This dissertation presents studies aimed at understanding the potential energy surfaces and dynamics of isolated negative ions, and the effects of solvent on each. Although negative ions play important roles in atmospheric and solution phase chemistry, to a large extent the ground and excited state potential energy surfaces of gas phase negative ions are poorly characterized, and solvent effects even less well understood. In an effort to fill this gap, the author's coworkers and the author have developed a new technique, anion femtosecond photoelectron spectroscopy, and applied it to gas phase photodissociation and charge transfer processes. Studies are presented that (1) characterize the ground and excited states of isolated and clustered anions, (2) monitor the photodissociation dynamics of isolated and clustered anions, and (3) explore the charge-transfer-to-solvent states of atomic iodide clustered with polar and non-polar solvents.

Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying {sup 2}{Sigma} and {sup 2}{Pi} states of C{sub 2n}H (n = 1--4) have been studied. The anion photoelectron spectra yielded electron affinities, term values, and vibrational frequencies for these combustion and astrophysically relevant species. Photoelectron angular distributions allowed the author to correctly assign the electronic symmetry of the ground and first excited states and to assess the degree of vibronic coupling in C{sub 2}H and C{sub 4}H. Other radicals studied include NCN and I{sub 3}. The author was able to observe the low-lying singlet and triplet states of NCN for the first time. Measurement of the electron affinity of I{sub 3} revealed that it has a bound ground state and attachment of an argon atom to this moiety enabled him to resolve the symmetric stretching progression.

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Au/Ni metallization has become increasingly common in microelectronic packaging when Cu pads are joined with Pb-Sn solder. The outermost Au layer serves to protect the pad from corrosion and oxidation and the Ni layer provides a diffusion barrier to inhibit detrimental growth of Cu-Sn intermetallics. As a result of reflowing eutectic Pb-Sn on top of Au/Ni metallization, the as-solidified joints have AuSn{sub 4} precipitates distributed throughout the bulk of the solder joint, and Ni{sub 3}Sn{sub 4} intermetallics at the interface. Recent work has shown that the Au-Sn redeposits onto the interface during aging, compromising the strength of the joint. The present work shows that the redeposited intermetallic layer is a ternary compound with stoichiometry Au{sub 0.5}Ni{sub 0.5}Sn{sub 4}. The growth of this intermetallic layer was investigated, and results show that the ternary compound is observed to grow after as little as 3 hours at 150 C and after 3 weeks at 150 C has grown to a thickness of 10 {micro}m. Additionally, methods for inhibiting the growth of the ternary layer were investigated and it was determined that multiple reflows, both with and without additional aging can substantially limit the thickness of the ternary layer.

The photodissociation spectroscopy and dynamics of free radicals and ions is studied to characterize the dissociative electronic states in these species. To accomplish this, a special method of radical production, based on the photodetachment of the corresponding negative ion, has been combined with the technique of fast beam photofragment translational spectroscopy. The photofragment yield as a function of photon energy is obtained, mapping out the dissociative and predissociative electronic states. Branching ratios to various product channels, the translational energy distributions of the fragments, and bond dissociation energies are then determined at selected photon energies. The detailed picture of photodissociation dynamics is provided with the aid of ab initio calculations and a statistical model to interpret the observed data. Important reaction intermediates in combustion reactions have been studied: CCO, C{sub 2}H{sub 5}O, and linear C{sub n} (n = 4--6).

Along with Mn, calcium and chloride ions are necessary cofactors for oxygen evolution in Photosystem II (PS II). To further test and verify whether Ca is close to the Mn cluster, the authors substituted strontium for Ca and probed from the Sr point of view for any nearby Mn. The extended X-ray absorption fine structure (EXAFS) of Sr-reactivated PS II indicates major differences between the intact and NH{sub 2}OH-treated samples. In intact samples, the Fourier transform of the Sr EXAFS shows a Fourier peak that is missing in inactive samples. This peak II is best simulated by two Mn neighbors at a distance of 3.5 Angstrom, confirming the proximity of Ca (Sr) cofactor to the Mn cluster. In addition, polarized Sr EXAFS on oriented Sr-reactivated samples shows this peak II is dichroic: large magnitude at 10 degrees (angle between the PS II membrane normal and the x-ray electric field vector) and small at 80 degrees. Analysis of the dichroism yields the relative angle between the Sr-Mn vector and membrane normal (23 degrees {+-} 4 degrees), and the isotropic coordination number for these layered samples. X-ray absorption spectroscopy has also been employed to assess the degree of similarity between the manganese …

Partial transient liquid phase (PTLP) bonding is a technique which can be used to join ceramics with metals and is used to form niobium-based joints for alumina. The principal advantage to PTLP bonding is that it enables refractory joints to be fabricated at temperatures below those typically required by solid state diffusion bonding. A thorough review of the important parameters (chemical compatibility, thermal expansion match, sufficient wettability of the liquid phase on the solid phases) in choosing a joining material for ceramics by the PTLP method is provided. As in conventional PTLP joining, the current study uses thin (=3 (mu)m) copper layers sandwiched between the alumina (bulk) and niobium (127 (mu)m). However, unlike the case of copper/nickel/copper obium is limited. Consequently, the copper is not entirely dissolved in the process, resulting in a two phase (copper-rich and niobium-rich phases) microstructure. Different processing conditions (temperature and applied load) result in different morphologies of the copper-rich and niobium-rich phases at the interface. These different microstructures exhibit distinct strength characteristics. Extended annealing of as-processed joints can influence the strengths differently depending on the ambient partial oxygen pressure at the annealing temperature. The focus of this work is to correlate processing conditions, microstructure, and …

Thesis written by a student in the UNT Honors College comparing the philosophies and ethics of Albert Camus and Immanuel Kant.

Measurements of electrical resistivity as a function of temperature from 25 to 1,500 C were conducted on polycrystalline samples in the Mo-Si-B system. Single phase, or nearly single phase, samples were prepared for the following phases: Mo{sub 3}Si, Mo{sub 5}SiB{sub 2}, Mo{sub 5}Si{sub 3}B{sub x}, MoB, MoSi{sub 2}, and Mo{sub 5}Si{sub 3}. Thesis materials all exhibit resistivity values within a narrow range(4--22 x 10{sup {minus}7}{Omega}-m), and the low magnitude suggests these materials are semi-metals or low density of states metals. With the exception of MoSi{sub 2}, all single phase materials in this study were also found to have low temperature coefficient of resistivity(TCR) values. These values ranged from 2.10 x 10{sup {minus}10} to 4.74 x 10{sup {minus}10}{Omega}-m/{degree} C, and MoSi{sub 2} had a TCR of 13.77 x 10{sup {minus}10}{Omega}-m/{degree} C. The results from the single phase sample measurements were employed in a natural log rule-of-mixtures model to relate the individual phase resistivity values to those of multiphase composites. Three Mo-Si-B phase regions were analyzed: the binary Mo{sub 5}Si{sub 3}-MoSi{sub 2} system, the ternary phase field Mo{sub 5}Si{sub 3}B{sub x}MoB-MoSi{sub 2}, and the Mo{sub 3}Si-Mo{sub 5}SiB{sub 2}-Mo{sub 5} Si{sub 3}B{sub x} ternary region. The experimental data for samples in each of …

By definition a plasma is an electrically conducting gaseous mixture containing a significant concentration of cations and electrons. The Inductively Coupled Plasma (ICP) is an electrodeless discharge in a gas at atmospheric pressure. This discharge is an excellent one for vaporizing, atomizing, and ionizing elements. The early development of the ICP began in 1942 by Babat and then by Reed in the early 1960s. This was then followed by the pioneering work of Fassel and coworkers in the late 1960s. Commercial ICP spectrometers were introduced in the mid 1970s. A major breakthrough in the area of ICP took place in the early 1980s when the ICP was shown to be an excellent ion source for mass spectrometry.

This dissertation presented several results which add to the general knowledge base regarding organothiolates monolayer spontaneously adsorbed at gold films. Common to the body of this work is the use of voltammetric reductive resorption and variants of scanning probe microscopy to gain insight into the nature of the monolayer formation process as well as the resulting interface. The most significant result from this work is the success of using friction force microscopy to discriminate the end group orientation of monolayer chemisorbed at smooth gold surfaces with micrometer resolution (Chapter 4). The ability to detect the differences in the orientational disposition is demonstrated by the use PDMS polymer stamp to microcontact print an adlayer of n-alkanethiolate of length n in a predefine pattern onto a gold surface, followed by the solution deposition of a n-alkanethiol of n {+-} 1 to fill in the areas on the gold surface intentionally not coated by the stamping process. These two-component monolayers can be discriminated by using friction force microscopy which detects differences in friction contributed by the differences in the orientation of the terminal groups at surfaces. This success has recently led to the detection of the orientation differences at nanometer scale. Although the …

Fast methods for separation and detection of important neurotransmitters and the releases in central nervous system (CNS) were developed. Enzyme based immunoassay combined with capillary electrophoresis was used to analyze the contents of amino acid neurotransmitters from single neuron cells. The release of amino acid neurotransmitters from neuron cultures was monitored by laser induced fluorescence imaging method. The release and signal transduction of adenosine triphosphate (ATP) in CNS was studied with sensitive luminescence imaging method. A new dual-enzyme on-column reaction method combined with capillary electrophoresis has been developed for determining the glutamate content in single cells. Detection was based on monitoring the laser-induced fluorescence of the reaction product NADH, and the measured fluorescence intensity was related to the concentration of glutamate in each cell. The detection limit of glutamate is down to 10{sup {minus}8} M level, which is 1 order of magnitude lower than the previously reported detection limit based on similar detection methods. The mass detection limit of a few attomoles is far superior to that of any other reports. Selectivity for glutamate is excellent over most of amino acids. The glutamate content in single human erythrocyte and baby rat brain neurons were determined with this method and results …

This research involves using molten magnesium (Mg) to remove neodymium (Nd) from NdFeB magnet scrap by diffusion. The results show that liquid metal extraction of Nd may be a viable and inexpensive method for recovering the expensive rare earth element Nd for use in Mg castings.

Photonic band gap materials are artificial dielectric structures that give the promise of molding and controlling the flow of optical light the same way semiconductors mold and control the electric current flow. In this dissertation the author studied two areas of photonic band gap materials. The first area is focused on the properties of one-dimensional PBG materials doped with Kerr-type nonlinear material, while, the second area is focused on the mechanisms responsible for the gap formation as well as other properties of two-dimensional PBG materials. He first studied, in Chapter 2, the general adequacy of an approximate structure model in which the nonlinearity is assumed to be concentrated in equally-spaced very thin layers, or 6-functions, while the rest of the space is linear. This model had been used before, but its range of validity and the physical reasons for its limitations were not quite clear yet. He performed an extensive examination of many aspects of the model's nonlinear response and comparison against more realistic models with finite-width nonlinear layers, and found that the d-function model is quite adequate, capturing the essential features in the transmission characteristics. The author found one exception, coming from the deficiency of processing a rigid bottom …

Motivated by the need for establishing a reliable database useful for the application of x-ray spectroscopic tools for the diagnostic of very high temperature plasmas, high-resolution crystal spectrometer measurements have been performed investigating the characteristic K-shell radiation of highly charged krypton and xenon. The measurements, which have been performed at the Electron-Beam-Ion-Trap (EBIT) facility of the Lawrence Livermore National Laboratory, include the investigation of the n = 2 {yields} 1 transitions in heliumlike krypton (Kr{sup 34+}) and innershell excited lithiumlike krypton (Kr{sup 33+}) utilizing a conventional reflection-type crystal spectrometer of von Hamos geometry. The electron-excitation-energy selective measurements map the contribution of the dielectronic recombination lines providing the means of accurate interpretation of the line profiles of the characteristic K{alpha} x-ray emission of plasmas. The high-resolution measurements of the n = 2 {yields} 1 transitions in heliumlike xenon (Xe{sup 52+}) and hydrogenlike xenon (Xe{sup 53+}) were based on a new transmission-type crystal spectrometer of DuMond geometry. The resolving power of the developed spectrometer was sufficient for charge state specific observation allowing the determination of the electron-impact excitation cross section for the hydrogen- and heliumlike K{alpha} transitions. The disagreement with theoretically predicted values is a measure of the magnitude of the Breit …

The Semiconductor Industry Association (SIA) has identified the integration of copper (Cu) with low-dielectric-constant (low-k) materials as a critical goal for future interconnect architectures. A fundamental understanding of the chemical interaction of Cu with various substrates, including diffusion barriers and adhesion promoters, is essential to achieve this goal. The objective of this research is to develop novel organic polymers as Cu/low-k interfacial layers and to investigate popular barrier candidates, such as clean and modified tantalum (Ta) substrates. Carbon-silicon (C-Si) polymeric films have been formed by electron beam bombardment or ultraviolet (UV) radiation of molecularly adsorbed vinyl silane precursors on metal substrates under ultra-high vacuum (UHV) conditions. Temperature programmed desorption (TPD) studies show that polymerization is via the vinyl groups, while Auger electron spectroscopy (AES) results show that the polymerized films have compositions similar to the precursors. Films derived from vinyltrimethyl silane (VTMS) are adherent and stable on Ta substrates until 1100 K. Diffusion of deposited Cu overlayers is not observed below 800 K, with dewetting occurred only above 400 K. Hexafluorobenzene moieties can also be incorporated into the growing film with good thermal stability. Studies on the Ta substrates demonstrate that even sub-monolayer coverages of oxygen or carbide on polycrystalline …

The dissertation argues that the development of the British abolition movement was based on the abolitionists' perception that their actions were kairotic; they attempted to shape their own kairos by taking temporal events and reinterpreting them to construct a kairotic process that led to a perceived fulfillment: abolition. Thus, the dissertation examines the rhetorical strategies used by white abolitionists to construct an abolitionist kairos that was designed to produce salvation for white Britons more than it was to help free blacks. The dissertation especially examines the three major texts produced by black persons living in England during the late eighteenth centuryIgnatius Sancho's Letters of the Late Ignatius Sancho (1782), Ottobauh Cugoano's Thoughts and Sentiments on the Evil of Slavery (1787), and Olaudah Equiano's The Interesting Narrative of the Life of Olaudah Equiano, or Gustavus Vassa, the African (1789)to illustrate how black rhetoric was appropriated by whites to fulfill their own kairotic desires. By examining the rhetorical strategies employed in both white and black rhetorics, the dissertation illustrates how the abolitionists thought the movement was shaped by, and how they were shaping the movement through, kairotic time. While the dissertation contends that the abolition movement was rhetorically designed to provide redemption, …

This study consisted of an examination of how service quality should be measured within libraries and how library service quality relates to library success. A modified version of the SERVQUAL instrument was evaluated to determine how effectively it measures library service quality. Instruments designed to measure information center success and information system success were evaluated to determine how effectively they measure library success and how they relate to SERVQUAL. A model of library success was developed to examine how library service quality relates to other variables associated with library success. Responses from 385 end users at two U.S. Army Corps of Engineers libraries were obtained through a mail survey. Results indicate that library service quality is best measured with a performance-based version of SERVQUAL, and that measuring importance may be as critical as measuring expectations for management purposes. Results also indicate that library service quality is an important factor in library success and that library success is best measured with a combination of SERVQUAL and library success instruments. The findings have implications for the development of new instruments to more effectively measure library service quality and library success as well as for the development of new models of library service …

‘...and one of time.' is a reinterpretation of a small musical moment from Philip Glass' opera, Einstein on the Beach, centered around the phrase "Berne, Switzerland 1905." This reinterpretation is realized through the use of several different compositional techniques including spectral composition, micropolyphony and dodecaphony, as well as the application of extra-musical models developed by Alan Lightman, John Gardner, Italo Calvino and Albert Einstein.

A work of creative fiction in the form of a short novel, Asleep in the Arms of God is a limited-omniscient and omniscient narrative describing the experiences of a man named Wafer Roberts, born in Jack County, Texas, in 1900. The novel spans the years from 1900 to 1925, and moves from the Keechi Valley of North Texas, to Fort Worth and then France during World War One, and back again to the Keechi Valley. The dissertation opens with a preface, which examines the form of the novel, and regional and other aspects of this particular work, especially as they relate to the postmodern concern with fragmentation and conditional identity. Wafer confronts in the novel aspects of his own questionable history, which echo the larger concern with exploitative practices including racism, patriarchy, overplanting and overgrazing, and pollution, which contribute to and climax in the postmodern fragmentation. The novel attempts to make a critique of the exploitative rage of Western civilization.

An evaluation of American higher education distance education programs was conducted to explore how they approach intellectual property, copyright and information sharing/antitrust policy concerns for Internet-based programs. An evaluation of the current status of distance education and Internet-based training in higher education was conducted through a pilot study that included a random sample of 223 accredited institutions. Seventy-seven institutions responded to a survey, of which there were 14 Research I&II, 17 Doctorate I&II, and 46 Master's I&II institutions included in this study. A review of institutional policy approaches for these 77 institutions was conducted via Internet Web site and bulletin review. A multiple-case study was also conducted which included 10 of the top 30 accredited distance education institutions in America. Policy approaches were examined for all institutions and differences were discussed for public and private institutions as well as the following Carnegie Class institutions- Research I&II, Doctorate I&II and Master's I&II. Ten percent of all institutions that responded to the pilot study developed a written policy addressing antitrust/information-sharing concerns. Additionally, the data indicated that 22% of institutions in these Carnegie Class ranges published copyright and intellectual property policy on their institutions' Internet Web site. Ninety percent of the institutions in …

Cassette systems for creating intergeneric hybrid ATCases were constructed. An MluI restriction enzyme site was introduced at the carbamoylphosphate binding site within the pyrB genes of both Pseudomonas putida and Escherichia coli. Two hybrids, E. coli pyrB polar domain fused with P. putida pyrB equatorial domain and P. putida pyrB polar domain fused with E. coli pyrB equatorial domain, are possible. The intergeneric E. coli-P. putida hybrid pyrB gene was constructed and found to encode an active ATCase which complemented an E. coli Pyr- strain. These hybrids are useful for kinetic and expression studies of ATCase in E. coli.

Experiments were performed to assess the suitability of Rhabditis pellio, a nematode found in earthworms, as a challenge organism for use in development of a biomarker assay to determine the potential of chemicals to suppress the immunocompetence of the non-specific immune system. To accomplish this goal, information on the life cycle of R. pellio was determined; including effects of incubation time and temperature on growth rates; along with information on the immune response elicited in the earthworm, Lumbricus terrestris. Immune parameters measured were coelomocyte migration toward and attachment to R. pellio larvae and adults. Preliminary background information showed that R. pellio has potential as a challenge organism for development of a biomarker assay.

This study proposes the classification of the toolmark under the heads of zipper teeth as a subclass characteristic as outlined by the Association of Firearm and Toolmark Examiners (AFTE). Two separate cases in which zipper teeth were found at crime scenes prompted this study. Brass zipper teeth manufactured by YKK were taken from 20 pairs of jeans and studied using a Reichert comparison microscope at 4X power. Photographs were taken and over 750 comparisons made. It was found that the toolmarks on each side on the 20 zippers were unique and independent of all other sides. The observations made in this study indicate that classifying zipper teeth toolmarks as a subclass characteristic is valid.