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Resonant Inelastic X-ray Scattering of Rare-Earth and CopperSystems

Description: Rare earths and copper systems were studied using X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS). The use of monochromased synchotron radiation and improved energy resolution for RIXS made possible to obtain valuable information on the electronic structure in 4f, 5f and 3d systems. Experimental results for rare-earths (Ho, Gd, Cm, U, Np, Pu) were analyzed by atomic multiplet theory based on the Hartree-Fock calculations. The inelastic scattering structures in RIXS spectra at 5d edge of actinides found to be sensitive to actinide oxidation states in different systems. Comparison of experimental and calculated Cm 5d RIXS spectra gave direct information about valency of the 248-curium isotope in oxide. Scientific understanding of processes that control chemical changes of radioactive species from spent fuel is improved by studying interactions of actinide ions (U, Np, Pu) with corroded iron surfaces. RIXS measurements at the actinide 5d edge found to be sensitive to actinide oxidation states in different systems. Comparison of experimental and calculated Cm 5d RIXS spectra gave direct information about valency of the 248 curium isotope in oxide. Scientific understanding of processes that control chemical changes of radioactive species from spent fuel is improved by studying interactions of actinide ions (U, Np, Pu) with corroded iron surfaces. RIXS measurements at the actinide 5d edge indicate the reduction of U(VI), NP(V) and Pu(VI) to U(IV), Np(IV) and Pu(IV) by presence of iron ions. This thesis is also addressed to the study of changes in the electronic structure of copper films during interaction with synthetic groundwater solutions. The surface modifications induced by chemical reactions of oxidized 100 Angstrom Cu films with CL{sup -}, SO{sub 4}{sup 2-} and HCO{sub 3}{sup -} ions in aqueous solutions with various concentrations were studied in-situ using XAS. It was shown that the pH value, the concentration of ...
Date: July 11, 2007
Creator: Kvashnina, Kristina
Partner: UNT Libraries Government Documents Department

Structural Investigations of Surfaces and Orientation-SpecificPhenomena in Nanocrystals and Their Assemblies

Description: Studies of colloidal nanocrystals and their assemblies are presented. Two of these studies concern the atomic-level structural characterization of the surfaces, interfaces, and interiors present in II-VI semiconductor nanorods. The third study investigates the crystallographic arrangement of cobalt nanocrystals in self-assembled aggregates. Crystallographically-aligned assemblies of colloidal CdSe nanorods are examined with linearly-polarized Se-EXAFS spectroscopy, which probes bonding along different directions in the nanorod. This orientation-specific probe is used, because it is expected that the presence of specific surfaces in a nanorod might cause bond relaxations specific to different crystallographic directions. Se-Se distances are found to be contracted along the long axis of the nanorod, while Cd-Se distances display no angular dependence, which is different from the bulk. Ab-initio density functional theory calculations upon CdSe nanowires indicate that relaxations on the rod surfaces cause these changes. ZnS/CdS-CdSe core-shell nanorods are studied with Se, Zn, Cd, and S X-ray absorption spectroscopy (XAS). It is hypothesized that there are two major factors influencing the core and shell structures of the nanorods: the large surface area-to-volume ratio, and epitaxial strain. The presence of the surface may induce bond rearrangements or relaxations to minimize surface energy; epitaxial strain might cause the core and shell lattices to contract or expand to minimize strain energy. A marked contraction of Zn-S bonds is observed in the core-shell nanorods, indicating that surface relaxations may dominate the structure of the nanorod (strain might otherwise drive the Zn-S lattice to accommodate the larger CdS or CdSe lattices via bond expansion). EXAFS and X-ray diffraction (XRD) indicate that Cd-Se bond relaxations might be anisotropic, an expected phenomenon for a rod-shaped nanocrystal. Ordered self-assembled aggregates of cobalt nanocrystals are examined with transmission electron microscopy (TEM) and selected-area electron diffraction (SAED). SAED patterns from multilayered assemblies show that the nanocrystals have preferred crystallographic orientations. ...
Date: June 17, 2006
Creator: Aruguete, Deborah Michiko
Partner: UNT Libraries Government Documents Department

Electrochemical arsenic remediation for rural Bangladesh

Description: Arsenic in drinking water is a major public health problem threatening the lives of over 140 million people worldwide. In Bangladesh alone, up to 57 million people drink arsenic-laden water from shallow wells. ElectroChemical Arsenic Remediation(ECAR) overcomes many of the obstacles that plague current technologies and can be used affordably and on a small-scale, allowing for rapid dissemination into Bangladesh to address this arsenic crisis. In this work, ECAR was shown to effectively reduce 550 - 580 mu g=L arsenic (including both As[III]and As[V]in a 1:1 ratio) to below the WHO recommended maximum limit of 10 mu g=L in synthetic Bangladesh groundwater containing relevant concentrations of competitive ions such as phosphate, silicate, and bicarbonate. Arsenic removal capacity was found to be approximately constant within certain ranges of current density, but was found to change substantially between ranges. In order of decreasing arsenic removal capacity, the pattern was: 0.02 mA=cm2> 0.07 mA=cm2> 0.30 - 1.1 mA=cm2> 5.0 - 100 mA=cm2. Current processing time was found to effect arsenic removal capacity independent of either charge density or current density. Electrode polarization studies showed no passivation of the electrode in the tested range (up to current density 10 mA=cm2) and ruled out oxygen evolution as the cause of decreasing removal capacity with current density. Simple settling and decantation required approximately 3 days to achieve arsenic removal comparable to filtration with a 0.1 mu m membrane. X-ray Absorption Spectroscopy (XAS) showed that (1) there is no significant difference in the arsenic removal mechanism of ECAR during operation at different current densities and (2) the arsenic removal mechanism in ECAR is consistent with arsenate adsorption onto a homogenous Fe(III)oxyhydroxide similar in structure to 2-line ferrihydrite. ECAR effectively reduced high arsenic concentrations (100 - 500 mu g=L) in real Bangladesh tube well water collected from three ...
Date: January 1, 2009
Creator: Addy, Susan Amrose
Partner: UNT Libraries Government Documents Department

Structure and Function Evolution of Thiolate Monolayers on Gold

Description: The use of n-alkanethiolate self-assembled monolayers on gold has blossomed in the past few years. These systems have functioned as models for common interfaces. Thiolate monolayers are ideal because they are easily modified before or after deposition. The works contained within this dissertation include interfacial characterization (inbred reflection absorption spectroscopy, ellipsometry, contact angle, scanning probe microscopy, and heterogeneous electron-transfer kinetics) and various modeling scenarios. The results of these characterizations present ground-breaking insights into the structure, function, and reproducible preparation of these monolayers. Surprisingly, three interfacial properties (electron-transfer, contact angle, and ellipsometry) were discovered to depend directly on the odd-even character of the monolayer components. Molecular modeling was utilized to investigate adlayer orientation, and suggests that these effects are adlayer structure specific. Finally, the electric force microscopy and theoretical modeling investigations of monolayer samples are presented, which show that the film dielectric constant, thickness, and dipole moment directly affect image contrast. In addition, the prospects for utilization of this emerging technique are outlined.
Date: May 1, 2006
Creator: Edwards, Grant Alvin
Partner: UNT Libraries Government Documents Department

Measuring Atmospheric Ozone and Nitrogen Dioxide Concentration by Differential Optical Absorption Spectroscopy

Description: The main objective was to develop a procedure based on differential optical absorption spectroscopy (DOAS) to measure atmospheric total column of ozone, using the automated instrument developed at the University of North Texas (UNT) by Nebgen in 2006. This project also explored the ability of this instrument to provide measurements of atmospheric total column nitrogen dioxide. The instrument is located on top of UNT’s Environmental Education, Science and Technology Building. It employs a low cost spectrometer coupled with fiber optics, which are aimed at the sun to collect solar radiation. Measurements taken throughout the day with this instrument exhibited a large variability. The DOAS procedure derives total column ozone from the analysis of daily DOAS Langley plots. This plot relates the measured differential column to the airmass factor. The use of such plots is conditioned by the time the concentration of ozone remains constant. Observations of ozone are typically conducted throughout the day. Observations of total column ozone were conducted for 5 months. Values were derived from both DOAS and Nebgen’s procedure and compared to satellite data. Although differences observed from both procedures to satellite data were similar, the variability found in measurements was reduced from 70 Dobson units, with Nebgen’s procedure, to 4 Dobson units, with the DOAS procedure.A methodology to measure atmospheric nitrogen dioxide using DOAS was also investigated. Although a similar approach to ozone measurements could be applied, it was found that such measurements were limited by the amount of solar radiation collected by the instrument. Observations of nitrogen dioxide are typically conducted near sunrise or sunset, when solar radiation experiences most of the atmospheric absorption.
Date: December 2011
Creator: Jerez, Carlos J.
Partner: UNT Libraries

Collision Broadening in the Microwave Rotational Spectrum of Gaseous Monomeric Formaldehyde

Description: A source-modulation microwave spectrograph was utilized to measure line width parameters for several spectral lines in the pure rotational spectrum of formaldehyde (H₂CO). The spectrograph featured high-gain ac amplification and phase-sensitive detection, and was capable of measuring microwave lines having absorption coefficients as small as 10⁻⁷ cm⁻¹ with a frequency resolution on the order of 30 kHz. Center frequencies of the measured lines varied from 4,830 MHz to 72,838 MHz; hence, most of the observations were made on transitions between K-doublets in the rotational spectrum. Corrections were applied to the measured line width parameters to account for Doppler broadening and, where possible, for deviations due to magnetic hyperfine structure in some of the K-doubled lines. Low modulation voltages and low microwave power levels were used to minimize modulation and saturation broadenings; other extraneous broadenings were found to be insignificant. The primary broadening mechanism at low gas pressure is pressure broadening, and a review of this topic is included. Line width parameters for the several observed transitions were determined by graphing half-widths versus pressure for each spectral line, and performing a linear least-squares fit to the data points. Repeatability measurements indicated the accuracy of the line width parameters to be better than ±10 percent. The reasons for this repeatability spread are discussed, Broadening of each line was measured for self- and foreign-gas broadening by atomic helium and diatomic hydrogen. Effective collision diameters were calculated for each broadening interaction, based on the observed rates of broadening.
Date: December 1973
Creator: Rogers, David Valmore
Partner: UNT Libraries

Structural oxidation state studies of the manganese cluster in the oxygen evolving complex of photosystem II

Description: X-ray absorption spectroscopy (XAS) was performed on Photosystem II (PSII)-enriched membranes prepared from spinach to explore: (1) the correlation between structure and magnetic spin state of the Mn cluster in the oxygen evolving complex (OEC) in the S{sub 2} state; and (2) the oxidation state changes of the Mn cluster in the flash-induced S-states. The structure of the Mn cluster in the S{sub 2} state with the g{approx}4 electron paramagnetic resonance (EPR) signal (S{sub 2}-g4 state) was compared with that in the S{sub 2} state with multiline signal (S{sub 2}-MLS state) and the S{sub 1} state. The S{sub 2}-g4 state has a higher XAS inflection point energy than that of the S{sub 1} state, indicating the oxidation of Mn in the advance from the S{sub 1} to the S{sub 2}-g4 state. Differences in the edge shape and in the extended X-ray absorption fine structure (EXAFS) show that the structure of the Mn cluster in the S{sub 2}-g4 state is different from that in the S{sub 2}-MLS or the S{sub 1} state. In the S{sub 2}-g4 state, the second shell of backscatterers from the Mn absorber contains two Mn-Mn distances of 2.73 {angstrom} and 2.85 {angstrom}. Very little distance disorder exists in the second shell of the S{sub 1} or S{sub 2}-MLS states. The third shell of the S{sub 2}-g4 state at about 3.3 {angstrom} also contains increased heterogeneity relative to that of the S{sub 2}-MLS or the S{sub 1} state. Various S-states were prepared at room-temperature by saturating, single-turnover flashes. The flash-dependent oscillation in the amplitude of the MLS was used to characterize the S-state composition and to construct {open_quotes}pure{close_quotes} S-state Mn K-edge spectra. The edge position shifts to higher energy by 1.8 eV upon the S{sub 1} {yields} S{sub 2} transition.
Date: November 1, 1994
Creator: Liang, W.
Partner: UNT Libraries Government Documents Department

Infrared spectroscopy of nonclassical ions and their complexes

Description: This thesis describes an infrared spectroscopic study on the structures and dynamics of the nonclassical ions and their complexes, using ion trap vibrational predissociation spectroscopy. Chapter One provides an introduction to the experimental apparatus used in this work. Chapter Two describes the previous theoretical and experimental works on the carbonium ion CH{sub 5}{sup +} and infrared spectroscopic and theoretical works on CH{sub 5}{sup +}. CH{sub 5}{sup +} was predicted to scramble constantly without possessing a stable structure. In Chapter Three, the infrared spectroscopy for the molecular hydrogen solvated carbonium ions CH{sub 5}{sup +}(H{sub 2}){sub n} (n=1-6) in the frequency region of 2700-4200 cm{sup {minus}1} are presented and compared with the results of ab initio molecular dynamics simulation on CH{sub 5}{sup +}(H{sub 2}){sub n} (n=0-3). The results suggested that the scrambling of CH{sub 5}{sup +} slowed down considerably by the stabilization effects of the solvent H{sub 2} molecules, and it was completely frozen out when the first three H{sub 2} molecules were bound to the core CH{sub 5}{sup +}. Chapter Four presents the complete infrared spectra for the solvated carbonium ions, CH{sub 5}{sup +}(A){sub x}(B){sub y} (A,B=H{sub 2}, Ar, N{sub 2}, CH{sub 4};x,y=0-5) in the frequency region of 2500-3200 cm{sup {minus}1}. As the binding affinities of the solvent molecules and the number of the solvent molecules in the clusters increased, the scrambling of CH{sub 5}{sup +} slowed down substantially. The structures of the solvated carbonium ions and the evidence for rapid proton transfer in CH{sub 5}{sup +}(CH{sub 4}) were also presented. Chapter Five presents the vib-rotational spectrum for the H-H stretching mode of the silanium ion SiH{sub 5}{sup +}. The results suggested that SiH{sub 5}{sup +} can be described as a complex of SiH{sub 3}{sup +} and a freely internally rotating H{sub 2}, analogous to, but distinct from CH{sub 5}{sup +}.
Date: January 1, 1995
Creator: Boo, D.W.
Partner: UNT Libraries Government Documents Department

X-ray absorption spectroscopy on the calcium cofactor to the manganese cluster in photosynthetic oxygen evolution

Description: Along with Mn, calcium and chloride ions are necessary cofactors for oxygen evolution in Photosystem II (PS II). To further test and verify whether Ca is close to the Mn cluster, the authors substituted strontium for Ca and probed from the Sr point of view for any nearby Mn. The extended X-ray absorption fine structure (EXAFS) of Sr-reactivated PS II indicates major differences between the intact and NH{sub 2}OH-treated samples. In intact samples, the Fourier transform of the Sr EXAFS shows a Fourier peak that is missing in inactive samples. This peak II is best simulated by two Mn neighbors at a distance of 3.5 Angstrom, confirming the proximity of Ca (Sr) cofactor to the Mn cluster. In addition, polarized Sr EXAFS on oriented Sr-reactivated samples shows this peak II is dichroic: large magnitude at 10 degrees (angle between the PS II membrane normal and the x-ray electric field vector) and small at 80 degrees. Analysis of the dichroism yields the relative angle between the Sr-Mn vector and membrane normal (23 degrees {+-} 4 degrees), and the isotropic coordination number for these layered samples. X-ray absorption spectroscopy has also been employed to assess the degree of similarity between the manganese cluster in PS II and a family of synthetic manganese complexes containing the distorted cubane [Mn{sub 4}O{sub 3}X] core (X = benzoate, acetate, methoxide, hydroxide, azide, fluoride, chloride or bromide). In addition, Mn{sub 4}O{sub 3}Cl complexes containing three or six terminal Cl ligands at three of the Mn were included in this study. The EXAFS method detects the small changes in the core structures as X is varied in this series, and serves to exclude these distorted cubanes of C3v symmetry as a topological model for the Mn catalytic cluster. The sulfur K-edge x-ray absorption near-edge structure (XANES) spectra for ...
Date: December 16, 1999
Creator: Cinco, Roehl M.
Partner: UNT Libraries Government Documents Department

X-ray and vibrational spectroscopy of manganese complexes relevant to the oxygen-evolving complex of photosynthesis

Description: Manganese model complexes, relevant to the oxygen-evolving complex (OEC) in photosynthesis, were studied with Mn K-edge X-ray absorption near-edge spectroscopy (XANES), Mn Kb X-ray emission spectroscopy (XES), and vibrational spectroscopy. A more detailed understanding was obtained of the influence of nuclearity, overall structure, oxidation state, and ligand environment of the Mn atoms on the spectra from these methods. This refined understanding is necessary for improving the interpretation of spectra of the OEC. Mn XANES and Kb XES were used to study a di-(mu)-oxo and a mono-(mu)-oxo di-nuclear Mn compound in the (III,III), (III,IV), and (IV,IV) oxidation states. XANES spectra show energy shifts of 0.8 - 2.2 eV for 1-electron oxidation-state changes and 0.4 - 1.8 eV for ligand-environment changes. The shifts observed for Mn XES spectra were approximately 0.21 eV for oxidation state-changes and only approximately 0.04 eV for ligand-environment changes. This indicates that Mn Kb XES i s more sensitive to the oxidation state and less sensitive to the ligand environment of the Mn atoms than XANES. These complimentary methods provide information about the oxidation state and the ligand environment of Mn atoms in model compounds and biological systems. A versatile spectroelectrochemical apparatus was designed to aid the interpretation of IR spectra of Mn compounds in different oxidation states. The design, based on an attenuated total reflection device, permits the study of a wide spectral range: 16,700 (600 nm) - 225
Date: May 16, 2001
Creator: Visser, Hendrik
Partner: UNT Libraries Government Documents Department

Use of a semiconductor laser in infrared spectroscopy

Description: A semiconductor laser has certain properties which makes its use desirable as a continuous monitor of atmospheric pollutants. Its energy output is concentrated in widely separated energy modes of very narrow bandwidths (less than 10/sup -5/ cm/sup -1/) which can be centered on one infrared absorption line of one gas. This makes the laser quite selective. The energy in each mode is typically greater than 200 ..mu.. watts, and, because of the laser's small size, its light energy can be collimated over large distances with minimal optical losses and be easily detected. One can rapidly measure the decrease in transmission of the light due to the absorption of the light by the gas being monitored, and, using certain analytical parameters, which are different for each absorption line, one can determine the concentration of the gas in question immediately. In addition to the line center (nu/sub 0/), these analytical parameters are the intensity (S) and the half width at half maximum (..gamma..). The intensity (S) is dependent only on temperature when expressed in a per concentration basis and ..gamma.. is dependent on pressure. The Lorentzian lineshape equation K(nu) + S/..pi gamma..(((nu - nu/sub 0/)/..gamma..)/sup 2/ + 1)/sup -1/ is the equation which describes the absorption profile of a gas at ambient atmospheric pressure. Having determined K(nu) and knowing atmospheric pressure and path length of the laser light, one can obtain the concentration of the gas in question. Infrared absorption lines of N/sub 2/O, SO/sub 2/, and H/sub 2/S are observed from low pressure (equal or approximately equal 0.1 torr) to a total pressure of one atmosphere when mixed with room air. The analytical parameters S and ..gamma.. are determined for some lines of N/sub 2/O, and nu/sub 0/, S, and ..gamma.. are determined for several absorption lines of SO/sub 2/. Also ...
Date: December 1, 1977
Creator: Morris, R. N.
Partner: UNT Libraries Government Documents Department

The dynamics of azulene in liquids and compressed gases on ultrafast timescales

Description: The ultrafast dynamics of vibrationally hot ground state azulene molecules have been time resolved by picosecond transient absorption spectroscopy in a variety of solvents including hexane, chloromethanes, methanol, CClF{sub 3}, Xe and Kr. A high pressure optical cell was used to liquify gases for use as solvents and change their density and temperature, independently, over the entire liquid density range. Experimental results indicate the vibrational cooling rate is strongly solvent dependent, with cooling rates of approximately 20 psec in molecular solvents and approximately 150 psec in atomic solvents. Comparison of the rates in Xe and Kr at constant density demonstrates the strong effect of solvent mass on energy transfer. The effect of solvent temperature on vibrational cooling is minimal, as is the effect of solvent density. This latter result is quite surprising in light of earlier experiments on simpler molecular systems, such as I{sub 2} in Xe. This anomalous density effect is examined in light of Isolated Binary Collision (IBC) theory and bulk thermal transport models. Both theories accurately model all experimental results obtained with the exception of the density effort. Possible explanations for the breakdown of the IBC theory in this case are offered along with methods to improve IBC theory for application to complex three dimensional molecular systems.
Date: February 1, 1992
Creator: Schultz, K. E.
Partner: UNT Libraries Government Documents Department

Trapping the M{sub 1} and M{sub 2} substrates of bacteriorhodopsin for electron diffraction studies

Description: Visible and Fourier transform infrared (FTIR) absorption spectroscopies are used to observe protein conformational changes occuring during the bacteriorhodopsin photocycle. Spectroscopic measurements which define the conditions under which bacteriorhodopsin can be isolated and trapped in two distinct substates of the m intermediate of the photocycle, M{sub 1}, and M{sub 2}, are described. A protocol that can be used for high-resolution electron diffraction studies is presented that will trap glucose-embedded purple membrane in the M{sub 1}and M{sub 2} substates at greater than 90% concentration. It was discovered that glucose alone does not provide a fully hydrated environment for bacteriorhodopsin. Equilibration of glucose-embedded samples at high humidity can result in a physical state that is demonstrably closer to the native, fully hydrated state. An extension of the C-T Model of bacteriorhodopsin functionality (Fodor et al., 1988; Mathies et al., 1991) is proposed based on FTIR results and guided by published spectra from resonance Raman and FTIR work. 105 refs.
Date: May 1, 1992
Creator: Perkins, G. A.
Partner: UNT Libraries Government Documents Department

X-ray absorption spectroscopic studies of the active sites of nickel- and copper-containing metalloproteins

Description: X-ray absorption spectroscopy (XAS) is a useful tool for obtaining structural and chemical information about the active sites of metalloproteins and metalloenzymes. Information may be obtained from both the edge region and the extended X-ray absorption fine structure (EXAFS) or post-edge region of the K-edge X-ray absorption spectrum of a metal center in a compound. The edge contains information about the valence electronic structure of the atom that absorbs the X-rays. It is possible in some systems to infer the redox state of the metal atom in question, as well as the geometry and nature of ligands connected to it, from the features in the edge in a straightforward manner. The EXAFS modulations, being produced by the backscattering of the ejected photoelectron from the atoms surrounding the metal atom, provide, when analyzed, information about the number and type of neighbouring atoms, and the distances at which they occur. In this thesis, analysis of both the edge and EXAFS regions has been used to gain information about the active sites of various metalloproteins. The metalloproteins studied were plastocyanin (Pc), laccase and nickel carbon monoxide dehydrogenase (Ni CODH). Studies of Cu(I)-imidazole compounds, related to the protein hemocyanin, are also reported here.
Date: June 1, 1993
Creator: Tan, G. O.
Partner: UNT Libraries Government Documents Department