Physics Commons^™

K-Shell X-Ray Spectroscopy Of Atomic Nitrogen, M. M. Sant'anna, Gunnar Ohrwall, Wayne C. Stolte, Alfred S. Schlachter, Dennis W. Lindle, B. M. Mclaughlin

Chemistry and Biochemistry Faculty Research

Absolute K-shell photoionization cross sections for atomic nitrogen have been obtained from both experiment and state-of-the-art theoretical techniques. Because of the difficulty of creating a target of neutral atomic nitrogen, no high-resolution K-edge spectroscopy measurements have been reported for this important atom. Interplay between theory and experiment enabled identification and characterization of the strong 1s → np resonance features throughout the threshold region. An experimental value of 409.64 ± 0.02 eV was determined for the K-shell binding energy.

Extraction Chromatographic Studies Of Rutherfordium And Dubnium Homologs, Megan E. Bennett

UNLV Theses, Dissertations, Professional Papers, and Capstones

Studying the chemistry of transactinide elements does not only allow for these elements to be properly placed in the Periodic Table, but it also permits for the extrapolation of the electronic structure based upon the position of the element in the Periodic Table. In addition it enable for the assessment of the role that relativistic effects play in the chemical behavior of the heaviest elements. An improved understanding of the role of relativistic effects in chemistry of the heaviest elements allows for a better understanding of the fundamentals principles that govern the Periodic Table. In order to investigate the chemistry …

Chemical And Electronic Structure Of Surfaces And Interfaces In Compound Semiconductors, Sujitra Pookpanratana

UNLV Theses, Dissertations, Professional Papers, and Capstones

The interface formation between two different materials is important in applications for optoelectronic devices. Often, the success or performance of these devices is dependent on the formation of these heterojunctions. In this work, the surface and interfaces in such materials for optoelectronic devices are investigated by a suite of X-ray analytical techniques including X-ray photoelectron (XPS), X-ray excited Auger electron (XAES), and X-ray emission (XES) spectroscopies to provide novel insight.

For the group III-nitrides (e.g., AlxGa1-xN) used in many light emitting devices, a significant challenge exists to form an Ohmic contact. The electron affinities and band gaps of GaN and …

Jahn-Teller Coupling And Fragmentation After Core-Shell Excitation Ini Cf4 Investigated By Partial-Ion-Yield Spectroscopy, Renaud Guillemin, Wayne C. Stolte, Maria Novella Piancastelli, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

We investigate fragmentation processes induced by core-level photoexcitation in CF4 at both the carbon and fluorine K edges by means of partial-ion-yield spectroscopy. The molecule CF₄ is a textbook example of systems in which Jahn-Teller coupling strongly manifests itself in the photoabsorption spectrum. Spectral features related to Jahn-Teller and quasi-Jahn-Teller splitting are observed, and important differences in the fragmentation pathways are revealed depending on the symmetries of the core-excited states. We interpret these experimental observations on the grounds of symmetry lowering from the Td to the C3v point group as well as preferential orientation with respect …

Full Multiple Scattering Analysis Of Xanes At The Cd L 3- And O K- Edges In Cdo Films Combined With A Soft-X-Ray Emission Investigation, I. N. Demchenko, J. D. Denlinger, M. Chernyshova, K. M. Yu, D. T. Speaks, P. Olalde-Velasco, Oliver Hemmers, W. Walukiewicz, A. Derkachova, K. Lawniczak-Jablonska

Environmental Studies Faculty Publications

X-ray absorption near edge structure (XANES) at the cadmium L3 and oxygen K edges for CdO thin films grown by pulsed laser deposition method, is interpreted within the real-space multiple scattering formalism, FEFF code. The features in the experimental spectra are well reproduced by calculations for a cluster of about six and ten coordination shells around the absorber for L3 edge of Cd and K edge of O, respectively. The calculated projected electronic density of states is found to be in good agreement with unoccupied electronic states in experimental data and allows to conclude that the orbital character of the …

Sulfur K-Edge Photo-Fragmentation Of Ethylene Sulfide, Wayne C. Stolte, Gunnar Ohrwall

Chemistry and Biochemistry Faculty Research

We have investigated the photofragmentation properties of the three-membered ring heterocyclic molecule ethylene sulfide or thiirane, C₂H₄S, by time-of-flight mass spectroscopy. Positive ions have been collected as a function of photon energy around the S K ionization threshold. Branching ratios were derived for all detected ions, which are informative of the decay dynamics and photofragmentation patterns of the core-excited species. We present a new assignment of the spectral features around the S K-edge.

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 …}

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 …

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 …

Optimization Of The Microprecipitation Procedure For Nuclear Forensics Applications, Lyndsey Renee Kelly

UNLV Theses, Dissertations, Professional Papers, and Capstones

Microprecipitation has become one of the most widely used sample preparation techniques for alpha spectroscopy. Many factors during the precipitation process can affect the yield and energy resolution by adding unwanted mass to the sample. Current applications in nuclear forensics call for an optimization of energy resolution and yield in order to improve identification and quantify specific radionuclides. The purpose of this research is to determine the optimal parameters used for microprecipitation. The optimal solution temperature, precipitation time, carrier amount, and hydrofluoric acid amount are used to investigate the influence of varying the type of carrier, as well as, the …

Linear Dichroism In Resonant Inelastic X-Ray Scattering To Molecular Spin-Orbit States, Renaud Guillemin, Stephane Carniato, Wayne C. Stolte, Loic Journel, Richard Taieb, Dennis W. Lindle, Marc Simon

Chemistry and Biochemistry Faculty Research

Polarization-dependent resonant inelastic x-ray scattering (RIXS) is shown to be a new probe of molecular-field effects on the electronic structure of isolated molecules. A combined experimental and theoretical analysis explains the linear dichroism observed in Cl 2p RIXS following Cl 1s excitation in HCl and CF₃Cl as due to molecular-field effects, including singlet-triplet exchange, indicating polarized-RIXS provides a direct probe of spin-orbit-state populations applicable to any molecule.

Photofragmentation Of Sif4 Upon Si 2p And F 1s Core Excitation: Cation And Anion Yield Spectroscopy, Maria Novella Piancastelli, Wayne C. Stolte, Renaud Guillemin, A. Wolska, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

We have studied the fragmentation dynamics of core-excited SiF₄ by means of soft-x-ray photoexcitation and partial positive and negative ion yield measurements around the Si L_2,3-shell and F K-shell ionization thresholds. All detectable ionic fragments are reported and we observe significant differences between the various partial ion yields near the Si 2p threshold. The differences are similar to our previous results from CH₃Cl showing more extended fragmentation in correspondence to transitions to Rydberg states. At variance with smaller systems, we observe negative ion production in the shape resonance region. This can be related …

Femtosecond Nuclear Motion Of Hcl Probed By Resonant X-Ray Raman Scattering In The Cl 1s Region, Marc Simon, Loic Journel, Stephane Carniato, Richard Taieb, I. Minkov, Faris Gel'mukhanov, P. Salek, H. Agren, Renaud Guillemin, Wayne C. Stolte, A. C. Hudson, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

Femtosecond dynamics are observed by resonant x-ray Raman scattering (RXS) after excitation along the dissociative Cl 1s→6ơ* resonance of gas-phase HCl. The short core-hole lifetime results in a complete breakdown of the common nondispersive behavior of soft-x-ray transitions between parallel potentials. We evidence a general phenomenon of RXS in the hard-x-ray region: a complete quenching of vibrational broadening. This opens up a unique opportunity for superhigh resolution x-ray spectroscopy beyond vibrational and lifetime limitations.

Anion And Cation-Yield Spectroscopy Of Core-Excited Sf6, Maria Novella Piancastelli, Wayne C. Stolte, Renaud Guillemin, A. Wolska, M. M. Sant'anna, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

We report an extensive study on total and partial-ion-yield spectroscopy around both the S 2p and F 1s thresholds in SF₆. All positive and negative single-ion channels have been measured. Below the F 1s threshold we detect a large variation in relative intensity of the resonant structures according to the specific channel monitored, indicating selective fragmentation. Above threshold, at variance with previous cases described by us, we detect high-intensity structures related to shape resonances not only in the cation channels but also for the anions. We discuss the applicability and limits of a model we …

Fragmentation Dynamics Of H2s Following S 2p Photoexcitation, Renaud Guillemin, S-W Yu, Wayne C. Stolte, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

The fragmentation dynamics of core-excited H₂S has been studied by means of partial anion and cation yield measurements around the S L_2,3-subshell ionization thresholds. All detectable ionic fragments are reported, and significant differences between partial ion yields are observed. Possible dissociation pathways are discussed by comparison to previous studies of electron spectra.

Near-Edge X-Ray Absorption Fine Structure Study Of Ion-Beam-Induced Phase Transformation In Gd2(Ti1-Yzry)2o7, Ponnusamy Nachimuthu, S. Thevuthasan, V. Shutthanandan, E. M. Adams, W. J. Weber, B. D. Begg, D. K. Shuh, Dennis W. Lindle, Eric M. Gullikson, Rupert C. Perera

Chemistry and Biochemistry Faculty Research

The structural and electronic properties of Gd₂(Ti_1−yZr_y)₂O₇ (y=0–1) pyrochlores following a 2.0-MeV Au²⁺ ion-beam irradiation (~5.0 X 10¹⁴ Au²⁺/cm²) have been investigated by Ti 2p and O 1s near-edge x-ray absorption fine structure (NEXAFS). The irradiation of Gd₂(Ti_1−yZr_y)₂O₇ leads to the phase transformation from the ordered pyrochlore structure (Fd3m) to the defect fluorite structure (Fm3m) regardless of Zr concentration. Irradiated Gd₂(Ti_{1−y …}

The Electrochemical Separation Of Curium And Americium: Quaterly Report August-December 2004, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

This research report outlines the current status and progress associated with the electrochemical separation of Curium and Americium. The following pages outline the progress on our project to date. We have been actively performing research on this project for three months and are currently on schedule in terms of the proposed timelines.

The initial focus of the project involved setting up the laboratories for the studies outlined in the grant proposal. The instrumentation needed included an electrochemical work station that will perform the bulk of the electrochemical studies. This instrument will complement the electrochemical instrumentation in Dr. Hatchett’s laboratory and …

Probing Cation Antisite Disorder In Gd2ti2o7 Pyrochlore By Site-Specific Nexafs And Xps, Ponnusamy Nachimuthu, S. Thevuthasan, Mark H. Engelhard, W. J. Weber, D. K. Shuh, N. M. Hamdan, B. S. Mun, E. M. Adams, D. E. Mccready, V. Shutthanandan, Dennis W. Lindle, G. Balakrishnan, R. C. Ewing

Chemistry and Biochemistry Faculty Research

Disorder in Gd₂Ti₂O₇ is investigated by near-edge x-ray-absorption fine structure (NEXAFS) and x-ray photoelectron spectroscopy (XPS). NEXAFS shows Ti⁴⁺ ions occupy octahedral sites with a tetragonal distortion induced by vacant oxygen sites. O 1s XPS spectra obtained with a charge neutralization system from Gd₂Ti₂O₇(100) and the Gd₂Ti₂O₇ pyrochlore used by Chen et al. [Phys. Rev. Lett. 88, 105901 (2002)], both yielded a single peak, unlike the previous result on the latter that found two peaks. The current results give no evidence for …

Electrochemical Separation Of Curium And Americium, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

The objective of this project is to develop a method for the separation of Am from Cm based on electrochemical techniques. Electrochemical systems that allow the thermodynamics of actinide and lanthanide complexes to be systematically evaluated and tuned will be examined. The influence of complex formation on the ability to selectively isolate a given species electrochemically will be evaluated. Metal-ligand complex formation provides a useful derivation technique to increase solubility in solution environments that favor precipitation. In addition, the thermodynamic properties of a complex relative to the isolated species may be shifted to more suitably measurable electrochemical separation regimes. Electrochemical …

The Electrochemical Separation Of Curium And Americium: Quaterly Report January - March 2004, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

This research report outlines the current status and progress associated with the electrochemical separation of Curium and Americium.

Data collection and analysis of the Ce³⁺/Ce⁴⁺ redox couple in various supporting electrolytes has continued. All electrolyte systems were investigated at Pt, Au, and Glassy Carbon working electrodes. Analysis of these data was accomplished by performing appropriate background subtractions to reveal net peaks due to Ce redox behavior. Successful identification of the Ce redox couple was achieved with all electrolyte/electrode systems, although a decline in peak resolution was observed with increasing acid concentration. Optimal conditions in this experiment were …

Performance Characteristics Of Beamline 6.3.1 From 200 Ev To 2000 Ev At The Advanced Light Source, Ponnusamy Nachimuthu, J. H. Underwood, C. D. Kemp, Eric M. Gullikson, Dennis W. Lindle, David K. Shuh, Rupert C. Perera

Chemistry and Biochemistry Faculty Research

Bend magnet beamline 6.3.1 at the Advanced Light Source operates from 200 eV to 2000 eV, primarily used for x-ray absorption fine structure investigations. The beamline optics consist of a compact, entrance-slitless, Hettrick-Underwood type variable-line-spacing plane-grating monochromator and refocusing mirrors to provide a 25 μm × 500 μm spot at the focal point in the reflectometer end station. Wavelength is scanned by the simple rotation of the grating and illuminates a fixed exit slit. The LabView based beamline control and data acquisition computer code has been implemented to provide a convenient interface to the user. The dedicated end station is …

Photofragmentation Dynamics Of Core-Excited Water By Anion-Yield Spectroscopy, Wayne C. Stolte, M. M. Sant'anna, Gunnar Ohrwall, Maria Novella Piancastelli, I. Dominguez-Lopez, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

Partial-anion and- cation yields from H₂O are presented for photon energies near the oxygen K edge. The O^- yield exhibits a feature above threshold attributed to doubly excited states, in contrast to the H^- and cation yields, which are nearly featureless above threshold. Additionally, the lack of the OH^- fragment indicates radiative decay and provides a negligible amount of anion formation.

Fragmentation Processes Following Core Excitation In Acetylene And Ethylene By Partial Ion Yield Spectroscopy, Maria Novella Piancastelli, Wayne C. Stolte, Gunnar Ohrwall, S-W Yu, D. Bull, K. Lantz, Alfred S. Schlachter, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

Partial ion yield spectroscopy provides a very detailed picture of fragmentation processes following core excitation in isolated molecules. We exploit this potential in the analysis of decay processes following C1s→π and C1s→Rydberg excitations in ethylene and acetylene. We show that the relative intensity of spectral features related to the excitation to empty molecular orbitals or to Rydberg states is a function of the time variation of the fragmentation process. Namely, we see an intensity increase in the Rydberg states compared to the molecular orbitals as the fragmentation process becomes more extensive, a result attributable to the diffuse nature of the …

Holographic Analysis Of Diffraction Structure Factors, S. Marchesini, N. Mannella, C. S. Fadley, M. A. Van Hove, J. J. Bucher, D. K. Shuh, L. Fabris, M. J. Press, M. W. West, Wayne C. Stolte, Z. Hussain

Chemistry and Biochemistry Faculty Research

We combine the theory of inside-source/inside-detector x-ray fluorescence holography and Kossel lines/x ray standing waves in kinematic approximation to directly obtain the phases of the diffraction structure factors. The influence of Kossel lines and standing waves on holography is also discussed. We obtain partial phase determination from experimental data obtaining the sign of the real part of the structure factor for several reciprocal lattice vectors of a vanadium crystal.

In-Situ X-Ray-Absorption Spectroscopy Study Of Hydrogen Absorption By Nickel-Magnesium Thin Films, B. Farangis, Ponnusamy Nachimuthu, T. J. Richardson, J. L. Slack, Rupert C. Perera, Eric M. Gullikson, Dennis W. Lindle, M. Rubin

Chemistry and Biochemistry Faculty Research

Structural and electronic properties of co-sputtered Ni-Mg thin films with varying Ni to Mg ratio were studied by in-situ x-ray absorption spectroscopy in the Ni L-edge and Mg K-edge regions. Co-deposition of the metals led to increased disorder and decreased coordination around Ni and Mg compared to pure metal films. Exposure of the metallic films to hydrogen resulted in formation of hydrides and increased disorder. The presence of hydrogen as a near neighbor around Mg caused a drastic reduction in the intensities of multiple scattering resonances at higher energies. The optical switching behavior and changes in the x-ray spectra varied …

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.

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.

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.