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.

Bacteria induce the precipitation of calcium carbonate in the laboratory and in nature by altering their chemical environment. Geologists are recognizing the possibility that bacterially induced precipitates may form significant mineral deposits, unfortunately, there are currently no sound criteria by which they can be recognized in recent sediments, or in the rock record. Cultures of aerobic and facultative bacteria from cyanobacterial mats on Andros Island, Bahamas, and Baffin Bay, Texas, induced the precipitation of calcium carbonate under controlled conditions. Crusts, the largest features formed, are composed of 5--200{mu}m diameter bundles which are, in turn, composed of numerous individual crystals. The smallest observed features are 0.1--0.4{mu}m spheres and rods which comprise some individual crystals and crystal bundles. Crystal bundles resembling rhombohedra, tetragonal disphenoids, tetragonal dipyramids, and calcite dumbbells appear to be uniquely bacterial in origin, and they have all been observed in recent sediments. Swollen rods, discs, curved dumbbells, and 50--200{mu}m optically continuous crystals resembling brushes may be uniquely bacterial in origin, however, they have not been reported by other laboratories nor observed in natural settings. Presence of any of these forms in recent sediments should be taken as strong evidence for bacterial influence. Spheres and aragonite dumbbells have also been …

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 …

We present {tau}{sup {minus}} lepton branching fraction measurements based on data from the TPC/Two-Gamma detector at PEP. Using a sample of{tau}{sup {minus}} {yields} {nu}{sub {tau}}K{sup {minus}}{pi}{sup +}{pi}{sup {minus}} events, we examine the resonance structure of the K{sup {minus}}{pi}{sup +}{pi}{sup {minus}} system and obtain the first measurements of branching fractions for {tau}{sup {minus}} {yields} {nu}{sub {tau}}K{sub 1}{sup {minus}}(1270) and {tau}{sup {minus}} {yields} {nu}{sub {tau}}K{sub 1}{sup {minus}}(1400). We also describe a complete set of branching fraction measurements in which all the decays of the {tau}{sup {minus}} lepton are separated into classes defined by the identities of the charged particles and an estimate of the number of neutrals. This is the first such global measurement with decay classes defined by the four possible charged particle species, e, {mu}, {pi}, and K.

Photoemission intensities from the molecular orbitals of c(2x2)CO/Pt(111) over a wide photon energy range were measured and analyzed by the same methods developed for structural studies using core levels. The 4{sigma} orbital center of gravity is found to be concentrated between the C and O atoms, while that of the 5{sigma} orbital lies between the C atom and the Pt surface. The C 1s photoelectron diffraction was used to determine the adsorption geometry. The earlier ambiguity that multiple scattering is needed to correctly model a {chi} curve while single scattering is sufficient for understanding major peaks in the ARPEFS-FTS is clarified by studying the clean Ni(111) surface. In the normal emission case, several different combinations of scattering events have similar path length differences (PLDs), and can either cancel each other or enhance the corresponding FT peak. In the off-normal case the degeneracy is greatly reduced due to the lower degree of symmetry. In normal emission AR PEFS, up to third order multiple scattering is needed to describe fully both the {chi} curve and its FT spectrum. To improve the spectral resolution in the ARPEFS-FT analysis, several new spectral analysis methods are introduced. With both autocorrelation autoregression (ACAR) and autocorrelation eigenvector …

This dissertation describes recent developments in solid state nuclear magnetic resonance (NMR), for the most part involving the use of dynamic-angle spinning (DAS) NMR to study quadrupolar nuclei. Chapter 1 introduces some of the basic concepts and theory that will be referred to in later chapters, such as the density operator, product operators, rotations, coherence transfer pathways, phase cycling, and the various nuclear spin interactions, including the quadrupolar interaction. Chapter 2 describes the theory behind motional averaging experiments, including DAS, which is a technique where a sample is spun sequentially about two axis oriented at different angles with respect to the external magnetic field such that the chemical shift and quadrupolar anisotropy are averaged to zero. Work done on various rubidium-87 salts is presented as a demonstration of DAS. Chapter 3 explains how to remove sidebands from DAS and magic-angle spinning (MAS) experiments, which result from the time-dependence of the Hamiltonian under sample spinning conditions, using rotor-synchronized {pi}-pulses. Data from these experiments, known as DAH-180 and MAH-180, respectively, are presented for both rubidium and lead salts. In addition, the applicability of this technique to double rotation (DOR) experiments is discussed. Chapter 4 concerns the addition of cross-polarization to DAS (CPDAS). …

The chemical-properties of rutherfordium (Rf) and its group 4 homologs were studied by sorption on glass support surfaces coated with cobalt(II)ferrocyanide and by solvent extraction with tributylphosphate (TBP) and triisooctylamine (TIOA). The surface studies showed that the hydrolysis trend in the group 4 elements and the pseudogroup 4 element, lb, decreases in the order Rf>Zr{approx}Hf>Th. This trend was attributed to relativistic effects which predicted that Rf would be more prone to having a coordination number of 6 than 8 in most aqueous solutions due to a destabilization of the 6d{sub 5/2} shell and a stabilization of the 7p{sub l/2} shell. This hydrolysis trend was confirmed in the TBP/HBr solvent extraction studies which showed that the extraction trend decreased in the order Zr>Hf>Rf?Ti for HBr, showing that Rf and Ti did not extract as well because they hydrolyzed more easily than Zr and Hf. The TIOA/HF solvent extraction studies showed that the extraction trend for the group 4 elements decreased in the order Ti>Zr{approx}Hf>Rf, in inverse order from the trend of ionic radii Rf>Zr{approx}Hf>Ti. An attempt was made to produce {sup 263}Rf (a) via the {sup 248}Cm({sup 22}Ne, {alpha}3n) reaction employing thenoyltrifluoroacetone (TTA) solvent extraction chemistry and (b) via the {sup …

This report discusses the following topics: Circular magnetic x-ray dichroism at the ER L{sub 3} Edge; angular dependence of circular magnetic x-ray dichroism in rare earth compounds: and circular magnetic x-ray dichroism in crystalline and amorphous GDFE{sub 2}.

Radioactive metal waste makes up a significant portion of the waste currently being sent for disposal. Recovery of this metal as a valuable resource is possible through the use of decontamination technologies. Through the development and use of expert systems a comparison can be made of laser decontamination, a technology currently under development at Ames Laboratory, with currently available decontamination technologies for applicability to the types of metal waste being generated and the effectiveness of these versus simply disposing of the waste. These technologies can be technically and economically evaluated by the use of expert systems techniques to provide a waste management decision making tool that generates, given an identified metal waste, waste management recommendations. The user enters waste characteristic information as input and the system then recommends decontamination technologies, determines residual contamination levels and possible waste management strategies, carries out a cost analysis and then ranks, according to cost, the possibilities for management of the waste. The expert system was developed using information from literature and personnel experienced in the use of decontamination technologies and requires validation by human experts and assignment of confidence factors to the knowledge represented within.