The first chapter gives a brief overview of the system discussed in this dissertation. Chapters 2--5 and Appendix B of this dissertation consist of papers that are published, or have been submitted, which show experimental data regarding the phonon softening of LuNi{sub 2}B{sub 2}C. These papers have been removed and processed separately. Chapter 6 will contain a summary of the conclusions up to date. Appendix A will consist of a brief derivation of {chi}(q) which is talked about in the introduction of the dissertation. Appendix B will contain a Born-von Karman model fit to the experimental LuNi{sub 2}B{sub 2}C data and a comparison with experimental data. Appendix C will contain a brief summary of the work done on LuNi{sub 2}B{sub 2}C as well as a complete listing of experimental data taken on the crystals which may be needed later for theoretical models of this system. Appendix D will outline a brief introduction covering some of the field theory used in the theoretical work for this thesis.

In this dissertation, the author reports on the surface structure of i-Al-Pd-Mn twofold, threefold, fivefold and i-Al-Cu-Fe fivefold surfaces. The LEED studies indicate the existence of two distinct stages in the regrowth of all four surfaces after Ar{sup +} sputtering. In the first stage, upon annealing at relatively low temperature: 500K--800K (depending on different surfaces), a cubic phase appears. The cubic LEED patterns transform irreversibly to unreconstructed quasicrystalline patterns upon annealing to higher temperatures, indicating that the cubic overlayers are metastable. Based upon the data for three chemically-identical, but symmetrically-inequivalent surfaces, a model is developed for the relation between the cubic overlayers and the quasicrystalline substrate. The model is based upon the related symmetries of cubic close-packed and icosahedral-packed materials. These results may be general among Al-rich, icosahedral materials. STM study of Al-Pd-Mn fivefold surface shows that terrace-step-kink structures start to form on the surface after annealing above 700K. Large, atomic ally-flat terraces were formed after annealing at 900K. Fine structures with fivefold icosahedral symmetry were found on those terraces. Data analysis and comparison of the STM images and structure model of icosahedral Al-Pd-Mn suggest that the fine structures in the STM images may be the pseudo Mackay (PMI) clusters …

The equations of motion describing turbulent flows (in both the low and high Reynolds-number regimes) are well established. However, present day computers cannot meet the enormous computational requirement for numerically solving the governing equations for common engineering flows in the high Reynolds number turbulent regime. The characteristics that make turbulent, high Reynolds number flows difficult to simulate is the extreme range of time and space scales of motion. Most current engineering calculations are performed using semi-empirical equations, developed in terms of the flow mean (average) properties. These turbulence{open_quote} models{close_quote} (semi-empirical/analytical approximations) do not explicitly account for the eddy structures and thus, the temporal and spatial flow fluctuations are not resolved. In these averaging approaches, it is necessary to approximate all the turbulent structures using semi-empirical relations, and as a result, the turbulence models must be tailored for specific flow conditions and geometries with parameters obtained (usually) from physical experiments. The motivation for this research is the development of a finite element turbulence modeling approach which will ultimately be used to predict the wind flow around buildings. Accurate turbulence models of building flow are needed to predict the dispersion of airborne pollutants. The building flow turbulence models used today are not …

Over the previous twenty years, ternary molybdenum chalcogenides of the general formula M{sub x}Mo{sub 6}Y{sub 8} (M = ternary metal cation; Y = chalcogenide), known as Chevrel phases, have been extensively studied. Many of these compounds have been found to have superconductivity, catalytic activity and ionic conductivity. The rich chemistry of the Chevrel phases raises considerable interest in finding the tungsten analogues of these phases. However, no such analogue has ever been synthesized, although the Chevrel phases are usually prepared directly from elements at high temperatures above 1000{degrees}C. The absence of the tungsten analogues may be caused by their thermodynamic instability at such high temperatures. Thus it might be necessary to avoid high-temperature synthetic procedures in order to establish the ternary and binary tungsten chalcogenides. A major focus of the McCarley research group has been on the preparation of M{sub 6}Y{sub 8}L{sub 6} (M = Mo, W; Y = S, Se, Te) cluster complexes as low temperature pathways to the Chevrel phases.

This report consists of five studies as follows: A laser photofragmentation time-of-flight mass spectrometric study of acetophenone at 193 and 248 nm; A 193 nm laser photofragmentation time-of-flight mass spectrometric study of dimethylsulfoxide; 193 nm laser photofragmentation time-of-flight mass spectrometric study of HSCH{sub 2}CH{sub 2}SH; Thiophene biradical decay of the primary laser photofragmentation product at 193 nm; and Scattering cross sections for O({sup 3}P)[SO(X,{sup 3}{Sigma}{sup {minus}})] + He[Ne, Ar, Kr]. Chapters are included for the introduction and general conclusions.

Investigations into the preparation of tungsten nitrides have involved the synthesis of molecular precursors, and their conversion to tungsten nitrides at relatively low temperatures. Two interesting molecular precursors, [WNCl{sub 3}{center_dot}NCCH{sub 3}]{sub 4} and WN(N{sub 3}){sub 3}{center_dot}xNCCH{sub 3}, have been prepared and characterized. The molecular structure of the first consists of a W{sub 4}N{sub 4} tetrameric core with multiple and single W-N bonds arranged in an alternating fashion. Three new solid state phases, amorphous W{sub 3}N{sub 5}, cubic WN, and W{sub 2}N{sub 2}(C{sub 2}N{sub 2}), have been discovered by solid state and chemical vapor transport reactions. The structures have been investigated. A systematic study in the Ln{sub 2}O{sub 3}-MoO{sub 3}-Mo (Ln = La, Ce, Pr, Nd, Sm) system has been explored to better understand LnMo{sub 8}O{sub 14}. The study has shown that the sizes of the rare-earth cations affect the formation of these phases. Larger cations (La, Ce, and Pr) aid in the formation of trans-Mo{sub 8} bicapped octahedra, and the smaller cations (Nd, Sm) only stabilize the cis-Mo{sub 8} bicapped octahedra. Magnetic susceptibility measurements have indicated that no effective moment contribution arises from the Mo{sub 8} metal clusters, even though the cis-Mo{sub 8} cluster in LnMo{sub 8}O{sub 14}, containing all …

The goal of this work is to explore several new strategies and approaches to the surface modification and the microscopic characterization of interfaces in the areas mainly targeting sensor technologies that are of interest to environmental control or monitoring, and scanning probe microscopies techniques that can monitor interfacial chemical reactions in real time. Centered on the main theme, four specific topics are presented as four chapters in this dissertation following the general introduction. Chapter 1 describes the development of two immobilization schemes for covalently immobilizing fluoresceinamine at cellulose acetate and its application as a pH sensing film. Chapter 2 investigates the applicability of SFM to following the base-hydrolysis of a dithio-bis(succinimidylundecanoate) monolayer at gold in situ. Chapter 3 studies the mechanism for the accelerated rate of hydrolysis of the dithio-bis(succinimidylundecanoate) monolayer at Au(111) surface. Chapter 4 focuses on the development of an electrochemical approach to the elimination of chloride interference in Chemical Oxygen Demand (COD) analysis of waste water. The procedures, results and conclusions are described in each chapter. This report contains the introduction, references, and general conclusions. Chapters have been processed separately for inclusion on the data base. 95 refs.

It is not an exaggeration to say that much of chemistry involves ions in solution. A technique which allows for ions to be transferred from solution into the gas phase and subsequently analyzed by mass spectrometric detection would be of importance. If structural information, representative of the solution chemistry could be gained from these gas-phase ions, this would also be important. Electrospray mass spectrometry (ES-MS) is such a technique.

The focus of this dissertation is the use of a twin quadrupole inductively coupled plasma mass spectrometer (ICP-MS) for the simultaneous detection of two m/z values. The twin quadrupole ICP-MS is used with laser ablation sample introduction in both the steady state (10 Hz) and single pulse modes. Steady state signals are highly correlated and the majority of flicker noise cancels when the ratio is calculated. Using a copper sample, the isotope ratio {sup 63}Cu{sup +}/{sup 65}Cu{sup +} is measured with a relative standard deviation (RSD) of 0.26%. Transient signals for single laser pulses are also obtained. Copper isotope ratio measurements for several laser pulses are measured with an RSD of 0.85%. Laser ablation (LA) is used with steel samples to assess the ability of the twin quadrupole ICP-MS to eliminate flicker noise of minor components of steel samples. Isotopic and internal standard ratios are measured in the first part of this work. The isotope ratio {sup 52}Cr{sup +}/{sup 53}Cr{sup +} (Cr present at 1.31 %) can be measured with an RSD of 0.06 % to 0.1 %. For internal standard elements, RSDs improve from 1.9 % in the Cr{sup +} signal to 0.12% for the ratio of {sup 51}V{sup …

The selective hydrogenation of crotonaldehyde has been investigated over a monometallic Pt/SiO{sub 2} catalyst and platinum bimetallic catalysts where the second metal was either silver, copper, or tin. The effects of addition of a second metal to the Pt/SiO{sub 2} system on the selectivity to crotyl alcohol were investigated. The Pt-Sn bimetallic catalysts were characterized by hydrogen chemisorption, {sup 1}H NMR and microcalorimetry. The Pt-Ag/SiO{sub 2} and Pt-Cu/SiO{sub 2} catalysts were characterized by hydrogen chemisorption. Pt-Sn/SiO{sub 2} catalysts selectively hydrogenated crotonaldehyde to crotyl alcohol and the method of preparation of these catalysts affected the selectivity. The most selective Pt-Sn/SiO{sub 2} catalysts for the hydrogenation of crotonaldehyde to crotyl alcohol were those in which the Sn precursor was dissolved in a HCl solution. Sn increased both the rate of formation of butyraldehyde and the rate of formation of crotyl alcohol. The Pt/SiO{sub 2}, Pt-Ag/SiO{sub 2} and Pt-Cu/SiO{sub 2} catalysts produced only butyraldehyde. Initial heats of adsorption ({approximately}90 kJ/mol) measured using microcalorimetry were not affected by the presence of Sn on Pt. We can conclude that there is no through metal electronic interaction between Pt and Sn at least with respect to hydrogen surface bonds since the Pt and Pt-Sn at least …

Iron-aluminum alloys have been extensively evaluated as semi-continuous product such as sheet and bar, but have not been evaluated by net shape P/M processing techniques such as metal injection molding. The alloy compositions of iron-aluminum alloys have been optimized for room temperature ductility, but have limited high temperature strength. Hot extruded powder alloys in the Fe-Al-Si system have developed impressive mechanical properties, but the effects of sintering on mechanical properties have not been explored. This investigation evaluated three powder processed Fe-Al-Si alloys: Fe-15Al, Fe-15Al-2.8Si, Fe-15Al-5Si (atomic %). The powder alloys were produced with a high pressure gas atomization (HPGA) process to obtain a high fraction of metal injection molding (MIM) quality powder (D{sub 84} < 32 {micro}m). The powders were consolidated either by P/M hot extrusion or by vacuum sintering. The extruded materials were near full density with grain sizes ranging from 30 to 50 {micro}m. The vacuum sintering conditions produced samples with density ranging from 87% to 99% of theoretical density, with an average grain size ranging from 26 {micro}m to 104 {micro}m. Mechanical property testing was conducted on both extruded and sintered material using a small punch test. Tensile tests were conducted on extruded bar for comparison with …

A generalized solidification model has been developed based on a systematic investigation on the microstructure of melt spun Nd-Fe-B alloys. Melt spinning was conducted on initial stoichiometric and TiC added Nd{sub 2}Fe{sub 14}B (2-14-1) compositions to produce under, optimally and over quenched microstructures. Microstructural characterization was carried out by TEM, SEM, Optical microscopy, XRD, DTA, VSM and DC SQUID techniques. By taking the dendritic breakup during recalescence into consideration, this generalized model has successfully explained the solidification process of the melt spun Nd-Fe-B alloys. Challenging the conventional homogeneous nucleation models, the new model explains the fine and uniform equiaxed 2-14-1 microstructure in optimally quenched ribbons as a result of the breakup of the 2-14-1 dendrites which nucleate heterogeneously from the wheel surface and grow dendritically across the ribbon thickness due to the recalescence. Besides this dendritic breakup feature, the under quenched microstructure is further featured with another growth front starting with the primary solidification of Fe phase near the free side, which results in a coarsely grained microstructure with Fe dendritic inclusions and overall variation in microstructure across the ribbon thickness. In addition, because a epitaxy exists between the Fe phase and the 2-14-1, the so-formed coarse 2-14-1 grains may …

A centrifugal atomizer (spinning disk variety) was designed and constructed for the production of spherical metal powders, 100--1,000 microns in diameter in an inert atmosphere. Initial atomization experiments revealed the need for a better understanding of how the liquid metal was atomized and how the liquid droplets solidified. To investigate particle atomization, Ag was atomized in air and the process recorded on high-speed film. To investigate particle solidification, Al-32.7 wt.% Cu was atomized under inert atmosphere and the subsequent particles were examined microscopically to determine solidification structure and rate. This dissertation details the experimental procedures used in producing the Al-Cu eutectic alloy particles, examination of the particle microstructures, and determination of the solidification characteristics (e.g., solidification rate) of various phases. Finally, correlations are proposed between the operation of the centrifugal atomizer and the observed solidification spacings.

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 …

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 …

Since the invention of quantum mechanics, even the simplest example of collisional breakup in a system of charged particles, e{sup {minus}} + H {r_arrow} H{sup +} + e{sup {minus}} + e{sup {minus}}, has stood as one of the last unsolved fundamental problems in atomic physics. A complete solution requires calculating the energies and directions for a final state in which three charged particles are moving apart. Advances in the formal description of three-body breakup have yet to lead to a viable computational method. Traditional approaches, based on two-body formalisms, have been unable to produce differential cross sections for the three-body final state. Now, by using a mathematical transformation of the Schrodinger equation that makes the final state tractable, a complete solution has finally been achieved, Under this transformation, the scattering wave function can be calculated without imposing explicit scattering boundary conditions. This approach has produced the first triple differential cross sections that agree on an absolute scale with experiment as well as the first ab initio calculations of the single differential cross section.

A major focus of this dissertation is the development of functionals for the magnetic susceptibility and the chemical shielding within the context of magnetic field density functional theory (BDFT). These functionals depend on the electron density in the absence of the field, which is unlike any other treatment of these responses. There have been several advances made within this theory. The first of which is the development of local density functionals for chemical shieldings and magnetic susceptibilities. There are the first such functionals ever proposed. These parameters have been studied by constructing functionals for the current density and then using the Biot-Savart equations to obtain the responses. In order to examine the advantages and disadvantages of the local functionals, they were tested numerically on some small molecules.

In this thesis, both time-resolved, nonlinear optical spectroscopy and linear spectroscopy are used to investigate the interactions and dynamics of elementary excitations in strongly correlated electron systems. In the first part, we investigate the renormalization of magnetic elementary excitations in the transition metal oxide Cr{sub 2}O{sub 3}. We have created a non-equilibrium population of antiferromagnetic spin waves and characterized its dynamics, using frequency- and time-resolved optical spectroscopy of the exciton-magnon transition. We observed a time-dependent pump-probe line shape, which results from excitation induced renormalization of the spin wave band structure. We present a model that reproduces the basic characteristics of the data, in which we postulate the optical nonlinearity to be dominated by interactions with long-wavelength spin waves, and the dynamics due to spin wave thermalization. Using linear spectroscopy, coherent third-harmonic generation and pump-probe experiments, we measured the optical properties of the charge-transfer (CT) gap exciton in Sr{sub 2}CuO{sub 2}Cl{sub 2}, an undoped model compound for high-temperature superconductors. A model is developed which explains the pronounced temperature dependence and newly observed Urbach tail in the linear absorption spectrum by a strong, phonon-mediated coupling between the charge-transfer exciton and ligand field excitations of the Cu atoms. The third-order nonlinear optical susceptibility …

The purpose of this investigation was to determine the energy absorption characteristics of plastically deformed inclined struts under impact loading. This information is needed to provide a usable method by which designers and analysts of shipping casks for radioactive or fissile materials can determine the energy absorption capabilities of external longitudinal fins on cylindrical casks under specified impact conditions. A survey of technical literature related to experimental determination of the dynamic plastic behavior of struts revealed no information directly applicable to the immediate problem, especially in the impact velocity ranges desired, and an experimental program was conducted to obtain the needed data. Mild-steel struts with rectangular cross sections were impacted by free-falling weights dropped from known heights. These struts or fin specimens were inclined at five different angles to simulate different angles of impact that fins on a shipping cask could experience under certain accident conditions. The resisting force of the deforming strut was measured and recorded as a function of time by using load cells instrumented with resistance strain gage bridges, signal conditioning equipment, an oscilloscope, and a Polaroid camera. The acceleration of the impacting weight was measured and recorded as a function of time during the latter portion …

This project will develop an analytical tool to calculate performance of HMX based PBXs in the skid test. The skid-test is used as a means to measure sensitivity for large charges in handling situations. Each series of skid tests requires dozens of drops of large billets. It is proposed that the reaction (or lack of one) of PBXs in the skid test is governed by the mechanical properties of the binder. If true, one might be able to develop an analytical tool to estimate skid test behavior for new PBX formulations. Others over the past 50 years have tried to develop similar models. This project will research and summarize the works of others and couple the work of 3 into an analytical tool that can be run on a PC to calculate drop height of HMX based PBXs. Detonation due to dropping a billet is argued to be a dynamic thermal event. To avoid detonation, the heat created due to friction at impact, must be conducted into the charge or the target faster than the chemical kinetics can create additional energy. The methodology will involve numerically solving the Frank-Kamenetskii equation in one dimension. The analytical problem needs to be bounded …

We have measured the three-body photobreakup of {sup 3}He with the tagged photon beam and the CEBAF Large Acceptance Spectrometer in Hall B at the Thomas Jefferson National Accelerator Facility, in the photon energy range between 0.35 GeV and 1.55 GeV. This measurement constitutes a wide-ranging survey of two- and three-body processes in the gamma{sup 3}He {yields} ppn reaction channel, thanks to the high statistics and large kinematic coverage obtained with the CLAS. Total and partially integrated differential cross sections for the full ppn data set and for selected kinematics were extracted and are compared to theoretical predictions of Laget (up to 1.0 GeV). At low photon energies, the calculations are generally in fair agreement with the data. The comparison shows evidence of strong contributions of three-body absorption mechanisms, especially in the star kinematics, a symmetric configuration of the three final-state nucleons. Mostly the effects of two-body absorption mechanisms are se en, as expected, in the pp-pair-breakup kinematics, where the neutron does not participate in the reaction. The quasi-two-body breakup shows angular distributions consistent with preliminary gamma{sup 3}He --&gt; pd results, extracted from our experiment. The ratio of cross sections for the star configuration and for the two-body kinematics, shows …

This thesis is written to advance the reader's knowledge of precision-engineering principles and their application to designing machines that achieve both sufficient precision and minimum cost. It provides the concepts and tools necessary for the engineer to create new precision machine designs. Four case studies demonstrate the principles and showcase approaches and solutions to specific problems that generally have wider applications. These come from projects at the Lawrence Livermore National Laboratory in which the author participated: the Large Optics Diamond Turning Machine, Accuracy Enhancement of High- Productivity Machine Tools, the National Ignition Facility, and Extreme Ultraviolet Lithography. Although broad in scope, the topics go into sufficient depth to be useful to practicing precision engineers and often fulfill more academic ambitions. The thesis begins with a chapter that presents significant principles and fundamental knowledge from the Precision Engineering literature. Following this is a chapter that presents engineering design techniques that are general and not specific to precision machines. All subsequent chapters cover specific aspects of precision machine design. The first of these is Structural Design, guidelines and analysis techniques for achieving independently stiff machine structures. The next chapter addresses dynamic stiffness by presenting several techniques for Deterministic Damping, damping designs that …

A new experimental technique for the time-resolved study of anion reactions is presented. Using femtosecond laser pulses, which provide extremely fast ({approx} 100 fs) time resolution, in conjunction with photoelectron spectroscopy, which reveals differences between anion and neutral potential energy surfaces, a complex anion reaction can be followed from its inception through the formation of asymptotic products. Experimental data can be modeled quantitatively using established theoretical approaches, allowing for the refinement of potential energy surfaces as well as dynamical models. After a brief overview, a detailed account of the construction of the experimental apparatus is presented. Documentation of the data acquisition program is contained in the Appendix. The first experimental demonstration of the technique is then presented for I{sub 2}{sup -} photodissociation, modeled using a simulation program which is also detailed in the Appendix. The investigation of I{sub 2}{sup -} photodissociation in several size-selected I{sub 2}{sup -}(Ar){sub n} (n = 6-20) and I{sub 2}{sup -}(CO{sub 2}){sub n} (n = 4-16) clusters forms the heart of the dissertation. In a series of chapters, the numerous effects of solvation on this fundamental bond-breaking reaction are explored, the most notable of which is the recombination of I{sub 2}{sup -} on the ground {tilde …

The {sup 16}O(e,e'p)#8; reaction was studied in the #6;first physics experiment performed at Jefferson lab Hall A. In the quasielastic region cross sections were measured for both quasi#11;parallel and perpendicular kinematics at q = 1000 MeV and #2;{omega} = 445#14;#14;#15; MeV. From the data acquired in quasi#11;parallel kinematics#4; longitudinal and transverse response functions#4; R{sub L} and R{sub T} were separated for E{sub miss} < 60 MeV. The perpendicular kinematics data were used to extract R{sub LT}, #4; R{sub T},#4; and R{sub L#16;} + V{sub TT}/V{sub L}R{sub TT} response functions for the same E{sub miss} range and for P{sub miss} < 310 MeV#18;c. The {sub 16}O(#7;e,#4;e'p)#8; cross section was measured in the dip region at q = 1026 MeV and #2; {omega} = 586#12;#15;#19;#2; MeV for 10 MeV <#3; E{sub miss} < 320 MeV. This thesis presents the results for the missing energy continuum (#7;E{sub miss}>25#4; #3;#15; MeV)#8; from this experiment.