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 diffusionless 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 C and 1,100 C, respectively. Two novel methods were developed for the solution based synthesis of Ba{sub 2}YCu{sub 3}O{sub 7{minus}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{minus}x} and Bi{sub 2}Sr{sub 2}Ca{sub 2}Cu{sub 3}O{sub 10} were …

NMR and NQR at low frequencies are difficult prospects due to small nuclear spin polarization. Furthermore, the sensitivity'of the inductive pickup circuitry of standard spectrometers is reduced as the frequency is lowered. I have used a cw-SQUID (Superconducting QUantum Interference Device) spectrometer, which has no such frequency dependence, to study the local atomic environment of {sup 14}N via the quadrupolar interaction. Because {sup 14}N has spin I = 1 and a 0-6 MHz frequency range, it is not possible to obtain well-resolved spectra in high magnetic fields. I have used a technique to observe {sup 14}N NQR resonances via their effect on neighboring protons mediated by the heteronuclear dipolar interaction to study peptides and narcotics. The sensitivity of the SQUID is not enough to measure low-frequency surface (or other low spin density) systems. The application of spin-polarized xenon has been previously used to enhance polarization in conventional NMR experiments. Because xenon only polarizes spins with which it is in contact, it is surface selective. While differences in chemical shifts between surface and bulk spins are not large, it is expected that the differences in quadrupole coupling constant should be very large due to the drastic change of the electric field …

This report provides complete bibliographic citations, abstracts, and keywords for 212 doctoral and master`s theses supported fully or partly by the U.S. Department of Energy`s Environmental Sciences Division (and its predecessors) in the following areas: Atmospheric Sciences; Marine Transport; Terrestrial Transport; Ecosystems Function and Response; Carbon, Climate, and Vegetation; Information; Computer Hardware, Advanced Mathematics, and Model Physics (CHAMMP); Atmospheric Radiation Measurement (ARM); Oceans; National Institute for Global Environmental Change (NIGEC); Unmanned Aerial Vehicles (UAV); Integrated Assessment; Graduate Fellowships for Global Change; and Quantitative Links. Information on the major professor, department, principal investigator, and program area is given for each abstract. Indexes are provided for major professor, university, principal investigator, program area, and keywords. This bibliography is also available in various machine-readable formats (ASCII text file, WordPerfect{reg_sign} files, and PAPYRUS{trademark} files).

Wavelength and composition dependence of the time-resolved luminescence were examined. Effects of macroscopic composition gradient and microscopic alloy disorder on e{sup {minus}}-h{sup +} pair dynamics were probed. Materials with both increasing and decreasing S content with distance from the surface were examined, where 0{le} {times} {le}1 over the full range. In these graded materials, the band gap energy also varies with position. The graded semiconductor luminescence shows strong wavelength dependence, showing diffusion in both band gap and concentration gradients. A bottleneck in the diffusion is attributed to localization occurring primarily in the materials with greatest alloy disorder, i.e. around CdS{sub 0.5}Se{sub 0.50}. Homogeneous materials were studied for x = 0, 0.25, 0.50, 0.75, 1; the time-resolved luminescence depends strongly on the composition. The mixed compositions have longer decay constants than CdS and CdSe. Observed lifetimes agree with a picture of localized states induced by the alloy disorder. For a given homogeneous crystal, no wavelength dependence of the time decays was observed. Picosecond luminescence upconversion spectroscopy was used to study further the dependence of the luminescence on composition. Large nonexponential character in the decay functions was observed in the alloys; this long time tail can be attributed to a broad distribution …

A Lagrangian numerical method based on impulse variables is analyzed. A relation between impulse vectors and vortex dipoles with a prescribed dipole moment is presented. This relation is used to adapt the high-accuracy cutoff functions of vortex methods for use in impulse-based methods. A source of error in the long-time implementation of the impulse method is explained and two techniques for avoiding this error are presented. An application of impulse methods to the motion of a fluid surrounded by an elastic membrane is presented.

This thesis investigates the mixing and dispersion of indoor air pollutants under a variety of conditions using standard experimental methods. It also extensively tests and improves a novel technique for measuring contaminant concentrations that has the potential for more rapid, non-intrusive measurements with higher spatial resolution than previously possible. Experiments conducted in a sealed room support the hypothesis that the mixing time of an instantaneously released tracer gas is inversely proportional to the cube root of the mechanical power transferred to the room air. One table-top and several room-scale experiments are performed to test the concept of employing optical remote sensing (ORS) and computed tomography (CT) to measure steady-state gas concentrations in a horizontal plane. Various remote sensing instruments, scanning geometries and reconstruction algorithms are employed. Reconstructed concentration distributions based on existing iterative CT techniques contain a high degree of unrealistic spatial variability and do not agree well with simultaneously gathered point-sample data.

One of the great success stories of modern molecular genetics has been the ability of biologists to isolate and characterize the genes responsible for serious inherited diseases like fragile X syndrome, cystic fibrosis and myotonic muscular dystrophy. This dissertation concentrates on constructing high-resolution physical maps. It demonstrates how probabilistic modeling and statistical analysis can aid molecular geneticists in the tasks of planning, execution, and evaluation of physical maps of chromosomes and large chromosomal regions. The dissertation is divided into six chapters. Chapter 1 provides an introduction to the field of physical mapping, describing the role of physical mapping in gene isolation and ill past efforts at mapping chromosomal regions. The next two chapters review and extend known results on predicting progress in large mapping projects. Such predictions help project planners decide between various approaches and tactics for mapping large regions of the human genome. Chapter 2 shows how probability models have been used in the past to predict progress in mapping projects. Chapter 3 presents new results, based on stationary point process theory, for progress measures for mapping projects based on directed mapping strategies. Chapter 4 describes in detail the construction of all initial high-resolution physical map for human chromosome …

All models of lasing action require knowledge of the physical parameters involved, of which many can be measured or estimated. The value of the terminal level lifetime is an important parameter in modeling many high power laser systems since the terminal level lifetime can have a substantial impact on the extraction efficiency of the system. However, the values of the terminal level lifetimes for a number of important laser materials such as ND:YAG and ND:YLF are not well known. The terminal level lifetime, a measure of the time it takes for the population to drain out of the terminal (lower) lasing level, has values that can range from picoseconds to microseconds depending on the host medium, thus making it difficult to construct one definitive experiment for all materials. Until recently, many of the direct measurements of the terminal level lifetime employed complex energy extraction or gain recovery methods coupled with a numerical model which often resulted in large uncertainties in the measured lifetimes. In this report we demonstrate a novel and more accurate approach which employs a pump-probe technique to measure the terminal level lifetime of 16 neodymium-doped materials. An alternative yet indirect method, which is based on the ``Energy …

Photodissociation of M(CO){sub 6} (M=Cr,Mo,W) and the formation of solvated M(CO){sub 5}{center_dot}S complex was studied in cyclohexane; rate-limiting step is vibrational energy relaxation from the new bond to the solvent. For both M=Cr and Mo, the primary relaxation occurs in 18 ps; for Cr, there is an additional vibrational relaxation (150 ps time scale) of a CO group poorly coupled to other modes. Relaxation of M=W occurs in 42 ps; several possible mechanisms for the longer cooling are discussed. Vibrational relaxation is also investigated for I{sub 2}{sup -} and IBr{sup {minus}} in nonpolar and slightly polar solvents. Attempts were made to discover the mechanism for the fast energy transfer in nonpolar solvent. The longer time scale dynamics of I{sub 3}{sup {minus}} and IBr{sub 2}{sup {minus}} were also studied; both formed a metastable complex following photodissociation and 90-95% return to ground state in 100 ps, implying a barrier to recombination of 4.3 kcal/mol and a barrier to escape of {ge}5.5 kcal/mol. The more complex photochemistry of M{sub 3}(CO){sub 12} (M=Fe,Ru) is also investigated, using visible and ultraviolet radiations, dissociation, geminate recombination, vibrational relaxation, and bridging structures and their reactions were studied. Attempts were made to extend ultrafast spectroscopy into the mid-infrared, …

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 …

STM was applied to chemisorbed S layers on Re(000l) and Mo(100) surfaces. As function of coverage on both these surfaces, S orders into several different overlayer structures, which have been studied by dynamic LEED. STM images of all these structures were obtained. Approximate location of S atoms in the structures was determined by inspecting the images, especially the regions containing defects. Results are in agreement with LEED except for the p(2{times}l) overlayer of sulfur on Mo(100). The STM images were compared to calculations made with Electron Scattering Quantum Chemistry (ESQC) theory. Variation of contrast in experimental images is explained as a result of changes in STM tip termination structure. STM image contrast is a result of changes in the interference between different paths for the tunneling electrons. The simplest structure on the Mo(100) surface was used as a model for developing and testing a method of quantitative structure determination with the STM. Experimental STM images acquired under a range of tunneling conditions were compared to theoretical calculations of the images as a function of surface structure to determine the structure which best fit. Results matched within approximately 0.1 Angstroms a LEED structural determination. At lower S coverage, diffusion of S …

Hydrogenated amorphous silicon (a-Si:H) as a large-area thin film semiconductor with ease of doping and low-cost fabrication capability has given a new impetus to the field of imaging sensors; its high radiation resistance also makes it a good material for radiation detectors. In addition, large-area microelectronics based on a-Si:H or polysilicon can be made with full integration of peripheral circuits, including readout switches and shift registers on the same substrate. Thin a-Si:H p-i-n photodiodes coupled to suitable scintillators are shown to be suitable for detecting charged particles, electrons, and X-rays. The response speed of CsI/a-Si:H diode combinations to individual particulate radiation is limited by the scintillation light decay since the charge collection time of the diode is very short (< 10ns). The reverse current of the detector is analyzed in term of contact injection, thermal generation, field enhanced emission (Poole-Frenkel effect), and edge leakage. A good collection efficiency for a diode is obtained by optimizing the p layer of the diode thickness and composition. The CsI(Tl) scintillator coupled to an a-Si:H photodiode detector shows a capability for detecting minimum ionizing particles with S/N {approximately}20. In such an arrangement a p-i-n diode is operated in a photovoltaic mode (reverse bias). In …

The fundamental processes associated with a photochemical reaction are described with reference to experimental properties of azabenzenes. Consideration of both excitation and relaxation processes led to presentation of the symmetry propagator, a unifying principle which maps system fluctuations (perturbations acting on an initial state) with dissipations (transitions to different states), thus directing the energy flow along competing reactive and nonreactive pathways. A coherent picture of relaxation processes including chemical reactions was constructed with the aid of spectroscopic data. Pyrazine (1,4 diazine) possesses vibronically active modes which provide an efficient mechanism for internal conversion to the first excited singlet state, where other promoting modes of the correct symmetry induce both intersystem crossing to the triplet manifold, isomerization through diaza-benzvalene, and chemical reactions through cycloreversion of dewar pyrazine to yield HCN plus an azete. At higher energies simple H atom loss and internal conversion become more predominant, leading to ring opening followed by elimination of methylene nitrile and ground state reaction products. Efficiency of chemical transformations as dissipation mechanisms versus competing fluorescence, phosphorescence and radiationless relaxation was mapped from near ultraviolet to far ultraviolet by photodissociation quantum yields into reaction channels characterized by molecular beam photofragment translational spectroscopy. A reaction path model …

The dynamics of inelastic and reactive collisions in atomic beam-surface scattering are presented. The inelastic scattering of hyperthermal rare gaseous atoms from three alkali halide surfaces (LiF, NaCl, GI)was studied to understand mechanical energy transfer in unreactive systems. The dynamics of the chemical reaction in the scattering of H(D) atoms from the surfaces of LIF(001) and the basal plane of graphite were also studied.

The utility of microearthquake data for characterizing the Northwest Geysers geothermal field and the Long Valley Caldera (LVC) was investigated. Three-dimensional (3-D) P- and S-wave seismic velocity models were estimated for the Coldwater Creek Steam Field (CCSF) in the Northwest Geysers region. Hypocenters relocated using these 3-D models appear to be associated with the steam producing zone, with a deeper cluster of hypocenters beneath an active injection well. Spatial and temporal patterns of seismicity exhibit strong correlation with geothermal exploitation. A 3-D differential attenuation model was also developed for the CCSF from spectral ratios corrected for strong site effects. High-velocity anomalies and low attenuation in the near surface correspond to Franciscan metagraywacke and greenstone units. Microearthquakes recorded at seismographic stations located near the metagraywacke unit exhibit high corner frequencies. Low-velocity anomalies and higher attenuation in the near surface are associated with sections of Franciscan melange. Near-surface high attenuation and high Vp/Vs are interpreted to indicate liquid-saturated regions affected by meteoric recharge. High attenuation and low Vp/Vs marks the steam producing zone, suggesting undersaturation of the reservoir rocks. The extent of the high attenuation and low Vp/Vs anomalies suggest that the CCSF steam reservoir may extend northwestward beyond the known producing …

Understanding transport properties of sedimentary rocks, including permeability, relative permeability, and electrical conductivity, is of great importance for petroleum engineering, waste isolation, environmental restoration, and other applications. These transport properties axe controlled to a great extent by the pore structure. How pore geometry, topology, and the physics and chemistry of mineral-fluid and fluid-fluid interactions affect the flow of fluids through consolidated/partially consolidated porous media are investigated analytically and experimentally. Hydraulic and electrical conductivity of sedimentary rocks are predicted from the microscopic geometry of the pore space. Cross-sectional areas and perimeters of individual pores are estimated from two-dimensional scanning electron microscope (SEM) photomicrographs of rock sections. Results, using Berea, Boise, Massilon, and Saint-Gilles sandstones show close agreement between the predicted and measured permeabilities. Good to fair agreement is found in the case of electrical conductivity. In particular, good agreement is found for a poorly cemented rock such as Saint-Gilles sandstone, whereas the agreement is not very good for well-cemented rocks. The possible reasons for this are investigated. The surface conductance contribution of clay minerals to the overall electrical conductivity is assessed. The effect of partial hydrocarbon saturation on overall rock conductivity, and on the Archie saturation exponent, is discussed. The region …

Pond 207C at Rocky Flats Environmental Technology Site (RFETS) contains process wastewaters characterized by high levels of nitrates and other salts, heavy metal contamination, and low level alpha activity. The purpose of this research was to investigate the feasibility of treating a high-nitrate waste, contaminated with heavy metals, with a coupled dewateriug and S/S process, as well as to investigate the effects of biodenitrification pretreatment on the S/S process. Pond 207C residuals served as the target waste. A bench-scale treatability study was conducted to demonstrate an S/S process that would minimize final product volume without a significant decrease in contaminant stabilization or loss of desirable physical characteristics. The process formulation recommended as a result a previous S/S treatability study conducted on Pond 207C residuals was used as the baseline formulation for this research. Because the actual waste was unavailable due to difficulties associated with radioactive waste handling and storage, a surrogate waste, of known composition and representative of Pond 207C residuals, was used throughout this research. The contaminants of regulatory concern added to the surrogate were cadmium, chromium, nickel, and silver. Product volume reduction was achieved by dewatering the waste prior to S/S treatment. The surrogate was dewatered by evaporation …

A postulated severe loss of coolant accident in a nuclear reactor can lead to significant core damage due to residual heat generation. Subsequently, melted core materials (i.e.; corium) could migrate downward and impinge upon the lower head of the reactor pressure vessel (RPV). During this relocation, the complexity of the reactor structure could segregate the molten corium into various flow paths. A perforated flow plate could readily provide the mechanism to segregate the molten corium. The resulting small (a few cm) diameter melt streams, driven by gravity, could then penetrate the remaining coolant in the RPV and cause any of the following events: impingement of the high temperature melt streams on the lower head could breach the RPV; re-agglomeration of the corium melt on the lower head could influence the coolability of the debris bed; {open_quotes}pre-mixing{close_quotes} of the melt streams with the coolant could lead to a vapor explosion; or, sufficient quenching of the melt streams by the coolant could produce a stabilized debris bed. An overview of the thermo-science issues related to core-melt accidents is presented by Theofanous. Thus, insight into the melt stream breakup mechanisms (i.e.; interfacial conditions, fragmentation, and geometric spacing) during the melt-coolant interactions is necessary …

Fermilab Experiment 769 used a charge-selected, hadron beam of mean energy 250 GeV/c, composed of pions, kaons, and protons, impinging on beryllium, aluminum, copper and tungsten targets. Using a sample of approximately 4000 {Xi}{sub s}{sup {minus}} {yields} {Lambda}{sup 0}{pi}{sup {minus}} decays, measurements of the charm baryon forward cross sections times branching ratio {pi}{sup {+-}}N {yields} {Xi}{sub c}{sup +}X and {pi}{sup {+-}}N {yields} {Xi}{sub c}{sup 0}X are presented. Upper limits on {alpha} x BR are also determined for the states {Xi}{sub c}{sup +} {yields} {Xi}{sub s}{sup {minus}}{pi}{sup +}{pi}{sup +} and {Xi}{sub c}{sup 0} {yields} {Xi}{sub s}{sup {minus}}{pi}{sup +} produced in (p, {pi}{sup +}, {pi}{sup {minus}}, K{sup +}, K{sup {minus}})-nucleon interactions.

Partitioning and transmutation (P-T) is perhaps the most elegant means of high level waste disposal. Currently, the cost of fuel obtained from reprocessing spent fuel exceeds the cost of fuel obtained by mining. This has resulted in the once through fuel cycle dominating the US nuclear industry. Despite this fact P-T continues to be examined and debated by the US as well as abroad. The US first seriously considered P-T between approximately 1976 and 1982 but rejected the concept in favor of reprocessing. More recently, since about 1989, as a result of the once through fuel cycle and the growing problems of waste disposal, studies concerning P-T have resumed. This essay will seek to outline the incentives and goals of partitioning and transmutation as it would apply to the disposal of spent fuel in the US. Recent proposals by various US national laboratories for implementing partitioning and transmutation as a high level waste management and disposal device will also be discussed. The review will seek to examine the technical concepts utilized in each of the proposals and their feasibility. The major focus of this essay will be the transmutation methods themselves, while the partitioning methods will be discussed only briefly. …

Nuclear magnetic resonance spectroscopy was used to elucidate detailed structural information for peptide and protein molecules. A small peptide was designed and synthesized, and its three-dimensional structure was calculated using distance information derived from two-dimensional NMR measurements. The peptide was used to induce antibodies in mice, and the cross-reactivity of the antibodies with a related protein was analyzed with enzyme-linked immunosorbent assays. Two proteins which are involved in regulation of transcription in bacteria were also studied. The ferric uptake regulation (Fur) protein is a metal-dependent repressor which controls iron uptake in bacteria. Two- and three-dimensional NMR techniques, coupled with uniform and selective isotope labeling allowed the nearly complete assignment of the resonances of the metal-binding domain of the Fur protein. NTRC is a transcriptional enhancer binding protein whose N-terminal domain is a {open_quote}receiver domain{close_quote} in the family of {open_quote}two-component{close_quote} regulatory systems. Phosphorylation of the N-terminal domain of NTRC activates the initiation of transcription of aeries encoding proteins involved in nitrogen regulation. Three- and four-dimensional NMR spectroscopy methods have been used to complete the resonance assignments and determine the solution structure of the N-terminal receiver domain of the NTRC protein. Comparison of the solution structure of the NTRC receiver domain with …

A single Langmuir probe tip was used at TEXT-Upgrade to obtain I-V characteristics in a magnetized plasma. Noisy data were reduced by a boxcar-averaging routine. Unexpected effects, namely nonsaturation of ion current, hysterises in the characteristics and I(V)-data were observed, which are in disagreement to the common single probe model. A double probe model allows parameterization of the I(V) curves and to determine the plasma properties in the scrape-off layer. It is shown in this model that a Langmuir probe does perturb the local space potential in the plasma. Comparisons were made with the triple probe technique of measuring temperatures. The nonsaturation of ion current leads to an error in the triple probe technique of order 20%.

Over the past couple of decades, the Standard Model of high energy particle physics has clearly established itself as an invaluable tool in the analysis of high energy particle phenomenon. However, from a field theorists point of view, there are many dissatisfying aspects to the model. One of these, is the large number of free parameters in the theory arising from the Yukawa couplings of the Higgs doublet. In this thesis, we examine various issues relating to the Yukawa coupeng structure of high energy particle field theories. We begin by examining extensions to the Standard Model of particle physics which contain additional scalar fields. By appealing to the flavor structure observed in the fermion mass and Kobayashi-Maskawa matrices, we propose a reasonable phenomenological parameterization of the new Yukawa couplings based on the concept of approximate flavor symmetries. It is shown that such a parameterization eliminates the need for discrete symmetries which limit the allowed couplings of the new scalars. New scalar particles which can mediate exotic flavor changing reactions can have masses as low as the weak scale. Next, we turn to the issue of neutrino mass matrices, where we examine a particular texture which leads to matter independent neutrino …

The non-surgical brain cancer treatment modality, Boron Neutron Capture Therapy (BNCT), requires the use of an epithermal neutron beam. This purpose of this thesis was to design an epithermal neutron beam at the University of Virginia Research Reactor (UVAR) suitable for BNCT applications. A suitable epithermal neutron beam for BNCT must have minimal fast neutron and gamma radiation contamination, and yet retain an appreciable intensity. The low power of the UVAR core makes reaching a balance between beam quality and intensity a very challenging design endeavor. The MCNP monte carlo neutron transport code was used to develop an equivalent core radiation source, and to perform the subsequent neutron transport calculations necessary for beam model analysis and development. The code accuracy was validated by benchmarking output against experimental criticality measurements. An epithermal beam was designed for the UVAR, with performance characteristics comparable to beams at facilities with cores of higher power. The epithermal neutron intensity of this beam is 2.2 {times} 10{sup 8} n/cm{sup 2} {center_dot} s. The fast neutron and gamma radiation KERMA factors are 10 {times} 10{sup {minus}11}cGy{center_dot}cm{sup 2}/n{sub epi} and 20 {times} 10{sup {minus}11} cGy{center_dot}cm{sup 2}/n{sub epi}, respectively, and the current-to-flux ratio is 0.85. This thesis has shown …