The perturbed particle transport coefficients were determined for a range of plasma conditions in the Alcator C tokamak, a component of the Microwave Tokamak Experiment (MTX), from analysis of density perturbations created in gas modulation experiments. Density measurements from a 15 chord far-infrared interferometer were sufficiently detailed to allow radial profiles of the transport coefficients to be resolved. Gas modulation experiments were carried out on plasmas over a range of relatively low currents and a wide variety of line-averaged densities, including values near the Greenwald density limit. With this technique the perturbed diffusion coefficient D and the perturbed convection velocity V can be determined simultaneously. Measured profiles of D rise toward the outside of the plasma column in a manner generally similar to those determined previously for {chi}{sub e,HP} from sawtooth heat pulse propagation. Values of D are typically smaller than those of {chi}{sub e,HP} given for the same line-averaged densities by a factor of 2-5. Diffusion coefficients from a series of discharges at constant current showed little variation with density through most of the saturated ohmic confinement regime. At the Greenwald density limit threshold a dramatic increase occurred in both the perturbed convective and diffusive transport coefficients in the …

The dynamics of several elementary chemical reactions that are important in atmospheric chemistry are investigated. The reactive scattering of ground state chlorine or bromine atoms with ozone molecules and ground state chlorine atoms with nitrogen dioxide molecules is studied using a crossed molecular beams apparatus with a rotatable mass spectrometer detector. The Cl + O{sub 3} {yields} ClO + O{sub 2} reaction has been studied at four collision energies ranging from 6 kcal/mole to 32 kcal/mole. The derived product center-of-mass angular and translational energy distributions show that the reaction has a direct reaction mechanism and that there is a strong repulsion on the exit channel. The ClO product is sideways and forward scattered with respect to the Cl atom, and the translational energy release is large. The Cl atom is most likely to attack the terminal oxygen atom of the ozone molecule. The Br + O{sub 3} {yields} ClO + O{sub 2} reaction has been studied at five collision energies ranging from 5 kcal/mole to 26 kcal/mole. The derived product center-of-mass angular and translational energy distributions are quite similar to those in the Cl + O{sub 3} reaction. The Br + O{sub 3} reaction has a direct reaction mechanism similar …

This thesis reports a study of the mechanism of electromigration failure in Al-2Cu-1Si thin-film conducting lines on Si. Samples were patterned from 0.5 {mu}m thick vapor-deposited films with various mean grain sizes (G), and had lines widths (W) of 1.3, 2, 4 and 6 {mu}m. The lines were aged at various conditions to change the Cu-precipitate distribution and were tested to failure at T = 225{degrees}C and j = 2.5 {times} 10{sup 6} A/cm{sup 2}. Some samples were tested over a range of substrate temperatures, current densities and current reversal times. Aging produces an initially dense distribution of metastable {Theta}{prime} (Al{sub 2}Cu; coherent) in the grain interiors, with stable {Theta} (Al{sub 2}Cu; incoherent) at the grain boundaries. The intragranular {theta}{prime} is gradually absorbed into the grain boundary precipitates. In the wide lines the mean time to failure increases slowly and monotonically with pre-aging time and current reversal time. The failure mode is the formation and coalescence of voids that form on grain boundaries with an apparent activation energy of 0.65 eV. In the narrow lines, the lines failed by a transgranular-slit mechanism with an activation energy near 0.93 eV. The distribution of the polygranular segments and the kinetics of failure …

The development of a versatile picosecond ultraviolet/vacuum ultraviolet temporal spectrometer and its potential use for measuring internal energy redistribution in isolated molecules are described in detail. A detailed description of the double-pass Nd:YAG amplifier and the dye amplifiers is given with the pulse energies achieved in the visible, ultraviolet, and vacuum ultraviolet. The amplified visible pulses are shown to be of sub-picosecond duration and near transform limited. The instrument`s temporal response ({le}10 ps) is derived from an instrument limited measurement of the dissociation lifetime of methyl iodide at 266 nm. The methyl iodide experiment is used to discuss the various sources of noise and background signals that are intrinsic to this type of experiment. Non-time-resolved experiments measuring the branching ratio and kinetic energy distributions of products from the 193 nm photodissociation of cyclopentadiene and thiophene are presented. These studies were done using the molecular beam Photofragment Translational Spectroscopy (PTS) technique. The results from the cyclopentadiene experiment confirm that H atom elimination to yield the cyclopentadienyl radical is the dominant dissociation channel. A barrier of {ge}5 kcal/mol can be understood in terms of the delocalization of the radical electron of the cyclopentadienyl fragment. A concerted elimination yielding cyclopropene and acetylene was …

Compounds (RC{sub 5}H{sub 4}){sub 3}U(t-Bu) were prepared for R = H, Me, Et. Their decomposition products in aromatic solvents are consistent with a radical decomposition pathway induced by solvent-assisted U-C bond homolysis. NMR was used to study the reactions of (RC{sub 5}H{sub 4}){sub 3}UCl with t-BuLi (R = t-Bu, Me{sub 3}Si). Reactions of (MeC{sub 5}H{sub 4}){sub 3}U(t-Bu) with Lewis bases and fluorocarbons were studied. Analogous reaction chemistry between (RC{sub 5}H{sub 4}){sub 3}ThX systems and t-BuLi was also studied, and reactivity differences between U and Th are discussed. Synthesis of sterically crowded (RC{sub 5}H{sub 4}){sub 4}U compounds is next considered. Reaction of the trivalent (RC{sub 5}H{sub 4}){sub 3}U with (RC{sub 5}H{sub 4}){sub 2}Hg results in formation of (RC{sub 5}H{sub 4}){sub 4}U. Steric congestion, cyclopentadienyl ligand exchange, and electron transfer are discussed. (DLC)

In the past multiple-quantum filtered imaging of biexponential relaxation sodium-23 nuclei in the human brain has been limited by low signal to noise ratios; this thesis demonstrates that such imaging is feasible when using a modified gradient-selected triple-quantum filter at a repetition time which maximizes the signal to noise ratio. Nuclear magnetic resonance imaging of biexponential relaxation sodium-23 ({sup 23}Na) nuclei in the human brain may be useful for detecting ischemia, cancer, and pathophysiology related to manic-depression. Conventional single-quantum NMR imaging of in vivo biexponential relaxation {sup 23}Na signals is complicated by the presence of single-exponential relaxation {sup 23}Na signals. Multiple-quantum filters may be used to selectively image biexponential relaxation {sup 23}Na signals since these filters suppress single-exponential relaxation {sup 23}Na signals. In this thesis, the typical repetition times (200--300 ms) used for in vivo multiple-quantum filtered {sup 23}Na experiments are shown to be approximately 5 times greater than the optimal repetition time which maximizes multiple-quantum filtered SNR. Calculations and experimental verification show that the gradient-selected triple-quantum (GS3Q) filtered SNR for {sup 23}Na in a 4% agarose gel increases by a factor of two as the repetition time decreases from 300 ms to 55 ms. The measured relaxation times of …

This thesis solves the problem of finding the optimal linear noise-reduction filter for linear tomographic image reconstruction. The optimization is data dependent and results in minimizing the mean-square error of the reconstructed image. The error is defined as the difference between the result and the best possible reconstruction. Applications for the optimal filter include reconstructions of positron emission tomographic (PET), X-ray computed tomographic, single-photon emission tomographic, and nuclear magnetic resonance imaging. Using high resolution PET as an example, the optimal filter is derived and presented for the convolution backprojection, Moore-Penrose pseudoinverse, and the natural-pixel basis set reconstruction methods. Simulations and experimental results are presented for the convolution backprojection method.

The role of the L{sub cm} (I), {beta}{sup 18} (II), and {alpha}{sup AP-B} (III) chromoproteins in the phycobilisome (PBS) core was investigated using genetically engineered strains of Synechococcus missing different polypeptides. Intact cells, isolated PBS, and subcore preparations for each mutant were studied to determine the effect of that mutation on energy transfer within the PBS core and to the reaction centers. Three mutants lacked the II and/or III polypeptides, while the I chromophore was altered in others. A lower energy absorbing chromophore, A{sub max} = 695 nm, was substituted for the I chromophore. The deletion of the II and III subunits had no discernible effect on energy transfer from the PBS to PSII. In cells and isolated PBS, the altered I chromophore acts to quench the PBS complex and to redirect the energy which would be transferred to PSII. In the PBS and subcore preparations, deletion of the III subunit did not alter energy transfer within the core. The deletion of the II subunit from the PBS caused a small decrease in the excited state lifetimes of the final emitters indicating more disorder within the core. The I chromophore was found to absorb at 670nm and to emit at …

When an important compound`s discovery dates back as far as 1825, one would imagine that every facet of its chemical and physical properties has been illuminated in the meantime. Benzene, however, has not ceased to challenge the chemist`s notion of structure and bonding since its first isolation by Michael Faraday. This report is divided into the following six chapters: 1. Aromaticity -- Criteria, manifestations, structural limitations; 2. The role of delocalization in benzene; 3. The thermochemical properties of benzocyclobutadienologs; 4. Ab initio study of benzenes fused to four-membered rings; 5. Non-planar polycyclic aromatic hydrocarbons; and 6. Experimental details and input decks. 210 Refs.

The development of probability of detection (POD) models for a variety of nondestructive evaluation (NDE) methods is motivated by a desire to quantify the variability introduced during the process of testing. Sources of variability involved in eddy current methods of NDE include those caused by variations in liftoff, material properties, probe canting angle, scan format, surface roughness and measurement noise. This thesis presents a comprehensive POD model for eddy current NDE. Eddy current methods of nondestructive testing are used widely in industry to inspect a variety of nonferromagnetic and ferromagnetic materials. The development of a comprehensive POD model is therefore of significant importance. The model incorporates several sources of variability characterized by a multivariate Gaussian distribution and employs finite element analysis to predict the signal distribution. The method of mixtures is then used for estimating optimal threshold values. The research demonstrates the use of a finite element model within a probabilistic framework to the spread in the measured signal for eddy current nondestructive methods. Using the signal distributions for various flaw sizes the POD curves for varying defect parameters have been computed. In contrast to experimental POD models, the cost of generating such curves is very low and complex defect …

Theoretical electronic structure techniques are used to analyze widely different systems from Si clusters to transition metal solids and surfaces. For the Si clusters, first principles density functional methods are used to investigate Si{sub N} for N=2-8. Goal is to understand the different types of bonding that can occur in such small clusters where the atomic coordination differs substantially from tetrahedral bonding; such uncoordinated structures can test approximate models of Si surfaces. For the transition metal systems, non-self-consistent electronic structure methods are used to understand the driving force for surface relaxations. In-depth analysis of results is presented and physical basis of surface relaxation within the theory is discussed. Limitations inherent in calculations of metal surface relaxation are addressed. Finally, in an effort to understand approximate methods, a novel non-self- consistent density functional electronic structure method is developed that is about 1000 times faster than more sophisticated methods; this method is tested for various systems including diatomics, mixed clusters, surfaces, and bulk lattices.