New instrumentation for micro-imaging X-ray absorption spectroscopy using optical detection methods

Poolton, Nigel; Towlson, B.M.; Hamilton, B.; Evans, D.A., (2006) 'New instrumentation for micro-imaging X-ray absorption spectroscopy using optical detection methods', Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms 246(2) pp.445-451 RAE2008

High resolution X-ray spectroscopy in fast electron transport studies

A detailed knowledge of the physical phenomena underlying the generation and the transport of fast electrons generated in high-intensity laser-matter interactions is of fundamental importance for the fast ignition scheme for inertial confinement fusion.

Here we report on an experiment carried out with the VULCAN Petawatt beam and aimed at investigating the role of collisional return currents in the dynamics of the fast electron beam. To that scope, in the experiment counter-propagating electron beams were generated by double-sided irradiation of layered target foils containing a Ti layer. The experimental results were obtained for different time delays between the two laser beams as well as for single-sided irradiation of the target foils. The main diagnostics consisted of two bent mica crystal spectrometers placed at either side of the target foil. High-resolution X-ray spectra of the Ti emission lines in the range from the Ly alpha to the K alpha line were recorded. In addition, 2D X-ray images with spectral resolution were obtained by means of a novel diagnostic technique, the energy-encoded pin-hole camera, based on the use of a pin-hole array equipped with a CCD detector working in single-photon regime. The spectroscopic measurements suggest a higher target temperature for well-aligned laser beams and a precise timing between the two beams. The experimental results are presented and compared to simulation results.

High temperature thermal stability of the HfO2/Ge (100) interface as a function of surface preparation studied by synchrotron radiation core level photo emission

High resolution soft x-ray photoemission spectroscopy (SXPS) have been used to study the high temperature thermal stability of ultra-thin atomic layer deposited (ALD) HfO2 layers (∼1 nm) on sulphur passivated and hydrofluoric acid (HF) treated germanium surfaces. The interfacial oxides which are detected for both surface preparations following HfO2 deposition can be effectively removed by annealing upto 700 °C without any evidence of chemical interaction at the HfO2/Ge interface. The estimated valence and conduction band offsets for the HfO2/Ge abrupt interface indicated that effective barriers exist to inhibit carrier injection.

Root uptake and reduction of hexavalent chromium by aquatic macrophytes as assessed by high-resolution X-ray emission

Aquatic macrophytes Salvinia auriculata, Pistia stratiotes and Eichhornia crassipes were chosen to investigate the Cr(VI) reduced by root-based biosorption in a chromium uptake experiment, using a high-resolution XRF technique. These plants were grown in hydroponics medium supplied with non-toxic Cr concentrations during a 27-day metal uptake experiment. The high-resolution Cr-K beta fluorescence spectra for dried root tissues and Cr reference material (100% Cr, Cr(2)O(3), and CrO(3)) were measured using an XRF spectrometer. For all species of aquatic plant treated with Cr(VI), the energy of the Cr-K beta(2,5) line was shifted around 8 eV below the same spectral line identified for the Cr(VI) reference, but it was also near to the line identified for the Cr(III) reference. Moreover, there was a lack of the strong Cr-K beta"" line assigned to the Cr(VI) reference material within the Cr(VI)-treated plant spectra, suggesting the reduction of Cr(VI) for other less toxic oxidation states of Cr. As all Cr-K beta spectra of root tissue species were compared, the peak energies and lineshape patterns of the Cr-K beta(2,5) line are coincident for the same aquatic plant species, when they were treated with Cr(III) and Cr(VI). Based on the experimental evidence, the Cr(VI) reduction process has happened during metal biosorption by these plants. (C) 2009 Elsevier Ltd. All rights reserved.

The gaseous environment of radio galaxies: a new perspective from high-resolution x-ray spectroscopy

It is known that massive black holes have a profound effect on the evolution of galaxies, and possibly on their formation by regulating the amount of gas available for the star formation. However, how black hole and galaxies communicate is still an open problem, depending on how much of the energy released interacts with the circumnuclear matter. In the last years, most studies of feedback have primarily focused on AGN jet/cavity systems in the most massive galaxy clusters. This thesis intends to investigate the feedback phenomena in radio--loud AGNs from a different perspective studying isolated radio galaxies, through high-resolution spectroscopy. In particular one NLRG and three BLRG are studied, searching for warm gas, both in emission and absorption, in the soft X-ray band. I show that the soft spectrum of 3C33 originates from gas photoionized by the central engine. I found for the first time WA in 3C382 and 3C390.3. I show that the observed warm emitter/absorbers is not uniform and probably located in the NLR. The detected WA is slow implying a mass outflow rate and kinetic luminosity always well below 1% the L(acc) as well as the P(jet). Finally the radio--loud properties are compared with those of type 1 RQ AGNs. A positive correlation is found between the mass outflow rate/kinetic luminosity, and the radio loudness. This seems to suggest that the presence of a radio source (the jet?) affects the distribution of the absorbing gas. Alternatively, if the gas distribution is similar in Seyferts and radio galaxies, the M(out) vs rl relation could simply indicate a major ejection of matter in the form of wind in powerful radio AGNs.

Characterization and optimization of an x-ray laser for the spectroscopy of Li-like heavy-ions

Recent developments in the theory of plasma-based collisionally excited x-ray lasers (XRL) have shown an optimization potential based on the dependence of the absorption region of the pumping laser on its angle of incidence on the plasma. For the experimental proof of this idea, a number of diagnostic schemes were developed, tested, qualified and applied. A high-resolution imaging system, yielding the keV emission profile perpendicular to the target surface, provided positions of the hottest plasma regions, interesting for the benchmarking of plasma simulation codes. The implementation of a highly efficient spectrometer for the plasma emission made it possible to gain information about the abundance of the ionization states necessary for the laser action in the plasma. The intensity distribution and deflection angle of the pump laser beam could be imaged for single XRL shots, giving access to its refraction process within the plasma. During a European collaboration campaign at the Lund Laser Center, Sweden, the optimization of the pumping laser incidence angle resulted in a reduction of the required pumping energy for a Ni-like Mo XRL, which enabled the operation at a repetition rate of 10 Hz. Using the experiences gained there, the XRL performance at the PHELIX facility, GSI Darmstadt with respect to achievable repetition rate and at wavelengths below 20 nm was significantly improved, and also important information for the development towards multi-100 eV plasma XRLs was acquired. Due to the setup improvements achieved during the work for this thesis, the PHELIX XRL system now has reached a degree of reproducibility and versatility which is sufficient for demanding applications like the XRL spectroscopy of heavy ions. In addition, a European research campaign, aiming towards plasma XRLs approaching the water-window (wavelengths below 5 nm) was initiated.

The application of X-ray photoelectron spectroscopy to clay science

Photo-electron spectroscopy as an analytical tool has only received limited interest in the field of mineral science. Photo-electron spectroscopy, together with Auger electron spectroscopy, gives information about the positions of the energy levels in atoms or molecules. Application of this technique on solid materials will result in information of the band structure of these materials. The principle of photo electron spectroscopy is rather simple: photons with certain energy (wavelength) are allowed to collide with an atom, molecule or a solid material. These photons can then interact with electrons present in the atoms and one of these electrons can be excited from its orbital resulting in a situation similar to a free electron plus a positively charged atom or molecule.

Insight into Biological Small-Molecule Activation from Enzymes, Model Complexes, and X-ray Spectroscopy

Thesis (Ph.D.)--University of Washington, 2016-08

Homo- and heteronuclear meso,meso-(E)-Ethene-1,2-diyl-Linked Diporphyrins : preparation, X-ray crystal structure, electronic absorption and emission spectra and density functional theory calculations

Homo-and heteronuclear meso,meso-(E)-ethene-1,2-diyl-linked diporphyrins have been prepared by the Suzuki coupling of porphyrinylboronates and iodovinylporphyrins. Combinations comprising 5,10,15-triphenylporphyrin (TriPP) on both ends of the ethene-1,2-diyl bridge M 210 (M 2=H 2/Ni, Ni 2, Ni/Zn, H 4, H 2Zn, Zn 2) and 5,15-bis(3,5-di-tert-butylphenyl)porphyrinato-nickel(II) on one end and H 2, Ni, and ZnTriPP on the other (M 211), enable the first studies of this class of compounds possessing intrinsic polarity. The compounds were characterized by electronic absorption and steady state emission spectra, 1H NMR spectra, and for the Ni 2 bis(TriPP) complex Ni 210, single crystal X-ray structure determination. The crystal structure shows ruffled distortions of the porphyrin rings, typical of Ni II porphyrins, and the (E)-C 2H 2 bridge makes a dihedral angle of 50° with the mean planes of the macrocycles. The result is a stepped parallel arrangement of the porphyrin rings. The dihedral angles in the solid state reflect the interplay of steric and electronic effects of the bridge on interporphyrin communication. The emission spectra in particular, suggest energy transfer across the bridge is fast in conformations in which the bridge is nearly coplanar with the rings. Comparisons of the fluorescence behaviour of H 410 and H 2Ni10 show strong quenching of the free base fluorescence when the complex is excited at the lower energy component of the Soret band, a feature associated in the literature with more planar conformations. TDDFT calculations on the gas-phase optimized geometry of Ni 210 reproduce the features of the experimental electronic absorption spectrum within 0.1 eV. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural characterization of hydrogen peroxide‐oxidized anthracites by X-ray diffraction, Fourier transform infrared spectroscopy, and Raman spectra

The structural characteristics of raw coal and hydrogen peroxide (H2O2)-oxidized coals were investigated using scanning electron microscopy, X-ray diffraction (XRD), Raman spectra, and Fourier transform infrared (FT-IR) spectroscopy. The results indicate that the derivative coals oxidized by H2O2 are improved noticeably in aromaticity and show an increase first and then a decrease up to the highest aromaticity at 24 h. The stacking layer number of crystalline carbon decreases and the aspect ratio (width versus stacking height) increases with an increase in oxidation time. The content of crystalline carbon shows the same change tendency as the aromaticity measured by XRD. The hydroxyl bands of oxidized coals become much stronger due to an increase in soluble fatty acids and alcohols as a result of the oxidation of the aromatic and aliphatic C‐H bonds. In addition, the derivative coals display a decrease first and then an increase in the intensity of aliphatic C‐H bond and present a diametrically opposite tendency in the aromatic C‐H bonds with an increase in oxidation time. There is good agreement with the changes of aromaticity and crystalline carbon content as measured by XRD and Raman spectra. The particle size of oxidized coals (<200 nm in width) shows a significant decrease compared with that of raw coal (1 μm). This study reveals that the optimal oxidation time is ∼24 h for improving the aromaticity and crystalline carbon content of H2O2-oxidized coals. This process can help us obtain superfine crystalline carbon materials similar to graphite in structure.

Pt metal-CeO2 interaction: Direct observation of redox coupling between Pt-0/Pt2+/Pt4+ and Ce4+/Ce3+ states in Ce0.98Pt0.02O2-delta catalyst by a combined electrochemical and x-ray photoelectron spectroscopy study

Pt ions-CeO2 interaction in Ce1-xPtxO2-delta (x=0.02) has been studied for the first time by electrochemical method combined with x-ray diffraction and x-ray photoelectron spectroscopy. Working electrodes made of CeO2 and Ce0.98Pt0.02O2-delta mixed with 30% carbon are treated electrochemically between 0.0-1.2 V in potentiostatic (chronoamperometry) and potentiodynamic (cyclic voltametry) mode with reference to saturated calomel electrode. Reversible oxidation of Pt-0 to Pt2+ and Pt4+ state due to the applied positive potential is coupled to simultaneous reversible reduction of Ce4+ to Ce3+ state. CeO2 reduces to CeO2-y (y=0.35) after applying 1.2 V, which is not reversible; Ce0.98Pt0.02O2-delta reaches a steady state with Pt2+:Pt4+ in the ratio of 0.60:0.40 and Ce4+:Ce3+ in the ratio of 0.55:0.45 giving a composition Ce0.98Pt0.02O1.74 at 1.2 V, which is reversible. Composition of Pt ion substituted compound is reversible between Ce0.98Pt0.02O1.95 to Ce0.98Pt0.02O1.74 within the potential range of 0.0-1.2 V. Thus, Ce0.98Pt0.02O2-delta forms a stable electrode for oxidation of H2O to O-2 unlike CeO2. A linear relation between oxidation of Pt2+ to Pt4+ with simultaneous reduction in Ce4+ to Ce3+ is observed demonstrating Pt-CeO2 metal support interaction is due to reversible Pt-0/Pt2+/Pt4+ interaction with Ce4+/Ce3+ redox couple.

X-ray and ultraviolet photoelectron spectroscopy studies of the interaction of carbon monoxide with oxygen adsorbed on silver covered with potassium, caesium or barium

X-ray and He(II) ultraviolet photoelectron spectroscopy studies of the interaction of CO with oxygen on potassium-, caesium- and barium-covered Ag surfaces have shown the formation of carbonate at 300 K. While on a caesium-covered surface only carbonate formation takes place, on the potassium- and barium-covered surfaces molecularly chemisorbed CO is also formed. The variation of the surface concentrations of carbon and oxygen with temperature has been examined and a reaction sequence for the interaction of CO with adsorbed oxygen on potassium-, caesium- and barium-covered Ag surfaces is suggested.

X-ray spectroscopic study of chromium, nickel, and molybdenum compounds

Chemical shifts in the K-absorption edges, AE, of a series of chromium, nickel, and molybdenum compounds have been investigated. The AE values in a given series vary in the same direction as the metal-core-level binding energies obtained from X-ray photoelectron spectroscopy. The AI3 values are related to the effective atomic charge of the metal by a parabolic relation. In the case of molybdenum compounds, the chemical shifts of the K, emission lines vary in the same manner as M.

Study of strontium compounds and minerals by X-ray absorption spectroscopy. I. K-edge shifts

The chemical shifts in the X-ray K-absorption edge of strontium in various compounds and in six minerals are measured using a single crystal X-ray spectrometer. Besides valence, the shifts are found to be governed by ionic charges on the absorbing ions, which are calculated employing Pauling's method. For the minerals the plot of chemical shift against the theoretically calculated ionic charges is used to determine the charges on the strontium ions.