Atomic, Molecular and Optical Physics Commons^™

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.

E1-E2 Interference In The Vuv Photoionization Of He, E. P. Kanter, B. Krassig, S. H. Southworth, Renaud Guillemin, Oliver Hemmers, Dennis W. Lindle, R. Wehlitz, M. Ya Amusia, L. V. Chernysheva, N. L. S. Martin

Environmental Studies Faculty Publications

We have measured the forward-backward asymmetry of photoelectron angular distributions produced in the vacuum ultraviolet photoionization of helium. This asymmetry, a consequence of the breakdown of the dipole approximation, measures the real part of the ratio of the quadrupole and dipole matrix elements. In the autoionization region, the strong energy dependence of the asymmetry permits an experimental separation of the ratio of those magnitudes from their phase difference. We experimentally determined the Fano parameters of the 2p²¹D₂ quadrupole resonance, and report improved values of the width Γ and line profile parameter q from those previously available …

Measurement Of Proton Transfer Reaction Rates In A Microwave Cavity Discharge Flowing Afterglow, George M. Brooke Iv

Physics Theses & Dissertations

The reaction rate coefficients between the hydronium ion and the molecules ethene (C₂H₄), propene (C₃H₆), 1-butene (C₄H₈) and hydrogen sulfide (H₂S) were measured at 296 K. The measured reaction rates were compared to collision rates calculated using average dipole orientation (ADO) theory. Reaction efficiency depends primarily upon the proton affinity of the molecules. All the measurements were obtained using the newly developed microwave cavity discharge flowing afterglow (MCD-FA) apparatus. This device uses an Asmussen-type microwave cavity discharge ion source that is …

Investigation Of The Corrosion Of Steel By Lead-Bismuth Eutectic (Lbe) Using Scanning Electron Microscopy And X-Ray Photoelectron Spectroscopy, Daniel Koury

UNLV Theses, Dissertations, Professional Papers, and Capstones

Lead Bismuth Eutectic (LBE) has been proposed for use in programs for accelerator transmutation of waste. LBE is the leading candidate material as a spallation target and an option for the sub-critical blanket coolant. The corrosion of 316 and 316L stainless steels by LBE has been studied using UNLV's facilities for Scanning Electron Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS). We have compared exposed and unexposed samples and studied the differences. Some amount of surface contamination is present on the samples and has been removed by ionbeam etching. The unexposed samples reveal typical stainless steel characteristics: a chromium oxide passivation …

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 …

Non-Dipolar Electron Angular Distributions From Fixed-In-Space Molecules, Renaud Guillemin, Oliver Hemmers, Dennis W. Lindle, E. Shigemasa, K. Le Guen, D. Ceolin, C. Miron, N. Leclercq, P. Morin, Marc Simon, P. W. Langhoff

Environmental Studies Faculty Publications

The first indication of nondipole effects in the azimuthal dependence of photoelectron angular distributions emitted from fixed-in-space molecules is demonstrated in N₂. Comparison of the results with angular distributions observed for randomly oriented molecules and theoretical derivations for the nondipole correction first order in photon momentum suggests that higher orders will be needed to describe distributions measured in the molecular frame.

Photoexcitation Of A Dipole-Forbidden Resonance In Helium, B. Krassig, E. P. Kanter, S. H. Southworth, Renaud Guillemin, Oliver Hemmers, Dennis W. Lindle, R. Wehlitz, N. L. S. Martin

Environmental Studies Faculty Publications

We have observed photoexcitation of the dipole-forbidden 1s²¹S₀→2p²¹D₂ resonance in helium by measuring the nondipolar forward-backward asymmetry of photoelectron angular distributions in the 2ℓ2ℓ^′ autoionizing region. By exploiting the electric dipole-quadrupole interference in the excitation of both the 2s2p¹P₁ and 2p²¹D₂ levels, we have observed the quadrupole resonance in photoabsorption and extracted its Fano line shape parameters and the relative phase of the 1sEp and 1sEd continua. We find the quadrupole line profile index q₂ to be markedly different from theoretical expectations.

Large Nondipole Effects In The Angular Distributions Of K-Shell Photoelectrons From Molecular Nitrogen, Oliver Hemmers, H. Wang, P. Focke, I. A. Sellin, Dennis W. Lindle, J. C. Arce, J. A. Sheehy, P. W. Langhoff

Environmental Studies Faculty Publications

Measurements of angular distributions of K-shell electrons photoejected from molecular nitrogen are reported which reveal large deviations at relatively low photon energies ( ħω≤500eV) from emission patterns anticipated from the dipole approximation to interactions between radiation and matter. A concomitant theoretical analysis incorporating the effects of electromagnetic retardation attributes the observed large nondipole behaviors in N₂ to bond-length-dependent terms in the E1⊗(E2,M1) photoelectron emission amplitudes which are indicative of a potentially universal nondipole behavior in molecular photoionization.

Dynamical Relativistic Effects In Photoionization: Spin-Orbit-Resolved Angular Distributions Of Xenon 4d Photoelectrons Near The Cooper Minimum, H. Wang, G. Snell, Oliver Hemmers, M. M. Sant'anna, I. A. Sellin, N. Berrah, Dennis W. Lindle, P. C. Deshmukh, N. Haque, S. T. Manson

Environmental Studies Faculty Publications

Two decades ago, it was predicted [Y. S. Kim et al., Phys. Rev. Lett. 46, 1326 (1981)] that relativistic effects should alter the dynamics of the photoionization process in the vicinity of Cooper minima. The present experimental and theoretical study of the angular distributions of Xe 4d_3/2 and 4d_5/2 photoelectrons demonstrates this effect for the first time. The results clearly imply that relativistic effects are likely to be important for intermediate- Z atoms at most energies.

Relativistic Effects On Interchannel Coupling In Atomic Photoionization: The Photoelectron Angular Distribution Of Xe, Oliver Hemmers, S. T. Manson, M. M. Sant'anna, P. Focke, H. Wang, I. A. Sellin, Dennis W. Lindle

Environmental Studies Faculty Publications

Measurements of the photoelectron angular-distribution asymmetry parameter β for Xe 5s photoionization have been performed in the 80–200 eV photon-energy region. The results show a substantial deviation from the nonrelativistic value of β=2 and provide a clear signature of significant relativistic effects in interchannel coupling.

Anionic Photofragmentation Of Co: A Selective Probe Of Core-Level Resonances, Wayne C. Stolte, D. L. Hansen, Maria Novella Piancastelli, I. Dominguez-Lopez, A. Rizvi, Oliver Hemmers, H. Wang, Alfred S. Schlachter, M. S. Lubell, Dennis W. Lindle

Environmental Studies Faculty Publications

Anion-yield spectroscopy using x rays is shown to be a selective probe of molecular core-level processes, providing unique experimental verification of shape resonances. For CO, partial anion and cation yields are presented for photon energies near the C K edge. The O^- yield exhibits features above threshold related only to doubly excited states, in contrast to cation yields which also exhibit pronounced structure due to the well-known σ^* shape resonance. Because the shape resonance is completely suppressed for O^-, anion spectroscopy thus constitutes a highly selective probe, yielding information unobtainable with absorption or electron spectroscopy.

Interchannel Coupling In The Photoionization Of The M-Shell Of Kr Well Above Threshold: Experiment And Theory, H. S. Chakraborty, D. L. Hansen, Oliver Hemmers, P. C. Deshmukh, P. Focke, I. A. Sellin, Clemens Heske, Dennis W. Lindle, S. T. Manson

Environmental Studies Faculty Publications

Photoionization cross sections and asymmetry (β) parameters for Kr 3s, 3p, and 3d subshells have been measured and calculated in the 300–1300-eV photon energy range. Good agreement between experiment and theory is found for both cross-section branching ratios and β parameters. Interchannel coupling among the channels arising from 3s, 3p, and 3d subshells is found to be necessary for quantitative accuracy of the theory. This shows that the interchannel coupling phenomenology far above threshold, found previously for outer shells of Ne and Ar, is also operative for inner atomic shells.

Photoelectron Spectroscopy And The Dipole Approximation, Oliver Hemmers, Dennis W. Lindle

Environmental Studies Faculty Publications

Over the past three decades, the dipole approximation has facilitated a basic understanding of the photoionization process in atoms and molecules. Advances in gas-phase photoemission experiments using synchrotron radiation have recently highlighted nondipole effects at relatively low photon energies while probing the limits of the dipole approximation. Breakdowns in this approximation are manifested primarily as deviations from dipolar angular distributions of photoelectrons. Detailed new results demonstrate nondipolar angular-distribution effects are easily observable in atomic gases at energies well below 1 keV, and, in molecules, a previously unexpected phenomenon greatly enhances the breakdown of the dipole approximation just above the core-level …

Electric-Octupole And Pure-Electric-Quadrupole Effects In Soft X-Ray Photoemission, Andrei Derevianko, Oliver Hemmers, S. Oblad, P. Glans, H. Wang, S. B. Whitfield, R. Wehlitz, I. A. Sellin, W. R. Johnson, Dennis W. Lindle

Environmental Studies Faculty Publications

Second-order [O(k²), k = ω/c] nondipole effects in soft-x-ray photoemission are demonstrated via an experimental and a theoretical study of angular distributions of neon valence photoelectrons in the 100–1200 eV photon-energy range. A newly derived theoretical expression for nondipolar angular distributions characterizes the second-order effects using four new parameters with primary contributions from pure-quadrupole and octupole-dipole interference terms. Independent-particle calculations of these parameters account for a significant portion of the existing discrepancy between experiment and theory for Ne 2p first-order nondipole parameters.

Lifetime Effects On The Dissociation Of Core-Excited N2 And Co Molecules, N. Saito, A. Hempelmann, F. Heiserq, Oliver Hemmers, K. Wieliczek, J. Viefhaus, U. Becker

Environmental Studies Faculty Publications

Vibrational-resolved ion and ion-pair yield spectra of N₂ and CO taken at their 1s⃗π^* resonance excitations reveal decay-channel-dependent core hole lifetimes. The linewidths of the yield spectra tend to be shortened when the number of electrons ejected in the deexcitation process increases, finally becoming narrower than the total ion yield or absorption natural lifetime width of the core-excited states of N₂ and CO, respectively. In contrast to this, the linewidths of the yield spectra for the singly charged molecular ions, N₂⁺ and CO⁺, are shown to be broader than their corresponding natural linewidths. …

Beyond The Dipole Approximation: Angular-Distribution Effects In The 1s Photoemission From Small Molecules, Dennis W. Lindle, Oliver Hemmers, H. Wang, P. Focke, I. A. Sellin, J. D. Mills, J. A. Sheehy, P. W. Langhoff

Environmental Studies Faculty Publications

Over the past two decades, the dipole approximation has facilitated a basic understanding of the photoionization process in atoms and molecules. Recent experiments on the 1s inner shells of small molecules at relatively low photon energies (⩽ 1000 eV) show strong nondipole effects. They are significant and measurable at energies close to threshold, in conflict with a common assumption that the dipole approximation is valid for photon energies below 1 keV.

Validity Of The Independent-Particle Approximation In X-Ray Photoemission: The Exception, Not The Rule, D. Hansen, Oliver Hemmers, H. Wang, Dennis W. Lindle, P. Focke, I. A. Sellin, Clemens Heske, H. S. Chakraborty, P. C. Deshmukh, S. T. Manson

Environmental Studies Faculty Publications

A combined experimental and theoretical study of argon valence photoionization illustrates the discovery of the broad lack of validity of the independent-particle approximation (IPA) for x-ray photoemission. In addition to previously known breakdowns of the IPA, which are limited to high photon energies and regions very near threshold, the observed breakdown in photoionization at intermediate energies demonstrates generally that the IPA is valid only in very restricted domains. These restrictions are expected to be relevant throughout the periodic table, with consequences for a wide variety of applications.

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.

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.

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.

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 …

Kinetic-Energy- And Angular-Resolved Fragmentation Of Co In Vibrational-Resolved C 1s Excitation, N. Saito, Franz Heiser, Oliver Hemmers, K. Wieliczek, J. Viefhaus, U. Becker

Environmental Studies Faculty Publications

Angular distributions of C⁺+O⁺ from CO were measured, following vibrationally resolved C 1s excitations into the 2pπ, 3sσ, and 3pπ orbitals as well as into higher unresolved orbitals. A time-of-flight mass spectrometer, with a multihit-type position-sensitive anode, was used for the measurements. The anisotropy parameters (β) of C⁺+O⁺ approach their theoretically expected values as the released kinetic energy in the fragmentation increases. The value of the β parameters remains constant for all vibrational states within each orbital.

First Results From The High-Brightness X-Ray Spectroscopy Beamline 9.3.1 At Als, W. Ng, G. Jones, Rupert C. Perera, D. Hansen, J. Daniels, Oliver Hemmers, P. Glans, S. B. Whitfield, H. Wang, Dennis W. Lindle

Environmental Studies Faculty Publications

Beamline 9.3.1 at the Advanced Light Source (ALS) is a windowless beamline, covering the 1–6 keV photon energy range. This beamline is designed to achieve the goal of high brightness at the sample for use in the x‐ray atomic and molecular spectroscopy (XAMS) science, surface and interface science, biology and x‐ray optical development programs at ALS. X‐ray absorption and time‐of‐flight photoemission measurements in 2–5 keV photon energy range along with the flux, resolution, spot size and stability of the beamline will be discussed. Prospects for future XAMS measurements will also be presented.