Resource Type

A CCD Camera with Electron Decelerator for Intermediate Voltage Electron Microscopy (open access)

A CCD Camera with Electron Decelerator for Intermediate Voltage Electron Microscopy

Electron microscopists are increasingly turning to Intermediate Voltage Electron Microscopes (IVEMs) operating at 300 - 400 kV for a wide range of studies. They are also increasingly taking advantage of slow-scan charge coupled device (CCD) cameras, which have become widely used on electron microscopes. Under some conditions CCDs provide an improvement in data quality over photographic film, as well as the many advantages of direct digital readout. However, CCD performance is seriously degraded on IVEMs compared to the more conventional 100 kV microscopes. In order to increase the efficiency and quality of data recording on IVEMs, we have developed a CCD camera system in which the electrons are decelerated to below 100 kV before impacting the camera, resulting in greatly improved performance in both signal quality and resolution compared to other CCDs used in electron microscopy. These improvements will allow high-quality image and diffraction data to be collected directly with the CCD, enabling improvements in data collection for applications including high-resolution electron crystallography, single-particle reconstruction of protein structures, tomographic studies of cell ultrastructure and remote microscope operation. This approach will enable us to use even larger format CCD chips that are being developed with smaller pixels.
Date: March 17, 2008
Creator: Downing, Kenneth H; Downing, Kenneth H. & Mooney, Paul E.
System: The UNT Digital Library
Center-stabilized Yang-Mills Theory:Confinement and Large N Volume Independence (open access)

Center-stabilized Yang-Mills Theory:Confinement and Large N Volume Independence

We examine a double trace deformation of SU(N) Yang-Mills theory which, for large N and large volume, is equivalent to unmodified Yang-Mills theory up to O(1/N{sup 2}) corrections. In contrast to the unmodified theory, large N volume independence is valid in the deformed theory down to arbitrarily small volumes. The double trace deformation prevents the spontaneous breaking of center symmetry which would otherwise disrupt large N volume independence in small volumes. For small values of N, if the theory is formulated on R{sup 3} x S{sup 1} with a sufficiently small compactification size L, then an analytic treatment of the non-perturbative dynamics of the deformed theory is possible. In this regime, we show that the deformed Yang-Mills theory has a mass gap and exhibits linear confinement. Increasing the circumference L or number of colors N decreases the separation of scales on which the analytic treatment relies. However, there are no order parameters which distinguish the small and large radius regimes. Consequently, for small N the deformed theory provides a novel example of a locally four-dimensional pure gauge theory in which one has analytic control over confinement, while for large N it provides a simple fully reduced model for Yang-Mills theory. …
Date: March 21, 2008
Creator: Unsal, Mithat; /SLAC /Stanford U., Phys. Dept.; Yaffe, Laurence G. & /Washington U., Seattle
System: The UNT Digital Library
Low Mach Number Modeling of Type Ia Supernovae. II. EnergyEvolution (open access)

Low Mach Number Modeling of Type Ia Supernovae. II. EnergyEvolution

The convective period leading up to a Type Ia supernova (SNIa) explosion is characterized by very low Mach number flows, requiringhydrodynamical methods well-suited to long-time integration. We continuethe development of the low Mach number equation set for stellar scaleflows by incorporating the effects of heat release due to externalsources. Low Mach number hydrodynamics equations with a time-dependentbackground state are derived, and a numerical method based on theapproximate projection formalism is presented. We demonstrate throughvalidation with a fully compressible hydrodynamics code that this lowMach number model accurately captures the expansion of the stellaratmosphere as well as the local dynamics due to external heat sources.This algorithm provides the basis for an efficient simulation tool forstudying the ignition of SNe Ia.
Date: March 28, 2006
Creator: Almgren, Ann S.; Bell, John B.; Rendleman, Charles A. & Zingale,Mike
System: The UNT Digital Library
Microbunching and Beam Break Up in DUV FEL Accelerator (open access)

Microbunching and Beam Break Up in DUV FEL Accelerator

We present the results of electron beam longitudinal modulation studies in the DUV-FEL accelerator. For bunch length determination we used the 'zero-phasing' method, based on a measurement of the chirped electron bunch energy spectra. The measurements revealed a spiky structure in the longitudinal phase space [1]. A model based on space charge effect is considered [2] to explain of the obtained phenomena. The analysis of the energy spectra has shown a sensitivity of the structure to the electron beam peak current, energy and longitudinal non-uniformity of the RF gun drive laser. Analytical calculations have demonstrated a qualitative agreement with experimental observations. Several experiments have been made to compare with theory; measured results are reviewed in this paper. The obtained effect is briefly discussed in relation to high brightness accelerators.
Date: March 17, 2008
Creator: Shaftan, T.; Carr, L.; Loos, H.; Sheehy, B.; Graves, William S.; Huang, Z. et al.
System: The UNT Digital Library
Fox-2 Splicing Factor Binds to a Conserved Intron Motif to PromoteInclusion of Protein 4.1R Alternative Exon 16 (open access)

Fox-2 Splicing Factor Binds to a Conserved Intron Motif to PromoteInclusion of Protein 4.1R Alternative Exon 16

Activation of protein 4.1R exon 16 (E16) inclusion during erythropoiesis represents a physiologically important splicing switch that increases 4.1R affinity for spectrin and actin. Previous studies showed that negative regulation of E16 splicing is mediated by the binding of hnRNP A/B proteins to silencer elements in the exon and that downregulation of hnRNP A/B proteins in erythroblasts leads to activation of E16 inclusion. This paper demonstrates that positive regulation of E16 splicing can be mediated by Fox-2 or Fox-1, two closely related splicing factors that possess identical RNA recognition motifs. SELEX experiments with human Fox-1 revealed highly selective binding to the hexamer UGCAUG. Both Fox-1 and Fox-2 were able to bind the conserved UGCAUG elements in the proximal intron downstream of E16, and both could activate E16 splicing in HeLa cell co-transfection assays in a UGCAUG-dependent manner. Conversely, knockdown of Fox-2 expression, achieved with two different siRNA sequences resulted in decreased E16 splicing. Moreover, immunoblot experiments demonstrate mouse erythroblasts express Fox-2, but not Fox-1. These findings suggest that Fox-2 is a physiological activator of E16 splicing in differentiating erythroid cells in vivo. Recent experiments show that UGCAUG is present in the proximal intron sequence of many tissue-specific alternative exons, and …
Date: March 1, 2006
Creator: Ponthier, Julie L.; Schluepen, Christina; Chen, Weiguo; Lersch,Robert A.; Gee, Sherry L.; Hou, Victor C. et al.
System: The UNT Digital Library
The Life-cycle of Operons (open access)

The Life-cycle of Operons

Operons are a major feature of all prokaryotic genomes, buthow and why operon structures vary is not well understood. To elucidatethe life-cycle of operons, we compared gene order between Escherichiacoli K12 and its relatives and identified the recently formed anddestroyed operons in E. coli. This allowed us to determine how operonsform, how they become closely spaced, and how they die. Our findingssuggest that operon evolution may be driven by selection on geneexpression patterns. First, both operon creation and operon destructionlead to large changes in gene expression patterns. For example, theremoval of lysA and ruvA from ancestral operons that contained essentialgenes allowed their expression to respond to lysine levels and DNAdamage, respectively. Second, some operons have undergone acceleratedevolution, with multiple new genes being added during a brief period.Third, although genes within operons are usually closely spaced becauseof a neutral bias toward deletion and because of selection against largeoverlaps, genes in highly expressed operons tend to be widely spacedbecause of regulatory fine-tuning by intervening sequences. Althoughoperon evolution may be adaptive, it need not be optimal: new operonsoften comprise functionally unrelated genes that were already inproximity before the operon formed.
Date: March 15, 2007
Creator: Price, Morgan N.; Arkin, Adam P. & Alm, Eric J.
System: The UNT Digital Library
Stark Tuning of Donor Electron Spins of Silicon (open access)

Stark Tuning of Donor Electron Spins of Silicon

We report Stark shift measurements for {sup 121}Sb donor electron spins in silicon using pulsed electron spin resonance. Interdigitated metal gates on top of a Sb-implanted {sup 28}Si epi-layer are used to apply electric fields. Two Stark effects are resolved: a decrease of the hyperfine coupling between electron and nuclear spins of the donor and a decrease in electron Zeeman g-factor. The hyperfine term prevails at X-band magnetic fields of 0.35T, while the g-factor term is expected to dominate at higher magnetic fields. A significant linear Stark effect is also resolved presumably arising from strain.
Date: March 23, 2006
Creator: Bradbury, Forrest R.; Tyryshkin, Alexei M.; Sabouret, Guillaume; Bokor, Jeff; Schenkel, Thomas & Lyon, Stephen A.
System: The UNT Digital Library
Evidence for production of single top quarks (open access)

Evidence for production of single top quarks

We present first evidence for the production of single top quarks in the D0 detector at the Fermilab Tevatron p{bar p} collider. The standard model predicts that the electroweak interaction can produce a top quark together with an antibottom quark or light quark, without the antiparticle top quark partner that is always produced from strong coupling processes. Top quarks were first observed in pair production in 1995, and since then, single top quark production has been searched for in ever larger datasets. In this analysis, we select events from a 0.9 fb{sup -1} dataset that have an electron or muon and missing transverse energy from the decay of a W boson from the top quark decay, and two, three, or four jets, with one or two of the jets identified as originating from a b hadron decay. The selected events are mostly backgrounds such as W+jets and t{bar t} events, which we separate from the expected signals using three multivariate analysis techniques: boosted decision trees, Bayesian neural networks, and matrix element calculations. A binned likelihood fit of the signal cross section plus background to the data from the combination of the results from the three analysis methods gives a cross …
Date: March 1, 2008
Creator: Abazov, V. M.; Abbott, B.; Abolins, M.; Acharya, B. S.; Adams, M.; Adams, T. et al.
System: The UNT Digital Library
TRITIUM MOVEMENT AND ACCUMULATION IN THE NGNP SYSTEM INTERFACE AND HYDROGEN PLANT (open access)

TRITIUM MOVEMENT AND ACCUMULATION IN THE NGNP SYSTEM INTERFACE AND HYDROGEN PLANT

Tritium movement and accumulation in the Next Generation Nuclear Plant (NGNP) employing either a high-temperature electrolysis (HTE) process or a thermochemical water-splitting Sulfur-Iodine (SI) process to produce hydrogen is estimated by a numerical code, THYTAN, as a function of design, operational and material parameters. Estimated tritium concentrations in the hydrogen product and in the process chemicals of the hydrogen plant using the HTE process are slightly higher than the limit in drinking water defined by the U.S. Environmental Protection Agency (EPA) and in effluent at the boundary of an unrestricted area defined by the U.S. Nuclear Regulatory Commission (NRC), respectively. Estimated tritium concentrations in the NGNP using the SI hydrogen production process are significantly higher, and are largely affected by undetermined parameters (i.e., tritium permeability of heat exchanger materials, hydrogen concentration in the helium energy transport fluids, equilibrium constant of the tritium isotope exchange reaction between HT and H{sub 2}SO{sub 4}). These parameters should be measured or estimated in the near future, as should the tritium generation and release rate from the NGNP nuclear reactor core. Decreasing the tritium permeation rate between the primary and secondary heat transport circuits is an effective measure to decrease the tritium concentrations in the …
Date: March 20, 2008
Creator: Sherman, S
System: The UNT Digital Library
Greening the U.S. House of Representatives (open access)

Greening the U.S. House of Representatives

The Greening the Capitol initiative was launched in March, 2007 with the threefold goals of making the U.S. House of Representatives: 1) carbon neutral within 18 months, 2) reducing energy use by 50percent in ten years, and 3) becoming a model of sustainable operations. We report on the recommendations to meet these goals, looking at the targets of opportunity at the Capitol Power Plant, the existing buildings, and the overall operations of the complex. Our findings have shown that these goals are achievable, and that through an integrated approach the savings in carbon and energy can be met. Specific examples include the lighting retrofits in the House offices, parking areas, and the Capitol dome; the retrofits to the HVAC systems and controls, including duct sealing, improving the efficiency of the energy and water use in the food service areas; and improved operations of the steam and chilled water distribution system. A key aspect has been better tracking and feedback to the building operators of the actual energy consumption. We report on the technical opportunities presented by these historic and symbolic buildings in becoming models of sustainability.
Date: March 1, 2008
Creator: Diamond, Rick; Diamond, Rick & Payne, Christopher
System: The UNT Digital Library
Flashing Slurry Releases (open access)

Flashing Slurry Releases

The Hanford K Basin Closure Project involves the retrieval, transfer and processing of radioactive contaminated slurries containing partially corroded spent nuclear fuel from the K Basin spent fuel pools. The spent fuel is primarily metallic fuel from the operation of the Hanford reactors. The Sludge Treatment Project is being designed to treat and package this material in preparation for ultimate disposal. The processing of the contaminated slurries includes further corrosion of the remaining uncorroded uranium metal in a large heated vessel to form a more stable metal oxide for packaging and storage.
Date: March 14, 2007
Creator: Schmitt, Bruce E. & Young, Jonathan
System: The UNT Digital Library
Real time assessment of RF cardiac tissue ablation with optical spectroscopy (open access)

Real time assessment of RF cardiac tissue ablation with optical spectroscopy

An optical spectroscopy approach is demonstrated allowing for critical parameters during RF ablation of cardiac tissue to be evaluated in real time. The method is based on incorporating in a typical ablation catheter transmitting and receiving fibers that terminate at the tip of the catheter. By analyzing the spectral characteristics of the NIR diffusely reflected light, information is obtained on such parameters as, catheter-tissue proximity, lesion formation, depth of penetration of the lesion, formation of char during the ablation, formation of coagulum around the ablation site, differentiation of ablated from healthy tissue, and recognition of micro-bubble formation in the tissue.
Date: March 20, 2008
Creator: Demos, S G & Sharareh, S
System: The UNT Digital Library
A qualitative assessment of microclimatic perturbations in atunnel (open access)

A qualitative assessment of microclimatic perturbations in atunnel

Understanding microclimate dynamics in tunnels is importantfor designing and maintaining underground facilities. For example, in thegeological disposal of radioactive materials, condensation of vaporshould be minimized as it can accelerate waste package corrosion andradionuclide release. While microclimate dynamics are known to bedominated by the advection of heat and moisture, additional factors mayalso be important, such as the presence of fractures or faults. Wepresent a relatively inexpensive method to assess microclimaticperturbations within a tunnel. By combining standard temperature andrelative humidity sensors with low-cost sensors designed to detectchanges in condensation, we monitored microclimate dynamics along atunnel at the proposed geological repository at Yucca Mountain, Nevada.We observed significant differences in the pattern of condensation in afaulted zone relative to that of a nonfaulted zone, suggesting that themicroclimate dynamics of excavated cavities in fractured, partiallysaturated rocks can be highly complex.
Date: March 1, 2007
Creator: Salve, R. & Kowalsky, M. B.
System: The UNT Digital Library
Estimating solar access of typical residential rooftops: A case study in San Jose, CA (open access)

Estimating solar access of typical residential rooftops: A case study in San Jose, CA

Shadows cast by trees and buildings can limit the solar access of rooftop solar-energy systems, including photovoltaic panels and thermal collectors. This study characterizes rooftop shading in a residential neighborhood of San Jose, CA, one of four regions analyzed in a wider study of the solar access of California homes.High-resolution orthophotos and LiDAR (Light Detection And Ranging) measurements of surface height were used to create a digital elevation model of all trees and buildings in a 4 km2 residential neighborhood. Hourly shading of roofing planes (the flat elements of roofs) was computed geometrically from the digital elevation model. Parcel boundaries were used to determine the extent to which roofing planes were shaded by trees and buildings in neighboring parcels.In the year in which surface heights were measured (2005), shadows from all sources ("total shading") reduced the insolation received by S-, SW-, and W-facing residential roofing planes in the study area by 13 - 16percent. Shadows cast by trees and buildings in neighboring parcels reduced insolation by no more than 2percent. After 30 years of simulated maximal tree growth, annual total shading increased to 19 - 22percent, and annual extraparcel shading increased to 3 - 4percent.
Date: March 3, 2008
Creator: Levinson, Ronnen M.; Gupta, Smita; Akbari, Hashem & Pomerantz, Melvin
System: The UNT Digital Library
Ferromagnetism and suppression of metallic clusters in Fe implanted ZnO -- a phenomenon related to defects? (open access)

Ferromagnetism and suppression of metallic clusters in Fe implanted ZnO -- a phenomenon related to defects?

We investigated ZnO(0001) single crystals annealed in high vacuum with respect to their magnetic properties and cluster formation tendency after implant-doping with Fe. While metallic Fe cluster formation is suppressed, no evidence for the relevance of the Fe magnetic moment to the observed ferromagnetism was found. The latter along with the cluster suppression is discussed with respect to defects in the ZnO host matrix, since the crystalline quality of the substrates was lowered due to the preparation as observed by x-ray diffraction.
Date: March 12, 2008
Creator: Arenholz, Elke; Zhou, S.; Potzger, K.; Talut, G.; Reuther, H.; Kuepper, K. et al.
System: The UNT Digital Library
Colliding with a crunching bubble (open access)

Colliding with a crunching bubble

In the context of eternal inflation we discuss the fate of Lambda = 0 bubbles when they collide with Lambda< 0 crunching bubbles. When the Lambda = 0 bubble is supersymmetric, it is not completely destroyed by collisions. If the domain wall separating the bubbles has higher tension than the BPS bound, it is expelled from the Lambda = 0 bubble and does not alter its long time behavior. If the domain wall saturates the BPS bound, then it stays inside the Lambda = 0 bubble and removes a finite fraction of future infinity. In this case, the crunch singularity is hidden behind the horizon of a stable hyperbolic black hole.
Date: March 26, 2007
Creator: Freivogel, Ben; Freivogel, Ben; Horowitz, Gary T. & Shenker, Stephen
System: The UNT Digital Library
FINAL FRONTIER AT HANFORD TACKLING THE CENTRAL PLATEAU (open access)

FINAL FRONTIER AT HANFORD TACKLING THE CENTRAL PLATEAU

The large land area in the center of the vast Department of Energy (DOE) Hanford Site in southeast Washington State is known as 'the plateau'--aptly named because its surface elevations are 250-300 feet above the groundwater table. By contrast, areas on the 585-square mile Site that border the Columbia River sit just 30-80 feet above the water table. The Central Plateau, which covers an ellipse of approximately 70 square miles, contains Hanford's radiochemical reprocessing areas--the 200 East and 200 West Areas--and includes the most highly radioactive waste and contaminated facilities on the Site. Five 'canyons' where chemical processes were used to separate out plutonium (Pu), 884 identified soil waste sites (including approximately 50 miles of solid waste burial trenches), more than 900 structures, and all of Hanford's liquid waste storage tanks reside in the Central Plateau. (Notes: Canyons is a nickname given by Hanford workers to the chemical reprocessing facilities. The 177, underground waste tanks at Hanford comprise a separate work scope and are not under Fluor's management). Fluor Hanford, a DOE prime cleanup contractor at the Site for the past 12 years, has moved aggressively to investigate Central Plateau waste sites in the last few years, digging more than …
Date: March 4, 2008
Creator: MS, GERBER
System: The UNT Digital Library
Analyses of Oxyanion Materials by Prompt Gamma Activation Analysis (open access)

Analyses of Oxyanion Materials by Prompt Gamma Activation Analysis

Prompt gamma activation analysis (PGAA) has been used to analyze metal ion oxyanion materials that have multiple applications, including medicine, materials, catalysts, and electronics. The significance for the need for accurate, highly sensitive analyses for the materials is discussed in the context of quality control of end products containing the parent element in each material. Applications of the analytical data for input to models and theoretical calculations related to the electronic and other properties of the materials are discussed.
Date: March 24, 2008
Creator: Firestone, Richard B.; Perry, D. L.; English, G. A.; Firestone, R. B.; Leung, K. N.; Garabedian, G. et al.
System: The UNT Digital Library
Optical Switching in VO2 films by below-gap excitation (open access)

Optical Switching in VO2 films by below-gap excitation

We study the photo-induced insulator-metal transition in VO2, correlating threshold and dynamic evolution with excitation wavelength. In high-quality single crystal samples, we find that switching can only be induced with photon energies above the 670-meV gap. This contrasts with the case of polycrystalline films, where formation of the metallic state can also be triggered with photon energies as low as 180 meV, well below the bandgap. Perfection of this process may be conducive to novel schemes for optical switches, limiters and detectors, operating at room temperature in the mid-IR.
Date: March 14, 2008
Creator: Dipartimento di Fisica, Universita?di Brescia, Italy
System: The UNT Digital Library
A Lattice with Larger Momentum Compaction for the NLC Main Damping Rings (open access)

A Lattice with Larger Momentum Compaction for the NLC Main Damping Rings

Previous lattice designs for the Next Linear Collider Main Damping Rings [1] have met the specifications for equilibrium emittance, damping rate and dynamic aperture. Concerns about the effects of the damping wiggler on the beam dynamics [2] led to the aim of reducing the total length of the wiggler to a minimum consistent with the required damping rate, so high-field dipoles were used to provide a significant energy loss in the arcs. However, recent work has shown that the wiggler effects may not be as bad as previously feared. Furthermore, other studies have suggested the need for an increased momentum compaction (by roughly a factor of four) to raise the thresholds of various collective effects. We have therefore developed a new lattice design in which we increase the momentum compaction by reducing the field strength in the arc dipoles, compensating the loss in damping rate by increasing the length of the wiggler. The new lattice again meets the specifications for emittance, damping rate and dynamic aperture, while having the benefit of significantly higher thresholds for a number of instabilities.
Date: March 17, 2008
Creator: Woodley, M.; Raubenheimer, Tor O.; Wu, J.; Wolski, A. & /SLAC /LBL, Berkeley
System: The UNT Digital Library
Towards a deeper insight into strongly correlated electron systems- the symbiosis between experiment and theory (open access)

Towards a deeper insight into strongly correlated electron systems- the symbiosis between experiment and theory

None
Date: March 1, 2007
Creator: Fischer, Peter
System: The UNT Digital Library
Fragmentation Cross Sections of 290 and 400 MeV/nucleon 12C Beamson Elemental Targets (open access)

Fragmentation Cross Sections of 290 and 400 MeV/nucleon 12C Beamson Elemental Targets

Charge-changing and fragment production cross sections at 0circ have been obtained for interactions of 290 MeV/nucleon and 400MeV/nucleon carbon beams with C, CH2, Al, Cu, Sn, and Pb targets. Thesebeams are relevant to cancer therapy, space radiation, and the productionof radioactive beams. We compare to previously published results using Cand CH2 targets at similar beam energies. Due to ambiguities arising fromthe presence of multiple fragments on many events, previous publicationshave reported only cross sections for B and Be fragments. In this work wehave extracted cross sections for all fragment species, using dataobtained at three distinct values of angular acceptance, supplemented bydata taken with the detector stack placed off the beam axis. A simulationof the experiment with the PHITS Monte Carlo code shows fair agreementwith the data obtained with the large acceptance detectors, but agreementis poor at small acceptance. The measured cross sections are alsocompared to the predictions of the one-dimensional cross section modelsEPAX2 and NUCFRG2; the latter is presently used in NASA's space radiationtransport calculations. Though PHITS and NUCFRG2 reproduce thecharge-changing cross sections with reasonable accuracy, none of themodels is able to accurately predict the fragment cross sections for allfragment species and target materials.
Date: March 17, 2007
Creator: Zeitlin, C.; Guetersloh, S.; Heilbronn, L.; Miller, J.; Fukumura,A.; Iwata, Y. et al.
System: The UNT Digital Library
Development of a Multi Megawatt Circulator for X Band (open access)

Development of a Multi Megawatt Circulator for X Band

Research is in progress on a TeV-scale linear collider that will operate at 5-10 times the energy of present-generation accelerators. This will require development of high power RF sources generating of 50-100 MW per source. Transmission of power at this level requires overmoded waveguide to avoid breakdown. In particular, the TE{sub 01} circular waveguide mode is currently the mode of choice for waveguide transmission at Stanford Linear Accelerator Center (SLAC) in the Multimode Delay Line Distribution System (MDLDS). A common device for protecting an RF source from reflected power is the waveguide circulator. A circulator is typically a three-port device that allows low loss power transmission from the source to the load, but diverts power coming from the load (reflected power) to a third terminated port. To achieve a low loss, matched, three port junction requires nonreciprocal behavior. This is achieved using ferrites in a static magnetic field which introduces a propagation constant dependent on RF field direction relative to the static magnetic field. Circulators are currently available at X-Band for power levels up to 1 MW in fundamental rectangular waveguide; however, the next generation of RF sources for TeV-level accelerators will require circulators in the 50-100 MW range. Clearly, …
Date: March 24, 2008
Creator: Neilson, J.; Ives, L. & Tantawi, S. G.
System: The UNT Digital Library
Pyrrole Hydrogenation over Rh(111) and Pt(111) Single-Crystal Surfaces and Hydrogenation Promotion Mediated by 1-Methylpyrrole: A Kinetic and Sum-Frequency Generation Vibrational Spectroscopy Study (open access)

Pyrrole Hydrogenation over Rh(111) and Pt(111) Single-Crystal Surfaces and Hydrogenation Promotion Mediated by 1-Methylpyrrole: A Kinetic and Sum-Frequency Generation Vibrational Spectroscopy Study

Sum-frequency generation (SFG) surface vibrational spectroscopy and kinetic measurements using gas chromatography have been used to study the adsorption and hydrogenation of pyrrole over both Pt(111) and Rh(111) single-crystal surfaces at Torr pressures (3 Torr pyrrole, 30 Torr H{sub 2}) to form pyrrolidine and the minor product butylamine. Over Pt(111) at 298 K it was found that pyrrole adsorbs in an upright geometry cleaving the N-H bond to bind through the nitrogen evidenced by SFG data. Over Rh(111) at 298 K pyrrole adsorbs in a tilted geometry relative to the surface through the p-aromatic system. A pyrroline surface reaction intermediate, which was not detected in the gas phase, was seen by SFG during the hydrogenation over both surfaces. Significant enhancement of the reaction rate was achieved over both metal surfaces by adsorbing 1-methylpyrrole before reaction. SFG vibrational spectroscopic results indicate that reaction promotion is achieved by weakening the bonding between the N-containing products and the metal surface because of lateral interactions on the surface between 1-methylpyrrole and the reaction species, reducing the desorption energy of the products. It was found that the ring-opening product butylamine was a reaction poison over both surfaces, but this effect can be minimized by treating …
Date: March 4, 2008
Creator: Kliewer, Christopher J.; Bieri, Marco & Somorjai, Gabor A.
System: The UNT Digital Library