Sum frequency generation (SFG), a second-order nonlinear optical process, is electric-dipole forbidden in systems with inversion symmetry. As a result, it has been used to study chiral media and interfaces, systems intrinsically lacking inversion symmetry. This thesis describes recent progresses in the applications of and new insights into SFG from chiral media and interfaces. SFG from solutions of chiral amino acids is investigated, and a theoretical model explaining the origin and the strength of the chiral signal in electronic-resonance SFG spectroscopy is discussed. An interference scheme that allows us to distinguish enantiomers by measuring both the magnitude and the phase of the chiral SFG response is described, as well as a chiral SFG microscope producing chirality-sensitive images with sub-micron resolution. Exploiting atomic and molecular parity nonconservation, the SFG process is also used to solve the Ozma problems. Sum frequency vibrational spectroscopy is used to obtain the adsorption behavior of leucine molecules at air-water interfaces. With poly(tetrafluoroethylene) as a model system, we extend the application of this surface-sensitive vibrational spectroscopy to fluorine-containing polymers.

This thesis presents an indirect measurement of the width of the W boson using data collected at the D0 experiment, a multipurpose particle detector utilizing the Fermilab Tevatron. The W width was determined from the ratio of W {yields} {mu}{nu} to Z {yields} {mu}{sup +}{mu}{sup -} cross sections to be {Gamma}{sub W} = 2168 {+-} 22(stat) {+-} 62(syst){sub -16}{sup +24}(pdf) {+-} 4(other) MeV, in good agreement with the Standard Model prediction and other experimental measurements. In addition there is a description of how work made towards this measurement has been used to improve the parameterized detector simulation, a vital tool in the obtention of physics results from signals observed in the detector, and in estimating the uncertainty due to choice of PDF, which is of interest for all measurements made at hadron colliders.

Similar to elastic electron scattering, Compton Scattering on the proton at high momentum transfers(and high p⊥) can be an effective method to study its short-distance structure. An experiment has been carried out to measure the cross sections for Real Compton Scattering (RCS) on the proton for 2.3-5.7 GeV electron beam energies and a wide distribution of large scattering angles. The 25 kinematic settings sampled a domain of s = 5−11(GeV/c)2,−t = −7(GeV/c)2 and −u = 0.5−6.5(GeV/c)2. In addition, a measurement of longitudinal and transverse polarization transfer asymmetries was made at a 3.48 GeV beam energy and a scattering angle of θcm = 120o. These measurements were performed to test the existing theoretical mechanisms for this process as well as to determine RCS form factors. At the heart of the scientific motivation is the desire to understand the manner in which a nucleon interacts with external excitations at the above listed energies, by comparing and contrasting the two existing models – Leading Twist Mechanism and Soft Overlap “Handbag” Mechanism – and identify the dominant mechanism. Furthermore, the Handbag Mechanism allows one to calculate reaction observables in the framework of Generalized Parton Distributions (GPD), which have the function of bridging the wide …

Generalized Parton Distributions (GPDs) are universal functions which provide a comprehensive description of hadron properties in terms of quarks and gluons. Deeply Virtual Compton Scattering (DVCS) is the simplest hard exclusive process involving GPDs. In particular, the DVCS on the neutron is mostly sensitive to E, the less constrained GPD, wich allows to access to the quark angular momentum. The first dedicated DVCS experiment on the neutron ran in the Hall A of Jefferson Lab in fall 2004. The high luminosity of the experiment and the resulting background rate recquired specific devices which are decribed in this document. The analysis methods and the experiment results, leading to preliminary constraints on the GPD E, are presented.

We have studied the properties of a low emittance electron beam produced by laser pulses incident onto an rf gun photocathode. The experiments were carried out at the A0 photoinjector at Fermilab. Such beam studies are necessary for fixing the design of new Linear Colliders as well as for the development of Free Electron Lasers. An overview of the A0 photoinjector is given in Chapter 1. In Chapter 2 we describe the A0 photoinjector laser system. A stable laser system is imperative for reliable photoinjector operation. After the recent upgrade, we have been able to reach a new level of stability in the pulse-to-pulse fluctuations of the pulse amplitude, and of the temporal and transverse profiles. In Chapter 3 we present a study of transverse emittance versus the shape of the photo-cathode drive-laser pulse. For that purpose a special temporal profile laser shaping device called a pulse-stacker was developed. In Chapter 4 we discuss longitudinal beam dynamics studies using a two macro-particle bunch; this technique is helpful in analyzing pulse compression in the magnetic chicane, as well as velocity bunching effects in the rf-gun and the 9-cell accelerating cavity. In Chapter 5 we introduce a proposal for laser acceleration of …

This dissertation is organized in an alternate format. Several manuscripts which have already been published or are to be submitted for publication have been included as separate chapters. Chapter 1 is a general introduction which describes the dissertation organization and introduces the human bone and ceramic materials as bone substitute. Chapter 2 is the background and literature review on dissolution behavior of calcium phosphate, and discussion of motivation for this research. Chapter 3 is a manuscript entitled ''Si,Zn-modified tricalcium phosphate: a phase composition and crystal structure study'', which was published in ''Key Engineering Materials'' [1]. Chapter 4 gives more crystal structure details by neutron powder diffraction, which identifies the position for Si and Zn substitution and explains the stabilization mechanism of the structure. A manuscript entitled ''Crystal structure analysis of Si, Zn-modified Tricalcium phosphate by Neutron Powder Diffraction'' will be submitted to Biomaterials [2]. Chapter 5 is a manuscript, entitled ''Dissolution behavior and cytotoxicity test of Si, Zn-modified tricalcium phosphate'', which is to be submitted to Biomaterials [3]. This paper discusses the additives effect on the dissolution behavior of TCP, and cytotoxicity test result is also included. Chapter 6 is the study of hydrolysis process of {alpha}-tricalcium phosphate in the …

Studies of colloidal nanocrystals and their assemblies are presented. Two of these studies concern the atomic-level structural characterization of the surfaces, interfaces, and interiors present in II-VI semiconductor nanorods. The third study investigates the crystallographic arrangement of cobalt nanocrystals in self-assembled aggregates. Crystallographically-aligned assemblies of colloidal CdSe nanorods are examined with linearly-polarized Se-EXAFS spectroscopy, which probes bonding along different directions in the nanorod. This orientation-specific probe is used, because it is expected that the presence of specific surfaces in a nanorod might cause bond relaxations specific to different crystallographic directions. Se-Se distances are found to be contracted along the long axis of the nanorod, while Cd-Se distances display no angular dependence, which is different from the bulk. Ab-initio density functional theory calculations upon CdSe nanowires indicate that relaxations on the rod surfaces cause these changes. ZnS/CdS-CdSe core-shell nanorods are studied with Se, Zn, Cd, and S X-ray absorption spectroscopy (XAS). It is hypothesized that there are two major factors influencing the core and shell structures of the nanorods: the large surface area-to-volume ratio, and epitaxial strain. The presence of the surface may induce bond rearrangements or relaxations to minimize surface energy; epitaxial strain might cause the core and shell lattices …

The purposes of our research were: (1) To develop an economical, easy to use, automated, high throughput system for large scale protein crystallization screening. (2) To develop a new protein crystallization method with high screening efficiency, low protein consumption and complete compatibility with high throughput screening system. (3) To determine the structure of lactate dehydrogenase complexed with NADH by x-ray protein crystallography to study its inherent structural properties. Firstly, we demonstrated large scale protein crystallization screening can be performed in a high throughput manner with low cost, easy operation. The overall system integrates liquid dispensing, crystallization and detection and serves as a whole solution to protein crystallization screening. The system can dispense protein and multiple different precipitants in nanoliter scale and in parallel. A new detection scheme, native fluorescence, has been developed in this system to form a two-detector system with a visible light detector for detecting protein crystallization screening results. This detection scheme has capability of eliminating common false positives by distinguishing protein crystals from inorganic crystals in a high throughput and non-destructive manner. The entire system from liquid dispensing, crystallization to crystal detection is essentially parallel, high throughput and compatible with automation. The system was successfully demonstrated by …

Chapters 1 and 2 dealt with the chemistry of superoxo-, hydroperoxo-, and oxo- complexes of chromium, rhodium and cobalt. Chapter 3 dealt with the mechanism of oxygen-atom transfer catalyzed by an oxo-complex of rhenium. In Chapter 1, it was shown that hydroperoxometal complexes of cobalt and rhodium react with superoxochromium and chromyl ions, generating reduced chromium species while oxidizing the hydroperoxometal ions to their corresponding superoxometal ions. It was shown that the chromyl and superoxochromium ions are the more powerful oxidants. Evidence supports hydrogen atom transfer from the hydroperoxometal ion to the oxidizing superoxochromium or chromyl ion as the reaction mechanism. There is a significant H/D kinetic isotope effect. Comparisons to the rate constants of other known hydrogen atom transfer reactions show the expected correlation with bond dissociation energies. In Chapter 2, it was found that the superoxometal complexes Cr{sub aq}OO{sup 2+} and Rh(NH{sub 3}){sub 4}(H{sub 2}O)OO{sup 2+} oxidize stable nitroxyl radicals of the TEMPO series with rate constants that correlate with the redox potentials of both the oxidant and reductant. These reactions fit the Marcus equation for electron transfer near the theoretical value. Acid catalysis is important to the reaction, especially the thermodynamically limited cases involving Rh(NH{sub 3}){sub 4}(H{sub …

Yucca Mountain, Nevada is the proposed site of a geologic repository for the disposal of spent nuclear fuel and high-level radioactive waste in the United States. In the event repository engineered barriers fail, the saturated alluvium located south of Yucca Mountain is expected to serve as a natural barrier to the migration of radionuclides to the accessible environment. The purpose of this study is to improve the characterization of uranium retardation in the saturated zone at Yucca Mountain to support refinement of an assessment model. The distribution of uranium desorption rates from alluvium obtained from Nye County bore holes EWDP-19IM1, EWDP-10SA, EWDP-22SA were studied to address inconsistencies between results from batch sorption and column transport experiments. The alluvium and groundwater were characterized to better understand the underlying mechanisms of the observed behavior. Desorption rate constants were obtained using an activity based mass balance equation and column desorption experiments were analyzed using a mathematical model utilizing multiple sorption sites with different first-order forward and reverse reaction rates. The uranium desorption rate constants decreased over time, suggesting that the alluvium has multiple types of active sorption sites with different affinities for uranium. While a significant fraction of the initially sorbed uranium desorbed …

This thesis describes the first Run II measurement of b quark fragmentation into {bar B}{sup 0}, B{sup -}, and {bar B}{sub s}{sup 0} mesons and {Lambda}{sub b}{sup 0} baryons using semileptonic B decays. The result is based on 360 pb{sup -1} of data collected with the CDF detector in p{bar p} collisions at {radical}s = 1,960 GeV at the Tevatron Collider at Fermilab. The fragmentation fractions are measured for an effective {bar B} hadron p{sub T} threshold of 7 GeV/c to be f{sub u}/f{sub d} = 1.054 {+-} 0.018(stat){sub -0.045}{sup +0.025}(syst) {+-} 0.058(BR), f{sub s}/(f{sub u} + f{sub d}) = 0.160 {+-} 0.005(stat){sub -0.010}{sup +0.011}(syst){sub -0.034}{sup +0.057}(BR), and f{sub {Lambda}{sub b}}/(f{sub u} + f{sub d}) = 0.281 {+-} 0.012(stat){sub -0.056}{sup +0.058}(syst){sub -0.086}{sup +0.128}(BR). f{sub s}/(f{sub u} + f{sub d}) agrees both with previous CDF measurements and the world averages, dominated by the LEP measurements, with {approx} 1{sigma}. However, f{sub {Lambda}{sub b}}/(f{sub u} + f{sub d}) is approximately twice the value which has been measured at LEP and in CDF Run I and disagrees with the LEP results by approximately 2 {sigma}.

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Morphological evolution and selection of angular primary silicon is investigated in near-eutectic Al-Si alloys. Angular silicon arrays are grown directionally in a Bridgman furnace at velocities in the regime of 10{sup -3} m/sec and with a temperature gradient of 7.5 x 10{sup 3} K/m. Under these conditions, the primary Si phase grows as an array of twinned bicrystalline dendrites, where the twinning gives rise to a characteristic 8-pointed star-shaped primary morphology. While this primary Si remains largely faceted at the growth front, a complex structure of coherent symmetric twin boundaries enables various adjustment mechanisms which operate to optimize the characteristic spacings within the primary array. In the work presented here, this primary silicon growth morphology is examined in detail. In particular, this thesis describes the investigation of: (1) morphological selection of the twinned bicrystalline primary starshape morphology; (2) primary array behavior, including the lateral propagation of the starshape grains and the associated evolution of a strong <100> texture; (3) the detailed structure of the 8-pointed star-shaped primary morphology, including the twin boundary configuration within the central core; (4) the mechanisms of lateral propagation and spacing adjustment during array evolution; and (5) the thermosolutal conditions (i.e. operating state) at the primary …

Single Particle Aerosol Mass Spectrometry (SPAMS) was evaluated as a real-time detection technique for single particles of high explosives. Dual-polarity time-of-flight mass spectra were obtained for samples of 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitro-1,3,5-triazinane (RDX), and pentaerythritol tetranitrate (PETN); peaks indicative of each compound were identified. Composite explosives, Comp B, Semtex 1A, and Semtex 1H were also analyzed, and peaks due to the explosive components of each sample were present in each spectrum. Mass spectral variability with laser fluence is discussed. The ability of the SPAMS system to identify explosive components in a single complex explosive particle ({approx}1 pg) without the need for consumables is demonstrated. SPAMS was also applied to the detection of Chemical Warfare Agent (CWA) simulants in the liquid and vapor phases. Liquid simulants for sarin, cyclosarin, tabun, and VX were analyzed; peaks indicative of each simulant were identified. Vapor phase CWA simulants were adsorbed onto alumina, silica, Zeolite, activated carbon, and metal powders which were directly analyzed using SPAMS. The use of metal powders as adsorbent materials was especially useful in the analysis of triethyl phosphate (TEP), a VX stimulant, which was undetectable using SPAMS in the liquid phase. The capability of SPAMS to detect high explosives and CWA …

A measurement of the top pair production cross section in the dimuon final state for proton-antiproton collisions at ps = 1:96 TeV is presented. Approximately 420 pb{sup -1} of data collected with the Run II D{O} detector are used for this measurement. Two data events are observed with a total expected signal plus background yield of 3.6 events. Assuming a top mass of 175 GeV, the measured cross section is: {sigma}{sub {bar u}} = 3.13{sup +4.17}{sub -2.60}(stat){sup +0.92}{sub -0.86}(sys){+-}0.19(lumi)pb, which is consistent with a NNLO prediction of 6.77 {+-} 0.42 pb.

This dissertation was motivated by the alarming number of biomedical device failures reported in the literature, coupled with the growing trend towards the use of Nitinol for endovascular stents. The research is aimed at addressing two of the primary failure modes in Nitinol endovascular stents: fatigue-crack growth and overload fracture. The small dimensions of stents, coupled with their complex geometries and variability among manufacturers, make it virtually impossible to determine generic material constants associated with specific devices. Instead, the research utilizes a hybrid of standard test techniques (fracture mechanics and x-ray micro-diffraction) and custom-designed testing apparatus for the determination of the fracture properties of specimens that are suitable representations of self-expanding Nitinol stents. Specifically, the role of texture (crystallographic alignment of atoms) and the austenite-to-martensite phase transformation on the propagation of cracks in Nitinol was evaluated under simulated body conditions and over a multitude of stresses and strains. The results determined through this research were then used to create conservative safe operating and inspection criteria to be used by the biomedical community for the determination of specific device vulnerability to failure by fracture and/or fatigue.

The potential of single molecule detection as an analysis tool in biological and medical fields is well recognized today. This fast evolving technique will provide fundamental sensitivity to pick up individual pathogen molecules, and therefore contribute to a more accurate diagnosis and a better chance for a complete cure. Many studies are being carried out to successfully apply this technique in real screening fields. In this dissertation, several attempts are shown that have been made to test and refine the application of the single molecule technique as a clinical screening method. A basic applicability was tested with a 100% target content sample, using electrophoretic mobility and multiple colors as identification tools. Both electrophoretic and spectral information of individual molecule were collected within a second, while the molecule travels along the flow in a capillary. Insertion of a transmission grating made the recording of the whole spectrum of a dye-stained molecule possible without adding complicated instrumental components. Collecting two kinds of information simultaneously and combining them allowed more thorough identification, up to 98.8% accuracy. Probing mRNA molecules with fluorescently labeled cDNA via hybridization was also carried out. The spectral differences among target, probe, and hybrid were interpreted in terms of dispersion …

Much of the previous work in the large data visualization area has solely focused on handling the scale of the data. This task is clearly a great challenge and necessary, but it is not sufficient. Applying standard visualization techniques to large scale data sets often creates complicated pictures where meaningful trends are lost. A second challenge, then, is to also provide algorithms that simplify what an analyst must understand, using either visual or quantitative means. This challenge can be summarized as improving the legibility or reducing the complexity of massive data sets. Fully meeting both of these challenges is the work of many, many PhD dissertations. In this dissertation, we describe some new techniques to address both the scale and legibility challenges, in hope of contributing to the larger solution. In addition to our assumption of simultaneously addressing both scale and legibility, we add an additional requirement that the solutions considered fit well within an interoperable framework for diverse algorithms, because a large suite of algorithms is often necessary to fully understand complex data sets. For scale, we present a general architecture for handling large data, as well as details of a contract-based system for integrating advanced optimizations into a …

The United States economy is heavily dependent upon a vast network of pipeline systems to transport and distribute the nation's energy resources. As this network of pipelines continues to age, monitoring and maintaining its structural integrity remains essential to the nation's energy interests. Numerous pipeline accidents over the past several years have resulted in hundreds of fatalities and billions of dollars in property damages. These accidents show that the current monitoring methods are not sufficient and leave a considerable margin for improvement. To avoid such catastrophes, more thorough methods are needed. As a solution, the research of this thesis proposes a structural health monitoring (SHM) system for pipeline networks. By implementing a SHM system with pipelines, their structural integrity can be continuously monitored, reducing the overall risks and costs associated with current methods. The proposed SHM system relies upon the deployment of macro-fiber composite (MFC) patches for the sensor array. Because MFC patches are flexible and resilient, they can be permanently mounted to the curved surface of a pipeline's main body. From this location, the MFC patches are used to monitor the structural integrity of the entire pipeline. Two damage detection techniques, guided wave and impedance methods, were implemented as …

Microfluidic reactors are investigated as a mechanism tocontrol the growth of semiconductor nanocrystals and characterize thestructural evolution of colloidal quantum dots. Due to their shortdiffusion lengths, low thermal masses, and predictable fluid dynamics,microfluidic devices can be used to quickly and reproducibly alterreaction conditions such as concentration, temperature, and reactiontime, while allowing for rapid reagent mixing and productcharacterization. These features are particularly useful for colloidalnanocrystal reactions, which scale poorly and are difficult to controland characterize in bulk fluids. To demonstrate the capabilities ofnanoparticle microreactors, a size series of spherical CdSe nanocrystalswas synthesized at high temperature in a continuous-flow, microfabricatedglass reactor. Nanocrystal diameters are reproducibly controlled bysystematically altering reaction parameters such as the temperature,concentration, and reaction time. Microreactors with finer control overtemperature and reagent mixing were designed to synthesize nanoparticlesof different shapes, such as rods, tetrapods, and hollow shells. The twomajor challenges observed with continuous flow reactors are thedeposition of particles on channel walls and the broad distribution ofresidence times that result from laminar flow. To alleviate theseproblems, I designed and fabricated liquid-liquid segmented flowmicroreactors in which the reaction precursors are encapsulated inflowing droplets suspended in an immiscible carrier fluid. The synthesisof CdSe nanocrystals in such microreactors exhibited reduced depositionand residence time …