The possibility and feasibility is investigated of including in the modelling of nuclear cluster reactions a unified treatment of the effects both of the non-orthogonalities between transfer channels, and of the antisymmetrisation required by the Pauli Principle. The deuteron - nucleus interaction, the simplest cluster reaction, is considered in detail within the Coupled Channels framework. The Coupled Channels formalism was chosen because it accurately handles inelastic and transfer couplings of arbitary strengths. The fact that transfer channels are orthogonal to each other only asymptotically is taken into account by reallocating the wave function in the internal region, from the deuteron channels to the transfer channels, taking components from the deuteron channels in ways exactly analogous to the way the antisymmetrisation requirements remove blocked deuteron-core components. Thus a unified treatment of the two effects is facilitated. It is found further that when all possible transfer channels are included, along with all Pauli blockings from the core nucleons, then under certain conditions at low energies, the wave function in the deuteron channel is small and oscillatory in the internal region, leaving the deuteron as a cluster to have largely asymptotic significance. In this limit, the exact non-local potential governing the deuteron channel simplifies considerably in one approximation to be replaceable by just several orthogonality conditions, and these are easily modelled in solving the coupled equations for the radial wave functions. This simplified and unified model has the advantage, since the deuteron's internal wave form is significant only asymptotically, of allowing automatically for arbitary deuteron polarisation by the core (though not vice-versa). Furthermore, the asymptotic matching is not at a fixed radius as in R-matrix theory, but is a continuous process that depends on the binding energies of the actual proton & neutron bound states in the residual nucleus.

The possibility and feasibility is investigated of including in the modelling of nuclear cluster reactions a unified treatment of the effects both of the non-orthogonalities between transfer channels, and of the antisymmetrisation required by the Pauli Principle. The deuteron - nucleus interaction, the simplest cluster reaction, is considered in detail within the Coupled Channels framework. The Coupled Channels formalism was chosen because it accurately handles inelastic and transfer couplings of arbitary strengths. The fact that transfer channels are orthogonal to each other only asymptotically is taken into account by reallocating the wave function in the internal region, from the deuteron channels to the transfer channels, taking components from the deuteron channels in ways exactly analogous to the way the antisymmetrisation requirements remove blocked deuteron-core components. Thus a unified treatment of the two effects is facilitated. It is found further that when all possible transfer channels are included, along with all Pauli blockings from the core nucleons, then under certain conditions at low energies, the wave function in the deuteron channel is small and oscillatory in the internal region, leaving the deuteron as a cluster to have largely asymptotic significance. In this limit, the exact non-local potential governing the deuteron channel simplifies considerably in one approximation to be replaceable by just several orthogonality conditions, and these are easily modelled in solving the coupled equations for the radial wave functions. This simplified and unified model has the advantage, since the deuteron's internal wave form is significant only asymptotically, of allowing automatically for arbitary deuteron polarisation by the core (though not vice-versa). Furthermore, the asymptotic matching is not at a fixed radius as in R-matrix theory, but is a continuous process that depends on the binding energies of the actual proton & neutron bound states in the residual nucleus.

Les fontaines atomiques, basées sur une transition micro-onde du Césium ou du Rubidium, constituent l'état de l'art des horloges atomiques, avec une exactitude relative avoisinant 10^{-16}. Il apparaît cependant clairement aujourd'hui qu'il sera difficile de dépasser significativement ce niveau de performance avec un dispositif de ce type.<br /><br />L'utilisation d'une transition optique, toutes choses étant égales par ailleurs, ouvre la perspective d'une amélioration de 4 ou 5 ordres de grandeur de la stabilité et de l'incertitude relative sur la plupart des effets systématiques. Les effets liés au mouvement des atomes peuvent être, quant à eux, contrôlés d'une façon totalement différente, en les piégeant dans un réseau optique pour éviter la phase de vol ballistique caractéristique des fontaines. Le point clef de cette approche réside dans le fait que les paramètres de ce piège peuvent être ajustés de façon à s'affranchir du déplacement lumineux si l'on sélectionne une transition d'horloge faiblement permise J=0 -> J=0.<br /><br />A cet égard, l'atome de strontium est l'un des candidats les plus prometteurs, la transition ^1S_0 -> ^3P_0 présente une largeur naturelle de 1 mHz, et plusieurs autres transitions facilement accessibles peuvent être utilisées en vue d'un refroidissement laser efficace des atomes jusqu'à une température de 10 µK. Ce manuscrit de thèse d'une part démontre la faisabilité expérimentale d'une horloge à réseau optique basée sur l'atome de strontium, et d'autre part expose une évaluation préliminaire de l'exactitude relative avec l'isotope fermionique ^{87}Sr, à un niveau de quelques 10^{-15}.

<p>The elastic constants of Mg_(1-x)Al_xB₂ have been calculated in the regime 0<x<0.25. The calculations show that the ratio, B/G, between the bulk- and the shear-modulus stays well below the empirical ductility limit, 1.75, for all concentrations, indicating that the introduction of Al will not change the brittle behaviour of the material considerably. Furthermore, the tetragonal elastic constant C’ has been calculated for the transition metal alloys Fe-Co, Mo-Tc and W-Re, showing that if a suitable tuning of the alloying is made, these materials have a vanishingly low C'. Thermal expansion calculations of the 4d transition metals have also been performed, showing good agreement with experiment with the exception of Nb and Mo. The calculated phonon dispersions of the 4d metals all give reasonable agreement with experiment. First principles calculations of the thermal expansion of hcp Ti have been performed, showing that this element has a negative thermal expansion along the c-axis which is linked to the closeness of the Fermi level to an electronic topological transition. Calculations of the EOS of fcc Au give support to the suggestion that the ruby pressure scale might underestimate pressures with ~10 GPa at pressures ~150 GPa. The high temperature bcc phase of the group IV metals has been calculated with the novel self-consistent ab-initio dynamical (SCAILD) method. The results show good agreement with experiment, and the free energy resolution of < 1 meV suggests that this method might be suitable for calculating free energy differences between different crystallographic phases as a function of temperature.</p>

The elastic constants of Mg(1-x)AlxB2 have been calculated in the regime 0&lt;x&lt;0.25. The calculations show that the ratio, B/G, between the bulk- and the shear-modulus stays well below the empirical ductility limit, 1.75, for all concentrations, indicating that the introduction of Al will not change the brittle behaviour of the material considerably. Furthermore, the tetragonal elastic constant C’ has been calculated for the transition metal alloys Fe-Co, Mo-Tc and W-Re, showing that if a suitable tuning of the alloying is made, these materials have a vanishingly low C'. Thermal expansion calculations of the 4d transition metals have also been performed, showing good agreement with experiment with the exception of Nb and Mo. The calculated phonon dispersions of the 4d metals all give reasonable agreement with experiment. First principles calculations of the thermal expansion of hcp Ti have been performed, showing that this element has a negative thermal expansion along the c-axis which is linked to the closeness of the Fermi level to an electronic topological transition. Calculations of the EOS of fcc Au give support to the suggestion that the ruby pressure scale might underestimate pressures with ~10 GPa at pressures ~150 GPa. The high temperature bcc phase of the group IV metals has been calculated with the novel self-consistent ab-initio dynamical (SCAILD) method. The results show good agreement with experiment, and the free energy resolution of &lt; 1 meV suggests that this method might be suitable for calculating free energy differences between different crystallographic phases as a function of temperature.

The subject of this thesis relates to the design of new polymer electrolytes for battery and fuel cell applications. Classical Molecular Dynamics (MD) modelling studies are reported of the nano-structure and the local structure and dynamics for two types of polymer electrolyte host: poly(ethylene oxide) (PEO) for lithium batteries and perfluorosulfonic acid (PFSA) for polymer-based fuel cells. Both polymers have been modified by side-chain substitution, and the effect of this on charge-carrier transport has been investigated. The PEO system contains a 89-343 EO-unit backbone with 3-15 EO-unit side-chains, separated by 5-50 EO backbone units, for LiPF6 salt concentrations corresponding to Li:EO ratios of 1:10 and 1:30; the PFSA systems correspond to commercial Nafion®, Hyflon® (Dow®) and Aciplex® fuel-cell membranes, where the major differences again lie in the side-chain lengths. The PEO mobility is clearly enhanced by the introduction of side-chains, but is decreased on insertion of Li salts; mobilities differ by a factor of 2-3. At the higher Li concentration, many short side-chains (3-5 EO-units) give the highest ion mobility, while the mobility was greatest for side-chain lengths of 7-9 EO units at the lower concentration. A picture emerges of optimal Li+-ion mobility correlating with an optimal number of Li+ ions in the vicinity of mobile polymer segments, yet not involved in significant cross-linkages within the polymer host. Mobility in the PFSA-systems is promoted by higher water content. The influence of different side-chain lengths on local structure was minor, with Hyflon® displaying a somewhat lower degree of phase separation than Nafion®. Furthermore, the velocities of the water molecules and hydronium ions increase steadily from the polymer backbone/water interface towards the centre of the proton-conducting water channels. Because of its shorter side-chain length, the number of hydronium ions in the water channels is ~50% higher in Hyflon® than in Nafion® beyond the sulphonate end-groups; their hydronium-ion velocities are also ~10% higher. MD simulation has thus been shown to be a valuable tool to achieve better understanding of how to promote charge-carrier transport in polymer electrolyte hosts. Side-chains are shown to play a fundamental rôle in promoting local dynamics and influencing the nano-structure of these materials.

This thesis concerns multi-ionization coincidence measurements of atoms and small molecules using a magnetic bottle time-of-flight (TOF) spectrometer designed for multi-electron coincidence studies. Also, a time-of-flight mass spectrometer has been used together with the TOF electron  spectrometer for electron-ion coincidence measurements. The multi-ionization processes have been studied by employing a pulsed discharge lamp in the vacuum ultraviolet spectral region and synchrotron radiation in the soft X-ray region. The designs of the spectrometers are described in some detail, and several timing schemes suitable for the light sources mentioned above are presented. Studies have been performed on krypton, molecular oxygen, carbon disulfide and a series of alcohol molecules. For the latter, double ionization spectra have been recorded and new information has been obtained on the dicationic states. A recently found rule-of-thumb  and quantum chemical calculations have been used to quantify the effective distance of the two vacancies in the dications of these molecules. For Kr, O2, and CS2, single-photon core-valence spectra have been obtained at the synchrotron radiation facility BESSY II in Berlin and interpreted on the basis of quantum chemical calculations. These spectra show a remarkable similarity to conventional valence photoelectron spectra. Spectra of triply charged ions were recorded, also at BESSY II, for Kr and CS2 by measuring, in coincidence, all three electrons ejected. The complex transition channels leading to tricationic states were mapped in substantial detail for Kr. It was found that for 3d-ionized krypton, the tricationic states are dominantly populated by cascade Auger decays via distinct intermediate states whose energies have been determined. The triple ionization spectra of CS2 from the direct double Auger effect via S2p, S2s and C1s hole states contain several resolved features and show selectivity based on the initial charge localisation and on the identity of the initial state.

The properties of a Rydberg atom immersed in an ultracold environment were investigated. Two scenarios were considered, one of which involves the neighbouring ground-state atoms arranged in a spatially structured configuration, while the other involves them distributed randomly in space. To calculate the influence of the multiple ground-state atoms on the Rydberg atom, Fermi-pseudopotential was used, which simplified greatly the numerical effort. In many cases, the few-body interaction can be written down analytically which reveals the symmetry properties of the system. In the structured case, we report the first prediction of the formation of ``Rydberg Borromean trimers''. The few-body interactions and the dynamics of the linear A-B-A trimer, where A is the ground-state atom and B is the Rydberg atom, were investigated in the framework of normal mode analysis. This exotic ultralong-range triatomic bound state exists despite that the Rydberg-ground-state interaction is repulsive. Their lifetimes were estimated using both quantum scattering calculations and semi-classical approximations which are found to be typically sub-microseconds. In the disordered case, the Rydberg-excitation spectra of a frozen-gas were simulated, where the nuclear degrees of freedom can be ignored. The systematic change of the spectral shape with respect to the density of the gas and the excitation of the Rydberg atom were found and studied. Some parts of the spectral shape can be described by simple scaling laws with exponents given by the basic properties of the atomic species such as the polarizability and the zero-energy electron-atom scattering length.

This thesis reports on the setup of a new ion trap apparatus designed for experiments with single ⁴⁰Ca⁺ ions to perform molecular spectroscopy. The calcium ion is laser cooled, allowing for sympathetic cooling of the nonfluorescing molecular ion. The aim of these experiments is to explore loading and identifying molecular ions in RF-Paul traps, as well as developing new spectroscopic tools to measure transitions of molecular ions via the fluorescence of co-trapped ⁴⁰Ca⁺ ions. Ground state cooling of a mixed ion pair is implemented as a first step towards increasing the sensitivity of our technique to the level necessary to measure transitions with low scattering rates (like those present in molecular ions). Doppler cooling on the S(1/2)->P(1/2) transition of the calcium ion results in the formation of a Coulomb crystal, the behavior of which may be used to infer properties of the molecular ion. Following cooling, sideband spectroscopy on the narrow S(1/2)->D(5/2) quadrupole transition of calcium may be used to identify the mass of single molecular ions. This method is verified via a non-destructive measurement on ⁴⁰CaH⁺ and ⁴⁰Ca¹⁶O⁺. The normal modes of the Coulomb crystal can also be used to extract information from the target ion to the control ion. By driving the blue side of a transition, laser induced heating can be put into the two ion system, which leads to changes in fluorescence of the ⁴⁰Ca⁺ ion, first demonstrated with two Ca⁺ isotopes. Increasing the sensitivity of this technique requires ground state cooling of both the ⁴⁰Ca⁺ ion and the ion of interest, enabling the transfer of the ion's motional state into the ground state with high probability. This thesis demonstrates ground state cooling of the atomic ion and sympathetic cooling of a second ion (⁴⁴Ca⁺). Once in the ground state, heating of the Coulomb crystal by scattering photons off of the spectroscopy ion can be measured by monitoring the resolved motional sidebands of the S(1/2)->D(5/2) transition of ⁴⁰Ca⁺, allowing for spectral lines to be inferred. Future experiments will investigate this technique with molecular ions.

Thesis (Ph.D.); Submitted to Massachusetts Inst. of Tech., Cambridge, MA (US); 1 Sep 2003. / Published through the Information Bridge: DOE Scientific and Technical Information. "JLAB-PHY-03-167" "DOE/ER/40150-2745" Marat Rvachev. 09/01/2003. Report is also available in paper and microfiche from NTIS.