Surface sensitive synchrotron X-ray scattering studies were performed to obtain the distribution of monovalent ions next to a highly charged interface at room temperature. To control surface charge density, lipids, dihexadecyl hydrogen-phosphate (DHDP) and dimysteroyl phosphatidic acid (DMPA), were spread as monolayer materials at the air/water interface, containing CsI at various concentrations. Five decades in bulk concentrations (CsI) are investigated, demonstrating that the interfacial distribution is strongly dependent on bulk concentration. We show that this is due to the strong binding constant of hydronium H3O+ to the phosphate group, leading to proton-transfer back to the phosphate group and to a reduced surface charge. Using anomalous reflectivity off and at the L3 Cs+ resonance, we provide spatial counterion (Cs+) distributions next to the negatively charged interfaces. The experimental ion distributions are in excellent agreement with a renormalized surface charge Poisson-Boltzmann theory for monovalent ions without fitting parameters or additional assumptions. Energy Scans at four fixed momentum transfers under specular reflectivity conditions near the Cs+ L3 resonance were conducted on 10-3 M CsI with DHDP monolayer materials on the surface. The energy scans exhibit a periodic dependence on photon momentum transfer. The ion distributions obtained from the analysis are in excellent agreement …

The National Ignition Facility (NIF) will have many uses besides its primary mission in the US Department of Energy's Stockpile Stewardship Program. It will provide a broad array of applications to basic science, and will also play an important role in the development of commercial fusion energy.

The Stockpile Stewardship Program is an initiative to maintain the nuclear deterrent of the United States in the post-Cold War era. It is based on the maintenance of our stockpile through an ongoing process of surveillance, assessment, refurbishment, and recertification, without nuclear testing. At the heart of the SSP is an attempt to bring advanced experimental and computational tools to bear on the evaluation and certification of the stockpile itself; these advanced scientific capabilities are necessary because of the cessation of nuclear testing. This science-based approach requires new tools: advanced computers for more detailed 3-D simulations, multi-axis hydrodynamic facilities and plutonium research facilities for physics measurements of primaries, and the National Ignition Facility for fusion burn and high-energy-density science. The science basis requires summing up the pieces we can measure and simulate, which cannot be done without a complete set of tools. Refurbishing weapons with confidence, without testing, is a difficult challenge. Only with high-quality scientists and a complete set of tools, can the US accomplish this program. NIF is a unique element of the Stockpile Stewardship Program because it is the only facility that will allow the experimental study of thermonuclear burn and important regimes of high-energy-density science. Understanding …

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Matrix-assisted laser desorption/ionization(MALDI) mass spectrometry(MS) has been widely used for analysis of biological molecules, especially macromolecules such as proteins. However, MALDI MS has a problem in small molecule (less than 1 kDa) analysis because of the signal saturation by organic matrixes in the low mass region. In imaging MS (IMS), inhomogeneous surface formation due to the co-crystallization process by organic MALDI matrixes limits the spatial resolution of the mass spectral image. Therefore, to make laser desorption/ionization (LDI) MS more suitable for mass spectral profiling and imaging of small molecules directly from raw biological tissues, LDI MS protocols with various alternative assisting materials were developed and applied to many biological systems of interest. Colloidal graphite was used as a matrix for IMS of small molecules for the first time and methodologies for analyses of small metabolites in rat brain tissues, fruits, and plant tissues were developed. With rat brain tissues, the signal enhancement for cerebroside species by colloidal graphite was observed and images of cerebrosides were successfully generated by IMS. In addition, separation of isobaric lipid ions was performed by imaging tandem MS. Directly from Arabidopsis flowers, flavonoids were successfully profiled and heterogeneous distribution of flavonoids in petals was observed for …

The WARP code is a robust electrostatic particle-in-cell simulation package used to model charged particle beams with strong space-charge forces. A fundamental operation associated with seeding detailed simulations of a beam transport channel is to generate initial conditions where the beam distribution is matched to the structure of a periodic focusing lattice. This is done by solving for periodic, matched solutions to a coupled set of ODEs called the Kapchinskij-Vladimirskij (KV) envelope equations, which describe the evolution of low-order beam moments subject to applied lattice focusing, space-charge defocusing, and thermal defocusing forces. Recently, an iterative numerical method was developed (Lund, Chilton, and Lee, Efficient computation of matched solutions to the KV envelope equations for periodic focusing lattices, Physical Review Special Topics-Accelerators and Beams 9, 064201 2006) to generate matching conditions in a highly flexible, convergent, and fail-safe manner. This method is extended and implemented in the WARP code as a Python package to vastly ease the setup of detailed simulations. In particular, the Python package accommodates any linear applied lattice focusing functions without skew coupling, and a more general set of beam parameter specifications than its predecessor. Lattice strength iteration tools were added to facilitate the implementation of problems with …

The Standard Model predicts that the lifetime of the top quark is shorter than the typical time scale at which hadronization process occurs, and the spin information at its production is preserved. Spin correlation of the t{anti t} system from p{anti p} collisions at the Tevatron is analyzed using 6 events in the dilepton channels collected using the D0 detector. Spin correlation factor of {kappa} > {minus} 0.25 at 68% CL is obtained from the data.

Model heterogeneous catalysts have been synthesized and studied to better understand how the surface structure of noble metal nanoparticles affects catalytic performance. In this project, monodisperse rhodium and platinum nanoparticles of controlled size and shape have been synthesized by solution phase polyol reduction, stabilized by polyvinylpyrrolidone (PVP). Model catalysts have been developed using these nanoparticles by two methods: synthesis of mesoporous silica (SBA-15) in the presence of nanoparticles (nanoparticle encapsulation, NE) to form a composite of metal nanoparticles supported on SBA-15 and by deposition of the particles onto a silicon wafer using Langmuir-Blodgett (LB) monolayer deposition. The particle shapes were analyzed by transmission electron microscopy (TEM) and high resolution TEM (HRTEM) and the sizes were determined by TEM, X-ray diffraction (XRD), and in the case of NE samples, room temperature H2 and CO adsorption isotherms. Catalytic studies were carried out in homebuilt gas-phase reactors. For the nanoparticles supported on SBA-15, the catalysts are in powder form and were studied using the homebuilt systems as plug-flow reactors. In the case of nanoparticles deposited on silicon wafers, the same systems were operated as batch reactors. This dissertation has focused on the synthesis, characterization, and reaction studies of model noble metal heterogeneous catalysts. …

Laser vibrometry is a technique used to detect vibrations on objects using the interference of coherent light with itself. Most vibrometry systems process only one target location at a time, but processing multiple locations simultaneously provides improved detection capabilities. Traditional laser vibrometry systems employ oversampling to sample the incoming modulated-light signal, however as the number of channels increases in these systems, certain issues arise such a higher computational cost, excessive heat, increased power requirements, and increased component cost. This thesis describes a novel approach to laser vibrometry that utilizes undersampling to control the undesirable issues associated with over-sampled systems. Undersampling allows for significantly less samples to represent the modulated-light signals, which offers several advantages in the overall system design. These advantages include an improvement in thermal efficiency, lower processing requirements, and a higher immunity to the relative intensity noise inherent in laser vibrometry applications. A unique feature of this implementation is the use of a parallel architecture to increase the overall system throughput. This parallelism is realized using a hierarchical multi-channel architecture based on off-the-shelf programmable logic devices (PLDs).

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Determination of application times-to-solution for large-scale clustered computers continues to be a difficult problem in high-end computing, which will only become more challenging as multi-core consumer machines become more prevalent in the market. Both researchers and consumers of these multi-core systems desire reasonable estimates of how long their programs will take to run (time-to-solution, or TTS), and how many resources will be consumed in the execution. Currently there are few methods of determining these values, and those that do exist are either overly simplistic in their assumptions or require great amounts of effort to parameterize and understand. One previously untried method is queuing network modeling (QNM), which is easy to parameterize and solve, and produces results that typically fall within 10 to 30% of the actual TTS for our test cases. Using characteristics of the computer network (bandwidth, latency) and communication patterns (number of messages, message length, time spent in communication), the QNM model of the NAS-PB CG application was applied to MCR and ALC, supercomputers at LLNL, and the Keck Cluster at USF, with average errors of 2.41%, 3.61%, and -10.73%, respectively, compared to the actual TTS observed. While additional work is necessary to improve the predictive capabilities of …

The ammonia synthesis reaction has been studied using single crystal model catalysis combined with sum frequency generation (SFG) vibrational spectroscopy. The adsorption of gases N{sub 2}, H{sub 2}, O{sub 2} and NH{sub 3} that play a role in ammonia synthesis have been studied on the Fe(111) crystal surface by sum frequency generation vibrational spectroscopy using an integrated Ultra-High Vacuum (UHV)/high-pressure system. SFG spectra are presented for the dissociation intermediates, NH{sub 2} ({approx}3325 cm{sup -1}) and NH ({approx}3235 cm{sup -1}) under high pressure of ammonia or equilibrium concentrations of reactants and products on Fe(111) surfaces. Special attention was paid to understand how potassium promotion of the iron catalyst affects the intermediates of ammonia synthesis. An Fe(111) surface promoted with 0.2 monolayers of potassium red shifts the vibrational frequencies of the reactive surface intermediates, NH and NH{sub 2}, providing evidence for weakened the nitrogen-hydrogen bonds relative to clean Fe(111). Spectral features of these surface intermediates persisted to higher temperatures for promoted iron surfaces than for clean Fe(111) surfaces implying that nitrogen-iron bonds are stronger for the promoted surface. The ratio of the NH to NH{sub 2} signal changed for promoted surfaces in the presence of equilibrium concentrations of reactants and products. The …

We have studied the dissociation of CO catalyzed by platinum single crystals. At 40 torr of CO, the Pt(111) crystal dissociates CO at 673 K. Under the same conditions, Pt(100) dissociates CO at 500 K, and Pt(557) dissociates CO at 548 K. Hence, the CO dissociation reaction is a structure sensitive reaction. SFG was used to monitor the CO top site resonance as the platinum crystals were heated to the dissociation temperature when exposed to 40 torr of CO. In all three systems, the CO resonance shifts to lower frequency as the platinum crystal is heated. However, the frequency of the CO resonance at the dissociation frequency is lower on the (100) and (111) crystal faces than on the Pt(557) crystal. We believe that the (111) and (100) crystal faces must undergo roughening to expose step or kink sites in order to facilitate the dissociation reaction. This is supported by UHV studies of CO dissociation catalyzed by platinum crystals. These studies observe dissociation only when step or kink sites are present. Since the Pt(111) surface is very stable, it needs to be heated to 673 K to produce the low coordination number sites needed for CO dissociation. Since the Pt(100) …

Experimental, numerical, and analytical work has shown that the response of a shell to a distributed force wave possesses unique characteristics which are dependent on the nature of structure attached to the shell. Specific characteristics which influence the response are the distribution of the discontinuities around the circumference (periodic/aperiodic), the impedance of the discontinuities relative to that of the shell, and the type of impedance (mass or stiffness). Traditional shell theory predicts low frequency, radial-dominated structural mode shapes of a shell with a sinusoidal distribution of displacement amplitudes. Due to the orthogonal nature of these mode shapes, the response of the structure to a traveling radial force wave with sinusoidal content at a given harmonic is due solely to the response of the mode shape with harmonic content of the same order. Introduction of impedance discontinuities to a shell yield complex mode shapes, which may be characterized by the summation of several harmonic components. These modes are no longer orthogonal in the presence of discontinuities, yielding harmonic content across various modal orders. As a result, a purely sinusoidal forcing function can excite several modes of the structure. Structural scattering as discussed in this paper refers to the phenomena in which …

The fractionation of particles from their suspending fluid or noninvasive micromanipulation of particles in suspension has many applications ranging from the recovery of valuable reagents from process flows to the fabrication of microelectromechanical devices. Techniques based on size, density, solubility, or electromagnetic properties exist for fulfilling these needs, but many particles have traits that preclude their use such as small size, neutral buoyancy, or uniform electromagnetic characteristics. While separation by those techniques may not be possible, often compressibility differences exist between the particle and fluid that would allow fractionation by acoustic forces. The potential of acoustic separation is known, but due to inherent difficulties in achieving and maintaining accurate alignment of the transduction system, it is rarely utilized. The objective of this project is to investigate the use of structural excitation as a potentially efficient concentration/fractionation method for particles in suspension. It is demonstrated that structural excitation of a cylindrically symmetric cavity, such as a tube, allows non-invasive, fast, and low power concentration of particles suspended in a fluid. The inherent symmetry of the system eliminates the need for careful alignment inherent in current acoustic concentration devices. Structural excitation distributes the acoustic field throughout the volume of the cavity, which …

This dissertation reports on measurements of inclusive cross sections times branching fractions into electrons for W and Z bosons produced in p{anti p} collisions at {radical}s = 1.8 TeV. From an integrated luminosity of 84.5 pb{sup {minus}1} recorded in 1994--1995 by the D0 detector at the Fermilab Tevatron {Lambda} the cross sections are measured to be {sigma}p{anti p} {r_arrow} W + X {center_dot} B(W {r_arrow} e{nu}) = 2,310 {+-} 10 (stat) {+-} 50 (Syst) {+-} 100 (lum) pb and {sigma}(p{anti p} {r_arrow} Z + X) {center_dot} B(Z {r_arrow} ee) = 221 {+-} 3 (stat) {+-} 4 (Syst) {+-} 10 (lum) pb. The cross section ratio R is determined to be {sigma}(p{anti p} {r_arrow} W + X) {center_dot} B(W {r_arrow} e{nu})/{sigma}(p{bar p} {r_arrow} Z + X) {center_dot} B(Z {r_arrow} ee) = 10.43 {+-} 0.15 (stat) {+-} 0.20 (syst) {+-} 0.10 (NLO){Lambda} and R is used to determine B(W {r_arrow} e{nu}) = 0.1044 {+-} 0.0015 (stat) {+-} 0.0020 (syst) {+-} 0.0017 (theory) {+-} 0.0010 (NLO){Lambda} and {Lambda}{sub W} = 2.169 {+-} 0.031 (stat) {+-} 0.042 (syst) {+-} 0.041 (theory) {+-} 0.022 (NLO) GeV. The latter is used to set a 95% confidence level upper limit on the partial decay width of the …

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In an effort to understand the molecular ingredients of catalytic activity and selectivity toward the end of tuning a catalyst for 100% selectivity, advanced nanolithography techniques were developed and utilized to fabricate well-ordered two-dimensional model catalyst arrays of metal nanostructures on an oxide support for the investigation of reaction selectivity. In-situ and ex-situ surface science techniques were coupled with catalytic reaction data to characterize the molecular structure of the catalyst systems and gain insight into hydrocarbon conversion in heterogeneous catalysis. Through systematic variation of catalyst parameters (size, spacing, structure, and oxide support) and catalytic reaction conditions (hydrocarbon chain length, temperature, pressures, and gas composition), the data presented in this dissertation demonstrate the ability to direct a reaction by rationally adjusting, through precise control, the design of the catalyst system. Electron beam lithography (EBL) was employed to create platinum nanoparticles on an alumina (Al{sub 2}O{sub 3}) support. The Pt nanoparticle spacing (100-150-nm interparticle distance) was varied in these samples, and they were characterized using x-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM), both before and after reactions. The TEM studies showed the 28-nm Pt nanoparticles with 100 and 150-nm interparticle spacing on …

This dissertation presents the results of a research agenda aimed at improving integration and stability in nanocrystal-based solar cells through advances in active materials and device architectures. The introduction of 3-dimensional nanocrystals illustrates the potential for improving transport and percolation in hybrid solar cells and enables novel fabrication methods for optimizing integration in these systems. Fabricating cells by sequential deposition allows for solution-based assembly of hybrid composites with controlled and well-characterized dispersion and electrode contact. Hyperbranched nanocrystals emerge as a nearly ideal building block for hybrid cells, allowing the controlled morphologies targeted by templated approaches to be achieved in an easily fabricated solution-cast device. In addition to offering practical benefits to device processing, these approaches offer fundamental insight into the operation of hybrid solar cells, shedding light on key phenomena such as the roles of electrode-contact and percolation behavior in these cells. Finally, all-inorganic nanocrystal solar cells are presented as a wholly new cell concept, illustrating that donor-acceptor charge transfer and directed carrier diffusion can be utilized in a system with no organic components, and that nanocrystals may act as building blocks for efficient, stable, and low-cost thin-film solar cells.

The magnetic flux structures in the intermediate state of bulk, pinning-free Type-I superconductors are studied using a high resolution magneto-optical imaging technique. Unlike most previous studies, this work focuses on the pattern formation of the coexisting normal and superconducting phases in the intermediate state. The influence of various parameters such as sample shape, structure defects (pinning) and applied current are discussed in relation to two distinct topologies: flux tubes (closed topology) and laminar (open topology). Imaging and magnetization measurements performed on samples of different shapes (cones, hemispheres and slabs), show that contrary to previous beliefs, the tubular structure is the equilibrium topology, but it is unstable toward defects and flux motion. Moreover, the application of current into a sample with the geometric barrier can replace an established laminar structure with flux tubes. At very high currents, however, there exists a laminar 'stripe pattern.' Quantitative analysis of the mean tube diameter is shown to be in good agreement with the prediction proposed by Goren and Tinkham. This is the first time that this model has been confirmed experimentally. Further research into the flux tube phase shows a direct correlation with the current loop model proposed in the 1990's by Goldstein, Jackson …

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Remarkable advances have been made since rapid solidification was first introduced to the field of materials science and technology. New types of materials such as amorphous alloys and nanostructure materials have been developed as a result of rapid solidification techniques. While these advances are, in many respects, ground breaking, much remains to be discerned concerning the fundamental relationships that exist between a liquid and a rapidly solidified solid. The scope of the current dissertation involves an extensive set of experimental, analytical, and computational studies designed to increase the overall understanding of morphological selection, phase competition, and structural hierarchy that occurs under far-from equilibrium conditions. High pressure gas atomization and Cu-block melt-spinning are the two different rapid solidification techniques applied in this study. The research is mainly focused on Al-Si and Al-Sm alloy systems. Silicon and samarium produce different, yet favorable, systems for exploration when alloyed with aluminum under far-from equilibrium conditions. One of the main differences comes from the positions of their respective T{sub 0} curves, which makes Al-Si a good candidate for solubility extension while the plunging T{sub 0} line in Al-Sm promotes glass formation. The rapidly solidified gas-atomized Al-Si powders within a composition range of 15 to 50 …

Sum frequency generation (SFG) vibrational spectroscopy, atomic force microscopy (AFM), and other complementary surface-sensitive techniques have been used to study the surface molecular structure and surface mechanical behavior of biologically-relevant polymer systems. SFG and AFM have emerged as powerful analytical tools to deduce structure/property relationships, in situ, for polymers at air, liquid and solid interfaces. The experiments described in this dissertation have been performed to understand how polymer surface properties are linked to polymer bulk composition, substrate hydrophobicity, changes in the ambient environment (e.g., humidity and temperature), or the adsorption of macromolecules. The correlation of spectroscopic and mechanical data by SFG and AFM can become a powerful methodology to study and engineer materials with tailored surface properties. The overarching theme of this research is the interrogation of systems of increasing structural complexity, which allows us to extend conclusions made on simpler model systems. We begin by systematically describing the surface molecular composition and mechanical properties of polymers, copolymers, and blends having simple linear architectures. Subsequent chapters focus on networked hydrogel materials used as soft contact lenses and the adsorption of protein and surfactant at the polymer/liquid interface. The power of SFG is immediately demonstrated in experiments which identify the chemical …

Various single-molecule techniques were utilized for ultra-sensitive early diagnosis of viral DNA and antigen and basic mechanism study of enzymatic reactions. DNA of human papilloma virus (HPV) served as the screening target in a flow system. Alexa Fluor 532 (AF532) labeled single-stranded DNA probes were hybridized to the target HPV-16 DNA in solution. The individual hybridized molecules were imaged with an intensified charge-coupled device (ICCD) in two ways. In the single-color mode, target molecules were detected via fluorescence from hybridized probes only. This system could detect HPV-16 DNA in the presence of human genomic DNA down to 0.7 copy/cell and had a linear dynamic range of over 6 orders of magnitude. In the dual-color mode, fluorescence resonance energy transfer (FRET) was employed to achieve zero false-positive count. We also showed that DNA extracts from Pap test specimens did not interfere with the system. A surface-based method was used to improve the throughput of the flow system. HPV-16 DNA was hybridized to probes on a glass surface and detected with a total internal reflection fluorescence (TIRF) microscope. In the single-probe mode, the whole genome and target DNA were fluorescently labeled before hybridization, and the detection limit is similar to the flow …