Thesis (Ph. D.)--University of Hong Kong, 2006. / Title proper from title frame. Also available in printed format.

published_or_final_version / Physics / Master / Master of Philosophy

The Tin dioxide (SnO2) and Titanium dioxide (TiO2) are very promising materials in Material science. The SnO2 is commonly used as a gas sensor while the TiO2 is used as a catalyst in many reactions. Despite of the usefulness of these two substances, their surface structures lack detail investigations in the previous years. The Low Energy Electron Diffraction (LEED) technique is commonly used to characterize surfaces in the past 40 years, it is a mature system that many researches rely on its result. However, structural analysis in LEED requires comparison with computational results based on pre-defined structure models, which is a time-consuming method and the results are not guaranteed to be found. The direct determinations of structure by Patterson function inversion methods introduced by Huasheng Wu and S. Y. Tong could provide a different path to search for surface structure. In the Patterson function, each maximum in the function corresponds to a relative position vector of atomic pairs. Multiple-angle-incident LEED has to be performed to obtain an artifact-free Patterson function. Serveal SnO2 and TiO2 surfaces have been characterized by LEED and Patterson function inversion. SnO2 (110), (100), (101) , Rutile TiO2 (110), Anatase TiO2 (110) have been prepared by argon ion sputtering and annealing cycles and the cleanness has been checked by Auger Electron Spectroscopy and LEED. Reconstruction is observed based on the study of the LEED patterns. SnO2 (110) surface shows a 4 x 1 reconstruction in UHV environment while it gives 1 x 1 under annealing in oxygen and C(2 x 2) at higher annealing temperature afterward. SnO2 (100) , (101) and Rutile TiO2 (110) surfaces show 1 x 1 reconstruction in UHV environment and the reconstruction persists for further annealing. The Anatase TiO2 (110) surface shows a 3 x 4 reconstruction in UHV environment. The 3 x 4 reconstruction of Anatase TiO2 (110) surface would raise research interests as it is quite a special reconstruction. Multiple-angle-incident LEED has been performed on the SnO2 (100), (101) and Rutile TiO2 (110) surfaces. Patterson function inversion is performed on the surfaces SnO2 (100) and Rutile TiO2 (110) . Only LEED is performed on SnO2 (110) , (101) and Anatase TiO2 (110) surfaces. From Patterson functions analysis, the surface atoms positions are determined for the surface SnO2 (100) and Rutile TiO2 (110). The results show that their reconstructions are negligible, but they have obvious relaxations. / published_or_final_version / Physics / Master / Master of Philosophy

abstract / Physics / Doctoral / Doctor of Philosophy

In this thesis three studies of the geometric structure of the (110) surface of single crystal rutile TiO2 are presented. Firstly, quantitative low energy electron diffraction (LEED-IV) data acquired from TiO2(110)(1x1) are reanalysed to confirm the integrity of the previously reported optimized geometries by performing structural optimisation as a function of depth into the selvedge. The second study addresses the geometry of the x-linked (1x2) reconstruction of the same surface. Again, LEED-IV data are analysed to quantitatively determine the surface structure. Part of this effort involved substantial development of the code (SATLEED) employed for simulating the experimental data, to allow simultaneous optimisation of more than one surface termination. In contrast to recent scanning probe work, the analysis indicates that the surface consists of two differently relaxed Ti2O3 added rows. The last study concerns ab initio calculations of the structure of benzoate on TiO2(110)(1x1). Of particular interest is the impact of surface coverage on the orientation of the benzene ring. It is predicted that the benzene ring twists and tilts away from high symmetry with increasing coverage due to adsorbate-adsorbate interactions. No evidence is found to support the formation of benzoate dimers or trimers, as was concluded in earlier experimental work.

The threshold potentials were determined for the excitation energy necessary for low energy electrons to induce chemical reactions of carbon monoxide, and of nitric oxide adsorbed on a gold surface. The reactions were studied as a function of temperature (100 °C to 200 °C) and pressure (1.83 x 10-5 to 6.40 x 10-4 torr). The electron source was a thorium oxide coated iridium filament which was heated by a current between 1A and 3A to keep thermal distribution of the electrons to less than 0.4 ev. The reaction surface was a polycrystalline evaporated film prepared by subliming gold onto a stainless steel mesh support. Mass analysis was done by quadrupole mass spectrometry in a flow system. The general results of the research is that a technique has been developed to study the products of reactions of excited state atoms or molecules on metal surfaces. The electron-impact excitation method is an alternative to photochemical and other methods.

Low energy electron (LEE) driven chemistry underpins a wide range of interdisciplinary fields, including radiation biology, redox chemistry, astrochemistry and biomaterial design. A growing interest in the chemistry of LEEs concerns the radiative damage to DNA. Studies have found that LEEs can induce single and double-strand breaks in DNA by forming a negative ion resonance (NIR). These processes are remarkably site-specific and have been utilized to synthesize radiosensitizers, which aid in identifying target cells in hypoxic tumors in radiation therapy. Despite the prevalence of LEE-induced reactions, computational studies of such processes are limited compared to thermal and photochemical reactions. The relative scarcity in computational studies of LEE-induced reactions stems from the difficulties in the theoretical treatment of NIRs. In our work, we report new developments on the application of quantum chemical methods to NIRs. We demonstrate that the combination of approaches developed for resonances with multi reference electronic structure methods enables the computation of various types of NIRs in a single calculation. Additionally, we show that multi-reference methods can also quantify the mixing between NIRs. It is observed that the mixing between resonances can have significant consequences on their lifetimes. We also report the development of a new technique, the continuum remover Feshbach projection operator approach, which uses the conventional methods developed for bound states to characterize resonances. We show that this new approach is straightforward to implement with standard electronic structure packages, it is efficient, and provides promising results. / Chemistry

This thesis presents a series of electron impact ionization measurements on the gas phase targets of argon and krypton. The (e,2e) coincidence technique has been employed to measure the triple differential cross section (TDCS) using a new coincidence spectrometer designed to operate in the low energy regime (2 to 5 times the ionization energy) and in the coplanar geometry. The spectrometer is a conventional device utilizing a non-energy selected electron gun and two 1800 hemispherical electron analysers fitted with channel electron multipliers for detection of the outgoing electrons. A series of TDCS measurements were performed on the 3s inner-valence and 3p valence orbitals of argon employing coplanar asymmetric kinematics. Measurements for both orbitals were performed at an incident energy of 113.5 eV, ejected energies of 10, 7.5, 5 and 2 eV and a scattering angle of -15°. The energy of the scattered electron in each case was chosen to satis~' energy conservation and is dependent on the ionization energies of the different orbitals. The experimental cross sections are compared to theoretical TDCS calculations using the distorted wave Born approximation (DWBA) and variations of the DWBA in an attempt to investigate the role that post collisional interaction (PCI), polarization and electron exchange play in describing the TDCS in the low energy regime. To further extend this analysis, a series of TDCS measurements were performed on the 3s and 4s. orbitals of argon and krypton, respectively, employing coplanar symmetric kinematics. Measurements were performed for the 3s orbital at outgoing energies of 50, 20, 10 and 4eV and for the 4s orbital at outgoing energies of 85, 50, 20 and 10 eV. The kinematics were chosen to coincide with several of the (e,2e) measurements made in the same geometry on the 3p orbital of argon by Rouvellou et al (1998). The experimental results were again compared to a DWBA calculation and similar variations to those employed for the asymmetric measurements.

Nous avons étudié la structure de la surface de mica muscovite clivée à l?air par diffraction d?électrons lents en mode oscillant. Cette nouvelle méthode d?analyse structurale, que nous avons développée à partir d?un système optique standard de résolution conventionnelle, possède une grande sensibilité. En outre, elle permet de former des images de diffraction entières sans procéder, comme le font les autres diffractomètres à haute résolution, à une reconstitution ligne par ligne. Cette caractéristique permet aussi de réaliser des acquisitions d?image qui sont corrélées temporellement avec une excitation extérieure, ce qui rend possible toute une gamme d?expériences nouvelles, notamment dans le cadre de la réponse thermodynamique d?une surface au voisinage d?une transition de phase. Notre étude de la surface du mica muscovite par diffraction d?électrons lents en mode oscillant a permis pour la première fois de mettre en évidence la nanostructuration de sa couche superficielle. Notre interprétation est que lors du clivage, la surface du mica s?auto-organise pour former un arrangement d?îlots à l?intérieur desquels les atomes de potassium occupent les sites réguliers du cristal. Les îlots sont soit de taille définie soit séparés par une distance définie. Dans les zones interstitielles qui les séparent, les ions potassium, en concentration beaucoup plus faible, formeraient une couche amorphe.

Thesis (Ph. D.)--University of Missouri-Columbia, 1997. / Typescript. Vita. Includes bibliographical references (leaves 197-202). Also available on the Internet.