Chemistry Commons^™

Fragmentation Properties Of Three-Membered Ring Heterocyclic Molecules By Partial Ion Yield Spectroscopy: C2h4o And C2h4s, Wayne C. Stolte, I. Dumitriu, S-W Yu, Gunnar Ohrwall, Maria Novella Piancastelli, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

We investigated the photofragmentation properties of two three-membered ring heterocyclic molecules, C₂H₄O and C₂H₄S, by total and partial ion yield spectroscopy. Positive and negative ions have been collected as a function of photon energy around the C 1s and O 1s ionization thresholds in C₂H₄O, and around the S 2p and C 1s thresholds in C₂H₄S. We underline similarities and differences between these two analogous systems. We present a new assignment of the spectral features around the C K-edge and the sulfur L_{2 …}

Absolute Nitrogen Atom Density Measurements By Two-Photon Laser-Induced Fluorescence Spectroscopy In Atmospheric Pressure Dielectric Barrier Discharges Of Pure Nitrogen, Et-Touhami Es-Sebbar, Christian Sarra-Bournet, Nicolas Naudé, Françoise Massines, Nicolas Gherardi

Dr. Et-touhami Es-sebbar

In this paper, two-photon absorption laser induced fluorescence spectroscopy is used to follow the nitrogen atom density in flowing dielectric barrier discharges fed with pure nitrogen and operating at atmospheric pressure. Two different dielectric barrier discharge regimes are investigated: the Townsend regime, which is homogeneous although operating at atmospheric pressure, and the more common filamentary regime. In both regimes, densities as high as 3x1014 /cm3 are detected. However, the N atoms kinetic formation depends on the discharge regime. The saturation level is reached more rapidly with a filamentary discharge. For a given discharge regime, the N atom density depends strongly …

Contributions To The Development Of The S.E.T.U.P. (Experimental And Theoretical Simulations Useful For Planetology) Project, E. Arzoumanian, C. Romanzin, M-C. Gazeau, Et. Es-Sebbar, A. Jolly, S. Perrier, Y. Benilan

Dr. Et-touhami Es-sebbar

No abstract provided.

Multiwavelength Studies For Titan's Atmospheric Composition Analysis, Y. Benilan, Et. Es-Sebbar, N. Fray, M-C. Gazeau, A. Jolly, M. Schwell, J. Guillemin

Dr. Et-touhami Es-sebbar

Titan's atmosphere mainly made of nitrogen and methane is rich in organic molecules. Hydrocarbons are formed from the photolytic dissociation of CH4 and nitriles are created by dissociation of N2 followed by reactions with hydrocarbons. In order to understand the physicochemical mechanisms responsible for the evolution of Titan's atmosphere, photochemical models are built. The latter need constrains for vertical profiles of organic compounds from the high thermosphere down to the low stratosphere as well as photodissociation rates. Those profiles over the entire atmosphere can be retrieved from Cassini observations, in particular by limb sounding, coupling infrared and ultraviolet spectroscopy. However, …

Vuv Photostability Of Prebiotic Species, M. Schwell, Y. Bénilan, M.-C. Gazeau, N. Fray, A. Jolly, Et. Es-Sebbar, N. Champion, S. Leach, H. W Jochims, H. Baumgärtel, E. Rühl

Dr. Et-touhami Es-sebbar

No abstract provided.

S.E.T.U.P. Experimental And Theoretical Simulations Useful For Planetology- Related Studies In The Frame Of A Program Of Titan’S Atmosphere Laboratory Simulations, M.-C. Gazeau, Et. Es-Sebbar, E. Arzoumanian, C. Romanzin, A. Jolly, S. Perrier, Y. Bénilan

Dr. Et-touhami Es-sebbar

No abstract provided.

Experimental And Theoretical Investigation Of Molecular Field Effects By Polarization-Resolved Resonant Inelastic X-Ray Scattering, Stephane Carniato, Renaud Guillemin, Wayne C. Stolte, Loic Journel, Richard Taieb, Dennis W. Lindle, Marc Simon

Chemistry and Biochemistry Faculty Research

We present a combined theoretical and experimental study of molecular field effects on molecular core levels. Polarization-dependent resonant inelastic x-ray scattering is observed experimentally after resonant K-shell excitation of CF₃Cl and HCl. We explain the linear dichroism observed in spin-orbit level intensities as due to molecular field effects, including singlet-triplet exchange, and interpret this behavior in terms of population differences in the 2p_x,y,z inner-shell orbitals. We investigate theoretically the different factors that can affect the electronic populations and the dynamical R dependence of the spin-orbit ratio. Finally, the results obtained are used to interpret the L-shell …

Continued Development Of An Empirical Function For Predicting And Rationalizing Protein–Protein Binding Affinities, Joseph Audie

Chemistry & Physics Faculty Publications

Here we summarize recent work on the continued development of our fast and simple empirical equation for predicting and structurally rationalizing protein–protein and protein–peptide binding affinities. Our empirical expression consists of six regression-weighted physical descriptors and derives from two key simplifying assumptions: (1) the assumption of rigid-body association and (2) the assumption that all contributions not explicitly considered in the equation make a net contribution to binding of ≈0 kcal. Within the strict framework of rigid-body association, we tested relative binding affinity predictions using our empirical equation against the corresponding experimental binding free energy data for 197 interface alanine mutants. …

51st Rocky Mountain Conference On Analytical Chemistry

Rocky Mountain Conference on Magnetic Resonance

Final program, abstracts, and information about the 51st annual meeting of the Rocky Mountain Conference on Analytical Chemistry, co-endorsed by the Colorado Section of the American Chemical Society and the Society for Applied Spectroscopy. Held in Snowmass, Colorado, July 19-23, 2009.

Characterization Of An N2 Flowing Microwave Post-Discharge By Oes Spectroscopy And Determination Of Absolute Ground-State Nitrogen Atom Densities By Talif, Et. Es-Sebbar, Y. Benilan, A. Jolly, M-C. Gazeau

Dr. Et-touhami Es-sebbar

A flowing microwave post-discharge source sustained at 2.45 GHz in pure nitrogen has been investigated by optical emission spectroscopy (OES) and two-photon absorption laser-induced fluorescence (TALIF) spectroscopy. Variations of the optical emission along the post-discharge (near, pink and late afterglow) have been studied and the gas temperature has been determined. TALIF spectroscopy has been used in the late afterglow to determine the absolute ground-state nitrogen atomic densities using krypton as a reference gas. Measurements show that the microwave flowing post-discharge is an efficient source of N (4S) atoms in late afterglow. In our experimental conditions, the maximum N (4S) density …

The Initial And Final States Of Electron And Energy Transfer Processes: Diabatization As Motivated By System-Solvent Interactions, Joseph E. Subotnik, Robert J. Cave, Ryan P. Steele, Neil Shenvi

All HMC Faculty Publications and Research

For a system which undergoes electron or energy transfer in a polar solvent, we define the diabatic states to be the initial and final states of the system, before and after the nonequilibrium transfer process. We consider two models for the system-solvent interactions: A solvent which is linearly polarized in space and a solvent which responds linearly to the system. From these models, we derive two new schemes for obtaining diabatic states from ab initio calculations of the isolated system in the absence of solvent. These algorithms resemble standard approaches for orbital localization, namely, the Boys and Edmiston–Ruedenberg (ER) formalisms. …

Evaluation Of Low-Temperature Fluoride Routes To Synthesize Actinide Nitrides And Oxide Solid Solutions, Gunanda Waduge Chinthaka Silva

UNLV Theses, Dissertations, Professional Papers, and Capstones

Actinide mononitrides have been considered as a possible nuclear fuel for the Generation-IV nuclear reactor systems. In the process of evaluating these actinide mononitrides as nuclear fuel, it is important to study different chemical and physical characteristics of these compounds. Synthesis of the materials is thus important. Carbothermic reduction is one of the techniques that have been used to synthesize actinide mononitrides. In this method, a mixture of actinide oxide such as UO ₂ and excess carbon is heat treated at temperatures greater than 1700 °C under a nitrogen atmosphere. The technique is however not promising in synthesizing the actinide …

The Rotational Spectrum Of The Fed Radical In Its X4Δ State, Measured By Far-Infrared Laser Magnetic Resonance, Michael Jackson, Lyndon R. Zink, Jonathan P. Towle, Neil Riley, John M. Brown

All Faculty Scholarship for the College of the Sciences

Transitions between the spin-rotational levels of the FeD radical in the v = 0level of the X ⁴Δ ground state have been detected by the technique of laser magnetic resonance at far-infrared wavelengths. Pure-rotational transitions have been observed for the three lowest spin components. Lambda-type doubling is resolved on all the observed transitions; nuclear hyperfine structure is not observed. The energy levels of FeD are strongly affected by the breakdown of the Born–Oppenheimer approximation and cannot be modeled accurately by an effective Hamiltonian. The data are therefore fitted to an empirical formula to yield term values and g-factors for …

Visualizing Atomic Orbitals Using Second Life, Andrew Lang, David C. Kobilnyk

College of Science and Engineering Faculty Research and Scholarship

We demonstrate the usefulness of Second Life as a platform for enlivening major concepts in chemistry education. These concepts include absorption spectra, selection rules, quantum numbers, and atomic orbital shapes. We have built several exhibits in Second Life which provide 3-dimensional interactivity for each of those areas: an interactive experiment showing the absorption spectrum of hydrogen, an interactive model of selection rules showing allowed and forbidden transitions for each state, a 3-dimensional grid of orbitals showing the constraints on the values of quantum numbers, and a large-scale interactive orbital display allowing the user to choose and rotate to-scale atomic orbitals …

Volume 02, Joseph A. Mann, Kathryn J. Greenly, Scott E. Jenkins, Andrew E. Puckette, Daniel M. Honey, Jeffery P. Ravenhorst, Jamie Elizabeth Mesrobian, Thomas Scott, Jay Crowell, Sarah Spangenberg, Amy S. Eason, Kenny Wolfe, Liz Hale, Rachel Bouchard, Will Semonco, Carley York, Ryan Higgenbothom, Adrienne Heinbaugh, Melissa Dorton, Madeline Hunter, June Ashmore, Clark Barkley, Jay Haley

Incite: The Journal of Undergraduate Scholarship

Introduction from Dean Dr. Charles Ross

Mike's Nite: New Jazz for an Old Instrument by Joseph A. Mann

Investigation of the use of Cucumis Sativus for Remediation Of Chromium from Contaminated Environmental Matrices: An Interdisciplinary Instrumental Analysis Project by Kathryn J. Greenly, Scott E. Jenkins, and Andrew E. Puckette

Development of GC-MS and Chemometric Methods for the Analysis of Accelerants in Arson Cases by Scott Jenkins

Building and Measuring Scalable Computing Systems by Daniel M. Honey and Jeffery P. Ravenhorst

Nomini Hall: A Case Study in the Use of Archival Resources as Guides for Excavation at An Archaeological Site by …

Q-Switched And Mode Locked Short Pulses From A Diode Pumped, Yb-Doped Fiber Laser, Seth M. Swift

Theses and Dissertations

A diode-pumped, ytterbium (Yb)-doped fiber laser system was designed and demonstrated to operate in continuous wave (cw), passively Q-switched and possibly passively mode locked operation. To our knowledge, this was the first fiber laser oscillator built at the Air Force Institute of Technology. A Cr⁴⁺:YAG (Chromium: Ytterbium Aluminum Garnett) crystal was used as a saturable absorber to generate Q-switched pulses. Attempts to mode lock the laser were performed using a semiconductor saturable absorber mirror (SESAM) and through nonlinear polarization rotation (NPR). The best output power result was 5 Watts (W) while pumping at 8.3 W, yielding 60% efficiency …

Investigation Of Electrical And Optical Properties Of Bulk Iii-V Ternary Semiconductors, Travis C. Gomez

Theses and Dissertations

Bulk grown III-V ternary semiconductors of In_0.08Ga_0.92Sb and In_0.15Ga_0.85As were investigated through Hall-effect and photoluminescence measurements to determine carrier concentration, mobility, sheet resistivity, and luminescence spectrum. In the past, epitaxial layers of ternary compounds have been grown on binary compound substrates, and thus very limited lattice matched ternary alloys were available. Recently, bulk grown ternary substrates have been developed, and it has presented a renewed interest in using these substrates to grow high quality ternary compounds for use in many next generation optoelectronic devices. The results of photoluminescence (PL) study for the …

The Effective Potential Energy Surfaces Of The Nonadiabatic Collision B(2PJA) + H2(1Σ+G,Ν,J) ↔ B(2PJ'A) + H2(1Σ+G,Ν',J'), Matthew B. Garvin

Theses and Dissertations

Effective potential energy surfaces (PESs) are calculated for a nonadiabatic collision . This calculation employed 1 ²A', 2 ²A' and 1 ²A" adiabatic PESs numerically calculated at the state-averaged multiconfigurational self-consistent field (SA-MCSCF)/configuration interaction (CI) level for several values of the H₂ bond length, H₂ orientation angle, and boron distance. The associated nonadiabatic coupling terms (NACTs) were calculated from the SA-MCSCF/CI wave functions using analytic gradient techniques. A line integral through the NACTs was then used to determine the adiabatic-to-diabatic mixing angle required to transform from the 1 ²A' and 2 ²A' …

Development And Validation Of An Empirical Free Energy Function For Calculating Protein–Protein Binding Free Energy Surfaces, Joseph Audie

Chemistry & Physics Faculty Publications

In a previous paper, we described a novel empirical free energy function that was used to accurately predict experimental binding free energies for a diverse test set of 31 protein–protein complexes to within ≈1.0 kcal. Here, we extend that work and show that an updated version of the function can be used to (1) accurately predict native binding free energies and (2) rank crystallographic, native-like and non-native binding modes in a physically realistic manner. The modified function includes terms designed to capture some of the unfavorable interactions that characterize non-native interfaces. The function was used to calculate one-dimensional binding free …

Abc's Of Dew (Adi) Software, John Pickle

STEM Digital

Introduction to three color light, pixels, DEW (ADI) tools

A Review Of Helium Hamiltonians, Carl W. David

Chemistry Education Materials

Helium Hamiltonian transformations are discussed in extreme detail.

Pressure Induced Phase Transformation Of Sno2: An Ab Initio Constant Pressure Study, Daniel Tesfai Yehdego

Open Access Theses & Dissertations

The behavior of SnO2 under rapid hydrostatic pressures is studied using constant-pressure ab initio simulations. The rutile-type SnO2 gradually transforms into the CaCl2-type structure at 15 GPa. At a pressure of about 20 GPa, a phase transformation into a cubic fluorite-type structure is observed. The orthorhombic Pnma cotunnite-structured phase is observed above 150 GPa. The mechanisms of these phase transformations at the atomistic level are discussed.

Partial Ion Yield Sspectroscopy Around The Cl 2p And C 1s Ionization Thresholds In Cf3cl, D. Ceolin, Maria Novella Piancastelli, Wayne C. Stolte, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

We present a partial ion yield experiment on freon 13, CF₃Cl, excited in the vicinity of the C 1s and Cl 2p ionization thresholds. We have collected a large amount of cationic fragments and a few anionic fragments at both edges. We have observed a strong intensity dependence of Rydberg transitions with ion fragment size for the CF_nCl⁺ and CF_n⁺/F⁺ (n=0–3) series at both the Cl 2p and C 1s ionization edges. Selectivity in the fragmentation processes involving the C–Cl and C–F bonds are highlighted by the intensities of the C …

Yttrium And Hydrogen Superstructure And Correlation Of Lattice Expansion And Proton Conductivity In The Bazr0.9y0.1o2.95 Proton Conductor, A. Braun, A. Ovalle, V. Pomjakushin, A. Cervellino, S. Erat, Wayne C. Stolte, T. Graule

Chemistry and Biochemistry Faculty Research

Bragg reflections in Y-resonant x-ray diffractograms of BaZr_0.9Y_0.1O_2.95 (BZY10) reveal that Y is organized in a superstructure. Comparison with neutron diffraction superstructure reflections in protonated/deuterated BZY10 suggests that both superstructures are linked, and that protons move in the landscape imposed by the Y. The thermal lattice expansion decreases abruptly for protonated BZY10 at T≥648±20 K, coinciding with the onset of lateral proton diffusion and suggesting a correlation of structural changes and proton conductivity. The chemical shift in the Y L₁-shell x-ray absorption spectra reveals a reduction from Y³⁺ toward Y²⁺ upon …

Temperature Changes Resulting From A Gaalas Laser In The Decontamination Of A Failing Dental Implant, Adam B. Oppenheimer

Journal of the South Carolina Academy of Science

No abstract provided.

Observed Superspin-Glass Behavior In Ni0.5zn0.5fe2o4 Nanoparticles, Antony Adair

Open Access Theses & Dissertations

In this investigation we seek to identify the magnetic behavior of Ni0.5Zn0.5Fe2O4 nanoparticles though AC-susceptibility and DC-magnetization measurements. Powder x-ray diffraction was performed to determine the purity and average diameter ( ~ 9nm) of the particles. Aditionally, structure was confirmed by comparison through the International Centre for Diffraction Data's Powder Diffraction File [52] (PDF # 08-0234).

Zero-field cooled and field cooled DC magnetization measurements (bifurcation and blocking temperature), as well as M(H) hysteresis (below and above the blocking temperature) lead us to initially suggest that the material may in fact be superparamagnetic. However, further investigation of the real AC susceptibility …

Computational Modeling Studies Of The Structures And Properties Of Organotin(Iv) And Stannyl-Thioether Systems With Comparisons To X-Ray Crystallography, Michelle R. Stem Joseph

Open Access Theses & Dissertations

Controlling the toxic effects of organotin(IV) compounds involves engineering the structure of the molecules to optimize their properties. Molecular engineering, coupled with improved capabilities to generate reliable computational optimization models (COMs), will enable researchers to have greater success at harnessing the highly specific cytotoxicity of organotins. For example, as the thio_n ligand phenyl groups were replaced with Cl atoms, the S-Sn intramolecularity was strengthened, the bond distance decreased, and the stannyl tetrahedral structure was deformed from its triphenyl conformation. With each substitution, conformation deformations lowered the damaging bioactivity levels of thio_n. Bonding various ligands to organotin(IV) compounds …

Nanocomposite Thin Films Of Au Nanoparticles Embedded In Yttria-Stabilized Zirconia For Plasmonic-Based Harsh Environment Gas Detection, Phillip Henry Rogers

Legacy Theses & Dissertations (2009 - 2024)

Increased health concerns due to the emission of gases linked to the production of tropospheric ozone by petroleum based fuel burning engines has resulted in the codification of more stringent emissions regulations domestically. Emissions regulations on commercial jetliners are one of the areas to be met with stricter standards. Currently there is not a sensing technology that can detect the emissions gases in the exhaust stream of a jet turbine engine with lower detection limits that meet these standards.

Faculty Should Consider Peer Review As A Means Of Improving Students' Scientific Reasoning Skills, Briana Timmerman, Denise Strickland

Journal of the South Carolina Academy of Science

No abstract provided.

Evaluation Of Extraction Chromatography Resins For Rapid Actinide Analysis, Julie Marisa Gostic

UNLV Theses, Dissertations, Professional Papers, and Capstones

In this work, physical and chemical parameters associated with extraction chromatography separation procedures were investigated for rapid actinide analysis. A vacuum box system was designed in-house and was characterized in terms of flow rate reproducibility, matrix effects on flow rate for sequential elution, and actinide separation efficiency using different types of resin (TEVA, DGA and TRU). Results indicated that the columnar kinetics of the resins were sufficiently rapid to run high purity samples through the unit over a wide range of flow rates for all resin types. Single matrix interferences at a metal ion ratio of 1:10 6 relative to …