The transport of atoms or molecules over surfaces has been an important area of study for several decades now, with its progress generally limited by the available experimental techniques to characterize the phenomena. A number of methods have been developed over the years to measure surface diffusion yet only very few systems have been characterized to this day mainly due to the physical limitations inherent in these available methods. Even the STM with its astonishing atomically-resolved images of the surface has been limited in terms of its capability to determine mass transport properties. This is because the STM is inherently a ``slow`` instrument, i.e., a finite time is needed for signal averaging in order to produce the image. A need exists for additional surface diffusion measurement techniques, ideally ones which are able to study varied systems and measure a wide range of diffusion rates. The STM (especially because of its highly local nature) presents itself as a promising tool to conduct dynamical studies if its poor time resolution during ``normal operation`` can somehow be overcome. The purpose of this dissertation is to introduce a new technique of using the STM to measure adatom mobility on surfaces -- one with a …

Optical second harmonic generation (SHG) and sum frequency generation (SFG) were used to study C{sup 60} thin solid films (low energy ED forbidden electronic excitations), and electron spectroscopy was used to study organic overlayers (xylenes) on Pt(111). Theory of SHG from a thin film is described in terms of surface and bulk contributions as well as local and nonlocal contributions to the optical nonlinearities. (1)In situ SHG data on C{sub 60} films during UHV film growth can be described in terms of only nonlocal contributions to both surface and bulk nonlinear susceptibilities. Microscopic origin of SHG response is discussed in terms of electric quadrupole and ED transitions of C{sub 60}. (2)Adsorption and thermal decomposition of ortho- and para-xylene on Pt(111) is studied using HREELS, LEED, AES, and thermal desorption spectroscopy. We have observed preferential decomposition of the methyl groups which leads to distinct decomposition pathways for ortho- and para-xylene on Pt(111).

This thesis comprises three parts: Electrocatalysis of anodic oxygen-transfer reactions: aliphatic amines at mixed Ag-Pb oxide thin-film electrodes; oxidation of ammonia at anodized Ag-Pb eutectic alloy electrodes; and temperature effects on oxidation of ethylamine, alanine, and aquated ammonia.

This thesis showed that it is possible to achieve well ordered growth at low temperatures when chaing fluxes during the course of the deposition. It was also demonstrated that nucleation theory fails to predict or explain at least part of the results, in particular when deposition takes place at an initially low rate, with presumably a relatively low nucleation density, followed by a change to a high flux rate. This points to an inherent lack of nucleation theory; alternative explanations are presented based on flux-independent growth as reported by Roos (Surf. Sci. 302 (1994) 37).

Capillary zone electrophoresis (CZE), a powerful separation method based on the differential migration of charged species under the influence of an electric field, has been widely used for separations covering from small ions to big biomolecules. Chapter 1 describes the method, then discusses detection of the separated analytes by laser induced fluorescence and by chemical derivatization, and the use of O-phthaldialdehyde (OPA) as a post-column reagent. Chapter 2 describes a post-column reactor which uses two narrow bore capillaries connected coaxially. This reactor differs from other coaxial reactors in terms of capillary dimensions, reagent flow control, ease of construction and most importantly, better limits of detection. The derivatization reagent is electroosmotically driven into the reaction capillary and the reagent flow rate is independently controlled by a high voltage power supply. Amino acids, amines and proteins, derivatized by OPA/2-mercaptoethanol using this post-column reactor coupled with LIF detection, show low attomole mass limits of detection, and for the first time, the authors demonstrate single cell capability with a post-column derivatization scheme. The single cell capability shows that this reactor could find applications in assaying non-fluorescent or electrochemically inactive components in individual biological cells in the future.

This thesis reports on a search for right-handed W bosons (W{sub R}). Data collected with the D0 detector at the Fermilab Tevatron p{ovr p} collider at {radical}s=1.8 TeV were used to search for W{sub R} decays into an electron and a massive right-handed neutrino W{sub R}{sup {+-}} {r_arrow} e{sup {+-}}N{sub R}. Using the inclusive electron data, mass limits independent of the N{sub R} decay were set: m{sub W{sub R}} > 650 GeV/c{sup 2} and m{sub W{sub R}} > 720 GeV/c{sup 2} at the 95% confidence level, valid for m{sub N{sub R}} < {1/2}m{sub W{sub R}} and m{sub N{sub R}} {much_lt} m{sub W{sub R}} respectively (assuming Standard Model couplings). The latter also represents a new lower limit on the mass of a heavy left-handed W boson (W{prime}) decaying into e{nu}. In addition, limits on m{sub W{sub R}} valid for larger values of the N{sub R} mass were obtained assuming that N{sub R} decays to an electron and two jets. 50 refs., 58 figs., 14 tabs.

In the first part of the thesis, the electric resistivity, Seebeck coefficient, and Hall effect were measured in X{sub y}(Y{sub 2}S{sub 3}){sub 1-y} (X = Cu, B, or Al), for y = 0.05 (Cu, B) or 0.025-0.075 for Al, in order to determine their potential as high- temperature (HT)(300-1000 C) thermoelectrics. Results indicate that Cu, B, Al- doped Y{sub 2}S{sub 3} are not useful as HT thermoelectrics. In the second part, phase stability of {gamma}-cubic LaSe{sub 1.47-1.48} and NdSe{sub 1.47} was measured periodically during annealing at 800 or 1000 C for the same purpose. In the Nd selenide, {beta} phase increased with time, while the Nd selenide showed no sign of this second phase. It is concluded that the La selenide is not promising for use as HT thermoelectric due to the {gamma}-to-{beta} transformation, whereas the Nd selenide is promising.

An experimental investigation of soft x-ray production resulting from the interaction of intense near infra-red laser radiation with gases is presented in this thesis. Specifically, soft x-ray generation through high order harmonic generation or exploiting intense inverse bremsstrahlung heating is examined. Most of these studies are conducted with femtosecond, terawatt class Cr:LiSrAlF{sub 6} (LiSAF) laser, though results derived from studies with other laser systems are presented as well. The majority of this work is devoted to experimental investigations, however, theoretical and computational models are developed to interpret the data. These studies are motivated by the possibility of utilizing the physics of intense laser/matter interactions as a potential compact source of bright x-rays. Consequently, the thrust of many of the experiments conducted is aimed at characterizing the x-rays produced for possible use in applications. In general, the studies of this manuscript fall into three categories. First, a unique 130 fs, 8 TW laser that is based on chirped pulse amplification, is described, and its performance is evaluated. The generation of x-rays through high order harmonics is then discussed with emphasis on characterizing and optimizing harmonic generation. Finally, the generation of strong, incoherent x-ray radiation by the intense irradiation of large (>1,000 …

The variation in the oft-observed, thermally-forced, nocturnal katabatic winds along the east side of the Rocky Mountains can be explained by either internal variability or interactions with various other forcings. Though generally katabatic flows have been studied as an entity protected from external forcing by strong thermal stratification, this work investigates how drainage winds along the Colorado Front Range interact with, in particular, topographically forced mountain waves. Previous work has shown, based on measurements taken during the Atmospheric Studies in Complex Terrain 1993 field program, that the actual dispersion in katabatic flows is often greater than reflected in models of dispersion. The interaction of these phenomena is complicated and non-linear since the amplitude, wavelength and vertical structure of mountain waves developed by flow over the Rocky Mountain barrier are themselves partly determined by the evolving atmospheric stability in which the drainage flows develop. Perturbations to katabatic flow by mountain waves, relative to their more steady form in quiescent conditions, are found to be caused by both turbulence and dynamic pressure effects. The effect of turbulent interaction is to create changes to katabatic now depth, katabatic flow speed, katabatic jet height and, vertical thermal stratification. The pressure effect is found to …

A search for decays of the B{sub c} meson was performed using data collected from 1990--1995 with the OPAL detector on or near the Z{sup 0} peak at LEP. The decay channels B{sub c}{sup +} {r_arrow} J/{psi}{pi}{sup +}, B{sub c}{sup +} {r_arrow} J/{psi}a{sub 1}{sup +} and B{sub c}{sup +} {r_arrow} J/{psi}{ell}{sup +}{nu} were investigated, where {ell} denotes an electron or a muon. Two candidates are observed in the mode B{sub c}{sup +} {r_arrow} J/{psi}{pi}{sup +}, with an estimated background of (0.63 {+-} 0.20) events. The weighted mean of the masses of the two candidates is (6.32 {+-} 0.06) GeV/c{sup 2}, which is consistent with the predicted mass of the B{sub c} meson. One candidate event is observed in the mode B{sub c}{sup +} {r_arrow} J/{psi}{ell}{sup +}{nu}, with an estimated background of (0.82 {+-} 0.19) events. No candidate events are observed in the B{sub c}{sup +} {r_arrow} J/{psi}a{sub 1}{sup +} decay mode, with an estimated background of (1.10 {+-} 0.22) events. Upper bounds at the 90% confidence level are set on the production rates for these processes.

This thesis describes an infrared spectroscopic study on the structures and dynamics of the nonclassical ions and their complexes, using ion trap vibrational predissociation spectroscopy. Chapter One provides an introduction to the experimental apparatus used in this work. Chapter Two describes the previous theoretical and experimental works on the carbonium ion CH{sub 5}{sup +} and infrared spectroscopic and theoretical works on CH{sub 5}{sup +}. CH{sub 5}{sup +} was predicted to scramble constantly without possessing a stable structure. In Chapter Three, the infrared spectroscopy for the molecular hydrogen solvated carbonium ions CH{sub 5}{sup +}(H{sub 2}){sub n} (n=1-6) in the frequency region of 2700-4200 cm{sup {minus}1} are presented and compared with the results of ab initio molecular dynamics simulation on CH{sub 5}{sup +}(H{sub 2}){sub n} (n=0-3). The results suggested that the scrambling of CH{sub 5}{sup +} slowed down considerably by the stabilization effects of the solvent H{sub 2} molecules, and it was completely frozen out when the first three H{sub 2} molecules were bound to the core CH{sub 5}{sup +}. Chapter Four presents the complete infrared spectra for the solvated carbonium ions, CH{sub 5}{sup +}(A){sub x}(B){sub y} (A,B=H{sub 2}, Ar, N{sub 2}, CH{sub 4};x,y=0-5) in the frequency region of 2500-3200 cm{sup {minus}1}. …

Crenulative turbulence is a nonlinear extension of the Bell-Plesset instability, usually observed in a converging system in which there is a nonhomogeneous response of stress to strain and/or strain rate. In general, crenelation occurs in any circumstance in which the mean flow streamlines converge the material more strongly than the compressibility can accommodate. Elements of the material slip past each other, resulting in local fluctuations in velocity from that of the mean flow, producing a type of turbulence that is more kinematic than inertial. For a homogeneous material, crenelation occurs at the atomic or molecular scale. With nonhomogeneous stress response at larger scales, the crenulative process can also occur at those larger scales. The results are manifested by a decrease in the rate of dissipation to heat, and by the configurationally-irreversible mixing of nonhomogeneities across any mean-flow-transported interface. We obtain a mathematical description of the crenulative process by means of Reynolds decomposition of the appropriate variables, and the derivation of transport equations for the second-order moments that arise in the mean-flow momentum and energy equations. The theory is illustrated by application to the spherical convergence of an incompressible fluid with nonhomogeneous distribution of kinematic viscosity.

Effective on March 15, 1990, the Environmental Protection Agency established regulations controlling the emission of radionuclides to the air from Department of Energy facilities to limit the dose to the public to 10 mrem/yr. These regulations are detailed in 40 CFR 61, Subpart H, {open_quotes}National Emission Standards for Emissions of Radionuclides Other Than Radon from Department of Energy Facilities{close_quotes}. Part of these regulations require the operation of sampling systems on stacks meeting certain requirements. Although Los Alamos National Laboratory has a long history of stack sampling, the systems in place at the time the regulation became effective did not meet the specific design requirements of the new regulation. In addition, certain specific program elements did not exist or were not adequately documented. The Los Alamos National Laboratory has undertaken a major effort to upgrade its compliance program to meet the requirements of USEPA. This effort involved: developing new and technically superior sampling methods and obtaining approval from the Environmental Protection Agency for their use; negotiating specific methodologies with the Environmental Protection Agency to implement certain requirements of the regulation: implementing a complete, quality assured, compliance program; and upgrading sampling systems. After several years of effort, Los Alamos National Laboratory now …

Photosynthesis is a complex process which results in the conversion of solar radiation into chemical energy. This chemical energy is then used as the free energy source for all living organisms. In its basic form, photosynthesis can be described as the light-activated synthesis of carbohydrates from the simple molecules of water and carbon dioxide: 6H{sub 2}O + 6 CO{sub 2} light C{sub 6}H{sub 12}O{sub 6} + 6 O{sub 2} This basic mechanism actually requires numerous reaction steps. The two primary steps being: the capture of light by pigment molecules in light-harvesting antenna complexes and the transfer of this captured energy to the so-called photochemical reaction center. While the preferred pathway for energy absorbed by the chromophores in the antenna complexes is transfer to the reaction center, energy can be lost to competing processes such as internal conversion or radiative decay. Therefore, the energy transfer must be rapid, typically on the order of picoseconds, to successfully compete. The focus of the present work is on the construction of light-harvesting antenna complexes incorporating modular pigment-proteins.

Inductively coupled plasma mass spectrometry (ICP-MS) is the technique of choice for rapid, high precision, semiquantitative elemental and isotopic analysis for over 70 elements. Less than 20 years after the first mass spectrum was obtained by ICP-MS, this technique has applications in clinical chemistry, geochemistry, the semiconductor industry, the nuclear industry, environmental chemistry, and forensic chemistry. The determination of many elements, though, by ICP-MS is complicated by spectral interferences from background species, interelement spectral overlaps, and polyatomic ions of matrix elements. The emphasis of this thesis is the unique applications of solvent removal using cryogenic and membrane desolvation. Chapter 1 is a general introduction providing background information concerning the need for these methods and some information about the methods themselves. Chapter 5 discusses general conclusions and general observations pertaining to this work. Chapters 2, 3, and 4 have been processed separately for inclusion on the database. Chapter 2 describes a method to screen urine samples for vanadium using cryogenic desolvation. Chapter 3 compares solvent removal by cryogenic and membrane desolvation. Chapter 4 describes the use of cool plasma conditions for the determination of potassium in the presence of excess sodium by ICP-MS.

Scanning probe microscopy (SPM) offers access to the structural and material properties of interfaces, and when combined with macroscopic characterization techniques results in a powerful interfacial development tool. However, the relative infancy of SPM techniques has dictated that initial investigations concentrate on model interfacial systems as benchmarks for testing the control and characterization capabilities of SPM. One such family of model interfacial systems results from the spontaneous adsorption of alkyl thiols to gold. This dissertation examines the application of SPM to the investigation of the interfacial properties of these alkyl thiolate monolayers. Structural investigations result in a proposed explanation for counterintuitive correlations between substrate roughness and heterogeneous electron transfer barrier properties. Frictional measurements are used for characterization of the surface free energy of a series of end-group functionalized monolayers, as well as for the material properties of monolayers composed of varying chain length alkyl thiols. Additional investigations used these characterization techniques to monitor the real-time evolution of chemical and electrochemical surface reactions. The results of these investigations demonstrates the value of SPM technology to the compositional mapping of surfaces, elucidation of interfacial defects, creation of molecularly sized chemically heterogeneous architectures, as well as to the monitoring of surface reactions. However, …

Three-dimensional creeping flow around single, axisymmetric protrusions is studied numerically using the boundary-integral technique. Emphasis is placed upon cylindrical protrusions on plane walls for various height-to-radius (h-to-a) aspect ratios, but cones and sections of spheres protruding from plane walls are also briefly examined. The presented items include shear-stress distributions, shear-stress contours, extents of the fluid-flow disturbance, total forces and torques on the cylinders, streamlines, and skin-friction lines. Also included is a discussion of flow topology around axisymmetric geometries. No flow reversal is observed for cylindrical protrusions with aspect ratios greater than 2.4 to 2.6. At higher aspect ratios, the fluid tends to be swept around cylindrical protrusions with little vertical motion. At lower aspect ratios, the strength of the recirculation increases, and the recirculation region becomes wider in the transverse direction and narrower in the flow direction. Also, the recirculation pattern begins to resemble the closed streamline patterns in two-dimensional flow over square ridges. However, unlike two-dimensional flow, closed streamline patterns are not observed. For arbitrary axisymmetric geometries, the extent of the fluid-flow disturbance can be estimated with the total force that is exerted on the protrusion. When the same force is exerted on protrusions with different aspect ratios, the …

The Full Potential Linear Augmented Plane Wave (FPLAPW or FLAPW) method is used for a spin-polarized band calculation for ordered Fe{sub 3}Pt. As major purpose, the momentum distributions of the spin-polarized electrons are calculated and compared with results from a magnetic Compton scattering measurement. To get related information, the electronic behavior is also analyzed by examining the partial densities of states and the spatial electron distributions; the role of alloying effects is then explored by studying the electrons in some related alloys: Fe{sub 3}Ni, Fe{sub 3}Pd, Ni{sub 3}Pt and Co{sub 3}Pt.

The single crystals of TiNiSn and polycrystalline PtMnSb were grown by the flux and melt cooling method. Their lattice parameters and structures were determined by x-ray diffraction. The effect of impurities on the growth of TiNiSn single crystals was investigated. It was found that the concentration of chlorine plays a key role in determining the chemical composition of the phases that are formed. The heat capacity and magnetic susceptibility of TiNiSn was measured in a temperature range from 4.7 K to room temperature. Magnetic measurements show that the TiNiSn is paramagnetic, and that it does not order magnetically.

The main objectives of this project were to study the effects of low-temperature pretreatments on coal structure and their impacts on subsequent liquefaction. The effects of pretreatment temperatures, catalyst type, coal rank, and influence of solvent were examined. Specific objectives were to identify the basic changes in coal structure induced by catalytic and thermal pretreatments, and to determine the reactivity of the catalytically and thermally treated coals for liquefaction. In the original project management plan it was indicated that six coals would be used for the study. These were to include two each of bituminous, subbituminous, and lignite rank. For convenience in executing the experimental work, two parallel efforts were conducted. The first involved the two lignites and one subbituminous coal; and the second, the two bituminous coals and the remaining subbituminous coal. This Volume presents the results of the first portion of the work, studies on two lignites and one subbituminous coal. The remaining work accomplished under this project will be described and discussed in Volume 2 of this report. The objective of this portion of the project was to determine and compare the effects of solvents, catalysts and reaction conditions on coal liquefaction. Specifically, the improvements of reaction …

This thesis presents the results from the investigation of time dependent B{sub d}{sup 0} {bar B}{sub d}{sup 0} mixing in B {yields} lepton X, B{sub d}{sup 0} {yields} D*{sup -} {yields} {bar D}{sup 0} {pi}{sup -}, {bar D}{sup 0} {yields} K{sup +} {pi}{sup -} channel in p{bar p} collisions at {radical}s = 1.8 TeV using 110 pb{sup -1} data collected with the CDF detector at the Fermilab Tevatron Collider. The {bar D}{sup 0} vertex is reconstructed. The B{sub d}{sup 0} decay length is estimated using the distance from the primary vertex to the measured position of the D{sup 0} vertex. The B{sup 0} momentum is estimated using the D{sup 0} momentum and a kinematic correction factor from Monte Carlo. With the dilution floating, {Delta}M{sub d} = 0.55 {+-}{sub 0.16}{sup 0.15} (stat) {+-} 0.06 (syst)ps{sup -1} is measured.

The intent of this work was to broaden the applications of well-established surface modification techniques and to elucidate the various wear mechanisms that occur in sliding contact of ion-beam processed surfaces. The investigation included characterization and evaluation of coatings and modified surfaces synthesized by three surface engineering methods; namely, beam-line ion implantation, plasma-source ion implantation, and DC magnetron sputtering. Correlation among measured properties such as surface hardness, fracture toughness, and wear behavior was also examined. This dissertation focused on the following areas of research: (1) investigating the mechanical and tribological properties of mixed implantation of carbon and nitrogen into single crystal silicon by beam-line implantation; (2) characterizing the mechanical and tribological properties of diamond-like carbon (DLC) coatings processed by plasma source ion implantation; and (3) developing and evaluating metastable boron-carbon-nitrogen (BCN) compound coatings for mechanical and tribological properties. The surface hardness of a mixed carbon-nitrogen implant sample improved significantly compared to the unimplanted sample. However, the enhancement in the wear factor of this sample was found to be less significant than carbon-implanted samples. The presence of nitrogen might be responsible for the degraded wear behavior since nitrogen-implantation alone resulted in no improvement in the wear factor. DLC coatings have low …

Fe-K-edge X-ray absorption spectroscopy (XAS) has been used to investigate the electronic and geometric structure of the iron active site in non-heme iron enzymes. A new theoretical extended X-ray absorption fine structure (EXAFS) analysis approach, called GNXAS, has been tested on data for iron model complexes to evaluate the utility and reliability of this new technique, especially with respect to the effects of multiple-scattering. In addition, a detailed analysis of the 1s{yields}3d pre-edge feature has been developed as a tool for investigating the oxidation state, spin state, and geometry of iron sites. Edge and EXAFS analyses have then been applied to the study of non-heme iron enzyme active sites.

The author gives a pedagogical introduction to the differential calculus on quantum groups by stressing at all stages the connection with the classical case. He further analyzes the relation between differential calculus and quantum Lie algebra of left (right) invariant vectorfields. Equivalent definitions of bicovariant differential calculus are studied and their geometrical interpretation is explained. From these data he constructs and analyzes the space of vectorfields, and naturally introduces a contraction operator and a Lie derivative. Their properties are discussed.