The dynamics of S({sup 3}P{sub 2,1,0}, {sup 1}D{sub 2}) production from the 193 nm photodissociation of CH{sub 3}SCH{sub 3}, H{sub 2}S and CH{sub 3}SH have been studied using 2 + 1 resonance-enhanced multiphoton ionization (REMPI) techniques. The 193 nm photodissociation cross sections for the formation of S from CH{sub 3}S and HS initially prepared in the photodissociation of CH{sub 3}SCH{sub 3} and H{sub 2}S are estimated to be 1 {times} 10{sup {minus}18} and 1.1 {times} 10{sup {minus}18} cm{sup 2}, respectively. The dominant product from CH{sub 3}S is S({sup 1}D), while that from SH is S({sup 3}P). Possible potential energy surfaces involved in the 193 nm photodissociation of CH{sub 3}S({tilde X}) and SH(X) have been also examined. Threshold photoelectron (PE) spectra for SH and CH{sub 3}S formed in the ultraviolet photodissociation of H{sub 2}S and CH{sub 3}SH, respectively, have been measured using the nonresonant two-photon pulsed field ionization (N2P-PFI) technique. The rotationally resolved N2P-PFI-PE spectrum obtained for SH indicates that photoionization dynamics favors the rotational angular momentum change {Delta}N < 0 with the {Delta}N value up to {minus}3, an observation similar to that found in the PFI-PE spectra of OH (OD) and NO. The ionization energies for SH(X{sup 2}{product}{sub 3,2}) and …

The following report analyzes interactions of K+ and K- mesons and measures their lifetimes using a nuclear emulsion technique.

Magnetic flux leakage (MFL) is a technique used widely in non-destructive testing (NDT) of natural gas and petroleum transmission pipelines. This inspection method relies on magnetizing the pipe-wall in axial direction. The MFL inspection tool is equipped with an array of Hall sensors located around the circumference of the pipe, which registers the flux leakage caused by any defects present in the pipe-wall. Currently, the tool magnetizes the pipewall in axial direction making it largely insensitive to axially oriented defects. One type of defect, which is of a growing concern in the gas and petroleum industry is the stress corrosion crack (SCC). The SCCs are a result of aging, corrosion, fatigue and thermal stresses. SCCs are predominantly axially oriented and are extremely tight, which makes them impossible to be detected using current inspection technology. A possible solution to this problem is to utilize the remote field eddy current (RFEC) effect to detect axially oriented defects. The RFEC method has been widely used in industry in the inspection of tubular products. The method uses a pair of excitation and pick-up coils. The pick-up coil located in the remote field region, usually two, three pipe-diameters away from the excitation coil. With RFEC …

Studies of random laser systems are a new direction with promising potential applications and theoretical interest. The research is based on the theories of localization and laser physics. So far, the research shows that there are random lasing modes inside the systems which is quite different from the common laser systems. From the properties of the random lasing modes, they can understand the phenomena observed in the experiments, such as multi-peak and anisotropic spectrum, lasing mode number saturation, mode competition and dynamic processes, etc. To summarize, this dissertation has contributed the following in the study of random laser systems: (1) by comparing the Lamb theory with the Letokhov theory, the general formulas of the threshold length or gain of random laser systems were obtained; (2) they pointed out the vital weakness of previous time-independent methods in random laser research; (3) a new model which includes the FDTD method and the semi-classical laser theory. The solutions of this model provided an explanation of the experimental results of multi-peak and anisotropic emission spectra, predicted the saturation of lasing modes number and the length of localized lasing modes; (4) theoretical (Lamb theory) and numerical (FDTD and transfer-matrix calculation) studies of the origin of …

Submitted to Univ. of Tennessee, Knoxville. The fast neutron-induced fission cross section of U/sup 234/ was measured from threshold to 4-Mev neutron energy. A maximum of 1.26 barns was found at 850 kev followed by a minimum of 1.10 barns at 8050 kev. The angular ani-sotropy of the fragment distribution was measured for neutron energies from 400 kev to 4 Mev. Extrema in the ratio sigma /sub f//( sigma /sub f(90 deg ) were found at 500, 850, and 1050 kev; the distribution at 500 kev showing a maximum in the direction normal to the beam (side-wise peaking) while that at 850 kev showed a maximum along the beam direction. The distribution at 8050 kev showed forward peaking but to a lesser extent than for energies immediately higher or lower. The behavior was analyzed according to the theories of Bohr and Wheeler. The dip in cross section between 850 and 1050 kev is consistent with the suggestion of Wheeler that neutron competition in the decay of the compound nucleus enters with increased strength in this area. Vibration-rotational levels in U/sup 234/ beginning at 790 kev are known to exist and inelastic neutron scattering to these levels serves to depress the …

Very weak alpha branching in heavy elements was studied by a recently developed coincidence technique. This technique makes it possible to measure the energies and intensities of both alpha -particle groups and de-exciting radiation, even when the transition intensities are as low as 10/sup -8/ relative to the most intense alpha group. Twenty alpha -particle emitters from Po/sup 214/ to Fm were examined. 00+ states (beta vibrations) were observed in six even-even nuclei, and analogous states were found in three odd-mass nuclei. They are in general characterized by low alpha-decay hindrance factors and roughly equal de-excitation by electric monopole and quadrupole transitions. However, the deexcitation of these states is in disagreement with vibrational model predictions in certain cases; more important, the de-excitation and other properties of the states exhibit some irregular variations from nucleus to nucleus which are evidence for some particle character in the states. Information was also obtained about some other types of levels. A number of 1- states (octupole vibrations) were observed, and a possible 2- state was observed in U/sup 236/. A state that appears to be analogous to the 1-octupole states of even-even nuclei was observed in U/sup 235/. In Pu/sup 239/, a K = …

Astrocytes, a subtype of glial cell, have recently been shown to exhibit Ca{sup 2+} elevations in response to neurotransmitters. A Ca{sup 2+} elevation can propagate to adjacent astrocytes as a Ca{sup 2+} wave, which allows an astrocyte to communicate with its neighbors. Additionally, glutamate can be released from astrocytes via a Ca{sup 2+}-dependent mechanism, thus modulating neuronal activity and synaptic transmission. In this dissertation, the author investigated the roles of another endogenous signal, nitric oxide (NO), in astrocyte-neuron signaling. First the author tested if NO is generated during astrocytic Ca{sup 2+} signaling by imaging NO in purified murine cortical astrocyte cultures. Physiological concentrations of a natural messenger, ATP, caused a Ca{sup 2+}-dependent NO production. To test the roles of NO in astrocytic Ca{sup 2+} signaling, the author applied NO to astrocyte cultures via addition of a NO donor, S-nitrosol-N-acetylpenicillamine (SNAP). NO induced an influx of external Ca{sup 2+}, possibly through store-operated Ca{sup 2+} channels. The NO-induced Ca{sup 2+} signaling is cGMP-independent since 8-Br-cGMP, an agonistic analog of cGMP, did not induce a detectable Ca{sup 2+} change. The consequence of this NO-induced Ca{sup 2+} influx was assessed by simultaneously monitoring of cytosolic and internal store Ca{sup 2+} using fluorescent Ca{sup 2+} …

This dissertation focuses on techniques for (1) increasing ethanol yields from saccharification and fermentation of cellulose using immobilized cellulase, and (2) the characterization and classification of lignocellulosic feedstocks, and quantification of useful parameters such as the syringyl/guaiacyl (S/G) lignin monomer content using 1064 nm dispersive multichannel Raman spectroscopy and chemometrics.

Homeland security relies heavily on analytical chemistry to identify suspicious materials and persons. Traditionally this role has focused on attribution, determining the type and origin of an explosive, for example. But as technology advances, analytical chemistry can and will play an important role in the prevention and preemption of terrorist attacks. More sensitive and selective detection techniques can allow suspicious materials and persons to be identified even before a final destructive product is made. The work presented herein focuses on the use of commercial and novel detection techniques for application to the prevention of terrorist activities. Although drugs are not commonly thought of when discussing terrorism, narcoterrorism has become a significant threat in the 21st century. The role of the drug trade in the funding of terrorist groups is prevalent; thus, reducing the trafficking of illegal drugs can play a role in the prevention of terrorism by cutting off much needed funding. To do so, sensitive, specific, and robust analytical equipment is needed to quickly identify a suspected drug sample no matter what matrix it is in. Single Particle Aerosol Mass Spectrometry (SPAMS) is a novel technique that has previously been applied to biological and chemical detection. The current work …

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 Q{sub y}-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{sub a} (BChl{sub a}) …

With the recent discovery of the giant magnetocaloric effect and the beginning of extensive research on the properties of Gd{sub 5}(Si{sub x}Ge{sub 1-x}){sub 4}, a necessity has developed for a better understanding of the microstructure and crystal structure of this family of rare earth compounds with startling phenomenological properties. The aim of this research is to characterize the microstructure of the Gd{sub 5}(Si{sub x}Ge{sub 1-x}){sub 4}, with X {approx_equal} 2 and its phase change by using both transmission and electron microscopes. A brief history of past work on Gd{sub 5}(Si{sub x}Ge{sub 1-x}){sub 4} is necessary to understand this research in its proper context.

In core-collapse supernovae, strong blast waves drive interfaces susceptible to Rayleigh-Taylor (RT), Richtmyer-Meshkov (RM), and Kelvin-Helmholtz (KH) instabilities. In addition, perturbation growth can result from material expansion in large-scale velocity gradients behind the shock front. Laser-driven experiments are designed to produce a strongly shocked interface whose evolution is a scaled version of the unstable hydrogen-helium interface in core-collapse supernovae such as SN 1987A. The ultimate goal of this research is to develop an understanding of the effect of hydrodynamic instabilities and the resulting transition to turbulence on supernovae observables that remain as yet unexplained. In this dissertation, we present a computational study of unstable systems driven by high Mach number shock and blast waves. Using multi-physics radiation hydrodynamics codes and theoretical models, we consider the late nonlinear instability evolution of single mode, few mode, and multimode interfaces. We rely primarily on 2D calculations but present recent 3D results as well. For planar multimode systems, we show that compressibility effects preclude the emergence of a regime of self-similar instability growth independent of the initial conditions (IC's) by allowing for memory of the initial conditions to be retained in the mix-width at all times. The loss of transverse spectral information is demonstrated, …

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 …

Using computer simulations, the performance of several CdTe based photovoltaic structures has been studied. The advantages and disadvantages of band gap grading, through the use of (Zn, Cd)Te, have also been investigated in these structures. Grading at the front interface between a CdS window layer and a CdTe absorber layer, can arise due to interdiffusion between the materials during growth or due to the intentional variation of the material composition. This grading has been shown to improve certain performance metrics, such as the open-circuit voltage, while degrading others, such as the fill factor, depending on the amount and distance of the grading. The presence of a Schottky barrier as the back contact has also been shown to degrade the photovoltaic performance of the device, resulting in a characteristic IV curve. However, with the appropriate band gap grading at the back interface, it has been shown that the performance can be enhanced through more efficient carrier collection. These results were then correlated with experimental observations of the performance degradation in devices subjected to light and heat stress.

Effects due to elementary particle-like collisions within nuclear matter have been observed in several nuclear reactions caused by pions and protons. Simple nuclear reactions of the form ZA(a,an)Z/sup A-1/ and Z/sup A/(a,ap)(Z-1)/ sup A-1/ have excitation functions that are sensitive to changes in the elementary-particle cross sections. The excitation function for the reaction C/ sup 12/( pi /sup -/, pi /sup -/n)C/sup 11/ is measure d from 53 to 1610 Mev by bombarding targets of plastic scintillator with pions. The intensity of the pion beam is monitored with a two-counter telescope and 40 Mc scaling system. The scintillator target is mounted on a phototube and becomes the detector for the carbon-11 positron activity. Corrections are made for muon contamination in the beam, coincidence losses in the monitor system, carbon-11 activity produced by stray background at the accelerator, carbon-1l activity produced by secondaries in the target, and the efficiency of the carbon-11 detection system. The C/sup 12/( pi /sup -/, pi /sup -/n)C/sup 11/ cross sections rise to a peak of abo ut 70 mb at 190 Mev, that corresponds to the resonance in freeparticle pi /sup -/n scattering at 190 Mev. Calculations based on a knock-on'' collision mechanism and sharp-cutoff …

Capillary electrophoresis (CE) and high-performance liquid chromatography (HPLC) are widely used analytical separation techniques with many applications in chemical, biochemical, and biomedical sciences. Conventional analyte identification in these techniques is based on retention/migration times of standards; requiring a high degree of reproducibility, availability of reliable standards, and absence of coelution. From this, several new information-rich detection methods (also known as hyphenated techniques) are being explored that would be capable of providing unambiguous on-line identification of separating analytes in CE and HPLC. As further discussed, a number of such on-line detection methods have shown considerable success, including Raman, nuclear magnetic resonance (NMR), mass spectrometry (MS), and fluorescence line-narrowing spectroscopy (FLNS). In this thesis, the feasibility and potential of combining the highly sensitive and selective laser-based detection method of FLNS with analytical separation techniques are discussed and presented. A summary of previously demonstrated FLNS detection interfaced with chromatography and electrophoresis is given, and recent results from on-line FLNS detection in CE (CE-FLNS), and the new combination of HPLC-FLNS, are shown.

This thesis contains the results of organometallic studies of thiophene and selenophene coordination in transition metal complexes. Chromium tricarbonyl complexes of thiophene, selenophene, and their alkyl-substituted derivatives were prepared and variable-temperature {sup 13}C NMR spectra of these complexes were recorded in dimethyl ether. Bandshape analyses of these spectra yielded activation parameters for restricted rotation of the thiophene and selenophene ligands in these complexes. Extended Hueckel molecular orbital calculations (EHMO) of the free thiophene and selenophene ligands and selected chromium tricarbonyl thiophene complexes were performed to better explain the activation barriers of these complexes. The structure of Cr(CO){sub 3}({eta}{sup 5}-2,5-dimethylthiophene) was established by a single crystal X-ray diffraction study.

The partial oxidation of 1,3-butadiene has been investigated over VMoO catalysts synthesized by sol-gel techniques. Surface areas were 9-14 m{sup 2}/g, and compositions were within the solid solution regime, i.e. below 15.0 mol % MoO{sub 3}/(MoO{sub 3} + V{sub 2}O{sub 5}). Laser Raman Spectroscopy and XRD data indicated that solid solutions were formed, and pre- and post-reaction XPS data indicated that catalyst surfaces contained some V{sup +4} and were further reduced in 1,3-butadiene oxidation. A reaction pathway for 1,3-butadiene partial oxidation to maleic anhydride was shown to involve intermediates such as 3,4-epoxy-1-butene, crotonaldehyde, furan, and 2-butene-1,4-dial. The addition of water to the reaction stream substantially increased catalyst activity and improved selectivity to crotonaldehyde and furan at specific reaction temperatures. At higher water addition concentrations, furan selectivity increased from 12% to over 25%. The catalytic effects of water addition were related to competitive adsorption with various V{sub 2}O{sub 5}-based surface sites, including the vanadyl V=O, corner sharing V-O-V and edge sharing V-O oxygen. Higher levels of water addition were proposed to impose acidic character by dissociative adsorption. In addition, a novel combinatorial synthesis technique for VMoO was used to investigate the phase transitions of V{sub 2}O{sub 5}, solid solutions of Mo …

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 goal of this thesis is to develop a new Channel Interface device for the MPICH Implementation of the MPI (Message Passing Interface) standard using MP{_}Lite. MP{_}Lite is a lightweight message-passing library that is not a full MPI implementation, but offers high performance MPICH (Message Passing Interface CHameleon) is a full implementation of the MPI standard that has the p4 library as the underlying communication device for TCP/IP networks. By integrating MP{_}Lite as a Channel Interface device in MPICH, a parallel programmer can utilize the full MPI implementation of MPICH as well as the high bandwidth offered by MP{_}Lite. There are several layers in the MPICH library where one can tie a new device. The Channel Interface is the lowest layer that requires very few functions to add a new device. By attaching MP{_}Lite to MPICH at the lowest level, the Channel Interface, almost all of the performance of the MP{_}Lite library can be delivered to the applications using MPICH. MP{_}Lite can be implemented either as a blocking or a non-blocking Channel Interface device. The performance was measured on two separate test clusters, the PC and the Alpha miniclusters, having Gigabit Ethernet connections. The PC cluster has two 1.8 GHz …

InGaN based light emitting devices demonstrate excellent luminescence properties and have great potential in lighting applications. Though these devices are already being produced on an industrial scale, the nature of their radiative transition is still not well understood. In particular, the role of the huge (&gt;1MV/cm), built-in electric field in these transitions is still under debate. The luminescence characteristics of InGaN quantum well structures were investigated as a function of excitation power, temperature, and biaxial strain, with an intent of discerning the effects of the electric field and inhomogeneous indium distribution in the QW on the radiative transition. It was found that the luminescence energy did not scale only with the indium concentration but that the QW thickness must also be taken into account. The thickness affects the transition energy due to quantum confinement and carrier separation across a potential drop in the QW. The luminescence peak width was shown to increase with increased indium fraction, due to increased indium inhomogeneity. The carrier lifetime increased exponentially with QW thickness and luminescence wavelength, due to increased carrier separation. Measuring the luminescence energy and carrier lifetime as a function of excitation density showed that the electric field can be screened by strong …

In a cellular array, a range of primary spacing is found to be stable under given growth conditions. Since a strong coupling of solute field exists between the neighboring cells, primary spacing variation should also influence other microstructure features such as cell shape and cell length. The existence of multiple solutions is examined in this study both theoretically as well as experimentally. A theoretical model is developed that identifies and relates four important microstructural lengths, which are found to be primary spacing, tip radius, cell width and cell length. This general microstructural relationship is shown to be valid for different cells in an array as well as for other cellular patterns obtained under different growth conditions. The unique feature of the model is that the microstructure correlation does not depend on composition or growth conditions since these variables scale microstructural lengths to satisfy the relationship obtained in this study. Detailed directional solidification experimental studies have been carried out in the succinonitrile-salol system to characterize and measure these four length scales. Besides the validation of the model, experimental results showed additional scaling laws to be present. In the regime where only a cellular structure is formed, the shape of the cell, …

Throughout this thesis, the fundamental aspects involved in the electrocatalysis of anodic O-transfer reactions and cathodic H-transfer reactions have been studied. The investigation into anodic O-transfer reactions at undoped and Fe(III)[doped MnO{sub 2} films] revealed that MnO{sub 2} film electrodes prepared by a cycling voltammetry deposition show improved response for DMSO oxidation at the film electrodes vs. the Au substrate. Doping of the MnO{sub 2} films with Fe(III) further enhanced electrode activity. Reasons for this increase are believed to involve the adsorption of DMSO by the Fe(III) sites. The investigation into anodic O-transfer reactions at undoped and Fe(III)-doped RuO{sub 2} films showed that the Fe(III)-doped RuO{sub 2}-film electrodes are applicable for anodic detection of sulfur compounds. The Fe(III) sites in the Fe-RuO{sub 2} films are speculated to act as adsorption sites for the sulfur species while the Ru(IV) sites function for anodic discharge of H{sub 2}O to generate the adsorbed OH species. The investigation into cathodic H-transfer reactions, specifically nitrate reduction, at various pure metals and their alloys demonstrated that the incorporation of metals into alloy materials can create a material that exhibits bifunctional properties for the various steps involved in the overall nitrate reduction reaction. The Sb{sub 10}Sn{sub 20}Ti{sub …

NMR experiments are reported for Sr{sub 2}CuO{sub 2}Cl{sub 2}, HgBa{sub 2}CuO{sub 4+d}, YNi{sub 2}B{sub 2}C and YBa{sub 2}Cu{sub 3}O{sub 7}. NMR studies typify three different aspects of microscopic properties of HTSC. In non-superconducting antiferromagnetic (AF) prototype Sr{sub 2}CuO{sub 2}Cl{sub 2}, we used NMR to investigate Cu{sup 2+} correlated spin dynamics and AF phase transition in CuO2 layers. In the superconductors, we used NMR both to investigate the electronic properties of the Fermi-liquid in normal and superconducting states and to investigate flux lattice and flux-line dynamics in the superconducting state in presence of magnetic field. A summary of each study is given: {sup 35}Cl NMR was measured in Sr{sub 2}CuO{sub 2}Cl{sub 2} single crystals with T{sub N}=257K. {sub 35}Cl NMR relaxation rates showed crossover of Cu{sup 2+} spin dynamics from Heisenberg to XY-like correlation at 290 K well above T{sub N}. A field-dependent T{sub N} for H{perpendicular}c was observed and explained by a field-induced Ising-like anisotropy in ab plane. {sup 199}Hg NMR was measured in HgBa{sub 2}CuO{sub 4+d}. Properties of the Fermi-liquid are characterized by a single-spin fluid picture and opening of a spin pseudo-gap at q=0 above {Tc}. Below {Tc}, spin component of Knight shift decreases rapidly in agreement with …