Biological and Chemical Physics Commons^™

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.

Aspects Of Postcollision Interactions (Pci) Near The Ar L-Shell, James A.R. Samson, Y. Lu, Wayne C. Stolte

Chemistry and Biochemistry Faculty Research

In the present work we are interested in near-threshold photoionization experiments involving postcollision effects related to the Auger decay of a vacancy in the Ar L shell. In particular, we have measured the photoelectron energy spectrum resulting from the above postcollision interaction effects and have observed electrons produced by the process of electron capture and reemission.

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]

Cross Sections For The Production Of He+ (Np) 2p0 States By 50 To 150 Kev Proton Impact On Helium, Wayne C. Stolte, R. Bruch

Chemistry and Biochemistry Faculty Research

Cross sections have been measured for the production of He⁺ (np) ²P^o states, n=2,3,4, by proton impact on helium over a projectile velocity range of 1.42–2.45 a.u. (50 ≤E≤150 keV). Cross sections were determined by measuring the extreme ultraviolet photons emitted from excited He1 ions. The data indicate a lower energy than expected for the maximum cross section. A comparison of the present results in terms of projectile energy dependance with the cross sections for excitation to He (1snp) ¹P^o, ionization, and total electron capture suggests the primary mechanism …

Post-Collision Interactions In The Auger Decay Of The Ar L-Shell, James A.R. Samson, Wayne C. Stolte, Z. X. He, J. N. Cutler, D. Hansen

Chemistry and Biochemistry Faculty Research

The photoionization cross sections for Ar⁺ through Ar⁴⁺, produced by the Auger decay of a 2p hole in argon, have been measured between 242 eV and 253 eV by the use of synchrotron radiation. The high resolution of the monochromator has allowed a detailed study of the postcollision interactions that occur in this spectral region. The concept of photoelectron recapture by Ar²⁺ to produce the Ar⁺ continuum is studied. The relative values of the quantum-mechanical calculations of the photoelectron recapture probability are shown to be in excellent agreement with the present data. The magnitude …

Design And Performance Of The Advanced-Light-Source Double-Crystal Monochromator, G. Jones, S. Ryce, Dennis W. Lindle, B. A. Karlin, J. C. Woicik, Rupert C. Perera

Chemistry and Biochemistry Faculty Research

A new “Cowan type” double-crystal monochromator, based on the boomerang design used at National Synchrotron Light Source (NSLS) beamline X-24A, has been developed for beamline 9.3.1 at the Advanced Light Source (ALS), a windowless ultrahigh vacuum beamline covering the 1-6 keV photon-energy range. Beamline 9.3.1 is designed to simultaneously achieve the goals of high energy resolution, high flux, and high brightness at the sample. The mechanical design of the monochromator has been simplified, and recent developments in technology have been included. Measured mechanical precision of the monochromator shows significant improvement over existing designs. In tests with x-rays at NSLS beamline …

High-Brightness Beamline For X-Ray Spectroscopy At The Advanced Light Source, Rupert C. Perera, G. Jones, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

Beamline 9.3.1 at the Advanced Light Source (ALS) is a windowless beamline, covering the 1-6 keV photon-energy range, designed to achieve the goals of high energy resolution, high flux, and high brightness at the sample. When completed later this year, it will be the first ALS monochromatic hard-x-ray beamline, and its brightness will be an order-of-magnitude higher than presently available in this energy range. In addition, it will provide flux and resolution comparable to any other beamline now in operation. To achieve these goals, two technical improvements, relative to existing x-ray beamlines, were incorporated. First, a somewhat novel optical design …

High-Energy Behavior Of The Double Photoionization Of Helium From 2 To 12 Kev, Jon C. Levin, Ivan A. Sellin, B. M. Johnson, Dennis W. Lindle, R. D. Miller, Y. Azuma, H. G. Berry, D.-H. Lee, N. Berrah

Chemistry and Biochemistry Faculty Research

We report the ratio of double-to-single photoionization of He at several photon energies from 2 to 12 keV. By time-of-Aight methods, we find a ratio consistent with an asymptote at 1.5%±0.2%, essentially reached by h v≈4 keV. Fair agreement is obtained with older shake calculations of Byron and Joachain [Phys. Rev. 164, 1 (1967)], of Aberg [Phys. Rev. A 2, 1726 (1970)], and with recent many-body perturbation theory (MBPT) of Ishihara, Hino, and McGuire [Phys. Rev. A 44, 6980 (1991)]. The result lies below earlier MPBT calculations by Amusia et al. [J. Phys. B 8 …

Surface Structure Of √3x√3r 30 Cl/Ni(111) Determined Using Low-Temperature Angle-Resolved-Photoemission Extended Fine Structure, Li-Qiong Wang, Z. Hussain, Z. Q. Huang, A. E. Schach Von Wittenau, Dennis W. Lindle, D. A. Shirley

Chemistry and Biochemistry Faculty Research

A surface structural study of the √3 × √3 R30° Cl/Ni(111) adsorbate system was made using low-temperature angle-resolved photoemission extended fine structure. The experiments were performed along two emission directions, [111] and [110], and at two temperatures, 120 and 300 K. The multiple-scattering spherical-wave analysis determined that the Cl atom adsorbs in the fcc threefold hollow site, 1.837(8) Å above the first nickel layer, with a Cl-Ni bond length of 2.332(6) Å, and an approximate 5% contraction between the first and the second nickel layers (the errors in parentheses are statistical standard deviations only).

Measurement Of The Ratio Of Double-To-Single Photoionization Of Helium At 2.8 Kev Using Synchrotron Radiation, Jon C. Levin, Dennis W. Lindle, N. Keller, R. D. Miller, Y. Azuma, N. Berrah Mansour, H. G. Berry, Ivan A. Sellin

Chemistry and Biochemistry Faculty Research

We report the first measurement of the ratio of double-to-single photoionization of helium well above the double-ionization threshold. Using a time-of-flight technique, we find He⁺⁺/He⁺=1.6±0.3% at hν=2.8 keV. This value lies between calculations by Amusia (2.3%) and by Samson, who predicts 1.2% by analogy with electron-impact ionization cross sections of singly charged ions. Good agreement is obtained with older shake calculations of Byron and Joachain, and of Åberg, who predict 1.7%.

Anisotropy Of Polarized X-Ray Emission From Molecules, S. H. Southworth, Dennis W. Lindle, R. Mayer, P. L. Cowan

Chemistry and Biochemistry Faculty Research

Strongly anisotropic, polarized Cl K-V x-ray emission from gas-phase CF₃Cl has been observed following resonant excitation with a linearly polarized x-ray beam. Distinctively different angular distributions are observed for x-ray emission involving molecular orbitals of different symmetries. A classical model of the x-ray absorption-emission process accurately describes the observed radiation patterns.

Molecular-Orbital Studies Via Satellite-Free X-Ray Fluorescence: Cl-K Absorption And K–Valence-Level Emission Spectra Of Chlorofluoromethanes, Rupert C. Perera, P. L. Cowan, Dennis W. Lindle, R. E. Lavilla, T. Jach, R. D. Deslattes

Chemistry and Biochemistry Faculty Research

X-ray absorption and emission measurements in the vicinity of the chlorine K edge of the three chlorofluoromethanes have been made using monochromatic synchrotron radiation as the source of excitation. By selectively tuning the incident radiation to just above the Cl 1s single-electron ionization threshold for each molecule, less complex x-ray-emission spectra are obtained. This reduction in complexity is attributed to the elimination of multielectron transitions in the Cl K shell, which commonly produce satellite features in x-ray emission. The resulting "satellite-free" x-ray-emission spectra exhibit peaks due only to electrons in valence molecular orbitals filling a single Cl 1s vacancy. These …

Polarized X-Ray-Emission Studies Of Methyl Chloride And The Chlorofluoromethanes, Dennis W. Lindle, P. L. Cowan, T. Jach, R. E. Lavilla, R. D. Deslattes, Rupert C. Perera

Chemistry and Biochemistry Faculty Research

A new technique sensitive to molecular orientation and geometry, and based on measuring the polarization of x-ray emission, has been applied to the Cl-containing molecules methyl chloride (CH₃Cl) and the chlorofluoromethanes (CF₃Cl, CF₂Cl₂, and CFCl₃) in the gas phase. Upon selective excitation using monochromatic synchrotron radiation in the Cl K-edge (Cl 1s) near-threshold region, polarization-selective x-ray emission studies reveal highly polarized molecular valence x-ray fluorescence for all four molecules. The degree and the orientation of the polarized emission are observed to be sensitive to the incident excitation energy near …

Fine‐Structure Mixing Within The Zn(43pj) Multiplet By Collisions With The Noble Gases, Xianming Han, J. F. Kelly

Scholarship and Professional Work - LAS

Measurements of rate coefficients for intramultiplet state transfer of Zn(4 ³ P ₁→4 ³ P _J’) by collisions with the rare gases are presented. The state‐to‐state binary rate coefficients are derived from least‐squares fittings of the time‐resolved triexponential behavior of the 4 ³ P ₁fluorescence. These rate coefficients were studied systematically over a temperature range of 690–1100 K in order to characterize the velocity dependence of the collisional coupling. The systematic behavior of the rate coefficients with varying temperature and noble gas species is qualitatively consistent with a nearly adiabatic coupling limit for noncrossing levels.

Direct Determination Of Molecular-Orbital Symmetry Of H2s Using Polarized X-Ray Emission, R. Mayer, Dennis W. Lindle, S. H. Southworth, P. L. Cowan

Chemistry and Biochemistry Faculty Research

X-ray emission from the molecule H₂S is strongly polarized following excitation of a sulfur K-shell electron to an unoccupied subthreshold molecular orbital with a polarized x-ray beam. Changes in the polarization of the emission spectrum are observed as the incident beam's energy is swept across the subthreshold absorption resonance. The previously unresolved absorption resonance is shown experimentally to be primarily associated with a molecular orbital of b₂ symmetry, but with a high-excitation-energy component due to an orbital with a₁ symmetry. Satellite emission intensity is shown to depend on the primary photon energy and is therefore associated …

Argon-Photoion–Auger-Electron Coincidence Measurements Following K-Shell Excitation By Synchrotron Radiation, Jon C. Levin, C. Biedermann, N. Keller, L. Liljeby, C.-S. O, R. T. Short, Ivan A. Sellin, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

Argon photoion spectra have been obtained for the first time in coincidence with K-LL and K-LM Auger electrons, as a function of photon energy. The simplified charge distributions which result exhibit a much more pronounced photon-energy dependence than do the more complicated noncoincident spectra. In the near-K-threshold region, Rydberg shakeoff of np levels, populated by resonant excitation of K electrons, occurs with significant probability, as do double-Auger processes and recapture of the K photoelectron through postcollision interaction.

The Spectroscopy And Molecular Dynamics Of The High Frequency Ν1 6 Intermolecular Vibrations In Hcn‐‐‐Hf And Dcn‐‐‐Df, B. A. Wofford, M. W. Jackson, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

Gas phase rovibrational analysis of the high frequency intermolecular hydrogen bonded bending overtone 2ν⁰ ₆ [ν₀=1132.4783(2) cm^{− 1}] in HCN‐‐‐HF and its corresponding perdeuterated fundamental ν¹ ₆ [ν₀=409.1660(2) cm^{− 1}] are reported. Evaluated rovibrational parameters provide the basis for quantitative modeling of the molecular dynamics associated with this vibration. A quantum mechanical calculation permits determination of the quadratic and quartic force constants K _{6 6}=537(17) and K _{6 6 6 6}=4.98(12) cm^{− 1} which in turn are used to estimate the pertinent cubic band stretching interaction constants …

Erratum: Determination Of Dissociation Energies And Thermal Functions Of Hydrogen Bond Formation Using High Resolution Ftir Spectroscopy [J. Chem. Phys. 8 7, 5674 (1987)], B. A. Wofford, M. E. Eliades, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

Erratum

Determination Of Dissociation Energies And Thermal Functions Of Hydrogen‐Bond Formation Using High Resolution Ftir Spectroscopy, B. A. Wofford, M. E. Eliades, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

A technique which employs high resolution Fourier transform infrared spectroscopy is demonstrated for evaluation of hydrogen bonddissociation energiesD ₀ and D _e . Results for HCN‐‐HF give a D ₀=20.77(22) and D _e =28.77(45) kJ/mol which are compared with previously determined values obtained from microwave absolute intensity measurements and a b i n i t i o molecular orbital calculations. Rovibrational band information available for HCN‐‐HF also permits evaluation of thermal functions of dimer formation in kJ/mol: ΔU ^○ _298.2 =20.1(2), ΔH ^○ _298.2 =22.6(2), ΔG ^○ _298.2 =59.4(2), ΔS ^○ _298.2 =−0.1235.

Molecular Dynamics In Hydrogen‐Bonded Interactions: A Preliminary Experimentally Determined Harmonic Stretching Force Field For Hcn‐‐‐Hf, B. A. Wofford, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

Observation of the 2ν₁ overtone band in the hydrogen‐bonded complex HCN‐‐‐HF permits evaluation of the anharmonicity constant X _{1 1}=−116.9(1) cm^{− 1} and determination of the anharmonicity corrected fundamental frequency ω₁. This information, and available data from previous rovibrational analyses in the common and perdeuterated isotopic species of HCN‐‐‐HF, offer an opportunity for calculation of an approximate stretching harmonic force field. With the assumptions f _{1 2}=f _{2 4}=0.0, the remaining force constants (in mdyn/Å) are evaluated as: f _{1 1}=8.600(20), f _{2 2}=6.228(9), f _{3 3}=19.115(40), f _{4 …}

Preliminary Rovibrational Analysis Of The Nν6+Ν1−Nν6 Vibration In Hcn⋅⋅⋅Hf, E. Kyrö, K. Mcmillan, M. Eliades, D. Danzeiser, P. Shoja-Chaghervand, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

A preliminary rotation‐vibration analysis of the n=0 and n=1 subbands associated with the nν₆+ν₁−nν₆ hydrogen‐bonded vibration in HCN⋅⋅⋅HF has been completed. The following excited staterotational constantsB′ and band origin frequencies ν₀ have been determined for the complex. The results are consistent with a rotation‐vibration interaction constant α₁=−68.3±1 MHz which correlates with an excited stater(N⋅⋅⋅F) internuclear distance of 2.762 Å, a decrease of 0.034 Å relative to the ground state.Excited state lifetimes associated with assigned transitions are demonstrated to be …

Travelling-Wave Sub-Doppler Excited Molecule Energy Transfer Spectroscopy, Khalid Iqbal, Shannon G. Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

A general formulation of traveling‐wave sub‐Doppler excited molecule energy transferspectroscopy is presented. The line profile analysis is applied to that determined experimentally for the R(22) ν3 HCN transition. Pn the noise equivalent power of the detector is demonstrated to be ⩽10−12 W. Finally, the technique is applied to resolve the KsR(7) ν1 transition head in NH3.

Investigation Of The Alpha-Sub-Gamma Phase In Alnico 6, Cortez Samuel

Dissertations and Theses

The purpose of this research project was to study the αᵧ phase in Alnico 6. Other phases were studies for comparison. Also the effect of an applied magnetic field on the formation of the αᵧ phase was investigated.

Three single crystals of Alnico 6 were heat treated for one hour--one at 1250°C, one at 1000°C, and one at 800°C--and water-quenched. The microstructure of each sample was observed with the optical microscope, and X-ray diffraction patterns were taken to determine the crystal structure of the phases present.

Several single crystal samples of Alnico 6 were heat treated at 1000°C and furnace-cooled. …

Radiation Damage Studies Of Libyan Desert Silica Glass, Farkhonda Hassan

Archived Theses and Dissertations

No abstract provided.

Calibration Of An X-Ray Unit As To Effective Wave-Lengths By Comparing Absorption Coefficients, Jerome James Woyci

Bachelors’ Theses

The purpose of this paper is to determine by the mass absorption coefficients of various substances, namely, aluminum, copper and iron, the effective wave-length of an X-ray beam which passes through particular thicknesses of the above materials. Since an X-ray tube does not emit a monochromatic wavelength but emits heterogeneous wave-lengths, we had to use a comparative method in order to obtain the desired results. It happens that the mass coefficient of absorption of carbon does not vary appreciably with an increase or decrease in wavelength, hence, we can use carbon as our standard or material to which we can …

The Construction And Use Of The Barrett Camera, Theresa Pauline Radermacher

Bachelors’ Theses

The study of the crystal structure of metals under various conditions of strain is at the present time the object of a great deal of scientific endeavor. A greater knowledge of the condition of strained crystals will be a tremendous aid in the future development of metallic construction for one can then predict the effect of any type of strain on a metal by the reaction of the individual crystals to that particular strain. It is the purpose of this paper to describe the construction and use of the Barrett camera which is used in experiments of this kind.