Conversion reactions of hydrocarbons over Pt-Re model catalyst surfaces modified by sulfur and alumina have been studied. A plasma deposition source has been developed to deposit Pt, Re, and Al on metal substrates variable coverage in ultrahigh vacuum without excessive heating. Conversion of n-hexane was performed over the Re-covered Pt and Pt-covered Re surfaces. The presence of the second metal increased hydrogenolysis activity of both Pt-Re surfaces. Addition of sulfur on the model Catalyst surfaces suppressed hydrogenolysis activity and increased the cyclization rate of n-hexane to methylcyclopentane over Pt-Re surfaces. Sulfiding also increased the dehydrogenation rate of cyclohexane to benzene Over Pt-Re surfaces. It has been proposed that the PtRe bimetallic catalysts show unique properties when combined with sulfur, and electronic interactions exist between platinum, rhenium and sulfur. Decomposition of hydrocarbons on the sulfur-covered Pt-Re surfaces supported that argument. For the conversion of 1-butene over the planar Pt/AlO{sub x}, the addition of Pt increased the selectivity of hydrogenation over isomerization.

To enhance quality, an independent verification and validation (IV&V) review is conducted as software requirements are defined. Requirements are inspected for consistency and completeness. IV&V strives to detect defects early in the software development life cycle and to prevent problems before they occur. The IV&V review process of a massive software requirements specification, the Reserve Component Automation System (RCAS) Functional Description (FD) is explored. Analysis of the RCAS FD error history determined that there are no predictors of errors. The size of the FD mandates electronic analysis of the databases. Software which successfully performs automated consistency and completeness checks is discussed. The process of verifying the quality of analysis software is described. The use of intuitive ad hoc techniques, in addition to the automatic analysis of the databases, is required because of the varying content of the requirements databases. The ad hoc investigation process is discussed. Case studies are provided to illustrate how the process works. This thesis demonstrates that it is possible to perform an IV&V review on a massive software requirements specification. Automatic analysis enables inspecting for completeness and consistency. The work with the RCAS FD clearly indicates that the IV&V review process is not static; it must …

The first part of this thesis presents a first-order pseudopotential calculation at T=O of the total energy of small sodium clusters of size N<800. The calculation is based on a local-pseudopotential scheme and local-density correlation and exchange. A temperature-size (T-N) phase-diagram is then derived using the T=O results and Lindemann`s criterion for melting. The phase-diagram contains three regions of stability: (1) a liquid (jellium) phase at temperatures above the melting line T{sub M}(N) where cluster-stability occurs at electronic magic numbers: (2) a phase related to complete geometrical shells of body-centered-cubic structure at temperatures below the melting line; and (3) a close-packed structure at very low temperatures and sufficiently large N. The melting line drops to T{sub M}(N)=O for N<65, where electronic magic numbers are stable even at T=O. The phase diagram reduces asymptotically to the known phases of sodium as N{yields}{infinity}, including the known martensitic transformation at T{approximately}5 K. The second and the last part of this thesis consists of a study of small-cluster many-body systems by means of an on-site ``local`` chemical potential which allows the continuous variation of local electron-density. This method yields a criterion to distinguish particular features of a small cluster that are likely to survive …

This thesis details the first direct ultrafast measurements of the dynamic thermal expansion of a surface and the temperature dependent surface thermal diffusivity using a two-color reflection transient grating technique. Studies were performed on p-type, n-type, and undoped GaAs(100) samples over a wide range of temperatures. By utilizing a 90 fs ultraviolet probe with visible excitation beams, the effects of interband saturation and carrier dynamics become negligible; thus lattice expansion due to heating and subsequent contraction caused by cooling provided the dominant influence on the probe. At room temperature a rise due to thermal expansion was observed, corresponding to a maximum net displacement of {approximately} 1 {Angstrom} at 32 ps. The diffracted signal was composed of two components, thermal expansion of the surface and heat flow away from the surface, thus allowing a determination of the rate of expansion as well as the surface thermal diffusivity, D{sub S}. By varying the fringe spacing of the grating, this technique has the potential to separate the signal contributions to the expansion of the lattice in the perpendicular and parallel directions. In the data presented here a large fringe spacing was used, thus the dominant contribution to the rising edge of the signal …

Chemical properties of rutherfordium (Rf) have been investigated with the organic ligands triisooctylamine (TIOA), tributylphosphate (TBP), and thenoyltrifluoroacetone (TTA). The TIOA studies showed that Rf behaves differently than Th and Eu and most similarly to Zr, only Zr and Rf extract from 12 M HCI. This result is further evidence that Rf is a Group 4 element. Studies with TBP showed that Rf chemical behavior differed from the other Group 4 elements. The extraction by TBP at different chloride concentrations showed that Rf at times behaves more like Pu{sup 4+} than Zr or Hf. At high chloride concentrations, Rf and Pu extraction decreased. Under the same conditions, Zr, Hf and Th extraction increased. In addition, Rf extraction by TBP was affected by hydrogen ion concentration, while Zr and Hf extraction was not. TTA extractions were used to determine the K{sub eq}, K{sub hyd}, and the ionic radius of Rf. The of K{sub eq} for Rf with TTA was calculated to be 3.18 {plus minus} 0.90. The first four log K{sub hyd's} for Rf are calculated to be {minus}2.6 {plus minus} 0.7, {minus}5.9 {plus minus} 1.7, {minus}10.2 {plus minus} 2.9, and {minus}14.5 {plus minus} 4.1. These hydrolysis constants indicate that Rf …

Angle-resolved two-photon laser photoemission was used to observe the image potential electronic states on the (111) face of a silver single crystal. The transient image potential states were excited from the occupied bulk bands with photons whose energy was tunable around 4 eV. Photoemission of the image potential states was accomplished with photons of energy tunable around 2 eV. Image potential states were found to persist in the presence of physisorbed adlayers of xenon and cyclohexane. On clean Ag(111), the effective mass of the n=1 image potential state was found to be 1.4{plus_minus}0.1 times the mass of a free electron (m{sub e}). A binding energy of 0.77 eV, measured by earlier workers, was assumed in analysis of the data for the clean surface. On Ag(111), at 75 K covered by one monolayer of xenon, the binding energy of the n=1 image potential state was unchanged relative to its value on the clean surface. An effective mass of (1.00{plus_minus}0.05) {center_dot} m{sub e} was obtained. On Ag(111) at 167 K, covered by one monolayer of cyclohexane, the binding energy of the n=2 member of the image potential series was 0.30{plus_minus}0.05 eV. The energy of the n=1 state was again unchanged by deposition …

Chemical properties of rutherfordium (Rf) have been investigated with the organic ligands triisooctylamine (TIOA), tributylphosphate (TBP), and thenoyltrifluoroacetone (TTA). The TIOA studies showed that Rf behaves differently than Th and Eu and most similarly to Zr, only Zr and Rf extract from 12 M HCI. This result is further evidence that Rf is a Group 4 element. Studies with TBP showed that Rf chemical behavior differed from the other Group 4 elements. The extraction by TBP at different chloride concentrations showed that Rf at times behaves more like Pu{sup 4+} than Zr or Hf. At high chloride concentrations, Rf and Pu extraction decreased. Under the same conditions, Zr, Hf and Th extraction increased. In addition, Rf extraction by TBP was affected by hydrogen ion concentration, while Zr and Hf extraction was not. TTA extractions were used to determine the K{sub eq}, K{sub hyd}, and the ionic radius of Rf. The of K{sub eq} for Rf with TTA was calculated to be 3.18 {plus_minus} 0.90. The first four log K{sub hyd`s} for Rf are calculated to be {minus}2.6 {plus_minus} 0.7, {minus}5.9 {plus_minus} 1.7, {minus}10.2 {plus_minus} 2.9, and {minus}14.5 {plus_minus} 4.1. These hydrolysis constants indicate that Rf will not hydrolyze at conditions …

The experiments discussed in this thesis focus on identifying the protein segments or specific amino acids which provide ligands to the Mn cluster of photosystem II (PS II). This Mn cluster plays a central role in the oxygen-evolving complex (OEC) of PS II. The Mn cluster is thought to be bound by lumenal regions of the PS II reaction center proteins known as D1 and D2. First, several peptides were synthesized which correspond to specific lumenal segments of the D1 and D2 proteins. Next, polyclonal antibodies were successfully elicited using three of these peptides. The peptides recognized by these antibodies correspond to protein segments of the spinach reaction center proteins: Ile-321 to Ala-344 of D1 (D1-a), Asp-319 to Arg-334 of D1 (D1-b), and Val-300 to Asn-319 of D2 (D2-a). These antibodies were then used in assays which were developed to structurally or functionally probe the potential Mn-binding regions of the D1 and D2 proteins.

We have measured the transverse momentum spectra 1/p{sub T} dN/dp{sub T} and rapidity distributions dN/dy of negatively charged hadrons and protons for central {sup 32}S + {sup 32}S interactions at 200 GeV/nucleon incident energy. The negative hadron dN/dy distribution is too broad to be accounted for by thermal models which demand isotropic particle emission. It is compatible with models which emphasize longitudinal dynamics, by either a particle production mechanism, as in the Lund fragmentation model, or by introducing one-dimensional hydrodynamic expansion, as in the Landau model. The proton dN/dy distribution, although showing no evidence for a peak in the target fragmentation region, exhibits limited nuclear stopping power. We estimate the mean rapidity shift of participant target protons to be {Delta}y {approximately} 1.5, greater than observed for pp collisions, less than measured in central pA collisions, and much less than would be observed for a single equilibrated fireball at midrapidity. Both the negative hadron and proton dN/dy distributions can be fit by a symmetric Landau two-fireball model. Although the spectrum possesses a two-component structure, a comparison to pp data at comparable center-of-mass energy shows no evidence for enhanced production at low p{sub T}. The two-component structure can be explained by a …