Physical Sciences and Mathematics Commons^™

Linear Dichroism In Resonant Inelastic X-Ray Scattering To Molecular Spin-Orbit States, Renaud Guillemin, Stephane Carniato, Wayne C. Stolte, Loic Journel, Richard Taieb, Dennis W. Lindle, Marc Simon

Chemistry and Biochemistry Faculty Research

Polarization-dependent resonant inelastic x-ray scattering (RIXS) is shown to be a new probe of molecular-field effects on the electronic structure of isolated molecules. A combined experimental and theoretical analysis explains the linear dichroism observed in Cl 2p RIXS following Cl 1s excitation in HCl and CF₃Cl as due to molecular-field effects, including singlet-triplet exchange, indicating polarized-RIXS provides a direct probe of spin-orbit-state populations applicable to any molecule.

Solar Thermochemical Hydrogen Production Project – Progress Toward Industrial Scale Water Splitting, Roger Rennels

UNLV Renewable Energy Symposium

The 2008 UNLV Renewable Energy Symposium was presented by the Office of Strategic Energy Programs and co-sponsored by the Division of Research and Graduate Studies on August 20, 2008 on the UNLV campus.

The event focused on renewable energy production in Nevada, the US Southwest, and renewable research projects nationwide. It was a great opportunity for anyone working on renewable projects to collaborate with others in this field and exchange information. Over 230 individuals attended the event this year.

Stability And Equation Of State Of A Nanocrystalline Ga-Ge Mullite In A Vitroceramic Composite: A Synchrotron X-Ray Iffraction Study, Kristina E. Lipinska-Kalita, Patricia Kalita, Cedric Gobin, Oliver Hemmers, Thomas Hartmann, Gino Mariotto

Environmental Studies Faculty Publications

Synchrotron x-ray diffraction and diamond anvil cell techniques were used to characterize the phase transformations and to evaluate the structural stability at elevated pressures of a developed nanocrystalline composite. The optically transparent material was built of a germanium oxide-based amorphous host matrix with homogeneously dispersed 13±3 nm Ga-Ge mullite-type nanocrystals, which had a structure similar to the conventional Al₂O₃-SiO₂ mullite. The equation of state of the nanocrystals and the overall structural integrity of the nanocomposite were investigated in quasihydrostatic conditions on compression to 36 GPa and on the following decompression to ambient conditions. The overall …

Equation Of State Of Gallium Oxide To 70 Gpa: Comparison Of Quasihydrostatic And Nonhydrostatic Compression, Kristina E. Lipinska-Kalita, Patricia Kalita, Oliver Hemmers, Thomas Hartmann

Environmental Studies Faculty Publications

Synchrotron x-ray diffraction and diamond-anvil cell techniques were used to characterize pressure induced structural modifications in gallium oxide. Gallium oxide was studied on compression up to 70 GPa and on the following decompression. The effect of the pressure-transmitting medium on the structural transformations was investigated in two sets of compression and decompression runs, one with nitrogen as a quasihydrostatic pressure-transmitting medium and the other in nonhydrostatic pressure conditions. The x-ray diffraction data showed gradual phase transition from a low-density, monoclinic β-Ga₂O₃ to a high-density, rhombohedral α-Ga₂O₃. With the use of nitrogen as a …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Matrix, Spencer M. Steinberg, Gary Cerefice, David W. Emerson

Separations Campaign (TRP)

Observations related to the oxidation of iodide to iodine (I₂) or hypoiodic acid (HIO) by MnO₂ were continued. The formation of triiodide presumable involves the adsorption of iodide onto the MnO₂ surface (perhaps displacing a surface hydroxyl group). The iodide should be subsequently oxidized and released back into solution as IOH or I₂, which rapidly forms I₃ ^-. The kinetic data has been modeled as a first order process. First order rate constants have been obtained for the formation of iodine in the presence of MnO₂. The increase in iodide …

Evaluation Of Fluorapatite As A Waste-Form Material, Dennis W. Lindle, Oliver Hemmers, Dale L. Perry

Separations Campaign (TRP)

Argonne National Laboratory has proposed a new extraction procedure to handle TRISO-coated fuels, the Fluoride Extraction Process (FLEX). The FLEX process is designed to separate the uranium in the fuel from the actinides and most fission products by taking advantage of the unique properties of uranium hexafluoride (UF₆). In the FLEX process, the used TRISO fuel is reacted with zirconium fluoride salt, forming UF₆ and the fluoride salts of the actinides and fission products. At process temperatures, the UF₆ volatizes into a gas, and is released from the molten salt mixture. This leaves behind the actinides …

Electrochemical Separation Of Curium And Americium, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

The objective was to use electrochemical techniques to develop a thermodynamic understanding of actinide and lanthanide species in RTIL solutions, and use this data to effectively separate species with very similar chemical properties.

In consultation with a DOE collaborator, electrochemical methods and materials were evaluated and used to exploit the thermodynamic differences between similar chemical species enhancing the ability to selectively target and sequester individual species from mixtures. This project, in its third year, successfully completed phases 1, 2. Phase 3 was partially completed. The project expanded to include phase 4.

The following were specific goals for 2007-2008:

• To …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System, Kenneth Czerwinski

Separations Campaign (TRP)

The research objective is to experimentally evaluate the fundamental speciation of Pu and U in the TBP-dodecane-nitric acid- AHA system and the effect of pertechnetate, specifically:

• To determine the influence of nitrate on the speciation of U and Pu in the TBP-dodecane-nitric acid system. The aqueous and organic speciation of U and Pu are examined as a function of the nitric acid concentration, nitrate concentration, actinide ion concentration, temperature, and time.

• To determine the speciation of U and Pu with AHA in the presence and absence of TBP-dodecane organic phase. The aqueous and organic speciation of U and …

Evaluation Of Fundamental Radionuclide Extraction Data For Urex, Kenneth Czerwinski

Separations Campaign (TRP)

The speciation of technetium and actinides in advanced solvent extraction systems is the basis for their manipulation in separations. The ability to understand and predict radionuclide speciation is paramount to successful modeling of proposed separation systems. This project will examine the speciation of radionuclides in different stages of the uranium extraction (UREX) separation scheme, providing data useful to modeling. The areas to be examined include the speciation of uranium and plutonium with tributylphosphate and the kinetics and thermodynamics of lanthanides and actinides in the TALSPEAK (Trivalent actinide lanthanide separation by phosphorous reagent extraction from aqueous complexes) system. The complexation constants …

Criticality Studies For Urex Processes, Denis Beller

Separations Campaign (TRP)

The completion of criticality experiments for mixtures of transuranic actinides (TRU; includes neptunium, plutonium, americium, and curium) that will be created during the separation of used nuclear fuel may be a requirement in order to construct prototype plants for the Global Nuclear Energy Partnership (GNEP). In this program and the Advanced Fuel Cycle Research and Development (AFC R&D) program that supports it, economic and environmental methods are being developed to reduce the impact of waste from commercial nuclear fuel cycles.

Recycling of used fuel by chemically separating it into U, fission products, and TRU would be the first step in …

F-Element Electrochemistry In Rtil Solutions: Electrochemical Separation Of Lanthanides And Actinides, David W. Hatchett

Separations Campaign (TRP)

Electrochemical methods can be used to effectively separate actinide and lanthanide species from complex mixtures. This is based on the unique electrochemical properties of each specific target species. In studies it has been found that, with the exception of Ce, aqueous solutions provide unsuitable electrochemical windows to effectively evaluate the thermodynamic properties that are useful for chemical separations. Therefore, a more novel approach was examined which eliminated the aqueous solution with a room temperature ionic liquid (RTIL) solution. RTIL solutions do not suffer from the side reactions that are prominent in aqueous environments. In addition, the potential window is much …

Interaction Between Metal Fission Products And Triso Coating Materials, Clemens Heske

Fuels Campaign (TRP)

This project focuses on the chemical bonding and interface formation of metal fission products with the coating materials used in tri-isotropic (TRISO) fuel particles for gas-cooled reactors. By combining surface- and bulk-sensitive spectroscopic and microscopic methods, intermediate chemical phases at the interface, intermixing/diffusion behavior, and the electronic interface structure for different coating materials and metals are examined.

In detail, the project studies the interface formation of Pd, Cs, and Ag with SiC and pyrolytic carbon. Using SiC single crystals and highly-ordered pyrolytic carbon (HOPG) as substrates, interfaces are prepared under controlled conditions in an ultra-high vacuum environment and are studied …

Solution-Based Synthesis Of Nitride Fuels, Kenneth Czerwinski, Tyler A. Sullens

Fuels Campaign (TRP)

One of the original synthetic routes devised for the synthesis of U (III)N involved the entire reaction taking place in liquid ammonia. Several experimental reactions were conducted in an attempt to synthesize the UI₃(NH₃)_x and U(NH₂)₃(NH₃)_x precursors of U(III) N. Each attempt involved cleaning of the uranium metal to remove the oxide coating of the metal reagent with 3 washes of concentrated nitric acid, each followed by a rinse with liquid ammonia. Success of this cleaning procedure was varied, with a majority of cleaned metal oxidizing rapidly once …

Photofragmentation Of Sif4 Upon Si 2p And F 1s Core Excitation: Cation And Anion Yield Spectroscopy, Maria Novella Piancastelli, Wayne C. Stolte, Renaud Guillemin, A. Wolska, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

We have studied the fragmentation dynamics of core-excited SiF₄ by means of soft-x-ray photoexcitation and partial positive and negative ion yield measurements around the Si L_2,3-shell and F K-shell ionization thresholds. All detectable ionic fragments are reported and we observe significant differences between the various partial ion yields near the Si 2p threshold. The differences are similar to our previous results from CH₃Cl showing more extended fragmentation in correspondence to transitions to Rydberg states. At variance with smaller systems, we observe negative ion production in the shape resonance region. This can be related …