This dissertation reports the application of nonlinear optical effects for the investigation of vibrational and electronic spectroscopy of molecules adsorbed on thin film metal oxide surfaces and metal oxide surfaces. The main emphasis of the experiments cited here is to introduce the recently developed multi-photon technique, Waveguide Surface Coherent anti-Stokes Raman Scattering Spectroscopy (WSCARS), to the scientific community. Planar optical waveguides have been utilized to generate large optical field enhancements on metal oxide surfaces. Guided waves have been employed to obtain the surface coherent anti-Stokes Raman scattering spectra of pyridine, phenol, benzene, methanol, CD₃OD, 2,4-pentadione, oxygen, ammonia and ND₃ adsorbed onto a ZnO (0001) surface. Vibrational spectra of transient species (O₂⁻) adsorbed on ZnO (0001) surface are also presented. Furthermore, the WSCARS has been used to monitor catalytic hydrogenation of ethylene adsorbed on ZnO (0001) surface. The WSCARS technique is compared with the other vibrational surface probes. Future directions and limitations of the technique are also discussed. Electronic spectra of surface bound species have been examined by resonantly enhanced surface second harmonic generation (SSHG). SHG spectra of trans-cinnamic acid adsorbed on optically cleaned fused silica have been obtained at room temperature and at 4 K. Surface second harmonic generation has been applied to study the adsorption of water and acetone onto thermally grown silicon dioxide/silicon surface. SSHG has been successfully applied to monitor photo-oxidation and photo-reduction of a rutile (110) surface. Experiments are described, data are presented, and surface-adsorbate binding modes are discussed.

The air-water interface is an important natural boundary layer that has been neglected as an area of environmental field research. This study establishes that comparative microscopy can be an effective environmental method, and establishes that the term metallic surface films, is a more accurate descriptor than iron oxide surface films. This research shows that surface films are complex, often with layered structure, serve as habitat for significant biota, and act as a point of mineralization to several transition metal elements including manganese, iron, copper, nickel and zinc. This study demonstrates that surface films form under several conditions and can have diverse morphology. Activity of biota, microbes, particularly diatoms, suggests that bacteria and cyanobacteria integrate into the film often in patches, represented by forms and casts. Analytical imaging is used to document and compare film morphology and structures, using scanning electron microscopy, photoemission electron microscopy and transmission electron microscopy with elemental analysis by energy dispersive spectroscopy to confirm the hypothesis. Instrument parameters and strengths are reviewed. Component layers of a copper/zinc film were used to confirm metallic layers and elemental distribution. Bacterial casts were used to confirm film interaction, and to show entrainment and enrichment of the film to incorporate autochthonous and allochthonous materials into the films themselves. Most samples were from Oregon selected sites, with some samples from Maryland and Barbados.

Ces travaux s'inscrivent dans la thématique de l'inférence géométrique dont le but est de répondre au problème suivant : étant donné un objet géométrique dont on ne connaît qu'une approximation, peut-on estimer de manière robuste ses propriétés? On se place dans cette thèse dans le cas où l'approximation est un nuage de points ou un ensemble digital dans un espace euclidien de dimension finie. On montre tout d'abord un résultat de stabilité d'un estimateur de normale basé sur l'analyse en composante principale, ainsi qu'un résultat de convergence multigrille d'un estimateur du Voronoi Covariance Measure qui utilise des matrices de covariance de cellules de Voronoi. Ces deux résultats, comme la plupart des résultats en inférence géométrique, utilisent la stabilité de la fonction distance à un compact. Cependant, la présence d'un seul point aberrant suffit pour que les hypothèses des résultats de stabilité ne soient pas satisfaites. La distance à une mesure est une fonction distance généralisée introduite récemment qui est robuste aux points aberrants. Dans ce travail, on généralise le Voronoi Covariance Measure à des fonctions distances généralisées et on montre que cet estimateur appliqué à la distance à une mesure est robuste aux points aberrants. On en déduit en particulier un estimateur de normale très robuste. On présente également des résultats expérimentaux qui montrent une forte robustesse des estimations de normales, courbures, directions de courbure et arêtes vives. Ces résultats sont comparés favorablement à l'état de l'art. / The purpose of geometric inference is to answer the following problem : Given a geometric object that is only known through an approximation, can we get a robust estimation of its properties? We consider in this thesis the case where the approximation is a point cloud or a digital set in a finite dimensional Euclidean space. We first show a stability result for a normal estimator based on the principal component analysis, as well as a result of multigrid convergence of an estimator of the Voronoi covariance measure, which uses covariance matrices of Voronoi cells. As most of geometric inference results, these two last results use the robustness of the distance function to a compact set. However, the presence of a single outlier is sufficient to make the assumptions of these results not satisfied. The distance to a measure is a generalized distance function introduced recently, that is robust to outliers. In this work, we generalize the Voronoi Covariance Measure to generalized distance functions and we show that this estimator applied to the distance to a measure is robust to outliers. We deduce a very robust normal estimator. We present experiments showing the robustness of our approach for normals, curvatures, curvature directions and sharp features estimation. These results are favorably compared to the state of the art.

Le grippage dans le cas des aciers inoxydables est un phénomène complexe nécessitant une approche multi-échelle et multi-physique. Les 6 nuances d’aciers inoxydables sélectionnées au cours de cette thèse (316L, 316LN, Nitronic60, AISI660, Uranus45N et 17-4PH) ont été étudiées à l’état de réception et après traitements thermochimique de surface de type S3P. Ces matériaux ont subi un essai de grippage selon la norme ASTM G98 et les échantillons qui en résultent ont été caractérisés selon une approche d’abord surfacique (évolution de la morphologie de la surface, observations MEB…) puis en volume, notamment par le biais de l’approche originale de la microstructure (EBSD, DRX et MET notamment). Cette thèse a ainsi permis d’étudier les différents mécanismes intervenant lors du grippage des aciers inoxydables ainsi que d’étudier l’impact de différentes microstructures et composition chimiques sur ce phénomène. / Galling is a complex phenomenon requiring a multi-scale and multi-physical approach. During this thesis, 6 stainless steel grades (316L, 316LN, Nitronic60, AIS1660, Uranus45N et 17-4PH) are studied, both untreated and after S3P thermochemical heat surface treatment. These materials are tested according to ASTM G98 galling test and resulting samples are then characterized. This characterization is at first realized on the surface (surface morphology evolution, SEM investigations...), then on the bulk material, consisting mainly into a microstructural characterization based on EBSD, XRD and TEM investigations. It results from this thesis a better comprehension of the galling mechanisms in the case of stainless steel. The various effects of material composition, microstructure and material properties in general are also discussed.

The Riemann Zeta Function has a deep connection with the distribution of primes. This expository thesis will explain the techniques used in proving the properties of the Rieman Zeta Function, its analytic continuation to the complex plane, and the functional equation that the the Riemann Zeta Function satisfies.