We present revised measurements of the static electric dipole polarizabilities of K, Rb, and Cs based on atom interferometer experiments presented in [Phys. Rev. A 2015, 92, 052513] but now re-analyzed with new calibrations for the magnitude and geometry of the applied electric field gradient. The resulting polarizability values did not change, but the uncertainties were significantly reduced. Then, we interpret several measurements of alkali metal atomic polarizabilities in terms of atomic oscillator strengths f(ik), Einstein coefficients A(ik), state lifetimes tau(k), transition dipole matrix elements D-ik, line strengths S-ik, and van der Waals C-6 coefficients. Finally, we combine atom interferometer measurements of polarizabilities with independent measurements of lifetimes and C-6 values in order to quantify the residual contribution to polarizability due to all atomic transitions other than the principal ns-np(J) transitions for alkali metal atoms.

Challenges continue to exist in developing a comprehensive theory of diffusion in liquid metals, despite the advancement of several semi-empirical and theoretical models. One major difficulty in developing a theory is that experimental data are not available for many pure metals and binary metal systems, and when they do exist, data are often inaccurate. In addition to challenges with data quality, where deemed reliable, existing data are typically reported over limited temperature and concentration intervals. In this thesis research, interdiffusion data was obtained for the binary Al-Cu system using the solid wire long capillary technique (SWLC), and molecular dynamics (MD) simulation with a concentration-dependent embedded atom method (CD-EAM) interatomic potential. In the SWLC experiments the interdiffusion coefficient was determined at temperatures of 993 K, 1023 K, 1073 K, 1123 K, and 1193 K, over an Al-rich concentration range limited by the liquidus of the binary phase diagram at the given temperature. For liquid Al~100Cu~0 (tracer), Al80Cu20, and Al60Cu40, the interdiffusion coefficient is well described by the Arrhenius relationship D_AlCu=D_0*exp(-Q_0/RT) over the temperature range, with best fit parameter values of Q_0 = 20.85 ± 4.49 kJ/mol, D_0 = 8.21 (+5.4, -3.26) x 10^-8 m^2/s, Q_0 = 34.41 ± 3.71 kJ/mol, D_0 = 2.84 (+1.47, -0.97) x 10^-7 m^2/s, Q_0 = 38.74 ± 8.01 kJ/mol, D_0 = 4.03 (+5.89, -2.39) x 10^-7 m^2/s, respectively. For the MD simulations, a new Al-Cu CD-EAM interatomic potential was developed that is suitable for the study of diffusion phenomena in the liquid state. Self- and interdiffusion coefficients were determined over a temperature interval of 993-1493 K. Simulations are performed for liquid Al99.999Cu0.001 (tracer), Al80Cu20, and Al60Cu40, and interdiffusion is described by Q_0 = 22.81 ± 0.27 kJ/mol, D_0 = 1.04 (+0.03, -0.03) x 10^-7 m^2/s Q_0 = 30.15 ± 0.49 kJ/mol, D_0 = 1.78 (+0.08, -0.08) x 10^-7 m^2/s, Q_0 = 37.01 ± 1.48 kJ/mol, D_0 = 3.29 (+0.52, -0.45) x 10^-7 m^2/s, respectively. The calculated values of the interdiffusion coefficients from the MD simulation are in good agreement with those obtained using the SWLC technique, supporting the accuracy of these new experimental findings. / February 2017

Neutral atom systems are an appealing platform for the development and testing of quantum control and measurement techniques. This dissertation presents experimental investigations of control and measurement tools using as a testbed the 16-dimensional hyperfine manifold associated with the electronic ground state of cesium atoms. On the control side, we present an experimental realization of a protocol to implement robust unitary transformations in the presence of static and dynamic perturbations. We also present an experimental realization of inhomogeneous quantum control. Specifically, we demonstrate our ability to perform two different unitary transformations on atoms that see different light shifts from an optical addressing field. On the measurement side, we present experimental realizations of quantum state and process tomography. The state tomography project encompasses a comprehensive evaluation of several measurement strategies and state estimation algorithms. Our experimental results show that in the presence of experimental imperfections, there is a clear tradeoff between accuracy, efficiency and robustness in the reconstruction. The process tomography project involves an experimental demonstration of efficient reconstruction by using a set of intelligent probe states. Experimental results show that we are able to reconstruct unitary maps in Hilbert spaces with dimension ranging from d=4 to d=16. To the best of our knowledge, this is the first time that a unitary process in d=16 is successfully reconstructed in the laboratory.

This work was produced as part of a multidisciplinary study of the corrosion of zirconium alloys undertaken by a consortium of universities working in the MUZIC program; Oxford, Manchester and The Open University. The objective of the project as a whole was to further the understanding of the mechanisms of the breakaway oxidation process and to characterise these corrosion processes within a number of fuel rod cladding materials. This thesis describes laser 3D atom probe characterisation of the nano-scale chemical redistribution of oxygen and other solutes that occurs at the metal-oxide interface during corrosion, and a large body of technique development that was required to achieve this goal. The development of the metal-oxide interface of ZIRLO, a Zr-Nb-Sn-Fe-O alloy, is followed by generating 3D atomic scale reconstructions at four different stages of corrosion. The formation of a sub-oxide ZrO layer is seen during pre-transition oxide development. The ZrO interfacial layer is consumed by the rapid formation of oxide after the breakaway transition. After transition the chemistry of the interface is similar to the early pre-transition case, although an oxygen-saturated layer of metal adjacent to the interface formed during corrosion remains. The ZrO interfacial layer (Zr-ZrO-ZrO₂) and the region of oxygen-saturated material ahead of the metal-oxide interface alter the distribution of minor alloying additions such as niobium and iron. The ZrO layer increases the acceptance of niobium into the oxide, which is otherwise seen to be rejected at the Zr-ZrO2 interface along with iron. Niobium is seen to precipitate out of solution as nano-scale particles near the interface after around 100 days of corrosion. This is not seen in the bulk metal matrix of the corroded material due to the absence of other factors driving the process: the stress at the interface and a very high oxygen concentration in the metal ahead of the interface. The nano-scale niobium particles are found to be of a meta-stable composition. Iron is seen to redistribute in the corroded material and can be correlated with the local oxygen concentration. Similarities are seen in the behaviour of solutes within pre-transition ZIRLO and Zircaloy-4 (Zr-Sn-Fe-O). In both cases no redistribution of tin is seen at the metal-oxide interface. A Zr-Nb-Ti alloy with very poor corrosion resistance was also analysed in this way, and the similarities and differences with chemically-similar ZIRLO are discussed. The segregation of solutes to grain boundaries and solute clustering within the matrix are also examined before and after corrosion.

Charge state dependence of L-shell x-ray production cross sections have been measured for 4-14 MeV ¹⁶O^q (q=3⁺-8⁺) ions incident on ultra-clean, ultra-thin copper, and for 12 MeV ¹⁶O^q (q=3⁺-8⁺) on nickel, zinc, gallium and germanium solid foils. L-shell x-ray production cross section were measured using target foils of thickness ≤0.6 μg/cm² evaporated onto 5 μg/cm² carbon backings. Oxygen ions at MeV energies and charge state q were produced using a 3MV 9SDH-2 National Electrostatics Corporation tandem Pelletron accelerator. Different charge states, with and without K-vacancies, were produced using a post acceleration nitrogen striping gas cell or ¹²C stripping foils. L-shell x-rays from ultra-thin ₂₈Ni, ₂₉Cu,₃₀Zn,₃₁Ga, and ₃₂Ge targets were measured using a Si(Li) x-ray detector with a FWHM resolution of 135 eV at 5.9 keV. The scattered projectiles were detected simultaneously by means of silicon surface barrier detectors at angle of 45° and 169° with respect to the beam direction. The electron capture (EC) as well as direct ionization (DI) contributions were determined from the projectile charge state dependence of the target x-ray production cross sections under single collision conditions. The present work was undertaken to expand the measurements of L-shell x-ray production cross sections upon selected elements with low L-shell binding energies by energetic ¹⁶O^q (q=3⁺,4⁺,5⁺,6⁺,7⁺,8⁺) incident ions. Collision systems chosen for this work have sufficiently large Z₁/Z₂ ratios (0.25-0.28) so that EC may noticeably contribute to the x-ray production enhancement. In this region, reliable experimental data are particularly scarce, thus, fundamental work in this area is still necessary. DI and EC cross section measurements were compared with the ECPSSR and the first Born theories over the range of 0.25 <Z₁/Z₂ < 0.29 and 0.38 < v₁/v₂_L <0.72. The ECPSSR theoretical predictions (including DI and EC) are in closer agreement with the data than the first Born's.

The charge state dependence of M-shell x-ray production cross sections of 67HO bombarded by 2-12 MeV carbon ions with and without K-vacancies are reported. The experiment was performed using an NEC 9SDH-2 tandem accelerator at the Ion Beam Modification and Analysis Laboratory of the University of North Texas. The high charge state carbon ions were produced by a post-accelerator stripping gas cell. Ultra-clean holmium targets were used in ion-atom collision to generate M-shell x rays at energies from 1.05 to 1.58 keV. The x-ray measurements were made with a windowless Si(Li) x-ray detector that was calibrated using radiative sources, particle induced x-ray emission (PIXE), and the atomic field bremsstrahlung (AFB) techniques.

Typescript (photocopy). / Digitized by Kansas Correctional Industries

Plusieurs mécanismes de polymérisation radicalaire contrôlée (PRC) sous irradiation lumineuse ont récemment été développés. Ces approches offrent potentiellement de nombreux avantages, en permettant notamment d’introduire dans le mécanisme des PRCs certaines caractéristiques propres aux photopolymérisations, tels que les contrôles spatial et temporel de la réaction. Les travaux de thèse présentés dans ce manuscrit s’inscrivent dans ce contexte, en ayant pour objectif le développement et l’étude d’un nouveau mécanisme de polymérisation radicalaire par transfert d’atome (ATRP) photocatalysée. Après une étude bibliographique présentant l’état de l’art dans le domaine des PRCs sous irradiation lumineuse (chapitre 1), un complexe de bis(1,10-phenanthroline) cuivre (I) (Cu(I)) est utilisé comme catalyseur pour la synthèse de poly(méthacrylate de méthyle)s bien définis par ATRP menée sous l’irradiation d’une lampe LED bleue de faible intensité (chapitre 2). Le mécanisme proposé implique la formation de l’état excité Cu(I)* à partir de Cu(I) sous irradiation, suivie de sa désactivation oxydative par les composés bromés, générant les espèces actives propagatrices et la forme désactivante du complexe Cu(II). Le cycle catalytique est ensuite complété par l’ajout de triethylamine comme agent réducteur permettant la régénération in situ de la forme activante Cu(I) du complexe et conduisant ainsi à une polymérisation plus rapide. Le méthacrylate de glycidyle est ensuite considéré comme comonomère jouant simultanément le rôle d’un agent réducteur (chapitre 3). Des copolymères fonctionnels bien définis, avec une distribution contrôlée de groupes latéraux époxydes, sont ainsi synthétisés. Enfin, le mécanisme d’ATRP photocatalysé est amélioré en développant une procédure permettant la génération in situ de la forme activante Cu(I) en partant d’un complexe Cu(II) stable en présence d’air (chapitre 4). Le mécanisme ainsi développé présente une bonne tolérance à la présence d’oxygène ou d’inhibiteur dans le milieu réactionnel. Les effets de plusieurs paramètres (intensité lumineuse, concentration en ligand et nature du solvant ou du contre-ion) sont étudiés, suggérant un échange de ligand photo-induit comme processus photochimique additionnel impliqué dans le mécanisme d’ATRP photocatalysé étudié. / Several mechanisms of controlled radical polymerization (CRP) under light irradiation have been recently developed. These approaches offer potentially numerous advantages, enabling especially to introduce in the mechanism of CRPs some features characteristic of photopolymerizations, such as the spatial and temporal controls of the reaction. The PhD work presented in this manuscript comes in this framework, aiming at developing and studying a new mechanism of photocatalyzed atom transfer radical polymerization (ATRP). After a bibliographic study presenting the state-of-the-art in the domain of CRPs under light irradiation (chapter 1), a bis(1,10-phenanthroline) copper (I) complex (Cu(I)) is used as catalyst for the synthesis of well-defined poly(methyl methacrylate)s by ATRP carried out under the irradiation of a low intensity blue LED lamp (chapter 2). The proposed mechanism implies the formation of the excited state Cu(I)* from Cu(I) under irradiation, followed by its oxidative quenching by the brominated compounds, generating the growing active species and the deactivator form of the complex Cu(II). The catalytic cycle is then completed by the addition of triethylamine as a reducing agent enabling the in situ regeneration of the activator form of the complex Cu(I), therefore leading to a faster polymerization. Glycidyl methacrylate is then considered as a comonomer playing simultaneously the role of a reducing agent (chapter 3). Well-defined functional copolymers, with a controlled distribution of epoxide side groups, are thus synthesized. Finally, the photocatalyzed ATRP mechanism is improved by developing a procedure permitting the in situ generation of the activator Cu(I) starting directly from an air-stable Cu(II) complex (chapter 4). The mechanism developed in this way exhibits a good tolerance to the presence of oxygen or inhibitor in the reaction medium. The effects of several parameters (light intensity, ligand concentration and nature of the solvent or counter-ion) are studied, suggesting a photo-induced ligand-exchange as an additional photochemical process implied in the studied photocatalyzed ATRP mechanism.

Après plusieurs décennies de développement, l'interférométrie atomique est devenue un outil extrêmement performant pour mesurer des effets inertiels, tels que des accélérations et des rotations. De telles techniques sont maintenant envisagées pour une future génération de détecteurs d'ondes gravitationnelles afin de pousser les limites de l'état de l'art des détecteurs actuels. L'instrument MIGA (Matter-wave laser Interferometer Gravitation Antenna) couplera interférométrie atomique et optique pour étudier des perturbations du champ gravitationnel à basse fréquence (Hz et sub-Hz). Il consistera en un réseau de 3 interféromètres atomiques, simultanément interrogés par le champ électromagnétique résonnant au sein de deux cavités optiques de 150 m de long, en utilisant un ensemble d'impulsions de Bragg d'ordre π/2 - π - π/2. Des mesures gradiométriques permettront d'acquérir une forte immunité aux bruits sismique et newtonien, qui sont limitants pour les détecteurs terrestres optiques tels que LIGO et Virgo. Une expérience préliminaire est en développement au LP2N, à Talence (France), où un interféromètre est interrogé par deux cavités de 80 cm de long. Pour avoir une taille de faisceau suffisante afin d'interroger efficacement les atomes de 87Rb dans des cavités de cette longueur, nous utilisons une géométrie de cavité marginalement stable, constituée de deux miroirs plans situés à la focale d'une lentille biconvexe, où un mode gaussien de rayon de plusieurs mm peut résonner. / After few decades of development, atom interferometry has become an extremely efficient tool for measuring inertial effects such as accelerations and rotations. Such techniques are now envisioned for a future generation of gravitational wave detectors to push further the limit of the current optical detectors. The Matter-Wave Laser Interferometer Gravitation Antenna (MIGA) instrument will couple atom and optical interferometry to study perturbations of the gravitational field at low-frequencies (Hz and sub-Hz). It will consist of an array of 3 atom interferometers, simultaneously interrogated by the light field resonating inside two 150 m long optical cavities, using a set of high order Bragg pulses π/2 - π - π/2. Gradiometric measurements allows a strong immunity to seismic and newtonian noises which limit optical ground-based detectors such as LIGO and Virgo. A preliminary experiment is being developed at the LP2N laboratory, in Talence (France), where a single atomic cloud is interrogated inside two 80 cm long cavities. In order to interrogate efficiently the 87Rb atoms, a gaussian beam with a radius of several mm resonating inside these cavities is required. This can be achieved by using a marginally stable cavity geometry, composed by two plane mirrors located in the focal planes of a biconvex lens.

Em vista de recentes determinações experimentais do perfil de Compton (Eisenberger, Phys. Rev., A2, 1678(1970); Wellenstein e Bonham, Phys. Rev., A7, 1568(1973}, procuramos efetuar um estudo comparativo de cálculos teóricos do perfil de Compton para o átomo de hélio (1S). Para tal, o conjunto de funções de onda elaboradas por Shull e L6wdin (J.Chem.Phy., 23, 1362(1955); 23, 1565(1955}; 30, 617(1959} mostrou-se bastante adequado, visto que permitiu observar a influência da função de onda no cálculo de perfil de Compton. Nossos resultados mostram em contraste à idéia geralmente aceita, que mesmo funções de onda igualmente boas para o cálculo da energia podem fornecer perfis de Compton com um erro maior que o experimental. Alem disso, apresentamos um conjunto de novos dados para o perfil de Compton e para a distribuição radial de momentum. Procuramos, também explicar essas discrepâncias relacionando-as com a transformada de Fourier da função de onda no espaço de configuração. / In view of the recent experimental determination of the Compton profile (Eisenberger, Phys., Rev., A2,1678(1970); Wellenstein and Bonham, Phys, Rev., A7, 1568(1973), we have performed a comparative study of theoretical calcu1ation of the Compton profile for the helium atom (1S). For such, the set of wave functions elaborated by Shull and Löwdin (J.Chem. Phys., 23, 1362(1955); 23, 1565(1955); 30, 617(1959) show itself specially suftable since it was possible to observe the influence af the wave functions on the calculated profile. Our results show in, contrast to general accepted idea, that even equally good wave functions in the energy sense may give theoretical profiles in error greater than the experimental one. Besides, we have presented a set of new data for the Compton profile and radial momentum distribution. A1so we have tried to explain the source of these discrepancies relating them to the Fourier transformation of the wave function in the configuration space.