Isotope Geochemistry and Cosmochemistry group of the University of Manchester, in order to develop the Resonance Ionisation Mass Spectrometer for Krypton Isotopes. From that basis, it then sought to develop techniques and protocols for the analysis of extra-terrestrial samples, particularly those of very low mass. The thesis is broken down into three studies. The first involved the development of the mechanisms used to fill the Xe-Ar four-wave mixing cell. This section covers the development, implementation, and characterisation of the newly installed mass flow controllers. The additional control over the mixing ratio granted allowed an eightfold increase to the sensitivity of the instrument. The reproducibility of the gas ratio is consistently shown throughout, and has ultimately reduced the tuning time of the instrument from a number of weeks to a day. The second section details the required procedures involved in data reduction, and the development of protocols and software for the RIMSKI instrument. A range of approaches are assessed, including a novel approach to cosmic ray exposure age calculations. The methods are discussed and implemented on extra-terrestrial samples, the Stannern eucrite and the Bereba eucrite. Finally, the analytical limits of the RIMSKI instrument are expanded via the measurement of the krypton systems of individual calcium-aluminium-rich inclusions. It is observed that Allende CAIs show a trapped component, Br-derived Kr, as well as an anomalous 'heavy Kr' component (one that is enriched in 86Kr). It is additionally noted that there is a lack of cosmogenic krypton to be found in all but one of the measured inclusions. The implications of these findings are discussed.

O gênero Trichosporon é composto por leveduras artrosporadas do Filo Basidiomycota e é conhecido agente de infecção fúngica invasiva (IFI) em pacientes imunodeprimidos ou com outros fatores de risco. Em pacientes onco-hematológicos é a principal levedura responsável por IFI depois do gênero Candida. Entre as espécies responsáveis por infecções no homem encontram-se: T. asahii, T. inkin, T. mucoides, T. dermatis, T. jirovecii, T. ovoides, T. cutaneum, T. montevideense, T. domesticum, T. asteroides, T. coremiiforme, T. faecale, T. dohaense, T. lactis, T. japonicum. A tecnologia de identificação de fungos por espectrometria de massa (SM) MALDI-TOF ainda carece de padronização para identificação de fungos do gênero Trichosporon, mas a literatura mostra resultados encorajadores. O objetivo deste estudo é padronizar a técnica de espectrometria de massa MALDI-TOF para a identificação das espécies do gênero Trichosporon de importância médica. O estudo foi realizado em cooperação entre a Divisão de Laboratório Central do Hospital das Clínicas da Faculdade de Medicina da Universidade de São Paulo (DLC, HC-FMUSP), Instituto de Medicina Tropical da USP (IMT-USP), Instituto Adolfo Lutz (IAL) e Laboratoire de Parasitologie-Mycologie do Hospital Saint Antoine de Paris, vinculado ao grupo de pesquisa INSERM/UPMC UMR S945 \"Immunité et Infection\" Faculté de Medecine et Université Pierre et Marie Curie de Paris. Noventa e três cepas/isolados foram analisado(a)s, sendo dezenove cepas de referência adquiridas junto à coleção holandesa Centraalbureau Schimmelcultures (CBS), 19 isolados do HC-FMUSP e IAL, e 55 isolados de diferentes hospitais franceses. A identificação molecular foi realizada através do sequenciamento da região IGS1 do rDNA e foi considerada como método de referência. O protocolo de extração de proteínas foi estabelecido através da comparação do desempenho de três metodologias (Bruker®, Cassagne et al., Sendid et al.). Os espectros de massa foram obtidos no laboratório de bacteriologia do Hospital Saint Antoine de Paris através do aparelho Microflex LT®. A interpretação dos resultados qualitativos e quantitativos (logscore) foi realizada através do Software Biotyper 3.0®. O desempenho de identificação do banco de espectros de referência Biotyper 3.0® foi comparado a outros cinco bancos criados a partir de espectros de referência (ERs) derivados de 18 cepas de referência CBS, sete isolados clínicos e 11 ERs do banco Biotyper 3.0. O protocolo de extração de proteínas descrito por Sendid et al. foi escolhido como protocolo de referência pois os espectros produzidos tiveram logscore superiores àqueles obtidos através do método do fabricante. O banco de ERs Biotyper 3.0® apresentou 32,3% de identificações corretas das espécies, sendo que o banco de ERs in house (número 5, constituído cepas CBS e isolados clínicos) apresentou 98,5% de identificações de espécies. Espectros de referência do banco de dados Biotyper 3.0® foram submetidos à identificação com a utilização dos ERs criados a partir de cepas CBS e isolados clínicos e foram evidenciados com erros de identificação: T. mucoides (2), T. ovoides (1) e T. cutaneum (2). Após padronização do protocolo de extração e criação de banco de ERs com cepas CBS e isolados clínicos caracterizados pelo sequenciamento da região IGS, a SM por MALDI-TOF apresentou-se como potente uma ferramenta para a identificação de fungos do gênero Trichosporon. O banco de ERs Biotyper 3.0® apresentou um fraco desempenho, relacionado a ERs que foram criados a partir de cepas mal identificadas / Trichosporon spp. are arthrospored yeasts from the Filum Basidiomycota that are known to produce invasive fungal infection (IFI) in patients with immunosupression or other risk factors. After Candida, Trichosporon is the second genus of yeasts responsible for IFI in patients with onco-hematological diseases. The most important species related to human infection are: T. asahii, T. inkin, T. mucoides, T. dermatis, T. jirovecii, T. ovoides, T. cutaneum, T. montevideense, T. domesticum, T. asteroides, T. coremiiforme, T. faecale, T. dohaense, T. lactis, T. japonicum. The technology of mass spectrometry (MS) for identification of Trichosporon species has not yet been standardized. However, preliminary promising results can be found in the literature. The objective of this study is to analyse and validate MS MALDI-TOF for the identification of Trichosporon species of medical relevance. This was a multicentric study with collaboration from the Central Laboratory Section from Clinics Hospital of the Medical School from the University of São Paulo (DLC-HCFMUSP), Tropical Medicine Institute from the University of São Paulo (IMT-USP), Instituto Adolfo Lutz (IAL) and Laboratoire de Parasitologie-Mycologie from the Hospital Saint Antoine of Paris and INSERM/UPMC UMR S945 \"Immunité et Infection\", Faculté de Medecine et Université Pierre et Marie Curie of Paris. Ninety three strains/isolates belonging to sixteen Trichosporon species were analysed. Nineteen were purchased from Centraalbureau Schimmelcultures (CBS) yeast collection, 19 belonged to HC-FMUSP and IAL collections, 55 belonged to different French collections. The reference identification method was the IGS1 rDNA sequencing. A protein extraction protocol was first established after comparing the performance of three different methodologies (Bruker(TM), Cassagne et al., Sendid et al.). The mass spectra were obtained through a Microflex LT(TM) mass spectrometer located at the bacteriology laboratory from Saint Antoine Hospital, Paris. Mass spectra, qualitative and quantitative results were produced through the software Biotyper 3.0(TM). The performance of the original main spectrum (MSP) library was compared to other 5 in house libraries built with the combination of MSPs derived from CBS strains (18), clinical strains (7) or (Bruker Daltonics/BD, Germany/USA) (11). The extraction protocol described by Sendid et al. showed better performance when compared to the manufacturer\'s one and was chosen for the subsequent extractions. Among the 6 different reference spectra databases tested, a specific one composed of 18 reference strains plus 7 clinical isolates (database 5) allowed the correct identification of 66 amongst 67 clinical isolates (98,5%). Biotyper 3.0 library produced only 32,3% of correct identifications. Biotyper\'s MSPs were submitted to cross-identification with MSPs derived from CBS strains and clinical isolates and misidentified original MSPs were identified: T. mucoides (2), T. ovoides (1) e T. cutaneum (2). While until now less widely applied to basidiomycetous fungi, MALDI-TOF appears to be a valuable tool for identifying clinical Trichosporon isolates at the species level. The MSP library Biotyper 3.0 showed a poorer performance which was due to misidentified strains utilized as reference for the MSPs

Les menaces constantes de terrorisme nécessitent le développement d'instruments permettant de détecter efficacement des agents chimiques de guerre. L'objectif de ce travail était la réalisation d'un spectromètre de masse devant effectuer des analyses de type : LC/ESI-MS et GC/EI-MS, sur des échantillons sous tous les états : solide, liquide, gazeux et qui soit rapide. Une première partie de ce travail a consisté à étudier le fonctionnement du spectromètre de masse LTQ Velos, puis de faire une étude des modes d'injection axiale et radiale des ions par simulation à l'aide du logiciel SIMION. L'étude de l'injection radiale, nous a démontré la faisabilité de ce mode d'injection dans un piège linéaire. Ainsi, lors d'applications spécifiques dans lesquelles l'axe central doit être libéré, le mode d'activation par IRMPD peut être envisagé. Une deuxième partie de ce travail a consisté à modifier la source CI du module ETD en source EI. Trois sources EI (la Thermo, la NERMAG et la source trappe) ont été étudiées afin de déterminer celle qui serait la plus efficace et offrirait un bon compromis en terme de coût et de temps de développement. La source Thermo a été retenue et a ensuite été implémentée dans le module ETD du LTQ Velos qui a été couplé à un GC rapide pour effectuer des tests préliminaires de faisabilité de ce couplage. Ainsi, ces tests ont permis de caractériser le GC/EI-LTQ Velos comme étant capable d'effectuer des analyses en GC/MS rapide (de l'ordre de ? 5 min). Ce GC/MS rapide a ensuite été intégré dans le démonstrateur ainsi que le collecteur aérien chimique et le détecteur TIC et POC. Des essais préliminaires concluants ont été réalisés sur ce démonstrateur. / Constant threats of terrorism require the development of tools to effectively detect chemical warfare agents. The aim of this work was to develop a mass spectrometer capable of performing rapid LC/ESI-MS and GC/EI-MS analyses on samples from all states: solid, liquid and gaseous. The first part of this work was to study the principle of operation of the linear ion trap LTQ Velos, then to study axial and radial ion injection in the linear ion trap by means of computer simulation using SIMION. The feasibility of performing radial ion injection has been demonstrated, thus in specific applications in which the central axis needs to be released, the IRMPD activation mode may be considered. A second part of this work was to adapt the existing ETD module to accommodate EI. Three EI sources (the Thermo, the NERMAG and the trap source) were studied to determine which one would be the most effective and offer a good compromise in terms of cost and development time. The Thermo source has been selected and modified to conduct EI within the ETD module of the LTQ Velos which was interfaced to a fast GC (Heracles II). Preliminary tests characterized the dual pressure ion trap as a mass analyzer for performing rapid GC/MS analyses. The results showed that the GC-LIT with its high scanning speed was able to provide sufficient scans across chromatographic peaks when working in both the conventional and the fast GC modes, and further offered good EI spectral information. This GC/MS was then implemented into the demonstrator as well as the air sampler and the TIC/POC detector. Conclusive preliminary tests have been made on this demonstrator.

Le pétrole est une matrice complexe qui est raffinée afin d’être valorisée. Les fractions obtenues après raffinage sont variées et vont des composés légers (gaz, gazole …) aux composés lourds (distillats sous vide, bitumes...). La coupe naphta subit des traitements tels que le vapocraquage pour obtenir les oléfines qui sont ensuite polymérisés notamment grâce à la catalyse métallocène pour produire les polyoléfines. Ce travail de thèse a porté sur la caractérisation des distillats sous vide, des polyoléfines, et des catalyseurs métallocènes afin de mieux maitriser les différentes étapes du raffinage. Une comparaison des différentes sources à pression atmosphérique a été réalisée pour l’étude de distillats sous vide par spectrométrie de masse à mobilité ionique (IMMS). .L’electrospray (ESI+) permet d’ioniser sélectivement les composés azotés basiques alors que la source ASAP ainsi que la source photoionisation à pression atmosphérique (APPI) permettent une identification des composés soufrés de type benzothiophènes. Les données IMMS obtenues en ESI fournissent des informations sur l’isomérie des composés azotés de ce mélange complexe. Pour mieux comprendre ce contenu isomérique, un indicateur d’isomérie basé sur la largeur à mi-hauteur des pics de mobilité ionique, a été développé. L’analyse de polymère a été réalisée à l’aide de la source ASAP. En particulier, dans le cas du polypropylène (PP) et du polyéthylène (PE) de nombreux résidus pyrolytiques fortement oxydés ont été mis en évidence. Des différences significatives en terme d’abondances relatives et au niveau des temps de dérive en mobilité ionique sont observées entre les polyoléfines et notamment entre des PP tactiques et atactiques. Enfin, une méthode d’analyse par ASAP de composés sensibles à l’air a été développée et a permis l’analyse des composés de type métallocènes,utilisés pour la polymérisation des polyoléfines. / Petroleum is a highly complex mixture that needs to be refined in order to be commercialized. The petroleum fractions have various compositions from gasoline to petroleum coke. Naphtha distillation cut gives olefins by steam cracking which are polymerised using metallocene catalysts to produce polyolefins. This thesis work focused on the characterisation of vacuum gas oils, polyolefins and metallocene catalysts to better understand and optimized refining processes. A comparison of atmospheric pressure ionisation sources was realised for the characterisation of vacuum gas oils by ion mobility–mass spectrometry (IMMS). Electrospray (ESI+) source allows to selectively analyse the basic nitrogen containing species. The ASAP and APPI (atmospheric pressure photoionisation) sources allows to identify sulphur containing compounds like benzothiophenes. Based on the IMMS data, a new indicator based on the full width at half maximum (FWHM) of ion mobility peaks was developed to obtain isomeric information without any identification of the species. Polymers were also analysed using the ASAP source. In particular, polypropylene (PP) and polyethylene (PE) were analysed by ASAP-IMMS and allow us to identify the oxidized species obtained by atmospheric pressure pyrolysis. The relative abundance of these species and their drift time were significantly different between the different samples and notably between isotactic PP and atactic PP. Finally, a new method based on the ASAP source was developed to analyse air sensitive compounds like metallocene used for polyolefin polymerisation.

Im Rahmen dieser Arbeit wurde eine Frisch-Gitterionisationskammer zum Messen kleinster spezifischer Alphaaktivitäten realisiert. Im konkreten Fall soll der Detektor dafür genutzt werden, die Halbwertszeit von 144Nd erneut zu bestimmen. Da diese sehr lang (T1/2 = (2,29 ± 0,16) · 10^15 Jahre) und die Reichweite der emittierten Alphateilchen in Feststoffen sehr gering ist, können nur sehr dünne Proben untersucht werden. Die Fläche der Proben sollte sehr groß sein, um die nötige Aktivität zu erhalten. Im Vergleich haben sich Gitterionisationskammern als das geeignetste Detektorkonzept erwiesen. Es wurde eine Kammer realisiert, welche aus zwei Gitterionisationskammern mit geteilter Anode besteht. Mit Hilfe dieses Aufbaus ist es möglich den Detektornulleffekt zu reduzieren. Die Auslese der auf den Detektorelektroden induzierten Ladung erfolgt mit Hilfe eines Analog-Digital-Konverters. Die Auswertung der gewonnenen Daten wird vollständig nach der Messung durchgeführt. Anhand einer Pulsformanalyse können verschiedene Informationen über jedes, im Detektor stattgefundene, Ereignis gewonnen werden. So ist es möglich den Gitterdurchgriff und die damit verbundene Winkelabhängigkeit der Pulshöhen zu korrigieren und somit die Energieauflösung des Detektors zu verbessern. Es wird eine Energieauflösung von 0,86 % bei 5,1 MeV erreicht. Die Charakterisierung der Ereignisse wird außerdem für die Reduktion des Detektornulleffekts herangezogen. Aufgrund verschiedener Bedingungen, die für ein zu erwartendes Alphaereignis notwendig sind, kann ein Großteil der, die Messung störenden Ereignisse, unterdrückt werden. So kann der Nulleffekt im Energiebereich von 1 MeV bis 2,2 MeV von 435 Ereignissen pro Tag ohne Charakterisierung um etwa ein Faktor 20 auf 21,6 Ereignisse pro Tag mit Charakterisierung reduziert werden. Die Nachweiseffizienz wird davon nicht merklich beeinträchtigt. Für ausreichend lange Messzeiten ist eine Nachweisgrenze von weniger als 10 Ereignissen pro Tag zu erwarten. Für eine, für diesen Aufbau geeignete, Targetgeometrie ist mit etwa 50 Alphazerfällen des 144Nd pro Tag zu rechnen. Mit einer Nachweiseffizienz von etwas unter 50 % sollte die Messung am 144Nd gut möglich sein. / The realization of this work was the usage of a Frisch grid ionization chamber for measuring the lowest specific alpha activity. In the practical case the detector should be used to remeasure the half life of 144Nd. Only very thin targets can be used, due to the extreme long half life and the very short range of alpha particles in matter. The area of the samples must be big enough to get the required activity. In comparison gridded ionization chambers are the most practical devices. The chamber was realized in that way, that two gridded chambers shares a common anode. This could be used to minimize the detector background. The charge, which was induced in the detector electrodes, is acquired by an analog to digital converter. The full analysis of the data is done after the measurement. With the pulse form analysis it is possible to extract information about every event occurring in the detector. It is also possible to correct the grid inefficiency and the correlated angle dependence of the pulse height. This improves the energy resolution. A resolution of 0.86 % at 5.1 MeV is possible. The characterization of the events is also used for the suppression of the detector background. Due to different conditions for an assumed alpha event the majority of the events which disturbs the measurement could be removed. So it is possible to suppress the background in the range between 1 MeV to 2.2 MeV of 435 events per day without the characterization to 21.6 events per day with characterization, which is a factor of roughly 20. The detection efficiency is not noticeably effected. For sufficiently long measurements a lowest limit of detection of 10 counts per day is expectable. For a target geometry which can be used with this setup, about 50 alpha decays of 144Nd per day will occur. With a detection efficiency a bit below 50 % the measurement on Nd should be possible.

No / Surfactants are commonly used as cleansing agents and yet there are concerns they may also have a role in skin irritation. Presently, the lack of suitable methods for quantitative and qualitative analysis of surfactant deposition on skin has hindered the in-depth investigation of such effects. Here, we report the application of reverse phase liquid chromatography electrospray ionisation mass spectrometry (LC/ESI-MS/MS) assays for two surfactants commonly used in consumer products, namely sodium lauryl ether sulphate (SLES) and laurylamidopropyl betaine (LAPB), to a baseline study aiming to assess deposition levels on human skin. The linearity of the assays was established at 3-20 ng, with coefficient of variation below 5%. Detection limits were 100 pg for LAPB and 1 ng for SLES; quantitation limits were 500 pg for LAPB and 2.5 ng for SLES. The baseline study was conducted using a panel of 40 healthy volunteers. Skin extract samples were taken in triplicate from forearms, using ethanol. SLES was detected on most volunteers, with 75% of them having SLES deposits in the range of 100-600 ng/cm2. LAPB was detected on the skin of all volunteers with 85% of them having deposit levels within the concentration range of 1-100 ng/cm2. These results demonstrate the extent to which commonly used surfactants remain on the skin during the day. The analytical methods reported here can be applied to the investigation of surfactants in relation to general skin condition and the development and optimisation of new consumer wash products. / EPSRC

No / Surfactants are commonly used as cleansing agents and yet there are concerns that they may also have a role in skin irritation. The lack of suitable methods for the quantitative and qualitative analysis of surfactant deposition on skin has hindered the in-depth investigation of such effects. Here, we report the application of reversed-phase liquid chromatography/electrospray ionisation tandem mass spectrometry (LC/ESI-MS/MS) assays for two surfactants commonly used in consumer products, namely sodium lauryl ether sulfate (SLES) and laurylamidopropyl betaine (LAPB), to a baseline study aiming to assess deposition levels on human skin. The linearity of the assays was established at 3-20 ng, with coefficient of variation below 5%. The detection limits were 100 pg for LAPB and 1 ng for SLES; quantitation limits were 500 pg for LAPB and 2.5 ng for SLES. The baseline study was conducted using a panel of 40 healthy volunteers. Skin extract samples were taken in triplicate from forearms, using ethanol. SLES was detected on most volunteers, with 75% of them having SLES deposits in the range of 100-600 ng/cm(2). LAPB was detected on the skin of all volunteers with 85% of them having deposit levels within the concentration range of 1-100 ng/cm(2). These results demonstrate the extent to which commonly used surfactants remain on the skin during the day. The analytical methods reported here can be applied to the investigation of surfactants in relation to general skin condition and to the development and optimisation of new consumer wash products. / EPSRC-DTA award / School Life Sciences

Lorsqu'ils sont soumis à des pulses laser courts et intenses, des atomes peuvent perdre des électrons. Plusieurs canaux sont impliqués dans la double ionisation, comme la NSDI et le scénario associé de la recollision. La recollision est maintenant vue comme la “pierre d'angle de la physique en champ fort” pour les éclairages qu'elle donne dans l'organisation de la matière et en ce qu'elle constitue l'une des manifestations les plus flagrantes de la corrélation électron-électron dans la nature. Dans ce manuscrit, une analyse théorique des mécanismes de double ionisation est menée en utilisant la mécanique classique. Cette description complémente les modèles quantiques en observant la dynamique depuis un cadre de travail différent et avec l'éclairage de la dynamique nonlinéaire. L'analyse, menée dans l'espace des phases, permet l'identification des structures organisatrices qui régulent les différents mécanismes d'ionisation. Pour des champs laser polarisés linéairement, le mécanisme de la recollision est complété par l'image de l'électron interne. L'électron interne donne accès à une description fine de la dynamique de recollision et explique les différentes routes pour la double ionisation. Il permet également de faire des prédictions telles que l'intensité du coude dans la probabilité de double ionisation et explique complètement la RESI. En polarisation circulaire, il est communément cru que la recollision n'est pas possible, en dépit de résultats expérimentaux contradictoires. En fait, l'analyse de l'espace des phases montre que la recollision est possible mais pas accessible à tous les atomes, réconciliant par conséquent les contradictions expérimentales précédentes. / When subjected to strong and short laser pulses, atoms may lose electrons. Several ionization channels are involved in such double ionization events, like nonsequential double ionization (NSDI) and its associated recollision scenario. Recollision is now seen as the “keystone of strong field physics”, for its insights into the organization of matter, and is one of the most dramatic manifestations of electron-electron correlation in nature. In this manuscript a theoretical analysis of the double ionization mechanisms is carried out using classical mechanics. This description complements quantum treatments by observing the dynamics from a different framework, with the light of nonlinear dynamics, as both frameworks exhibit the main ingredient, i.e., strong electron-electron correlation. The analysis, carried out in phase space (e.g., through reduced models) enables the identification of the organizing structures that regulate the ionization channels. For linearly polarized lasers, the recollision mechanism is completed by the picture of the “inner” electron. The inner electron gives access to a fine description of the recollision dynamics and explains the routes to double ionization. It also enables verifiable predictions such as the location of the characteristic knee shape in the double ionization yield versus laser intensity and fully explains delayed ionizations like RESI. For circular polarization, it is commonly believed that recollision is not possible, despite apparently contradictory experimental results. In fact, the phase space analysis shows that recollision is possible but not accessible to all atoms, thus reconciling the previous experimental results.

233 U est le noyau fissile produit dans le cycle du combustible 232 T h/233 U qui a été proposé comme une alternative plus sûre et plus propre du cycle 238 U/239 P u. La connaissance précise de la section efficace de capture de neutrons de cet isotope est requise avec une haute précision pour la conception et le développement de réacteurs utilisant ce cycle du combustible. Les deux seuls jeux de données expérimentales fiables pour la section efficace de capture de l’233 U montrent des écarts important allant jusqu’à 20%. Ces différences peuvent être dues à desincertitudes systématiques associées à l'efficacité du détecteur, la correction du temps mort, la soustraction du bruit de fond et le phénomène d’empilement de signaux causé par la forteactivité α de l’échantillon. Un dispositif expérimental dédié a la mesure simultanée des sections efficaces de fission et de capture des noyaux fissiles radioactifs a été conçu, assemblé et optimiséau CENBG dans le cadre de ce travail. La mesure sera effectuée à l’installation de temps de vol de neutrons Gelina de l’IRMM, où les sections efficaces neutroniques peuvent être mesurées sur une large gamme d’énergie avec une haute résolution énergétique. Le détecteur de fission se compose d’une chambre à ionisation (CI) multi-plaque de haute efficacité. Les rayons γ produits dans les réactions de capture sont détectés par un ensemble de six scintillateurs C6 D6entourant la CI. Dans ces mesures, les rayons γ de la capture radiative sont masqués parle grand nombre de rayons γ de fission, ce qui représente le problème le plus délicat. Ces γ parasites doivent être soustraits par la détection des événements de fission avec une efficacité très bien connue (méthode de VETO). Une détermination précise de cette efficacité est assezdifficile. Dans ce travail, nous avons soigneusement étudié la méthode des neutrons prompts de fission pour la mesure de l'efficacité de la CI, apportant un éclairage nouveau sur la méthode, ce qui a permi d’obtenir une excellente précision sur l'efficacité de détection des fission d’une sourcede 252 Cf. Avec cette même source, plusieurs paramètres (pression du gaz, haute tension et la distance entre les électrodes) ont été étudiés afin de déterminer le comportement de la CI et detrouver le point de fonctionnement idéal : une bonne séparation énergétique entre les particulesα et les fragments de fission (FF) et une bonne résolution temporelle. Une bonne séparationα-FF a également été obtenue avec une cible d’233 U très radioactive. De plus, l’analyse deforme de signaux entre les rayons γ et les neutrons dans les détecteurs C6 D6 a été observée àGelina dans des conditions expérimentales réalistes. Pour conclure, le dispositif expérimentalet la méthode de VETO ont été soigneusement vérifiés et validés, ouvrant la voie à la mesure future des sections efficaces de capture et fission d’233 U . / 233U is the fissile nucleus produced in 232T h/233U fuel cycle which has been proposed as asafer and cleaner alternative to the 238U/239P u cycle. The accurate knowledge of the neutroncapture cross-section of this isotope is needed with high-precision for design and developmentof this fuel cycle. The only two reliable experimental data for the capture cross-section of233U show discrepancies up to 10%. These differences may be due to systematic uncertaintiesassociated with the detector efficiency, dead-time effects, background subtraction and signalpile-up caused by the α-activity of the sample. A special experimental set-up for simultaneousmeasurement of fission and capture cross sections of radioactive fissile nuclei was designed,assembled and optimized at CENBG in the frame of this work. The measurement will be per-formed at the Gelina neutron time-of-flight facility at IRMM, where neutron cross sectionscan be measured over a wide energy range with high energy resolution. The fission detectorconsists of a multi-plate high-efficiency ionization chamber (IC). The γ-rays produced in cap-ture reactions are detected by an array of six C6 D6 scintillators surrounding the IC. In thesemeasurements the radiative capture γ-rays are hidden in large background of fission γ-rays thatrepresents a challenging issue. The latter has then to be subtracted by detecting fission eventswith a very well known efficiency (VETO method). An accurate determination of this efficiencyis rather difficult. In this work we have thoroughly investigated the prompt-fission-neutronsmethod for the IC efficiency measurement, providing new insights on this method. Thanks tothis study the IC efficiency was determined with a very low uncertainty. Using a 252Cf source,several parameters (gas pressure, high voltage and the distance between the electrodes) havebeen studied to determine the behaviour of the IC in order to find the ideal operation point:a good energy separation between α-particles and fission fragments (FF) and a good timingresolution. A good α-FF separation has been obtained with a highly radioactive 233U target.Also, the pulse-shape discrimination between γ-rays and neutrons in the C6D6 detectors wasobserved at Gelina under realistic experimental conditions. To conclude, the experimentalset-up and the VETO method have been carefully checked and validated, opening the way tofuture measurements of the capture and fission cross sections of 233U.