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.

Research in the area of advanced batteries for electric-vehicle applications has increased steadily since the 1990 zero-emission-vehicle mandate of the California Air Resources Board. Due to their design flexibility and potentially high energy and power densities, lithium/polymer batteries are an emerging technology for electric-vehicle applications. Thermal modeling of lithium/polymer batteries is particularly important because the transport properties of the system depend exponentially on temperature. Two models have been presented for assessment of the thermal behavior of lithium/polymer batteries. The one-cell model predicts the cell potential, the concentration profiles, and the heat-generation rate during discharge. The cell-stack model predicts temperature profiles and heat transfer limitations of the battery. Due to the variation of ionic conductivity and salt diffusion coefficient with temperature, the performance of the lithium/polymer battery is greatly affected by temperature. Because of this variation, it is important to optimize the cell operating temperature and design a thermal management system for the battery. Since the thermal conductivity of the polymer electrolyte is very low, heat is not easily conducted in the direction perpendicular to cell layers. Temperature profiles in the cells are not as significant as expected because heat-generation rates in warmer areas of the cell stack are lower than …

Forest succession models and correlative models have predicted 200--650 kilometer shifts in the geographic range of temperate forests and forest species as one response to global climate change. Few studies have investigated whether population differences may effect the response of forest species to climate change. This study examines differences in tree-ring growth, and in the phenotypic plasticity of tree-ring growth in 16-year old white fir, Abies concolor, from ten populations grown in four common gardens in the Sierra Nevada of California. For each population, tree-ring growth was modelled as a function of precipitation and degree-day sums. Tree-ring growth under three scenarios of doubled C0{sub 2} climates was estimated.

In this study, the author examined the effect of grazing on phosphorus cycling in stream periphyton and leaf detritus communities using the snail Elimia clavaeformis. Phosphorus cycling fluxes and turnover rates were measured in a laboratory and in a natural stream, respectively, using radioactive tracer techniques.

Isotopically enriched {sup 70}Ge and {sup 74}Ge single crystals were successfully gown by a newly developed vertical Bridgman method. The system allows us to reliably grow high purity Ge single crystals of approximately 1 cm{sup 3} volume. To our knowledge, we have grown the first {sup 70}Ge single crystal. The electrically active chemical impurity concentration for both crystals was found to be {approximately}2 {times} cm{sup {minus}3} which is two order of magnitude better that of {sup 74}Ge crystals previously grown by two different groups. Isotopic enrichment of the {sup 70}Ge and the {sup 74}Ge crystals is 96.3% and 96.8%, respectively. The residual chemical impurities present in both crystals were identified as phosphorus, copper, aluminum, and indium. A wide variety of experiments which take advantage of the isotopic purity of our crystals are discussed.

Analysis of the literature indicated that radon transport models significantly and consistently underpredict the advective entry into houses of soil-gas borne radon. Advective entry is the dominant mechanism resulting in high concentrations of radon indoors. The author investigated the source of the model-measurement discrepancy via carefully controlled field experiments conducted at an experimental basement located in natural soil in Ben Lomond, California. Early experiments at the structure confirmed the existence and magnitude of the model-measurement discrepancy, ensuring that it was not merely an artifact of inherently complex and poorly understood field sites. The measured soil-gas entry rate during structure depressurization was found to be an order of magnitude larger than predicted by a current three-dimensional numerical model of radon transport. The exact magnitude of the discrepancy depends on whether the arithmetic or geometric mean of the small-scale measurements of permeability is used to estimate the effective permeability of the soil. This factor is a critical empirical input to the model and was determined for the Ben Lomond site in the typical fashion using single-probe static depressurization measurements at multiple locations. The remainder of the dissertation research tests a hypothesis to explain the observed discrepancy: that soil permeability assessed using relatively …

Angle-resolved photoemission extended fine structure (ARPEFS) was used to study molecular and metallic overlayers on metal surfaces through analysis of p2mg(2{times}1)CO/Ni(110) and the p(2{times}2)K/Ni(111) adsorption. For the dense p2mg(2{times}1)CO/Ni(110) surface layer, photoemission intensities from C 1s level were measured in three directions at photoelectron kinetic energies 60-400 eV. Using multiple-scattering spherical-wave (MSSW) modeling, it was found that CO molecules are adsorbed on short-bridge sites, with adjacent CO along the [110] direction displaced alternatively in opposite directions towards the [001] azimuths to form a zigzag chain geometry. The tilt angle is 16{plus_minus}2{degree} from the surface normal for the direction linking the C atom and the center of the Ni bridge. The carbon C-Ni interatomic distance was determined to be 1.94{plus_minus}0.02{Angstrom}. The first- to second-layer spacing of Ni is 1.27{plus_minus}0.04{Angstrom}, up from 1.10{Angstrom} for the clean Ni(110) surface, but close to the 1.25{Angstrom} Ni interlayer spacing in the bulk. The C-O bond length and tilt angle were varied within small ranges (1.10--1.20{Angstrom} and 15--23{degrees}) in our MSSW simulations. Best agreement between experiment and simulations was achieved at 1.16{Angstrom} and 19{degrees}. This yields an O-O distance of 2.95{Angstrom} for the two nearest CO molecules, (van der Waals` radius {approximately} 1.5 {Angstrom} for oxygen). …

This thesis discusses the following on resonant holographic measurements of laser ablation plume expansion: Introduction to laser ablation; applications of laser ablation; The study of plume expansion; holographic interferometry; resonant holographic interferometry; accounting for finite laser bandwidth; The solution for doppler broadening and finite bandwidth; the main optical table; the lumonics laser spot shape; developing and reconstructing the holograms; plume expansion in RF/Plasma Environments; Determining {lambda}{sub o}; resonant refraction effects; fringe shift interpretation; shot-to-shot consistency; laser ablation in vacuum and low pressure, inert, background gas; theoretically modeling plume expansion in vacuum and low pressure, inert, background gas; and laser ablation in higher pressure, inert, background gas.

Measurements and calculations of polarized light scattering are applied to chromosomes. Calculations of the Mueller matrix, which completely describes how the polarization state of light is altered upon scattering, are developed for helical structures related to that of chromosomes. Measurements of the Mueller matrix are presented for octopus sperm heads, and dinoflagellates. Comparisons of theory and experiment are made. A working theory of polarized light scattering from helices is developed. The use of the first Born approximation vs the coupled dipole approximation are investigated. A comparison of continuous, calculated in this work, and discrete models is also discussed. By comparing light scattering measurements with theoretical predictions the average orientation of DNA in an octopus sperm head is determined. Calculations are made for the Mueller matrix of DNA plectonemic helices at UV, visible and X-ray wavelengths. Finally evidence is presented that the chromosomes of dinoflagellates are responsible for observed differential scattering of circularly-polarized light. This differential scattering is found to vary in a manner that is possibly correlated to the cell cycle of the dinoflagellates. It is concluded that by properly choosing the wavelength probe polarized light scattering can provide a useful tool to study chromosome structure.

Measurements have been made of the scaled jet energies (x{sub 1}, x{sub 2}, x{sub 3}) and the Ellis-Karliner angle (cos{theta}{sub EK}), which are sensitive to the spill of the gluon, in the 3-jet hadronic events from the e{sup +}e{sup {minus}} annihilation at the Z{sup 0} resonance. The experiment is performed with the SLD detector at the Stanford Linear Accelerator Center (SLAC). The data used in this analysis was collected during the 1992 physics run, which includes 10,252 hadronic Z{sup 0} events that have CDC information written out. Only charged tracks measured in the central drift chamber are used for the measurements of the above variables. The raw data are found to be in good agreement with the Monte Carlo simulations passing the same set of track and event selection cuts. A bin-to-bin correction is done for the distributions of x{sub 1}, x{sub 2}, x{sub 3}, and cos{theta}{sub EK} to account for the effects of hadronization, detector acceptance and resolution. The corrected data is compared to the parton level distributions of x{sub 1}, x{sub 2}, x{sub 3}, and cos{theta}{sub EK} simulated from the vector QCD model and the scalar gluon model respectively. The systematic errors, calculated for all the bins in …

This dissertation studies methods for estimating extremely small probabilities by Monte Carlo simulation. Problems in radiation transport typically involve estimating very rare events or the expected value of a random variable which is with overwhelming probability equal to zero. These problems often have high dimensional state spaces and irregular geometries so that analytic solutions are not possible. Monte Carlo simulation must be used to estimate the radiation dosage being transported to a particular location. If the area is well shielded the probability of any one particular particle getting through is very small. Because of the large number of particles involved, even a tiny fraction penetrating the shield may represent an unacceptable level of radiation. It therefore becomes critical to be able to accurately estimate this extremely small probability. Importance sampling is a well known technique for improving the efficiency of rare event calculations. Here, a new set of probabilities is used in the simulation runs. The results are multiple by the likelihood ratio between the true and simulated probabilities so as to keep the estimator unbiased. The variance of the resulting estimator is very sensitive to which new set of transition probabilities are chosen. It is shown that a zero …

This thesis develops and applies a technique for the simultaneous determination of P and S wave velocity models and hypocenters from a set of arrival times. The velocity models are parameterized in terms of cubic B-splines basis functions which permit the retrieval of smooth models that can be used directly for generation of synthetic seismograms using the ray method. In addition, this type of smoothing limits the rise of instabilities related to the poor resolving power of the data. V{sub P}/V{sub S} ratios calculated from P and S models display generally instabilities related to the different ray-coverages of compressional and shear waves. However, V{sub P}/V{sub S} ratios are important for correct identification of rock types and this study introduces a new methodology based on adding some coupling (i.e., proportionality) between P and S models which stabilizes the V{sub P}/V{sub S} models around some average preset value determined from the data. Tests of the technique with synthetic data show that this additional coupling regularizes effectively the resulting models.

Heliumlike ions play an extremely important role in X-ray astrophysics because of their emissivity and because the relative intensities of their emission lines can be used to infer physical characteristics of X-ray emitting plasmas, including temperature, electron density, and ionization balance. In order to properly apply these diagnostics, accurate atomic data are required, including cross sections for collisional excitation and ionization, radiative rates, and the wavelengths and strengths of satellite lines. Although theoretical atomic models have been created to estimate many of the rates and cross sections involved, very few experimental results are available for comparison with theoretical predictions. This thesis describes an experimental study of heliumlike neon using an electron beam ion trap, a device specifically designed to study X-ray emission from highly charged ions. Using a low-energy X-ray spectrometer designed and built for this experiment, electron impact excitation cross sections and dielectronic satellite strengths were measured for all significant n = 2{yields}1 emission lines in He-like and Li-like Ne over a range of energy extending from well below the direct excitation threshold of the lines to over fourteen times the threshold energy. The cross section for innershell ionization of Li-like Ne, which excites the He-like forbidden line, was …

The deuteron elastic structure functions, A(Q{sup 2}) and B(Q{sup 2}), have been extracted from cross section measurements of elastic electron-deuteron scattering in coincidence using the Continuous Electron Beam Accelerator and Hall A Facilities of Jefferson Laboratory. Incident electrons were scattered off a high-power cryogenic deuterium target. Scattered electrons and recoil deuterons were detected in the two High Resolution Spectrometers of Hall A. A(Q{sup 2}) was extracted from forward angle cross section measurements in the squared four-momentum transfer range 0.684 ≤ Q{sup 2} ≤ 5.90 (GeV/c){sup 2}. B(Q{sup 2}) was determined by means of a Rosenbluth separation in the range 0.684 ≤ Q{sup 2} ≤ 1.325 (GeV/c){sup 2}. The data are compared to theoretical models based on the impulse approximation with the inclusion of meson-exchange currents and to predictions of quark dimensional scaling and perturbative quantum chromodynamics. The results are expected to provide insights into the transition from meson-nucleon to quark-gluon descriptions of the nuclear two-body system.

Thermal depinning has been studied for a single vortex trapped in a superconducting thin film in order to determine the value of the superconducting order parameter and the superfluid density when the vortex depins and starts to move around the film. For the Pb film in Pb/Al/Al{sub 2}O{sub 3}/PbBi junction having a gold line, the vortex depins from the artificial pinning site (Au line) and reproducibly moves through the same sequence of other pinning sites before it leaves the junction area of the Pb film. Values of the normalized order parameter {triangle}/{triangle}{sub o} vary from {triangle}/{triangle}{sub o}=0.20 at the first motion of the vortex to {triangle}/{triangle}{sub o}=0.16 where the vortex finally leaves the junction. Equivalently, the value of the normalized superfluid density changes from 4% to 2.5% for this sample in this same temperature interval. For the Nb film in Nb/Al/Al{sub 2}O{sub 3}/Nb junction, thermal depinning occurs when the value of {triangle}/{triangle}{sub o} is approximately 0.22 and the value of {rho}{sub s}/{rho}{sub so} is approximately 5%. These values are about 20% larger than those of a Pb sample having a gold line, but the values are really very close. For the Nb sample, grain boundaries are important pinning sites whereas, …

This thesis discusses characterization of two ferroelectric materials and the fabrication of bolometers. Potassium tantalate niobate (KTN) and potassium dihydrogen phosphate (KDP) are chosen because they can be optimized for operation near 100K. Chap. 2 reviews the physics underlying pyroelectric materials and its subclass of ferroelectric materials. Aspects of pyroelectric detection are discussed in Chap. 3 including measurement circuit, noise sources, and effects of materials properties on pyroelectric response. Chap. 4 discusses materials selection and specific characteristics of KTN and KDP; Chap. 5 describes materials preparation; and Chap. 6 presents detector configuration and a thermal analysis of the pyroelectric detector. Electrical techniques used to characterize the materials and devices and results are discussed in Chap. 7 followed by conclusions on feasibility of KDP and KTN pyroelectric detectors in Chap. 8.

The thesis is divided into the following 4 chapters: synthesis, characterization, and reactivity of trinuclear pentamethylcyclopentadienyl cobalt and nickel clusters with triply-bridging methylidyne groups; chemical and physical properties of pentamethylcyclopentadienyl acetylacetonate complexes of Co(II) and Ni(II); synthesis, characterization, and reactivity of pentamethylcyclopentadienyl halide complexes of Co and Ni; and crystallographic studies of distortions in metallocenes with C{sub 5}-symmetrical cyclopentadienyl rings.

A model has been developed which describes the ablation process of frozen hydrogen pellets in an electromagnetic railgun. The model incorporates the neutral gas shielding model in which the pellet surface is heated by incident electrons from the plasma arc. The heated surface then ablates, forming a neutral cloud which attenuates the incoming electrons. The energy lost in the cloud by the electrons heats the ablatant material as it flows into the plasma arc. Under steady-state conditions, a scaling law for the ablation rate was derived as a function of plasma-arc temperature and density. In addition, flow conditions and the criteria for the existence of a steady-state solution were formulated and subsequently examined under simplifying assumptions. Comparison with experimentally observed ablation rates shows good qualitative agreement.

Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu{sub 2}O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu{sub 2}O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu{sub 2}O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N{sub 2} and CO{sub 2}. At the end of each reaction, the catalyst was found to be Cu{sub 2}O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

The hydrogeologic properties of a shallow, fractured granitic rock aquifer in the foothills of the Sierra Nevada, California were investigated via the analysis of borehole geophysical logs and pumping tests. The drawdowns produced during these tests are not indicative of any simple conceptual aquifer model, and borehole logs show that the granite is intensely fractured. These observations are suggestive of a complex fracture-flow geometry which is extremely difficult to decipher. However, through the measurement of orientations of individual subsurface fractures from acoustic televiewer logs, and correlation between particular fractures and electrical resistivity and thermal-pulse flowmeter logs, it was found that the aquifer is, in general, comprised of two subhorizontal and nearly parallel zones of unloading fractures. Downhole flowmeter measurements taken in several wells provide further evidence for the inferred dual-layer structure of the aquifer, as well as yield quantitative measures of the contribution of flow from each zone. Analysis of drawdowns in pumped wells reveals that there are zones of relatively high transmissivity immediately around them. It was found that these properties, as well as a nearby zone of lower transmissivity, can account for their observed drawdowns. A numerical model was constructed to test whether these major heterogeneities could also …

This thesis describes a number of diverse experiments whose common theme is to elaborate some aspect of DNA supercoiling. The torsion elastic constant of DNA is measure as a function of superhelix density using the technique of picosecond Time Resolved Fluorescence Polarization Anisotropy (FPA) of intercalated ethidium bromide. The results agree with theories which predict that the anisotropy decay should vary with the square root of the relative viscosity. This experiment furthermore demonstrates a sensitivity of FPA to a change in torsion elastic constant of less than 10%. A number of covalently closed DNA samples, ranging in superhelix density from = {minus}0.123 to {plus}0.042, are then examined. A novel method for measuring changes in local supercoiling on a large PNA molecule which is sensitive to changes in supercoiling of regions of chromosomal DNA as short as 1 kilobase in length is presented. Study of chromosomal supercoiling regulating anaerobic gene expression in the facultative photosynthetic bacterium, Rhodobacter capsulatus showed that no stable change in chromosomal supercoiling upon a shift from aerobic respiratory growth to anaerobic photosynthetic conditions. Studies to detect transient changes in DNA supercoiling indicate that DNA downstream from heavily transcribed genes for the photosynthetic reaction center are relaxed or …

Goal was to study effect of power level and distribution on thermocapiilary-induced weld shape and of arc factors on weld shape. Thermocapillarity was apparent in both conduction mode EB welds and GTA welds, particularly in the former. A non-Gaussian arc distribution is suggested for accounting for the differences between the twoss processes. At higher current levels (200--300 A), plasma shear force also contributes to weld shape development. Evidence suggests that thermocapillary flow reversal is not a factor in normal GTA welds; EDB flow reversal occurs only at high power density levels where the keyhole mode is present.

Gamma-ray excited emission spectrum, absolute scintillation yield, rise and decay time constants, and thermoluminescence emissions of CsI(Tl) were measured at {minus}100 to +50 C, for crystals from 4 different vendors. The thermoluminescence glow curves were the only property that varied significantly from crystal to crystal; room temperature operation in current mode could be susceptible to temperature fluctuations. The CsI(Tl) emission spectrum has emission bands peaking around 400 and 560 nm; the former band disappears between {minus}50 and {minus}75 C. The RT absolute scintillation yield was calculated to be 65,500{plus_minus}4,100 photons/MeV. The two primary decay time constants increases about exponentially with inverse temperature. An ultra-fast decay component was confirmed. Applications are discussed.

Replicate column experiments were done to quantify the effects of temperature and bacterial motility on advective transport through repacked, but otherwise unaltered, natural aquifer sediment. The bacteria used in this study, A0500, was a flagellated, spore-forming rod isolated from the deep subsurface at DOE`s Savannah River Laboratory. Motility was controlled by turning on flagellar metabolism at 18{degrees}C but off at 40{degrees}C. Microspheres were used to independently quantify the effects of temperature on the sticking efficiency ({alpha}), estimated using a steady-state filtration model. The observed greater microsphere removal at the higher temperature agreed with the physical-chemical model, but bacteria removal at 18{degrees}C was only half that at 4{degrees}C. The sticking efficiency for non-motile A0500 (4{degrees}C) was over three times that of the motile A0500 (18{degrees}C), 0.073 versus 0.022 respectively. Analysis of complete breakthrough curves using a non-steady, kinetically limited, transport model to estimate the time scales of attachment and detachment suggested that motile A 0500 bacteria traveled twice as far as non-motile A 0500 bacteria before becoming attached. Once attached, non-motile colloids detached on the time scale of 9 to 17 days. The time scale for detachment of motile A0500 bacteria was shorter, 4 to 5 days. Results indicate that bacterial …