This dissertation presents an investigation of ordering in FCC based systems using the pair potential approximation in the ground state and mean field limits. The theoretical approach is used to explain the occurrence of observed equilibrium phases and characteristics of thermodynamic instabilities, in particular, spinodal ordering and decomposition. It is shown that the stability of non-integer domain sizes in long period superstructures such as Al{sub 3}Ti and Ag{sub 3}Mg may result from the tendency of a system to reduce the number of non-dominant ordering waves, thus producing domain sizes that have rational fraction form n/m. This conclusion is used to explain the domain size stability with respect to variations in temperature and electron concentration. The cation ordering in the precipitate phases in calcite and dolomite is analyzed by analogy with ordering in FCC based metals. The ordered phases in calcite and dolomite are shown to be consistent with pair potential minima at {l brace}100{r brace} and {l brace}1/2, 1/2, 1/2{r brace} positions in reciprocal space respectively. 32 refs., 6 figs.

Lateral changes in geology pose a serious problem in data interpretation for any surface geophysical method. Although many geophysical techniques are designed to probe vertically, the source signal invariably spreads laterally, so any lateral variations in geology will affect the measurements and interpretation. This problem is particularly acute for controlled source electromagnetic soundings because only a few techniques are available to interpret the data if lateral effects are present. In this thesis we examine the effects of geological contacts for the time domain electromagnetic sounding method (TDEM). Using two simple two-dimensional models, the truncated thin-sheet and the quarter-space, we examine the system response for several commonly used TDEM sounding configurations. For each system we determine the sensitivity to the contact, establish how to the contact anomaly may be distinguished from other anomalies and, when feasible, develop methods for interpreting the contact geometry and for stripping the contact anomaly from the observed data. Since no numerical models were available when this work was started, data were collected using scale models with a system designed at the University of California at Berkeley. The models were assembled within a table-top modeling tank from sheets or blocks of metal using air or mercury as …

The capacitance of the edge plane of pyrolytic graphite electrodes, in acetonitrile solutions, is measured by recording the current response to an applied triangular voltage sweep; TVS, and then fitting the current response with an appropriate function, (via a set of adjustable parameters). The pretreatment of the electrodes, the supporting electrolyte concentration used, and the frequency of the input TVS, were all found to affect the measured capacitance. In these experiments, a background current was also seen and the shape of the current output for the TVS; the charging/discharging curve, is shown to correlate with the magnitude of this background current. In addition, the size of the background current was found to have some dependence on the type of electrode pretreatment procedure used. 60 refs., 49 figs., 3 tabs.

A reproducible, high-yield synthesis of mono([8]annulene)uranium(4)dichloride (1) is reported, along with the X-ray crystal structural of the bis(pyridine) adduct. Metathesis reactions of the half-sandwich complex 1 with a variety of simple alkyl and alkoxy reagents failed to generate any isolable mono-ring complexes. Reactions of 1 with polydentate, delocalized anions did produce stable derivatives, including mono([8]annulene)uranium(4)bis(acetylacetonate) (4). An X-ray crystal structure of 4 is reported.

A series of six nitroxide spin-labeled psoralens were designed, synthesized and tested as probes for DNA dynamics. The synthesis of these spin-labeled psoralen derivatives and their photoreactivity with double-stranded DNA fragments is described. The spin labels (nitroxides) were demonstrated to survive the uv irradiation required to bind the probe to the target DNA. EPR spectra of the photobound spin-labels indicate that they do not wobble with respect to the DNA on the time-scales investigated. The author has used psoralen modified DNA as a model for the study of DNA repair enzyme systems in human cell free extracts. He has shown that damage-induced DNA synthesis is associated with removal of psoralen adducts and therefore is {open_quotes}repair synthesis{close_quotes} and not an aberrant DNA synthesis reaction potentiated by deformation of the DNA by adducts. He has found that all DNA synthesis induced by psoralen monoadducts is the consequence of removal of these adducts. By the same approach he has obtained evidence that this in vitro system is capable of removing psoralen cross-links as well. Reported here are synthetic methods that make use of high intensity lasers coupled with HPLC purification to make homogeneous and very pure micromole quantities of furan-side monoadducted, cross-linked, and …

Many future linear collider designs call for electron and positron beams with normalized rms horizontal and vertical emittances of {gamma}{epsilon}{sub x} = 3{times}10{sup {minus}6} m-rad and {gamma}{epsilon}{sub y} = 3{times}10{sup {minus}8} m-rad; these are a factor of 10 to 100 below those observed in the Stanford Linear Collider. In this dissertation, we examine the feasibility of achieving beams with these very small vertical emittances. We examine the limitations encountered during both the generation and the subsequent acceleration of such low emittance beams. We consider collective limitations, such as wakefields, space charge effects, scattering processes, and ion trapping; and also how intensity limitations, such as anomalous dispersion, betatron coupling, and pulse-to-pulse beam jitter. In general, the minimum emittance in both the generation and the acceleration stages is limited by the transverse misalignments of the accelerator components. We describe a few techniques of correcting the effect of these errors, thereby easing the alignment tolerances by over an order of magnitude. Finally, we also calculate ``fundamental`` limitations on the minimum vertical emittance; these do not constrain the current designs but may prove important in the future.

A simple empirical valence bond (EVB) model approach is suggested for constructing global potential energy surfaces for reactions of polyatomic molecular systems. This approach produces smooth and continuous potential surfaces which can be directly utilized in a dynamical study. Two types of reactions are of special interest, the unimolecular dissociation and the unimolecular isomerization. For the first type, the molecular dissociation dynamics of formaldehyde on the ground electronic surface is investigated through classical trajectory calculations on EVB surfaces. The product state distributions and vector correlations obtained from this study suggest very similar behaviors seen in the experiments. The intramolecular hydrogen atom transfer in the formic acid dimer is an example of the isomerization reaction. High level ab initio quantum chemistry calculations are performed to obtain optimized equilibrium and transition state dimer geometries and also the harmonic frequencies.

Using the 5.8 {times} 10{sup 6} J/{psi} events collected by the MARK 3 experiment on the SPEAR e{sup +}e{sup {minus}} storage ring at SLAC, a mass independent amplitude analysis of the J/{psi} {yields} {gamma} K{sub s}K{sub s} and J/{psi} {yields} K{sup +}K{sup {minus}} decays is presented. For K{bar K} systems having mass less than 2 GeV/c{sup 2}, the efficiency-corrected spherical harmonic moments of the J/{psi} joint decay angular distribution are measured. Fits are then performed in each independent mass interval in order to extract the underlying helicity amplitude structure; amplitudes describing K{bar K} systems of spin zero and spin two are included simultaneously. For the first time, a large spin zero component in the {theta}(1720) mass region is observed; consistent results are obtained for the data samples corresponding to the individual decay modes. This structure is attributed to the production of an S wave resonance, the f{sub 0}(1710), of mass and width M = 1710 {plus_minus} 10 MeV/c{sup 2}, {Gamma} = 186 {plus_minus} 30 MeV/c{sup 2}, respectively, with branching fraction Bf(J/{psi} {yields} {gamma}f{sub 0}, f{sub 0} {yields} K{bar K}) = (6.47 {plus_minus} 1.14 {plus_minus} 0.84) {times} 10{sup {minus}4}. A small amount ({approximately}24%) of spin two component in this mass region …

The characterization of electrochemically modified polycrystalline platinum surfaces has been accomplished through the use of four major electrochemical techniques. These were chronoamperometry, chronopotentiommetry, cyclic voltammetry, and linear sweep voltammetry. A systematic study on the under-potential deposition of several transition metals has been performed. The most interesting of these were: Ag, Cu, Cd, and Pb. It was determined, by subjecting the platinum electrode surface to a single potential scan between {minus}0.24 and +1.25 V{sub SCE} while stirring the solution, that the electrocatalytic activity would be regenerated. As a consequence of this study, a much simpler method for producing ultra high purity water from acidic permanganate has been developed. This method results in water that surpasses the water produced by pyrocatalytic distillation. It has also been seen that the wettability of polycrystalline platinum surfaces is greatly dependent on the quantity of oxide present. Oxide-free platinum is hydrophobic and gives a contact angle in the range of 55 to 62 degrees. We have also modified polycrystalline platinum surface with the electrically conducting polymer poly-{rho}-phenylene. This polymer is very stable in dilute sulfuric acid solutions, even under applied oxidative potentials. It is also highly resistant to electrochemical hydrogenation. The wettability of the polymer modified …

The divalent lanthanide complex, (Me{sub 5}C{sub 5}){sub 2}Yb, reacts with methylcopper to produce the base-free, ytterbium-methyl complex, (Me{sub 5}C{sub 5}){sub 2}YbMe. This product forms a asymmetric, methyl-bridged dimer in the solid state. The bulky alkyl complex, (Me{sub 5}C{sub 5}){sub 2}YbCH(SiMe{sub 3}){sub 2}, displays similar chemistry to (Me{sub 5}C{sub 5}){sub 2}YbMe, but at a reduced reaction rate due to the limited accessibility of the metal in (Me{sub 5}C{sub 5}){sub 2}YbCH(SiMe{sub 3}){sub 2}. Copper and silver halide salts react with (Me{sub 5}C{sub 5}){sub 2}V to produce the trivalent halide derivatives, (Me{sub 5}C{sub 5}){sub 2}VX (X + F, Cl, Br, I). The chloride complex, (Me{sub 5}C{sub 5}){sub 2}VCl, reacts with lithium reagents to form the phenyl and borohydride species. Nitrous oxide transfers an oxygen atom to (Me{sub 5}C{sub 5}){sub 2}V producing the vanadium-oxo complex, (Me{sub 5}Ce{sub 5}){sub 2}VO. The trivalent titanium species, (Me{sub 5}C{sub 5}){sub 2}TiX (X = Cl, Br, Me, BH{sub 4}), form bimetallic coordination complexes with (Me{sub 5}C{sub 5}){sub 2}Yb. The magnetic behavior of the products indicates that electron transfer has not occurred. The solid state structures of the chloride and bromide complexes show unusual bend angles for the halide bridges between ytterbium and titanium. A model based on frontier orbital …

The quasiparticle tunneling current in a superconductor-insulator- superconductor (SIS) tunnel junction is highly nonlinear. Such a nonlinearity can be used to mix two millimeter wave signals to produce a signal at a much lower intermediate frequency. We have constructed several millimeter and sub-millimeter wave SIS mixers in order to study high frequency response of the quasiparticle tunneling current and the physics of high frequency mixing. We have made the first measurement of the out-of-phase tunneling currents in an SIS tunnel junction. We have developed a method that allows us to determine the parameters of the high frequency embedding circuit by studying the details of the pumped I-V curve. We have constructed a 80--110 GHz waveguide-based mixer test apparatus that allows us to accurately measure the gain and added noise of the SIS mixer under test. Using extremely high quality tunnel junctions, we have measured an added mixer noise of 0.61 {plus_minus} 0.36 quanta, which is within 25 percent of the quantum limit imposed by the Heisenberg uncertainty principle. This measured performance is in excellent agreement with that predicted by Tucker`s theory of quantum mixing. We have also studied quasioptically coupled millimeter- and submillimeter-wave mixers using several types of integrated tuning …

This thesis describes a measurement of the heavy-ion induced electromagnetic dissociation of a 120 MeV/A {sup 238}U beam incident on five targets: {sup 9}Be, {sup 27}Al, {sup nat}Cu, {sup nat}Ag, and {sup nat}U. Electromagnetic dissociation at this beam energy is essentially a two step process involving the excitation of a giant resonance followed by particle decay. At 120 MeV/A there is predicted to be a significant contribution of the giant quadrupole resonance to the EMD cross sections. The specific exit channel which was looked at was projectile fission. The two fission fragments were detected in coincidence by an array of solid-state {Delta}E-E detectors, allowing the changes of the fragments to be determined to within {plus_minus} .5 units. The events were sorted on the basis of the sums of the fragments` charges, acceptance corrections were applied, and total cross sections for the most peripheral events were determined. Electromagnetic fission at the beam energy of this experiment always leads to a true charge sum of 92. Due to the imperfect resolution of the detectors, charge sums of 91 and 93 were included in order to account for all of the electromagnetic fission events. The experimentally observed cross sections are due to nuclear …

This (<100 {Angstrom}) silica-alumina layers were tested as potential model heterogeneous acid catalysts for combined surface science and catalysis studies. Three preparation methods were used: oxidation of r3 {times} r3 R30 Al/Si(111) structure in UHV; deposition on Si(lll) from aqueous solution; and argon ion beam sputter deposition in UHV. The homogeneous thin layers are amorphous, and the chemical environment of surface atoms is similar to that of Si, Al and oxygen atoms on high surface area acid catalysts. Since the ion beam-deposited thin layer of silica-alumina has the same composition as the target zeolite this deposition method is a promising tool to prepare model catalysts using practical catalyst targets. The silica-alumina layers are active in cumene cracking, a typical acid catalyzed reaction. In order to clearly distinguish background reactions and the acid catalyzed reaction at least 20 cm{sup 2} catalyst surface area is needed. Two series of model platinum-alumina catalysts were prepared in a combined UHV -- high pressure reactor cell apparatus by depositing alumina on polycrystalline Pt foil and by vapor depositing Pt on a thin alumina layer on Au. Both model surfaces have been prepared with and without chlorine. AES, CO desorption as well as methyl cyclopentane (MCP) …

This thesis is an investigation of methods for processing multidimensional signals acquired using modern tomography systems that have an anisotropic or spatially variant response function. The main result of this research is the discovery of a new method to obtain better estimators of an unknown spatial intensity distribution by incorporating detailed knowledge about the tomograph system response function and statistical properties of the acquired signal into a mathematical model.

A formalism is developed for the tomographic inversion of seismic travel time residuals. The travel time equations are solved both simultaneously, for velocity model terms and corrections to the source locations, and progressively, for each set of terms in succession. The methods differ primarily in their treatment of source mislocation terms. Additionally, the system of equations is solved directly, neglecting source terms. The efficacy of the algorithms is explored with synthetic data as we perform simulations of the general procedure used to produce tomographic images of Earth`s mantle from global earthquake data. The patterns of seismic heterogeneity in the mantle that would be returned reliably by a tomographic inversion are investigated. We construct synthetic data sets based on real ray sampling of the mantle by introducing spherical harmonic patterns of velocity heterogeneity and perform inversions of the synthetic data.

For the semiconductor SiC to fulfill its potential as an electronic material, methods must be developed to produce insulating surface oxide layers in a reproducible fashion. Auger electron spectroscopy (AES), low energy electron diffraction (LEED) and x-ray photoelectron spectroscopy (XPS) were used to investigate the oxidation of single crystal {alpha}-SiC over a wide temperature and O{sub 2} pressure range. The {alpha}-SiC surface becomes graphitic at high temperatures and low O{sub 2} pressures due to Si and SiO sublimation from the surface. Amorphous SiO{sub 2} surface layers from on {alpha}-SiC at elevated O{sub 2} pressures and temperatures. Both the graphitization and oxidation of {alpha}-SiC appears to be enhanced by surface roughness. Chemical vapor deposition (CVD) is currently the preferred method of producing single crystal SiC, although the method is slow and prone to contamination. We have attempted to produce SiC films at lower temperatures and higher deposition rates using plasma enhanced CVD with CH{sub 3}SiH{sub 3}. Scanning AES, XPS and scanning electron microscopy (SEM) were utilized to study the composition and morphology of the deposited Si{sub x}C{sub y}H{sub z} films as a function of substrate temperature, plasma power and ion flux bombardment of the film during deposition. High energy ion bombardment …

We have improved and extended a novel ac calorimetric technique for measuring the heat capacity of adsorbates on evaporated metal films. Metallic substrates are of particular interest in current studies of the thermodynamics of adsorbed molecules. The method described in the present work is only calorimetric technique which allows measurements of molecules on simple metallic surfaces. Among other improvements, we have achieved significant progress in the preparation and characterization of the evaporated metal film. We have applied this novel technique to a study of hydrogen multilayers on gold and sapphire substrates. We have shown that samples of normal-hydrogen with a nominal coverage n of approximately 25 monolayers (ML) undergo a bulk-like orientational ordering transition. The transition is suppressed as the coverage is decreased, and no sign of the transition remains above 1.6 K for n {approx} 1 ML. For n {approx_lt} 8 ML, the peak in the heat capacity exhibits signs of finite-size effects. At higher coverages, finite-size effects are not observed, and the shape of the peak depends strongly on the substrate. We conclude that the peak is inhomogeneously broadened for n {approx_lt} 8 ML. This work represents the first measurements of the heat capacity due to orientational ordering …

Nuclear Magnetic Resonance (NMR) spectroscopy of xenon has become an important tool for investigating a wide variety of materials, especially those with high surface area. The sensitivity of its chemical shift to environment, and its chemical inertness and adsorption properties make xenon a particularly useful NMR probe. This work discusses the application of optical pumping to enhance the sensitivity of xenon NMR experiments, thereby allowing them to be used in the study of systems with lower surface area. A novel method of optically-pumping {sup 129}Xe in low magnetic field below an NMR spectrometer and subsequent transfer of the gas to high magnetic field is described. NMR studies of the highly polarized gas adsorbed onto powdered samples with low to moderate surface areas are now possible. For instance, NMR studies of optically-pumped xenon adsorbed onto polyacrylic acid show that xenon has a large interaction with the surface. By modeling the low temperature data in terms of a sticking probability and the gas phase xenon-xenon interaction, the diffusion coefficient for xenon at the surface of the polymer is determined. The sensitivity enhancement afforded by optical pumping also allows the NMR observation of xenon thin films frozen onto the inner surfaces of different …

An in vitro system using neuroglia from neonatal rat brain was developed to examine the morphologic, immunocytochemical and biochemical response of oligodendroglia to ionizing radiation. Following acute {gamma}-irradiation at day-in-culture (DIC) 8, oligodendrocyte counts at DIC 14 were 55% to 65% of control values after 2 Gy, and 29% to 36% after 5 Gy. Counts increased to near-normal levels at DIC 21 in the 2 Gy group and to 75% of normal in the 5 Gy group. Myelin basic protein levels (MBP) at DIC 14 were 60% of control values after 2 Gy, and 40% after 5 Gy. At DIC 21, MBP after 2 Gy was 45% greater than that observed at DIC 14, but MBP, as a fraction of age-matched control values, dropped from 60% to 50%. Following 5 Gy, absolute MBP changed little between DIC 14 and DIC 21, but decreased from 40% to 25% of control cultures. The response to split-dose irradiation indicated that nearly all sublethal damage in the oligodendrocyte population (and its precursors) was repaired within 3 h to 4 h. A new compartmental cell model for radiation response in vitro of the oligodendrocyte population is proposed and examined in relation to the potential reaction …

Magnetic flux noise and flux creep in thin films and single crystals of YBa{sub 2}Cu{sub 3}O{sub 7-x}, Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8+x}, Tl{sub 2}Ca{sub 2}Ba{sub 2}Cu{sub 3}O{sub x}, and TlCa{sub 2}Ba{sub 2}Cu{sub 3}O{sub x} are measured with a superconducting quantum interference device (SQUID). The noise power spectrum generally scales as 1/f (f is frequency) from 1 Hz to 1 kHz, increases with temperature, and decreases in higher-quality films. It is proportional to the magnetic field B in which the sample is cooled, at least in the range 0.1 mT < B < 3 mT. A model of thermally activated vortex motion is developed which explains the dependence of the noise on frequency, temperature, current, and applied magnetic field. The pinning potential is idealized as an ensemble of double wells, each with a different activation energy separating the two states. From the noise measurements, this model yields the distribution of pinning energies in the samples, the vortex hopping distance, the number density of mobile vortices, and the restoring force on a vortex at a typical pinning site. The distribution of pinning energies in YBa{sub 2}Cu{sub 3}O{sub 7-x} shows a broad peak below 0.1 eV. The small ambient magnetic field, and the …

This thesis is concerned with the development and application of high resolution threshold photodetachment spectroscopy of negative ions. Chapter I deals with the principles of our photodetachment technique, and in chapter II a detailed description of the apparatus is presented. The threshold photodetachment spectra of I{sup {minus}}, and SH{sup {minus}}, presented in the last sections of chapter II, indicated that a resolution of 3 cm{sup {minus}1} can be achieved using our technique. In chapter III the threshold photodetachment spectroscopy study of the transition state region of I + HI and I + Di reactions is discussed. Our technique probes the transition state region directly, and the results of our study are the first unambiguous observations of reactive resonances in a chemical reaction. Chapters IV, V and VI are concerned with the spectroscopy of small silicon and carbon clusters. From our spectra we were able to assign electronic state energies and vibrational frequencies for the low lying electronics states of Si{sub n} (n=2,3,4), C{sub 5} and their corresponding anions.

We have utilized a combination of photochemical cross-linking techniques and site-directed mutagenesis to obtain secondary and tertiary structure information for the self-cleaving, self-ligating subsequence of RNA from the negative strand of Satellite Tobacco Ringspot Virus. We have found that the helical regions fold about a hinge to promoting four different possible tertiary interactions, creating a molecular of similar shape to a paperclip. A model suggesting that the ``paperclip`` and ``hammerhead`` RNAs share a similar three dimensional structure is proposed. We have used a self-cleaving RNA molecule related to a subsequence of plant viroids, a ``hammerhead,`` to study the length-dependent folding of RNA produced during transcription by RNA polymerase. We have used this method to determine the length of RNA sequestered within elongating E. coli and T7 RNA polymerase complexes. The data show that for E. coli RNA polymerase 12{plus_minus}1 nucleotides are sequestered within the ternary complex, which is consistent with the presence of an RNA-DNA hybrid within the transcription bubble, as proposed by others. The result for T7 RNA polymerase differs from E. coli RNA polymerase, with only 10{plus_minus}1 nucleotides sequestered within the ternary complex, setting a new upper limit for the minimum RNA-DNA required for a stable elongating complex. …

The diffusion of electromagnetic fields in time and the three spatial dimensions can be modelled using a new numerical algorithm that is tailored for geophysical applications. The novel feature of the algorithm is that a large part of the computation is done in the wavenumber domain. Here, the spatial Fourier transforms of the vertical magnetic field and the vertical current density are used to define two scalar potentials. For either a vertical electric or a vertical magnetic dipole source at the subsurface these wavenumber potentials can be represented by a simple Gaussian distribution function. In the air, the fields satisfy the Laplace equation. The flow of this algorithm is as follows: the potentials are defined in the wavenumber domain as an initial condition depending on the source configuration, the vector current density J in space is obtained from the potentials using the inverse Fourier transform, the vector electric field E is obtained by multiplying J by resistivity, the updated potentials are then obtained from the forward Fourier transform of E. Using the updated potential as a subsequent initial condition these steps are repeated until the solution reaches the final time. Since spatial derivatives can be exactly evaluated in the wavenumber …

I have used a scanning tunneling microscope (STM) to image simultaneously the atomic lattice and the charge density wave (CDW) superstructure in tantalum disulfide (1T-TaS{sub 2}) over the temperature range of 370-77K. In the lowest temperature (commensurate) phase, present below 180K, the CDW is at an angle of 13.9{degrees} relative to the lattice and is uniformly commensurate. In the incommensurate phase, present above 353K, the CDW is aligned with the lattice. 1T-TaS{sub 2} exhibits two other phases; the triclinic (T) phase which is present between 223K and 283K upon warming the sample, and the nearly-commensurate (NC) phase which is present between 353K and 180K upon cooling the sample and between 283K and 353K upon warming the sample. In both of these phases, discommensurate models where the CDW is arranged in small commensurate domains have been proposed. In the NC phase the CDW is rotated between 10{degrees} and 12.5{degrees} relative to the atomic lattice. Such a rotated CDW would create an interference pattern with the underlying atomic lattice regardless of the existence of a true domain superstructure. Previous work on 1T-TaS{sub 2} has not adequately accounted for the possibility of this moire pattern. However, around each fundamental CDW peak in the …