Physical Sciences and Mathematics Commons^™

Einstein Oscillators In Thallium Filled Antimony Skutterudites, Raphaël P. Hermann, Rongying Jin, Werner Schweika, Fernande Grandjean, David G. Mandrus, Brian C. Sales, Gary J. Long

Chemistry Faculty Research & Creative Works

Heat capacity measurements were performed on Tl_0.8Co₄Sb₁₁Sn. An Einstein vibrating behavior for the thallium atoms was found. The inelastic neutron scattering measurements on T_0.8Co₄Sb₁₁Sn, Tl_0.5Co_3.5Fe_0.5Sb₁₂, and Tl_0.8Co₃FeSb₁₂ showed a localized vibrational mode, which confirmed this Einstein vibrational behavior. Furthermore, the 56±2 K temperature of the Einstein vibrational mode obtained from the heat capacity measurements showed excellent agreement with the 5 meV energy or 57±2 K values obtained from the neutron scattering measurements.

Properties Of A Mixed-Valent Iron Compound With The Kagomé Lattice, Chintamani Nagesa Ramachandra Rao, Geo L. Paul, Amitava Choudhury, Echur Varadadesikan Sampathkumaran, Arup Kumar R. Raychaudhuri, Suryanarayanasastry Ramasesha, Indranil Rudra

Chemistry Faculty Research & Creative Works

An organically templated iron sulfate of the formula [HN(CH₂)₆NH][Fe^III Fe₂ ^IIF₆(SO₄)₂] ·[H₃O] possessing the kagomé lattice has been prepared and characterized by single-crystal crystallography and other techniques. This mixed-valent iron compound shows complex magnetic properties including spin-glass behavior and magnetic hysteresis. The low-temperature specific heat data show deviation from the T² behavior found in two-dimensional frustrated systems. Simple calculations have been carried out to understand the properties of this kagomé compound.

Peptide-Protein Interactions: Photoinduced Electron-Transfer Within The Preformed And Encounter Complexes Of A Designed Metallopeptide And Cytochrome C, Robin C. Lasey, Liu Liu, Ling Zang, Michael Y. Ogawa

Chemistry Faculty Publications

Photoinduced electron-transfer (ET) occurs between a negatively charged metallopeptide, [Ru(bpy)2(phen-am)-Cys-(Glu)(5)-Gly](3-) = RuCE(5)G, and ferricytochrome c = Cyt c. In the presence of Cyt c, the triplet state lifetime of the ruthenium metallopeptide is shortened, and the emission decays via biexponential kinetics, which indicates the existence of two excited-state populations of ruthenium peptides. The faster decay component displays concentration-independent kinetics demonstrating the presence of a preformed peptide-protein complex that undergoes intra-complex electron-transfer. Values of K-b = (3.5 +/- 0.2) x 10(4) M-1 and k(ET)(obs) = (2.7 +/- 0.4) x 10(6) s(-1) were observed at ambient temperatures. The magnitude of k(ET)(obs) decreases …

Teachers' Resource For Materials And Environmental Chemistry, Carnetta Skipworth

Masters Theses & Specialist Projects

In many secondary education chemistry classrooms, teachers have a difficult time introducing chemistry topics in a way that will be interesting to the high school student. The development of a materials and environmental chemistry teacher's manual will help teachers introduce a variety of selected topics in an interesting fashion to the students. This manual focuses on the subjects covered for freshman and sophomore level students. The manual uses five separate experiments to introduce topics such as the electromagnetic spectrum and solubility. The five experiments include a test on tennis shoe stiffness and energy dissipation ability, pesticides in water, grease in …

Measurement Of Proton Transfer Reaction Rates In A Microwave Cavity Discharge Flowing Afterglow, George M. Brooke Iv

Physics Theses & Dissertations

The reaction rate coefficients between the hydronium ion and the molecules ethene (C₂H₄), propene (C₃H₆), 1-butene (C₄H₈) and hydrogen sulfide (H₂S) were measured at 296 K. The measured reaction rates were compared to collision rates calculated using average dipole orientation (ADO) theory. Reaction efficiency depends primarily upon the proton affinity of the molecules. All the measurements were obtained using the newly developed microwave cavity discharge flowing afterglow (MCD-FA) apparatus. This device uses an Asmussen-type microwave cavity discharge ion source that is …

Water-Soluble Organic Components In Aerosols Associated With Savanna Fires In Southern Africa: Identification, Evolution, And Distribution, Song Gao, Dean A. Hegg, Peter V. Hobbs, Thomas W. Kirchstetter, Brian I. Magi, Martin Sadilek

Chemistry and Physics Faculty Articles

During the SAFARI 2000 field campaign, both smoke aerosols from savanna fires and haze aerosols in the boundary layer and in the free troposphere were collected from an aircraft in southern Africa. These aerosol samples were analyzed for their water-soluble chemical components, particularly the organic species. A novel technique, electrospray ionization-ion trap mass spectrometry, was used concurrently with an ion chromatography system to analyze for carbohydrate species. Seven carbohydrates, seven organic acids, five metallic elements, and three inorganic anions were identified and quantified. On the average, these 22 species comprised 36% and 27% of the total aerosol mass in haze …

Emissions Of Trace Gases And Particles From Savanna Fires In Southern Africa, Parikhit Sinha, Peter V. Hobbs, Robert J. Yokelson, I. T. Bertschi, Donald R. Blake, Isobel J. Simpson, Song Gao, Thomas W. Kirschsetter, Tica Novakov

Chemistry and Biochemistry Faculty Publications

[1] Airborne measurements made on initial smoke from 10 savanna fires in southern Africa provide quantitative data on emissions of 50 gaseous and particulate species, including carbon dioxide, carbon monoxide, sulfur dioxide, nitrogen oxides, methane, ammonia, dimethyl sulfide, nonmethane organic compounds, halocarbons, gaseous organic acids, aerosol ionic components, carbonaceous aerosols, and condensation nuclei (CN). Measurements of several of the gaseous species by gas chromatography and Fourier transform infrared spectroscopy are compared. Emission ratios and emission factors are given for eight species that have not been reported previously for biomass burning of savanna in southern Africa (namely, dimethyl sulfide, methyl nitrate, …

Chlorine Budget And Partitioning During The Stratospheric Aerosol And Gas Experiment (Sage) Iii Ozone Loss And Validation Experiment (Solve), S. M. Schauffler, E. L. Atlas, Stephen G. Donnelly Ph.D., A. Andrews, S. A. Montzka, J. W. Elkins, D. F. Hurst, P. A. Romashkin, G. S. Dutton, V. Stroud

Chemistry Faculty Publications

The amount of chlorine in the stratosphere has a direct influence on the magnitude of chlorine-catalyzed ozone loss. A comprehensive suite of organic source gases of chlorine in the stratosphere was measured during the NASA Stratospheric Aerosol and Gas Experiment (SAGE) III Ozone Loss and Validation Experiment (SOLVE) campaign in the arctic winter of 2000. Measurements included chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), halon 1211, solvents, methyl chloride, N2O, and CH4. Inorganic chlorine contributions from each compound were calculated using the organic chlorine measurements, mean age of air, tropospheric trends, and a method to account for mixing in the stratosphere. Total organic …

Concerning The Stability Of Dichlorodiazene, Gregory S. Tschumper, Michael C. Heaven, Keiji Morokuma

Chemistry Faculty Research & Creative Works

The stability of N2Cl2 with respect to dissociation into N2 + 2Cl has been investigated using ab initio electronic structure techniques. Triple-ζ basis sets with d- and f-functions were required to obtain qualitative agreement between multi-reference and highly correlated single reference methods regarding the stability of the cis- and trans-isomers. The CCSD(T) method predicts a barrier to dissociation of 7-8 kcal mol-1 for the two isomers. CASPT2 barrier heights are substantially smaller (≤1.5 kcal mol^-1), indicating that these species are barely bound. © 2003 Elsevier Science B.V. All rights reserved.

Stress Corrosion Cracking Of Type 422 Stainless Steel For Applications In Spallation-Neutron-Target Systems, Ramprashad Prabhakaran

Transmutation Sciences Materials (TRP)

Introduction

• This research program is aimed at evaluating different types of environment-induced degradation of candidate target materials for applications in transmutation of spent nuclear fuels (SNF).

• Transmutation refers to the elimination of long-lived actinides and fission products from SNF.

Objectives

• Evaluate susceptibility of candidate target materials to stress corrosion cracking (SCC) and localized corrosion (pitting and crevice) in neutral and acidic aqueous environments at ambient and elevated temperatures

• Determine the extent and morphology of cracking in tested materials as functions of experimental and environmental variables including pH, temperature, loading conditions and specimen geometry

• Develop mechanistic …

Electrochemical Detection Of Oxidative Stress, Alice Harper, Mark Anderson

Mark R. Anderson

No abstract is currently available.

Method Of Solubilizing Carbon Nanotubes In Organic Solutions, Robert C. Haddon, Mark A. Hamon

Chemistry Faculty Patents

Carbon nanotubes are dissolved in organic solutions by attaching an aliphatic carbon chain (which may contain aromatic residues) so as to render the carbon nanotubes soluble.

Studies Of Monolayer Films As Adhesion Promoters, Huimin Li, Mark Anderson

Mark R. Anderson

No abstract is currently available.

Capillary Electrophoresis To Determine Oxidative Stress, Stephanie Hooper, Mark Anderson

Mark R. Anderson

No abstract is currently available.

Evolution Of Gases And Particles From A Savanna Fire In South Africa, Peter V. Hobbs, Parikhit Sinha, Robert J. Yokelson, Ted J. Christian, Donald R. Blake, Song Gao, Thomas W. Kirschsetter, Tica Novakov, Peter Pilewskie

Chemistry and Biochemistry Faculty Publications

[1] Airborne measurements of particles and gases from a 1000-ha savanna fire in South Africa are presented. These measurements represent the most extensive data set reported on the aging of biomass smoke. The measurements include total concentrations of particles (CN), particle sizes, particulate organic carbon and black carbon, light-scattering coefficients, downwelling UV fluxes, and mixing ratios for 42 trace gases and 7 particulate species. The ratios of excess nitrate, ozone, and gaseous acetic acid to excess CO increased significantly as the smoke aged over ∼40–45 min, indicating that these species were formed by photochemistry in the plume. For 17 other …

Raman Spectroscopy Of Rhombohedral P4o10, Sean J. Gilliam, Scott Kirkby, Clifton N. Merrow, Daniel Zeroka, Ajit Banerjee, James O. Jensen

Scott J. Kirkby

Ab Initio Studies Of Quasi-One-Dimensional Pentagon And Hexagon Ice Nanotubes, Jaeil Bai, C.-R. Su, R. D. Parra, Xiao Cheng Zeng, H. Tanaka, K. Koga, J.-M. Li

Xiao Cheng Zeng Publications

Ab initio plane-wave total-energy calcuation is carried out to study the relative stability of the quasi-one-dimensional (Q1D) pentagon and hexagon ice nanotubes. Electronic structure calculations indicate the two Q1D ice nanotubes have nearly the same band structures and energy bandgap as those of proton-ordered bulk ice I_h . Ab initio molecular-orbital and density-functional theory calculations, as well as three classical potential models of water, are also employed to investigate the relative stability of the pentagon and hexagon water clusters (H₂O) ₃₀, (H₂O) ₆₀ , and (H₂O) ₁₂₀ . Clusters of this kind …

The Solvent Boundary Potential: A New Approach For Computer Simulation Of Large Systems, Valentin Gogonea

Chemistry Faculty Publications

The paper presents the theoretical framework for the development of a new solvent boundary method for computer simulations and its possible application to the simulation of nitric oxide synthase. Different approaches for the construction of a solvent boundary potential are reviewed and their strengths and weaknesses are discussed. A new solvent boundary potential is proposed which combines the mean field force approximation with the Green's function approach for treating long-range electrostatic interactions, and introduces a novel strategy to treat electrostriction effects due to ions crossing the solvent boundary. Finally, a series of computational tests are devised in order to assess …

Synthesis Of (+)-Decarestrictine L, Julie Lukesh, William Donaldson

Chemistry Faculty Research and Publications

A synthesis of (+)-decarestrictine L 1, a cholesterol biosynthesis inhibitory metabolite isolated from Penicillium simplicissimum, is described. Beginning from tri-O-acetyl- -glucal, alkylation with trimethylaluminum introduced the axial methyl group at C-2 in a stereoselective fashion. Chain extension at the C-6 carbon was accomplished by generation of the primary tosylate, followed by displacement with cyanide anion. The synthesis of (+)-1 was completed in 13 steps and 6.3% overall yield.

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix: Quarterly Report January-March 2003, 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 sorption materials and processes, such as natural organic matter (NOM) and other promising alternatives. …

Dynamics Of Adsorbed Poly(Methyl Acrylate) And Poly(Methyl Methacrylate) On Silica, Frank D. Blum, Wuu-Yung Lin, Crystal E. Porter

Chemistry Faculty Research & Creative Works

Deuterium NMR and modulated differential scanning calorimetry (MDSC) were used to probe the behavior of ultrathin adsorbed poly(methyl acrylate) (PMA). The spectra for the bulk methyl-labeled PMA-d3 were consistent with the motions of the polymer segments being spatially homogeneous. For the polymers adsorbed on silica, multicomponent line shapes were observed. The segmental mobility of the surface polymers increased with increased adsorbed amounts. In contrast to the behavior of the polymers in bulk, the adsorbed lower-molecular-mass PMA-d3 was less mobile than the adsorbed high-molecular-mass polymer. The presence of a polymer overlayer was sufficient to suppress the enhanced mobility of the more-mobile …

Magnetic And Mössbauer Spectral Study Of Erfe₁₁Ti And Erfe₁₁Tih, Cristina Piquer, Raphäel P. Hermann, Fernande Grandjean, Gary J. Long, Olivier Isnard

Chemistry Faculty Research & Creative Works

The influence of the insertion of hydrogen into the crystal lattice of ErFe₁₁Ti upon its spin reorientation was investigated. It was found that the insertion of hydrogen into ErFe₁₁Ti to form ErFe₁₁TiH expanded the lattice by 1% and increased the Curie temperature by 56 K. The presence of one titanium near neighbor in the environment of an iron site decreased the hyperfine field by ~2T and changed the isomer shift by ~0.05 mm/s.

Analysis Of Anion Distributions In The Developing Strata Of A Constructed Wetland Used For Chlorinated Ethene Remediation, Joshua D. Kovacic

Theses and Dissertations

Perchloroethene (PCE), Trichloroethene (TCE) and their degradation products are among the most common organic groundwater contaminants in the United States. Constructed wetlands utilizing upward flow harbor reduction-oxidation conditions that have demonstrated the potential to promote both partial and total mineralization of PCE and TCE through the process of natural attenuation. Organic acid and inorganic anion concentrations are indicative of reduction-oxidation processes that drive chlorinated ethene degradation. These analytes were investigated to assess their development within three vertically stratified regions of a constructed wetland cell at Wright-Patterson Air Force Base fed by groundwater contaminated with PCE and TCE. Data collected during …

Environment-Induced Degradation And Crack-Growth Studies Of Candidate Target Materials, Ajit K. Roy, Brendan O'Toole

Transmutation Sciences Materials (TRP)

During the past two years (2001-2002) of this project, the primary effort was focused on evaluating the effect of hydrogen on the cracking behavior of candidate target materials namely, Alloys EP-823, HT-9 and 422 in aqueous environments of different pH values at ambient and elevated temperatures. More recently, emphasis is being placed to evaluate the cracking behavior of these materials in molten lead-bismuth eutectic (LBE) environment at much higher testing temperatures so as to compare the cracking susceptibility in environments containing molten metals and aqueous solutions, respectively. The most recent tests to evaluate the cracking susceptibility were primarily based on …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics: Quarterly Progress Report 12/1/02- 2/28/03, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The Lead-Bismuth eutectic (LBE) has been determined from previous experimental studies by the Russians and the European scientific community to be a potential material that can be used as a spallation target and coolant for the AAA proposed application.

Properly controlling the oxygen content in LBE can drastically reduce the LBE corrosion to structural steels. However, existing knowledge of material corrosion performance was obtained from point-wise testing with very limited density. The transport of oxygen and corrosion products, their interaction and variation of corrosion/precipitation along the flow are not well understood.

The first subtask of this project involves using a …

Enhanced Magnetic Quantum Oscillations In The Mixed State Of A Two-Dimensional Organic Superconductor, J. Wosnitza, J. Hagel, P. J. Meeson, D. Bintley, J. A. Schlueter, Javid Mohtasham, Rolf Walter Winter, Gary L. Gard

Chemistry Faculty Publications and Presentations

We report on de Haas–van Alphen (dHvA) oscillations observed in the mixed state of the organic superconductor β″–(BEDT-TTF)₂SF₅CH₂CF₂SO₃ (BEDT-TTF stands for bisethylenedithio-tetrathiafulvalene) utilizing the field-modulation technique and torque magnetometry. At low temperatures (30 mK), the dHvA signal persists down to 1.4 T well below the upper critical field Bc2≈3.6T. Contrary to most theoretical predictions and previous experimental findings, no additional damping of the dHvA-oscillation amplitude, but a reduced damping of the dHvA signal is found. This highly unusual effect might indicate a reduced quasiparticle scattering rate or an additional oscillatory contribution in the superconducting state.

Magnetic Resonance Studies On Lithium Intercalation Into Carbons, Xiao-Rong Zhou, Zhen-Ming Du, Lin Zhuang, Jun-Tao Lu

Journal of Electrochemistry

The electron spin resonance(ESR) and 7Li_NMR magnetic resonance (7Li_NMR) studies on lithium intercalation into carbons were reviewed based on recently published papers, including those by the authors of this review. Two kinds of electronic spins were found in ESR studies. One corresponds to the charge carrier electrons and is called the Pauli spin. From the ESR intensity of Pauli spins, the curve of the density of electronic states can be deduced for the carbon material studied and, in turn, the contribution of the band model mechanism to the lithium intercalation can be calculated for the given carbon sample. The other …

The Electrochemical Performance Studies On Novel Lifepo_4 Cathode Materials For Li_Ion Batteries, Zhi-Cong Shi, Chen Li, Yong Yang

Journal of Electrochemistry

The cathode materials of LiFePO4 and LiFePO4 coated with carbon were synthesized by means of solid state reaction and ballmilling. The samples were characterized by X_ray diffraction, scanning electron microscopy, gas_phase element analysis and titration analysis methods. Electrochemical tests of two kinds of materials showed that both of them exhibit a 3.4V discharge voltage plateau, however,the coated samples demonstrated the improved performance in terms of discharge capacity and cyclic stability.

Application Of Biphenyl Electroploymerization For Overcharge Protection In Li-Ion Batteries, Li-Fen Xiao, Xin-Ping Ai, Yu-Liang Cao, Han-Xi Yang

Journal of Electrochemistry

The electropolymerization of biphenyl at overcharged positive electrode was investigated for overcharge protection of Li_ion batteries. Biphenyl in electrolyte as an additive can electrochemically polymerize at 4.5～4.75 V(vs. Li/Li+) to form a layer of conductive film on cathode surface. The surface film increases the internal resistance and the gases released during the electropolymerization also increases the internal pressure of the batteries, which therefore enhance the sensitivities of the electrical disconnecting devices. During prolonged overcharge, the growth of the conductive polymer film can create short circuit between the positive and negative electrodes and cause self_discharge of the batteries to a safer …

In Situ Measurements Of Solution Conductivity In Microwave Field, Yong-Qing Su, Chun-Peng Liu

Journal of Electrochemistry

The curves of the conductivity as a function of temperature for 24 kinds of solutions have been in situ measured both in the microwave field and in absence of microwave field. The results indicated that the relationship between the conductivity in microwave field (Lw) and temperature (T) can be expressed by an equation Lw=a′+b′T+c′T2 , similar to the one that is valid in absence of the microwave field Ln=a+bT+cT2. Conductivity in the absence and presence of microwave field can be linked by the equation ln Lw=A+BLn+CL2n.