Second harmonic generation (SHG) and infrared-visible sum frequency generation (SFG) spectroscopies have been shown to be powerful and versatile for studying surfaces with submonolayer sensitivity. They have been used in this work to study bare diamond surfaces and molecular adsorption on them. In particular, infrared-visible SFG as a surface vibrational spectroscopic technique has been employed to identify and monitor in-situ surface bonds and species on the diamond (111) surface. The CH stretch spectra allow us to investigate hydrogen adsorption, desorption, abstraction, and the nature of the hydrogen termination. The C(111) surface dosed with atomic hydrogen was found to be in a monohydride configuration with the hydrogen atoms situated at top-sites. The ratio of the abstraction rate to the adsorption rate was appreciable during atomic hydrogen dosing. Kinetic parameters for thermal desorption of H on C(111) were determined showing a near first-order kinetics. For the fully H-terminated (111) surface, a large (110 cm{sup {minus}1}) anharmonicity and {approximately}19 psec lifetime were measured for the first-excited CH stretch mode. The bare reconstructed C(111)-(2 {times} l) surface showed the presence of CC stretch modes which were consistent with the Pandey {pi}-bonded chain structure. When exposed to the methyl radical, the SFG spectra of the …

This dissertation describes several three-body dissociations and the photodissociation of methyl radicals studied using photofragment translational spectroscopy. The first chapter provides an introduction to three body dissociation, examines current experimental methodology, and includes a discussion on the treatment of photofragment translational spectroscopy data arising from three-body fragmentation. The ultraviolet photodissociation of azomethane into two methyl radicals and nitrogen is discussed in chapter 2. Chapter 3 describes the photodissociation of acetone at 248 nm and 193 nm. At 248 nm the translational energy release from the initial C-C bond cleavage matches the exit barrier height and a comparison with results at 266 nm suggests that <E{sub T}> is invariant to the available energy. A fraction of the nascent CH{sub 3}CO radicals spontaneously dissociate following rotational averaging. The <E{sub T}> for the second C-C bond cleavage also matches the exit barrier height. At 193 nm the experimental data can be successfully fit assuming that the dynamics are analogous to those at 248 nm. A simplified model of energy partitioning which adequately describes the experimental results is discussed. Experiments on acetyl halides provide additional evidence to support the proposed acetone dissociation mechanism. A value of 17.0{+-}1.0 kcal/mole for the barrier height, CH{sub 3}CO …

Quantum Monte Carlo (QMC) methods have been found to give excellent results when applied to chemical systems. The main goal of the present work is to use QMC to perform electronic structure calculations. In QMC, a Monte Carlo simulation is used to solve the Schroedinger equation, taking advantage of its analogy to a classical diffusion process with branching. In the present work the author focuses on how to extend the usefulness of QMC to more meaningful molecular systems. This study is aimed at questions concerning polyatomic and large atomic number systems. The accuracy of the solution obtained is determined by the accuracy of the trial wave function`s nodal structure. Efforts in the group have given great emphasis to finding optimized wave functions for the QMC calculations. Little work had been done by systematically looking at a family of systems to see how the best wave functions evolve with system size. In this work the author presents a study of trial wave functions for C, CH, C{sub 2}H and C{sub 2}H{sub 2}. The goal is to study how to build wave functions for larger systems by accumulating knowledge from the wave functions of its fragments as well as gaining some knowledge …

Conventional solid state reactions are diffusion limited processes that require high temperatures and long reaction times to reach completion. In this work, several solution based methods were utilized to circumvent this diffusion limited reaction and achieve product formation at lower temperatures. The solution methods studied all have the common goal of trapping the homogeneity inherent in a solution and transferring this homogeneity to the solid state, thereby creating a solid atomic mixture of reactants. These atomic mixtures can yield solid state products through {open_quotes}diffusionless{close_quotes} mechanisms. The effectiveness of atomic mixtures in solid state synthesis was tested on three classes of materials, varying in complexity. A procedure was invented for obtaining the highly water soluble salt, titanyl nitrate, TiO(NO{sub 3}){sub 2}, in crystalline form, which allowed the production of titanate materials by freeze drying. The freeze drying procedures yielded phase pure, nanocrystalline BaTiO{sub 3} and the complete SYNROC-B phase assemblage after ten minute heat treatments at 600{degrees}C and 1100{degrees}C, respectively. Two novel methods were developed for the solution based synthesis of Ba{sub 2}YCu{sub 3}O{sub 7-x} and Bi{sub 2}Sr{sub 2}Ca{sub 2}Cu{sub 3}O{sub 10}. Thin and thick films of Ba{sub 2}YCu{sub 3}O{sub 7-x} and Bi{sub 2}Sr{sub 2}Ca{sub 2}Cu{sub 3}O{sub 10} were synthesized by …

Problems with MoSi{sub 2} include low-temperature fracture toughness, high-temperature creep resistance, and ``pest`` phenomena. Oxygen introduced by powder processing may be the cause of some of these problems. This study led to the following conclusions: Supplied powders have significant oxygen present prior to processing (up to 2.5 %), in the form of silica on the surface. This oxygen contamination did not increase by exposure to air at room temperature. An improved powder processing method was developed that uses glass encapsulation. Analysis of microstructures created from powders that contained 4900 to 24,100 ppM oxygen showed that the silica was transferred to the fully dense MoSi{sub 2} as SiO{sub 2} inclusions. A method of producing MoSi{sub 2} with less oxygen was attempted.

For the last decade, the Trahanovsky research group has focused on the study of various reactive molecules such as o-quinodimethanes (o-QDM`s) and p-quinodimethanes (p-QDM`s) derived from benzene, furan, and thiophene. These types of molecules are reactive and dimerize or polymerize at room temperature. One of the group`s interests is to understand the dimerization mechanism of these molecules. Paper 1 describes the preparation and dimerization product analyses of 2-ethylidene-5-methylene-2,5-dihydrothiophene. Insights provided by these results into the mechanism of the dimerization of 2,5-dimethylene-2,5-dihydrothiophene are discussed. In paper 2, a convenient synthesis of cyclooctadecane is presented.

This report discusses the following topics on support minimized inversion of acoustic and elastic wave scattering: Minimum support inversion; forward modelling of elastodynamic wave scattering; minimum support linearized acoustic inversion; support minimized nonlinear acoustic inversion without absolute phase; and support minimized nonlinear elastic inversion.

In this work, a measurement of the strong coupling constant {alpha}{sub s} in e{sup +}e{sup {minus}} annihilation at a center-of-mass energy of 91.6 GeV is presented. The measurement was performed with the SLD at the Stanford Linear Collider facility located at the Stanford Linear Accelerator Center in California. The procedure used consisted of measuring the rate of hard gluon radiation from the primary quarks in a sample of 9,878 hadronic events. After defining the asymptotic manifestation of partons as `jets`, various phenomenological models were used to correct for the hadronization process. A value for the QCD scale parameter {Lambda}{sub bar MS}, defined in the {sub bar MS} renormalization convention with 5 active quark flavors, was then obtained by a direct fit to O({alpha}{sub s}{sup 2}) calculations. The value of {alpha}{sub s} obtained was {alpha}{sub s}(M{sub z0}) = 0.122 {plus_minus} 0.004 {sub {minus}0.007} {sup +0.008} where the uncertainties are experimental (combined statistical and systematic) and theoretical (systematic) respectively. Equivalently, {Lambda}{sub bar MS} = 0.28 {sub {minus}0.10}{sup +0.16} GeV where the experimental and theoretical uncertainties have been combined.

Crosswell electromagnetic measurements are a promising new geophysical technique for mapping subsurface electrical conductivity which can provide information about the subsurface distribution of water, oil or steam. In this work the fields from a low frequency vertical magnetic dipole have been examined from the specific point of view of their application to the determination of the conductivity of a layered medium. The source and the receiver were placed inside two separate boreholes. The range of penetration of such a crosswell system for typical earth resistivities and for currently available transmitter and receiver technologies was found to be up to 1,000 meters so problems in ground water and petroleum reservoir characteristics can be practically examined. An analysis of the behavior of the magnetic fields at the boundary between two half-spaces showed that the horizontal magnetic field component, H{rho}, and the vertical derivative of a vertical component, {delta}H{sub z}/{delta}z, are more sensitive to conductivity variations than H{sub z}. The analysis of derivatives led to the concept of measuring the conductivity directly using a second vertical derivative of H{sub z}. Conductivity profiles interpreted from field data using this technique reproduced accurately the electrical logs for a test site near Devine, Texas. It was …

We introduce several ways in which approximate flavor symmetries act on fermions and which are consistent with observed fermion masses and mixings. Flavor changing interactions mediated by new scalars appear as a consequence of approximate flavor symmetries. We discuss the experimental limits on masses of the new scalars, and show that the masses can easily be of the order of weak scale. Some implications for neutrino physics are also discussed. Such flavor changing interactions would easily erase any primordial baryon asymmetry. We show that this situation can be saved by simply adding a new charged particle with its own asymmetry. The neutrality of the Universe, together with sphaleron processes, then ensures a survival of baryon asymmetry. Several topics on flavor structure of the supersymmetric grand unified theories are discussed. First, we show that the successful predictions for the Kobayashi-Maskawa mixing matrix elements, V{sub ub}/V{sub cb} = {radical}m{sub u}/m{sub c} and V{sub td}/V{sub ts} = {radical}m{sub d}/m{sub s}, are a consequence of a large class of models, rather than specific properties of a few models. Second, we discuss how the recent observation of the decay {beta} {yields} s{gamma} constrains the parameter space when the ratio of the vacuum expectation values of …

Changes in protein structure that occur during the formation of the M photointermediate of bacteriorhodopsin can be directly visualized by electron diffraction techniques. Samples containing a high percentage of the M intermediate were trapped by rapidly cooling the crystals with liquid nitrogen following illumination with filtered green light at 240K and 260K respectively. Difference Fourier projection maps for M minus bR at two temperatures and for M{sub 260K} minus M{sub 240K} are presented. While it is likely that a unique M-substate is trapped when illuminated at 260K produces a mixture of the M{sub 240K} substate and a second M-substate which may have a protein structure similar to the N-intermediate. The diffraction data clearly show that statistically significant structural changes occur upon formation of the M{sub 240K} specimen and then further upon formation of the second substate which is present in the mixture that is produced at 260K. A preliminary 3-D difference map, based on data collected with samples tilted up to 30{degree}, has been constructed at a resolution of 3.5{angstrom} parallel to the membrane plane and a resolution of 8.5{angstrom} perpendicular to the membrane. The data have been analyzed by a number of different criteria to ensure that the differences …

Utilizing self-consistent Hartree-Fock calculations, several aspects of multilayers and interfaces are explored: enhancement and reduction of the local magnetic moments, magnetic coupling at the interfaces, magnetic arrangements within each film and among non-neighboring films, global symmetry of the systems, frustration, orientation of the various moments with respect to an outside applied field, and magnetic-field induced transitions. Magnetoresistance of ferromagnetic-normal-metal multilayers is found by solving the Boltzmann equation. Results explain the giant negative magnetoresistance encountered in these systems when an initial antiparallel arrangement is changed into a parallel configuration by an external magnetic field. The calculation depends on (1) geometric parameters (thicknesses of layers), (2) intrinsic metal parameters (number of conduction electrons, magnetization, and effective masses in layers), (3) bulk sample properties (conductivity relaxation times), (4) interface scattering properties (diffuse scattering versus potential scattering at the interfaces, and (5) outer surface scattering properties (specular versus diffuse surface scattering). It is found that a large negative magnetoresistance requires considerable asymmetry in interface scattering for the two spin orientations. Features of the interfaces that may produce an asymmetrical spin-dependent scattering are studied: varying interfacial geometric random roughness with no lateral coherence, correlated (quasi-periodic) roughness, and varying chemical composition of the interfaces. The interplay …

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Helium is attractive for use as a fusion blanket coolant for a number of reasons. It is neutronically and chemically inert, nonmagnetic, and will not change phase during any off-normal or accident condition. A significant disadvantage of helium, however, is its low density and volumetric heat capacity. This disadvantage manifests itself most clearly during undercooling accident conditions such as a loss of coolant accident (LOCA) or a loss of flow accident (LOFA). This thesis describes a new helium-cooled tritium breeding blanket concept which performs significantly better during such accidents than current designs. The proposed blanket uses reduced-activation ferritic steel as a structural material and is designed for neutron wall loads exceeding 4 MW/m{sup 2}. The proposed geometry is based on the nested-shell concept developed by Wong, but some novel features are used to reduce the severity of the first wall temperature excursion. These features include the following: (1) A ``beryllium-joint`` concept is introduced, which allows solid beryllium slabs to be used as a thermal conduction path from the first wall to the cooler portions of the blanket. The joint concept allows for significant swelling of the beryllium (10 percent or more) without developing large stresses in the blanket structure. (2) …

In an effort to mathematically describe the anisotropic diffusion of infrared radiation in biological tissue Gruenbaum posed an anisotropic diffusion boundary value problem in 1989. In order to accommodate anisotropy, he discretized the temporal as well as the spatial domain. The probabilistic interpretation of the diffusion equation is retained; radiation is assumed to travel according to a random walk (of sorts). In this random walk the probabilities with which photons change direction depend upon their previous as well as present location. The forward problem gives boundary value data as a function of the Markov transition probabilities. The inverse problem requires finding the transition probabilities from boundary value data. Problems in the plane are studied carefully in this thesis. Consistency conditions amongst the data are derived. These conditions have two effects: they prohibit inversion of the forward map but permit smoothing of noisy data. Next, a recursive algorithm which yields a family of solutions to the inverse problem is detailed. This algorithm takes advantage of all independent data and generates a system of highly nonlinear algebraic equations. Pluecker-Grassmann relations are instrumental in simplifying the equations. The algorithm is used to solve the 4 {times} 4 problem. Finally, the smallest nontrivial problem …

A new simple, self consistent theoretical model is presented that describes the phenomena of quench propagation in Cable-In-Conduit superconducting magnets. The model (Quencher) circumvents many of the difficulties associated with obtaining numerical solutions in more general existing models. Specifically, a factor of 30-50 is gained in CPU time over the general, explicit time dependent codes used to study typical quench events. The corresponding numerical implementation of the new model is described and the numerical results are shown to agree very well with those of the more general models, as well as with experimental data. Further, well justified approximations lead to the MacQuench model that is shown to be very accurate and considerably more efficient than the Quencher model. The MacQuench code is suitable for performing quench studies on a personal computer, requiring only several minutes of CPU time. In order to perform parametric studies on new conductor designs it is required to utilize a model such as MacQuench because of the high computational efficiency of this model. Finally, a set of analytic solutions for the problem of quench propagation in Cable-In-Conduit Conductors is presented. These analytic solutions represent the first such results that remain valid for the long time scales …

In this dissertation the author examines a variety of different problems in the physics of strongly-bound systems. Each is elucidated by a different standard method of analysis developed to probe the properties of such systems. He begins with an examination of the properties and consequences of the current algebra of weak currents in the limit of heavy quark spin-flavor symmetry. In particular, he examines the assumptions in the proof of the Ademollo-Gatto theorem in general and for spin-flavor symmetry, and exhibit the constraints imposed upon matrix elements by this theorem. Then he utilizes the renormalization-group method to create composite fermions in a three-generation electroweak model. Such a model is found to reproduce the same low energy behavior as the top-condensate electroweak model, although in general it may have strong constraints upon its Higgs sector. Next he uncovers subtleties in the nonrelativistic quark model that drastically alter the picture of the physical origins of meson electromagnetic and hyperfine mass splittings; in particular, the explicit contributions due to (m{sub d}{minus}m{sub u}) and electrostatic potentials may be overwhelmed by other effects. Such novel effects are used to explain the anomalous pattern of mass splittings recently measured in bottom mesons. Finally, he considers the …

Theoretical electronic structure techniques are used to analyze widely different systems from Si clusters to transition metal solids and surfaces. For the Si clusters, first principles density functional methods are used to investigate Si{sub N} for N=2-8. Goal is to understand the different types of bonding that can occur in such small clusters where the atomic coordination differs substantially from tetrahedral bonding; such uncoordinated structures can test approximate models of Si surfaces. For the transition metal systems, non-self-consistent electronic structure methods are used to understand the driving force for surface relaxations. In-depth analysis of results is presented and physical basis of surface relaxation within the theory is discussed. Limitations inherent in calculations of metal surface relaxation are addressed. Finally, in an effort to understand approximate methods, a novel non-self- consistent density functional electronic structure method is developed that is about 1000 times faster than more sophisticated methods; this method is tested for various systems including diatomics, mixed clusters, surfaces, and bulk lattices.

The development of probability of detection (POD) models for a variety of nondestructive evaluation (NDE) methods is motivated by a desire to quantify the variability introduced during the process of testing. Sources of variability involved in eddy current methods of NDE include those caused by variations in liftoff, material properties, probe canting angle, scan format, surface roughness and measurement noise. This thesis presents a comprehensive POD model for eddy current NDE. Eddy current methods of nondestructive testing are used widely in industry to inspect a variety of nonferromagnetic and ferromagnetic materials. The development of a comprehensive POD model is therefore of significant importance. The model incorporates several sources of variability characterized by a multivariate Gaussian distribution and employs finite element analysis to predict the signal distribution. The method of mixtures is then used for estimating optimal threshold values. The research demonstrates the use of a finite element model within a probabilistic framework to the spread in the measured signal for eddy current nondestructive methods. Using the signal distributions for various flaw sizes the POD curves for varying defect parameters have been computed. In contrast to experimental POD models, the cost of generating such curves is very low and complex defect …

The perturbed particle transport coefficients were determined for a range of plasma conditions in the Alcator C tokamak, a component of the Microwave Tokamak Experiment (MTX), from analysis of density perturbations created in gas modulation experiments. Density measurements from a 15 chord far-infrared interferometer were sufficiently detailed to allow radial profiles of the transport coefficients to be resolved. Gas modulation experiments were carried out on plasmas over a range of relatively low currents and a wide variety of line-averaged densities, including values near the Greenwald density limit. With this technique the perturbed diffusion coefficient D and the perturbed convection velocity V can be determined simultaneously. Measured profiles of D rise toward the outside of the plasma column in a manner generally similar to those determined previously for {chi}{sub e,HP} from sawtooth heat pulse propagation. Values of D are typically smaller than those of {chi}{sub e,HP} given for the same line-averaged densities by a factor of 2-5. Diffusion coefficients from a series of discharges at constant current showed little variation with density through most of the saturated ohmic confinement regime. At the Greenwald density limit threshold a dramatic increase occurred in both the perturbed convective and diffusive transport coefficients in the …

The development of a versatile picosecond ultraviolet/vacuum ultraviolet temporal spectrometer and its potential use for measuring internal energy redistribution in isolated molecules are described in detail. A detailed description of the double-pass Nd:YAG amplifier and the dye amplifiers is given with the pulse energies achieved in the visible, ultraviolet, and vacuum ultraviolet. The amplified visible pulses are shown to be of sub-picosecond duration and near transform limited. The instrument`s temporal response ({le}10 ps) is derived from an instrument limited measurement of the dissociation lifetime of methyl iodide at 266 nm. The methyl iodide experiment is used to discuss the various sources of noise and background signals that are intrinsic to this type of experiment. Non-time-resolved experiments measuring the branching ratio and kinetic energy distributions of products from the 193 nm photodissociation of cyclopentadiene and thiophene are presented. These studies were done using the molecular beam Photofragment Translational Spectroscopy (PTS) technique. The results from the cyclopentadiene experiment confirm that H atom elimination to yield the cyclopentadienyl radical is the dominant dissociation channel. A barrier of {ge}5 kcal/mol can be understood in terms of the delocalization of the radical electron of the cyclopentadienyl fragment. A concerted elimination yielding cyclopropene and acetylene was …

The dynamics of several elementary chemical reactions that are important in atmospheric chemistry are investigated. The reactive scattering of ground state chlorine or bromine atoms with ozone molecules and ground state chlorine atoms with nitrogen dioxide molecules is studied using a crossed molecular beams apparatus with a rotatable mass spectrometer detector. The Cl + O{sub 3} {yields} ClO + O{sub 2} reaction has been studied at four collision energies ranging from 6 kcal/mole to 32 kcal/mole. The derived product center-of-mass angular and translational energy distributions show that the reaction has a direct reaction mechanism and that there is a strong repulsion on the exit channel. The ClO product is sideways and forward scattered with respect to the Cl atom, and the translational energy release is large. The Cl atom is most likely to attack the terminal oxygen atom of the ozone molecule. The Br + O{sub 3} {yields} ClO + O{sub 2} reaction has been studied at five collision energies ranging from 5 kcal/mole to 26 kcal/mole. The derived product center-of-mass angular and translational energy distributions are quite similar to those in the Cl + O{sub 3} reaction. The Br + O{sub 3} reaction has a direct reaction mechanism similar …

This thesis solves the problem of finding the optimal linear noise-reduction filter for linear tomographic image reconstruction. The optimization is data dependent and results in minimizing the mean-square error of the reconstructed image. The error is defined as the difference between the result and the best possible reconstruction. Applications for the optimal filter include reconstructions of positron emission tomographic (PET), X-ray computed tomographic, single-photon emission tomographic, and nuclear magnetic resonance imaging. Using high resolution PET as an example, the optimal filter is derived and presented for the convolution backprojection, Moore-Penrose pseudoinverse, and the natural-pixel basis set reconstruction methods. Simulations and experimental results are presented for the convolution backprojection method.

This thesis reports a study of the mechanism of electromigration failure in Al-2Cu-1Si thin-film conducting lines on Si. Samples were patterned from 0.5 {mu}m thick vapor-deposited films with various mean grain sizes (G), and had lines widths (W) of 1.3, 2, 4 and 6 {mu}m. The lines were aged at various conditions to change the Cu-precipitate distribution and were tested to failure at T = 225{degrees}C and j = 2.5 {times} 10{sup 6} A/cm{sup 2}. Some samples were tested over a range of substrate temperatures, current densities and current reversal times. Aging produces an initially dense distribution of metastable {Theta}{prime} (Al{sub 2}Cu; coherent) in the grain interiors, with stable {Theta} (Al{sub 2}Cu; incoherent) at the grain boundaries. The intragranular {theta}{prime} is gradually absorbed into the grain boundary precipitates. In the wide lines the mean time to failure increases slowly and monotonically with pre-aging time and current reversal time. The failure mode is the formation and coalescence of voids that form on grain boundaries with an apparent activation energy of 0.65 eV. In the narrow lines, the lines failed by a transgranular-slit mechanism with an activation energy near 0.93 eV. The distribution of the polygranular segments and the kinetics of failure …