The photofragmentation pathways of chemically reactive free radicals have been examined using the technique of fast beam photofragment translational spectroscopy. Measurements of the photodissociation cross-sections, product branching ratios, product state energy distributions, and angular distributions provide insight into the excited state potential energy surfaces and nonadiabatic processes involved in the dissociation mechanisms. Photodissociation spectroscopy and dynamics of the predissociative {tilde A}{sup 2}A{sub 1} and {tilde B}{sup 2}A{sub 2} states of CH{sub 3}S have been investigated. At all photon energies, CH{sub 3} + S({sup 3}P{sub j}), was the main reaction channel. The translational energy distributions reveal resolved structure corresponding to vibrational excitation of the CH{sub 3} umbrella mode and the S({sup 3}P{sub j}) fine-structure distribution from which the nature of the coupled repulsive surfaces is inferred. Dissociation rates are deduced from the photofragment angular distributions, which depend intimately on the degree of vibrational excitation in the C-S stretch. Nitrogen combustion radicals, NCN, CNN and HNCN have also been studied. For all three radicals, the elimination of molecular nitrogen is the primary reaction channel. Excitation to linear excited triplet and singlet electronic states of the NCN radical generates resolved vibrational structure of the N{sub 2} photofragment. The relatively low fragment rotational excitation …

A number of experiments have accumulated over the years a large amount of solar neutrino data. The data indicate that the observed solar neutrino flux is significantly smaller than expected and, furthermore, that the electron neutrino survival probability is energy dependent. This ''solar neutrino problem'' is best solved by assuming that the electron neutrino oscillates into another neutrino species. Even though one can classify the solar neutrino deficit as strong evidence for neutrino oscillations, it is not yet considered a definitive proof. Traditional objections are that the evidence for solar neutrino oscillations relies on a combination of hard, different experiments, and that the Standard Solar Model (SSM) might not be accurate enough to precisely predict the fluxes of different solar neutrino components. Even though it seems unlikely that modifications to the SSM alone can explain the current solar neutrino data, one still cannot completely discount the possibility that a combination of unknown systematic errors in some of the experiments and certain modifications to the SSM could conspire to yield the observed data. To conclusively demonstrate that there is indeed new physics in solar neutrinos, new experiments are aiming at detecting ''smoking gun'' signatures of neutrino oscillations, such as an anomalous …

Two ionic and one neutral methyl(oxo)rhenium(V) compounds were synthesized and structurally characterized. They were compared in reactivity towards the ligands triphenylphosphane, pyridines, pyridine N-oxides. Assistance from Broensted bases was found on ligand displacement of ionic rhenium compounds as well as nucleophile assistance on oxidation of all compounds. From the kinetic data, crystal structures, and an analysis of the intermediates, a structural formula of PicH{sup +}3{sup -} and mechanisms of ligand displacement and oxidation were proposed.

The Matteucci effect, which mainly manifests itself as the change of magnetization of a material with torsional stress, is currently of great technological interest because of the search for magnetic torque sensors. Magnetic torque sensors are important to future improvements of automobiles and industrial robots. It is well known that the magnetic state of a material depends on both the external magnetic field and external stress which causes strain and change in magnetization of the material. The former phenomenon has been well understood in both theory and application. However, the magnetic state dependence of stress is not adequately understood and the experimental data is of limited extent. In this project, the Matteucci effect in iron, cobalt, nickel and permalloy rods has been documented when they were in magnetic remanence status along the axis and nickel ring when they were in remanence status along the circumference. The effect of annealing on the magnetomechanical effect in nickel and the temperature dependence of the magnetomechanical sensitivity has also been examined. Factors related to the sensitivity at equilibrium condition have been theoretically developed. it is found in the experiments that the mechanism of magnetic domain wall movement plays an important role rather than the …

This dissertation describes the efforts to design and implement the Generalized Portable SHMEM library, GPSHMEM, as well as supplementary tools. There are two major components of the GPSHMEM project: the GPSHMEM library itself and the Fortran 77 source-to-source translator. The rest of this thesis is divided into two parts. Part I introduces the shared memory model and the distributed shared memory model. It explains the motivation behind GPSHMEM and presents its functionality and performance results. Part II is entirely devoted to the Fortran 77 translator call fgpp. The need for such a tool is demonstrated, functionality goals are stated, and the design issues are presented along with the development of the solutions.

Organic light emitting devices (OLEDs) are among the most promising for flat panel display technologies. They are light, bright, flexible, and cost effective. And while they are emerging in commercial product, their low power efficiency and long-term degradation are still challenging. The aim of this work was to investigate their device physics and improve their performance. Violet and blue OLEDs were studied. The devices were prepared by thermal vapor deposition in high vacuum. The combinatorial method was employed in device preparation. Both continuous wave and transient electroluminescence (EL) were studied. A new efficient and intense UV-violet light emitting device was developed. At a current density of 10 mA/cm{sup 2}, the optimal radiance R could reach 0.38 mW/cm{sup 2}, and the quantum efficiency was 1.25%. using the delayed EL technique, electron mobilities in DPVBi and CBP were determined to be {approx} 10{sup -5} cm{sup 2}/Vs and {approx} 10{sup -4} cm{sup 2}/Vs, respectively. Overshoot effects in the transient El of blue light emitting devices were also observed and studied. This effect was attributed to the charge accumulation at the organic/organic and organic/cathode interfaces.

The work presented in this dissertation has investigated three distinct areas of interest in the field of quasicrystals: bulk structure, transport properties, and electronic structure. First, they have described the results of a study which explored the fundamental interactions between the atomic species of the icosahedral Al-Pd-Mn quasicrystal. The goal of this work was to determine whether the pseudo-MacKay or Bergman type clusters have a special stability or are merely a geometric coincidence. This was carried out by using laser vaporization to produce gas-phase metal clusters, which were analyzed using time-of-flight mass spectrometry. Both the kinetic and thermodynamic stabilities of the clusters were probed. The data indicated no special stability for either pseudo-MacKay or Bergman type clusters as isolated units. This, however, is not proof that these clusters are simply a geometric coincidence. It is possible that such clusters only have stability in the framework of the bulk matrix and do not exist as isolated units. Next, they have reported their investigations of the bulk thermal transport properties of a decagonal Al-Ni-Co two dimensional quasicrystal in the temperature range 373K-873K. The properties of a sample oriented along the periodic axis and another oriented along the aperiodic axis were measured. A …

A magnetic tunnel junction is a device that changes its electrical resistance with a change in an applied magnetic field. A typical junction consists of two magnetic electrodes separated by a nonmagnetic insulating layer. The magnetizations of the two electrodes can have two possible extreme configurations, parallel and antiparallel. The antiparallel configuration is observed to have the higher measured resistance and the parallel configuration has the lower resistance. To switch between these two configurations a magnetic field is applied to the device which is primarily used to change the orientation of the magnetization of one electrode usually called the free layer, although with sufficient high magnetic field the orientation of the magnetizations of both of the electrodes can be changed. The most commonly used models for describing and explaining the electronic behavior of tunnel junctions are the Simmons model and the Brinkman model. However, both of these models were designed for simple, spin independent tunneling. The Simmons model does not address the issue of applied magnetic fields nor does it address the form of the electronic band structure in the metallic electrodes, including the important factor of spin polarization. The Brinkman model is similar, the main difference between the two …

Capillary electrophoresis (CE) offers many advantages over conventional analytical methods, such as speed, simplicity, high resolution, low cost, and small sample consumption, especially for the separation of enantiomers. However, chiral method developments still can be time consuming and tedious. They designed a comprehensive enantioseparation protocol employing neutral and sulfated cyclodextrins as chiral selectors for common basic, neutral, and acidic compounds with a 96-capillary array system. By using only four judiciously chosen separation buffers, successful enantioseparations were achieved for 49 out of 54 test compounds spanning a large variety of pKs and structures. Therefore, unknown compounds can be screened in this manner to identify optimal enantioselective conditions in just one rn. In addition to superior separation efficiency for small molecules, CE is also the most powerful technique for DNA separations. Using the same multiplexed capillary system with UV absorption detection, the sequence of a short DNA template can be acquired without any dye-labels. Two internal standards were utilized to adjust the migration time variations among capillaries, so that the four electropherograms for the A, T, C, G Sanger reactions can be aligned and base calling can be completed with a high level of confidence. the CE separation of DNA can be …

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CFD (Computational Fluid Dynamics) is a widely used technique in engineering design field. It uses mathematical methods to simulate and predict flow characteristics in a certain physical space. Since the numerical result of CFD computation is very hard to understand, VR (virtual reality) and data visualization techniques are introduced into CFD post-processing to improve the understandability and functionality of CFD computation. In many cases CFD datasets are very large (multi-gigabytes), and more and more interactions between user and the datasets are required. For the traditional VR application, the limitation of computing power is a major factor to prevent visualizing large dataset effectively. This thesis presents a new system designing to speed up the traditional VR application by using parallel computing and distributed computing, and the idea of using hand held device to enhance the interaction between a user and VR CFD application as well. Techniques in different research areas including scientific visualization, parallel computing, distributed computing and graphical user interface designing are used in the development of the final system. As the result, the new system can flexibly be built on heterogeneous computing environment, dramatically shorten the computation time.

The oxidation resistance of a high-temperature alloy is dependent upon sustaining the formation of a protective scale, which is strongly related to the alloying composition and the oxidation condition. The protective oxide scale only provides a finite period of oxidation resistance owing to its eventual breakdown, which is especially accelerated under thermal cycling conditions. This current study focuses on the long-term cyclic oxidation behavior of a number of commercial wrought alloys. The alloys studied were Fe- and Ni-based, containing different levels of minor elements, such as Si, Al, Mn, and Ti. Oxidation testing was conducted at 1000 and 1100 C in still air under both isothermal and thermal cycling conditions (1-day and 7-days). The specific aspects studied were the oxidation behavior of chromia-forming alloys that are used extensively in industry. The current study analyzed the effects of alloying elements, especially the effect of minor element Si, on cyclic oxidation resistance. The behavior of oxide scale growth, scale spallation, subsurface changes, and chromium interdiffusion in the alloy were analyzed in detail. A novel model was developed in the current study to predict the life-time during cyclic oxidation by simulating oxidation kinetics and chromium interdiffusion in the subsurface of chromia-forming alloys.

The scientific community has recently experienced an overall effort to reduce the physical size of many experimental components to the nanometer size range. This size is unique as the characteristics of this regime involve aspects of pure physics, biology, and chemistry. One extensively studied example of a nanometer sized experimental component, which acts as a junction between these three principle scientific theologies, is deoxyribonucleic acid (DNA) or ribonucleic acid (RNA). These biopolymers not only contain the biological genetic guide to code for the production of life-sustaining materials, but are also being probed by physicists as a means to create electrical circuits and furthermore as controllable architectural and sensor motifs in the chemical disciplines. Possibly the most common nano-sized component between these sciences are nanoparticles composed of a variety of materials. The cross discipline employment of nanoparticles is evident from the vast amount of literature that has been produced from each of the individual communities within the last decade. Along these cross-discipline lines, this dissertation examines the use of several different types of nanoparticles with a wide array of surface chemistries to understand their adsorption properties and to construct unique miniaturized analytical and immunoassay platforms. This introduction will act as a …

This thesis presents a measurement of the cross-section of the purely electromagnetic production of e{sup +}e{sup -} pairs accompanied by mutual nuclear Coulomb excitation AuAu {yields} Au*Au* + e{sup +}e{sup -}, in ultra-peripheral gold-gold collisions at RHIC at the center-of-mass collision energy of {radical}S{sub NN} = 200 GeV per nucleon. These reactions were selected by detecting neutron emission by the excited gold ions in the Zero Degree Calorimeters. The charged tracks in the e{sup +}e{sup -} events were reconstructed with the STAR Time Projection Chamber. The detector acceptance limits the kinematical range of the observed e{sup +}e{sup -} pairs; therefore the measured cross-section is extrapolated to 4{pi} with the use of Monte Carlo simulations. We have developed a Monte Carlo simulation for ultra-peripheral e{sup +}e{sup -} production at RHIC based on the Equivalent Photon Approximation, the lowest-order QED e{sup +}e{sup -} production cross-section by two real photons and the assumption that the mutual nuclear excitations and the e{sup +}e{sup -} production are independent (EPA model). We compare our experimental results to two models: the EPA model and a model based on full QED calculation of the e{sup +}e{sup -} production, taking the photon virtuality into account. The measured differential cross-section …

Organic light-emitting devices (OLEDs) constitute a new and exciting emissive display technology. In general, the basic OLED structure consists of a stack of fluorescent organic layers sandwiched between a transparent conducting-anode and metallic cathode. When an appropriate bias is applied to the device, holes are injected from the anode and electrons from the cathode; some of the recombination events between the holes and electrons result in electroluminescence (EL). Until now, most of the efforts in developing OLEDs have focused on display applications, hence on devices within the visible range. However some organic devices have been developed for ultraviolet or infrared emission. Various aspects of the device physics of doped small molecular OLEDs were described and discussed. The doping layer thickness and concentration were varied systematically to study their effects on device performances, energy transfer, and turn-off dynamics. Low-energy-gap DCM2 guest molecules, in either {alpha}-NPD or DPVBi host layers, are optically efficient fluorophores but also generate deep carrier trap-sites. Since their traps reduce the carrier mobility, the current density decreases with increased doping concentration. At the same time, due to efficient energy transfer, the quantum efficiency of the devices is improved by light doping or thin doping thickness, in comparison with …

Low temperature Nonphotochemical Hole Burning (NPHB) Spectroscopy of the dye rhodamine 800 (MF680) was applied for the purpose of discerning differences between cultured normal and carcinoma ovarian surface epithelial (OSE) cells. Both the cell lines were developed and characterized at the Mayo Clinic (Rochester, MN), with the normal cell line having been transfected with a strain of temperature sensitive Simian Virus 40 Large T Antigen (SV40) for the purpose of extending the life of the cell culture without inducing permanent changes in the characteristics of the cell line. The cationic lipophilic fluorophore rhodamine 800 preferentially locates in in situ mitochondria due to the high lipid composition of mitochondria and the generation of a large negative membrane potential (relative to the cellular cytoplasm) for oxidative phosphorylation. Results presented for NPHB of MF680 located in the cells show significant differences between the two cell lines. The results are interpreted on the basis of the NPHB mechanism and characteristic interactions between the host (cellular mitochondrial) and the guest (MF680) in the burning of spectral holes, thus providing an image of the cellular ultrastructure. Hole growth kinetics (HGK) were found to differ markedly between the two cell lines, with the carcinoma cell line burning …

A unique approach to crack-free joining of heterogeneous ceramics is demonstrated by the use of sialon polytypoids as Functionally Graded Materials (FGM) as defined by the phase diagram in the system, Si3N4-Al2O3. Polytypoids in the Al2O3-Si3N4 system offer a path to compatibility for such heterogeneous ceramics. The first part of the dissertation describes successful hot press sintering of multilayered FGM's with 20 layers of thickness 500 mm each. Transmission Electron Microscopy was used to identify the polytypoids at the interfaces of different areas of the joint. It has been found that the 15R polytypoid was formed in the Al2O3-contained layers and the 12H polytypoid was formed in the Si3N4-contained layers. The second part of the dissertation discusses the mechanical properties of these polytypoidally joined Si3N4-Al2O3. The thermal stresses of this FGM junction were analyzed using a finite element analysis program (FEAP) taking into account both coefficient of thermal expansion (CTE) and modulus variations. From this analysis, the result showed a dramatic decrease in radial, axial and hoop stresses as the FGM changes from three layers to 20 graded layers. Scaling was considered, showing that the graded transition layer should constitute about 75 percent or more of the total sample thickness …

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This thesis contains the candidate's original work on excitonic structure and energy transfer dynamics of two bacterial antenna complexes as studied using spectral hole-burning spectroscopy. The general introduction is divided into two chapters (1 and 2). Chapter 1 provides background material on photosynthesis and bacterial antenna complexes with emphasis on the two bacterial antenna systems related to the thesis research. Chapter 2 reviews the underlying principles and mechanism of persistent nonphotochemical hole-burning (NPHB) spectroscopy. Relevant energy transfer theories are also discussed. Chapters 3 and 4 are papers by the candidate that have been published. Chapter 3 describes the application of NPHB spectroscopy to the Fenna-Matthews-Olson (FMO) complex from the green sulfur bacterium Prosthecochloris aestuarii; emphasis is on determination of the low energy vibrational structure that is important for understanding the energy transfer process associated within three lowest energy Qy-states of the complex. The results are compared with those obtained earlier on the FMO complex from Chlorobium tepidum. In Chapter 4, the energy transfer dynamics of the B800 molecules of intact LH2 and B800-deficient LH2 complexes of the purple bacterium Rhodopseudomonas acidophila are compared. New insights on the additional decay channel of the B800 ring of bacteriochlorophyll a (BChl a) molecules …

The ideal structural steel combines high strength with high fracture toughness. This dissertation discusses the toughening mechanism of the Fe/Co/Ni/Cr/Mo/C steel, AerMet 100, which has the highest toughness/strength combination among all commercial ultrahigh strength steels. The possibility of improving the toughness of this steel was examined by considering several relevant factors.

In this work, the authors have undertaken a theoretical approach to the complex problem of modeling the flow of electromagnetic waves in photonic crystals. The focus is to address the feasibility of using the exciting phenomena of photonic gaps (PBG) in actual applications. The authors start by providing analytical derivations of the computational electromagnetic methods used in their work. They also present a detailed explanation of the physics underlying each approach, as well as a comparative study of the strengths and weaknesses of each method. The Plane Wave expansion, Transfer Matrix, and Finite Difference time Domain Methods are addressed. They also introduce a new theoretical approach, the Modal Expansion Method. They then shift the attention to actual applications. They begin with a discussion of 2D photonic crystal wave guides. The structure addressed consists of a 2D hexagonal structure of air cylinders in a layered dielectric background. Comparison with the performance of a conventional guide is made, as well as suggestions for enhancing it. The studies provide an upper theoretical limit on the performance of such guides, as they assumed no crystal imperfections and non-absorbing media. Next, they study 3D metallic PBG materials at near infrared and optical wavelengths. The main …

Industrial synthesis of sulfur-containing organic chemicals basically focuses on the broad categories of mercaptans (thiols), alkylsulfides (thioethers), polysulfides, and thiophenes. Of the organo-sulfur compounds produced, by far the most important in terms of quantities produced is methyl mercaptan (methanethiol or MeSH), which is produced mainly for the downstream production of methionine and methanesulfonyl chloride. Higher thiols are also used in the manufacture of rubber and plastics as polymerization regulators, chain transfer agents, or initiators. Other important organosulfur chemicals are dimethyl sulfide (DMS) and dimethyl disulfide (DMDS), both of which are used extensively for presulfiding of industrial hydroprocessing catalysts, and substituted thiophenes which are used as intermediates for production of agrochemicals, dyes, and pharmaceuticals. Thiols are produced commercially at the rate of about 10{sup 4} ton/yr from hydrogen sulfide (H{sub 2}S) and alcohols or olefins, using homogeneous free-radical synthesis, or heterogeneous catalysts based on solid acids or supported metal oxides and/or sulfides. Despite this large production rate, and the industrial importance of the organosulfur compounds, only limited research has been devoted to the development of new catalytic materials for their synthesis. Additionally, for most organosulfur catalytic reactions, only limited information exists about reaction mechanisms, active sites, adsorbed surface species, and especially …

The consideration of compliant mechanisms as Microelectromechanical Systems (MEMS) is the focus of this research endeavor. MEMS are micron to millimeter devices that combine electrical, mechanical, and information processing capabilities on the same device. These MEMS need some mechanical motion or parts that move relative to each other. This relative motion, using multiple parts, is not desired because of the assembly requirement and the friction introduced. Compliant devices limits or eliminates friction and the need for multi-component assembly. Compliant devices improve designs by creating single piece mechanisms. The purpose of this research is to validate surface micromachining as a viable fabrication process for compliant MEMS designs. Specifically, this research has sought to fabricate a micro-compliant gripper and a micro-compliant clamp to illustrate the process. While other researchers have created compliant MEMS, most have used comb-drive actuation methods and bulk micromachining processes. This research focuses on fully-compliant devices that use device flexibility for motion and actuation. Validation of these compliant MEMS is achieved by structural optimization of device design and functional performance testing. This research contributes to the ongoing research in MEMS by evaluating the potential of using surface micromachining as a process for fabricating compliant micro-mechanisms.

Alkali metal aluminohydrides have high potential as solid hydrogen storage materials. They have been known for their irreversible dehydrogenation process below 100 atm until Bogdanovic et al [1, 2] succeeded in the re-hydrogenation of NaAlH{sub 4} below 70 atm. They achieved 4 wt.% H{sub 2} reversible capacity by doping NaAlH{sub 4} with Ti and/or Fe organo-metalic compounds as catalysts. This suggests that other alkali and, possibly alkaline earth metal aluminohydrides can be used for reversible hydrogen storage when modified by proper dopants. In this research, Zr{sub 27}Ti{sub 9}Ni{sub 38}V{sub 5}Mn{sub 16}Cr{sub 5}, LaNi{sub 4.85}Sn{sub 0.15}, Al{sub 3}Ti, and PdCl{sub 2} were combined , LaNi4.85Sn0.15, Al3Ti, and PdCl2 were combined with LiAlH{sub 4} by ball-milling to study whether or not LiAlH{sub 4} is capable to both absorb and desorb hydrogen near ambient conditions. X-ray powder diffraction, differential thermal analysis, and scanning electron microscopy were employed for sample characterizations. All four compounds worked as catalysts in the dehydrogenation reactions of both LiAlH{sub 4} and Li{sub 3}AlH{sub 6} by inducing the decomposition at lower temperature. However, none of them was applicable as catalyst in the reverse hydrogenation reaction at low to moderate hydrogen pressure.