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.

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 work is concerned with the development of approximate methods to describe relatively large chemical systems. This effort has been divided into two primary directions: First, we have extended and applied a semiclassical transition state theory (SCTST) originally proposed by Miller to obtain microcanonical and canonical (thermal) rates for chemical reactions described by a nonseparable Hamiltonian, i.e. most reactions. Second, we have developed a method to describe the fluctuations of decay rates of individual energy states from the average RRKM rate in systems where the direct calculation of individual rates would be impossible. Combined with the semiclassical theory this latter effort has provided a direct comparison to the experimental results of Moore and coworkers. In SCTST, the Hamiltonian is expanded about the barrier and the ``good`` action-angle variables are obtained perturbatively; a WKB analysis of the effectively one-dimensional reactive direction then provides the transmission probabilities. The advantages of this local approximate treatment are that it includes tunneling effects and anharmonicity, and it systematically provides a multi-dimensional dividing surface in phase space. The SCTST thermal rate expression has been reformulated providing increased numerical efficiency (as compared to a naive Boltzmann average), an appealing link to conventional transition state theory (involving a …

The characteristics of martensitic transformations in solids are largely determined by the elastic strain that develops as martensite particles grow and interact. To study the development of microstructure, a finite-element computer simulation model was constructed to mimic the transformation process. The transformation is athermal and simulated at each incremental step by transforming the cell which maximizes the decrease in the free energy. To determine the free energy change, the elastic energy developed during martensite growth is calculated from the theory of linear elasticity for elastically homogeneous media, and updated as the transformation proceeds.

The coordination chemistry and solution behavior of the toxic ions lead(II) and plutonium(IV, V, VI) have been investigated. The ligand pK{sub a}s and ligand-lead(II) stability constants of one hydroxamic acid and four thiohydroaxamic acids were determined. Solution thermodynamic results indicate that thiohydroxamic acids are more acidic and slightly better lead chelators than hydroxamates, e.g., N-methylthioaceto-hydroxamic acid, pK{sub a} = 5.94, log{beta}{sub 120} = 10.92; acetohydroxamic acid, pK{sub a} = 9.34, log{beta}{sub l20} = 9.52. The syntheses of lead complexes of two bulky hydroxamate ligands are presented. The X-ray crystal structures show the lead hydroxamates are di-bridged dimers with irregular five-coordinate geometry about the metal atom and a stereochemically active lone pair of electrons. Molecular orbital calculations of a lead hydroxamate and a highly symmetric pseudo octahedral lead complex were performed. The thermodynamic stability of plutonium(IV) complexes of the siderophore, desferrioxamine B (DFO), and two octadentate derivatives of DFO were investigated using competition spectrophotometric titrations. The stability constant measured for the plutonium(IV) complex of DFO-methylterephthalamide is log{beta}{sub 110} = 41.7. The solubility limited speciation of {sup 242}Pu as a function of time in near neutral carbonate solution was measured. Individual solutions of plutonium in a single oxidation state were added to …

Several experiments have measured nominally-charge-symmetric scattering of pions from tritium ({sup 3}H) and {sup 3}He. These experiments have covered incident pion energies from 142 MeV to 295 MeV and scattering angles up to 110{degrees} in the laboratory. The results have been used to study charge-symmetry breaking and nuclear scattering systematics. In the work I have extended these measurements to angles near 180{degrees} for pion energies of 142 MeV, 180 MeV, 220 MeV, and 256 MeV, which bracket the {Delta}{sub 33} pion-nucleon resonance. This is the most extensive set of {pi}T and {pi}{sup 3}He data in this kinematical region. It will allow tests of scattering theory of pion-nucleus interactions and charge-symmetry breaking in back-angle scattering, and, within the limits of these two theories, it may help improve our understanding of the structure of these nuclei.

The photodissociation of free radicals is studied in order to characterize the spectroscopy and dissociation dynamics of the dissociative electronic states in these species. To accomplish this, a novel method of radical production, based on the photodetachment of the corresponding negative ion, has been combined with a highly complementary form of photofragment translational spectroscopy. The optical spectroscopy of transitions to dissociative states is determined by monitoring the total photofragment yield as a function of dissociation photon energy. Branching ratios to various product channels, internal energy distributions of the fragments, bond dissociation energies, and the translational energy-dependent photofragment recoil angular distributions are then determined at selected excitation energies. A detailed picture of the dissociation dynamics can then be formulated, allowing insight concerning the interactions of potential energy surfaces involved in the dissociation. After an introduction to the concepts and techniques mentioned above, the experimental apparatus used in these experiments is described in detail. The basis and methods used in the treatment of data, especially in the dissociation dynamics experiments, are then put forward.

The Resource Conservation and Recovery Act (RCRA) of 1976 and its subsequent amendments have had a dramatic impact on hazardous waste management for business and industry. The complexity of this law and the penalties for noncompliance have made it one of the most challenging regulatory programs undertaken by the Environmental Protection Agency (EPA). The fundamentals of RCRA include ``cradle to grave`` management of hazardous waste, covering generators, transporters, and treatment, storage, and disposal facilities. The regulations also address extensive definitions and listing/identification mechanisms for hazardous waste along with a tracking system. Treatment is favored over disposal and emphasis is on ``front-end`` treatment such as waste minimization and pollution prevention. A study of large corporations such as Xerox, 3M, and Dow Chemical, as well as the public sector, has shown that well known and successful hazardous waste management programs emphasize pollution prevention and employment of techniques such as proactive environmental management, environmentally conscious manufacturing, and source reduction. Nearly all successful hazardous waste programs include some aspects of Total Quality Management, which begins with a strong commitment from top management. Hazardous waste management at the Rocky Flats Plant is further complicated by the dominance of ``mixed waste`` at the facility. The mixed …

Internet Privacy Enhanced Mail (PEM) provides security services to users of Internet electronic mail. PEM is designed with the intention that it will eventually obtain public key certificates from the X.500 directory service. However, such a capability is not present in most PEM implementations today. While the prevalent PEM implementation uses a public key certificate-based strategy, certificates are mostly distributed via e-mail exchanges, which raises several security and performance issues. In this thesis research, we changed the reference PEM implementation to make use of the X.500 directory service instead of local databases for public key certificate management. The thesis discusses some problems with using the X.500 directory service, explores the relevant issues, and develops an approach to address them. The approach makes use of a memory cache to store public key certificates. We implemented a centralized cache server and addressed the denial-of-service security problem that is present in the server. In designing the cache, we investigated several cache management strategies. One result of our study is that the use of a cache significantly improves performance. Our research also indicates that security incurs extra performance cost. Different cache replacement algorithms do not seem to yield significant performance differences, while delaying dirty-writes …

The growth of YBa{sub 2}Cu{sub 3}O{sub 7-{delta}} (YBCO) high-temperature superconductor thin films has largely been limited to deposition on single-crystal substrates to date. In order to expand the range of potential applications, growth on polycrystalline and amorphous substrates is desirable. In particular, the deposition of YBCO thin films with high critical current densities on polycrystalline metal alloys would allow the manufacture of superconducting tapes. However, it is shown that it is not possible to grow YBCO thin films directly on this type of substrate due to chemical and structural incompatibility. This work investigates the use of a yttria-stabilized zirconia (YSZ) intermediate layer to address this problem. An ion-assisted pulsed-laser deposition process is developed to provide control of orientation during the growth of the YSZ layers. The important properties of YBCO and YSZ are summarized and the status of research on thin film growth of these materials is reviewed. An overview of the pulsed-laser deposition (PLD) technique is presented. The use of ion-assisted deposition techniques to control thin film properties is discussed.

This study of laser-light interactions with solid materials ranges from low-temperature heating to explosive, plasma-forming reactions. Contained are four works concerning laser-energy coupling: laser (i) heating and (ii) melting monitored using a mirage effect technique, (iii) the mechanical stress-power generated during high-powered laser ablation, and (iv) plasma-shielding. First, a photothermal deflection (PTD) technique is presented for monitoring heat transfer during modulated laser heating of opaque solids that have not undergone phase-change. Of main interest is the physical significance of the shape, magnitude, and phase for the temporal profile of the deflection signal. Considered are the effects that thermophysical properties, boundary conditions, and geometry of the target and optical probe-beam have on the deflection response. PTD is shown to monitor spatial and temporal changes in heat flux leaving the surface due to changes in laser energy coupling. The PTD technique is then extended to detect phase-change at the surface of a solid target. Experimental data shows the onset of melt for indium and tin targets. The conditions for which melt can be detected by PTD is analyzed in terms of geometry, incident power and pulse length, and thermophysical properties of the target and surroundings. Next, monitoring high-powered laser ablation of materials …

The production cross section times decay branching ratio for W{sub +{gamma}} in the electron decay channel in {radical}s = 1.8 TeV {bar p}-p collisions has been measured using W {yields} e{gamma} data sample obtained from the CDF 1988--1989 Tevatron collider run. For photons in the central region ({vert_bar}{eta}{sub {gamma}}{vert_bar} < 1.1) of the CDF detector with transverse energies E{sub T}{sup {gamma}} 5.0 GeV and lepton-photon angular separation {Delta}R{sub {ell}}{gamma} > 0.7, eight electron W{sub {gamma}} candidates were observed. From these events, the production cross section times decay branching ratio for the electron sample was measured to be a {sigma} {center_dot} B(W{sub {gamma}}){sub exp} = 17.0{sub {minus}13.4}{sup +13.6}(stat. + syst.)pb. The W{sub {gamma}} cross section is sensitive to the anomalous couplings of the W boson. Using the W{sub {gamma}} cross section measurement, the absence of an excess of large E{sub T} photons accompanying the production of a W boson enables one to obtain direct limits on anomalous WW{sub {gamma}} couplings. The experimental limits on the anomalous couplings was measured to be {minus}7.2 < {Delta}{kappa} < +7.7 ({lambda} = 0) and {minus}3.5 < {lambda} < +3.4 ({Delta}{kappa} = 0) at 95% CL. These experimental limits impose contraints on possible internal structure of …

The mechanical behavior and microstructure of eutectic Bi-Sn and In-Sn solders were studied in parallel in order to better understand high temperature deformation of these alloys. Bi-Sn solder joints were made with Cu substrates, and In-Sn joints were made with either Cu or Ni substrates. The as-cast microstructure of Bi-Sn is complex regular, with the two eutectic phases interconnected in complicated patterns. The as-cast microstructure of In-Sn depends on the substrate. In-Sn on Cu has a non-uniform microstructure caused by diffusion of Cu into the solder during sample preparation, with regions of the Sn-rich {gamma} phase imbedded in a matrix of the In-rich {beta} phase. The microstructure of In-Sn on Ni is uniform and lamellar and the two phases are strongly coupled. The solders deform non-uniformly, with deformation concentrating in a band along the length of the sample for Bi-Sn and In-Sn on Cu, though the deformation is more diffuse in In-Sn than in Bi-Sn. Deformation of In-Sn on Ni spreads throughout the width of the joint. The different deformation patterns affect the shape of the stress-strain curves. Stress-strain curves for Bi-Sn and In-Sn on Cu exhibit sharp decays in the engineering stress after reaching a peak. Most of this …

Rigorous calculations of cross sections and rate constants for elementary gas phase chemical reactions are performed for comparison with experiment, to ensure that our picture of the chemical reaction is complete. We focus on the H/D+H{sub 2} {yields} H{sub 2}/DH + H reaction, and use the time independent integral equation technique in quantum reactive scattering theory. We examine the sensitivity of H+H{sub 2} state resolved integral cross sections {sigma}{sub v{prime}j{prime},vj}(E) for the transitions (v = 0,j = 0) to (v{prime} = 1,j{prime} = 1,3), to the difference between the Liu-Siegbahn-Truhlar-Horowitz (LSTH) and double many body expansion (DMBE) ab initio potential energy surfaces (PES). This sensitivity analysis is performed to determine the origin of a large discrepancy between experimental cross sections with sharply peaked energy dependence and theoretical ones with smooth energy dependence. We find that the LSTH and DMBE PESs give virtually identical cross sections, which lends credence to the theoretical energy dependence.

With the advent of powerful workstations with windowing systems, the scientific community has become interested in user friendly interfaces as a means of promoting the distribution of scientific codes to colleagues. Distributing scientific codes to a wider audience can, however, be problematic because scientists, who are familiar with the problem being addressed but not aware of necessary operational details, are encouraged to use the codes. A more friendly environment that not only guides user inputs, but also helps catch errors is needed. This thesis presents a dynamic graphical user interface (GUI) creation system with user controlled support for error detection and handling. The system checks a series of constraints defining a valid input set whenever the state of the system changes and notifies the user when an error has occurred. A naive checking scheme was implemented that checks every constraint every time the system changes. However, this method examines many constraints whose values have not changed. Therefore, a minimum evaluation scheme that only checks those constraints that may have been violated was implemented. This system was implemented in a prototype and user testing was used to determine if it was a success. Users examined both the GUI creation system and …

The HBT-EP Tokamak has been designed, built, and is now fully operational in the Columbia University Plasma Physics Laboratory. One of the primary purposes of this facility is to study the effects of a conducting wall on the MHD modes that lead up to plasma disruptions. Of particular interest are the types of instabilities that are driven by the kinetic pressure of the plasma, because these instabilities are believed to be responsible for the present limit to plasma {beta} with {beta} {proportional_to} <p>/B{sup 2}, where the <p> is the volume averaged pressure and B is the magnetic field. To this end, a movable conducting wall has been installed inside the HBT-EP vacuum chamber. The primary result of this thesis are the initial results from experiments that study the effect of this wall on plasma instabilities. The experiment shows that the conducting wall significantly reduces the growth rate of instabilities that precede a plasma disruption that occurs when the value of {beta} is near the Troyon limit. The location of the wall required for significant stabilization is b/a {approximately}1.2 where a is the minor radius of the plasma and b is the minor radial location of the wall. Moving the wall …

An innovative and state of the art pair spectrometer system to measure the photon component of {mu}{sup +} decay to obtain an improved branching ratio limit for the decay {mu} {yields} e{gamma} is investigated. Analysis algorithms are developed and an experimental inner bremsstrahlung spectrum is obtained and agrees well with Monte Carlo simulations. Background sources are investigated and found to be highly suppressed at various stages of acquisition and analysis.

The LAMPF E1179 experiment used the {pi}{sup 0} spectrometer and an array of charged particle range counters to detect and record {pi}{sup +}{pi}{sup 0}, {pi}{sup 0}p, and {pi}{sup +}{pi}{sup 0}p coincidences following the reaction {pi}{sup +}p {yields} {pi}{sup 0}{pi}{sup +}p near threshold. The total cross sections for single pion production were measured at the incident pion kinetic energies 190, 200, 220, 240, and 260 MeV. Absolute normalizations were fixed by measuring {pi}{sup +}p elastic scattering at 260 MeV. A detailed analysis of the {pi}{sup 0} detection efficiency was performed using cosmic ray calibrations and pion single charge exchange measurements with a 30 MeV {pi}{sup {minus}} beam. All published data on {pi}N {yields} {pi}{pi}N, including our results, are simultaneously fitted to yield a common chiral symmetry breaking parameter {xi} ={minus}0.25{plus_minus}0.10. The threshold matrix element {vert_bar}{alpha}{sub 0}({pi}{sup 0}{pi}{sup +}p){vert_bar} determined by linear extrapolation yields the value of the s-wave isospin-2 {pi}{pi} scattering length {alpha}{sub 0}{sup 2}({pi}{pi}) = {minus}0.041{plus_minus}0.003 m{sub {pi}}{sup {minus}1}, within the framework of soft-pion theory.

The three dimensional structure of several peptides were determined by NMR spectroscopy and distance geometry calculations. Each peptide formed a predictable, rigid structure, consisting of an {alpha}-helix, a {open_quotes}scaffold{close_quotes} region which packed along one face of the helix, and two disulfide bridges which covalently connect the helix and scaffold regions. The peptide Apa-M5 was designed to constrain the M5 peptide from MLCK in a helical geometry using the apamin disulfide scaffold. This scaffold constrains the N- terminal end of the helix with two disulfide bridges and a reverse turn. Like the M5 peptide, Apa-M5 was found to bind calmodulin in a Ca{sup 2+}-dependent 1:1 stoichiometry. However, the dissociation constant of the (Apa-M5)-calmodulin complex, 107 nM, was 100-fold higher than the dissociation constant of the M5-calmodulin complex. This difference was due to a putative steric overlap between the Apa-M5 scaffold and calmodulin. The peptide Apa-Cro was designed to replace the large structural protein matrix of {lambda} Cro with the apamin disulfide scaffold. However, Apa-Cro did not bind the consensus DNA operator half-site of {lambda} Cro, probably due to a steric overlap between the Apa-Cro disulfide framework and the DNA. The amino acid sequence of the scaffold-disulfide bridge arrangement of the peptide …

Thesis written by a student in the UNT Honors College discussing five of the author's experimental short stories.

Preparation, characterization, and reactivity of ({eta}{sup 2}- alkyne)(meso-tetratolylpoprphrinato)titanium(II) complexes are described, along with inetermetal oxygen atom transfer reactions involving Ti(IV) and Ti(III) porphyrin complexes. The {eta}{sup 2}- alkyne complexes are prepared by reaction of (TTP)TiCl{sub 2} with LiAlH{sub 4} in presence of alkyne. Structure of (OEP)Ti({eta}{sup 2}-Ph-C{triple_bond}C-Ph) (OEP=octaethylporphryin) was determined by XRD. The compounds undergo simple substitution to displace the alkyne and produce doubly substituted complexes. Structure of (TTP)Ti(4-picoline){sub 2} was also determined by XRD. Reaction of (TTP)Ti{double_bond}O with (OEP)Ti-Cl yields intermetal O/Cl exchange, which is a one-electron redox process mediated by O atom transfer. Also a zero-electron redox process mediated by atom transfer is observed when (TTP)TiCl{sub 2} is reacted with (OEP)Ti{double_bond}O.

W boson + QCD Jet events, produced in 1.8 TeV proton-antiproton collisions and measured by the Collider Detector at Fermilab (CDF), were used to measure the center-of-mass production angle of the W + jet system, and were also used to place limits on the production of excited quark states. The center-of-mass production angular distribution agrees well with leading order and next-to-leading order QCD predictions. Excited quark states were searched for in the reaction q + g {yields} q* {yields} q + W. Upper limits on the q* cross section, as a function of the q* mass, are shown. Comparison with a theoretical prediction for q* production excludes excited quark states with a mass in the range 150--530 GeV/c{sup 2}, at 95% confidence.