A reproducible, high-yield synthesis of mono([8]annulene)uranium(4)dichloride (1) is reported, along with the X-ray crystal structural of the bis(pyridine) adduct. Metathesis reactions of the half-sandwich complex 1 with a variety of simple alkyl and alkoxy reagents failed to generate any isolable mono-ring complexes. Reactions of 1 with polydentate, delocalized anions did produce stable derivatives, including mono([8]annulene)uranium(4)bis(acetylacetonate) (4). An X-ray crystal structure of 4 is reported.

The electrochemistry of the heterobimetallic complexes (fulvalene)WFe(CO){sub 5} (30) and (fulvalene)WRu(CO){sub 5} (31) has been investigated. Compound 30 is reduced in two one-electron processes, and this behavior was exploited synthetically to prepare a tetranuclear dimer by selective metal reduction. Complex 31 displayed a distinction between the metals upon reoxidation of the dianion, allowing the formation of a dimer by selective metal anion oxidation. The redox behavior of 30 led to an investigation of the use of electrocatalysis to effect metal-specific ligand substitution. It was found that reduction of 30 with a catalytic amount of CpFe(C{sub 6}Me{sub 6}) (97) in the presence of excess P(OMe){sub 3} or PMe{sub 3} led to the formation of the zwitterions (fulvalene)[W(CO){sub 3}{sup {minus}}][Fe(CO)PR{sub 3}{sup +}] (107, R = P(OMe){sub 3}; 108, R = PMe{sub 3}). Compound 31 also displayed unique behavior with different reducing agents, as the monosubstituted zwitterion (fulvalene)[W(CO){sub 3}{sup {minus}}][Ru(CO){sub 2}(PMe{sub 3}){sup +}] was obtained when 97 was used while the disubstituted complex (fulvalene) [W(CO){sub 3}{sup {minus}}] [Ru(CO)(PMe{sub 3}){sub 2}{sup +}] was produced when Cp*Fe(C{sub 6}Me{sub 6}) was the catalyst. Potential synthetic routes to quatercyclopentadienyl complexes were also explored. Various attempts to couple heterobimetallic fulvalene compounds proved to be unsuccessful. 138 refs.

Time variability analyses have been applied to data composed of event times of X-rays emitted from the binary system Cygnus X-1 to search for unique black hole signatures. The X-ray data analyzed was collected at ten microsecond time resolution or better from two instruments, the High Energy Astrophysical Observatory (HEAO) A-1 detector and the Rossi X-ray Timing Explorer (XTE) Proportional Counter Array (PCA). HEAO A-1 and RXTE/PCA collected data from 1977--79 and from 1996 on with energy sensitivity from 1--25 keV and 2--60 keV, respectively. Variability characteristics predicted by various models of an accretion disk around a black hole have been searched for in the data. Drop-offs or quasi-periodic oscillations (QPOs) in the Fourier power spectra are expected from some of these models. The Fourier spectral technique was applied to the HEAO A-1 and RXTE/PCA data with careful consideration given for correcting the Poisson noise floor for instrumental effects. Evidence for a drop-off may be interpreted from the faster fall off in variability at frequencies greater than the observed breaks. Both breaks occur within the range of Keplerian frequencies associated with the inner edge radii of advection-dominated accretion disks predicted for Cyg X-1. The break between 10--20 Hz is also …

We have improved and extended a novel ac calorimetric technique for measuring the heat capacity of adsorbates on evaporated metal films. Metallic substrates are of particular interest in current studies of the thermodynamics of adsorbed molecules. The method described in the present work is only calorimetric technique which allows measurements of molecules on simple metallic surfaces. Among other improvements, we have achieved significant progress in the preparation and characterization of the evaporated metal film. We have applied this novel technique to a study of hydrogen multilayers on gold and sapphire substrates. We have shown that samples of normal-hydrogen with a nominal coverage n of approximately 25 monolayers (ML) undergo a bulk-like orientational ordering transition. The transition is suppressed as the coverage is decreased, and no sign of the transition remains above 1.6 K for n {approx} 1 ML. For n {approx_lt} 8 ML, the peak in the heat capacity exhibits signs of finite-size effects. At higher coverages, finite-size effects are not observed, and the shape of the peak depends strongly on the substrate. We conclude that the peak is inhomogeneously broadened for n {approx_lt} 8 ML. This work represents the first measurements of the heat capacity due to orientational ordering …

Experimentation validated a simple moisture conditioning scheme to prepare Gr/Ep composite parts for precision applications by measuring dimensional changes over 90 days. It was shown that an elevated temperature moisture conditioning scheme produced a dimensionally stable part from which precision structures could be built/machined without significant moisture induced dimensional changes after fabrication. Conversely, that unconditioned Gr/Ep composite panels exhibited unacceptably large dimensional changes (i.e., greater than 125 ppM). It was also shown that time required to produce stable parts was shorter, by more than an order of magnitude, employing the conditioning scheme than using no conditioning scheme (46 days versus 1000+ days). Two final use environments were chosen for the experiments: 50% RH/21C and 0% RH/21C. Fiberite 3034K was chosen for its widespread use in aerospace applications. Two typical lay-ups were chosen, one with low sensitivity to hygrothermal distortions and the other high sensitivity: [0, {plus_minus} 45, 90]s, [0, {plus_minus} 15, 0]s. By employing an elevated temperature, constant humidity conditioning scheme, test panels achieved an equilibrium moisture content in less time, by more than an order of magnitude, than panels exposed to the same humidity environment and ambient temperature. Dimensional changes, over 90 days, were up to 4 times lower …

We present data from our study of a device known as the inverse free electron laser. First, numerical simulations were performed to optimize the design parameters for an experiment that accelerates electrons in the presence of an undulator by stimulated absorption of radiation. The Columbia free electron laser (FEL) was configured as an auto-accelerator (IFELA) system; high power (MW`s) FEL radiation at {approximately}1.65 mm is developed along the first section of an undulator inside a quasi-optical resonator. The electron beam then traverses a second section of undulator where a fraction of the electrons is accelerated by stimulated absorption of the 1.65 mm wavelength power developed in the first undulator section. The second undulator section has very low gain and does not generate power on its own. We have found that as much as 60% of the power generated in the first section can be absorbed in the second section, providing that the initial electron energy is chosen correctly with respect to the parameters chosen for the first and second undulators. An electron momentum spectrometer is used to monitor the distribution of electron energies as the electrons exit the IFELA. We have found; using our experimental parameters, that roughly 10% of …

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The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO{sub 2}{sup +}) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO{sub 2}{sup +}; therefore, cation-cation complexes indicate something unique about AnO{sub 2}{sup +} cations compared to actinide cations in general. The first cation-cation complex, NpO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO{sub 2}{sup +} species, the cation-cation complexes of NpO{sub 2}{sup +} have been studied most extensively while the other actinides have not. The only PuO{sub 2}{sup +} cation-cation complexes that have been studied are with Fe{sup 3+} and Cr{sup 3+} and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, NpO{sub 2}{sup +}{center_dot}Th{sup 4+}, PuO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, …

This thesis describes a new method for the numerical solution of partial differential equations of the parabolic type on an adaptively refined mesh in two or more spatial dimensions. The method is motivated and developed in the context of the level set formulation for the curvature dependent propagation of surfaces in three dimensions. In that setting, it realizes the multiple advantages of decreased computational effort, localized accuracy enhancement, and compatibility with problems containing a range of length scales.

The syntheses of silicon-containing compounds and the studies of their rearrangements have been active research areas in the Barton research group. Previously, the addition of disilanes to acetylenes was studied in the group and an intramolecular 2S + 2A mechanism has been proposed. In this thesis, the work is focused on the addition of disilanes to cumulenes. The syntheses of the precursors are discussed and the possible mechanisms for their thermal, photochemical and catalytic rearrangements are proposed. Conjugated organic polymers have been studied in the group since 1985 because of their potential for exhibiting high electroconductivity, photoconductivity, strong non-linear optical response and intense fluorescence. In the second section of this dissertation, the synthesis and property studies of poly(phenylene vinylene) analogues are discussed.

This research has shown that epilayers with residual impurity concentrations of 5 x 10{sup 13} cm{sup {minus}3} can be grown by producing the purest Pb available in the world. These epilayers have extremely low minority acceptor concentrations, which is ideal for fabrication of IR absorbing layers. The Pb LPE growth of Ge also has the advantageous property of gettering Cu from the epilayer and the substrate. Epilayers have been grown with intentional Sb doping for IR absorption on lightly doped substrates. This research has proven that properly working Ge BIB detectors can be fabricated from the liquid phase as long as pure enough solvents are available. The detectors have responded at proper wavelengths when reversed biased even though the response did not quite reach minimum wavenumbers. Optimization of the Sb doping concentration should further decrease the photoionization energy of these detectors. Ge BIB detectors have been fabricated that respond to 60 cm{sup {minus}1} with low responsivity. Through reduction of the minority residual impurities, detector performance has reached responsivities of 1 A/W. These detectors have exhibited quantum efficiency and NEP values that rival conventional photoconductors and are expected to provide a much more sensitive tool for new scientific discoveries in a …

This has application to astronomy and astrophysics. Selenium in Ge has been studied with a doping technique which limits complex formation. Only one ionization level has been found to correspond to selenium, which presumably occupies a substitutional site. This level is extremely unstable and its concentration decreases after annealing at 400C. Future work is planned to anneal the fast neutron damage before much selenium has formed in the {sup 74/76}Ge samples. It is expected that the observed selenium level can be better characterized and the missing selenium level is more likely to be discovered if other defects are removed before {sup 77}Se formation.

This dissertation describes nuclear magnetic resonance experiments and theory which have been developed to study quadrupolar nuclei (those nuclei with spin greater than one-half) in the solid state. Primarily, the technique of dynamic-angle spinning (DAS) is extensively reviewed and expanded upon in this thesis. Specifically, the improvement in both the resolution (two-dimensional pure-absorptive phase methods and DAS angle choice) and sensitivity (pulse-sequence development), along with effective spinning speed enhancement (again through choice of DAS conditions or alternative multiple pulse schemes) of dynamic-angle spinning experiment was realized with both theory and experimental examples. The application of DAS to new types of nuclei (specifically the {sup 87}Rb and {sup 85}Rb nuclear spins) and materials (specifically amorphous solids) has also greatly expanded the possibilities of the use of DAS to study a larger range of materials. This dissertation is meant to demonstrate both recent advances and applications of the DAS technique, and by no means represents a comprehensive study of any particular chemical problem.

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This study investigates effects of aging in air and argon at 170 C on Cu coupons which were pretinned with 75Sn-25Pb, 8Sn-92Pb, and 5Sn-95Pb solders. Coatings were applied using electroplating or hot dipping techniques. The coating thickness was controlled between 3 to 3{mu}m and the specimens were aged for 0 hours, 2 hours, 24 hours and 2 weeks. Wetting balance tests were used to evaluate the wettability of the test specimens. Microstructural development was evaluated using X-ray diffraction, energy dispersive X-ray and Auger spectroscopy, as well as optical and scanning electron microscopy. The wetting behavior of the test specimens is interpreted with respect to observed microstructural changes and as a function of aging time, solder composition, and processing conditions.

This dissertation derives a new method for estimating current source amplitudes in the brain and heart from external magnetic field measurements and prior knowledge about the probable source positions and amplitudes. The minimum mean square error estimator for the linear inverse problem with statistical prior information was derived and is called the optimal constrained linear inverse method (OCLIM). OCLIM includes as special cases the Shim-Cho weighted pseudoinverse and Wiener estimators but allows more general priors and thus reduces the reconstruction error. Efficient algorithms were developed to compute the OCLIM estimate for instantaneous or time series data. The method was tested in a simulated neuromagnetic imaging problem with five simultaneously active sources on a grid of 387 possible source locations; all five sources were resolved, even though the true sources were not exactly at the modeled source positions and the true source statistics differed from the assumed statistics.

The {alpha}-induced thick-target {gamma}-ray yield from light elements has been measured in the energy range 5.6 MeV {le} E{sub {alpha}} {le} 10 MeV. The {gamma}-ray yield for > 2.1 MeV from thick targets of beryllium, boron nitride, sodium fluoride, magnesium, aluminum and silicon were measured using the {alpha}-particle beam from the Lawrence Berkeley Laboratories 88 in. cyclotron. The elemental yields from this experiment were used to construct the {alpha}-induced direct production {gamma}-ray spectrum from materials in the SNO detector, a large volume ultra-low background neutrino detector located in the Creighton mine near Sudbury, Canada. This background source was an order of magnitude lower than predicted by previous calculations. These measurements are in good agreement with theoretical calculations of this spectrum based on a statistical nuclear model of the reaction, with the gross high energy spectrum structure being reproduced to within a factor of two. Detailed comparison of experimental and theoretical excitation population distribution of several residual nuclei indicate the same level of agreement within experimental uncertainties.

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.

Using the 5.8 {times} 10{sup 6} J/{psi} events collected by the MARK 3 experiment on the SPEAR e{sup +}e{sup {minus}} storage ring at SLAC, a mass independent amplitude analysis of the J/{psi} {yields} {gamma} K{sub s}K{sub s} and J/{psi} {yields} K{sup +}K{sup {minus}} decays is presented. For K{bar K} systems having mass less than 2 GeV/c{sup 2}, the efficiency-corrected spherical harmonic moments of the J/{psi} joint decay angular distribution are measured. Fits are then performed in each independent mass interval in order to extract the underlying helicity amplitude structure; amplitudes describing K{bar K} systems of spin zero and spin two are included simultaneously. For the first time, a large spin zero component in the {theta}(1720) mass region is observed; consistent results are obtained for the data samples corresponding to the individual decay modes. This structure is attributed to the production of an S wave resonance, the f{sub 0}(1710), of mass and width M = 1710 {plus_minus} 10 MeV/c{sup 2}, {Gamma} = 186 {plus_minus} 30 MeV/c{sup 2}, respectively, with branching fraction Bf(J/{psi} {yields} {gamma}f{sub 0}, f{sub 0} {yields} K{bar K}) = (6.47 {plus_minus} 1.14 {plus_minus} 0.84) {times} 10{sup {minus}4}. A small amount ({approximately}24%) of spin two component in this mass region …

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.

The focus of this dissertation is the use of chromatographic methods coupled with electrospray mass spectrometry (ES-MS) for the determination of both organic and inorganic compounds in aqueous solutions. The combination of liquid chromatography (LC) methods and ES-MS offers one of the foremost methods for determining compounds in complex aqueous solutions. In this work, LC-ES-MS methods are devised using ion exclusion chromatography, reversed phase chromatography, and ion exchange chromatography, as well as capillary electrophoresis (CE). For an aqueous sample, these LC-ES-MS and CE-ES-MS techniques require no sample preparation or analyte derivatization, which makes it possible to observe a wide variety of analytes as they exist in solution. The majority of this work focuses on the use of LC-ES-MS for the determination of unknown products and intermediates formed during electrochemical incineration (ECI), an experimental waste remediation process. This report contains a general introduction to the project and the general conclusions. Four chapters have been removed for separate processing. Titles are: Chapter 2: Determination of small carboxylic acids by ion exclusion chromatography with electrospray mass spectrometry; Chapter 3: Electrochemical incineration of benzoquinone in aqueous media using a quaternary metal oxide electrode in the absence of a soluble supporting electrolyte; Chapter 4: The …

The behavior of two structural clay tile infilled frames subjected to dynamic loading is investigated. The testing was performed by USACERL using a biaxial shake table machine on which two framed infills were spaced nine feet apart and connected by steel trusses and an eight inch concrete roof slab. The infills were composed of structural clay tile block which were laid with the cores horizontal. The specimen was loaded in both the out-of-plane and in-plane directions using a site specific time history record. The testing focused on determining frame and panel load-deflection behavior, acceleration amplification, and frequency degradation characteristics. The out-of-plane tests resulted in little degradation of frequency which means there was little loss of stiffness. There was no evidence of the infill {open_quotes}walking-out{close_quotes} of the steel frame; in fact the infill still had substantial stability after completion of the out-of-plane tests. As a result of the gradual increase in ground motion in the in-plane testing, the stiffness of the specimen gradually decreased. Strength and stiffness characteristics obtained from the dynamic testing were comparable to results and behavior seen in static tests. Degradation in the panel was much more rapid under the stronger ground motions which were produced during the …

The availability of high resolution digital images of borehole walls using the Borehole Scanner System has made it possible to develop new methods of in-situ rock characterization. This thesis addresses particularly new approaches to the characterization of in-situ joint strength arising from surface roughness. An image processing technique is used to extract the roughness profile from joints in the unrolled image of the borehole wall. A method for estimating in-situ Rengers envelopes using this data is presented along with results from using the method on joints in a borehole in porphyritic granite. Next, an analysis of the joint dilation angle anisotropy is described and applied to the porphyritic granite joints. The results indicate that the dilation angle of the joints studied are anisotropic at small scales and tend to reflect joint waviness as scale increases. A procedure to unroll the opposing roughness profiles to obtain a two dimensional sample is presented. The measurement of apertures during this process is shown to produce an error which increases with the dip of the joint. The two dimensional sample of opposing profiles is used in a new kinematic analysis of the joint shear stress-shear deformation behavior. Examples of applying these methods on the …

An analysis is presented of events with a single jet and significant missing transverse energy selected from 4.7 pb{sup {minus}1} of data collected at the Fermilab Tevatron with the CDF detector. The goal is to identify events of the type p{bar p} {yields} Z{sup 0} + jet; Z{sup 0} {yields} {nu}{bar {nu}}. Event selection and backgrounds are discussed. The number of observed monojet events is compared to the number of observed Z{sup 0} {yields} e{sup +}{sup {minus}} events in which the Z{sup 0} is accompanied by a jet. We measure the number of light neutrino species to be N{sub {nu}} = 2.2{plus_minus}1.5 and we place an upper limit on the number of neutrino species at N{sub {nu}} < 5 (90% C.L.).