Chemistry Commons^™

Models For Molybdenum Coordination During The Catalytic Cycle Of Periplasmic Nitrate Reductase From Paracoccus Denitrificans Derived From Epr And Exafs Spectroscopy, Clive S. Butler, John M. Charnock, Brian Bennett, Heather J. Sears, Ann J. Reilly, Stuart J. Ferguson, C. David Garner, David J. Lowe, Andrew J. Thomson, Ben C. Berks, David J. Richardson

Physics Faculty Research and Publications

The periplasmic nitrate reductase from Paracoccus denitrificans is a soluble two-subunit enzyme which binds two hemes (c-type), a [4Fe-4S] center, and a bis molybdopterin guanine dinucleotide cofactor (bis-MGD). A catalytic cycle for this enzyme is presented based on a study of these redox centers using electron paramagnetic resonance (EPR) and extended X-ray absorption fine structure (EXAFS) spectroscopies. The Mo(V) EPR signal of resting NAP (High g [resting]) has g_av = 1.9898 is rhombic, exhibits low anisotropy, and is split by two weakly interacting protons which are not solvent-exchangeable. Addition of exogenous ligands to this resting …

In Situ Measurement Of The Aerosol Size Distribution In Stratospheric Solid Rocket Motor Exhaust Plumes, Martin N. Ross, Philip D. Whitefield, Donald E. Hagen, Alfred R. Hopkins

Chemistry Faculty Research & Creative Works

The concentration and size distribution of aerosol in the stratospheric exhaust plumes of two Space Shuttle rockets and one Titan IV rocket were measured using a two component aerosol sampling system carried aboard a WB‐57F aircraft. Aerosol size distribution in the 0.01 µm to 4 µm diameter size range was measured using a two component sampling system. The measured distributions display a trimodal form with modes near 0.005 µm, 0.09 µm, and 2.03 µm and are used to infer the relative mass fractionation among the three modes. While the smallest mode has been estimated to contain as much as 10% …

X-Ray Absorption, Neutron Diffraction, And Mössbauer Effect Studies Of Mnzn-Ferrite Processed Through High-Energy Ball Milling, D. J. Fatemi, V. G. Harris, Mingxing Chen, Satish K. Malik, William B. Yelon, Gary J. Long, Amitabh Mohan

Physics Faculty Research & Creative Works

MnZn-ferrite has been prepared via high-energy ball milling of elemental oxides MnO, ZnO, and α-Fe₂O₃. Neutron diffraction measurements suggest a high density of vacancies in a spinel structure. The spinel phase appears to comprise 99.8 wt % of the material in the sample milled for 40 h, with the remainder attributable to unreacted α-Fe₂O₃. The x-ray absorption near-edge structure was analyzed to provide an understanding of the charge state of the constituent Fe ions. This analysis reveals about 2/3 of Fe cations to be trivalent, increasing to about 3/4 after a 5 …

Preparation Of Phase Homogeneous Mn-Zn Ferrite Powder By Spray Pyrolysis, Xinyu Zhao, Baicun Zheng, Hongchen Gu, Chunzhong Li, Shi C. Zhang, P. D. Ownby

Materials Science and Engineering Faculty Research & Creative Works

Two kinds of aqueous precursor solutions are used to synthesize Mn-Zn ferrite powders: (i) nitrate (NO) precursor-derived from solutions of Mn(NO₃)₂, Zn(NO₃)₂, and Fe(NO₃)₃; and (ii) acetate (AC) precursor-derived from solutions of Mn(CH₃COOO)₂, Zn(CHCH₃COOO)₂, and Fe(NO₃)₃. The composition of the powders synthesized from the precursor AC is very uniform, whereas powders derived from the precursor NO have Mn and Zn segregated on the particle surfaces. In addition, the powders synthesized from precursor AC are solid spherical …

Magnetic And Crystallographic Properties Of Lani₅₋ₓfex, C. Tan, Oran Allan Pringle, Mingxing Chen, William B. Yelon, J. Gebhardt, Naushad Ali, C. Y. Tai, G. K. Marasinghe, George Daniel Waddill, William Joseph James

Physics Faculty Research & Creative Works

No abstract provided.

Reply To Comment On ‘Nondipole Resonant X-Ray-Raman Spectroscopy: Polarized Inelastic Scattering At The K Edge Of Cl2,’, J. D. Mills, J. A. Sheehy, T. A. Ferrett, S. H. Southworth, R. Mayer, Dennis W. Lindle, P. W. Langhoff

Chemistry and Biochemistry Faculty Research

Mills et al. Reply: In their Comment on our Letter [1], Gel’mukhanov and Ågren [2] reiterate recent assertions [3] based on their earlier theoretical studies [4]. The primary purpose of their Comment is apparently to refute our stated conclusion that core-excited-state localization/ delocalization mechanisms are irrelevant to interpretations of reported Raman scattering experiments on homonuclear diatomic molecules.

High-Resolution Electron Time-Of-Flight Apparatus For The Soft-X-Ray Region, Oliver Hemmers, S. B. Whitfield, P. Glans, H. Wang, Dennis W. Lindle, R. Wehlitz, I. A. Sellin

Environmental Studies Faculty Publications

A gas-phase time-of-flight (TOF) apparatus, capable of supporting as many as six electron-TOF analyzers viewing the same interaction region, has been developed to measure energy- and angle-resolved electrons with kinetic energies up to 5 keV. Each analyzer includes a newly designed lens system that can retard electrons to about 2% of their initial kinetic energy without significant loss of transmission; the analyzers can thus achieve a resolving power (E/ΔE) greater than 10⁴ over a wide kinetic-energy range. Such high resolving power is comparable to the photon energy resolution of state-of-the-art synchrotron–radiation beamlines in the soft …

Photofragmentation Of Third-Row Hydrides Following Photoexcitation At Deep-Core Levels, D. Hansen, M. E. Arrasate, J. Cotter, G. R. Fisher, Oliver Hemmers, K. T. Leung, Jon C. Levin, R. Martin, Paul Neill, Rupert C. Perera, I. A. Sellin, Marc Simon, Y. Uehara, B. Vanderford, S. B. Whitfield, Dennis W. Lindle

Environmental Studies Faculty Publications

The relaxation dynamics of HCl, DCl, H₂S, and D₂S following photoexcitation in the vicinities of the Cl and S K-shell thresholds (∼2.8keV for Cl, ∼2.5 keV for S) were studied by means of ion time-of-flight mass spectroscopy. In all cases, the onset of pre-edge core-shell photoionization precedes the formation on resonance of a significant amount of neutral hydrogen as well as postcollision-interaction effects above threshold. Examination of the width of the H⁺ peak in spectra taken with the analyzer parallel and perpendicular to the polarization vector of the incident light indicates that on resonance, the …

Auger Resonance Decay Process In Ar 2p Shell Excitation And Ionization, Y. Lu, Wayne C. Stolte, J.A. R. Samson

Chemistry and Biochemistry Faculty Research

The production and subsequent autoionization of the Ar⁺ (¹D₂)6d¹ satellite state that is formed either by shake-up or recapture during the Auger decay of a 2p vacancy in Ar has been studied by photoelectron spectroscopy in the energy region from 243 to 256 eV. The creation of near zero energy electrons below and immediately above the Ar 2p ionization threshold is discussed. Some ambiguous points in previous studies are clarified.

Chemical Signals From Submarine Fluid Advection Onto The Continental Shelf, W. S. Moore, Timothy J. Shaw

Faculty Publications

No abstract provided.

Neutron Diffraction And Mössbauer Spectral Study Of Nd₂Fe₁₆Ti And Its Nitride, Fernande Grandjean, Peter C. Ezekwenna, Gary J. Long, Oran Allan Pringle, P. H. L'Héritier, Mohamed Ellouze, H. P. Luo, William B. Yelon

Chemistry Faculty Research & Creative Works

The 295 K powder neutron diffraction patterns and the temperature dependence of the Mössbauer spectra of Nd₂Fe_17-xTi_x and Nd₂Fe_17-xTi_xN_x have been measured. A Rietveld refinement of the neutron diffraction patterns yields the Nd₂Fe_16.32Ti_0.68 and Nd₂Fe_16.32Ti_0.68N_2.7 stoichiometries for the two compounds and indicates that titanium occupies only the 6c crystallographic site and nitrogen only the 9e site in the rhombohedral Th₂Zn₁₇ structure. The insertion of interstitial nitrogen into Nd₂Fe_16.32Ti_{0.68 …}

40th Rocky Mountain Conference On Analytical Chemistry

Rocky Mountain Conference on Magnetic Resonance

Final program, abstracts, and information about the 40th annual meeting of the Rocky Mountain Conference on Analytical Chemistry, co-sponsored by the Colorado Section of the American Chemical Society and the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Denver, Colorado, July 25 - August 1, 1998.

Particulate Sizing And Emission Indices For A Jet Engine Exhaust Sampled At Cruise, Donald E. Hagen, Philip D. Whitefield, J. Paladino, Max B. Trueblood, H. Lilenfeld

Physics Faculty Research & Creative Works

Particle size and emission indices measurements for jet engines, primarily the Rolls Royce RB211 engines on a NASA 757 aircraft are reported. These data were used to estimate the fraction of fuel sulfur that was converted to particulates. These measurements were made in-situ with the sampling aircraft several kilometers behind the source. Some complimentary ground measurements on the same source aircraft and engines are also reported. Significant differences are seen between the ground observations and the in-situ observations, indicating that plume processes are changing the aerosol' s characteristics.

Particle Concentration Characterization For Jet Engine Emissions Under Cruise Conditions, Jonathan D. Paladino, Philip D. Whitefield, Donald E. Hagen, Alfred R. Hopkins, Max B. Trueblood

Chemistry Faculty Research & Creative Works

Airborne particle measurements during NASA project SUCCESS have shown that particle concentration profiles serve as good indicators of aircraft exhaust plume encounters. During exhaust plume penetrations there is a strong anticorrelation between the ratio of nonvolatile/total particulates and Nitrogen Oxide (NO) concentrations. an increase in fuel sulfur content was found to increase the total particle emission index, while the nonvolatile emission index remained unchanged. the EI's increased by a factor of 2.6 as the fuel sulfur increased from 70 - 700 ppm. the large particle size distribution (200-400 nm) was seen as a good long term indicator of an aircraft …

Particulate Sizing And Emission Indices For A Jet Engine Exhaust Sampled At Cruise, Donald E. Hagen, Philip D. Whitefield, Jonathan D. Paladino, Max B. Trueblood

Physics Faculty Research & Creative Works

Particle size and emission indices measurements for jet engines, primarily the Rolls Royce RB211 engines on a NASA 757 aircraft are reported. These data were used to estimate the fraction of fuel sulfur that was converted to particulates. These measurements were made in-situ with the sampling aircraft several kilometers behind the source. Some complimentary ground measurements on the same source aircraft and engines are also reported. Significant differences are seen between the ground observations and the in-situ observations, indicating that plume processes are changing the aerosol's characteristics.

Neutral Dissociation Of Hydrogen Following Photoexcitation Of Hcl At The Chlorine K Edge, D. L. Hansen, J. Cotter, G. R. Fisher, K. T. Leung, R. Martin, Paul Neill, Rupert C. Perera, I. A. Sellin, Marc Simon, Y. Uehara, B. Vanderford, S. B. Whitfield

Chemistry and Biochemistry Faculty Research

Time-of-flight mass spectroscopy was used to study the relaxation dynamics of HCl following photoexcitation in the vicinity of the Cl K edge (~2.8 keV) using monochromatic synchrotron radiation. At the lowest resonant excitation to the 6ơ* antibonding orbital, almost half of the excited molecules decay by emission of a neutral H atom, mostly in coincidence with a highly charged Cln1 ion. The present work demonstrates that neutral-atom emission can be a significant decay channel for excited states with very short lifetimes (1 fs). [S1050-2947(98)03604-X]

Double Photoionization Of Helium, James A.R. Samson, Wayne C. Stolte, Z. X. He, Y. Lu, J. N. Cutler, R. J. Bartlett

Chemistry and Biochemistry Faculty Research

The cross sections for double photoionization of helium and the ratios of double to single ionization have been measured from the double-ionization threshold to 820 eV. The results are in very good agreement with several recent calculations.

Ab Initio Study Of Formazan And 3-Nitroformazan, G. Buemi, F. Zuccarello, P. Venuvanalingam, M. Ramalingam, Salai Cheettu Ammal

Faculty Publications

Formazan and 3-nitroformazan have been investigated at abinitio level (MP2/6-31G** and B3LYP/6-31G**) in all their possible conformations, for studying the various possibilities of intramolecular hydrogen bonding formation. The trans-syn-s-cis (TSSC), known also asyellowform, has been found to be the most stable conformer (at least in the gas phase) in both compounds. This particular structure is strongly stabilized by a N–H···N hydrogen bridge, which gives rise to a hexatomic chelate ring, with the possibility of a proton transfer process.This closely resembles that of malondialdehyde, previously studied, in the evolution of the …

Ab Initio And Dft Investigations Of Lithium/Hydrogen Bonded Complexes Of Trimethylamine, Dimethyl Ether And Dimethyl Sulfide, Salai Cheettu Ammal, P. Venuvanalingam

Faculty Publications

Ab initio and DFT computations have been carried out on LiF and HF complexes of a set of n-donors viz. trimethylamine, dimethyl ether and dimethyl sulfide with a 6-31++G(d,p) basis set. The effect of correlation has been included with MP2, MP4 and DFT calculations. NBO analyses of the wavefunctions have been performed to examine the intermolecular interaction at the orbital level. Calculations reveal that these donors form strong n→σ* complexes and computed binding energies of the (CH₃)₂O···HF complex agree very well with the experimental binding energies from IR spectroscopy. LiF forms stronger complexes than HF, …

Near-Field Measurements On Contrail Properties From Fuels With Different Sulfur Content, Andreas Petzold, Reinhold Busen, Franz Peter Schroder, Robert Baumann, Markus Kuhn, Johan Strom, Donald E. Hagen, Philip D. Whitefield, Darrel G. Baumgardner, Frank Arnold, Stephan Borrmann, Ulrich Schumann

Physics Faculty Research & Creative Works

Microphysical properties of jet exhaust aerosol and contrails were studied in the near field of the emitting aircraft for different fuel sulfur contents. Measurements were performed behind two different aircraft (ATTAS test aircraft of type VFW 614 and Airbus A310-300) using fuels with sulfur contents of 6 ppm and 2700 ppm, respectively. At closest approach (plume age < 1 s), the total number concentrations exceeded the measuring range of the condensation particle counter, i.e., N > 10⁵ cm^-3. The concentration of the dry accumulation mode aerosol, i.e., predominantly soot particles, was not affected by the fuel sulfur content. At a plume age of 10 s, an increase in total number concentration (Dp > 0.01 μm) by a …

Hybrid Quantum And Molecular Mechanics Embedded Cluster Models For Chemistry On Silicon And Silicon Carbide Surfaces, James R. Shoemaker

Theses and Dissertations

Fabrication of silicon carbide SiC semiconductor devices are of interest for aerospace applications because of their high-temperature tolerance. Growth of an insulating SiO₂ layer on SiC is a poorly understood process, and sometimes produces interface defects that degrade device performance. Accurate theoretical models of surface chemistry, using quantum mechanics QM, do not exist because of the huge computational cost of solving Schroedingers equation for a molecular cluster large enough to represent a surface. Molecular mechanics MM, which describes a molecule as a collection of atoms interacting through classical potentials, is a fast computational method, good at predicting molecular structure, …

39th Rocky Mountain Conference On Analytical Chemistry

Rocky Mountain Conference on Magnetic Resonance

Preliminary program and registration information for the 39th annual meeting of the Rocky Mountain Conference on Analytical Chemistry, co-sponsored by the Colorado Section of the American Chemical Society and the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Denver, Colorado, August 3-7, 1997.

Nondipole Resonant X-Ray-Raman Spectroscopy: Polarized Inelastic Scattering At The K Edge Of Cl2, J. D. Mills, J. A. Sheehy, T. A. Ferrett, S. H. Southworth, R. Mayer, Dennis W. Lindle, P. W. Langhoff

Chemistry and Biochemistry Faculty Research

Experimental and theoretical studies are reported on the inelastic (Raman) scattering of wavelength-selected polarized x rays from the K edge of gas-phase chlorine molecules. The polarized emission spectra exhibit prominent nondipole features consequent of phase variations of the incident and emitted radiation over molecular dimensions, as predicted by the Kramers-Heisenberg scattering formalism. Issues pursuant to the detection of core-hole localization by resonant Raman scattering from homonuclear diatomic molecules are critically examined. [S0031-9007(97)03486-8]

Breakdown Of The Independent Particle Approximation In High-Energy Photoionization, E. W. B. Dias, H. S. Chakraborty, P. C. Deshmukh, S. T. Manson, Oliver Hemmers, P. Glans, D. Hansen, H. Wang, S. B. Whitfield, Dennis W. Lindle, R. Wehlitz, Jon C. Levin, I. A. Sellin

Environmental Studies Faculty Publications

The independent particle approximation is shown to break down for the photoionization of both inner and outer nℓ (ℓ>0) electrons of all atoms, at high enough energy, owing to interchannel interactions with the nearby ns photoionization channels. The effect is illustrated for Ne 2p in the 1 keV photon energy range through a comparison of theory and experiment. The implications for x-ray photoelectron spectroscopy of molecules and condensed matter are discussed.

Computer Modeling Of Molecular Vibration Frequencies And Its Application To The Modeling Of Silane Compounds, Ryan T. Merrell

Honors Capstone Projects and Theses

No abstract provided.

In Situ Observations Of Air Traffic Emission Signatures In The North Atlantic Flight Corridor, Hans Schlager, Paul Konopka, P. Schulte, U. Schumann, H. Ziereis, F. Arnold, M. Klemm, Donald E. Hagen, Philip D. Whitefield, J. Ovarlez

Physics Faculty Research & Creative Works

Focussed aircraft measurements have been carried out over the eastern North Atlantic to search for signals of air traffic emissions in the flight corridor region. Observations include NO, NO₂, HNO₃, SO₂, O₃, H₂O, total condensation nuclei (CN), and meteorological parameters. A flight pattern with constant-altitude north-south legs across the major North Atlantic air traffic tracks was flown. Signatures of air traffic emissions were clearly detected for NO_x, SO₂, and CN with peak concentrations of 2 ppbv, 0.25 ppbv, and 500 cm^-3, respectively, exceeding background …

Studies Of V, Nb, Cr, And Zr Substituted 2:17 Compounds And Their Carbides Using Neutron Diffraction, H. Luo, Z. Hu, Muguo Chen, William B. Yelon, G. K. Marasinghe, Peter C. Ezekwenna, William Joseph James, W. C. Chang, S. H. Tsai

Physics Faculty Research & Creative Works

Samples of Nd₂Fe_17-xT_xC_y with T=V, Nb, Cr, and Zr were prepared by melting of the constituent elements including C and studied by neutron diffraction. Comparing with their uncarbided counterparts, we found that the substituents transfer, more or less, from the 6c site to the 18f and 18h sites with the introduction of C atoms. This behavior appears to relate to the electronegativities between the C atoms and the early transition series elements because the 18f and 18h sites are near neighbors of the interstitial C site. However, the C effects in the V. …

Magnetic And Structural Properties Of Nd₂Fe₁₇₋ₓmnₓ Solid Solutions, Peter C. Ezekwenna, G. K. Marasinghe, William Joseph James, Oran Allan Pringle, Gary J. Long, H. Luo, Z. Hu, William B. Yelon, Ph. I'Héritier

Chemistry Faculty Research & Creative Works

A series of Nd₂Fe_17-xMn_x solid solutions with x values between 0 and and 6 were prepared and analyzed using magnetic measurements, neutron diffraction, and Mössbauer spectroscopy. All of the Nd₂Fe_17-xMn_x samples crystallized in the Th₂Zn_17-x-type rhombohedral structure. The lattice parameters and unit cell volumes decrease with increasing manganese content up to ∼ x equal to 2, and then increase for higher manganese content. The magnetizations of Nd₂Fe_17-xMn_x decrease with increasing manganese content and Nd₂Fe_17-xMn_x is paramagnetic …

Observation Of Upper Tropospheric Sulfur Dioxide- And Acetone-Pollution: Potential Implications For Hydroxyl Radical And Aerosol Formation, F. Arnold, J. Schneider, K. Gollinger, H. Schlager, P. Schulte, Donald E. Hagen, Philip D. Whitefield, Peter F. J. Van Velthoven

Physics Faculty Research & Creative Works

Aircraft-based measurements of sulfur dioxide, acetone, carbon dioxide, and condensation nuclei (CN) were made over the north-eastern Atlantic at upper tropospheric altitudes, around 9000 m. On October 14, 1993, strong SO ₂- and acetone-pollution (both up to 3 ppbv) were observed, which were accompanied by a CO ₂-enhancement of up to 6 ppmv, and large CN-concentrations of up to about 1500 cm ^-3 (for radii ≥ 6 nm). CN, excess CO ₂, and to a lesser degree also acetone, were positively correlated with SO ₂. Air mass trajectory analyses indicate, that most of the air masses …

Characterization Of Iron Oxides And Atmospheric Corrosion Of Steel, Sei Jin Oh

Physics Theses & Dissertations

The study of corrosion behavior was performed using three different analytical techniques, which provided information on the formation, development and layering of iron oxides on the corrosion products as a function of atmospheric conditions, exposure time and type of steel. In particular, the protective layer formed on weathering steel was investigated as a function of different amounts of alloying elements in the steel, atmospheric conditions and exposure times. Combined together, the results provided a better understanding of the atmospheric corrosion behavior of steel, and formed a part of database of the atmospheric corrosion characteristics.

Accurate characterization of the iron oxides …