Chemical properties of rutherfordium (Rf) have been investigated with the organic ligands triisooctylamine (TIOA), tributylphosphate (TBP), and thenoyltrifluoroacetone (TTA). The TIOA studies showed that Rf behaves differently than Th and Eu and most similarly to Zr, only Zr and Rf extract from 12 M HCI. This result is further evidence that Rf is a Group 4 element. Studies with TBP showed that Rf chemical behavior differed from the other Group 4 elements. The extraction by TBP at different chloride concentrations showed that Rf at times behaves more like Pu{sup 4+} than Zr or Hf. At high chloride concentrations, Rf and Pu extraction decreased. Under the same conditions, Zr, Hf and Th extraction increased. In addition, Rf extraction by TBP was affected by hydrogen ion concentration, while Zr and Hf extraction was not. TTA extractions were used to determine the K{sub eq}, K{sub hyd}, and the ionic radius of Rf. The of K{sub eq} for Rf with TTA was calculated to be 3.18 {plus minus} 0.90. The first four log K{sub hyd's} for Rf are calculated to be {minus}2.6 {plus minus} 0.7, {minus}5.9 {plus minus} 1.7, {minus}10.2 {plus minus} 2.9, and {minus}14.5 {plus minus} 4.1. These hydrolysis constants indicate that Rf …

In the past multiple-quantum filtered imaging of biexponential relaxation sodium-23 nuclei in the human brain has been limited by low signal to noise ratios; this thesis demonstrates that such imaging is feasible when using a modified gradient-selected triple-quantum filter at a repetition time which maximizes the signal to noise ratio. Nuclear magnetic resonance imaging of biexponential relaxation sodium-23 ({sup 23}Na) nuclei in the human brain may be useful for detecting ischemia, cancer, and pathophysiology related to manic-depression. Conventional single-quantum NMR imaging of in vivo biexponential relaxation {sup 23}Na signals is complicated by the presence of single-exponential relaxation {sup 23}Na signals. Multiple-quantum filters may be used to selectively image biexponential relaxation {sup 23}Na signals since these filters suppress single-exponential relaxation {sup 23}Na signals. In this thesis, the typical repetition times (200--300 ms) used for in vivo multiple-quantum filtered {sup 23}Na experiments are shown to be approximately 5 times greater than the optimal repetition time which maximizes multiple-quantum filtered SNR. Calculations and experimental verification show that the gradient-selected triple-quantum (GS3Q) filtered SNR for {sup 23}Na in a 4% agarose gel increases by a factor of two as the repetition time decreases from 300 ms to 55 ms. The measured relaxation times of …

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 …

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.

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) …

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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 …

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 …

To enhance quality, an independent verification and validation (IV&V) review is conducted as software requirements are defined. Requirements are inspected for consistency and completeness. IV&V strives to detect defects early in the software development life cycle and to prevent problems before they occur. The IV&V review process of a massive software requirements specification, the Reserve Component Automation System (RCAS) Functional Description (FD) is explored. Analysis of the RCAS FD error history determined that there are no predictors of errors. The size of the FD mandates electronic analysis of the databases. Software which successfully performs automated consistency and completeness checks is discussed. The process of verifying the quality of analysis software is described. The use of intuitive ad hoc techniques, in addition to the automatic analysis of the databases, is required because of the varying content of the requirements databases. The ad hoc investigation process is discussed. Case studies are provided to illustrate how the process works. This thesis demonstrates that it is possible to perform an IV&V review on a massive software requirements specification. Automatic analysis enables inspecting for completeness and consistency. The work with the RCAS FD clearly indicates that the IV&V review process is not static; it must …

The first part of this thesis presents a first-order pseudopotential calculation at T=O of the total energy of small sodium clusters of size N<800. The calculation is based on a local-pseudopotential scheme and local-density correlation and exchange. A temperature-size (T-N) phase-diagram is then derived using the T=O results and Lindemann`s criterion for melting. The phase-diagram contains three regions of stability: (1) a liquid (jellium) phase at temperatures above the melting line T{sub M}(N) where cluster-stability occurs at electronic magic numbers: (2) a phase related to complete geometrical shells of body-centered-cubic structure at temperatures below the melting line; and (3) a close-packed structure at very low temperatures and sufficiently large N. The melting line drops to T{sub M}(N)=O for N<65, where electronic magic numbers are stable even at T=O. The phase diagram reduces asymptotically to the known phases of sodium as N{yields}{infinity}, including the known martensitic transformation at T{approximately}5 K. The second and the last part of this thesis consists of a study of small-cluster many-body systems by means of an on-site ``local`` chemical potential which allows the continuous variation of local electron-density. This method yields a criterion to distinguish particular features of a small cluster that are likely to survive …

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 …

We have utilized a combination of photochemical cross-linking techniques and site-directed mutagenesis to obtain secondary and tertiary structure information for the self-cleaving, self-ligating subsequence of RNA from the negative strand of Satellite Tobacco Ringspot Virus. We have found that the helical regions fold about a hinge to promoting four different possible tertiary interactions, creating a molecular of similar shape to a paperclip. A model suggesting that the ``paperclip`` and ``hammerhead`` RNAs share a similar three dimensional structure is proposed. We have used a self-cleaving RNA molecule related to a subsequence of plant viroids, a ``hammerhead,`` to study the length-dependent folding of RNA produced during transcription by RNA polymerase. We have used this method to determine the length of RNA sequestered within elongating E. coli and T7 RNA polymerase complexes. The data show that for E. coli RNA polymerase 12{plus_minus}1 nucleotides are sequestered within the ternary complex, which is consistent with the presence of an RNA-DNA hybrid within the transcription bubble, as proposed by others. The result for T7 RNA polymerase differs from E. coli RNA polymerase, with only 10{plus_minus}1 nucleotides sequestered within the ternary complex, setting a new upper limit for the minimum RNA-DNA required for a stable elongating complex. …

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 …

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.

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.

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.

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 …

This thesis details the first direct ultrafast measurements of the dynamic thermal expansion of a surface and the temperature dependent surface thermal diffusivity using a two-color reflection transient grating technique. Studies were performed on p-type, n-type, and undoped GaAs(100) samples over a wide range of temperatures. By utilizing a 90 fs ultraviolet probe with visible excitation beams, the effects of interband saturation and carrier dynamics become negligible; thus lattice expansion due to heating and subsequent contraction caused by cooling provided the dominant influence on the probe. At room temperature a rise due to thermal expansion was observed, corresponding to a maximum net displacement of {approximately} 1 {Angstrom} at 32 ps. The diffracted signal was composed of two components, thermal expansion of the surface and heat flow away from the surface, thus allowing a determination of the rate of expansion as well as the surface thermal diffusivity, D{sub S}. By varying the fringe spacing of the grating, this technique has the potential to separate the signal contributions to the expansion of the lattice in the perpendicular and parallel directions. In the data presented here a large fringe spacing was used, thus the dominant contribution to the rising edge of the signal …

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 …

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 …

Compounds (RC{sub 5}H{sub 4}){sub 3}U(t-Bu) were prepared for R = H, Me, Et. Their decomposition products in aromatic solvents are consistent with a radical decomposition pathway induced by solvent-assisted U-C bond homolysis. NMR was used to study the reactions of (RC{sub 5}H{sub 4}){sub 3}UCl with t-BuLi (R = t-Bu, Me{sub 3}Si). Reactions of (MeC{sub 5}H{sub 4}){sub 3}U(t-Bu) with Lewis bases and fluorocarbons were studied. Analogous reaction chemistry between (RC{sub 5}H{sub 4}){sub 3}ThX systems and t-BuLi was also studied, and reactivity differences between U and Th are discussed. Synthesis of sterically crowded (RC{sub 5}H{sub 4}){sub 4}U compounds is next considered. Reaction of the trivalent (RC{sub 5}H{sub 4}){sub 3}U with (RC{sub 5}H{sub 4}){sub 2}Hg results in formation of (RC{sub 5}H{sub 4}){sub 4}U. Steric congestion, cyclopentadienyl ligand exchange, and electron transfer are discussed. (DLC)

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 …

Angle-resolved two-photon laser photoemission was used to observe the image potential electronic states on the (111) face of a silver single crystal. The transient image potential states were excited from the occupied bulk bands with photons whose energy was tunable around 4 eV. Photoemission of the image potential states was accomplished with photons of energy tunable around 2 eV. Image potential states were found to persist in the presence of physisorbed adlayers of xenon and cyclohexane. On clean Ag(111), the effective mass of the n=1 image potential state was found to be 1.4{plus_minus}0.1 times the mass of a free electron (m{sub e}). A binding energy of 0.77 eV, measured by earlier workers, was assumed in analysis of the data for the clean surface. On Ag(111), at 75 K covered by one monolayer of xenon, the binding energy of the n=1 image potential state was unchanged relative to its value on the clean surface. An effective mass of (1.00{plus_minus}0.05) {center_dot} m{sub e} was obtained. On Ag(111) at 167 K, covered by one monolayer of cyclohexane, the binding energy of the n=2 member of the image potential series was 0.30{plus_minus}0.05 eV. The energy of the n=1 state was again unchanged by deposition …

Chemical properties of rutherfordium (Rf) have been investigated with the organic ligands triisooctylamine (TIOA), tributylphosphate (TBP), and thenoyltrifluoroacetone (TTA). The TIOA studies showed that Rf behaves differently than Th and Eu and most similarly to Zr, only Zr and Rf extract from 12 M HCI. This result is further evidence that Rf is a Group 4 element. Studies with TBP showed that Rf chemical behavior differed from the other Group 4 elements. The extraction by TBP at different chloride concentrations showed that Rf at times behaves more like Pu{sup 4+} than Zr or Hf. At high chloride concentrations, Rf and Pu extraction decreased. Under the same conditions, Zr, Hf and Th extraction increased. In addition, Rf extraction by TBP was affected by hydrogen ion concentration, while Zr and Hf extraction was not. TTA extractions were used to determine the K{sub eq}, K{sub hyd}, and the ionic radius of Rf. The of K{sub eq} for Rf with TTA was calculated to be 3.18 {plus_minus} 0.90. The first four log K{sub hyd`s} for Rf are calculated to be {minus}2.6 {plus_minus} 0.7, {minus}5.9 {plus_minus} 1.7, {minus}10.2 {plus_minus} 2.9, and {minus}14.5 {plus_minus} 4.1. These hydrolysis constants indicate that Rf will not hydrolyze at conditions …