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The Development and Application of Capillary Absorption Cells

Description: Abstract: "Various types of capillary absorption cells have been constructed from a variety of materials. These cells, having volumes as low as 160 microliters, have been used to increase the sensitivity of several colorimetrics methods as much as 1000 fold without appreciable loss of accuracy. Small volumes of solution must be used in order to concentrate the colored material present."
Date: 1951
Creator: Rosenfels, R. S.; Kirk, P. L.; Kitson, R. E.; Patton, R. L. & Curtis, R. E.
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

Temperature Dependence of the Absolute Third-order Rate Constant for the Reaction between Na + O₂ + N₂ over the Range 571 - 1016 K Studied by Time-resolved Atomic Resonance Absorption Spectroscopy

Description: Article on temperature dependence of the absolute third-order rate constant for the reaction between Na + O₂ + N₂ over the range 571-1016 K studied by time-resolved atomic resonance absorption spectroscopy.
Date: 1985
Creator: Husain, David; Marshall, Paul & Plane, John M. C.
Partner: UNT College of Arts and Sciences

Detection and Quantification of Pu(III, IV, V, and VI) Using a1.0-meter Liquid Core Waveguide

Description: Detection and quantification of the aquo ions of Pu in 1 MHClO4 was carried out using a 1-meter liquid core waveguide (LCW) coupledto a fiber optic UV-Vis spectrometer. Detection limits of 7 x 10-7 M forPu(VI), 1.6 x 10-5 M for Pu(V), 5 x 10-6 M for Pu(IV) and 8 x 10-6 M forPu(III) were achieved. The limits of detection represent increases of 18to 33 times those achievable using a conventional 1-cm path length.Because of the much lower detection limits of the LCW, routineidentification of the oxidation states in dilute Pu solutions can bemade.
Date: February 15, 2005
Creator: Wilson, Richard E.; Hu, Yung-Jin & Nitsche, Heino
Partner: UNT Libraries Government Documents Department

Effects of backlight structure on absorption experiments

Description: The impact of spectral details in the backlight of absorption spectroscopy experiments is considered. It is shown that experimentally unresolved structure in the backlight spectrum can introduce significant errors in the inferred transmission. Furthermore, it is shown that a valuable experimental procedure previously used to test the accuracy of the data fails to reveal these errors.
Date: November 8, 2004
Creator: Iglesias, C A
Partner: UNT Libraries Government Documents Department

Effect of Mn Substitution for Multiferroic BiFeO3 Probed by High-Resolution Soft-X-Ray Spectroscopy

Description: The electronic structures of BiFeO{sub 3} (BF) and Mn-doped BiFeO{sub 3} (BF(Mn)) have been studied by X-ray absorption spectroscopy (XAS) and soft-X-ray emission spectroscopy (SXES). The BF and BF(Mn) have the mixed valence state of Fe{sup 2+} and Fe{sup 3+}. The valence band is mainly composed of O 2p state hybridized with the majority-spin t{sub 2g} and e{sub g} orbitals of Fe 3d state. The conduction band is composed of the minority-spin t{sub 2g} and e{sub g} orbitals of Fe 3d. The band gaps of BF and BF(Mn) are estimated to be 1.3 eV and 2.7 eV, respectively. The increase of band gap with Mn substitution contributes to the change of bandwidth of valence band.
Date: July 11, 2008
Creator: Higuchi, Tohru; Higuchi, T.; Hattori, T.; Sakamoto, W.; Itoh, N.; Shimura, T. et al.
Partner: UNT Libraries Government Documents Department

Electronic Structure of the ID Conductor K0.3MoO3 studied using resonant inelastic x-ray scattering and soft x-ray emission spectroscopy

Description: The electronic structure of the quasi-one dimensional conductor K{sub 0.3}MoO{sub 3} has been measured using high resolution resonant inelastic x-ray scattering and x-ray absorption spectroscopy. The data is compared to that from the related two dimensional insulator {alpha}-MoO{sub 3}. Scattering features are observed from both oxides that are explained in terms of the band momentum selectivity of the scattering process, allowing a comparison of the scattering data to recent band structure calculations.
Date: September 24, 2008
Creator: Learmonth, T.; Glans, P.-A.; McGuinness, C.; Plucinski, L.; Zhang, Y.; Guo, J.-H. et al.
Partner: UNT Libraries Government Documents Department

Probing Compositional Variation within Hybrid Nanostructures

Description: We present a detailed analysis of the structural and magnetic properties of solution-grown PtCo-CdS hybrid structures in comparison to similar free-standing PtCo alloy nanoparticles. X-ray absorption spectroscopy is utilized as a sensitive probe for identifying subtle differences in the structure of the hybrid materials. We found that the growth of bimetallic tips on a CdS nanorod substrate leads to a more complex nanoparticle structure composed of a PtCo alloy core and thin CoO shell. The core-shell architecture is an unexpected consequence of the different nanoparticle growth mechanism on the nanorod tip, as compared to free growth in solution. Magnetic measurements indicate that the PtCo-CdS hybrid structures are superparamagnetic despite the presence of a CoO shell. The use of X-ray spectroscopic techniques to detect minute differences in atomic structure and bonding in complex nanosystems makes it possible to better understand and predict catalytic or magnetic properties for nanoscale bimetallic hybrid materials.
Date: June 22, 2010
Creator: Yuhas, Benjamin D.; Habas, Susan E.; Fakra, Sirine C. & Mokari, Taleb
Partner: UNT Libraries Government Documents Department

Ultrafast and nonlinear optical characterization of optical limiting processes in fullerenes

Description: The authors present recent results of broadband femotosecond (fs) transient absorption (TA) and broadband nanosecond (ns) optical limiting (OL) studies of C{sub 60} and derivatized C{sub 60}. Improvements in measurement techniques for fs TA spectra provide sensitivity to 10{sup {minus}5} in differential transmission, allowing detailed comparison of excited-state spectra with established energy level diagrams, as well as comparison of the ratio of triplet to singlet excited-state absorption cross sections from TA spectra with those obtained by modeling time transients at different wavelengths. For derivatized fullerenes, which provide enhanced solubility and a ground-state absorption extended into the infrared compared with C{sub 60} there is no spectral region where the triplet absorption cross section dominates the singlet as strongly as demonstrating broadband limiting in all 6, 6 mono-adducts and neat C{sub 60}. The authors report new approaches to processing sol-gel encapsulated fullerenes to improve the OL performance of solid-state materials to approach the response of solution limiters.
Date: October 1, 1997
Creator: Kohlman, R.; Klimov, V. & Shi, X.
Partner: UNT Libraries Government Documents Department

Recent advances in the measurement of high temperature bimolecular rate constants

Description: Recent advances in the measurement of high temperature reaction rate constants are discussed. The studies carried out by shock tube methods are particularly considered because these results are important not only in theoretical chemical kinetics but also in practical applications. The work on 5 chemical reactions are reviewed in detail. These are: D + H{sub 2}, Cl + H{sub 2}, H + O{sub 2}, CH{sub 3} + CH{sub 3}, and H + NO{sub 2}.
Date: July 1, 1995
Creator: Michael, J.V.
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

DOE/SC0001389 Final technical report: Investigation of uranium attenuation and release at column and pore scales in response to advective geochemical gradients

Description: Experimental approach Column experiments were devised to investigate the role of changing fluid composition on mobility of uranium through a sequence of geologic media. Fluids and media were chosen to be relevant to the ground water plume emanating from the former S-3 ponds at the Oak Ridge Integrated Field Research Challenge (ORIFC) site. Synthetic ground waters were pumped upwards at 0.05 mL/minute for 21 days through layers of quartz sand alternating with layers of uncontaminated soil, quartz sand mixed with illite, quartz sand coated with iron oxides, and another soil layer. Increases in pH or concentration of phosphate, bicarbonate, or acetate were imposed on the influent solutions after each 7 pore volumes while uranium (as uranyl) remained constant at 0.1mM. A control column maintained the original synthetic groundwater composition with 0.1mM U. Pore water solutions were extracted to assess U retention and release in relation to the advective ligand or pH gradients. Following the column experiments, subsamples from each layer were characterized using microbeam X-ray absorption spectroscopy (XANES) in conjunction with X-ray fluorescence mapping and compared to sediment core samples from the ORIFC, at SSRL Beam Line 2-3. Results U retention of 55 – 67 mg occurred in phosphate >pH >control >acetate >carbonate columns. The mass of U retained in the first-encountered quartz layer in all columns was highest and increased throughout the experiment. The rate of increase in acetate- and bicarbonate-bearing columns declined after ligand concentrations were raised. U also accumulated in the first soil layer; the pH-varied column retained most, followed by the increasing-bicarbonate column. The mass of U retained in the upper layers was far lower. Speciation of U, interpreted from microbeam XANES spectra and XRF maps, varied within and among the columns. Evidence of minor reduction to U(IV) was observed in the first-encountered quartz layer in ...
Date: May 13, 2013
Creator: Savage, Kaye S.; Zhu, Wenyi & Barnett, Mark O.
Partner: UNT Libraries Government Documents Department

Orbital Moment Determination in (MnxFe1-x)3O4 Nanoparticles

Description: Nanoparticles of (Mn{sub x}Fe{sub 1-x}){sub 3}O{sub 4} with a concentration ranging from x = 0 to 1 and a crystallite size of 14-15 nm were measured using X-ray absorption spectroscopy and X-ray magnetic circular dichroism to determine the ratio of the orbital moment to the spin moment for Mn and Fe. At low Mn concentrations, the Mn substitutes into the host Fe{sub 3}O{sub 4} spinel structure as Mn{sup 2+} in the tetrahedral A-site. The net Fe moment, as identified by the X-ray dichroism intensity, is found to increase at the lowest Mn concentrations then rapidly decrease until no dichroism is observed at 20% Mn. The average Fe orbit/spin moment ratio is determined to initially be negative and small for pure Fe{sub 3}O{sub 4} nanoparticles and quickly go to 0 by 5%-10% Mn addition. The average Mn moment is anti-aligned to the Fe moment with an orbit/spin moment ratio of 0.12 which gradually decreases with Mn concentration.
Date: October 22, 2010
Creator: Pool, V. L.; Jolley, C.; Douglas, T.; Arenholz, E. & Idzerda, Y. U.
Partner: UNT Libraries Government Documents Department

Controlled Assembly of Heterobinuclear Sites on Mesoporous Silica: Visible Light Charge-Transfer Units with Selectable Redox Properties

Description: Mild synthetic methods are demonstrated for the selective assembly of oxo-bridged heterobinuclear units of the type TiOCrIII, TiOCoII, and TiOCeIII on mesoporous silica support MCM-41. One method takes advantage of the higher acidity and, hence, higher reactivity of titanol compared to silanol OH groups towards CeIII or CoII precursor. The procedure avoids the customary use of strong base. The controlled assembly of the TiOCr system exploits the selective redox reactivity of one metal towards another (TiIII precursor reacting with anchored CrVI centers). The observed selectivity for linking a metal precursor to an already anchored partner versus formation of isolated centers ranges from a factor of six (TiOCe) to complete (TiOCr, TiOCo). Evidence for oxo bridges and determination of the coordination environment of each metal centers is based on K-edge EXAFS (TiOCr), L-edge absorption spectroscopy (Ce), and XANES measurements (Co, Cr). EPR, optical, FT-Raman and FT-IR spectroscopy furnish additional details on oxidation state and coordination environment of donor and acceptor metal centers. In the case of TiOCr, the integrity of the anchored group upon calcination (350 oC) and cycling of the Cr oxidation state is demonstrated. The binuclear units possess metal-to-metal charge-transfer transitions that absorb deep in the visible region. The flexible synthetic method for assembling the units opens up the use of visible light charge transfer pumps featuring donor or acceptor metals with selectable redox potential.
Date: June 4, 2008
Creator: Frei, Heinz; Han, Hongxian & Frei, Heinz
Partner: UNT Libraries Government Documents Department

Examination of the local structure in composite and lowdimensional semiconductor by X-ray Absorption Spectroscopy

Description: X-ray absorption methods have been successfully used to obtain quantitative information about local atomic composition of two different materials. X-ray Absorption Near Edge Structure analysis and X-Ray Photoelectron Spectroscopy allowed us to determine seven chemical compounds and their concentrations in c-BN composite. Use of Extended X-ray Absorption Fine Structure in combination with Transmission Electron Microscopy enabled us to determine the composition and size of buried Ge quantum dots. It was found that the quantum dots consisted out of pure Ge core covered by 1-2 monolayers of a layer rich in Si.
Date: September 25, 2006
Creator: Lawniczak-Jablonska, K.; Demchenko, I.N.; Piskorska, E.; Wolska,A.; Talik, E.; Zakharov, D.N. et al.
Partner: UNT Libraries Government Documents Department

Femtosecond induced transparency and absorption in the extremeultraviolet by coherent coupling of the He 2s2p (1Po) and 2p2 (1Se)double excitation states with 800 nm light

Description: Femtosecond high-order harmonic transient absorption spectroscopy is used to observe electromagnetically induced transparency-like behavior as well as induced absorption in the extreme ultraviolet by laser dressing of the He 2s2p ({sup 1}P{sup 0}) and 2p{sup 2} ({sup 1}S{sup e}) double excitation states with an intense 800 nm field. Probing in the vicinity of the 1s{sup 2} {yields} 2s2p transition at 60.15 eV reveals the formation of an Autler-Townes doublet due to coherent coupling of the double excitation states. Qualitative agreement with the experimental spectra is obtained only when optical field ionization of both double excitation states into the N = 2 continuum is included in the theoretical model. Because the Fano q-parameter of the unperturbed probe transition is finite, the laser-dressed He atom exhibits both enhanced transparency and absorption at negative and positive probe energy detunings, respectively.
Date: August 1, 2007
Creator: Loh, Z.-H.; Greene, C.H. & Leone, S.R.
Partner: UNT Libraries Government Documents Department