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Physical Chemistry

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2002

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Articles 1 - 14 of 14

Full-Text Articles in Chemistry

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix: Quarterly Report September-December 2002, Spencer M. Steinberg Dec 2002

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix: Quarterly Report September-December 2002, Spencer M. Steinberg

Separations Campaign (TRP)

The recovery of iodine released during the processing of used nuclear fuel poses a significant challenge to the transmutation of radioactive iodine. This proposal will develop and examine the use of Fullerene Containing Carbon (FCC) compounds as potential sorbents for iodine release from the reprocessing of nuclear fuel. This work will also include the development of bench-scale testing capabilities at UNLV to allow the testing of the FCC material in a simulated process off-gas environment. This experimental capability will also be used to test other potential sorbtion materials and processes, such as natural organic matter (NOM) and other promising alternatives. …


Fragmentation Processes Following Core Excitation In Acetylene And Ethylene By Partial Ion Yield Spectroscopy, Maria Novella Piancastelli, Wayne C. Stolte, Gunnar Ohrwall, S-W Yu, D. Bull, K. Lantz, Alfred S. Schlachter, Dennis W. Lindle Nov 2002

Fragmentation Processes Following Core Excitation In Acetylene And Ethylene By Partial Ion Yield Spectroscopy, Maria Novella Piancastelli, Wayne C. Stolte, Gunnar Ohrwall, S-W Yu, D. Bull, K. Lantz, Alfred S. Schlachter, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

Partial ion yield spectroscopy provides a very detailed picture of fragmentation processes following core excitation in isolated molecules. We exploit this potential in the analysis of decay processes following C1s→π and C1s→Rydberg excitations in ethylene and acetylene. We show that the relative intensity of spectral features related to the excitation to empty molecular orbitals or to Rydberg states is a function of the time variation of the fragmentation process. Namely, we see an intensity increase in the Rydberg states compared to the molecular orbitals as the fragmentation process becomes more extensive, a result attributable to the diffuse nature of the …


Creating Nanocavities Of Tunable Sizes: Hollow Helices, Bing Gong, Huaqiang Zeng, Jin Zhu, Lihua Yuan, Yaohua Han, Shizhi Cheng, Mako Furukawa, Ruben D. Parra, Audrey Y. Kovalevsky, Jeffrey L. Mills, Ewa Skrzypczak-Jankun, Suzana Martinovic, Richard D. Smith, Chong Zheng, Thomas Szyperski, Xiao Cheng Zeng Sep 2002

Creating Nanocavities Of Tunable Sizes: Hollow Helices, Bing Gong, Huaqiang Zeng, Jin Zhu, Lihua Yuan, Yaohua Han, Shizhi Cheng, Mako Furukawa, Ruben D. Parra, Audrey Y. Kovalevsky, Jeffrey L. Mills, Ewa Skrzypczak-Jankun, Suzana Martinovic, Richard D. Smith, Chong Zheng, Thomas Szyperski, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

A general strategy for creating nanocavities with tunable sizes based on the folding of unnatural oligomers is presented. The backbones of these oligomers are rigidified by localized, threecenter intramolecular hydrogen bonds, which lead to well-defined hollow helical conformations. Changing the curvature of the oligomer backbone leads to the adjustment of the interior cavity size. Helices with interior cavities of 10 Å to >30 Å across, the largest thus far formed by the folding of unnatural foldamers, are generated. Cavities of these sizes are usually seen at the tertiary and quaternary structural levels of proteins. The ability to tune molecular dimensions …


Holographic Analysis Of Diffraction Structure Factors, S. Marchesini, N. Mannella, C. S. Fadley, M. A. Van Hove, J. J. Bucher, D. K. Shuh, L. Fabris, M. J. Press, M. W. West, Wayne C. Stolte, Z. Hussain Sep 2002

Holographic Analysis Of Diffraction Structure Factors, S. Marchesini, N. Mannella, C. S. Fadley, M. A. Van Hove, J. J. Bucher, D. K. Shuh, L. Fabris, M. J. Press, M. W. West, Wayne C. Stolte, Z. Hussain

Chemistry and Biochemistry Faculty Research

We combine the theory of inside-source/inside-detector x-ray fluorescence holography and Kossel lines/x ray standing waves in kinematic approximation to directly obtain the phases of the diffraction structure factors. The influence of Kossel lines and standing waves on holography is also discussed. We obtain partial phase determination from experimental data obtaining the sign of the real part of the structure factor for several reciprocal lattice vectors of a vanadium crystal.


Synthesis And Characterization Of Hydroxyapatite-Collagen Biocomposite Materials, Vuk Uskoković, Nenad Ignjatović, Nadejda Petranović Sep 2002

Synthesis And Characterization Of Hydroxyapatite-Collagen Biocomposite Materials, Vuk Uskoković, Nenad Ignjatović, Nadejda Petranović

Pharmacy Faculty Articles and Research

Hydroxyapatite-collagen composite is a prosperous biomaterial in reconstructive surgery for the reparation of defects within human hard tissue. Within this research, three-dimensional blocks of HAp/collagen composite biomaterial were synthesized by homogenizing the HAp/collagen mixture by cold and hot (T=60oC) pressing (P=49 MPa). The changes in the system were followed by using thermal analysis (DSC & TGA), FT-IR spectroscopy and scanning electron microscopy (SEM). The identification and kinetic analysis of appearing phase transition were done. FT-IR spectrum of the biocomposite shows that neither cold nor hot pressing had significant influence on the individual components of the composite. SEM of the fracture …


Non-Dipolar Electron Angular Distributions From Fixed-In-Space Molecules, Renaud Guillemin, Oliver Hemmers, Dennis W. Lindle, E. Shigemasa, K. Le Guen, D. Ceolin, C. Miron, N. Leclercq, P. Morin, Marc Simon, P. W. Langhoff Jul 2002

Non-Dipolar Electron Angular Distributions From Fixed-In-Space Molecules, Renaud Guillemin, Oliver Hemmers, Dennis W. Lindle, E. Shigemasa, K. Le Guen, D. Ceolin, C. Miron, N. Leclercq, P. Morin, Marc Simon, P. W. Langhoff

Environmental Studies Faculty Publications

The first indication of nondipole effects in the azimuthal dependence of photoelectron angular distributions emitted from fixed-in-space molecules is demonstrated in N2. Comparison of the results with angular distributions observed for randomly oriented molecules and theoretical derivations for the nondipole correction first order in photon momentum suggests that higher orders will be needed to describe distributions measured in the molecular frame.


In-Situ X-Ray-Absorption Spectroscopy Study Of Hydrogen Absorption By Nickel-Magnesium Thin Films, B. Farangis, Ponnusamy Nachimuthu, T. J. Richardson, J. L. Slack, Rupert C. Perera, Eric M. Gullikson, Dennis W. Lindle, M. Rubin Jul 2002

In-Situ X-Ray-Absorption Spectroscopy Study Of Hydrogen Absorption By Nickel-Magnesium Thin Films, B. Farangis, Ponnusamy Nachimuthu, T. J. Richardson, J. L. Slack, Rupert C. Perera, Eric M. Gullikson, Dennis W. Lindle, M. Rubin

Chemistry and Biochemistry Faculty Research

Structural and electronic properties of co-sputtered Ni-Mg thin films with varying Ni to Mg ratio were studied by in-situ x-ray absorption spectroscopy in the Ni L-edge and Mg K-edge regions. Co-deposition of the metals led to increased disorder and decreased coordination around Ni and Mg compared to pure metal films. Exposure of the metallic films to hydrogen resulted in formation of hydrides and increased disorder. The presence of hydrogen as a near neighbor around Mg caused a drastic reduction in the intensities of multiple scattering resonances at higher energies. The optical switching behavior and changes in the x-ray spectra varied …


Evaluation Of Fluorapatite As A Waste-Form Material, Dennis W. Lindle, Dale L. Perry Jun 2002

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

Separations Campaign (TRP)

Fluorapatite, fluorinated calcium phosphate, has been identified as a potential matrix for the entombment of the zirconium fluoride fission product waste stream from the proposed FLEX process. If the efficacy of fluorapatite based waste-storage can be demonstrated, then new and potentially more-efficient options for handling and separating high-level wastes, based on fluoride-salt extraction, will become feasible. This proposal will develop a dual-path research project to develop a process to fabricate a synthetic fluorapatite waste form for the ZrF4, FP waste stream, characterize the waste form, examine its performance under environmental conditions, and correlate the behavior of the waste …


Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix, Spencer M. Steinberg Jun 2002

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix, Spencer M. Steinberg

Separations Campaign (TRP)

The recovery of iodine released during the processing of used nuclear fuel poses a significant challenge to the transmutation of radioactive iodine. This proposal will develop and examine the use of Fullerene Containing Carbon (FCC) compounds as potential sorbents for iodine release from the reprocessing of nuclear fuel. This work will also include the development of bench-scale testing capabilities at UNLV to allow the testing of the FCC material in a simulated process off-gas environment. This experimental capability will also be used to test other potential sorbtion materials and processes, such as natural organic matter (NOM) and other promising alternatives. …


Photoexcitation Of A Dipole-Forbidden Resonance In Helium, B. Krassig, E. P. Kanter, S. H. Southworth, Renaud Guillemin, Oliver Hemmers, Dennis W. Lindle, R. Wehlitz, N. L. S. Martin May 2002

Photoexcitation Of A Dipole-Forbidden Resonance In Helium, B. Krassig, E. P. Kanter, S. H. Southworth, Renaud Guillemin, Oliver Hemmers, Dennis W. Lindle, R. Wehlitz, N. L. S. Martin

Environmental Studies Faculty Publications

We have observed photoexcitation of the dipole-forbidden 1s21S0→2p21D2 resonance in helium by measuring the nondipolar forward-backward asymmetry of photoelectron angular distributions in the 2ℓ2ℓ autoionizing region. By exploiting the electric dipole-quadrupole interference in the excitation of both the 2s2p1P1 and 2p21D2 levels, we have observed the quadrupole resonance in photoabsorption and extracted its Fano line shape parameters and the relative phase of the 1sEp and 1sEd continua. We find the quadrupole line profile index q2 to be markedly different from theoretical expectations.


C-Cl Bond Fission, Hcl Elimination, And Secondary Radical Decomposition In The 193 Nm Photodissociation Of Allyl Chloride, M. L. Morton, L. J. Butler, Thomas Alex Stephenson, F. Qi Feb 2002

C-Cl Bond Fission, Hcl Elimination, And Secondary Radical Decomposition In The 193 Nm Photodissociation Of Allyl Chloride, M. L. Morton, L. J. Butler, Thomas Alex Stephenson, F. Qi

Chemistry & Biochemistry Faculty Works

The primary photodissociation dynamics of allyl chloride upon excitation at 193 nm is investigated in a crossed laser-molecular beam scattering apparatus. Tunable vacuum ultraviolet (VUV) photoionization of the products provides a unique ability to learn about the secondary reaction products of the nascent photoproducts formed. The data show evidence for four significant primary reaction channels: a previously unidentified low kinetic energy C-Cl bond fission channel producing unstable allyl radicals, an excited state C-Cl bond fission channel producing Cl atoms with high translational energy, an HCl elimination pathway releasing significant energy to product translation to HCl and its momentum-matched mass 40 …


Collision-Induced Electronic Energy Transfer From V=0 Of The E(0+G) Ion-Pair State In I2: Collisions With He And Ar, Christopher J. Fecko , '98, Miriam Arak Freedman , '00, Thomas Alex Stephenson Jan 2002

Collision-Induced Electronic Energy Transfer From V=0 Of The E(0+G) Ion-Pair State In I2: Collisions With He And Ar, Christopher J. Fecko , '98, Miriam Arak Freedman , '00, Thomas Alex Stephenson

Chemistry & Biochemistry Faculty Works

The electronic energy transfer pathways that occur following collisions between I-2 in the E ion-pair electronic state (v = 0, J = 55) and He and Ar atoms have been determined. The nearby D, D', and beta ion-pair states are populated, but with relative branching ratios that vary with the rare gas collision partner. In He/I-2 collisions, the D state is preferentially populated, while Ar/I-2 collisions preferentially populate the beta electronic state. Bimolecular rate constants and effective hard sphere collision cross sections have been determined for each channel; the cross sections range from 7.0 +/- 1.0 Angstrom(2) for populating the …


Chemical Analysis By X-Ray Spectroscopy Near Phase Transitions In The Solid State, Juana Vivó Acrivos, L. Nguyen, T. Norman, C. T. Lin, W. Y. Liang, J. M. Honig, P Somasundaran Jan 2002

Chemical Analysis By X-Ray Spectroscopy Near Phase Transitions In The Solid State, Juana Vivó Acrivos, L. Nguyen, T. Norman, C. T. Lin, W. Y. Liang, J. M. Honig, P Somasundaran

Faculty Publications, Chemistry

The methods discussed in this work show that the types of changes which may be observed, by precise XAS measurements of Absorbance A versus temperature, across a phase transition are: the changes in the relaxation time of the final states  due to fluctuations near a phase transition; the detection of the anomalous Bragg condition coupled to phonon modes XAS enhancement that identifies the temperature interval where the phonon modes are active, the symmetry changes which introduce new allowed transitions to finite states below an element edge, near Tc indicate what symmetry changes occur, and the method of XTDAFST0 = …


Article Are Hydrogen Bonds Unique Among Weak Interactions In Their Ability To Mediate Electronic Coupling?, Emily Cukier '03, Sarah Daniels '02, Eric Vinson '01, Robert J. Cave Jan 2002

Article Are Hydrogen Bonds Unique Among Weak Interactions In Their Ability To Mediate Electronic Coupling?, Emily Cukier '03, Sarah Daniels '02, Eric Vinson '01, Robert J. Cave

All HMC Faculty Publications and Research

Superexchange effects on the electronic coupling element for electron transfer are investigated using water dimers and atomic donors and acceptors. We compare the electronic coupling elements obtained with H-bonded dimers to those obtained for other water dimer geometries at given donor−acceptor and oxygen−oxygen distances. The H-bonded orientation does not yield significantly different coupling elements from non-H-bonded orientations at a given oxygen−oxygen distance. In addition, the distance dependence of the coupling mediated by H-bonds is not significantly different from that for other dimer geometries. It is found that protonation of the intervening waters has a significant effect on coupling elements for …