Soft X-ray spectroscopy of nanoparticles by velocity map imaging

DOE PAGES

Kostko, O.; Xu, B.; Jacobs, M. I.; ...

2017-05-05

Velocity map imaging (VMI), a technique traditionally used to study chemical dynamics in the gas phase, is applied to study X-ray photoemission from aerosol nanoparticles. Soft X-rays from the Advanced Light Source synchrotron, probe a beam of nanoparticles, and the resulting photoelectrons are velocity mapped to obtain their kinetic energy distributions. A new design of the VMI spectrometer is described. The spectrometer is benchmarked by measuring vacuum ultraviolet photoemission from gas phase xenon and squalene nanoparticles followed by measurements using soft X-rays. It is demonstrated that the photoelectron distribution from X-ray irradiated squalene nanoparticles is dominated by secondary electrons. Bymore » scanning the photon energies and measuring the intensities of these secondary electrons, a near edge X-ray absorption fine structure (NEXAFS) spectrum is obtained. The NEXAFS technique is used to obtain spectra of aqueous nanoparticles at the oxygen K edge. By varying the position of the aqueous nanoparticle beam relative to the incident X-ray beam, evidence is presented such that the VMI technique allows for NEXAFS spectroscopy of water in different physical states. Finally, we discuss the possibility of applying VMI methods to probe liquids and solids via X-ray spectroscopy.« less

Optimizing soft X-ray NEXAFS spectroscopy in the laboratory

NASA Astrophysics Data System (ADS)

Mantouvalou, I.; Jonas, A.; Witte, K.; Jung, R.; Stiel, H.; Kanngießer, B.

2017-05-01

Near edge X-ray absorption fine structure (NEXAFS) spectroscopy in the soft X-ray range is feasible in the laboratory using laser-produced plasma sources. We present a study using seven different target materials for optimized data analysis. The emission spectra of the materials with atomic numbers ranging from Z = 6 to Z = 79 show distinct differences, rendering the adapted selection of a suitable target material for specialized experiments feasible. For NEXAFS spectroscopy a 112.5 nm thick polyimide film is investigated as a reference exemplifying the superiority of quasi-continuum like emission spectra.

X-ray astronomical spectroscopy

NASA Technical Reports Server (NTRS)

Holt, Stephen S.

1987-01-01

The contributions of the Goddard group to the history of X-ray astronomy are numerous and varied. One role that the group has continued to play involves the pursuit of techniques for the measurement and interpretation of the X-ray spectra of cosmic sources. The latest development is the selection of the X-ray microcalorimeter for the Advanced X-ray Astrophysics Facility (AXAF) study payload. This technology is likely to revolutionize the study of cosmic X-ray spectra.

Recent applications of hard x-ray photoelectron spectroscopy

DOE PAGES

Weiland, Conan; Rumaiz, Abdul K.; Pianetta, Piero; ...

2016-05-05

Recent applications of hard x-ray photoelectron spectroscopy (HAXPES) demonstrate its many capabilities in addition to several of its limitations. Examples are given, including measurement of buried interfaces and materials under in-situ or in-operando conditions, as well as measurements under x-ray standing-wave and resonant excitation. We also present physical considerations that differentiate HAXPES from photoemission measurements utilizing soft and ultraviolet x rays.

Hard X-ray imaging spectroscopy of FOXSI microflares

NASA Astrophysics Data System (ADS)

Glesener, Lindsay; Krucker, Sam; Christe, Steven; Buitrago-Casas, Juan Camilo; Ishikawa, Shin-nosuke; Foster, Natalie

2015-04-01

The ability to investigate particle acceleration and hot thermal plasma in solar flares relies on hard X-ray imaging spectroscopy using bremsstrahlung emission from high-energy electrons. Direct focusing of hard X-rays (HXRs) offers the ability to perform cleaner imaging spectroscopy of this emission than has previously been possible. Using direct focusing, spectra for different sources within the same field of view can be obtained easily since each detector segment (pixel or strip) measures the energy of each photon interacting within that segment. The Focusing Optics X-ray Solar Imager (FOXSI) sounding rocket payload has successfully completed two flights, observing microflares each time. Flare images demonstrate an instrument imaging dynamic range far superior to the indirect methods of previous instruments like the RHESSI spacecraft.In this work, we present imaging spectroscopy of microflares observed by FOXSI in its two flights. Imaging spectroscopy performed on raw FOXSI images reveals the temperature structure of flaring loops, while more advanced techniques such as deconvolution of the point spread function produce even more detailed images.

Soft X-ray absorption spectroscopy and resonant inelastic X-ray scattering spectroscopy below 100 eV: probing first-row transition-metal M-edges in chemical complexes

PubMed Central

Wang, Hongxin; Young, Anthony T.; Guo, Jinghua; Cramer, Stephen P.; Friedrich, Stephan; Braun, Artur; Gu, Weiwei

2013-01-01

X-ray absorption and scattering spectroscopies involving the 3d transition-metal K- and L-edges have a long history in studying inorganic and bioinorganic molecules. However, there have been very few studies using the M-edges, which are below 100 eV. Synchrotron-based X-ray sources can have higher energy resolution at M-edges. M-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) could therefore provide complementary information to K- and L-edge spectroscopies. In this study, M 2,3-edge XAS on several Co, Ni and Cu complexes are measured and their spectral information, such as chemical shifts and covalency effects, are analyzed and discussed. In addition, M 2,3-edge RIXS on NiO, NiF2 and two other covalent complexes have been performed and different d–d transition patterns have been observed. Although still preliminary, this work on 3d metal complexes demonstrates the potential to use M-edge XAS and RIXS on more complicated 3d metal complexes in the future. The potential for using high-sensitivity and high-resolution superconducting tunnel junction X-ray detectors below 100 eV is also illustrated and discussed. PMID:23765304

X-ray-induced photo-chemistry and X-ray absorption spectroscopy of biological samples

PubMed Central

George, Graham N.; Pickering, Ingrid J.; Pushie, M. Jake; Nienaber, Kurt; Hackett, Mark J.; Ascone, Isabella; Hedman, Britt; Hodgson, Keith O.; Aitken, Jade B.; Levina, Aviva; Glover, Christopher; Lay, Peter A.

2012-01-01

As synchrotron light sources and optics deliver greater photon flux on samples, X-ray-induced photo-chemistry is increasingly encountered in X-ray absorption spectroscopy (XAS) experiments. The resulting problems are particularly pronounced for biological XAS experiments. This is because biological samples are very often quite dilute and therefore require signal averaging to achieve adequate signal-to-noise ratios, with correspondingly greater exposures to the X-ray beam. This paper reviews the origins of photo-reduction and photo-oxidation, the impact that they can have on active site structure, and the methods that can be used to provide relief from X-ray-induced photo-chemical artifacts. PMID:23093745

X-ray absorption fine structure (XAFS) spectroscopy using synchrotron radiation

NASA Astrophysics Data System (ADS)

Shrivastava, B. D.

2012-05-01

The X-ray absorption fine structure (XAFS) spectra are best recorded when a highly intense beam of X-rays from a synchrotron is used along with a good resolution double crystal or curved crystal spectrometer and detectors like ionization chambers, scintillation counters, solid state detectors etc. Several synchrotrons around the world have X-ray beamlines dedicated specifically to XAFS spectroscopy. Fortunately, the Indian synchrotron (Indus-2) at Raja Ramanna Centre for Advanced Technology (RRCAT) at Indore has started operation. A dispersive type EXAFS beamline called BL-8 has been commissioned at this synchrotron and another beamline having double crystal monochromator (DCM) is going to be commissioned shortly. In Indian context, in order that more research workers use these beamlines, the study of XAFS spectroscopy using synchrotron radiation becomes important. In the present work some of the works done by our group on XAFS spectroscopy using synchrotron radiation have been described.

In situ/Operando studies of electrocatalysts using hard X-ray spectroscopy

DOE PAGES

Lassalle-Kaiser, Benedikt; Gul, Sheraz; Kern, Jan; ...

2017-05-02

This review focuses on the use of X-ray absorption and emission spectroscopy techniques using hard X-rays to study electrocatalysts under in situ/operando conditions. The importance and the versatility of methods in the study of electrodes in contact with the electrolytes are described, when they are being cycled through the catalytic potentials during the progress of the oxygen-evolution, oxygen reduction and hydrogen evolution reactions. The catalytic oxygen evolution reaction is illustrated with examples using three oxides, Co, Ni and Mn, and two sulfides, Mo and Co. These are used as examples for the hydrogen evolution reaction. A bimetallic, bifunctional oxygen evolvingmore » and oxygen reducing Ni/Mn oxide is also presented. The various advantages and constraints in the use of these techniques and the future outlook are discussed.« less

Structural studies of homoisoflavonoids: NMR spectroscopy, X-ray diffraction, and theoretical calculations

NASA Astrophysics Data System (ADS)

Sievänen, Elina; Toušek, Jaromír; Lunerová, Kamila; Marek, Jaromír; Jankovská, Dagmar; Dvorská, Margita; Marek, Radek

2010-08-01

In this article we present a detailed structural investigation for five homoisoflavonoids, molecules important from the pharmacological point of view. For studying the electron distribution as well as its influence on the physicochemical properties, NMR spectroscopy, X-ray diffraction, and theoretical calculations have been used. Nuclear magnetic shieldings obtained by using DFT calculations for optimized molecular geometries are correlated with the experimentally determined chemical shifts. The theoretical data are well in agreement with the experimental values. The single crystal X-ray structures of homoisoflavonoid derivatives 1, 3, and 4 have been solved. The molecular geometries and crystal packing determined by X-ray diffraction are used for characterizing the intermolecular interactions. Electron distribution is crucial for the stability of radicals and hence the antioxidant efficiency of flavonoid structures. The hydrogen bonding governs the formation of complexes of homoisoflavonoids with biological targets.

Photon statistics and speckle visibility spectroscopy with partially coherent X-rays.

PubMed

Li, Luxi; Kwaśniewski, Paweł; Orsi, Davide; Wiegart, Lutz; Cristofolini, Luigi; Caronna, Chiara; Fluerasu, Andrei

2014-11-01

A new approach is proposed for measuring structural dynamics in materials from multi-speckle scattering patterns obtained with partially coherent X-rays. Coherent X-ray scattering is already widely used at high-brightness synchrotron lightsources to measure dynamics using X-ray photon correlation spectroscopy, but in many situations this experimental approach based on recording long series of images (i.e. movies) is either not adequate or not practical. Following the development of visible-light speckle visibility spectroscopy, the dynamic information is obtained instead by analyzing the photon statistics and calculating the speckle contrast in single scattering patterns. This quantity, also referred to as the speckle visibility, is determined by the properties of the partially coherent beam and other experimental parameters, as well as the internal motions in the sample (dynamics). As a case study, Brownian dynamics in a low-density colloidal suspension is measured and an excellent agreement is found between correlation functions measured by X-ray photon correlation spectroscopy and the decay in speckle visibility with integration time obtained from the analysis presented here.

Development of Compton X-ray spectrometer for high energy resolution single-shot high-flux hard X-ray spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kojima, Sadaoki, E-mail: kojima-s@ile.osaka-u.ac.jp, E-mail: sfujioka@ile.osaka-u.ac.jp; Ikenouchi, Takahito; Arikawa, Yasunobu

Hard X-ray spectroscopy is an essential diagnostics used to understand physical processes that take place in high energy density plasmas produced by intense laser-plasma interactions. A bundle of hard X-ray detectors, of which the responses have different energy thresholds, is used as a conventional single-shot spectrometer for high-flux (>10{sup 13} photons/shot) hard X-rays. However, high energy resolution (Δhv/hv < 0.1) is not achievable with a differential energy threshold (DET) X-ray spectrometer because its energy resolution is limited by energy differences between the response thresholds. Experimental demonstration of a Compton X-ray spectrometer has already been performed for obtaining higher energy resolutionmore » than that of DET spectrometers. In this paper, we describe design details of the Compton X-ray spectrometer, especially dependence of energy resolution and absolute response on photon-electron converter design and its background reduction scheme, and also its application to the laser-plasma interaction experiment. The developed spectrometer was used for spectroscopy of bremsstrahlung X-rays generated by intense laser-plasma interactions using a 200 μm thickness SiO{sub 2} converter. The X-ray spectrum obtained with the Compton X-ray spectrometer is consistent with that obtained with a DET X-ray spectrometer, furthermore higher certainly of a spectral intensity is obtained with the Compton X-ray spectrometer than that with the DET X-ray spectrometer in the photon energy range above 5 MeV.« less

Extracting chemical information from high-resolution Kβ X-ray emission spectroscopy

NASA Astrophysics Data System (ADS)

Limandri, S.; Robledo, J.; Tirao, G.

2018-06-01

High-resolution X-ray emission spectroscopy allows studying the chemical environment of a wide variety of materials. Chemical information can be obtained by fitting the X-ray spectra and observing the behavior of some spectral features. Spectral changes can also be quantified by means of statistical parameters calculated by considering the spectrum as a probability distribution. Another possibility is to perform statistical multivariate analysis, such as principal component analysis. In this work the performance of these procedures for extracting chemical information in X-ray emission spectroscopy spectra for mixtures of Mn2+ and Mn4+ oxides are studied. A detail analysis of the parameters obtained, as well as the associated uncertainties is shown. The methodologies are also applied for Mn oxidation state characterization of double perovskite oxides Ba1+xLa1-xMnSbO6 (with 0 ≤ x ≤ 0.7). The results show that statistical parameters and multivariate analysis are the most suitable for the analysis of this kind of spectra.

A whole-system approach to x-ray spectroscopy in cargo inspection systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Langeveld, Willem G. J.; Gozani, Tsahi; Ryge, Peter

The bremsstrahlung x-ray spectrum used in high-energy, high-intensity x-ray cargo inspection systems is attenuated and modified by the materials in the cargo in a Z-dependent way. Therefore, spectroscopy of the detected x rays yields information about the Z of the x-rayed cargo material. It has previously been shown that such ZSpectroscopy (Z-SPEC) is possible under certain circumstances. A statistical approach, Z-SCAN (Z-determination by Statistical Count-rate ANalysis), has also been shown to be effective, and it can be used either by itself or in conjunction with Z-SPEC when the x-ray count rate is too high for individual x-ray spectroscopy. Both techniquesmore » require fast x-ray detectors and fast digitization electronics. It is desirable (and possible) to combine all techniques, including x-ray imaging of the cargo, in a single detector array, to reduce costs, weight, and overall complexity. In this paper, we take a whole-system approach to x-ray spectroscopy in x-ray cargo inspection systems, and show how the various parts interact with one another. Faster detectors and read-out electronics are beneficial for both techniques. A higher duty-factor x-ray source allows lower instantaneous count rates at the same overall x-ray intensity, improving the range of applicability of Z-SPEC in particular. Using an intensity-modulated advanced x-ray source (IMAXS) allows reducing the x-ray count rate for cargoes with higher transmission, and a stacked-detector approach may help material discrimination for the lowest attenuations. Image processing and segmentation allow derivation of results for entire objects, and subtraction of backgrounds. We discuss R and D performed under a number of different programs, showing progress made in each of the interacting subsystems. We discuss results of studies into faster scintillation detectors, including ZnO, BaF{sub 2} and PbWO{sub 4}, as well as suitable photo-detectors, read-out and digitization electronics. We discuss high

Mode-Locked Multichromatic X-Rays in a Seeded Free-Electron Laser for Single-Shot X-Ray Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiang, Dao; Ding, Yuantao; Raubenheimer, Tor

2012-05-10

We present the promise of generating gigawatt mode-locked multichromatic x rays in a seeded free-electron laser (FEL). We show that, by using a laser to imprint periodic modulation in electron beam phase space, a single-frequency coherent seed can be amplified and further translated to a mode-locked multichromatic output in an FEL. With this configuration the FEL output consists of a train of mode-locked ultrashort pulses which span a wide frequency gap with a series of equally spaced sharp lines. These gigawatt multichromatic x rays may potentially allow one to explore the structure and dynamics of a large number of atomicmore » states simultaneously. The feasibility of generating mode-locked x rays ranging from carbon K edge ({approx}284 eV) to copper L{sub 3} edge ({approx}931 eV) is confirmed with numerical simulation using the realistic parameters of the linac coherent light source (LCLS) and LCLS-II. We anticipate that the mode-locked multichromatic x rays in FELs may open up new opportunities in x-ray spectroscopy (i.e. resonant inelastic x-ray scattering, time-resolved scattering and spectroscopy, etc.).« less

Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and Emission Spectroscopy Study

DOE PAGES

Chuang, Cheng-Hao; Ray, Sekhar C.; Mazumder, Debarati; ...

2017-02-10

Nitrogen-doped graphene oxides (GO:N x) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH 2) 2 ]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:N x synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at%), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at%) graphitic nitrogen was formed in whichmore » each N-atom trigonally bonds to three distinct sp 2 -hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:N x . The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements.« less

X-ray Photoelectron Spectroscopy study of CaV1-xMoxO3-δ

NASA Astrophysics Data System (ADS)

Belyakov, S. A.; Kuznetsov, M. V.; Shkerin, S. N.

2018-06-01

An investigation was carried out on perovskite-based derivatives of CaV1-xMoxO3-δ using X-ray Photoelectron Spectroscopy (XPS). According to the XRD pattern, the area of homogeneity covers the region from x = 0 to x = 0.6. Wide XPS-peaks of Ca, V, Mo and O are observed, signalling that elements are presented in multiple states. A model for explaining the large chemical shifts of XPS peaks due to different charging effects on different parts of the sample surface is proposed.

X-Ray photoelectron Spectroscopy Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Engelhard, Mark H.; Droubay, Timothy C.; Du, Yingge

2017-01-03

With capability for obtaining quantitative elemental composition, chemical and electronic state, and overlayer thickness information from the top ~10 nm of a sample surface, X-ray Photoelectron Spectroscopy (XPS) or Electron Spectroscopy for Chemical Analysis (ESCA) is a versatile and widely used technique for analyzing surfaces. The technique is applied to a host of materials, from insulators to conductors in virtually every scientific field and sub-discipline. More recently, XPS has been extended under in-situ and operando conditions. Following a brief introduction to XPS principles and instrument components, this article exemplifies widely ranging XPS applications in material and life sciences.

X-Ray spectroscopy of cooling flows

NASA Technical Reports Server (NTRS)

Prestwich, Andrea

1996-01-01

Cooling flows in clusters of galaxies occur when the cooling time of the gas is shorter than the age of the cluster; material cools and falls to the center of the cluster potential. Evidence for short X-ray cooling times comes from imaging studies of clusters and X-ray spectroscopy of a few bright clusters. Because the mass accretion rate can be high (a few 100 solar mass units/year) the mass of material accumulated over the lifetime of a cluster can be as high as 10(exp 12) solar mass units. However, there is little evidence for this material at other wavelengths, and the final fate of the accretion material is unknown. X-ray spectra obtained with the Einstein SSS show evidence for absorption; if confirmed this result would imply that the accretion material is in the form of cool dense clouds. However ice on the SSS make these data difficult to interpret. We obtained ASCA spectra of the cooling flow cluster Abell 85. Our primary goals were to search for multi-temperature components that may be indicative of cool gas; search for temperature gradients across the cluster; and look for excess absorption in the cooling region.

Extended x-ray absorption fine structure spectroscopy and x-ray absorption near edge spectroscopy study of aliovalent doped ceria to correlate local structural changes with oxygen vacancies clustering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shirbhate, S. C.; Acharya, S. A., E-mail: saha275@yahoo.com; Yadav, A. K.

2016-04-04

This study provides atomic scale insight to understand the role of aliovalent dopants on oxygen vacancies clustering and dissociation mechanism in ceria system in order to enhance the performance of oxy-ion conductor. Dopants induced microscale changes in ceria are probed by extended X-ray absorption fine structure spectroscopy, X-ray absorption near edge spectra, and Raman spectroscopy. The results are explored to establish a correlation between atomic level structural changes (coordination number, interatomic spacing) → formation of dimer and trimer type cation-oxygen vacancies defect complex (intrinsic and extrinsic) → dissociation of oxygen vacancies from defect cluster → ionic conductivity temperature. It ismore » a strategic approach to understand key physics of ionic conductivity mechanism in order to reduce operating temperature of electrolytes for intermediate temperature (300–450 °C) electrochemical devices for the first time.« less

A structural study of bone changes in knee osteoarthritis by synchrotron-based X-ray fluorescence and X-ray absorption spectroscopy techniques

NASA Astrophysics Data System (ADS)

Sindhupakorn, Bura; Thienpratharn, Suwittaya; Kidkhunthod, Pinit

2017-10-01

Osteoarthritis (OA) is characterized by degeneration of articular cartilage and thickening of subchondral bone. The present study investigated the changing of biochemical components of cartilage and bone compared between normal and OA people. Using Synchrotron-based X-ray fluorescence (SR-XRF) and X-ray absorption spectroscopy (XAS) techniquesincluding X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) were employed for the bone changes in kneeosteoarthritisstudies. The bone samples were collected from various osteoarthritis patients with both male and female in the ages range between 20 and 74 years old. SR-XRF results excited at 4240 eV for Ca elements show a majority three main groups, based on their XRF intensities, 20-36 years, 40-60 years and over 70 years, respectively. By employing XAS techniques, XANES features can be used to clearly explain in term of electronic transitions occurring in bone samples which are affected from osteoarthritis symptoms. Moreover, a structural change around Ca ions in bone samples is obviously obtained by EXAFS results indicating an increase of Ca-amorphous phase when the ages increase.

Stimulated x-ray emission spectroscopy in transition metal complexes

DOE PAGES

Kroll, Thomas; Weninger, Clemens; Alonso-Mori, Roberto; ...

2018-03-27

We report the observation and analysis of the gain curve of amplified Kα X-ray emission from solutions of Mn(II) and Mn(VII) complexes using an X-ray free electron laser to create the 1s core-hole population inversion. We find spectra at amplification levels extending over four orders of magnitude until saturation. We observe bandwidths below the Mn 1s core-hole lifetime broadening in the onset of the stimulated emission. In the exponential amplification regime the resolution corrected spectral width of ~1.7 eV FWHM is constant over three orders of magnitude, pointing to the build-up of transform limited pulses of ~1fs duration. Driving the amplification into saturation leads to broadening and shift of the line. Importantly, the chemical sensitivity of the stimulated X-ray emission to the Mn oxidation state is preserved at power densities ofmore » $$\\sim10 20$$~W/cm 2 for the incoming X-ray pulses. Differences in signal sensitivity and spectral information compared to conventional (spontaneous) X-ray emission spectroscopy are discussed. Our findings build a baseline for nonlinear X-ray spectroscopy for a wide range of transition metal complexes in inorganic chemistry, catalysis and materials science.« less

Stimulated x-ray emission spectroscopy in transition metal complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kroll, Thomas; Weninger, Clemens; Alonso-Mori, Roberto

We report the observation and analysis of the gain curve of amplified Kα X-ray emission from solutions of Mn(II) and Mn(VII) complexes using an X-ray free electron laser to create the 1s core-hole population inversion. We find spectra at amplification levels extending over four orders of magnitude until saturation. We observe bandwidths below the Mn 1s core-hole lifetime broadening in the onset of the stimulated emission. In the exponential amplification regime the resolution corrected spectral width of ~1.7 eV FWHM is constant over three orders of magnitude, pointing to the build-up of transform limited pulses of ~1fs duration. Driving the amplification into saturation leads to broadening and shift of the line. Importantly, the chemical sensitivity of the stimulated X-ray emission to the Mn oxidation state is preserved at power densities ofmore » $$\\sim10 20$$~W/cm 2 for the incoming X-ray pulses. Differences in signal sensitivity and spectral information compared to conventional (spontaneous) X-ray emission spectroscopy are discussed. Our findings build a baseline for nonlinear X-ray spectroscopy for a wide range of transition metal complexes in inorganic chemistry, catalysis and materials science.« less

Stimulated X-Ray Emission Spectroscopy in Transition Metal Complexes

NASA Astrophysics Data System (ADS)

Kroll, Thomas; Weninger, Clemens; Alonso-Mori, Roberto; Sokaras, Dimosthenis; Zhu, Diling; Mercadier, Laurent; Majety, Vinay P.; Marinelli, Agostino; Lutman, Alberto; Guetg, Marc W.; Decker, Franz-Josef; Boutet, Sébastien; Aquila, Andy; Koglin, Jason; Koralek, Jake; DePonte, Daniel P.; Kern, Jan; Fuller, Franklin D.; Pastor, Ernest; Fransson, Thomas; Zhang, Yu; Yano, Junko; Yachandra, Vittal K.; Rohringer, Nina; Bergmann, Uwe

2018-03-01

We report the observation and analysis of the gain curve of amplified K α x-ray emission from solutions of Mn(II) and Mn(VII) complexes using an x-ray free electron laser to create the 1 s core-hole population inversion. We find spectra at amplification levels extending over 4 orders of magnitude until saturation. We observe bandwidths below the Mn 1 s core-hole lifetime broadening in the onset of the stimulated emission. In the exponential amplification regime the resolution corrected spectral width of ˜1.7 eV FWHM is constant over 3 orders of magnitude, pointing to the buildup of transform limited pulses of ˜1 fs duration. Driving the amplification into saturation leads to broadening and a shift of the line. Importantly, the chemical sensitivity of the stimulated x-ray emission to the Mn oxidation state is preserved at power densities of ˜1020 W /cm2 for the incoming x-ray pulses. Differences in signal sensitivity and spectral information compared to conventional (spontaneous) x-ray emission spectroscopy are discussed. Our findings build a baseline for nonlinear x-ray spectroscopy for a wide range of transition metal complexes in inorganic chemistry, catalysis, and materials science.

Probing molecular dynamics in solution with x-ray valence-to-core spectroscopy

NASA Astrophysics Data System (ADS)

Doumy, Gilles; March, Anne Marie; Tu, Ming-Feng; Al Haddad, Andre; Southworth, Stephen; Young, Linda; Walko, Donald; Bostedt, Christoph

2017-04-01

Hard X-ray spectroscopies are powerful tools for probing the electronic and geometric structure of molecules in complex or disordered systems and have been particularly useful for studying molecules in the solution phase. They are element specific, sensitive to the electronic structure and the local arrangements of surrounding atoms of the element being selectively probed. When combined in a pump-probe scheme with ultrafast lasers, X-ray spectroscopies can be used to track the evolution of structural changes that occur after photoexcitation. Efficient use of hard x-ray radiation coming from high brilliance synchrotrons and upcoming high repetition rate X-ray Free Electron Lasers requires MHz repetition rate lasers and data acquisition systems. High information content Valence-to-Core x-ray emission is directly sensitive to the molecular orbitals involved in photochemistry. We report on recent progress towards fully enabling this photon-hungry technique for the study of time-resolved molecular dynamics, including efficient detection and use of polychromatic x-ray micro-probe at the Advanced Photon Source. Work was supported by the U.S. Department of Energy, Office of Science, Chemical Sciences, Geosciences, and Biosciences Division.

Soft x-ray spectroscopy of high pressure liquid.

PubMed

Qiao, Ruimin; Xia, Yujian; Feng, Xuefei; Macdougall, James; Pepper, John; Armitage, Kevin; Borsos, Jason; Knauss, Kevin G; Lee, Namhey; Allézy, Arnaud; Gilbert, Benjamin; MacDowell, Alastair A; Liu, Yi-Sheng; Glans, Per-Anders; Sun, Xuhui; Chao, Weilun; Guo, Jinghua

2018-01-01

We describe a new experimental technique that allows for soft x-ray spectroscopy studies (∼100-1000 eV) of high pressure liquid (∼100 bars). We achieve this through a liquid cell with a 100 nm-thick Si 3 N 4 membrane window, which is sandwiched by two identical O-rings for vacuum sealing. The thin Si 3 N 4 membrane allows soft x-rays to penetrate, while separating the high-pressure liquid under investigation from the vacuum required for soft x-ray transmission and detection. The burst pressure of the Si 3 N 4 membrane increases with decreasing size and more specifically is inversely proportional to the side length of the square window. It also increases proportionally with the membrane thickness. Pressures > 60 bars could be achieved for 100 nm-thick square Si 3 N 4 windows that are smaller than 65 μm. However, above a certain pressure, the failure of the Si wafer becomes the limiting factor. The failure pressure of the Si wafer is sensitive to the wafer thickness. Moreover, the deformation of the Si 3 N 4 membrane is quantified using vertical scanning interferometry. As an example of the performance of the high-pressure liquid cell optimized for total-fluorescence detected soft x-ray absorption spectroscopy (sXAS), the sXAS spectra at the Ca L edge (∼350 eV) of a CaCl 2 aqueous solution are collected under different pressures up to 41 bars.

Soft x-ray spectroscopy of high pressure liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qiao, Ruimin; Xia, Yujian; Feng, Xuefei

Here, we describe a new experimental technique that allows for soft x-ray spectroscopy studies (~100-1000 eV) of high pressure liquid (~100 bars). We achieve this through a liquid cell with a 100 nm-thick Si 3N 4 membrane window, which is sandwiched by two identical O-rings for vacuum sealing. The thin Si 3N 4 membrane allows soft x-rays to penetrate, while separating the high-pressure liquid under investigation from the vacuum required for soft x-ray transmission and detection. The burst pressure of the Si 3N 4 membrane increases with decreasing size and more specifically is inversely proportional to the side length ofmore » the square window. It also increases proportionally with the membrane thickness. Pressures > 60 bars could be achieved for 100 nm-thick square Si 3N 4 windows that are smaller than 65 μm. However, above a certain pressure, the failure of the Si wafer becomes the limiting factor. The failure pressure of the Si wafer is sensitive to the wafer thickness. Moreover, the deformation of the Si 3N 4 membrane is quantified using vertical scanning interferometry. As an example of the performance of the high-pressure liquid cell optimized for total-fluorescence detected soft x-ray absorption spectroscopy (sXAS), the sXAS spectra at the Ca L edge (~350 eV) of a CaCl 2 aqueous solution are collected under different pressures up to 41 bars.« less

Soft x-ray spectroscopy of high pressure liquid

DOE PAGES

Qiao, Ruimin; Xia, Yujian; Feng, Xuefei; ...

2018-01-01

Here, we describe a new experimental technique that allows for soft x-ray spectroscopy studies (~100-1000 eV) of high pressure liquid (~100 bars). We achieve this through a liquid cell with a 100 nm-thick Si 3N 4 membrane window, which is sandwiched by two identical O-rings for vacuum sealing. The thin Si 3N 4 membrane allows soft x-rays to penetrate, while separating the high-pressure liquid under investigation from the vacuum required for soft x-ray transmission and detection. The burst pressure of the Si 3N 4 membrane increases with decreasing size and more specifically is inversely proportional to the side length ofmore » the square window. It also increases proportionally with the membrane thickness. Pressures > 60 bars could be achieved for 100 nm-thick square Si 3N 4 windows that are smaller than 65 μm. However, above a certain pressure, the failure of the Si wafer becomes the limiting factor. The failure pressure of the Si wafer is sensitive to the wafer thickness. Moreover, the deformation of the Si 3N 4 membrane is quantified using vertical scanning interferometry. As an example of the performance of the high-pressure liquid cell optimized for total-fluorescence detected soft x-ray absorption spectroscopy (sXAS), the sXAS spectra at the Ca L edge (~350 eV) of a CaCl 2 aqueous solution are collected under different pressures up to 41 bars.« less

Hetero-site-specific X-ray pump-probe spectroscopy for femtosecond intramolecular dynamics

PubMed Central

Picón, A.; Lehmann, C. S.; Bostedt, C.; Rudenko, A.; Marinelli, A.; Osipov, T.; Rolles, D.; Berrah, N.; Bomme, C.; Bucher, M.; Doumy, G.; Erk, B.; Ferguson, K. R.; Gorkhover, T.; Ho, P. J.; Kanter, E. P.; Krässig, B.; Krzywinski, J.; Lutman, A. A.; March, A. M.; Moonshiram, D.; Ray, D.; Young, L.; Pratt, S. T.; Southworth, S. H.

2016-01-01

New capabilities at X-ray free-electron laser facilities allow the generation of two-colour femtosecond X-ray pulses, opening the possibility of performing ultrafast studies of X-ray-induced phenomena. Particularly, the experimental realization of hetero-site-specific X-ray-pump/X-ray-probe spectroscopy is of special interest, in which an X-ray pump pulse is absorbed at one site within a molecule and an X-ray probe pulse follows the X-ray-induced dynamics at another site within the same molecule. Here we show experimental evidence of a hetero-site pump-probe signal. By using two-colour 10-fs X-ray pulses, we are able to observe the femtosecond time dependence for the formation of F ions during the fragmentation of XeF2 molecules following X-ray absorption at the Xe site. PMID:27212390

Hetero-site-specific X-ray pump-probe spectroscopy for femtosecond intramolecular dynamics

DOE PAGES

Picón, A.; Lehmann, C. S.; Bostedt, C.; ...

2016-05-23

New capabilities at X-ray free-electron laser facilities allow the generation of two-colour femtosecond X-ray pulses, opening the possibility of performing ultrafast studies of X-ray-induced phenomena. Specifically, the experimental realization of hetero-site-specific X-ray-pump/X-ray-probe spectroscopy is of special interest, in which an X-ray pump pulse is absorbed at one site within a molecule and an X-ray probe pulse follows the X-ray-induced dynamics at another site within the same molecule. In this paper, we show experimental evidence of a hetero-site pump-probe signal. By using two-colour 10-fs X-ray pulses, we are able to observe the femtosecond time dependence for the formation of F ionsmore » during the fragmentation of XeF 2 molecules following X-ray absorption at the Xe site.« less

Hetero-site-specific X-ray pump-probe spectroscopy for femtosecond intramolecular dynamics.

PubMed

Picón, A; Lehmann, C S; Bostedt, C; Rudenko, A; Marinelli, A; Osipov, T; Rolles, D; Berrah, N; Bomme, C; Bucher, M; Doumy, G; Erk, B; Ferguson, K R; Gorkhover, T; Ho, P J; Kanter, E P; Krässig, B; Krzywinski, J; Lutman, A A; March, A M; Moonshiram, D; Ray, D; Young, L; Pratt, S T; Southworth, S H

2016-05-23

New capabilities at X-ray free-electron laser facilities allow the generation of two-colour femtosecond X-ray pulses, opening the possibility of performing ultrafast studies of X-ray-induced phenomena. Particularly, the experimental realization of hetero-site-specific X-ray-pump/X-ray-probe spectroscopy is of special interest, in which an X-ray pump pulse is absorbed at one site within a molecule and an X-ray probe pulse follows the X-ray-induced dynamics at another site within the same molecule. Here we show experimental evidence of a hetero-site pump-probe signal. By using two-colour 10-fs X-ray pulses, we are able to observe the femtosecond time dependence for the formation of F ions during the fragmentation of XeF2 molecules following X-ray absorption at the Xe site.

A flexible gas flow reaction cell for in situ x-ray absorption spectroscopy studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kroner, Anna B., E-mail: anna.kroner@diamond.ac.uk; Gilbert, Martin; Duller, Graham

2016-07-27

A capillary-based sample environment with hot air blower and integrated gas system was developed at Diamond to conduct X-ray absorption spectroscopy (XAS) studies of materials under time-resolved, in situ conditions. The use of a hot air blower, operating in the temperature range of 298-1173 K, allows introduction of other techniques e.g. X-ray diffraction (XRD), Raman spectroscopy for combined techniques studies. The flexibility to use either quartz or Kapton capillaries allows users to perform XAS measurement at energies as low as 5600 eV. To demonstrate performance, time-resolved, in situ XAS results of Rh catalysts during the process of activation (Rh K-edge,more » Ce L{sub 3}-edge and Cr K-edge) and the study of mixed oxide membrane (La{sub 0.6}Sr{sub 0.4}Co{sub 0.2}Fe{sub 0.8}O{sub 3−δ}) under various partial oxygen pressure conditions are described.« less

X-Ray Spectroscopies of Warm Dense Matter

NASA Astrophysics Data System (ADS)

Hoidn, Oliver

This dissertation provides a perspective on the role of x-ray spectroscopy and diffraction diagnostics in experimental studies of warm dense matter (WDM). The primary focus of the work I discuss is the development of techniques to measure the structure and state variables of laboratory-generated WDM with a view towards both phenomenlogy and placing contraints on theoretical models. I present techniques adapted to two experimental venues for WDM studies: large-scale laser plasma facilities and x-ray free electron lasers. My focus is on the latter, in the context of which I have studied a dose enhancement technique that exploits nonlocal heat transport in nanostructured targets and considered several aspects of optimizing x-ray diffraction measurements. This work came into play in beam runs at the Linac Coherent Light Source (LCLS) in which my group performed x-ray diffraction studies of several materials heated to eV-scale temperatures. The results from these experiments include confirmation of the persistence of long-range crystalline order upon heating of metal oxides to tens of eV temperarures on the 40 fs timescale. One material, MgO, additionally manifested a surprising anomalous early onset in delocalization of valence charge density, contradicting predictions of all models based on either ground state electronic structure or (high-energy density) plasma physics. This particular result outlines a future path for studies of ordered insulators heated to temperatures on the order of the band gap. Such experiments will offer strong tests of electronic strucure theory, implementing a scientific approach that sees measurement of real-space charge density via x-ray diffraction (XRD) as a particularly effectve means to constrain density functional theory (DFT)-based modeling of the solid state/plasma transitional regime.

Calcium in the Oxygen-Evolving Complex: Structural and Mechanistic Role Determined by X-ray Spectroscopy

PubMed Central

Yachandra, Vittal K.; Yano, Junko

2011-01-01

This review describes the results from X-ray absorption spectroscopy studies that have contributed to an understanding of the role of Ca in the photosynthetic water oxidation reaction. The results include the first Mn, Ca and Sr X-ray spectroscopy studies using Ca or Sr-substituted PS II samples that established the presence of a MnCa heteronuclear structure and its orientation, and the most recent Sr X-ray spectroscopy study using biosynthetically prepared Sr-containing PS II in the various S-states that provide important insights into the requirement for Ca in the mechanism of the Mn4Ca catalytic center. PMID:21524917

Energy-dispersive X-ray emission spectroscopy using an X-ray free-electron laser in a shot-by-shot mode

DOE PAGES

Alonso-Mori, Roberto; Kern, Jan; Gildea, Richard J.; ...

2012-11-05

The ultrabright femtosecond X-ray pulses provided by X-ray free-electron lasers open capabilities for studying the structure and dynamics of a wide variety of systems beyond what is possible with synchrotron sources. Recently, this “probe-before-destroy” approach has been demonstrated for atomic structure determination by serial X-ray diffraction of microcrystals. There has been the question whether a similar approach can be extended to probe the local electronic structure by X-ray spectroscopy. To address this, we have carried out femtosecond X-ray emission spectroscopy (XES) at the Linac Coherent Light Source using redox-active Mn complexes. XES probes the charge and spin states as wellmore » as the ligand environment, critical for understanding the functional role of redox-active metal sites. Kβ 1,3 XES spectra of Mn II and Mn 2 III,IV complexes at room temperature were collected using a wavelength dispersive spectrometer and femtosecond X-ray pulses with an individual dose of up to >100 MGy. The spectra were found in agreement with undamaged spectra collected at low dose using synchrotron radiation. Our results demonstrate that the intact electronic structure of redox active transition metal compounds in different oxidation states can be characterized with this shot-by-shot method. This opens the door for studying the chemical dynamics of metal catalytic sites by following reactions under functional conditions. Furthermore, the technique can be combined with X-ray diffraction to simultaneously obtain the geometric structure of the overall protein and the local chemistry of active metal sites and is expected to prove valuable for understanding the mechanism of important metalloproteins, such as photosystem II.« less

Energy-dispersive X-ray emission spectroscopy using an X-ray free-electron laser in a shot-by-shot mode

PubMed Central

Alonso-Mori, Roberto; Kern, Jan; Gildea, Richard J.; Sokaras, Dimosthenis; Weng, Tsu-Chien; Lassalle-Kaiser, Benedikt; Tran, Rosalie; Hattne, Johan; Laksmono, Hartawan; Hellmich, Julia; Glöckner, Carina; Echols, Nathaniel; Sierra, Raymond G.; Schafer, Donald W.; Sellberg, Jonas; Kenney, Christopher; Herbst, Ryan; Pines, Jack; Hart, Philip; Herrmann, Sven; Grosse-Kunstleve, Ralf W.; Latimer, Matthew J.; Fry, Alan R.; Messerschmidt, Marc M.; Miahnahri, Alan; Seibert, M. Marvin; Zwart, Petrus H.; White, William E.; Adams, Paul D.; Bogan, Michael J.; Boutet, Sébastien; Williams, Garth J.; Zouni, Athina; Messinger, Johannes; Glatzel, Pieter; Sauter, Nicholas K.; Yachandra, Vittal K.; Yano, Junko; Bergmann, Uwe

2012-01-01

The ultrabright femtosecond X-ray pulses provided by X-ray free-electron lasers open capabilities for studying the structure and dynamics of a wide variety of systems beyond what is possible with synchrotron sources. Recently, this “probe-before-destroy” approach has been demonstrated for atomic structure determination by serial X-ray diffraction of microcrystals. There has been the question whether a similar approach can be extended to probe the local electronic structure by X-ray spectroscopy. To address this, we have carried out femtosecond X-ray emission spectroscopy (XES) at the Linac Coherent Light Source using redox-active Mn complexes. XES probes the charge and spin states as well as the ligand environment, critical for understanding the functional role of redox-active metal sites. Kβ1,3 XES spectra of MnII and Mn2III,IV complexes at room temperature were collected using a wavelength dispersive spectrometer and femtosecond X-ray pulses with an individual dose of up to >100 MGy. The spectra were found in agreement with undamaged spectra collected at low dose using synchrotron radiation. Our results demonstrate that the intact electronic structure of redox active transition metal compounds in different oxidation states can be characterized with this shot-by-shot method. This opens the door for studying the chemical dynamics of metal catalytic sites by following reactions under functional conditions. The technique can be combined with X-ray diffraction to simultaneously obtain the geometric structure of the overall protein and the local chemistry of active metal sites and is expected to prove valuable for understanding the mechanism of important metalloproteins, such as photosystem II. PMID:23129631

Resonant Polarization Spectroscopy for Hot X-ray Plasmas

DOE PAGES

Chen, Guo -Xin

2016-04-28

X-ray line polarization spectroscopy is a method of choice for probing hot plasma conditions. The precise roles of resonant structures in this method have not been realized and fully understood. With a sophisticated relativistic close coupling Dirac R-matrix calculation of polarized radiation of the quadrupole magnetic M2 line at 2.717 Å in Ba 46+, we revealed the nature of resonant structures in x-ray line polarization spectroscopy. We found that signatures with a heavy resonance forest imprinting on polarization may be used for a sensitive new spectroscopic method. The resonant polarization spectrum was used to determine or constrain the directional beammore » electron distribution of the laboratory Ba plasma. Lastly, our results provide a start of resonant polarization spectroscopy as a method for diagnostics of laboratory, fusion and astrophysical plasma source conditions.« less

Methods development for diffraction and spectroscopy studies of metalloenzymes at X-ray free-electron lasers

PubMed Central

Kern, Jan; Hattne, Johan; Tran, Rosalie; Alonso-Mori, Roberto; Laksmono, Hartawan; Gul, Sheraz; Sierra, Raymond G.; Rehanek, Jens; Erko, Alexei; Mitzner, Rolf; Wernet, Phillip; Bergmann, Uwe; Sauter, Nicholas K.; Yachandra, Vittal; Yano, Junko

2014-01-01

X-ray free-electron lasers (XFELs) open up new possibilities for X-ray crystallographic and spectroscopic studies of radiation-sensitive biological samples under close to physiological conditions. To facilitate these new X-ray sources, tailored experimental methods and data-processing protocols have to be developed. The highly radiation-sensitive photosystem II (PSII) protein complex is a prime target for XFEL experiments aiming to study the mechanism of light-induced water oxidation taking place at a Mn cluster in this complex. We developed a set of tools for the study of PSII at XFELs, including a new liquid jet based on electrofocusing, an energy dispersive von Hamos X-ray emission spectrometer for the hard X-ray range and a high-throughput soft X-ray spectrometer based on a reflection zone plate. While our immediate focus is on PSII, the methods we describe here are applicable to a wide range of metalloenzymes. These experimental developments were complemented by a new software suite, cctbx.xfel. This software suite allows for near-real-time monitoring of the experimental parameters and detector signals and the detailed analysis of the diffraction and spectroscopy data collected by us at the Linac Coherent Light Source, taking into account the specific characteristics of data measured at an XFEL. PMID:24914169

Nanosecond X-ray Photon Correlation Spectroscopy on Magnetic Skyrmions

DOE PAGES

Seaberg, M. H.; Holladay, B.; Lee, J. C. T.; ...

2017-08-09

We report an X-ray photon correlation spectroscopy method that exploits the recent development of the two-pulse mode at the Linac Coherent Light Source. By using coherent resonant X-ray magnetic scattering, we studied spontaneous fluctuations on nanosecond timescales in thin films of multilayered Fe/Gd that exhibit ordered stripe and skyrmion lattice phases. The correlation time of the fluctuations was found to differ between the skyrmion phase and near the stripe-skyrmion boundary. As a result, this technique will enable a significant new area of research on the study of equilibrium fluctuations in condensed matter.

Nanosecond X-ray Photon Correlation Spectroscopy on Magnetic Skyrmions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seaberg, M. H.; Holladay, B.; Lee, J. C. T.

We report an X-ray photon correlation spectroscopy method that exploits the recent development of the two-pulse mode at the Linac Coherent Light Source. By using coherent resonant X-ray magnetic scattering, we studied spontaneous fluctuations on nanosecond timescales in thin films of multilayered Fe/Gd that exhibit ordered stripe and skyrmion lattice phases. The correlation time of the fluctuations was found to differ between the skyrmion phase and near the stripe-skyrmion boundary. As a result, this technique will enable a significant new area of research on the study of equilibrium fluctuations in condensed matter.

X-ray absorption spectroscopy and EPR studies of oriented spinach thylakoid preparations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andrews, J.C.

In this study, oriented Photosystem II (PS II) particles from spinach chloroplasts are studied with electron paramagnetic resonance (EPR) and x-ray absorption spectroscopy (XAS) to determine more details of the structure of the oxygen evolving complex (OEC). The nature of halide binding to Mn is also studied with Cl K-edge and Mn EXAFS (extended x-ray absorption fine structure) of Mn-Cl model compounds, and with Mn EXAFS of oriented PS II in which Br has replaced Cl. Attention is focused on the following: photosynthesis and the oxygen evolving complex; determination of mosaic spread in oriented photosystem II particles from signal IImore » EPR measurement; oriented EXAFS--studies of PS II in the S{sub 2} state; structural changes in PS II as a result of treatment with ammonia: EPR and XAS studies; studies of halide binding to Mn: Cl K-edge and Mn EXAFS of Mn-Cl model compounds and Mn EXAFS of oriented Br-treated photosystem II.« less

Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and Emission Spectroscopy Study

NASA Astrophysics Data System (ADS)

Chuang, Cheng-Hao; Ray, Sekhar C.; Mazumder, Debarati; Sharma, Surbhi; Ganguly, Abhijit; Papakonstantinou, Pagona; Chiou, Jau-Wern; Tsai, Huang-Ming; Shiu, Hung-Wei; Chen, Chia-Hao; Lin, Hong-Ji; Guo, Jinghua; Pong, Way-Faung

2017-02-01

Nitrogen-doped graphene oxides (GO:Nx) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH2)2]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:Nx synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at%), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at%) graphitic nitrogen was formed in which each N-atom trigonally bonds to three distinct sp2-hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:Nx. The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements.

Ultrafast Time-Resolved Hard X-Ray Emission Spectroscopy on a Tabletop

NASA Astrophysics Data System (ADS)

Miaja-Avila, Luis; O'Neil, Galen C.; Joe, Young I.; Alpert, Bradley K.; Damrauer, Niels H.; Doriese, William B.; Fatur, Steven M.; Fowler, Joseph W.; Hilton, Gene C.; Jimenez, Ralph; Reintsema, Carl D.; Schmidt, Daniel R.; Silverman, Kevin L.; Swetz, Daniel S.; Tatsuno, Hideyuki; Ullom, Joel N.

2016-07-01

Experimental tools capable of monitoring both atomic and electronic structure on ultrafast (femtosecond to picosecond) time scales are needed for investigating photophysical processes fundamental to light harvesting, photocatalysis, energy and data storage, and optical display technologies. Time-resolved hard x-ray (>3 keV ) spectroscopies have proven valuable for these measurements due to their elemental specificity and sensitivity to geometric and electronic structures. Here, we present the first tabletop apparatus capable of performing time-resolved x-ray emission spectroscopy. The time resolution of the apparatus is better than 6 ps. By combining a compact laser-driven plasma source with a highly efficient array of microcalorimeter x-ray detectors, we are able to observe photoinduced spin changes in an archetypal polypyridyl iron complex [Fe (2 ,2'-bipyridine)3]2 + and accurately measure the lifetime of the quintet spin state. Our results demonstrate that ultrafast hard x-ray emission spectroscopy is no longer confined to large facilities and now can be performed in conventional laboratories with 10 times better time resolution than at synchrotrons. Our results are enabled, in part, by a 100- to 1000-fold increase in x-ray collection efficiency compared to current techniques.

Electron cyclotron resonance ion source plasma characterization by X-ray spectroscopy and X-ray imaging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mascali, David, E-mail: davidmascali@lns.infn.it; Castro, Giuseppe; Celona, Luigi

2016-02-15

An experimental campaign aiming to investigate electron cyclotron resonance (ECR) plasma X-ray emission has been recently carried out at the ECRISs—Electron Cyclotron Resonance Ion Sources laboratory of Atomki based on a collaboration between the Debrecen and Catania ECR teams. In a first series, the X-ray spectroscopy was performed through silicon drift detectors and high purity germanium detectors, characterizing the volumetric plasma emission. The on-purpose developed collimation system was suitable for direct plasma density evaluation, performed “on-line” during beam extraction and charge state distribution characterization. A campaign for correlating the plasma density and temperature with the output charge states and themore » beam intensity for different pumping wave frequencies, different magnetic field profiles, and single-gas/gas-mixing configurations was carried out. The results reveal a surprisingly very good agreement between warm-electron density fluctuations, output beam currents, and the calculated electromagnetic modal density of the plasma chamber. A charge-coupled device camera coupled to a small pin-hole allowing X-ray imaging was installed and numerous X-ray photos were taken in order to study the peculiarities of the ECRIS plasma structure.« less

A von Hamos x-ray spectrometer based on a segmented-type diffraction crystal for single-shot x-ray emission spectroscopy and time-resolved resonant inelastic x-ray scattering studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szlachetko, J.; Institute of Physics, Jan Kochanowski University, 25-406 Kielce; Nachtegaal, M.

2012-10-15

We report on the design and performance of a wavelength-dispersive type spectrometer based on the von Hamos geometry. The spectrometer is equipped with a segmented-type crystal for x-ray diffraction and provides an energy resolution in the order of 0.25 eV and 1 eV over an energy range of 8000 eV-9600 eV. The use of a segmented crystal results in a simple and straightforward crystal preparation that allows to preserve the spectrometer resolution and spectrometer efficiency. Application of the spectrometer for time-resolved resonant inelastic x-ray scattering and single-shot x-ray emission spectroscopy is demonstrated.

Coherent Multidimensional Core Spectroscopy of Molecules with Multiple X-ray pulses

NASA Astrophysics Data System (ADS)

Mukamel, Shaul

2017-04-01

Multidimensional spectroscopy uses sequences of optical pulses to study dynamical processes in complex molecules through correlation plots involving several time delay periods. Extensions of these techniques to the x-ray regime will be discussed. Ultrafast nonlinear x-ray spectroscopy is made possible by newly developed free electron laser and high harmonic generation sources. The attosecond duration of X-ray pulses and the atomic selectivity of core X-ray excitations offer a uniquely high spatial and temporal resolution. We demonstrate how stimulated Raman detection of an X-ray probe may be used to monitor the phase and dynamics of the nonequilibrium valence electronic state wavepacket created by e.g. photoexcitation, photoionization and Auger processes. Spectroscopy of multiplecore excitations provides a new window into electron correlations. Applications will be presented to long-range charge transfer in proteins and to excitation energy transfer in porphyrin arrays. Conical intersections (CoIn) dominate the pathways and outcomes of virtually all photophysical and photochemical molecular processes. Despite extensive experimental and theoretical effort CoIns have not been directly observed yet and the experimental evidence is being inferred from fast reaction rates and some vibrational signatures. Novel ultrafast X ray probes for these processes will be presented. Short X-ray pulses can directly detect the passage through a CoIn with the adequate temporal and spectral sensitivity. The technique is based on a coherent Raman process that employs a composite femtosecond/attosecond X-ray pulse to directly detect the electronic coherences (rather than populations) that are generated as the system passes through the CoIn. Streaking of time-resolved photoelectron spectroscopy (TRPES) signals offers another powerful window into the joint electronic/vibrational dynamics at concial intersections. Strong coupling of molecules to the vacuum field of micro cavities can modify

Inter-diffusion of copper and hafnium as studied by x-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Pearson, Justin; Chourasia, A. R.

The Cu/Hf interface has been characterized by x-ray photoelectron spectroscopy. Thin films (thicknesses ranging from 100 nm to 150 nm) of hafnium were deposited on a silicon substrate. About 80 nm of copper was then deposited on such samples. The e-beam method was used for the deposition. The samples were annealed for 30 min at temperatures of 100, 200, 300, 400, and 500°C. The inter-diffusion of copper and hafnium was investigated by sequential sputter depth profiling and x-ray photoelectron spectroscopy. The interdiffusion in each case was analyzed by the Matano-Boltzmann's procedure using the Fick's second law. The interdiffusion coefficients and the width of the interface as determined from the data have been correlated with the annealing temperature. Supported by Organized Research, TAMU-Commerce.

Synchrotron-based ambient pressure X-ray photoelectron spectroscopy of hydrogen and helium

NASA Astrophysics Data System (ADS)

Zhong, Jian-Qiang; Wang, Mengen; Hoffmann, William H.; van Spronsen, Matthijs A.; Lu, Deyu; Boscoboinik, J. Anibal

2018-02-01

Contrary to popular belief, it is possible to obtain X-ray photoelectron spectra for elements lighter than lithium, namely hydrogen and helium. The literature is plagued with claims of this impossibility, which holds true for lab-based X-ray sources. However, this limitation is merely technical and is related mostly to the low X-ray photoionization cross-sections of the 1s orbitals of hydrogen and helium. In this letter, we show that, using ambient pressure X-ray photoelectron spectroscopy (XPS), a bright-enough X-ray source allows the study of these elusive elements. This has important implications in the understanding of the limitations of one of the most useful techniques in materials science, and moreover, it potentially opens the possibility of using XPS to directly study the most abundant element in the universe.

An upgraded x-ray spectroscopy diagnostic on MST.

PubMed

Clayton, D J; Almagri, A F; Burke, D R; Forest, C B; Goetz, J A; Kaufman, M C; O'Connell, R

2010-10-01

An upgraded x-ray spectroscopy diagnostic is used to measure the distribution of fast electrons in MST and to determine Z(eff) and the particle diffusion coefficient D(r). A radial array of 12 CdZnTe hard-x-ray detectors measures 10-150 keV Bremsstrahlung from fast electrons, a signature of reduced stochasticity and improved confinement in the plasma. A new Si soft-x-ray detector measures 2-10 keV Bremsstrahlung from thermal and fast electrons. The shaped output pulses from both detector types are digitized and the resulting waveforms are fit with Gaussians to resolve pileup and provide good time and energy resolution. Lead apertures prevent detector saturation and provide a well-known etendue, while lead shielding prevents pickup from stray x-rays. New Be vacuum windows transmit >2 keV x-rays, and additional Al and Be filters are sometimes used to reduce low energy flux for better resolution at higher energies. Measured spectra are compared to those predicted by the Fokker-Planck code CQL3D to deduce Z(eff) and D(r).

High-pressure studies with x-rays using diamond anvil cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shen, Guoyin; Mao, Ho Kwang

2016-11-22

Pressure profoundly alters all states of matter. The symbiotic development of ultrahigh-pressure diamond anvil cells, to compress samples to sustainable multi-megabar pressures; and synchrotron x-ray techniques, to probe materials' properties in situ, has enabled the exploration of rich high-pressure (HP) science. In this article, we first introduce the essential concept of diamond anvil cell technology, together with recent developments and its integration with other extreme environments. We then provide an overview of the latest developments in HP synchrotron techniques, their applications, and current problems, followed by a discussion of HP scientific studies using x-rays in the key multidisciplinary fields. Thesemore » HP studies include: HP x-ray emission spectroscopy, which provides information on the filled electronic states of HP samples; HP x-ray Raman spectroscopy, which probes the HP chemical bonding changes of light elements; HP electronic inelastic x-ray scattering spectroscopy, which accesses high energy electronic phenomena, including electronic band structure, Fermi surface, excitons, plasmons, and their dispersions; HP resonant inelastic x-ray scattering spectroscopy, which probes shallow core excitations, multiplet structures, and spin-resolved electronic structure; HP nuclear resonant x-ray spectroscopy, which provides phonon densities of state and time-resolved Mössbauer information; HP x-ray imaging, which provides information on hierarchical structures, dynamic processes, and internal strains; HP x-ray diffraction, which determines the fundamental structures and densities of single-crystal, polycrystalline, nanocrystalline, and non-crystalline materials; and HP radial x-ray diffraction, which yields deviatoric, elastic and rheological information. Integrating these tools with hydrostatic or uniaxial pressure media, laser and resistive heating, and cryogenic cooling, has enabled investigations of the structural, vibrational, electronic, and

High-pressure studies with x-rays using diamond anvil cells

NASA Astrophysics Data System (ADS)

Shen, Guoyin; Mao, Ho Kwang

2017-01-01

Pressure profoundly alters all states of matter. The symbiotic development of ultrahigh-pressure diamond anvil cells, to compress samples to sustainable multi-megabar pressures; and synchrotron x-ray techniques, to probe materials’ properties in situ, has enabled the exploration of rich high-pressure (HP) science. In this article, we first introduce the essential concept of diamond anvil cell technology, together with recent developments and its integration with other extreme environments. We then provide an overview of the latest developments in HP synchrotron techniques, their applications, and current problems, followed by a discussion of HP scientific studies using x-rays in the key multidisciplinary fields. These HP studies include: HP x-ray emission spectroscopy, which provides information on the filled electronic states of HP samples; HP x-ray Raman spectroscopy, which probes the HP chemical bonding changes of light elements; HP electronic inelastic x-ray scattering spectroscopy, which accesses high energy electronic phenomena, including electronic band structure, Fermi surface, excitons, plasmons, and their dispersions; HP resonant inelastic x-ray scattering spectroscopy, which probes shallow core excitations, multiplet structures, and spin-resolved electronic structure; HP nuclear resonant x-ray spectroscopy, which provides phonon densities of state and time-resolved Mössbauer information; HP x-ray imaging, which provides information on hierarchical structures, dynamic processes, and internal strains; HP x-ray diffraction, which determines the fundamental structures and densities of single-crystal, polycrystalline, nanocrystalline, and non-crystalline materials; and HP radial x-ray diffraction, which yields deviatoric, elastic and rheological information. Integrating these tools with hydrostatic or uniaxial pressure media, laser and resistive heating, and cryogenic cooling, has enabled investigations of the structural, vibrational, electronic, and

X-ray absorption spectroscopy: EXAFS (Extended X-ray Absorption Fine Structure) and XANES (X-ray Absorption Near Edge Structure)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alp, E.E.; Mini, S.M.; Ramanathan, M.

1990-04-01

The x-ray absorption spectroscopy (XAS) had been an essential tool to gather spectroscopic information about atomic energy level structure in the early decades of this century. It has also played an important role in the discovery and systematization of rare-earth elements. The discovery of synchrotron radiation in 1952, and later the availability of broadly tunable synchrotron based x-ray sources have revitalized this technique since the 1970's. The correct interpretation of the oscillatory structure in the x-ray absorption cross-section above the absorption edge by Sayers et. al. has transformed XAS from a spectroscopic tool to a structural technique. EXAFS (Extended X-raymore » Absorption Fine Structure) yields information about the interatomic distances, near neighbor coordination numbers, and lattice dynamics. An excellent description of the principles and data analysis techniques of EXAFS is given by Teo. XANES (X-ray Absorption Near Edge Structure), on the other hand, gives information about the valence state, energy bandwidth and bond angles. Today, there are about 50 experimental stations in various synchrotrons around the world dedicated to collecting x-ray absorption data from the bulk and surfaces of solids and liquids. In this chapter, we will give the basic principles of XAS, explain the information content of essentially two different aspects of the absorption process leading to EXAFS and XANES, and discuss the source and samples limitations.« less

Stochastic stimulated electronic x-ray Raman spectroscopy

PubMed Central

Kimberg, Victor; Rohringer, Nina

2016-01-01

Resonant inelastic x-ray scattering (RIXS) is a well-established tool for studying electronic, nuclear, and collective dynamics of excited atoms, molecules, and solids. An extension of this powerful method to a time-resolved probe technique at x-ray free electron lasers (XFELs) to ultimately unravel ultrafast chemical and structural changes on a femtosecond time scale is often challenging, due to the small signal rate in conventional implementations at XFELs that rely on the usage of a monochromator setup to select a small frequency band of the broadband, spectrally incoherent XFEL radiation. Here, we suggest an alternative approach, based on stochastic spectroscopy, which uses the full bandwidth of the incoming XFEL pulses. Our proposed method is relying on stimulated resonant inelastic x-ray scattering, where in addition to a pump pulse that resonantly excites the system a probe pulse on a specific electronic inelastic transition is provided, which serves as a seed in the stimulated scattering process. The limited spectral coherence of the XFEL radiation defines the energy resolution in this process and stimulated RIXS spectra of high resolution can be obtained by covariance analysis of the transmitted spectra. We present a detailed feasibility study and predict signal strengths for realistic XFEL parameters for the CO molecule resonantly pumped at the O1s→π* transition. Our theoretical model describes the evolution of the spectral and temporal characteristics of the transmitted x-ray radiation, by solving the equation of motion for the electronic and vibrational degrees of freedom of the system self consistently with the propagation by Maxwell equations. PMID:26958585

Synchrotron-based ambient pressure X-ray photoelectron spectroscopy of hydrogen and helium

DOE PAGES

Zhong, Jian-Qiang; Wang, Mengen; Hoffmann, William H.; ...

2018-03-01

Contrary to popular belief, it is possible to obtain X-ray photoelectron spectra for elements lighter than lithium, namely hydrogen and helium. The literature is plagued with claims of this impossibility, which holds true for lab-based X-ray sources. However, this limitation is merely technical and is related mostly to the low X-ray photoionization cross-sections of the 1s orbitals of hydrogen and helium. Here, we show that, using ambient pressure X-ray photoelectron spectroscopy (XPS), a bright-enough X-ray source allows the study of these elusive elements. This has important implications in the understanding of the limitations of one of the most useful techniquesmore » in materials science, and moreover, it potentially opens the possibility of using XPS to directly study the most abundant element in the universe.« less

Synchrotron-based ambient pressure X-ray photoelectron spectroscopy of hydrogen and helium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhong, Jian-Qiang; Wang, Mengen; Hoffmann, William H.

Contrary to popular belief, it is possible to obtain X-ray photoelectron spectra for elements lighter than lithium, namely hydrogen and helium. The literature is plagued with claims of this impossibility, which holds true for lab-based X-ray sources. However, this limitation is merely technical and is related mostly to the low X-ray photoionization cross-sections of the 1s orbitals of hydrogen and helium. Here, we show that, using ambient pressure X-ray photoelectron spectroscopy (XPS), a bright-enough X-ray source allows the study of these elusive elements. This has important implications in the understanding of the limitations of one of the most useful techniquesmore » in materials science, and moreover, it potentially opens the possibility of using XPS to directly study the most abundant element in the universe.« less

AXSIS: Exploring the frontiers in attosecond X-ray science, imaging and spectroscopy.

PubMed

Kärtner, F X; Ahr, F; Calendron, A-L; Çankaya, H; Carbajo, S; Chang, G; Cirmi, G; Dörner, K; Dorda, U; Fallahi, A; Hartin, A; Hemmer, M; Hobbs, R; Hua, Y; Huang, W R; Letrun, R; Matlis, N; Mazalova, V; Mücke, O D; Nanni, E; Putnam, W; Ravi, K; Reichert, F; Sarrou, I; Wu, X; Yahaghi, A; Ye, H; Zapata, L; Zhang, D; Zhou, C; Miller, R J D; Berggren, K K; Graafsma, H; Meents, A; Assmann, R W; Chapman, H N; Fromme, P

2016-09-01

X-ray crystallography is one of the main methods to determine atomic-resolution 3D images of the whole spectrum of molecules ranging from small inorganic clusters to large protein complexes consisting of hundred-thousands of atoms that constitute the macromolecular machinery of life. Life is not static, and unravelling the structure and dynamics of the most important reactions in chemistry and biology is essential to uncover their mechanism. Many of these reactions, including photosynthesis which drives our biosphere, are light induced and occur on ultrafast timescales. These have been studied with high time resolution primarily by optical spectroscopy, enabled by ultrafast laser technology, but they reduce the vast complexity of the process to a few reaction coordinates. In the AXSIS project at CFEL in Hamburg, funded by the European Research Council, we develop the new method of attosecond serial X-ray crystallography and spectroscopy, to give a full description of ultrafast processes atomically resolved in real space and on the electronic energy landscape, from co-measurement of X-ray and optical spectra, and X-ray diffraction. This technique will revolutionize our understanding of structure and function at the atomic and molecular level and thereby unravel fundamental processes in chemistry and biology like energy conversion processes. For that purpose, we develop a compact, fully coherent, THz-driven atto-second X-ray source based on coherent inverse Compton scattering off a free-electron crystal, to outrun radiation damage effects due to the necessary high X-ray irradiance required to acquire diffraction signals. This highly synergistic project starts from a completely clean slate rather than conforming to the specifications of a large free-electron laser (FEL) user facility, to optimize the entire instrumentation towards fundamental measurements of the mechanism of light absorption and excitation energy transfer. A multidisciplinary team formed by laser

X-ray absorption spectroscopy study of Gd3+-loaded ultra-short carbon nanotubes

NASA Astrophysics Data System (ADS)

Ma, Q.; Jebb, M.; Tweedle, M. F.; Wilson, L. J.

2013-04-01

We present an x-ray absorption spectroscopy study of the local structure around the Gd3+ion loaded in ultra short (20-100 nm) carbon nanotubes (GNTs). X-ray Gd L3 absorption near edge structure data shows that the 31.2-μM GNT suspension exhibits a clear characteristic of hydration at the [GdOn] cluster. Extended x-ray absorption fine structure data show that the Gd3+ ion is coordinated by about 9 oxygen ions and that this first coordination shell exhibits an asymmetry similar to that found in triclinic Gd-acetate or Gd[C2H3O2]3·4H2O or GdAc. After correction for the asymmetry using the cumulant of the third order, the Gd-O bond distance is found to be 2.345 Å, instead of 2.406 Å for a symmetrical (or Gaussian) distribution. It is shorter than that in the Gd-containing MRI contrast agents currently in clinical uses. This may account in part for high proton relaxivity observed for the GNT suspension.

Effect of X-ray flux on polytetrafluoroethylene in X-ray photoelectron spectroscopy

NASA Technical Reports Server (NTRS)

Wheeler, D. R.; Pepper, S. V.

1982-01-01

The effect of the X-ray flux in X-ray photoelectron spectroscopy (STAT) on the constitution of the polytetrafluoroethylene (PTFE) surface has been examined. The radiation dose rate for our specimen was about 10 to the 7th rad/s. The structure, magnitude and binding energy of the C(1s) and F(1s) features of the XPS spectrum and the mass spectrum of gaseous species evolved during irradiation are observed. The strong time dependence of these signals over a period of several hours indicated that the surface constitution of PTFE is greatly affected by this level of radiation dose. The results are consistent with the development of a heavily cross-linked or branched structure in the PTFE surface region and the evolution of short chain fragments into the gas phase.

Kinoform optics applied to X-ray photon correlation spectroscopy.

PubMed

Sandy, A R; Narayanan, S; Sprung, M; Su, J-D; Evans-Lutterodt, K; Isakovic, A F; Stein, A

2010-05-01

Moderate-demagnification higher-order silicon kinoform focusing lenses have been fabricated to facilitate small-angle X-ray photon correlation spectroscopy (XPCS) experiments. The geometric properties of such lenses, their focusing performance and their applicability for XPCS measurements are described. It is concluded that one-dimensional vertical X-ray focusing via silicon kinoform lenses significantly increases the usable coherent flux from third-generation storage-ring light sources for small-angle XPCS experiments.

Soft X-ray spectroscopy of transition metal compounds: a theoretical perspective

NASA Astrophysics Data System (ADS)

Bokarev, S. I.; Hilal, R.; Aziz, S. G.; Kühn, O.

2017-01-01

To date, X-ray spectroscopy has become a routine tool that can reveal highly local and element-specific information on the electronic structure of atoms in complex environments. Here, we report on the development of an efficient and versatile theoretical methodology for the treatment of soft X-ray spectra of transition metal compounds based on the multi-configurational self-consistent field electronic structure theory. A special focus is put on the L-edge photon-in/photon-out and photon-in/electron-out processes, i.e. X-ray absorption, resonant inelastic scattering, partial fluorescence yield, and photoelectron spectroscopy, all treated on the same theoretical footing. The investigated systems range from small prototypical coordination compounds and catalysts to aggregates of biomolecules.

A reaction cell for ambient pressure soft x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Castán-Guerrero, C.; Krizmancic, D.; Bonanni, V.; Edla, R.; Deluisa, A.; Salvador, F.; Rossi, G.; Panaccione, G.; Torelli, P.

2018-05-01

We present a new experimental setup for performing X-ray Absorption Spectroscopy (XAS) in the soft X-ray range at ambient pressure. The ambient pressure XAS setup is fully compatible with the ultra high vacuum environment of a synchrotron radiation spectroscopy beamline end station by means of ultrathin Si3N4 membranes acting as windows for the X-ray beam and seal of the atmospheric sample environment. The XAS detection is performed in total electron yield (TEY) mode by probing the drain current from the sample with a picoammeter. The high signal/noise ratio achievable in the TEY mode, combined with a continuous scanning of the X-ray energies, makes it possible recording XAS spectra in a few seconds. The first results show the performance of this setup to record fast XAS spectra from sample surfaces exposed at atmospheric pressure, even in the case of highly insulating samples. The use of a permanent magnet inside the reaction cell enables the measurement of X-ray magnetic circular dichroism at ambient pressure.

Novel applications of X-ray photoelectron spectroscopy on unsupported nanoparticles

NASA Astrophysics Data System (ADS)

Kostko, Oleg; Xu, Bo; Jacobs, Michael I.; Ahmed, Musahid

X-ray photoelectron spectroscopy (XPS) is a powerful technique for chemical analysis of surfaces. We will present novel results of XPS on unsupported, gas-phase nanoparticles using a velocity-map imaging (VMI) spectrometer. This technique allows for probes of both the surfaces of nanoparticles via XPS as well as their interiors via near edge X-ray absorption fine structure (NEXAFS) spectroscopy. A recent application of this technique has confirmed that arginine's guanidinium group exists in a protonated state even in strongly basic solution. Moreover, the core-level photoelectron spectroscopy can provide information on the effective attenuation length (EAL) of low kinetic energy electrons. This contradictory value is important for determining the probing depth of XPS and in photolithography. A new method for determining EALs will be presented.

A new endstation at the Swiss Light Source for ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy measurements of liquid solutions.

PubMed

Brown, Matthew A; Redondo, Amaia Beloqui; Jordan, Inga; Duyckaerts, Nicolas; Lee, Ming-Tao; Ammann, Markus; Nolting, Frithjof; Kleibert, Armin; Huthwelker, Thomas; Müächler, Jean-Pierre; Birrer, Mario; Honegger, Juri; Wetter, Reto; Wörner, Hans Jakob; van Bokhoven, Jeroen A

2013-07-01

A new liquid microjet endstation designed for ultraviolet (UPS) and X-ray (XPS) photoelectron, and partial electron yield X-ray absorption (XAS) spectroscopies at the Swiss Light Source is presented. The new endstation, which is based on a Scienta HiPP-2 R4000 electron spectrometer, is the first liquid microjet endstation capable of operating in vacuum and in ambient pressures up to the equilibrium vapor pressure of liquid water at room temperature. In addition, the Scienta HiPP-2 R4000 energy analyzer of this new endstation allows for XPS measurements up to 7000 eV electron kinetic energy that will enable electronic structure measurements of bulk solutions and buried interfaces from liquid microjet samples. The endstation is designed to operate at the soft X-ray SIM beamline and at the tender X-ray Phoenix beamline. The endstation can also be operated using a Scienta 5 K ultraviolet helium lamp for dedicated UPS measurements at the vapor-liquid interface using either He I or He II α lines. The design concept, first results from UPS, soft X-ray XPS, and partial electron yield XAS measurements, and an outlook to the potential of this endstation are presented.

Feasibility of Valence-to-Core X-ray Emission Spectroscopy for Tracking Transient Species

DOE PAGES

March, Anne Marie; Assefa, Tadesse A.; Bressler, Christian; ...

2015-02-09

X-ray spectroscopies, when combined in laser-pump, X-ray-probe measurement schemes, can be powerful tools for tracking the electronic and geometric structural changes that occur during the course of a photoinitiated chemical reaction. X-ray absorption spectroscopy (XAS) is considered an established technique for such measurements, and X-ray emission spectroscopy (XES) of the strongest core-to-core emission lines (Kα and Kβ) is now being utilized. Flux demanding valence-to-core XES promises to be an important addition to the time-resolved spectroscopic toolkit. Here In this paper we present measurements and density functional theory calculations on laser-excited, solution-phase ferrocyanide that demonstrate the feasibility of valence-to-core XES formore » time-resolved experiments. Lastly, we discuss technical improvements that will make valence-to-core XES a practical pump–probe technique.« less

High-order multilayer coated blazed gratings for high resolution soft x-ray spectroscopy

DOE PAGES

Voronov, Dmitriy L.; Goray, Leonid I.; Warwick, Tony; ...

2015-02-17

A grand challenge in soft x-ray spectroscopy is to drive the resolving power of monochromators and spectrometers from the 10 4 achieved routinely today to well above 10 5. This need is driven mainly by the requirements of a new technique that is set to have enormous impact in condensed matter physics, Resonant Inelastic X-ray Scattering (RIXS). Unlike x-ray absorption spectroscopy, RIXS is not limited by an energy resolution dictated by the core-hole lifetime in the excitation process. Using much higher resolving power than used for normal x-ray absorption spectroscopy enables access to the energy scale of soft excitations inmore » matter. These excitations such as magnons and phonons drive the collective phenomena seen in correlated electronic materials such as high temperature superconductors. RIXS opens a new path to study these excitations at a level of detail not formerly possible. However, as the process involves resonant excitation at an energy of around 1 keV, and the energy scale of the excitations one would like to see are at the meV level, to fully utilize the technique requires the development of monochromators and spectrometers with one to two orders of magnitude higher energy resolution than has been conventionally possible. Here we investigate the detailed diffraction characteristics of multilayer blazed gratings. These elements offer potentially revolutionary performance as the dispersive element in ultra-high resolution x-ray spectroscopy. In doing so, we have established a roadmap for the complete optimization of the grating design. Traditionally 1st order gratings are used in the soft x-ray region, but we show that as in the optical domain, one can work in very high spectral orders and thus dramatically improve resolution without significant loss in efficiency.« less

X-ray photoelectron spectroscopy for characterization of wood surfaces in adhesion studies

Treesearch

James F. Beecher; Charles R. Frihart

2005-01-01

X-ray photoelectron spectroscopy (XPS) is one of a set of tools that have been used to characterize wood surfaces. Among the advantages of XPS are surface sensitivity, identification of nearly all elements, and frequently, discrimination of bonding states. For these reasons, XPS seemed to be an appropriate tool to help explain the differences in bond strength under wet...

Infrared x-ray pump-probe spectroscopy of the NO molecule

NASA Astrophysics Data System (ADS)

Guimarães, F. F.; Kimberg, V.; Felicíssimo, V. C.; Gel'Mukhanov, F.; Cesar, A.; Ågren, H.

2005-07-01

Two color infrared x-ray pump-probe spectroscopy of the NO molecule is studied theoretically and numerically in order to obtain a deeper insight of the underlying physics and of the potential of this suggested technology. From the theoretical investigation a number of conclusions could be drawn: It is found that the phase of the infrared field strongly influences the trajectory of the nuclear wave packet, and hence, the x-ray spectrum. The trajectory experiences fast oscillations with the vibrational frequency with a modulation due to the anharmonicity of the potential. The dependences of the x-ray spectra on the delay time, the duration, and the shape of the pulses are studied in detail. It is shown that the x-ray spectrum keep memory about the infrared phase after the pump field left the system. This memory effect is sensitive to the time of switching-off the pump field and the Rabi frequency. The phase effect takes maximum value when the duration of the x-ray pulse is one-fourth of the infrared field period, and can be enhanced by a proper control of the duration and intensity of the pump pulse. The manifestation of the phase is different for oriented and disordered molecules and depends strongly on the intensity of the pump radiation.

STROBE-X: X-ray Timing & Spectroscopy on Dynamical Timescales from Milliseconds to Years

NASA Technical Reports Server (NTRS)

Wilson-Hodge, Colleen A.; Ray, P. S.; Maccarone, T; Chakrabarty, D.; Gendreau, K.; Arzoumanian, Z.; Jenke, P.; Ballantyne, D.; Bozzo, E.; Brandt, S.;

STROBE-X: X-Ray Timing Spectroscopy on Dynamical Timescales from Microseconds to Years

NASA Technical Reports Server (NTRS)

Wilson-Hodge, Colleen A.; Ray, P. S.; Gendreau, K.; Arzoumanian, Z.; Chakrabarty, D.; Remillard, R.; Feroci, M.; Maccarone, T.; Wood, K.; Jenke, P.

2017-01-01

We describe a probe-class mission concept that provides an unprecedented view of the X-ray sky, performing timing and 0.2-30 keV spectroscopy over timescales from microseconds to years. The Spectroscopic Time-Resolving Observatory for Broadband Energy X-rays (STROBE-X) comprises three primary instruments. The first uses an array of lightweight optics (3-m focal length) that concentrate incident photons onto solid state detectors with CCD-level (85-130 eV) energy resolution, 100 ns time resolution, and low background rates to cover the 0.2-12 keV band. This technology is scaled up from NICER, with enhanced optics to take advantage of the longer focal length of STROBE-X. The second uses large-area collimated silicon drift detectors, developed for ESA's LOFT, to cover the 2-30 keV band. These two instruments each provide an order of magnitude improvement in effective area compared with its predecessor (NICER and RXTE, respectively). Finally, a sensitive sky monitor triggers pointed observations, provides high duty cycle, high time resolution, high spectral resolution monitoring of the X-ray sky with approx. 20 times the sensitivity of the RXTE ASM, and enables multi-wavelength and multi-messenger studies on a continuous, rather than scanning basis.For the first time, the broad coverage provides simultaneous study of thermal components, non-thermal components, iron lines, and reflection features from a single platform for accreting black holes at all scales. The enormous collecting area allows detailed studies of the dense matter equation of state using both thermal emission from rotation-powered pulsars and harder emission from X-ray burst oscillations. The combination of the wide-field monitor and the sensitive pointed instruments enables observations of potential electromagnetic counterparts to LIGO and neutrino events. Additional extragalactic science, such as high quality spectroscopy of clusters of galaxies and unprecedented timing investigations of active

STROBE-X: X-ray Timing & Spectroscopy on Dynamical Timescales from Microseconds to Years

NASA Astrophysics Data System (ADS)

Wilson-Hodge, Colleen A.; Ray, Paul S.; Gendreau, Keith; Chakrabarty, Deepto; Feroci, Marco; Maccarone, Thomas J.; Arzoumanian, Zaven; Remillard, Ronald A.; Wood, Kent; Griffith, Christopher; Jenke, Peter

2017-08-01

We describe a probe-class mission concept that provides an unprecedented view of the X-ray sky, performing timing and 0.2-30 keV spectroscopy over timescales from microseconds to years. The Spectroscopic Time-Resolving Observatory for Broadband Energy X-rays (STROBE-X) comprises three primary instruments. The first uses an array of lightweight optics (3-m focal length) that concentrate incident photons onto solid state detectors with CCD-level (85-130 eV) energy resolution, 100 ns time resolution, and low background rates to cover the 0.2-12 keV band. This technology is scaled up from NICER, with enhanced optics to take advantage of the longer focal length of STROBE-X. The second uses large-area collimated silicon drift detectors, developed for ESA's LOFT, to cover the 2-30 keV band. These two instruments each provide an order of magnitude improvement in effective area compared with its predecessor (NICER and RXTE, respectively). Finally, a sensitive sky monitor triggers pointed observations, provides high duty cycle, high time resolution, high spectral resolution monitoring of the X-ray sky with ~20 times the sensitivity of the RXTE ASM, and enables multi-wavelength and multi-messenger studies on a continuous, rather than scanning basis.For the first time, the broad coverage provides simultaneous study of thermal components, non-thermal components, iron lines, and reflection features from a single platform for accreting black holes at all scales. The enormous collecting area allows detailed studies of the dense matter equation of state using both thermal emission from rotation-powered pulsars and harder emission from X-ray burst oscillations. The combination of the wide-field monitor and the sensitive pointed instruments enables observations of potential electromagnetic counterparts to LIGO and neutrino events. Additional extragalactic science, such as high quality spectroscopy of clusters of galaxies and unprecedented timing investigations of active galactic

Pixel detectors for x-ray imaging spectroscopy in space

NASA Astrophysics Data System (ADS)

Treis, J.; Andritschke, R.; Hartmann, R.; Herrmann, S.; Holl, P.; Lauf, T.; Lechner, P.; Lutz, G.; Meidinger, N.; Porro, M.; Richter, R. H.; Schopper, F.; Soltau, H.; Strüder, L.

2009-03-01

Pixelated semiconductor detectors for X-ray imaging spectroscopy are foreseen as key components of the payload of various future space missions exploring the x-ray sky. Located on the platform of the new Spectrum-Roentgen-Gamma satellite, the eROSITA (extended Roentgen Survey with an Imaging Telescope Array) instrument will perform an imaging all-sky survey up to an X-ray energy of 10 keV with unprecedented spectral and angular resolution. The instrument will consist of seven parallel oriented mirror modules each having its own pnCCD camera in the focus. The satellite born X-ray observatory SIMBOL-X will be the first mission to use formation-flying techniques to implement an X-ray telescope with an unprecedented focal length of around 20 m. The detector instrumentation consists of separate high- and low energy detectors, a monolithic 128 × 128 DEPFET macropixel array and a pixellated CdZTe detector respectively, making energy band between 0.5 to 80 keV accessible. A similar concept is proposed for the next generation X-ray observatory IXO. Finally, the MIXS (Mercury Imaging X-ray Spectrometer) instrument on the European Mercury exploration mission BepiColombo will use DEPFET macropixel arrays together with a small X-ray telescope to perform a spatially resolved planetary XRF analysis of Mercury's crust. Here, the mission concepts and their scientific targets are briefly discussed, and the resulting requirements on the detector devices together with the implementation strategies are shown.

A high-temperature furnace for in situ synchrotron X-ray spectroscopy under controlled atmospheric conditions.

PubMed

Eeckhout, Sigrid Griet; Gorges, Bernard; Barthe, Laurent; Pelosi, Orietta; Safonova, Olga; Giuli, Gabriele

2008-09-01

A high-temperature furnace with an induction heater coil has been designed and constructed for in situ X-ray spectroscopic experiments under controlled atmospheric conditions and temperatures up to 3275 K. The multi-purpose chamber design allows working in backscattering and normal fluorescence mode for synchrotron X-ray absorption and emission spectroscopy. The use of the furnace is demonstrated in a study of the in situ formation of Cr oxide between 1823 K and 2023 K at logPO(2) values between -10.0 and -11.3 using X-ray absorption near-edge spectroscopy. The set-up is of particular interest for studying liquid metals, alloys and other electrically conductive materials under extreme conditions.

Elemental-sensitive Detection of the Chemistry in Batteries through Soft X-ray Absorption Spectroscopy and Resonant Inelastic X-ray Scattering.

PubMed

Wu, Jinpeng; Sallis, Shawn; Qiao, Ruimin; Li, Qinghao; Zhuo, Zengqing; Dai, Kehua; Guo, Zixuan; Yang, Wanli

2018-04-17

Energy storage has become more and more a limiting factor of today's sustainable energy applications, including electric vehicles and green electric grid based on volatile solar and wind sources. The pressing demand of developing high-performance electrochemical energy storage solutions, i.e., batteries, relies on both fundamental understanding and practical developments from both the academy and industry. The formidable challenge of developing successful battery technology stems from the different requirements for different energy-storage applications. Energy density, power, stability, safety, and cost parameters all have to be balanced in batteries to meet the requirements of different applications. Therefore, multiple battery technologies based on different materials and mechanisms need to be developed and optimized. Incisive tools that could directly probe the chemical reactions in various battery materials are becoming critical to advance the field beyond its conventional trial-and-error approach. Here, we present detailed protocols for soft X-ray absorption spectroscopy (sXAS), soft X-ray emission spectroscopy (sXES), and resonant inelastic X-ray scattering (RIXS) experiments, which are inherently elemental-sensitive probes of the transition-metal 3d and anion 2p states in battery compounds. We provide the details on the experimental techniques and demonstrations revealing the key chemical states in battery materials through these soft X-ray spectroscopy techniques.

A study of mercuric iodide near melting using differential scanning calorimetry, Raman spectroscopy and X-ray diffraction

NASA Astrophysics Data System (ADS)

Burger, A.; Morgan, S.; Jiang, H.; Silberman, E.; Schieber, M.; Van Den Berg, L.; Keller, L.; Wagner, C. N. J.

1989-11-01

High-temperature studies of mercuric iodide (HgI2) involving differential scanning calorimetry (DSC), Raman spectroscopy and X-ray powder diffraction have failed to confirm the existence of a red-colored tetragonal high-temperature phase called α'-HgI2 reported by S.N. Toubektsis et al. [J. Appl. Phys. 58 (1988) 2070] using DSC measurements. The multiple DSC peaks near melting reported by Toubektsis are found by the present authors only if the sample is heated in a stainless-steel container. Using a Pyrex container or inserting a platinum foil between the HgI2 and the stainless-steel container yields only one sharp, single DSC peak at the melting point. The nonexistence of the α' phase is confirmed by high-temperature X-ray diffraction and Raman spectroscopy performed in the vicinity of the melting point. These methods clearly, indicate the existence of only the yellow orthorhombic β-HgI2 phase. The experimental high-temperature DSC, Raman and X-ray diffraction data are presented and discussed.

X-ray scattering and spectroscopy studies on diesel soot from oxygenated fuel under various engine load conditions

USGS Publications Warehouse

Braun, Andreas; Shah, N.; Huggins, Frank E.; Kelly, K.E.; Sarofim, A.; Jacobsen, C.; Wirick, S.; Francis, H.; Ilavsky, J.; Thomas, G.E.; Huffman, G.P.

2005-01-01

Diesel soot from reference diesel fuel and oxygenated fuel under idle and load engine conditions was investigated with X-ray scattering and X-ray carbon K-edge absorption spectroscopy. Up to five characteristic size ranges were found. Idle soot was generally found to have larger primary particles and aggregates but smaller crystallites, than load soot. Load soot has a higher degree of crystallinity than idle soot. Adding oxygenates to diesel fuel enhanced differences in the characteristics of diesel soot, or even reversed them. Aromaticity of idle soot from oxygenated diesel fuel was significantly larger than from the corresponding load soot. Carbon near-edge X-ray absorption fine structure (NEXAFS) spectroscopy was applied to gather information about the presence of relative amounts of carbon double bonds (CC, CO) and carbon single bonds (C-H, C-OH, COOH). Using scanning X-ray transmission microspectroscopy (STXM), the relative amounts of these carbon bond states were shown to vary spatially over distances approximately 50 to 100 nm. The results from the X-ray techniques are supported by thermo-gravimetry analysis and high-resolution transmission electron microscopy. ?? 2005 Elsevier Ltd. All rights reserved.

New developments in high pressure x-ray spectroscopy beamline at High Pressure Collaborative Access Team

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiao, Y. M., E-mail: yxiao@carnegiescience.edu; Chow, P.; Boman, G.

The 16 ID-D (Insertion Device - D station) beamline of the High Pressure Collaborative Access Team at the Advanced Photon Source is dedicated to high pressure research using X-ray spectroscopy techniques typically integrated with diamond anvil cells. The beamline provides X-rays of 4.5-37 keV, and current available techniques include X-ray emission spectroscopy, inelastic X-ray scattering, and nuclear resonant scattering. The recent developments include a canted undulator upgrade, 17-element analyzer array for inelastic X-ray scattering, and an emission spectrometer using a polycapillary half-lens. Recent development projects and future prospects are also discussed.

Electronic structure of the organic semiconductor Alq3 (aluminum tris-8-hydroxyquinoline) from soft x-ray spectroscopies and density functional theory calculations.

PubMed

DeMasi, A; Piper, L F J; Zhang, Y; Reid, I; Wang, S; Smith, K E; Downes, J E; Peltekis, N; McGuinness, C; Matsuura, A

2008-12-14

The element-specific electronic structure of the organic semiconductor aluminum tris-8-hydroxyquinoline (Alq(3)) has been studied using a combination of resonant x-ray emission spectroscopy, x-ray photoelectron spectroscopy, x-ray absorption spectroscopy, and density functional theory (DFT) calculations. Resonant and nonresonant x-ray emission spectroscopy were used to measure directly the carbon, nitrogen and oxygen 2p partial densities of states in Alq(3), and good agreement was found with the results of DFT calculations. Furthermore, resonant x-ray emission at the carbon K-edge is shown to be able to measure the partial density of states associated with individual C sites. Finally, comparison of previous x-ray emission studies and the present data reveal the presence of clear photon-induced damage in the former.

The X-ray correlation spectroscopy instrument at the Linac Coherent Light Source

DOE PAGES

Alonso-Mori, Roberto; Caronna, Chiara; Chollet, Matthieu; ...

2015-03-03

The X-ray Correlation Spectroscopy instrument is dedicated to the study of dynamics in condensed matter systems using the unique coherence properties of free-electron lasers. It covers a photon energy range of 4–25 keV. The intrinsic temporal characteristics of the Linac Coherent Light Source, in particular the 120 Hz repetition rate, allow for the investigation of slow dynamics (milliseconds) by means of X-ray photon correlation spectroscopy. Double-pulse schemes could probe dynamics on the picosecond timescale. In addition, a description of the instrument capabilities and recent achievements is presented.

STROBE-X: X-ray Timing & Spectroscopy on Dynamical Timescales from Microseconds to Years

NASA Astrophysics Data System (ADS)

Wilson-Hodge, Colleen A.; Ray, Paul S.; Gendreau, Keith; Chakrabarty, Deepto; Feroci, Marco; Maccarone, Tom; Arzoumanian, Zaven; Remillard, Ronald A.; Wood, Kent; Griffith, Christopher; STROBE-X Collaboration

2017-01-01

We describe a proposed probe-class mission concept that will provide an unprecedented view of the X-ray sky, performing timing and spectroscopy over a broad band (0.2-30 keV) probing timescales from microseconds to years. The Spectroscopic Time-Resolving Observatory for Broadband Energy X-rays (STROBE-X) comprises two primary instruments. The soft band (0.2-12 keV) will be covered by an array of lightweight optics (3-m focal length) that concentrate incident photons onto small solid state detectors with CCD-level (85-130 eV) energy resolution, 100 ns time resolution, and low background rates. This technology, fully developed for NICER, would be scaled up with enhanced optics to take advantage of the longer focal length of STROBE-X. The harder band (2 to at least 30 keV) would be covered by large-area collimated silicon drift detectors,developed for the European LOFT mission concept. Each instrument would provide an order of magnitude improvement in effective area compared with its predecessor (NICER in the soft band and RXTE in the hard band). A sensitive sky monitor would act as a trigger for pointed observations, provide high duty cycle, high time resolution, high spectral resolution monitoring of the X-ray sky with ~20 times the sensitivity of the RXTE ASM, and enable multi-wavelength and multi-messenger studies on a continuous, rather than scanning basis.The broad coverage will enable thermal components, non-thermal components, iron lines, and reflection features to be studied simultaneously from a single platform for the first time in accreting black holes at all scales. The enormous collecting area will enable studies of the dense matter equation of state using both soft thermal emission from rotation-powered pulsars and harder emission from X-ray burst oscillations. Revolutionary science, such as high quality spectroscopy of clusters of galaxies and unprecedented timing investigations of active galactic nuclei, would also be obtained.We describe the mission

Probing molecular orientations in thin films by x-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Li, Y.; Li, P.; Lu, Z.-H.

2018-03-01

A great number of functional organic molecules in active thin-film layers of optoelectronic devices have highly asymmetric structures, such as plate-like, rod-like, etc. This makes molecular orientation an important aspect in thin-films as it can significantly affect both the optical and electrical performance of optoelectronic devices. With a combination of in-situ ultra violet photoelectron spectroscopy (UPS) and x-ray photoelectron spectroscopy (XPS) investigations for organic molecules having a broad range of structural properties, we discovered a rigid connection of core levels and frontier highest occupied molecular orbital levels at organic interfaces. This finding opens up opportunities of using X-ray photoemission spectroscopy as an alternative tool to UPS for providing an easy and unambiguous data interpretation in probing molecular orientations.

Distinct charge dynamics in battery electrodes revealed by in situ and operando soft X-ray spectroscopy

PubMed Central

Liu, Xiaosong; Wang, Dongdong; Liu, Gao; Srinivasan, Venkat; Liu, Zhi; Hussain, Zahid; Yang, Wanli

2013-01-01

Developing high-performance batteries relies on material breakthroughs. During the past few years, various in situ characterization tools have been developed and have become indispensible in studying and the eventual optimization of battery materials. However, soft X-ray spectroscopy, one of the most sensitive probes of electronic states, has been mainly limited to ex situ experiments for battery research. Here we achieve in situ and operando soft X-ray absorption spectroscopy of lithium-ion battery cathodes. Taking advantage of the elemental, chemical and surface sensitivities of soft X-rays, we discover distinct lithium-ion and electron dynamics in Li(Co1/3Ni1/3Mn1/3)O2 and LiFePO4 cathodes in polymer electrolytes. The contrast between the two systems and the relaxation effect in LiFePO4 is attributed to a phase transformation mechanism, and the mesoscale morphology and charge conductivity of the electrodes. These discoveries demonstrate feasibility and power of in situ soft X-ray spectroscopy for studying integrated and dynamic effects in batteries. PMID:24100759

Note: application of a pixel-array area detector to simultaneous single crystal X-ray diffraction and X-ray absorption spectroscopy measurements.

PubMed

Sun, Cheng-Jun; Zhang, Bangmin; Brewe, Dale L; Chen, Jing-Sheng; Chow, G M; Venkatesan, T; Heald, Steve M

2014-04-01

X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) are two main x-ray techniques in synchrotron radiation facilities. In this Note, we present an experimental setup capable of performing simultaneous XRD and XAS measurements by the application of a pixel-array area detector. For XRD, the momentum transfer in specular diffraction was measured by scanning the X-ray energy with fixed incoming and outgoing x-ray angles. By selecting a small fixed region of the detector to collect the XRD signal, the rest of the area was available for collecting the x-ray fluorescence for XAS measurements. The simultaneous measurement of XRD and X-ray absorption near edge structure for Pr0.67Sr0.33MnO3 film was demonstrated as a proof of principle for future time-resolved pump-probe measurements. A static sample makes it easy to maintain an accurate overlap of the X-ray spot and laser pump beam.

X-ray Photoelectron Spectroscopy Database (Version 4.1)

National Institute of Standards and Technology Data Gateway

SRD 20 X-ray Photoelectron Spectroscopy Database (Version 4.1) (Web, free access)   The NIST XPS Database gives access to energies of many photoelectron and Auger-electron spectral lines. The database contains over 22,000 line positions, chemical shifts, doublet splittings, and energy separations of photoelectron and Auger-electron lines.

Chemical speciation using high energy resolution PIXE spectroscopy in the tender X-ray range

NASA Astrophysics Data System (ADS)

Kavčič, Matjaž; Petric, Marko; Vogel-Mikuš, Katarina

2018-02-01

High energy resolution X-ray emission spectroscopy employing wavelength dispersive (WDS) crystal spectrometers can provide energy resolution on the level of core-hole lifetime broadening of the characteristic emission lines. While crystal spectrometers have been traditionally used in combination with electron excitation for major and minor element analysis, they have been rarely considered in proton induced X-ray emission (PIXE) trace element analysis mainly due to low detection efficiency. Compared to the simplest flat crystal WDS spectrometer the efficiency can be improved by employing cylindrically or even spherically curved crystals in combination with position sensitive X-ray detectors. When such spectrometer is coupled to MeV proton excitation, chemical bonding effects are revealed in the high energy resolution spectra yielding opportunity to extend the analytical capabilities of PIXE technique also towards chemical state analysis. In this contribution we will focus on the high energy resolution PIXE (HR-PIXE) spectroscopy in the tender X-ray range performed in our laboratory with our home-built tender X-ray emission spectrometer. Some general properties of high energy resolution PIXE spectroscopy in the tender X-ray range are presented followed by an example of sulfur speciation in biological tissue illustrating the capabilities as well as limitations of HR-PIXE method used for chemical speciation in the tender X-ray range.

High-resolution X-ray emission spectroscopy with transition-edge sensors: present performance and future potential

DOE Office of Scientific and Technical Information (OSTI.GOV)

Uhlig, J.; Doriese, W. B.; Fowler, J. W.

2015-04-21

X-ray emission spectroscopy (XES) is a powerful element-selective tool to analyze the oxidation states of atoms in complex compounds, determine their electronic configuration, and identify unknown compounds in challenging environments. Until now the low efficiency of wavelength-dispersive X-ray spectrometer technology has limited the use of XES, especially in combination with weaker laboratory X-ray sources. More efficient energy-dispersive detectors have either insufficient energy resolution because of the statistical limits described by Fano or too low counting rates to be of practical use. This paper updates an approach to high-resolution X-ray emission spectroscopy that uses a microcalorimeter detector array of superconducting transition-edgemore » sensors (TESs). TES arrays are discussed and compared with conventional methods, and shown under which circumstances they are superior. It is also shown that a TES array can be integrated into a table-top time-resolved X-ray source and a soft X-ray synchrotron beamline to perform emission spectroscopy with good chemical sensitivity over a very wide range of energies.« less

Solid state structural investigations of the bis(chalcone) compound with single crystal X-ray crystallography, DFT, gamma-ray spectroscopy and chemical spectroscopy methods

NASA Astrophysics Data System (ADS)

Yakalı, Gül; Biçer, Abdullah; Eke, Canel; Cin, Günseli Turgut

2018-04-01

A bis(chalcone), (2E,6E)-2,6-bis((E)-3phenylallidene)cyclohexanone, was characterized by 1H NMR, 13C NMR, FTIR, UV-Vis spectroscopy, gamma-ray spectroscopy and single crystal X- ray structural analysis. The optimized molecular structure of the compound is calculated using DFT/B3LYP with 6-31G (d,p) level. The calculated geometrical parameters are in good agreement with the experimental data obtained from our reported X-ray structure. The powder and single crystal compounds were gama-irradiated using clinical electron linear accelerator and 60Co gamma-ray source, respectively. Spectral studies (1H NMR, 13C NMR, FTIR and UV-Vis) of powder chalcone compound were also investigated before and after irradiation. Depending on the irradiation notable changes were observed in spectral features powder sample. Single crystal X-ray diffraction investigation shows that both unirradiated and irradiated single crystal samples crystallizes in a orthorhombic crystal system in the centrosymmetric space group Pbcn and exhibits an C-H..O intramolecular and intermolecular hydrogen bonds. The crystal packing is stabilised by strong intermolecular bifurcate C-H..O hydrogen bonds and π…π stacking interactions. The asymmetric unit of the title compound contains one-half of a molecule. The other half of the molecule is generated with (1-x,y,-3/2-z) symmetry operator. The molecule is almost planar due to having π conjugated system of chalcones. However, irradiated single crystal compound showed significant changes lattice parameters, crystal volume and density. According to results of gamma-ray spectroscopy, radioactive elements of powder compound which are 123Sb(n,g),124Sb,57Fe(g,p),56Mn, 55Mn(g,n), and 54Mn were determined using photoactivation analysis. However, the most intensive gamma-ray energy signals are 124Sb.

Development of picosecond time-resolved X-ray absorption spectroscopy by high-repetition-rate laser pump/X-ray probe at Beijing Synchrotron Radiation Facility.

PubMed

Wang, Hao; Yu, Can; Wei, Xu; Gao, Zhenhua; Xu, Guang Lei; Sun, Da Rui; Li, Zhenjie; Zhou, Yangfan; Li, Qiu Ju; Zhang, Bing Bing; Xu, Jin Qiang; Wang, Lin; Zhang, Yan; Tan, Ying Lei; Tao, Ye

2017-05-01

A new setup and commissioning of transient X-ray absorption spectroscopy are described, based on the high-repetition-rate laser pump/X-ray probe method, at the 1W2B wiggler beamline at the Beijing Synchrotron Radiation Facility. A high-repetition-rate and high-power laser is incorporated into the setup with in-house-built avalanche photodiodes as detectors. A simple acquisition scheme was applied to obtain laser-on and laser-off signals simultaneously. The capability of picosecond transient X-ray absorption spectroscopy measurement was demonstrated for a photo-induced spin-crossover iron complex in 6 mM solution with 155 kHz repetition rate.

X-ray and synchrotron methods in studies of cultural heritage sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koval’chuk, M. V.; Yatsishina, E. B.; Blagov, A. E.

2016-09-15

X-ray and synchrotron methods that are most widely used in studies of cultural heritage objects (including archaeological sites)—X-ray diffraction analysis, X-ray spectroscopy, and visualization techniques— have been considered. The reported examples show high efficiency and informativeness of natural science studies when solving most diverse problems of archaeology, history, the study of art, museology, etc.

X-ray magnetic circular dichroism and hard X-ray photoelectron spectroscopy of tetragonal Mn72Ge28 epitaxial thin film

NASA Astrophysics Data System (ADS)

Kim, Jinhyeok; Mizuguchi, Masaki; Inami, Nobuhito; Ueno, Tetsuro; Ueda, Shigenori; Takanashi, Koki

2018-04-01

An epitaxially grown Mn72Ge28 film with a tetragonal crystal structure was fabricated. It was clarified that the film had a perpendicular magnetization and a high perpendicular magnetic anisotropy energy of 14.3 Merg/cm3. The electronic structure was investigated by X-ray magnetic circular dichroism and hard X-ray photoelectron spectroscopy. The obtained X-ray magnetic circular dichroism spectrum revealed that the Mn orbital magnetic moment governed the magnetocrystalline anisotropy of the Mn72Ge28 film. A doublet structure was observed for the Mn 2p3/2 peak of hard X-ray photoelectron spectrum, indicating the spin exchange interaction between the 2p core-hole and 3d valence electrons.

Development of a spectro-electrochemical cell for soft X-ray photon-in photon-out spectroscopy

NASA Astrophysics Data System (ADS)

Ishihara, Tomoko; Tokushima, Takashi; Horikawa, Yuka; Kato, Masaru; Yagi, Ichizo

2017-10-01

We developed a spectro-electrochemical cell for X-ray absorption and X-ray emission spectroscopy, which are element-specific methods to study local electronic structures in the soft X-ray region. In the usual electrochemical measurement setup, the electrode is placed in solution, and the surface/interface region of the electrode is not normally accessible by soft X-rays that have low penetration depth in liquids. To realize soft X-ray observation of electrochemical reactions, a 15-nm-thick Pt layer was deposited on a 150-nm-thick film window with an adhesive 3-nm-thick Ti layer for use as both the working electrode and the separator window between vacuum and a sample liquid under atmospheric pressure. The designed three-electrode electrochemical cell consists of a Pt film on a SiC window, a platinized Pt wire, and a commercial Ag|AgCl electrode as the working, counter, and reference electrodes, respectively. The functionality of the cell was tested by cyclic voltammetry and X-ray absorption and emission spectroscopy. As a demonstration, the electroplating of Pb on the Pt/SiC membrane window was measured by X-ray absorption and real-time monitoring of fluorescence intensity at the O 1s excitation.

Time-resolved X-ray Absorption Spectroscopy for Electron Transport Study in Warm Dense Gold

NASA Astrophysics Data System (ADS)

Lee, Jong-Won; Bae, Leejin; Engelhorn, Kyle; Heimann, Philip; Ping, Yuan; Barbrel, Ben; Fernandez, Amalia; Beckwith, Martha Anne; Cho, Byoung-Ick; GIST Team; IBS Team; LBNL Collaboration; SLAC Collaboration; LLNL Collaboration

2015-11-01

The warm dense Matter represents states of which the temperature is comparable to Fermi energy and ions are strongly coupled. One of the experimental techniques to create such state in the laboratory condition is the isochoric heating of thin metal foil with femtosecond laser pulses. This concept largely relies on the ballistic transport of electrons near the Fermi-level, which were mainly studied for the metals in ambient conditions. However, they were barely investigated in warm dense conditions. We present a time-resolved x-ray absorption spectroscopy measured for the Au/Cu dual layered sample. The front Au layer was isochorically heated with a femtosecond laser pulse, and the x-ray absorption changes around L-edge of Cu, which was attached on the backside of Au, was measured with a picosecond resolution. Time delays between the heating of the `front surface' of Au layer and the alternation of x-ray spectrum of Cu attached on the `rear surface' of Au indicate the energetic electron transport mechanism through Au in the warm dense conditions. IBS (IBS-R012-D1) and the NRF (No. 2013R1A1A1007084) of Korea.

Probing interfacial characteristics of rubrene/pentacene and pentacene/rubrene bilayers with soft X-ray spectroscopy.

PubMed

Seo, J H; Pedersen, T M; Chang, G S; Moewes, A; Yoo, K-H; Cho, S J; Whang, C N

2007-08-16

The electronic structure of rubrene/pentacene and pentacene/rubrene bilayers has been investigated using soft X-ray absorption spectroscopy, resonant X-ray emission spectroscopy, and density-functional theory calculations. X-ray absorption and emission measurements reveal that it has been possible to alter the lowest unoccupied and the highest occupied molecular orbital states of rubrene in rubrene/pentacene bilayer. In the reverse case, one gets p* molecular orbital states originating from the pentacene layer. Resonant X-ray emission spectra suggest a reduction in the hole-transition probabilities for the pentacene/rubrene bilayer in comparison to reference pentacene layer. For the rubrenepentacene structure, the hole-transition probability shows an increase in comparison to the rubrene reference. We also determined the energy level alignment of the pentacene-rubrene interface by using X-ray and ultraviolet photoelectron spectroscopy. From these comparisons, it is found that the electronic structure of the pentacene-rubrene interface has a strong dependence on interface characteristics which depends on the order of the layers used.

The X-ray Correlation Spectroscopy instrument at the Linac Coherent Light Source

PubMed Central

Alonso-Mori, Roberto; Caronna, Chiara; Chollet, Matthieu; Curtis, Robin; Damiani, Daniel S.; Defever, Jim; Feng, Yiping; Flath, Daniel L.; Glownia, James M.; Lee, Sooheyong; Lemke, Henrik T.; Nelson, Silke; Bong, Eric; Sikorski, Marcin; Song, Sanghoon; Srinivasan, Venkat; Stefanescu, Daniel; Zhu, Diling; Robert, Aymeric

2015-01-01

The X-ray Correlation Spectroscopy instrument is dedicated to the study of dynamics in condensed matter systems using the unique coherence properties of free-electron lasers. It covers a photon energy range of 4–25 keV. The intrinsic temporal characteristics of the Linac Coherent Light Source, in particular the 120 Hz repetition rate, allow for the investigation of slow dynamics (milli­seconds) by means of X-ray photon correlation spectroscopy. Double-pulse schemes could probe dynamics on the picosecond timescale. A description of the instrument capabilities and recent achievements is presented. PMID:25931061

Origin of Pressure-induced Superconducting Phase in K xFe 2-ySe 2 studied by Synchrotron X-ray Diffraction and Spectroscopy

DOE PAGES

Yamamoto, Yoshiya; Yamaoka, Hitoshi; Tanaka, Masashi; ...

2016-08-08

Pressure dependence of the electronic and crystal structures of K xFe 2–ySe 2, which has pressure-induced two superconducting domes of SC I and SC II, was investigated by x-ray emission spectroscopy and diffraction. X-ray diffraction data show that compressibility along the c-axis changes around 12 GPa, where a new superconducting phase of SC II appears. This suggests a possible tetragonal to collapsed tetragonal phase transition. X-ray emission spectroscopy data also shows the change in the electronic structure around 12 GPa. These results can be explained by the scenario that the two SC domes under pressure originate from the change ofmore » Fermi surface topology. Lastly, our results here show the pronounced increase of the density of states near the Fermi surface under pressure with a structural phase transition, which can help address our fundamental understanding for the appearance of the SC II phase.« less

Pushing x-ray photon correlation spectroscopy beyond the continuous frame rate limit

DOE PAGES

Dufresne, Eric M.; Narayanan, Suresh; Sandy, Alec R.; ...

2016-01-06

We demonstrate delayed-frame X-ray Photon Correlation Spectroscopy with 120 microsecond time resolution, limited only by sample scattering rates, with a prototype Pixel-array detector capable of taking two image frames separated by 153 ns or less. Although the overall frame rate is currently limited to about 4 frame pairs per second, we easily measured millisecond correlation functions. In conclusion, this technology, coupled to the use of brighter synchrotrons such as Petra III or the NSLS-II should enable X-ray Photon Correlation Spectroscopy on microsecond time scales on a wider variety of materials.

X-ray induced dimerization of cinnamic acid: Time-resolved inelastic X-ray scattering study

NASA Astrophysics Data System (ADS)

Inkinen, Juho; Niskanen, Johannes; Talka, Tuomas; Sahle, Christoph J.; Müller, Harald; Khriachtchev, Leonid; Hashemi, Javad; Akbari, Ali; Hakala, Mikko; Huotari, Simo

2015-11-01

A classic example of solid-state topochemical reactions is the ultraviolet-light induced photodimerization of α-trans-cinnamic acid (CA). Here, we report the first observation of an X-ray-induced dimerization of CA and monitor it in situ using nonresonant inelastic X-ray scattering spectroscopy (NRIXS). The time-evolution of the carbon core-electron excitation spectra shows the effects of two X-ray induced reactions: dimerization on a short time-scale and disintegration on a long time-scale. We used spectrum simulations of CA and its dimerization product, α-truxillic acid (TA), to gain insight into the dimerization effects. From the time-resolved spectra, we extracted component spectra and time-dependent weights corresponding to CA and TA. The results suggest that the X-ray induced dimerization proceeds homogeneously in contrast to the dimerization induced by ultraviolet light. We also utilized the ability of NRIXS for direct tomography with chemical-bond contrast to image the spatial progress of the reactions in the sample crystal. Our work paves the way for other time-resolved studies on chemical reactions using inelastic X-ray scattering.

Investigation of nanoparticulate silicon as printed layers using scanning electron microscopy, transmission electron microscopy, X-ray absorption spectroscopy and X-ray photoelectron spectroscopy

DOE PAGES

Unuigbe, David M.; Harting, Margit; Jonah, Emmanuel O.; ...

2017-08-21

The presence of native oxide on the surface of silicon nanoparticles is known to inhibit charge transport on the surfaces. Scanning electron microscopy (SEM) studies reveal that the particles in the printed silicon network have a wide range of sizes and shapes. High-resolution transmission electron microscopy reveals that the particle surfaces have mainly the (111)- and (100)-oriented planes which stabilizes against further oxidation of the particles. X-ray absorption spectroscopy (XANES) and X-ray photoelectron spectroscopy (XPS) measurements at the O 1s-edge have been utilized to study the oxidation and local atomic structure of printed layers of silicon nanoparticles which were milledmore » for different times. XANES results reveal the presence of the +4 (SiO 2) oxidation state which tends towards the +2 (SiO) state for higher milling times. Si 2pXPS results indicate that the surfaces of the silicon nanoparticles in the printed layers are only partially oxidized and that all three sub-oxide, +1 (Si 2O), +2 (SiO) and +3 (Si 2O 3), states are present. The analysis of the change in the sub-oxide peaks of the silicon nanoparticles shows the dominance of the +4 state only for lower milling times.« less

An X-ray absorption spectroscopy study of the interactions of Ni2+ with yeast enolase.

PubMed

Wang, S; Scott, R A; Lebioda, L; Zhou, Z H; Brewer, J M

1995-05-15

An x-ray absorption spectroscopy (XAS) study was carried out at pH 7.6 on solutions of Ni2+ and yeast enolase depleted of its physiological cofactor (Mg2+) in the presence or absence of substrate/product, the very strongly bound competitive inhibitor 2-phosphonoacetohydroxamate and Mg2+. Both "conformational" and "catalytic" Ni2+ are distorted octahedral in coordination, in agreement with several spectroscopic studies but in contrast to the coordination in the crystal at pH 6.0. The data are consistent with direct coordination of what must be the catalytic Ni2+ to the phosphate of the substrate, in agreement with some previous data but in disagreement with recent interpretations by other workers. The ligands around the metal ions obtained from the x-ray structure give simulated XAS spectra in good agreement with the observed spectra.

Electronic Structure of the Organic Semiconductor Alq3 (aluminum tris-8-hydroxyquinoline) from Soft X-ray Spectroscopies and Density Functional Theory Calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

DeMasi, A.; Piper, L; Zhang, Y

2008-01-01

The element-specific electronic structure of the organic semiconductor aluminum tris-8-hydroxyquinoline (Alq3) has been studied using a combination of resonant x-ray emission spectroscopy, x-ray photoelectron spectroscopy, x-ray absorption spectroscopy, and density functional theory (DFT) calculations. Resonant and nonresonant x-ray emission spectroscopy were used to measure directly the carbon, nitrogen and oxygen 2p partial densities of states in Alq3, and good agreement was found with the results of DFT calculations. Furthermore, resonant x-ray emission at the carbon K-edge is shown to be able to measure the partial density of states associated with individual C sites. Finally, comparison of previous x-ray emission studiesmore » and the present data reveal the presence of clear photon-induced damage in the former.« less

Plasma synthesis, Mössbauer spectroscopy and X-ray diffraction studies of nanosized iron oxides

NASA Astrophysics Data System (ADS)

Paneva, Daniela; Zaharieva, Katerina; Grabis, Janis; Mitov, Ivan; Vissokov, Gheorghi

2010-06-01

In this article synthesis and study of iron oxide nanopowders are described. The synthesis of sample 1 and sample 2—iron oxides—was carried out by electric arc plasma cutting of ordinary steel. The sample 3 was prepared by evaporation of Fe2O3/FeO mixture in radio-frequency nitrogen plasma. The characterization of the as prepared iron oxide nanoproducts was achieved by means of Mössbauer spectroscopy and X-ray diffraction analysis. The presence of different phases of iron oxide with a basic phase Fe3 - xO4 (magnetite), additional Fe1 - xO (wüstite) and α or γ-Fe2O3 (hematite or maghemite) with superparamagnetic particles for sample 1 and sample 2 and Fe3 - xO4 (magnetite) for sample 3 is observed.

Biological X-ray absorption spectroscopy (BioXAS): a valuable tool for the study of trace elements in the life sciences.

PubMed

Strange, Richard W; Feiters, Martin C

2008-10-01

Using X-ray absorption spectroscopy (XAS) the binding modes (type and number of ligands, distances and geometry) and oxidation states of metals and other trace elements in crystalline as well as non-crystalline samples can be revealed. The method may be applied to biological systems as a 'stand-alone' technique, but it is particularly powerful when used alongside other X-ray and spectroscopic techniques and computational approaches. In this review, we highlight how biological XAS is being used in concert with crystallography, spectroscopy and computational chemistry to study metalloproteins in crystals, and report recent applications on relatively rare trace elements utilised by living organisms and metals involved in neurodegenerative diseases.

Structure of the manganese complex in photosystem II: insights from X-ray spectroscopy.

PubMed Central

Yachandra, Vittal K

2002-01-01

We have used Mn K-edge absorption and Kbeta emission spectroscopy to determine the oxidation states of the Mn complex in the various S states. We have started exploring the new technique of resonant inelastic X-ray scattering spectroscopy; this technique can be characterized as a Raman process that uses K-edge energies (1s to 4p, ca. 6550 eV) to obtain L-edge-like spectra (2p to 3d, ca. 650 eV). The relevance of these data to the oxidation states and structure of the Mn complex is presented. We have obtained extended X-ray absorption fine structure data from the S(0) and S(3) states and observed heterogeneity in the Mn-Mn distances leading us to conclude that there may be three rather than two di-mu-oxo-bridged units present per tetranuclear Mn cluster. In addition, we have obtained data using Ca and Sr X-ray spectroscopy that provide evidence for a heteronuclear Mn-Ca cluster. The possibility of three di-mu-oxo-bridged Mn-Mn moieties and the proximity of Ca is incorporated into developing structural models for the Mn cluster. The involvement of bridging and terminal O ligands of Mn in the mechanism of oxygen evolution is discussed in the context of our X-ray spectroscopy results. PMID:12437873

Excited state X-ray absorption spectroscopy: Probing both electronic and structural dynamics

NASA Astrophysics Data System (ADS)

Neville, Simon P.; Averbukh, Vitali; Ruberti, Marco; Yun, Renjie; Patchkovskii, Serguei; Chergui, Majed; Stolow, Albert; Schuurman, Michael S.

2016-10-01

We investigate the sensitivity of X-ray absorption spectra, simulated using a general method, to properties of molecular excited states. Recently, Averbukh and co-workers [M. Ruberti et al., J. Chem. Phys. 140, 184107 (2014)] introduced an efficient and accurate L 2 method for the calculation of excited state valence photoionization cross-sections based on the application of Stieltjes imaging to the Lanczos pseudo-spectrum of the algebraic diagrammatic construction (ADC) representation of the electronic Hamiltonian. In this paper, we report an extension of this method to the calculation of excited state core photoionization cross-sections. We demonstrate that, at the ADC(2)x level of theory, ground state X-ray absorption spectra may be accurately reproduced, validating the method. Significantly, the calculated X-ray absorption spectra of the excited states are found to be sensitive to both geometric distortions (structural dynamics) and the electronic character (electronic dynamics) of the initial state, suggesting that core excitation spectroscopies will be useful probes of excited state non-adiabatic dynamics. We anticipate that the method presented here can be combined with ab initio molecular dynamics calculations to simulate the time-resolved X-ray spectroscopy of excited state molecular wavepacket dynamics.

Novel visualization studies of lignocellulosic oxidation chemistry by application of C-near edge X-ray absorption fine structure spectroscopy

Treesearch

Douglas G. Mancosky; Lucian A. Lucia; Hiroki Nanko; Sue Wirick; Alan W. Rudie; Robert Braun

2005-01-01

The research presented herein is the first attempt to probe the chemical nature of lignocellulosic samples by the application of carbon near edge X-ray absorption fine structure spectroscopy (C-NEXAFS). C-NEXAFS is a soft X-ray technique that principally provides selective interrogation of discrete atomic moieties using photoelectrons of variable energies. The X1A beam...

Studies by Near Edge X-ray Absorption Spectroscopies of Bonding Dynamics at the Graphene/Guanine Interface - A Proposal for High Mobility, Organic Graphene Field Effect Transistors

DTIC Science & Technology

2015-07-01

AFRL-AFOSR-UK-TR-2015-0034 Studies by Near Edge X-ray Absorption Spectroscopies of Bonding Dynamics at the Graphene /Guanine...Interface – A Proposal for High Mobility, Organic Graphene Field Effect Transistors Eva Campo BANGOR UNIVERSITY COLLEGE ROAD BANGOR...April 2015 4. TITLE AND SUBTITLE Studies by Near Edge X-ray Absorption Spectroscopies of Bonding Dynamics at the Graphene /Guanine Interface - A

Rolf Mewe: a career devoted to X-ray spectroscopy

NASA Astrophysics Data System (ADS)

Kaastra, Jelle S.; Mewe, Rolf

2005-06-01

An overview of the life and work of Rolf Mewe (1935-2004) as an X-ray spectroscopist is given. He was one of the pioneers in the field of X-ray spectroscopy. His work illustrates nicely how this field developed from the early days up to the present high-resolution era. His plasma emission codes, developed by him and collaborators over several decades, is one of the most widely used. His thorough knowledge of the field, as well as his ability and enthousiasm to cooperate with many colleagues, made his career a succes. He will be missed by all of us for his work and personality.

Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy

DOE PAGES

Sneeden, Eileen Y.; Hackett, Mark J.; Cotelesage, Julien J. H.; ...

2017-07-27

Sulfur-based thiyl radicals are known to be involved in a wide range of chemical and biological processes, but they are often highly reactive, which makes them difficult to observe directly. We report herein X-ray absorption spectra and analysis that support the direct observation of two different thiyl species generated photochemically by X-ray irradiation. The thiyl radical sulfur K-edge X-ray absorption spectra of both species are characterized by a uniquely low energy transition at about 2465 eV, which occurs at a lower energy than any previously observed feature at the sulfur K-edge and corresponds to a 1s → 3p transition tomore » the singly occupied molecular orbital of the free radical. In conclusion, our results constitute the first observation of substantial levels of thiyl radicals generated by X-ray irradiation and detected by sulfur K-edge X-ray absorption spectroscopy.« less

A Broadband X-Ray Imaging Spectroscopy with High-Angular Resolution: the FORCE Mission

NASA Technical Reports Server (NTRS)

Mori, Koji; Tsuru, Takeshi Go; Nakazawac, Kazuhiro; Ueda, Yoshihiro; Okajima, Takashi; Murakami, Hiroshi; Awaki, Hisamitsu; Matsumoto, Hironori; Fukazawai, Yasushi; Tsunemi, Hiroshi;

Photon-in photon-out hard X-ray spectroscopy at the Linac Coherent Light Source

DOE PAGES

Alonso-Mori, Roberto; Sokaras, Dimosthenis; Zhu, Diling; ...

2015-04-15

X-ray free-electron lasers (FELs) have opened unprecedented possibilities to study the structure and dynamics of matter at an atomic level and ultra-fast timescale. Many of the techniques routinely used at storage ring facilities are being adapted for experiments conducted at FELs. In order to take full advantage of these new sources several challenges have to be overcome. They are related to the very different source characteristics and its resulting impact on sample delivery, X-ray optics, X-ray detection and data acquisition. Here it is described how photon-in photon-out hard X-ray spectroscopy techniques can be applied to study the electronic structure andmore » its dynamics of transition metal systems with ultra-bright and ultra-short FEL X-ray pulses. In particular, some of the experimental details that are different compared with synchrotron-based setups are discussed and illustrated by recent measurements performed at the Linac Coherent Light Source.« less

An alignment method for mammographic X-ray spectroscopy under clinical conditions.

PubMed

Miyajima, S; Imagawa, K; Matsumoto, M

2002-09-01

This paper describes an alignment method for mammographic X-ray spectroscopy under clinical conditions. A pinhole, a fluorescent screen, a laser device and the case for a detector are used for alignment of the focal spot, a collimator and a detector. The method determines the line between the focal spot and the point of interest in an X-ray field radiographically. The method allows alignment for both central axis and off-axis directions.

X-ray absorption fine structure and X-ray excited optical luminescence studies of II-VI semiconducting nanostructures

NASA Astrophysics Data System (ADS)

Murphy, Michael Wayne

2010-06-01

Various II-VI semiconducting nanomaterials such as ZnO-ZnS nanoribbons (NRs), CdSxSe1-x nanostructures, ZnS:Mn NRs, ZnS:Mn,Eu nanoprsims (NPs), ZnO:Mn nanopowders, and ZnO:Co nanopowders were synthesized for study. These materials were characterized by techniques such as scanning electron microscopy, transmission electron microscopy, element dispersive X-ray spectroscopy, selected area electron diffraction, and X-ray diffraction. The electronic and optical properties of these nanomaterials were studied by X-ray absorption fine structure (XAFS) spectroscopy and X-ray excited optical luminescence (XEOL) techniques, using tuneable soft X-rays from a synchrotron light source. The complementary nature ofthe XAFS and XEOL techniques give site, element and chemical specific measurements which allow a better understanding of the interplay and role of each element in the system. Chemical vapour deposition (CVD) of ZnS powder in a limited oxygen environment resulted in side-by-side biaxial ZnO-ZnS NR heterostructures. The resulting NRs contained distinct wurtzite ZnS and wurtzite ZnO components with widths of 10--100 nm and 20 --500 nm, respectively and a uniform interface region of 5-15 nm. XAFS and XEOL measurements revealed the luminescence of ZnO-ZnS NRs is from the ZnO component. The luminescence of CdSxSe1-x nanostructures is shown to be dependent on the S to Se ratio, with the band-gap emission being tunable between that of pure CdS and CdSe. Excitation of the CdSxSe 1-x nanostructures by X-ray in XEOL has revealed new de-excitation channels which show a defect emission band not seen by laser excitation. CVD of Mn2+ doped ZnS results in nanostructures with luminescence dominated by the yellow Mn2+ emission due to energy transfer from the ZnS host to the Mn dopant sites. The addition of EuCl3 to the reactants in the CVD process results in a change in morphology from NR to NP. Zn1-xMnxO and Zn1-xCOxO nanopowders were prepared by sol-gel methods at dopant concentrations

X-ray induced dimerization of cinnamic acid: Time-resolved inelastic X-ray scattering study

PubMed Central

Inkinen, Juho; Niskanen, Johannes; Talka, Tuomas; Sahle, Christoph J.; Müller, Harald; Khriachtchev, Leonid; Hashemi, Javad; Akbari, Ali; Hakala, Mikko; Huotari, Simo

2015-01-01

A classic example of solid-state topochemical reactions is the ultraviolet-light induced photodimerization of α-trans-cinnamic acid (CA). Here, we report the first observation of an X-ray-induced dimerization of CA and monitor it in situ using nonresonant inelastic X-ray scattering spectroscopy (NRIXS). The time-evolution of the carbon core-electron excitation spectra shows the effects of two X-ray induced reactions: dimerization on a short time-scale and disintegration on a long time-scale. We used spectrum simulations of CA and its dimerization product, α-truxillic acid (TA), to gain insight into the dimerization effects. From the time-resolved spectra, we extracted component spectra and time-dependent weights corresponding to CA and TA. The results suggest that the X-ray induced dimerization proceeds homogeneously in contrast to the dimerization induced by ultraviolet light. We also utilized the ability of NRIXS for direct tomography with chemical-bond contrast to image the spatial progress of the reactions in the sample crystal. Our work paves the way for other time-resolved studies on chemical reactions using inelastic X-ray scattering. PMID:26568420

Tracking reaction dynamics in solution by pump-probe X-ray absorption spectroscopy and X-ray liquidography (solution scattering).

PubMed

Kim, Jeongho; Kim, Kyung Hwan; Oang, Key Young; Lee, Jae Hyuk; Hong, Kiryong; Cho, Hana; Huse, Nils; Schoenlein, Robert W; Kim, Tae Kyu; Ihee, Hyotcherl

2016-03-07

Characterization of transient molecular structures formed during chemical and biological processes is essential for understanding their mechanisms and functions. Over the last decade, time-resolved X-ray liquidography (TRXL) and time-resolved X-ray absorption spectroscopy (TRXAS) have emerged as powerful techniques for molecular and electronic structural analysis of photoinduced reactions in the solution phase. Both techniques make use of a pump-probe scheme that consists of (1) an optical pump pulse to initiate a photoinduced process and (2) an X-ray probe pulse to monitor changes in the molecular structure as a function of time delay between pump and probe pulses. TRXL is sensitive to changes in the global molecular structure and therefore can be used to elucidate structural changes of reacting solute molecules as well as the collective response of solvent molecules. On the other hand, TRXAS can be used to probe changes in both local geometrical and electronic structures of specific X-ray-absorbing atoms due to the element-specific nature of core-level transitions. These techniques are complementary to each other and a combination of the two methods will enhance the capability of accurately obtaining structural changes induced by photoexcitation. Here we review the principles of TRXL and TRXAS and present recent application examples of the two methods for studying chemical and biological processes in solution. Furthermore, we briefly discuss the prospect of using X-ray free electron lasers for the two techniques, which will allow us to keep track of structural dynamics on femtosecond time scales in various solution-phase molecular reactions.

High-temperature cuprate superconductors studied by x-ray Compton scattering and positron annihilation spectroscopies

NASA Astrophysics Data System (ADS)

Barbiellini, Bernardo

2013-06-01

The bulk Fermi surface in an overdoped (x = 0.3) single crystal of La2-xSrxCuO4 has been observed by using x-ray Compton scattering. This momentum density technique also provides a powerful tool for directly seeing what the dopant Sr atoms are doing to the electronic structure of La2CuO4. Because of wave function effects, positron annihilation spectroscopy does not yield a strong signature of the Fermi surface in extended momentum space, but it can be used to explore the role of oxygen defects in the reservoir layers for promoting high temperature superconductivity.

Impact of Oriented Clay Particles on X-Ray Spectroscopy Analysis

NASA Astrophysics Data System (ADS)

Lim, A. J. M. S.; Syazwani, R. N.; Wijeyesekera, D. C.

2016-07-01

Understanding the engineering properties of the mineralogy and microfabic of clayey soils is very complex and thus very difficult for soil characterization. Micromechanics of soils recognize that the micro structure and mineralogy of clay have a significant influence on its engineering behaviour. To achieve a more reliable quantitative evaluation of clay mineralogy, a proper sample preparation technique for quantitative clay mineral analysis is necessary. This paper presents the quantitative evaluation of elemental analysis and chemical characterization of oriented and random oriented clay particles using X-ray spectroscopy. Three different types of clays namely marine clay, bentonite and kaolin clay were studied. The oriented samples were prepared by placing the dispersed clay in water and left to settle on porous ceramic tiles by applying a relatively weak suction through a vacuum pump. Images form a Scanning Electron Microscope (SEM) was also used to show the comparison between the orientation patterns of both the sample preparation techniques. From the quantitative analysis of the X-ray spectroscopy, oriented sampling method showed more accuracy in identifying mineral deposits, because it produced better peak intensity on the spectrum and more mineral content can be identified compared to randomly oriented samples.

A broadband x-ray imaging spectroscopy with high-angular resolution: the FORCE mission

NASA Astrophysics Data System (ADS)

Mori, Koji; Tsuru, Takeshi Go; Nakazawa, Kazuhiro; Ueda, Yoshihiro; Okajima, Takashi; Murakami, Hiroshi; Awaki, Hisamitsu; Matsumoto, Hironori; Fukazawa, Yasushi; Tsunemi, Hiroshi; Takahashi, Tadayuki; Zhang, William W.

2016-07-01

We are proposing FORCE (Focusing On Relativistic universe and Cosmic Evolution) as a future Japan-lead Xray observatory to be launched in the mid 2020s. Hitomi (ASTRO-H) possesses a suite of sensitive instruments enabling the highest energy-resolution spectroscopy in soft X-ray band, a broadband X-ray imaging spectroscopy in soft and hard X-ray bands, and further high energy coverage up to soft gamma-ray band. FORCE is the direct successor to the broadband X-ray imaging spectroscopy aspect of Hitomi (ASTRO-H) with significantly higher angular resolution. The current design of FORCE defines energy band pass of 1-80 keV with angular resolution of < 15 in half-power diameter, achieving a 10 times higher sensitivity above 10 keV compared to any previous missions with simultaneous soft X-ray coverage. Our primary scientific objective is to trace the cosmic formation history by searching for "missing black holes" in various mass-scales: "buried supermassive black holes (SMBHs)" (> 104 M⊙) residing in the center of galaxies in a cosmological distance, "intermediate-mass black holes" (102-104 M⊙) acting as the possible seeds from which SMBHs grow, and "orphan stellar-mass black holes" (< 102 M⊙) without companion in our Galaxy. In addition to these missing BHs, hunting for the nature of relativistic particles at various astrophysical shocks is also in our scope, utilizing the broadband X-ray coverage with high angular-resolution. FORCE are going to open a new era in these fields. The satellite is proposed to be launched with the Epsilon vehicle that is a Japanese current solid-fuel rocket. FORCE carries three identical pairs of Super-mirror and wide-band X-ray detector. The focal length is currently planned to be 10 m. The silicon mirror with multi-layer coating is our primary choice to achieve lightweight, good angular optics. The detector is a descendant of hard X-ray imager onboard Hitomi (ASTRO-H) replacing its silicon strip detector with SOI-CMOS silicon pixel

Prediction of Ba, Co and Ni for tropical soils using diffuse reflectance spectroscopy and X-ray fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Arantes Camargo, Livia; Marques Júnior, José; Reynaldo Ferracciú Alleoni, Luís; Tadeu Pereira, Gener; De Bortoli Teixeira, Daniel; Santos Rabelo de Souza Bahia, Angélica

2017-04-01

Environmental impact assessments may be assisted by spatial characterization of potentially toxic elements (PTEs). Diffuse reflectance spectroscopy (DRS) and X-ray fluorescence spectroscopy (XRF) are rapid, non-destructive, low-cost, prediction tools for a simultaneous characterization of different soil attributes. Although low concentrations of PTEs might preclude the observation of spectral features, their contents can be predicted using spectroscopy by exploring the existing relationship between the PTEs and soil attributes with spectral features. This study aimed to evaluate, in three geomorphic surfaces of Oxisols, the capacity for predicting PTEs (Ba, Co, and Ni) and their spatial variability by means of diffuse reflectance spectroscopy (DRS) and X-ray fluorescence spectroscopy (XRF). For that, soil samples were collected from three geomorphic surfaces and analyzed for chemical, physical, and mineralogical properties, and then analyzed in DRS (visible + near infrared - VIS+NIR and medium infrared - MIR) and XRF equipment. PTE prediction models were calibrated using partial least squares regression (PLSR). PTE spatial distribution maps were built using the values calculated by the calibrated models that reached the best accuracy using geostatistics. PTE prediction models were satisfactorily calibrated using MIR DRS for Ba, and Co (residual prediction deviation - RPD > 3.0), Vis DRS for Ni (RPD > 2.0) and FRX for all the studied PTEs (RPD > 1.8). DRS- and XRF-predicted values allowed the characterization and the understanding of spatial variability of the studied PTEs.

Background radiation in inelastic X-ray scattering and X-ray emission spectroscopy. A study for Johann-type spectrometers

NASA Astrophysics Data System (ADS)

Paredes Mellone, O. A.; Bianco, L. M.; Ceppi, S. A.; Goncalves Honnicke, M.; Stutz, G. E.

2018-06-01

A study of the background radiation in inelastic X-ray scattering (IXS) and X-ray emission spectroscopy (XES) based on an analytical model is presented. The calculation model considers spurious radiation originated from elastic and inelastic scattering processes along the beam paths of a Johann-type spectrometer. The dependence of the background radiation intensity on the medium of the beam paths (air and helium), analysed energy and radius of the Rowland circle was studied. The present study shows that both for IXS and XES experiments the background radiation is dominated by spurious radiation owing to scattering processes along the sample-analyser beam path. For IXS experiments the spectral distribution of the main component of the background radiation shows a weak linear dependence on the energy for the most cases. In the case of XES, a strong non-linear behaviour of the background radiation intensity was predicted for energy analysis very close to the backdiffraction condition, with a rapid increase in intensity as the analyser Bragg angle approaches π / 2. The contribution of the analyser-detector beam path is significantly weaker and resembles the spectral distribution of the measured spectra. Present results show that for usual experimental conditions no appreciable structures are introduced by the background radiation into the measured spectra, both in IXS and XES experiments. The usefulness of properly calculating the background profile is demonstrated in a background subtraction procedure for a real experimental situation. The calculation model was able to simulate with high accuracy the energy dependence of the background radiation intensity measured in a particular XES experiment with air beam paths.

The characterization of Cr secondary oxide phases in ZnO films studied by X-ray spectroscopy and photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Chiou, J. W.; Chang, S. Y.; Huang, W. H.; Chen, Y. T.; Hsu, C. W.; Hu, Y. M.; Chen, J. M.; Chen, C.-H.; Kumar, K.; Guo, J.-H.

2011-03-01

X-ray absorption near-edge structure (XANES), X-ray emission spectroscopy (XES), and X-ray photoemission spectroscopy (XPS) were used to characterize the Cr secondary oxide phases in ZnO films that had been prepared using a co-sputtering method. Analysis of the Cr L3,2-edge XANES spectra reveals that the intensity of white-line features decreases subtly as the sputtering power increases, indicating that the occupation of Cr 3 d orbitals increases with Cr concentration in (Zn, Cr)O films. The O K-edge spectra show that the intensity of XANES features of (Zn, Cr)O films is lower than those of ZnO film, suggesting enhanced occupation of O 2 p-derived states through O 2 p-Cr 3 d hybridization. The XES and XPS spectra indicate that the line shapes in the valence band of (Zn, Cr)O films are quite different from those of ZnO and that the Cr 2O 3 phase dominates the spinel structure of (Zn, Cr)O films increasingly as the Cr sputtering power is increased. Over all results suggest that the non-ferromagnetic behavior of (Zn, Cr)O films can be attributed to the dominant presence of Cr 2O 3, whereas the bulk comprise phase segregations of Cr 2O 3 and/or ZnCr 2O 4, which results them the most stable TM-doped ZnO material against etching.

Study of Cr(VI) adsorption onto magnetite nanoparticles using synchrotron-based X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Chen, Yen-Hua; Liu, Dian-Yu; Lee, Jyh-Fu

2018-04-01

In this study, the efficiency of Cr(VI) adsorption onto nano-magnetite was examined by batch experiments, and the Cr(VI) adsorption mechanism was investigated using synchrotron-based X-ray absorption spectroscopy. Magnetite nanoparticles with a mean diameter of 10 nm were synthesized using an inexpensive and simple co-precipitation method. It shows a saturation magnetization of 54.3 emu/g, which can be recovered with an external magnetic field. The adsorption data fitted the Langmuir adsorption isotherm well, implying a monolayer adsorption behavior of Cr(VI) onto nano-magnetite. X-ray absorption spectroscopy results indicate that the adsorption mechanism involves electron transfer between Fe(II) in nano-magnetite (Fe2+OFe3+ 2O3) and Cr(VI) to transform into Cr(III), which may exist as an Fe(III)-Cr(III) mixed solid phase. Moreover, the Cr(III)/Cr(VI) ratio in the final products can be determined by the characteristic pre-edge peak area of Cr(VI) in the Cr K-edge spectrum. These findings suggest that nano-magnetite is effective for Cr(VI) removal from wastewater because it can transform highly poisonous Cr(VI) species into nontoxic Cr(III) compounds, which are highly insoluble and immobile under environmental conditions.

X-ray Spectroscopy and Magnetism in Mineralogy

NASA Astrophysics Data System (ADS)

Sainctavit, Philippe; Brice-Profeta, Sandrine; Gaudry, Emilie; Letard, Isabelle; Arrio, Marie-Anne

The objective of this paper is to present the kind of information that can be gained in the field of mineralogy from the use of x-ray magnetic spectroscopies. We review some of the questions that are unsettled and that could benefit from an interdisciplinary approach where magnetism, spectroscopy and mineralogy could be mixed. Most of the attention is focused on iron and some other 3d transition elements. The mineralogy of planetary cores and its relation with known meteorites are exemplified. The various oxide phases in the mantle and the nature of iron in these phases is also underlined. The presence of transition elements in insulating minerals and its relation with macroscopic properties such as the color of gemstones are reviewed. Finally an introduction to paleomagnetism is given with a special attention to nanomaghemites.

Diamond sensors and polycapillary lenses for X-ray absorption spectroscopy.

PubMed

Ravel, B; Attenkofer, K; Bohon, J; Muller, E; Smedley, J

2013-10-01

Diamond sensors are evaluated as incident beam monitors for X-ray absorption spectroscopy experiments. These single crystal devices pose a challenge for an energy-scanning experiment using hard X-rays due to the effect of diffraction from the crystalline sensor at energies which meet the Bragg condition. This problem is eliminated by combination with polycapillary lenses. The convergence angle of the beam exiting the lens is large compared to rocking curve widths of the diamond. A ray exiting one capillary from the lens meets the Bragg condition for any reflection at a different energy from the rays exiting adjacent capillaries. This serves to broaden each diffraction peak over a wide energy range, allowing linear measurement of incident intensity over the range of the energy scan. Extended X-ray absorption fine structure data are measured with a combination of a polycapillary lens and a diamond incident beam monitor. These data are of comparable quality to data measured without a lens and with an ionization chamber monitoring the incident beam intensity.

Studies of x-ray localization and thickness dependence in atomic-scale elemental mapping by STEM energy-dispersive x-ray spectroscopy using single-frame scanning method

DOE PAGES

Lu, Ping; Moya, Jaime M.; Yuan, Renliang; ...

2018-03-01

The delocalization of x-ray signals limits the spatial resolution in atomic-scale elemental mapping by scanning transmission electron microscopy (STEM) using energy-dispersive x-ray spectroscopy (EDS). In this study, using a SrTiO 3 [001] single crystal, we show that the x-ray localization to atomic columns is strongly dependent on crystal thickness, and a thin crystal is critical for improving the spatial resolution in atomic-scale EDS mapping. A single-frame scanning technique is used in this study instead of the multiple-frame technique to avoid peak broadening due to tracking error. The strong thickness dependence is realized by measuring the full width at half maximamore » (FWHM) as well as the peak-to-valley (P/V) ratio of the EDS profiles for Ti K and Sr K+L, obtained at several crystal thicknesses. A FWHM of about 0.16 nm and a P/V ratio of greater than 7.0 are obtained for Ti K for a crystal thickness of less than 20 nm. In conclusion, with increasing crystal thickness, the FWHM and P/V ratio increases and decreases, respectively, indicating the advantage of using a thin crystal for high-resolution EDS mapping.« less

Studies of x-ray localization and thickness dependence in atomic-scale elemental mapping by STEM energy-dispersive x-ray spectroscopy using single-frame scanning method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Ping; Moya, Jaime M.; Yuan, Renliang

The delocalization of x-ray signals limits the spatial resolution in atomic-scale elemental mapping by scanning transmission electron microscopy (STEM) using energy-dispersive x-ray spectroscopy (EDS). In this study, using a SrTiO 3 [001] single crystal, we show that the x-ray localization to atomic columns is strongly dependent on crystal thickness, and a thin crystal is critical for improving the spatial resolution in atomic-scale EDS mapping. A single-frame scanning technique is used in this study instead of the multiple-frame technique to avoid peak broadening due to tracking error. The strong thickness dependence is realized by measuring the full width at half maximamore » (FWHM) as well as the peak-to-valley (P/V) ratio of the EDS profiles for Ti K and Sr K+L, obtained at several crystal thicknesses. A FWHM of about 0.16 nm and a P/V ratio of greater than 7.0 are obtained for Ti K for a crystal thickness of less than 20 nm. In conclusion, with increasing crystal thickness, the FWHM and P/V ratio increases and decreases, respectively, indicating the advantage of using a thin crystal for high-resolution EDS mapping.« less

Studies of x-ray localization and thickness dependence in atomic-scale elemental mapping by STEM energy-dispersive x-ray spectroscopy using single-frame scanning method.

PubMed

Lu, Ping; Moya, Jaime M; Yuan, Renliang; Zuo, Jian Min

2018-03-01

The delocalization of x-ray signals limits the spatial resolution in atomic-scale elemental mapping by scanning transmission electron microscopy (STEM) using energy-dispersive x-ray spectroscopy (EDS). In this study, using a SrTiO 3 [001] single crystal, we show that the x-ray localization to atomic columns is strongly dependent on crystal thickness, and a thin crystal is critical for improving the spatial resolution in atomic-scale EDS mapping. A single-frame scanning technique is used in this study instead of the multiple-frame technique to avoid peak broadening due to tracking error. The strong thickness dependence is realized by measuring the full width at half maxima (FWHM) as well as the peak-to-valley (P/V) ratio of the EDS profiles for Ti K and Sr K + L, obtained at several crystal thicknesses. A FWHM of about 0.16 nm and a P/V ratio of greater than 7.0 are obtained for Ti K for a crystal thickness of less than 20 nm. With increasing crystal thickness, the FWHM and P/V ratio increases and decreases, respectively, indicating the advantage of using a thin crystal for high-resolution EDS mapping. Published by Elsevier B.V.

Simultaneous Femtosecond X-ray Spectroscopy and Diffraction of Photosystem II at Room Temperature

PubMed Central

Kern, Jan; Alonso-Mori, Roberto; Tran, Rosalie; Hattne, Johan; Gildea, Richard J.; Echols, Nathaniel; Glöckner, Carina; Hellmich, Julia; Laksmono, Hartawan; Sierra, Raymond G.; Lassalle-Kaiser, Benedikt; Koroidov, Sergey; Lampe, Alyssa; Han, Guangye; Gul, Sheraz; DiFiore, Dörte; Milathianaki, Despina; Fry, Alan R.; Miahnahri, Alan; Schafer, Donald W.; Messerschmidt, Marc; Seibert, M. Marvin; Koglin, Jason E.; Sokaras, Dimosthenis; Weng, Tsu-Chien; Sellberg, Jonas; Latimer, Matthew J.; Grosse-Kunstleve, Ralf W.; Zwart, Petrus H.; White, William E.; Glatzel, Pieter; Adams, Paul D.; Bogan, Michael J.; Williams, Garth J.; Boutet, Sébastien; Messinger, Johannes; Zouni, Athina; Sauter, Nicholas K.; Yachandra, Vittal K.; Bergmann, Uwe; Yano, Junko

2013-01-01

Intense femtosecond X-ray pulses produced at the Linac Coherent Light Source (LCLS) were used for simultaneous X-ray diffraction (XRD) and X-ray emission spectroscopy (XES) of microcrystals of Photosystem II (PS II) at room temperature. This method probes the overall protein structure and the electronic structure of the Mn4CaO5 cluster in the oxygen-evolving complex of PS II. XRD data are presented from both the dark state (S1) and the first illuminated state (S2) of PS II. Our simultaneous XRD/XES study shows that the PS II crystals are intact during our measurements at the LCLS, not only with respect to the structure of PS II, but also with regard to the electronic structure of the highly radiation sensitive Mn4CaO5 cluster, opening new directions for future dynamics studies. PMID:23413188

Simultaneous femtosecond X-ray spectroscopy and diffraction of photosystem II at room temperature.

PubMed

Kern, Jan; Alonso-Mori, Roberto; Tran, Rosalie; Hattne, Johan; Gildea, Richard J; Echols, Nathaniel; Glöckner, Carina; Hellmich, Julia; Laksmono, Hartawan; Sierra, Raymond G; Lassalle-Kaiser, Benedikt; Koroidov, Sergey; Lampe, Alyssa; Han, Guangye; Gul, Sheraz; Difiore, Dörte; Milathianaki, Despina; Fry, Alan R; Miahnahri, Alan; Schafer, Donald W; Messerschmidt, Marc; Seibert, M Marvin; Koglin, Jason E; Sokaras, Dimosthenis; Weng, Tsu-Chien; Sellberg, Jonas; Latimer, Matthew J; Grosse-Kunstleve, Ralf W; Zwart, Petrus H; White, William E; Glatzel, Pieter; Adams, Paul D; Bogan, Michael J; Williams, Garth J; Boutet, Sébastien; Messinger, Johannes; Zouni, Athina; Sauter, Nicholas K; Yachandra, Vittal K; Bergmann, Uwe; Yano, Junko

2013-04-26

Intense femtosecond x-ray pulses produced at the Linac Coherent Light Source (LCLS) were used for simultaneous x-ray diffraction (XRD) and x-ray emission spectroscopy (XES) of microcrystals of photosystem II (PS II) at room temperature. This method probes the overall protein structure and the electronic structure of the Mn4CaO5 cluster in the oxygen-evolving complex of PS II. XRD data are presented from both the dark state (S1) and the first illuminated state (S2) of PS II. Our simultaneous XRD-XES study shows that the PS II crystals are intact during our measurements at the LCLS, not only with respect to the structure of PS II, but also with regard to the electronic structure of the highly radiation-sensitive Mn4CaO5 cluster, opening new directions for future dynamics studies.

X-ray Fluorescence Spectroscopy of Pre-Federal American Currency

NASA Astrophysics Data System (ADS)

Raddell, Mark; Manukyan, Khachatur; Aprahamian, Ani; Wiescher, Michael; Jordan, Louis

2017-09-01

X-ray Fluorescence Spectroscopy (XRF) was used to study 17th and 18th century Mexican, Potosí, and Massachusetts silver colonial coins from the University of Notre Dame's Rare Books and Special Collections. Using different configurations and devices, we have learned more about the limitations and optimizations of the method. We have developed a moveable stand that may be used for XRF mapping of coin surfaces. We created standard silver alloy materials for quantification of the elemental composition of the coins. Inductively coupled plasma (ICP) spectroscopy was applied to determine the precise composition of the standards for accurate and non-destructive analyses of the colonial coins. XRF measurements were performed using two different XRF spectrometers, in both air and vacuum conditions, as well as an x-ray beam tube of varying diameters from 2 mm, 1 mm, and 0.03 mm. We quantified both the major elements and the bulk and surface impurities for 90 coins. We are using PCA to look at possible correlations between compositions of coinage from different geographical regions. Preliminary data analyses suggest that Massachusetts coins were minted using silver from Latin American sources. These results are of great interest to historians in tracing the origins of the currency. This work was made possible by the Notre Dame College of Science Summer Undergraduate Research Fellowships (COS-SURF).

Tenth International Colloquium on UV and X-Ray Spectroscopy of Astrophysical and Laboratory Plasmas

NASA Astrophysics Data System (ADS)

Silver, Eric H.; Kahn, Steven M.

UV and X-ray spectroscopy of astrophysical and laboratory plasmas draws interest from many disciplines. Contributions from international specialists are collected together in this book from a timely recent conference. In astrophysics, the Hubble Space Telescope, Astro 1 and ROSAT observatories are now providing UV and X-ray spectra and images of cosmic sources in unprecedented detail, while the Yohkoh mission recently collected superb data on the solar corona. In the laboratory, the development of ion-trap facilities and novel laser experiments are providing vital new data on high temperature plasmas. Recent innovations in the technology of spectroscopic instrumentation are discussed. These papers constitute an excellent up-to-date review of developments in short-wavelength spectroscopy and offer a solid introduction to its theoretical and experimental foundations. These proceedings give an up-to-date review of developments in short-wavelength spectroscopy and offer a solid introduction to its theoretical and experimental foundations. Various speakers presented some of the first results from the high resolution spectrograph on the Hubble Space Telescope, the high sensitivity far ultraviolet and X-ray spectrometers of the ASTRO 1 Observatory, the imaging X-ray spectrometer on the ROSAT Observatory, and the high resolution solar X-ray spectrometer on Yohkoh. The development of ion trap devices had brought about a revolution in laboratory investigations of atomic processes in highly charged atoms. X-ray laser experiments had not only yielded considerable insight into electron ion interactions in hot dense plasmas, but also demonstrated the versatility of laser plasmas as laboratory X-ray sources. Such measurements also motivated and led to refinements in the development of large-scale atomic and molecular codes. On the instrumental side, the design and development of the next series of very powerful short wavelength observatories had generated a large number of

Characterization of aluminum nitride based films with high resolution X-ray fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Anagnostopoulos, D. F.; Siozios, A.; Patsalas, P.

2018-02-01

X-ray fluorescence spectra of Al based films are measured, using a lab-scale wavelength dispersive flat crystal spectrometer. Various structures of AlN films were studied, like single layered, capped, stratified, nanostructured, crystalline, or amorphous. By optimizing the set-up for enhanced energy resolution and detection efficiency, the measured line shapes of Κα, Kβ, and KLL radiative Auger transitions are shown to be adequately detailed to allow chemical characterization. The chemistry identification is based on the pattern comparison of the emitted line shape from the chemically unknown film and the reference line shapes from standard materials, recorded under identical experimental conditions. The ultimate strength of lab-scale high resolution X-ray fluorescence spectroscopy on film analysis is verified, in cases that ordinary applied techniques like X-ray photoelectron and X-ray diffraction fail, while the characterization refers to the non-destructive determination of the bulk properties of the film and not to its surface, as the probed depth is in the micrometer range.

Deconvolving instrumental and intrinsic broadening in core-shell x-ray spectroscopies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fister, T. T.; Seidler, G. T.; Rehr, J. J.

2007-05-01

Intrinsic and experimental mechanisms frequently lead to broadening of spectral features in core-shell spectroscopies. For example, intrinsic broadening occurs in x-ray absorption spectroscopy (XAS) measurements of heavy elements where the core-hole lifetime is very short. On the other hand, nonresonant x-ray Raman scattering (XRS) and other energy loss measurements are more limited by instrumental resolution. Here, we demonstrate that the Richardson-Lucy (RL) iterative algorithm provides a robust method for deconvolving instrumental and intrinsic resolutions from typical XAS and XRS data. For the K-edge XAS of Ag, we find nearly complete removal of {approx}9.3 eV full width at half maximum broadeningmore » from the combined effects of the short core-hole lifetime and instrumental resolution. We are also able to remove nearly all instrumental broadening in an XRS measurement of diamond, with the resulting improved spectrum comparing favorably with prior soft x-ray XAS measurements. We present a practical methodology for implementing the RL algorithm in these problems, emphasizing the importance of testing for stability of the deconvolution process against noise amplification, perturbations in the initial spectra, and uncertainties in the core-hole lifetime.« less

Hydrothermal Diamond Anvil Cell (HDAC): From Visual Observation to X-ray Absorption Spectroscopy

NASA Astrophysics Data System (ADS)

Bassett, W. A.; Mibe, K.

2006-05-01

A fluid sample contained in a Re gasket between two diamond anvils can be subjected to pressures up to 2.5 GPa and temperatures up to 1200°C in a resistively heated hydrothermal diamond anvil cell (HDAC). Thermocouples are used to measure temperature. The constant-volume sample chamber permits isochoric measurements that can be used to determine pressure from the equation of state of H2O and to map phases and properties in P-T space. A movie of reactions between K-feldspar and water up to 2.5 GPa and 880°C illustrates the use of visual observations for mapping coexisting solution, melt, and solid phases. X-ray absorption spectroscopy of ZnBr2 in solution up to 500°C and 500 MPa shows hydrogen bond breaking in the hydration shells of the ZnBr42- and Br- ions with increasing temperature. In other studies the stability field of ikaite (CaCO3·6H2O) has been mapped by visual observation and Raman spectroscopy; the phases of montmorillonite have been mapped by X-ray diffraction; and the leaching of Pb from zircon has been measured by X-ray microprobe.

X-ray diagnostics of massive star winds

NASA Astrophysics Data System (ADS)

Oskinova, L. M.; Ignace, R.; Huenemoerder, D. P.

2017-11-01

Observations with powerful X-ray telescopes, such as XMM-Newton and Chandra, significantly advance our understanding of massive stars. Nearly all early-type stars are X-ray sources. Studies of their X-ray emission provide important diagnostics of stellar winds. High-resolution X-ray spectra of O-type stars are well explained when stellar wind clumping is taking into account, providing further support to a modern picture of stellar winds as non-stationary, inhomogeneous outflows. X-ray variability is detected from such winds, on time scales likely associated with stellar rotation. High-resolution X-ray spectroscopy indicates that the winds of late O-type stars are predominantly in a hot phase. Consequently, X-rays provide the best observational window to study these winds. X-ray spectroscopy of evolved, Wolf-Rayet type, stars allows to probe their powerful metal enhanced winds, while the mechanisms responsible for the X-ray emission of these stars are not yet understood.

Annealing induced atomic rearrangements on (Ga,In) (N,As) probed by hard X-ray photoelectron spectroscopy and X-ray absorption fine structure.

PubMed

Ishikawa, Fumitaro; Higashi, Kotaro; Fuyuno, Satoshi; Morifuji, Masato; Kondow, Masahiko; Trampert, Achim

2018-04-13

We study the effects of annealing on (Ga 0.64 ,In 0.36 ) (N 0.045 ,As 0.955 ) using hard X-ray photoelectron spectroscopy and X-ray absorption fine structure measurements. We observed surface oxidation and termination of the N-As bond defects caused by the annealing process. Specifically, we observed a characteristic chemical shift towards lower binding energies in the photoelectron spectra related to In. This phenomenon appears to be caused by the atomic arrangement, which produces increased In-N bond configurations within the matrix, as indicated by the X-ray absorption fine structure measurements. The reduction in the binding energies of group-III In, which occurs concomitantly with the atomic rearrangements of the matrix, causes the differences in the electronic properties of the system before and after annealing.

Ultra-Small-Angle X-ray Scattering – X-ray Photon Correlation Spectroscopy Studies of Incipient Structural Changes in Amorphous Calcium Phosphate Based Dental Composites

PubMed Central

Zhang, F.; Allen, A.J.; Levine, L.E.; Espinal, L.; Antonucci, J.M.; Skrtic, D.; O’Donnell, J.N.R.; Ilavsky, J.

2012-01-01

The local structural changes in amorphous calcium phosphate (ACP) based dental composites were studied under isothermal conditions using both static, bulk measurement techniques and a recently developed methodology based on combined ultra-small angle X-ray scattering – X-ray photon correlation spectroscopy (USAXS-XPCS), which permits a dynamic approach. While results from conventional bulk measurements do not show clear signs of structural change, USAXS-XPCS results reveal unambiguous evidence for local structural variations on a similar time scale to that of water loss in the ACP fillers. A thermal-expansion based simulation indicates that thermal behavior alone does not account for the observed dynamics. Together, these results suggest that changes in the water content of ACP affect the composite morphology due to changes in ACP structure that occur without an amorphous-to-crystalline conversion. It is also noted that biomedical materials research could benefit greatly from USAXS-XPCS, a dynamic approach. PMID:22374649

Oxidant K edge x-ray emission spectroscopy of UF 4 and UO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tobin, J. G.; Yu, S. -W.; Qiao, R.

The K-Edge (1s) x-ray emission spectroscopy of uranium tetrafluoride and uranium dioxide were compared to each other and to the results of a pair of earlier cluster calculations. Here, using a very simplified approach, it is possible to qualitatively reconstruct the main features of the x-ray emission spectra from the cluster calculation state energies and 2p percentages.

Oxidant K edge x-ray emission spectroscopy of UF 4 and UO 2

DOE PAGES

Tobin, J. G.; Yu, S. -W.; Qiao, R.; ...

2018-01-31

The K-Edge (1s) x-ray emission spectroscopy of uranium tetrafluoride and uranium dioxide were compared to each other and to the results of a pair of earlier cluster calculations. Here, using a very simplified approach, it is possible to qualitatively reconstruct the main features of the x-ray emission spectra from the cluster calculation state energies and 2p percentages.

A reaction cell with sample laser heating for in situ soft X-ray absorption spectroscopy studies under environmental conditions.

PubMed

Escudero, Carlos; Jiang, Peng; Pach, Elzbieta; Borondics, Ferenc; West, Mark W; Tuxen, Anders; Chintapalli, Mahati; Carenco, Sophie; Guo, Jinghua; Salmeron, Miquel

2013-05-01

A miniature (1 ml volume) reaction cell with transparent X-ray windows and laser heating of the sample has been designed to conduct X-ray absorption spectroscopy studies of materials in the presence of gases at atmospheric pressures. Heating by laser solves the problems associated with the presence of reactive gases interacting with hot filaments used in resistive heating methods. It also facilitates collection of a small total electron yield signal by eliminating interference with heating current leakage and ground loops. The excellent operation of the cell is demonstrated with examples of CO and H2 Fischer-Tropsch reactions on Co nanoparticles.

Soft X-ray photoemission study of Co2(Cr1-xFex)Ga Heusler compounds

NASA Astrophysics Data System (ADS)

Tsunekawa, Masanori; Hattori, Yoshiro; Sekiyama, Akira; Fujiwara, Hidenori; Suga, Shigemasa; Muro, Takayuki; Kanomata, Takeshi; Imada, Shin

2015-08-01

We have performed soft X-ray photoemission spectroscopy (SXPES) and X-ray absorption spectroscopy (XAS) of the Co-based Heusler compounds Co2(Cr1-xFex)Ga (x = 0.0, 0.4, and 1.0) in order to study their electronic structures. Band-structure calculation was carried out and compared with the experimental results. SXPES spectra show hν-dependence, revealing the contributions of the Co, Cr, and Fe 3d electronic states in the valence band. The band width observed by the SXPES seems to be narrower than that predicted by the band-structure calculation. XAS spectra depend strongly on the the value of x in Co2(Cr1-xFex)Ga. The electron correlation effects are found to be stronger as x changes from 0.0 to 1.0.

Surface layering and melting in an ionic liquid studied by resonant soft X-ray reflectivity

PubMed Central

Mezger, Markus; Ocko, Benjamin M.; Reichert, Harald; Deutsch, Moshe

2013-01-01

The molecular-scale structure of the ionic liquid [C18mim]+[FAP]− near its free surface was studied by complementary methods. X-ray absorption spectroscopy and resonant soft X-ray reflectivity revealed a depth-decaying near-surface layering. Element-specific interfacial profiles were extracted with submolecular resolution from energy-dependent soft X-ray reflectivity data. Temperature-dependent hard X-ray reflectivity, small- and wide-angle X-ray scattering, and infrared spectroscopy uncovered an intriguing melting mechanism for the layered region, where alkyl chain melting drove a negative thermal expansion of the surface layer spacing. PMID:23431181

STROBE-X: X-ray Timing & Spectroscopy on Dynamical Timescales from Microseconds to Years

NASA Astrophysics Data System (ADS)

Wilson-Hodge, Colleen A.; Ray, Paul S.; Maccarone, Thomas J.; Chakrabarty, Deepto; Gendreau, Keith C.; Arzoumanian, Zaven; Jenke, Peter; Ballantyne, David; Bozzo, Enrico; Brandt, Soren; Brenneman, Laura; Christophersen, Marc; DeRosa, Alessandra; Feroci, Marco; Goldstein, Adam; Hartmann, Dieter; Hernanz, Margarita; McDonald, Michael; Phlips, Bernard; Remillard, Ronald; Stevens, Abigail; Tomsick, John; Watts, Anna; Wood, Kent S.; Zane, Silvia; STROBE-X Collaboration

2018-01-01

We describe a probe-class mission concept that provides an unprecedented view of the X-ray sky, performing timing and 0.2-30 keV spectroscopy over timescales from microseconds to years. The Spectroscopic Time-Resolving Observatory for Broadband Energy X-rays (STROBE-X) comprises three primary instruments. The first uses an array of lightweight optics (3-m focal length) that concentrate incident photons onto solid state detectors with CCD-level (85-130 eV) energy resolution, 100 ns time resolution, and low background rates to cover the 0.2-12 keV band. This technology is scaled up from NICER, with enhanced optics to take advantage of the longer focal length of STROBE-X. The second uses large-area collimated silicon drift detectors, developed for ESA's LOFT, to cover the 2-30 keV band. These two instruments each provide an order of magnitude improvement in effective area compared with its predecessor (NICER and RXTE, respectively). Finally, a sensitive sky monitor triggers pointed observations, provides high duty cycle, high time resolution, high spectral resolution monitoring of the X-ray sky with ~20 times the sensitivity of the RXTE ASM, and enables multi-wavelength and multi-messenger studies on a continuous, rather than scanning basis. We include updated instrument designs resulting from the GSFC IDL run in November 2017.For the first time, the broad coverage provides simultaneous study of thermal components, non-thermal components, iron lines, and reflection features from a single platform for accreting black holes at all scales. The enormous collecting area allows detailed studies of the dense matter equation of state using both thermal emission from rotation-powered pulsars and harder emission from X-ray burst oscillations. The combination of the wide-field monitor and the sensitive pointed instruments enables observations of potential electromagnetic counterparts to LIGO/Virgo and neutrino events. Extragalactic science, such as constraining bulk metalicity

Metalloprotein structures at ambient conditions and in real-time: biological crystallography and spectroscopy using X-ray free electron lasers

DOE PAGES

Kern, Jan; Yachandra, Vittal K.; Yano, Junko

2015-09-02

We have studied the structure of enzymes and the chemistry at the catalytic sites, intensively and have acquired an understanding of the atomic-scale chemistry which requires a new approach beyond steady state X-ray crystallography and X-ray spectroscopy at cryogenic temperatures. Following the dynamic changes in the geometric and electronic structure of metallo-enzymes at ambient conditions, while overcoming the severe X-ray-induced changes to the redox active catalytic center, is key for deriving reaction mechanisms. Such studies become possible by the intense and ultra-short femtosecond (fs) X-ray pulses from an X-ray free electron laser (XFEL) by acquiring a signal before the samplemore » is destroyed. Our review describes the recent and pioneering uses of XFELs to study the protein structure and dynamics of metallo-enzymes using crystallography and scattering, as well as the chemical structure and dynamics of the catalytic complexes (charge, spin, and covalency) using spectroscopy during the reaction to understand the electron-transfer processes and elucidate the mechanism.« less

Metalloprotein structures at ambient conditions and in real-time: biological crystallography and spectroscopy using X-ray free electron lasers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kern, Jan; Yachandra, Vittal K.; Yano, Junko

We have studied the structure of enzymes and the chemistry at the catalytic sites, intensively and have acquired an understanding of the atomic-scale chemistry which requires a new approach beyond steady state X-ray crystallography and X-ray spectroscopy at cryogenic temperatures. Following the dynamic changes in the geometric and electronic structure of metallo-enzymes at ambient conditions, while overcoming the severe X-ray-induced changes to the redox active catalytic center, is key for deriving reaction mechanisms. Such studies become possible by the intense and ultra-short femtosecond (fs) X-ray pulses from an X-ray free electron laser (XFEL) by acquiring a signal before the samplemore » is destroyed. Our review describes the recent and pioneering uses of XFELs to study the protein structure and dynamics of metallo-enzymes using crystallography and scattering, as well as the chemical structure and dynamics of the catalytic complexes (charge, spin, and covalency) using spectroscopy during the reaction to understand the electron-transfer processes and elucidate the mechanism.« less

Diagnosis of a two wire X-pinch by X-ray absorption spectroscopy utilizing a doubly curved ellipsoidal crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cahill, A. D., E-mail: adc87@cornell.edu; Hoyt, C. L., E-mail: adc87@cornell.edu; Shelkovenko, T. A., E-mail: adc87@cornell.edu

2014-12-15

X-ray absorption spectroscopy is a powerful tool for the diagnosis of plasmas over a wide range of both temperature and density. However, such a measurement is often limited to probing plasmas with temperatures well below that of the x-ray source in order to avoid object plasma emission lines from obscuring important features of the absorption spectrum. This has excluded many plasmas from being investigated by this technique. We have developed an x-ray spectrometer that provides the ability to record absorption spectra from higher temperature plasmas than the usual approach allows without the risk of data contamination by line radiation emittedmore » by the plasma under study. This is accomplished using a doubly curved mica crystal which is bent both elliptically and cylindrically. We present here initial absorption spectra obtained from an aluminum x-pinch plasma.« less

Low Dose X-Ray Speckle Visibility Spectroscopy Reveals Nanoscale Dynamics in Radiation Sensitive Ionic Liquids

NASA Astrophysics Data System (ADS)

Verwohlt, Jan; Reiser, Mario; Randolph, Lisa; Matic, Aleksandar; Medina, Luis Aguilera; Madsen, Anders; Sprung, Michael; Zozulya, Alexey; Gutt, Christian

2018-04-01

X-ray radiation damage provides a serious bottleneck for investigating microsecond to second dynamics on nanometer length scales employing x-ray photon correlation spectroscopy. This limitation hinders the investigation of real time dynamics in most soft matter and biological materials which can tolerate only x-ray doses of kGy and below. Here, we show that this bottleneck can be overcome by low dose x-ray speckle visibility spectroscopy. Employing x-ray doses of 22-438 kGy and analyzing the sparse speckle pattern of count rates as low as 6.7 ×10-3 per pixel, we follow the slow nanoscale dynamics of an ionic liquid (IL) at the glass transition. At the prepeak of nanoscale order in the IL, we observe complex dynamics upon approaching the glass transition temperature TG with a freezing in of the alpha relaxation and a multitude of millisecond local relaxations existing well below TG . We identify this fast relaxation as being responsible for the increasing development of nanoscale order observed in ILs at temperatures below TG .

Pushing the Boundaries of X-ray Grating Spectroscopy in a Suborbital Rocket

NASA Technical Reports Server (NTRS)

McEntaffer, Randall L.; DeRoo, Casey; Schultz, Ted; Zhang, William W.; Murray, Neil J.; O'Dell, Stephen; Cash, Webster

2013-01-01

Developments in grating spectroscopy are paramount for meeting the soft X-ray science goals of future NASA X-ray Observatories. While developments in the laboratory setting have verified the technical feasibility of using off-plane reflection gratings to reach this goal, flight heritage is a key step in the development process toward large missions. To this end we have developed a design for a suborbital rocket payload employing an Off-Plane X-ray Grating Spectrometer. This spectrometer utilizes slumped glass Wolter-1 optics, an array of gratings, and a CCD camera. We discuss the unique capabilities of this design, the expected performance, the science return, and the perceived impact to future missions.

X-ray Spectroscopy of a TDE

NASA Astrophysics Data System (ADS)

Kochanek, Christopher

2017-09-01

Tidal disruption events (TDE), where supermassive black holes destroy stars to produce accretion flares, are of great current observational and theoretical interest. Here we propose a four epoch HRC/LETG X-ray spectroscopic ``movie'' of a TDE spread over the first 40 days of an X-ray bright TDE, including any discovered by our ASAS-SN survey, supported and extended by higher cadence Swift XRT/UVOT observations over the first 100 days. For this next X-ray bright TDE, we will measure the evolution of the X-ray emission (luminosity/temperature) from the hot accretion disk, the emission reprocessed by the debris into UV/optical, and use X-ray absorption (or emission) features to look at the abundances and the evolution of the kinematics and ionization parameter.

Component analyses of urinary nanocrystallites of uric acid stone formers by combination of high-resolution transmission electron microscopy, fast Fourier transformation, energy dispersive X-ray spectroscopy, X-ray diffraction and Fourier transform infrared spectroscopy.

PubMed

Sun, Xin-Yuan; Xue, Jun-Fa; Xia, Zhi-Yue; Ouyang, Jian-Ming

2015-06-01

This study aimed to analyse the components of nanocrystallites in urines of patients with uric acid (UA) stones. X-ray diffraction (XRD), Fourier transform infrared spectroscopy, high-resolution transmission electron microscopy (HRTEM), fast Fourier transformation (FFT) of HRTEM, and energy dispersive X-ray spectroscopy (EDS) were performed to analyse the components of these nanocrystallites. XRD and FFT showed that the main component of urinary nanocrystallites was UA, which contains a small amount of calcium oxalate monohydrate and phosphates. EDS showed the characteristic absorption peaks of C, O, Ca and P. The formation of UA stones was closely related to a large number of UA nanocrystallites in urine. A combination of HRTEM, FFT, EDS and XRD analyses could be performed accurately to analyse the components of urinary nanocrystallites.

An x-ray absorption spectroscopy study of Ni-Mn-Ga shape memory alloys.

PubMed

Sathe, V G; Dubey, Aditi; Banik, Soma; Barman, S R; Olivi, L

2013-01-30

The austenite to martensite phase transition in Ni-Mn-Ga ferromagnetic shape memory alloys was studied by extended x-ray absorption fine structure (EXAFS) and x-ray absorption near-edge structure (XANES) spectroscopy. The spectra at all the three elements', namely, Mn, Ga and Ni, K-edges in several Ni-Mn-Ga samples (with both Ni and Mn excess) were analyzed at room temperature and low temperatures. The EXAFS analysis suggested a displacement of Mn and Ga atoms in opposite direction with respect to the Ni atoms when the compound transforms from the austenite phase to the martensite phase. The first coordination distances around the Mn and Ga atoms remained undisturbed on transition, while the second and subsequent shells showed dramatic changes indicating the presence of a modulated structure. The Mn rich compounds showed the presence of antisite disorder of Mn and Ga. The XANES results showed remarkable changes in the unoccupied partial density of states corresponding to Mn and Ni, while the electronic structure of Ga remained unperturbed across the martensite transition. The post-edge features in the Mn K-edge XANES spectra changed from a double peak like structure to a flat peak like structure upon phase transition. The study establishes strong correlation between the crystal structure and the unoccupied electronic structure in these shape memory alloys.

Soft X-ray synchrotron radiation spectroscopy study of molecule-based nanoparticles

NASA Astrophysics Data System (ADS)

Lee, Eunsook; Kim, D. H.; Kang, J.-S.; Kim, Kyung Hyun; Kim, Pil; Baik, Jaeyoon; Shin, H. J.

2014-11-01

The electronic structures of molecule-based nanoparticles, such as biomineralized Helicobacter pylori ferritin (Hpf), Heme, and RbCo[Fe(CN)6]H2O (RbCoFe) Prussian blue analogue, have been investigated by employing photoemission spectroscopy and soft X-ray absorption spectroscopy. Fe ions are found to be nearly trivalent in Hpf and Heme nanoparticles, which provides evidence that the amount of magnetite (Fe3O4) should be negligible in the Hpf core and that the biomineralization of Fe oxides in the high-Fe-bound-state Hpf core arises from a hematite-like formation. On the other hand, Fe ions are nearly divalent and Co ions are Co2+-Co3+ mixed-valent in RbCoFe. Therefore this finding suggests that the mechanism of the photo-induced transition in RbCoFe Prussian blue analogue is not a simple spin-state transition of Fe2+-Co3+ → Fe3+-Co2+. It is likely that Co2+ ions have the high-spin configuration while Fe2+ ions have the low-spin configuration.

STUDIES OF THE ORIGIN OF HIGH-FREQUENCY QUASI-PERIODIC OSCILLATIONS OF MASS-ACCRETING BLACK HOLES IN X-RAY BINARIES WITH NEXT-GENERATION X-RAY TELESCOPES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beheshtipour, Banafsheh; Hoormann, Janie K.; Krawczynski, Henric, E-mail: b.beheshtipour@wustl.edu

Observations with RXTE ( Rossi X-ray Timing Explorer ) revealed the presence of high-frequency quasi-periodic oscillations (HFQPOs) of the X-ray flux from several accreting stellar-mass black holes. HFQPOs (and their counterparts at lower frequencies) may allow us to study general relativity in the regime of strong gravity. However, the observational evidence today does not yet allow us to distinguish between different HFQPO models. In this paper we use a general-relativistic ray-tracing code to investigate X-ray timing spectroscopy and polarization properties of HFQPOs in the orbiting Hotspot model. We study observational signatures for the particular case of the 166 Hz quasi-periodicmore » oscillation (QPO) in the galactic binary GRS 1915+105. We conclude with a discussion of the observability of spectral signatures with a timing-spectroscopy experiment such as the LOFT ( Large Observatory for X-ray Timing ) and polarization signatures with space-borne X-ray polarimeters such as IXPE ( Imaging X-ray Polarimetry Explorer ), PolSTAR ( Polarization Spectroscopic Telescope Array ), PRAXyS ( Polarimetry of Relativistic X-ray Sources ), or XIPE ( X-ray Imaging Polarimetry Explorer ). A mission with high count rate such as LOFT would make it possible to get a QPO phase for each photon, enabling the study of the QPO-phase-resolved spectral shape and the correlation between this and the flux level. Owing to the short periods of the HFQPOs, first-generation X-ray polarimeters would not be able to assign a QPO phase to each photon. The study of QPO-phase-resolved polarization energy spectra would thus require simultaneous observations with a first-generation X-ray polarimeter and a LOFT -type mission.« less

Development of polycapillary x-ray optics for x-ray spectroscopy

NASA Astrophysics Data System (ADS)

Adams, Bernhard W.; Attenkofer, Klaus; Bond, Justin L.; Craven, Christopher A.; Cremer, Till; O'Mahony, Aileen; Minot, Michael J.; Popecki, Mark A.

2016-09-01

Bundles of hollow glass capillaries can be tapered to produce quasi-focusing x-ray optics. These optics are known as Kumakhov lenses. These optics are interesting for lab-based sources because they can be used to collimate and concentrate x-rays originating from a point, such as a laser focus or an electron-beam focus in a microtube.

X-ray Photoelectron Spectroscopy Study of Argon-Plasma-Treated Fluoropolymers

NASA Technical Reports Server (NTRS)

Golub, Morton A.; Lopata, Eugene S.; Finney, Lorie S.

1994-01-01

Films of poly(tetrafluoroethylene) (PTFE) and of a tetrafluoroethylene-perfluoroalkyl vinyl ether (approximately 49:1) copolymer (PFA) were exposed to a radio-frequency argon plasma and then examined by X-ray photoelectron spectroscopy (XPS). The use of fluoropolymer films nearly free of surface hydrocarbon contamination as well as the use of a monochromatized X-ray source for XPS removed two factors contributing to conflicting reports on the effect of exposure time on the fluorine-to-carbon (F/C) and oxygen-to-carbon (O/C) ratios for several Ar-plasma-treated fluoropolymers. Contrary to literature indications, a common pattern was found for PTFE and PFA: a moderate decrease in F/C ratio (from 1.99 to 1.40, and from 1.97 to 1.57, respectively), together with a moderate increase in O/C ratio (from negligible to about 0.10, and from 0.012 to about O.10, respectively) at very short exposures, after which the F/C ratios remained essentially constant on prolonged exposures, while the O/C ratios for PTFE and PFA leveled off at 0.11 and 0.15, respectively. The XPS C(sub 1s), spectra for these polymers exposed to the Ar plasma for 20 min were similar and presented, besides a prominent peak at 292.0 eV (CF2,) and a minor peak at 294.0 or 294.1 eV (CF3), a composite band of four curve-resolved peaks (approximately 285-290 eV) representing various CH, CC, CO, CN, and CF functionalities.

Study of a chemically amplified resist for X-ray lithography by Fourier transform infrared spectroscopy.

PubMed

Tan, T L; Wong, D; Lee, P; Rawat, R S; Patran, A

2004-11-01

Future applications of microelectromechanical systems (MEMS) require lithographic performance of very high aspect ratio. Chemically amplified resists (CARs) such as the negative tone commercial SU-8 provide critical advantages in sensitivity, resolution, and process efficiency in deep ultraviolet, electron-beam, and X-ray lithographies (XRLs), which result in a very high aspect ratio. In this investigation, an SU-8 resist was characterized and optimized for X-ray lithographic applications by studying the cross-linking process of the resist under different conditions of resist thickness and X-ray exposure dose. The exposure dose of soft X-ray (SXR) irradiation at the average weighted wavelength of 1.20 nm from a plasma focus device ranges from 100 to 1600 mJ/cm(2) on the resist surface. Resist thickness varies from 3.5 to 15 mum. The cross-linking process of the resist during post-exposure bake (PEB) was accurately monitored using Fourier transform infrared (FT-IR) spectroscopy. The infrared absorption peaks at 862, 914, 972, and 1128 cm(-1) in the spectrum of the SU-8 resist were found to be useful indicators for the completion of cross-linking in the resist. Results of the experiments showed that the cross-linking of SU-8 was optimized at the exposure dose of 800 mJ/cm(2) for resist thicknesses of 3.5, 9.5, and 15 microm. PEB temperature was set at 95 degrees C and time at 3 min. The resist thickness was measured using interference patterns in the FT-IR spectra of the resist. Test structures with an aspect ratio 3:1 on 10 microm thick SU-8 resist film were obtained using scanning electron microscopy (SEM).

X-ray Absorption Spectroscopy Study of the Effect of Rh doping in Sr2IrO4

PubMed Central

Sohn, C. H.; Cho, Deok-Yong; Kuo, C.-T.; Sandilands, L. J.; Qi, T. F.; Cao, G.; Noh, T. W.

2016-01-01

We investigate the effect of Rh doping in Sr2IrO4 using X-ray absorption spectroscopy (XAS). We observed appearance of new electron-addition states with increasing Rh concentration (x in Sr2Ir1−xRhxO4) in accordance with the concept of hole doping. The intensity of the hole-induced state is however weak, suggesting weakness of charge transfer (CT) effect and Mott insulating ground states. Also, Ir Jeff = 1/2 upper Hubbard band shifts to lower energy as x increases up to x = 0.23. Combined with optical spectroscopy, these results suggest a hybridisation-related mechanism, in which Rh doping can weaken the (Ir Jeff = 1/2)–(O 2p) orbital hybridisation in the in-planar Rh-O-Ir bond networks. PMID:27025538

Differentiation of dental restorative materials combining energy-dispersive X-ray fluorescence spectroscopy and post-mortem CT.

PubMed

Merriam, Tim; Kaufmann, Rolf; Ebert, Lars; Figi, Renato; Erni, Rolf; Pauer, Robin; Sieberth, Till

2018-06-01

Today, post-mortem computed tomography (CT) is routinely used for forensic identification. Mobile energy-dispersive X-ray fluorescence (EDXRF) spectroscopy of a dentition is a method of identification that has the potential to be easier and cheaper than CT, although it cannot be used with every dentition. In challenging cases, combining both techniques could facilitate the process of identification and prove to be advantageous over chemical analyses. Nine dental restorative material brands were analyzed using EDXRF spectroscopy. Their differentiability was assessed by comparing each material's x-ray fluorescence spectrum and then comparing the spectra to previous research investigating differentiability in CT. To verify EDXRF's precision and accuracy, select dental specimens underwent comparative electron beam excited x-ray spectroscopy (EDS) scans, while the impact of the restorative surface area was studied by scanning a row of dental specimens with varying restorative surface areas (n = 10). EDXRF was able to differentiate all 36 possible pairs of dental filling materials; however, dual-energy CT was only able to differentiate 33 out of 36. The EDS scans showed correlating x-ray fluorescence peaks on the x-ray spectra compared to our EDXRF. In addition, the surface area showed no influence on the differentiability of the dental filling materials. EDXRF has the potential to facilitate corpse identification by differentiating and comparing restorative materials, providing more information compared to post-mortem CT alone. Despite not being able to explicitly identify a brand without a control sample or database, its fast and mobile use could accelerate daily routines or mass victim identification processes. To achieve this goal, further development of EDXRF scanners for this application and further studies evaluating the method within a specific routine need to be performed.

On the Electronic Structure of Cu Chlorophyllin and Its Breakdown Products: A Carbon K-Edge X-ray Absorption Spectroscopy Study.

PubMed

Witte, Katharina; Mantouvalou, Ioanna; Sánchez-de-Armas, Rocío; Lokstein, Heiko; Lebendig-Kuhla, Janina; Jonas, Adrian; Roth, Friedrich; Kanngießer, Birgit; Stiel, Holger

2018-02-15

Using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, the carbon backbone of sodium copper chlorophyllin (SCC), a widely used chlorophyll derivative, and its breakdown products are analyzed to elucidate their electronic structure and physicochemical properties. Using various sample preparation methods and complementary spectroscopic methods (including UV/Vis, X-ray photoelectron spectroscopy), a comprehensive insight into the SCC breakdown process is presented. The experimental results are supported by density functional theory calculations, allowing a detailed assignment of characteristic NEXAFS features to specific C bonds. SCC can be seen as a model system for the large group of porphyrins; thus, this work provides a novel and detailed description of the electronic structure of the carbon backbone of those molecules and their breakdown products. The achieved results also promise prospective optical pump/X-ray probe investigations of dynamic processes in chlorophyll-containing photosynthetic complexes to be analyzed more precisely.

High-resolution x-ray absorption spectroscopy studies of metal compounds in neurodegenerative brain tissue

NASA Astrophysics Data System (ADS)

Collingwood, J. F.; Mikhaylova, A.; Davidson, M. R.; Batich, C.; Streit, W. J.; Eskin, T.; Terry, J.; Barrea, R.; Underhill, R. S.; Dobson, J.

2005-01-01

Fluorescence mapping and microfocus X-ray absorption spectroscopy are used to detect, locate and identify iron biominerals and other inorganic metal accumulations in neurodegenerative brain tissue at sub-cellular resolution (<5 microns). Recent progress in developing the technique is reviewed. Synchrotron X-rays are used to map tissue sections for metals of interest, and XANES and XAFS are used to characterise anomalous concentrations of the metals in-situ so that they can be correlated with tissue structures and disease pathology. Iron anomalies associated with biogenic magnetite, ferritin and haemoglobin are located and identified in an avian tissue model with a pixel resolution ~5 microns. Subsequent studies include brain tissue sections from transgenic Huntington's mice, and the first high-resolution mapping and identification of iron biominerals in human Alzheimer's and control autopsy brain tissue. Technical developments include use of microfocus diffraction to obtain structural information about biominerals in-situ, and depositing sample location grids by lithography for the location of anomalies by conventional microscopy. The combined techniques provide a breakthrough in the study of both intra- and extra-cellular iron compounds and related metals in tissue. The information to be gained from this approach has implications for future diagnosis and treatment of neurodegeneration, and for our understanding of the mechanisms involved.

A time-correlation function approach to nuclear dynamical effects in X-ray spectroscopy.

PubMed

Karsten, Sven; Bokarev, Sergey I; Aziz, Saadullah G; Ivanov, Sergei D; Kühn, Oliver

2017-06-14

Modern X-ray spectroscopy has proven itself as a robust tool for probing the electronic structure of atoms in complex environments. Despite working on energy scales that are much larger than those corresponding to nuclear motions, taking nuclear dynamics and the associated nuclear correlations into account may be of importance for X-ray spectroscopy. Recently, we have developed an efficient protocol to account for nuclear dynamics in X-ray absorption and resonant inelastic X-ray scattering spectra [Karsten et al., J. Phys. Chem. Lett. 8, 992 (2017)], based on ground state molecular dynamics accompanied with state-of-the-art calculations of electronic excitation energies and transition dipoles. Here, we present an alternative derivation of the formalism and elaborate on the developed simulation protocol using gas phase and bulk water as examples. The specific spectroscopic features stemming from the nuclear motions are analyzed and traced down to the dynamics of electronic energy gaps and transition dipole correlation functions. The observed tendencies are explained on the basis of a simple harmonic model, and the involved approximations are discussed. The method represents a step forward over the conventional approaches that treat the system in full complexity and provides a reasonable starting point for further improvements.

A time-correlation function approach to nuclear dynamical effects in X-ray spectroscopy

NASA Astrophysics Data System (ADS)

Karsten, Sven; Bokarev, Sergey I.; Aziz, Saadullah G.; Ivanov, Sergei D.; Kühn, Oliver

2017-06-01

Modern X-ray spectroscopy has proven itself as a robust tool for probing the electronic structure of atoms in complex environments. Despite working on energy scales that are much larger than those corresponding to nuclear motions, taking nuclear dynamics and the associated nuclear correlations into account may be of importance for X-ray spectroscopy. Recently, we have developed an efficient protocol to account for nuclear dynamics in X-ray absorption and resonant inelastic X-ray scattering spectra [Karsten et al., J. Phys. Chem. Lett. 8, 992 (2017)], based on ground state molecular dynamics accompanied with state-of-the-art calculations of electronic excitation energies and transition dipoles. Here, we present an alternative derivation of the formalism and elaborate on the developed simulation protocol using gas phase and bulk water as examples. The specific spectroscopic features stemming from the nuclear motions are analyzed and traced down to the dynamics of electronic energy gaps and transition dipole correlation functions. The observed tendencies are explained on the basis of a simple harmonic model, and the involved approximations are discussed. The method represents a step forward over the conventional approaches that treat the system in full complexity and provides a reasonable starting point for further improvements.

Single- and double-core-hole ion emission spectroscopy of transient neon plasmas produced by ultraintense x-ray laser pulses

NASA Astrophysics Data System (ADS)

Gao, Cheng; Zeng, Jiaolong; Yuan, Jianmin

2016-02-01

Single-core-hole (SCH) and double-core-hole (DCH) spectroscopy is investigated systematically for neon gas in the interaction with ultraintense x-ray pulses with photon energy from 937 eV to 2000 eV. A time-dependent rate equation, implemented in detailed level accounting approximation, is utilized to study the dynamical evolution of the level population and emission properties of the laser-produced highly transient plasmas. The plasma-density effects on level populations and charge-state distribution are demonstrated with an x-ray photon energy of 2000 eV. It is shown that atomic number density of relevant experiment is about 1 × 1018 cm-3, which is comparable to a recent experiment. At this density, we systematically investigate the emissivity of the transient neon plasmas. For laser photon energy in the range 937-1360 eV, resonant absorptions (RA) of 1s\\to {np} (n≥slant 2) transitions play important roles in time evolution of the population and DCH emission spectroscopy. The RA effects are illustrated in detail for an x-ray pulse of 944 eV photon energy, which creates the 1s\\to 2p RA from the SCH states (1s2{s}22{p}4, 1s2s2p5, and 1s2p6) of Ne3+. After averaging over the space and time distribution of x-ray pulse, DCH emission spectroscopy is studied at x-ray photon energies of 937, 944, 955, 968, 980, and 990 eV, where there exist 1s\\to 2p resonances from SCH states of Ne2+-Ne7+. The processes with producing DCH states are discussed. For x-ray photon energy larger than 1360 eV, no RA exist and transient plasmas show different features in the DCH spectroscopy.

Toward picosecond time-resolved X-ray absorption studies of interfacial photochemistry

NASA Astrophysics Data System (ADS)

Gessner, Oliver; Mahl, Johannes; Neppl, Stefan

2016-05-01

We report on the progress toward developing a novel picosecond time-resolved transient X-ray absorption spectroscopy (TRXAS) capability for time-domain studies of interfacial photochemistry. The technique is based on the combination of a high repetition rate picosecond laser system with a time-resolved X-ray fluorescent yield setup that may be used for the study of radiation sensitive materials and X-ray spectroscopy compatible photoelectrochemical (PEC) cells. The mobile system is currently deployed at the Advanced Light Source (ALS) and may be used in all operating modes (two-bunch and multi-bunch) of the synchrotron. The use of a time-stamping technique enables the simultaneous recording of TRXAS spectra with delays between the exciting laser pulses and the probing X-ray pulses spanning picosecond to nanosecond temporal scales. First results are discussed that demonstrate the viability of the method to study photoinduced dynamics in transition metal-oxide semiconductor (SC) samples under high vacuum conditions and at SC-liquid electrolyte interfaces during photoelectrochemical water splitting. Opportunities and challenges are outlined to capture crucial short-lived intermediates of photochemical processes with the technique. This work was supported by the Department of Energy Office of Science Early Career Research Program.

Ultrafast X-Ray Absorption Spectroscopy of Isochorically Heated Warm Dense Matter

NASA Astrophysics Data System (ADS)

Engelhorn, Kyle Craig

This dissertation will present a series of new tools, together with new techniques, focused on the understanding of warm and dense matter. We report on the development of a high time resolution and high detection efficiency x-ray camera. The camera is integrated with a short pulse laser and an x-ray beamline at the Advanced Light Source synchrotron. This provides an instrument for single shot, broadband x-ray absorption spectroscopy of warm and dense matter with 2 picosecond time resolution. Warm and dense matter is created by isochorically heating samples of known density with an ultrafast optical laser pulse, and X-ray absorption spectroscopy probes the unoccupied electronic density of states before the onset of hydrodynamic expansion and electron-ion equilibrium is reached. Measured spectra from a variety of materials are compared with first principle molecular dynamics and density functional theory calculations. In heated silicon dioxide spectra, two novel pre-edge features are observed, a peak below the band gap and absorption within the band gap, while a reduction was observed in the features above the edge. From consideration of the calculated spectra, the peak below the gap is attributed to valence electrons that have been promoted to the conduction band, the absorption within the gap is attributed to broken Si-O bonds, and the reduction above the edge is attributed to an elevated ionic temperature. In heated copper spectra, a time-dependent shift and broadening of the absorption edge are observed, consistent with and elevated electron temperature. The temporal evolution of the electronic temperature is accurately determined by fitting the measured spectra with calculated spectra. The electron-ion equilibration is studied with a two-temperature model. In heated nickel spectra, a shift of the absorption edge is observed. This shift is found to be inconsistent with calculated spectra and independent of incident laser fluence. A shift of the chemical potential

The Generation-X X-ray Observatory Vision Mission and Technology Study

NASA Technical Reports Server (NTRS)

Figueroa-Feliciano, Enectali

2004-01-01

The new frontier in astrophysics is the study of the birth and evolution of the first stars, galaxies and black holes in the early Universe. X-ray astronomy opens a window into these objects by studying the emission from black holes, supernova explosions and the gamma-ray burst afterglows of massive stars. However, such objects are beyond the grasp of current or near-future observatories. X-ray imaging and spectroscopy of such distant objects will require an X-ray telescope with large collecting area and high angular resolution. Our team has conceived the Generation-X Vision Mission based on an X-ray observatory with 100 sq m collecting area at 1 keV (1000 times larger than Chandra) and 0.1 arcsecond angular resolution (several times better than Chandra and 50 times better than the Constellation-X resolution goal). Such an observatory would be capable of detecting the earliest black holes and galaxies in the Universe, and will also study extremes of density, gravity, magnetic fields, and kinetic energy which cannot be created in laboratories. NASA has selected the Generation-X mission for study under its Vision Mission Program. We describe the studies being performed to develop the mission concept and define candidate technologies and performance requirements for Generation-X. The baseline Generation-X mission involves four 8m diameter X-ray telescopes operating at Sun-Earth L2. We trade against an alternate concept of a single 26m diameter telescope with focal plane instruments on a separate spacecraft. A telescope of this size will require either robotic or human-assisted in-flight assembly. The required effective area implies that extremely lightweight grazing incidence X-ray optics must be developed. To achieve the required aerial density of at least 100 times lower than in Chandra, we will study 0.1mm thick mirrors which have active on-orbit figure control. We discuss the suite of required detectors, including a large FOV high angular resolution imager, a

High-Resolution Spectroscopy with the Chandra X-ray Observatory

ScienceCinema

Canizares, Claude R. [MIT, Cambridge, Massachusetts, United States

2017-12-09

The capabilities of the Chandra X-ray Observatory and XMM-Newton for high-resolution spectroscopy have brought tradition plasma diagnostic techniques to the study of cosmic plasma. Observations have probed nearly every class of astronomical object, from young proto-starts through massive O starts and black hole binaries, supernova remnants, active galactic nuclei, and the intergalactic medium. Many of these sources show remarkable rich spectra that reveal new physical information, such as emission measure distributions, elemental abundances, accretion disk and wind signatures, and time variability. This talk will present an overview of the Chandra instrumentaton and selected examples of spectral observations of astrophysical and cosmological importance.

Reactor for tracking catalyst nanoparticles in liquid at high temperature under a high-pressure gas phase with X-ray absorption spectroscopy.

PubMed

Nguyen, Luan; Tao, Franklin Feng

2018-02-01

Structure of catalyst nanoparticles dispersed in liquid phase at high temperature under gas phase of reactant(s) at higher pressure (≥5 bars) is important for fundamental understanding of catalytic reactions performed on these catalyst nanoparticles. Most structural characterizations of a catalyst performing catalysis in liquid at high temperature under gas phase at high pressure were performed in an ex situ condition in terms of characterizations before or after catalysis since, from technical point of view, access to the catalyst nanoparticles during catalysis in liquid phase at high temperature under high pressure reactant gas is challenging. Here we designed a reactor which allows us to perform structural characterization using X-ray absorption spectroscopy including X-ray absorption near edge structure spectroscopy and extended X-ray absorption fine structure spectroscopy to study catalyst nanoparticles under harsh catalysis conditions in terms of liquid up to 350 °C under gas phase with a pressure up to 50 bars. This reactor remains nanoparticles of a catalyst homogeneously dispersed in liquid during catalysis and X-ray absorption spectroscopy characterization.

Near- and Extended-Edge X-Ray-Absorption Fine-Structure Spectroscopy Using Ultrafast Coherent High-Order Harmonic Supercontinua

NASA Astrophysics Data System (ADS)

Popmintchev, Dimitar; Galloway, Benjamin R.; Chen, Ming-Chang; Dollar, Franklin; Mancuso, Christopher A.; Hankla, Amelia; Miaja-Avila, Luis; O'Neil, Galen; Shaw, Justin M.; Fan, Guangyu; Ališauskas, Skirmantas; Andriukaitis, Giedrius; Balčiunas, Tadas; Mücke, Oliver D.; Pugzlys, Audrius; Baltuška, Andrius; Kapteyn, Henry C.; Popmintchev, Tenio; Murnane, Margaret M.

2018-03-01

Recent advances in high-order harmonic generation have made it possible to use a tabletop-scale setup to produce spatially and temporally coherent beams of light with bandwidth spanning 12 octaves, from the ultraviolet up to x-ray photon energies >1.6 keV . Here we demonstrate the use of this light for x-ray-absorption spectroscopy at the K - and L -absorption edges of solids at photon energies near 1 keV. We also report x-ray-absorption spectroscopy in the water window spectral region (284-543 eV) using a high flux high-order harmonic generation x-ray supercontinuum with 109 photons/s in 1% bandwidth, 3 orders of magnitude larger than has previously been possible using tabletop sources. Since this x-ray radiation emerges as a single attosecond-to-femtosecond pulse with peak brightness exceeding 1026 photons/s /mrad2/mm2/1 % bandwidth, these novel coherent x-ray sources are ideal for probing the fastest molecular and materials processes on femtosecond-to-attosecond time scales and picometer length scales.

Characterization of Colloidal Quantum Dot Ligand Exchange by X-ray Photoelectron Spectroscopy

NASA Astrophysics Data System (ADS)

Atewologun, Ayomide; Ge, Wangyao; Stiff-Roberts, Adrienne D.

2013-05-01

Colloidal quantum dots (CQDs) are chemically synthesized semiconductor nanoparticles with size-dependent wavelength tunability. Chemical synthesis of CQDs involves the attachment of long organic surface ligands to prevent aggregation; however, these ligands also impede charge transport. Therefore, it is beneficial to exchange longer surface ligands for shorter ones for optoelectronic devices. Typical characterization techniques used to analyze surface ligand exchange include Fourier-transform infrared spectroscopy, x-ray diffraction, transmission electron microscopy, and nuclear magnetic resonance spectroscopy, yet these techniques do not provide a simultaneously direct, quantitative, and sensitive method for evaluating surface ligands on CQDs. In contrast, x-ray photoelectron spectroscopy (XPS) can provide nanoscale sensitivity for quantitative analysis of CQD surface ligand exchange. A unique aspect of this work is that a fingerprint is identified for shorter surface ligands by resolving the regional XPS spectrum corresponding to different types of carbon bonds. In addition, a deposition technique known as resonant infrared matrix-assisted pulsed laser evaporation is used to improve the CQD film uniformity such that stronger XPS signals are obtained, enabling more accurate analysis of the ligand exchange process.

Single and double core-hole ion emission spectroscopy of transient neon plasmas produced by ultraintense x-ray laser pulses

NASA Astrophysics Data System (ADS)

Gao, Cheng; Zeng, Jiaolong; Yuan, Jianmin

2016-05-01

Single core-hole (SCH) and double core-hole (DCH) spectroscopy is investigated systematically for neon gas in the interaction with ultraintense x-ray pulses with photon energy from 937 eV to 2000 eV. A time-dependent rate equation, implemented in the detailed level accounting approximation, is utilized to study the dynamical evolution of the level population and emission properties of the laser-produced highly transient plasmas. The plasma density effects on level populations are demonstrated with an x-ray photon energy of 2000 eV. For laser photon energy in the range of 937 - 1360 eV, resonant absorptions (RA) of 1s-np (n> = 2) transitions play important roles in time evolution of the population and DCH emission spectroscopy. For x-ray photon energy larger than 1360 eV, no RA exist and transient plasmas show different features in the DCH spectroscopy.

Studies of electrode structures and dynamics using coherent X-ray scattering and imaging

DOE Office of Scientific and Technical Information (OSTI.GOV)

You, H.; Liu, Y.; Ulvestad, A.

2017-08-01

Electrochemical systems studied in situ with advanced surface X-ray scattering techniques are reviewed. The electrochemical systems covered include interfaces of single-crystals and nanocrystals with respect to surface modification, aqueous dissolution, surface reconstruction, and electrochemical double layers. An emphasis will be given on recent results by coherent X-ray techniques such as X-ray photon correlation spectroscopy, Bragg coherent diffraction imaging, and surface ptychography.

X-ray photoelectron spectroscopy study of excimer laser treated alumina films

NASA Astrophysics Data System (ADS)

Georgiev, D. G.; Kolev, K.; Laude, L. D.; Mednikarov, B.; Starbov, N.

1998-01-01

Amorphous alumina layers are deposited on a single crystal Si substrate by a e-gun evaporation technique. These films are then thermally annealed in oxygen to be crystallized and, further, irradiated with an excimer laser beam. At each stage of the film preparation, an x-ray photoelectron spectroscopy analysis is performed at the film surface and in depth, upon ion beam grinding. Results give evidence for the formation of an aluminosilicate upon thermal annealing of the film in oxygen. At the surface itself, this compound is observed to decompose upon excimer laser irradiation at energy densities exceeding 1.75 J/cm2, giving rise to free Si atoms and SiO2, however with complete disappearance of Al atoms. Model photochemical reactions are proposed to explain such transformations.

Very high resolution UV and X-ray spectroscopy and imagery of solar active regions

NASA Technical Reports Server (NTRS)

Bruner, M.; Brown, W. A.; Haisch, B. M.

1987-01-01

A scientific investigation of the physics of the solar atmosphere, which uses the techniques of high resolution soft X-ray spectroscopy and high resolution UV imagery, is described. The experiments were conducted during a series of three sounding rocket flights. All three flights yielded excellent images in the UV range, showing unprecedented spatial resolution. The second flight recorded the X-ray spectrum of a solar flare, and the third that of an active region. A normal incidence multi-layer mirror was used during the third flight to make the first astronomical X-ray observations using this new technique.

Composition of RF-sputtered refractory compounds determined by X-ray photoelectron spectroscopy

NASA Technical Reports Server (NTRS)

Wheeler, D. R.; Brainard, W. A.

1978-01-01

RF-sputtered coatings of CrB2, MoSi2, Mo2C, TiC, and MoS2 were examined by X-ray photoelectron spectroscopy (XPS). Data on stoichiometry, impurity content, and chemical bonding were obtained. The influences of sputtering target history, deposition time, RF power level, and substrate bias were studied. Significant deviations from stoichiometry and high oxide levels were related to target outgassing. The effect of substrate bias depended on the particular coating material studied.

An x-ray absorption spectroscopy study of Cd binding onto a halophilic archaeon

NASA Astrophysics Data System (ADS)

Showalter, Allison R.; Szymanowski, Jennifer E. S.; Fein, Jeremy B.; Bunker, Bruce A.

2016-05-01

X-ray absorption spectroscopy (XAS) and cadmium (Cd) isotherm experiments determine how Cd adsorbs to the surface of halophilic archaeon Halobacterium noricense. This archaeon, isolated from the Waste Isolation Pilot Plant (WIPP) near Carlsbad, New Mexico could be involved with the transport of toxic metals stored in the transuranic waste in the salt mine. The isotherm experiments show that adsorption is relatively constant across the tolerable pH range for H. noricense. The XAS results indicate that Cd adsorption occurs predominately via a sulfur site, most likely sulfhydryl, with the same site dominating all measured pH values.

Pump-Flow-Probe X-Ray Absorption Spectroscopy as a Tool for Studying Intermediate States of Photocatalytic Systems.

PubMed

Smolentsev, Grigory; Guda, Alexander; Zhang, Xiaoyi; Haldrup, Kristoffer; Andreiadis, Eugen; Chavarot-Kerlidou, Murielle; Canton, Sophie E; Nachtegaal, Maarten; Artero, Vincent; Sundstrom, Villy

2013-08-29

A new setup for pump-flow-probe X-ray absorption spectroscopy has been implemented at the SuperXAS beamline of the Swiss Light Source. It allows recording X-ray absorption spectra with a time resolution of tens of microseconds and high detection efficiency for samples with sub-mM concentrations. A continuous wave laser is used for the photoexcitation, with the distance between laser and X-ray beams and velocity of liquid flow determining the time delay, while the focusing of both beams and the flow speed define the time resolution. This method is compared with the alternative measurement technique that utilizes a 1 kHz repetition rate laser and multiple X-ray probe pulses. Such an experiment was performed at beamline 11ID-D of the Advanced Photon Source. Advantages, limitations and potential for improvement of the pump-flow-probe setup are discussed by analyzing the photon statistics. Both methods, with Co K-edge probing were applied to the investigation of a cobaloxime-based photo-catalytic reaction. The interplay between optimizing for efficient photoexcitation and time resolution as well as the effect of sample degradation for these two setups are discussed.

Pump-Flow-Probe X-Ray Absorption Spectroscopy as a Tool for Studying Intermediate States of Photocatalytic Systems

PubMed Central

Smolentsev, Grigory; Guda, Alexander; Zhang, XIaoyi; Haldrup, Kristoffer; Andreiadis, Eugen; Chavarot-Kerlidou, Murielle; Canton, Sophie E.; Nachtegaal, Maarten; Artero, Vincent; Sundstrom, Villy

2014-01-01

A new setup for pump-flow-probe X-ray absorption spectroscopy has been implemented at the SuperXAS beamline of the Swiss Light Source. It allows recording X-ray absorption spectra with a time resolution of tens of microseconds and high detection efficiency for samples with sub-mM concentrations. A continuous wave laser is used for the photoexcitation, with the distance between laser and X-ray beams and velocity of liquid flow determining the time delay, while the focusing of both beams and the flow speed define the time resolution. This method is compared with the alternative measurement technique that utilizes a 1 kHz repetition rate laser and multiple X-ray probe pulses. Such an experiment was performed at beamline 11ID-D of the Advanced Photon Source. Advantages, limitations and potential for improvement of the pump-flow-probe setup are discussed by analyzing the photon statistics. Both methods, with Co K-edge probing were applied to the investigation of a cobaloxime-based photo-catalytic reaction. The interplay between optimizing for efficient photoexcitation and time resolution as well as the effect of sample degradation for these two setups are discussed. PMID:24443663

Sulfur Speciation in Biochars by Very High Resolution Benchtop Kα X-ray Emission Spectroscopy.

PubMed

Holden, William M; Seidler, Gerald T; Cheah, Singfoong

2018-05-30

The analytical chemistry of sulfur-containing materials poses substantial technical challenges, especially due to the limitations of 33 S NMR and the time-intensive preparations required for wet-chemistry analyses. A number of prior studies have found that synchrotron-based X-ray absorption near edge structure (XANES) measurements can give detailed speciation of sulfur chemistry in such cases. However, due to the obvious access limitations, synchrotron XANES of sulfur cannot be part of routine analytical practice across the chemical sciences community. Here, in a study of the sulfur chemistry in biochars, we compare and contrast the chemical inferences available from synchrotron XANES with that given by benchtop, extremely high resolution wavelength-dispersive X-ray fluorescence (WD-XRF) spectroscopy, also often called X-ray emission spectroscopy (XES). While the XANES spectra have higher total information content, often giving differentiation between different moieties having the same oxidation state, the lower sensitivity of the S Kα XES to coordination and local structure provides pragmatic benefit for the more limited goal of quantifying the S oxidation state distribution. Within that constrained metric, we find good agreement between the two methods. As the sulfur concentrations were as low as 150 ppm, these measurements provide proof-of-principle for characterization of the sulfur chemistry of biochars and potential applications to other areas such as soils, batteries, catalysts, and fossil fuels and their combustion products.

Sequential single shot X-ray photon correlation spectroscopy at the SACLA free electron laser

DOE PAGES

Lehmkühler, Felix; Kwaśniewski, Paweł; Roseker, Wojciech; ...

2015-11-27

In this study, hard X-ray free electron lasers allow for the first time to access dynamics of condensed matter samples ranging from femtoseconds to several hundred seconds. In particular, the exceptional large transverse coherence of the X-ray pulses and the high time-averaged flux promises to reach time and length scales that have not been accessible up to now with storage ring based sources. However, due to the fluctuations originating from the stochastic nature of the self-amplified spontaneous emission (SASE) process the application of well established techniques such as X-ray photon correlation spectroscopy (XPCS) is challenging. Here we demonstrate a single-shotmore » based sequential XPCS study on a colloidal suspension with a relaxation time comparable to the SACLA free-electron laser pulse repetition rate. High quality correlation functions could be extracted without any indications for sample damage. This opens the way for systematic sequential XPCS experiments at FEL sources.« less

Sequential single shot X-ray photon correlation spectroscopy at the SACLA free electron laser

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lehmkühler, Felix; Kwaśniewski, Paweł; Roseker, Wojciech

In this study, hard X-ray free electron lasers allow for the first time to access dynamics of condensed matter samples ranging from femtoseconds to several hundred seconds. In particular, the exceptional large transverse coherence of the X-ray pulses and the high time-averaged flux promises to reach time and length scales that have not been accessible up to now with storage ring based sources. However, due to the fluctuations originating from the stochastic nature of the self-amplified spontaneous emission (SASE) process the application of well established techniques such as X-ray photon correlation spectroscopy (XPCS) is challenging. Here we demonstrate a single-shotmore » based sequential XPCS study on a colloidal suspension with a relaxation time comparable to the SACLA free-electron laser pulse repetition rate. High quality correlation functions could be extracted without any indications for sample damage. This opens the way for systematic sequential XPCS experiments at FEL sources.« less

Monitoring the recrystallisation of amorphous xylitol using Raman spectroscopy and wide-angle X-ray scattering.

PubMed

Palomäki, Emmi; Ahvenainen, Patrik; Ehlers, Henrik; Svedström, Kirsi; Huotari, Simo; Yliruusi, Jouko

2016-07-11

In this paper we present a fast model system for monitoring the recrystallization of quench-cooled amorphous xylitol using Raman spectroscopy and wide-angle X-ray scattering. The use of these two methods enables comparison between surface and bulk crystallization. Non-ordered mesoporous silica micro-particles were added to the system in order to alter the rate of crystallization of the amorphous xylitol. Raman measurements showed that adding silica to the system increased the rate of surface crystallization, while X-ray measurements showed that the rate of bulk crystallization decreased. Using this model system it is possible to measure fast changes, which occur in minutes or within a few hours. Raman-spectroscopy and wide-angle X-ray scattering were found to be complementary techniques when assessing surface and bulk crystallization of amorphous xylitol. Copyright © 2016 Elsevier B.V. All rights reserved.

Origin of Pressure-induced Superconducting Phase in KxFe2-ySe2 studied by Synchrotron X-ray Diffraction and Spectroscopy

NASA Astrophysics Data System (ADS)

Yamamoto, Yoshiya; Yamaoka, Hitoshi; Tanaka, Masashi; Okazaki, Hiroyuki; Ozaki, Toshinori; Takano, Yoshihiko; Lin, Jung-Fu; Fujita, Hidenori; Kagayama, Tomoko; Shimizu, Katsuya; Hiraoka, Nozomu; Ishii, Hirofumi; Liao, Yen-Fa; Tsuei, Ku-Ding; Mizuki, Jun'Ichiro

2016-08-01

Pressure dependence of the electronic and crystal structures of KxFe2-ySe2, which has pressure-induced two superconducting domes of SC I and SC II, was investigated by x-ray emission spectroscopy and diffraction. X-ray diffraction data show that compressibility along the c-axis changes around 12 GPa, where a new superconducting phase of SC II appears. This suggests a possible tetragonal to collapsed tetragonal phase transition. X-ray emission spectroscopy data also shows the change in the electronic structure around 12 GPa. These results can be explained by the scenario that the two SC domes under pressure originate from the change of Fermi surface topology. Our results here show the pronounced increase of the density of states near the Fermi surface under pressure with a structural phase transition, which can help address our fundamental understanding for the appearance of the SC II phase.

Femtosecond time-resolved X-ray absorption spectroscopy of anatase TiO2 nanoparticles using XFEL

PubMed Central

Obara, Yuki; Ito, Hironori; Ito, Terumasa; Kurahashi, Naoya; Thürmer, Stephan; Tanaka, Hiroki; Katayama, Tetsuo; Togashi, Tadashi; Owada, Shigeki; Yamamoto, Yo-ichi; Karashima, Shutaro; Nishitani, Junichi; Yabashi, Makina; Suzuki, Toshinori; Misawa, Kazuhiko

2017-01-01

The charge-carrier dynamics of anatase TiO2 nanoparticles in an aqueous solution were studied by femtosecond time-resolved X-ray absorption spectroscopy using an X-ray free electron laser in combination with a synchronized ultraviolet femtosecond laser (268 nm). Using an arrival time monitor for the X-ray pulses, we obtained a temporal resolution of 170 fs. The transient X-ray absorption spectra revealed an ultrafast Ti K-edge shift and a subsequent growth of a pre-edge structure. The edge shift occurred in ca. 100 fs and is ascribed to reduction of Ti by localization of generated conduction band electrons into shallow traps of self-trapped polarons or deep traps at penta-coordinate Ti sites. Growth of the pre-edge feature and reduction of the above-edge peak intensity occur with similar time constants of 300–400 fs, which we assign to the structural distortion dynamics near the surface. PMID:28713842

New developments in fabrication of high-energy-resolution analyzers for inelastic x-ray spectroscopy.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Said, A. H.; Sinn, H.; Divan, R.

2011-05-01

In this work new improvements related to the fabrication of spherical bent analyzers for 1 meV energy-resolution inelastic X-ray scattering spectroscopy are presented. The new method includes the use of a two-dimensional bender to achieve the required radius of curvature for X-ray analyzers. The advantage of this method is the ability to monitor the focus during bending, which leads to higher-efficiency analyzers.

The CAT-ACT Beamline at ANKA: A new high energy X-ray spectroscopy facility for CATalysis and ACTinide research

NASA Astrophysics Data System (ADS)

Zimina, A.; Dardenne, K.; Denecke, M. A.; Grunwaldt, J. D.; Huttel, E.; Lichtenberg, H.; Mangold, S.; Pruessmann, T.; Rothe, J.; Steininger, R.; Vitova, T.

2016-05-01

A new hard X-ray beamline for CATalysis and ACTinide research has been built at the synchrotron radiation facility ANKA. The beamline design is dedicated to X-ray spectroscopy, including ‘flux hungry’ photon-in/photon-out and correlative techniques with a special infrastructure for radionuclide and catalysis research. The CAT-ACT beamline will help serve the growing need for high flux/hard X-ray spectroscopy in these communities. The design, the first spectra and the current status of this project are reported.

Clocking Femtosecond Collisional Dynamics via Resonant X-Ray Spectroscopy

NASA Astrophysics Data System (ADS)

van den Berg, Q. Y.; Fernandez-Tello, E. V.; Burian, T.; Chalupský, J.; Chung, H.-K.; Ciricosta, O.; Dakovski, G. L.; Hájková, V.; Hollebon, P.; Juha, L.; Krzywinski, J.; Lee, R. W.; Minitti, M. P.; Preston, T. R.; de la Varga, A. G.; Vozda, V.; Zastrau, U.; Wark, J. S.; Velarde, P.; Vinko, S. M.

2018-02-01

Electron-ion collisional dynamics is of fundamental importance in determining plasma transport properties, nonequilibrium plasma evolution, and electron damage in diffraction imaging applications using bright x-ray free-electron lasers (FELs). Here we describe the first experimental measurements of ultrafast electron impact collisional ionization dynamics using resonant core-hole spectroscopy in a solid-density magnesium plasma, created and diagnosed with the Linac Coherent Light Source x-ray FEL. By resonantly pumping the 1 s →2 p transition in highly charged ions within an optically thin plasma, we have measured how off-resonance charge states are populated via collisional processes on femtosecond time scales. We present a collisional cross section model that matches our results and demonstrates how the cross sections are enhanced by dense-plasma effects including continuum lowering. Nonlocal thermodynamic equilibrium collisional radiative simulations show excellent agreement with the experimental results and provide new insight on collisional ionization and three-body-recombination processes in the dense-plasma regime.

Time-resolved x-ray absorption spectroscopy: Watching atoms dance

NASA Astrophysics Data System (ADS)

Milne, Chris J.; Pham, Van-Thai; Gawelda, Wojciech; van der Veen, Renske M.; El Nahhas, Amal; Johnson, Steven L.; Beaud, Paul; Ingold, Gerhard; Lima, Frederico; Vithanage, Dimali A.; Benfatto, Maurizio; Grolimund, Daniel; Borca, Camelia; Kaiser, Maik; Hauser, Andreas; Abela, Rafael; Bressler, Christian; Chergui, Majed

2009-11-01

The introduction of pump-probe techniques to the field of x-ray absorption spectroscopy (XAS) has allowed the monitoring of both structural and electronic dynamics of disordered systems in the condensed phase with unprecedented accuracy, both in time and in space. We present results on the electronically excited high-spin state structure of an Fe(II) molecular species, [FeII(bpy)3]2+, in aqueous solution, resolving the Fe-N bond distance elongation as 0.2 Å. In addition an analysis technique using the reduced χ2 goodness of fit between FEFF EXAFS simulations and the experimental transient absorption signal in energy space has been successfully tested as a function of excited state population and chemical shift, demonstrating its applicability in situations where the fractional excited state population cannot be determined through other measurements. Finally by using a novel ultrafast hard x-ray 'slicing' source the question of how the molecule relaxes after optical excitation has been successfully resolved using femtosecond XANES.

SUT-NANOTEC-SLRI beamline for X-ray absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klysubun, Wantana; Kidkhunthod, Pinit; Tarawarakarn, Pongjakr

2017-04-04

The SUT-NANOTEC-SLRI beamline was constructed in 2012 as the flagship of the SUT-NANOTEC-SLRI Joint Research Facility for Synchrotron Utilization, co-established by Suranaree University of Technology (SUT), National Nanotechnology Center (NANOTEC) and Synchrotron Light Research Institute (SLRI). It is an intermediate-energy X-ray absorption spectroscopy (XAS) beamline at SLRI. The beamline delivers an unfocused monochromatic X-ray beam of tunable photon energy (1.25–10 keV). The maximum normal incident beam size is 13 mm (width) × 1 mm (height) with a photon flux of 3 × 10 8to 2 × 10 10 photons s -1(100 mA) -1varying across photon energies. Details of the beamlinemore » and XAS instrumentation are described. To demonstrate the beamline performance,K-edge XANES spectra of MgO, Al 2O 3, S 8, FeS, FeSO 4, Cu, Cu 2O and CuO, and EXAFS spectra of Cu and CuO are presented.« less

High resolution x-ray absorption and emission spectroscopy of Li x CoO2 single crystals as a function delithiation

NASA Astrophysics Data System (ADS)

Simonelli, L.; Paris, E.; Iwai, C.; Miyoshi, K.; Takeuchi, J.; Mizokawa, T.; Saini, N. L.

2017-03-01

The effect of delithiation in Li x CoO2 is studied by high resolution Co K-edge x-ray absorption and x-ray emission spectroscopy. Polarization dependence of the x-ray absorption spectra on single crystal samples is exploited to reveal information on the anisotropic electronic structure. We find that the electronic structure of Li x CoO2 is significantly affected by delithiation in which the Co ions oxidation state tending to change from 3+  to 4+. The Co intersite (intrasite) 4p-3d hybridization suffers a decrease (increase) by delithiation. The unoccupied 3d t 2g orbitals with a 1g symmetry, containing substantial O 2p character, hybridize isotropically with Co 4p orbitals and likely to have itinerant character unlike anisotropically hybridized 3d e g orbitals. Such a peculiar electronic structure could have significant effect on the mobility of Li in Li x CoO2 cathode and hence the battery characteristics.

Centaurus X-3. [early x-ray binary star spectroscopy

NASA Technical Reports Server (NTRS)

Hutchings, J. B.; Cowley, A. P.; Crampton, D.; Van Paradus, J.; White, N. E.

1979-01-01

Spectroscopic observations of Krzeminski's star at dispersions 25-60 A/mm are described. The primary is an evolved star of type O6-O8(f) with peculiarities, some of which are attributable to X-ray heating. Broad emission lines at 4640A (N III), 4686 A(He II) and H-alpha show self-absorption and do not originate entirely from the region near the X-ray star. The primary is not highly luminous (bolometric magnitude about -9) and does not show signs of an abnormally strong stellar wind. The X-ray source was 'on' at the time of optical observations. Orbital parameters are presented for the primary, which yield masses of 17 + or - 2 and 1.0 + or - 3 solar masses for the stars. The optical star is undermassive for its luminosity, as are other OB-star X-ray primaries. The rotation is probably synchronized with the orbital motion. The distance to Cen X-3 is estimated to be 10 + or - 1 kpc. Basic data for 12 early-type X-ray primaries are discussed briefly

The Advanced X-ray Spectroscopy and Imaging Observatory (AXSIO)

NASA Technical Reports Server (NTRS)

White, Nicholas E.; Bookbinder, Jay; Petre, Robert; Smith, Randall; Ptak, Andrew; Tananbaum, Harvey; Garcia, Michael

2012-01-01

Following recommendations from the 2010 "New Worlds, New Horizons" (NWNH) report, the Advanced X-ray Spectroscopy and Imaging Observatory (AXSIO) concept streamlines the International X-ray Observatory (IXO) mission to concentrate on the science objectives that are enabled by high-resolution spectroscopic capabilities. AXSIO will trace orbits close to the event horizon of black holes, measure black hole spin for tens of supermassive black holes (SMBH), use spectroscopy to characterize outflows and the environment of AGN during their peak activity, observe 5MBH out to redshift z=6, map bulk motions and turbulence in galaxy clusters, find the missing baryons in the cosmic web using background quasars, and observe the process of cosmic feedback where black holes and supernovae inject energy on galactic and intergalactic scales. These measurements are enabled by a 0.9 sq m collecting area at 1.25 keV, a micro calorimeter array providing high-resolution spectroscopic imaging and a deployable high efficiency grating spectrometer. AXSIO delivers a 30-fold increase in effective area for high resolution spectroscopy. The key simplifications are guided by recommendations in the NWNH panel report include a reduction in focal length from 20m to 10m, eliminating the extendable optical bench, and a reduction in the instrument complement from six to two, avoiding a movable instrument platform. A focus on spectroscopic science allows the spatial resolution requirement to be relaxed to 10 arc sec (with a 5 arc sec goal). These simplifications decrease the total mission cost to under the $2B cost to NASA recommended by NWNH. AXSIO will be available to the entire astronomical community with observing allocations based on peer-review.

In situ study of an oxidation reaction on a Pt/C electrode by ambient pressure hard X-ray photoelectron spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Takagi, Yasumasa, E-mail: ytakagi@ims.ac.jp; Uemura, Yohei; Yokoyama, Toshihiko

2014-09-29

We have constructed an ambient pressure X-ray photoelectron spectroscopy instrument that uses hard X-ray radiation at the high-performance undulator beamline BL36XU of SPring-8. The dependence of the Au 4f peak intensity from Au foil on the ambient N{sub 2} pressure was measured. At a photon energy of 7.94 keV, the Au 4f peak intensity maintained 40% at 3000 Pa compared with that at high vacuum. We designed a polymer electrolyte fuel cell that allows us to perform X-ray photoelectron spectroscopy measurements of an electrode under working conditions. The oxidized Pt peaks were observed in the Pt 3d{sub 5/2} level of Pt nanoparticlesmore » in the cathode, and the peaks clearly depended on the applied voltage between the anode and cathode. Our apparatus can be applied as a valuable in situ tool for the investigation of the electronic states and adsorbed species of polymer electrolyte fuel cell electrode catalysts under the reaction conditions.« less

Combined soft and hard X-ray ambient pressure photoelectron spectroscopy studies of semiconductor/electrolyte interfaces

DOE PAGES

Starr, David E.; Favaro, Marco; Abdi, Fatwa F.; ...

2017-05-18

The development of solar fuel generating materials would greatly benefit from a molecular level understanding of the semiconductor/electrolyte interface and changes in the interface induced by an applied potential and illumination by solar light. Ambient pressure photoelectron spectroscopy techniques with both soft and hard X-rays, AP-XPS and AP-HAXPES respectively, have the potential to markedly contribute to this understanding. In this paper we initially provide two examples of current challenges in solar fuels material development that AP-XPS and AP-HAXPES can directly a ddress. This will be followed by a brief description of the distinguishing and complementary characteristics of soft and hardmore » X-ray AP-XPS and AP-HAXPES and best approaches to achieving monolayer sensitivity in solid/aqueous electrolyte studies. In particular we focus on the detection of surface adsorbed hydroxyl groups in the presence of aqueous hydroxide anions in the electrolyte, a common situation when investigating photoanodes for solar fuel generating applications. Finally, the article concludes by providing an example of a combined AP-XPS and AP-HAXPES study of a semiconductor/aqueous electrolyte interface currently used in water splitting devices specifically the BiVO 4/aqueous potassium phosphate electrolyte interface.« less

A novel X-ray photoelectron spectroscopy study of the Al/SiO2 interface

NASA Technical Reports Server (NTRS)

Hecht, M. H.; Vasquez, R. P.; Grunthaner, F. J.; Zamani, N.; Maserjian, J.

1985-01-01

The nondestructive measurement of the chemical and physical characteristics of the interface between bulk SiO2 and thick aluminum films is reported. Both X-ray phototelectron spectroscopy (XPS) and electrical measurements of unannealed, resistively evaporated Al films on thermal SiO2 indicate an atomically abrupt interface. Post metallization annealing at 450 C induces reduction of the SiO2 by the aluminum, at a rate consistent with the bulk reaction rate. The XPS measurement is performed from the SiO2 side after the removal of the Si substrate with XeF2 gas and thinning of the SiO2 layer with HF:ETOH. This represents a powerful new approach to the study of metal-insulator and related interfaces.

The surface of 1-euro coins studied by X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Gou, F.; Gleeson, M. A.; Villette, J.; Kleyn, S. E. F.; Kleyn, A. W.

2004-03-01

The two alloy surfaces (pill and ring) that are present on 1-euro coins have been studied by X-ray photoelectron spectroscopy (XPS). Comparison is made between coins from general circulation and coin surfaces that have been subjected to a variety of cleaning and oxidation treatments. The concentrations and possible oxidation states of the metals (nickel, copper and zinc) at the surface were derived from analysis of the 2p 3/2 core levels. The surface atomic ratios measured for the pill and the ring parts of the euro coins were compared to the official bulk ratios. This study shows a clear nickel enrichment of both pill and ring surfaces. Nickel at surface seems to be present mainly in hydroxide form although the chloride form cannot be excluded. A small concentration of zinc was present on the surface of the pill, even though it is not present in the bulk alloy. Evidence of both nickel and zinc surface enrichment is observed for the ring. No surface enrichment is observed for the atomically clean or oxidized alloy surfaces over a 60-h time scale.

Dual crystal x-ray spectrometer at 1.8 keV for high repetition-rate single-photon counting spectroscopy experiments

DOE PAGES

Gamboa, E. J.; Bachmann, B.; Kraus, D.; ...

2016-08-01

The recent development of high-repetition rate x-ray free electron lasers (FEL), makes it possible to perform x-ray scattering and emission spectroscopy measurements from thin foils or gasses heated to high-energy density conditions by integrating over many experimental shots. Since the expected signal may be weaker than the typical CCD readout noise over the region-of-interest, it is critical to the success of this approach to use a detector with high-energy resolution so that single x-ray photons may be isolated. We describe a dual channel x-ray spectrometer developed for the Atomic and Molecular Optics endstation at the Linac Coherent Light Source (LCLS)more » for x-ray spectroscopy near the K-edge of aluminum. The spectrometer is based on a pair of curved PET (002) crystals coupled to a single pnCCD detector which simultaneously measures x-ray scattering and emission in the forward and backward directions. Furthermore, the signals from single x-ray photons are accumulated permitting continuous single-shot acquisition at 120 Hz.« less

High resolution X- and gamma-ray spectroscopy of cosmic X-ray sources

NASA Technical Reports Server (NTRS)

Lin, R. P.

1983-01-01

A high resolution X-ray spectrometer and large area phoswich detector were designed and co-aligned in a common elevation mounting in order to measure solar and cosmic X-ray and gamma ray emission in the 13 to 600 KeV energy range from a balloon. The instrument is described and results obtained for the Crab Nebula, the supernova remnant Cas A, and the Sun are discussed and analyzed.

X-ray photoelectron study of Si+ ion implanted polymers

NASA Astrophysics Data System (ADS)

Tsvetkova, T.; Balabanov, S.; Bischoff, L.; Krastev, V.; Stefanov, P.; Avramova, I.

2010-11-01

X-ray photoelectron spectroscopy was used to characterize different polymer materials implanted with low energy Si+ ions (E=30 keV, D= 1.1017 cm-2). Two kinds of polymers were studied - ultra-high-molecular-weight poly-ethylene (UHMWPE), and poly-methyl-methacrylate (PMMA). The non-implanted polymer materials show the expected variety of chemical bonds: carbon-carbon, carbon being three- and fourfold coordinated, and carbon-oxygen in the case of PMMA samples. The X-ray photoelectron and Raman spectra show that Si+ ion implantation leads to the introduction of additional disorder in the polymer material. The X-ray photoelectron spectra of the implanted polymers show that, in addition to already mentioned bonds, silicon creates new bonds with the host elements - Si-C and Si-O, together with additional Si dangling bonds as revealed by the valence band study of the implanted polymer materials.

Sulfur Speciation in Biochars by Very High Resolution Benchtop Ka X-Ray Emission Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheah, Singfoong; Holden, William M.; Seidler, Gerald T.

The analytical chemistry of sulfur-containing materials poses substantial technical challenges, especially due to the limitations of 33S NMR and the time-intensive preparations required for wet-chemistry analyses. A number of prior studies have found that synchrotron-based X-ray absorption near edge structure (XANES) measurements can give detailed speciation of sulfur chemistry in such cases. However, due to the obvious access limitations, synchrotron XANES of sulfur cannot be part of routine analytical practice across the chemical sciences community. Here, in a study of the sulfur chemistry in biochars, we compare and contrast the chemical inferences available from synchrotron XANES with that given bymore » benchtop, extremely high resolution wavelength-dispersive X-ray fluorescence (WD-XRF) spectroscopy, also often called X-ray emission spectroscopy (XES). While the XANES spectra have higher total information content, often giving differentiation between different moieties having the same oxidation state, the lower sensitivity of the S Ka XES to coordination and local structure provides pragmatic benefit for the more limited goal of quantifying the S oxidation state distribution. Within that constrained metric, we find good agreement between the two methods. As the sulfur concentrations were as low as 150 ppm, these measurements provide proof-of-principle for characterization of the sulfur chemistry of biochars and potential applications to other areas such as soils, batteries, catalysts, and fossil fuels and their combustion products.« less

Near-edge x-ray absorption fine structure spectroscopy at atmospheric pressure with a table-top laser-induced soft x-ray source

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kühl, Frank-Christian, E-mail: Frank-christian.kuehl@mail.de; Müller, Matthias, E-mail: matthias.mueller@llg-ev.de; Schellhorn, Meike

2016-07-15

The authors present a table-top soft x-ray absorption spectrometer, accomplishing investigations of the near-edge x-ray absorption fine structure (NEXAFS) in a laboratory environment. The system is based on a low debris plasma ignited by a picosecond laser in a pulsed krypton gas jet, emitting soft x-ray radiation in the range from 1 to 5 nm. For absorption spectroscopy in and around the “water window” (2.3–4.4 nm), a compact helium purged sample compartment for experiments at atmospheric pressure has been constructed and tested. NEXAFS measurements on CaCl{sub 2} and KMnO{sub 4} samples were conducted at the calcium and manganese L-edges, as well asmore » at the oxygen K-edge in air, atmospheric helium, and under vacuum, respectively. The results indicate the importance of atmospheric conditions for an investigation of sample hydration processes.« less

X-Ray Absorption near Edge Structure Spectroscopy of Nanodiamonds from the Allende Meteorite

NASA Technical Reports Server (NTRS)

Flynn, G. J.; Keller, L. P.; Hill, H.; Jacobsen, C.; Wirick, S.

2000-01-01

Carbon X-ray Absorption Near Edge Structure Spectroscopy shows Allende DM nanodiamonds have two pre-edge peaks, consistent with other small diamonds, but fail to show a diamond exciton which is seen in 3.6 nm diamond thin films.

Ultrafast Absorption Spectroscopy of Aluminum Plasmas Created by LCLS using Betatron X-Ray Radiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Albert, Felicie

2016-10-12

This document summarizes the goals and accomplishments of a six month-long LDRD project, awarded through the LLNL director Early and Mid Career Recognition (EMCR) program. This project allowed us to support beamtime awarded at the Matter under Extreme Conditions (MEC) end station of the Linac Coherent Light Source (LCLS). The goal of the experiment was to heat metallic samples with the bright x-rays from the LCLS free electron laser. Then, we studied how they relaxed back to equilibrium by probing them with ultrafast x-ray absorption spectroscopy using laser-based betatron radiation. Our work enabled large collaborations between LLNL, SLAC, LBNL, andmore » institutions in France and in the UK, while providing training to undergraduate and graduate students during the experiment. Following this LDRD project, the PI was awarded a 5-year DOE early career research grant to further develop applications of laser-driven x-ray sources for high energy density science experiments and warm dense matter states.« less

X-ray Raman spectroscopy of lithium-ion battery electrolyte solutions in a flow cell.

PubMed

Ketenoglu, Didem; Spiekermann, Georg; Harder, Manuel; Oz, Erdinc; Koz, Cevriye; Yagci, Mehmet C; Yilmaz, Eda; Yin, Zhong; Sahle, Christoph J; Detlefs, Blanka; Yavaş, Hasan

2018-03-01

The effects of varying LiPF 6 salt concentration and the presence of lithium bis(oxalate)borate additive on the electronic structure of commonly used lithium-ion battery electrolyte solvents (ethylene carbonate-dimethyl carbonate and propylene carbonate) have been investigated. X-ray Raman scattering spectroscopy (a non-resonant inelastic X-ray scattering method) was utilized together with a closed-circle flow cell. Carbon and oxygen K-edges provide characteristic information on the electronic structure of the electrolyte solutions, which are sensitive to local chemistry. Higher Li + ion concentration in the solvent manifests itself as a blue-shift of both the π* feature in the carbon edge and the carbonyl π* feature in the oxygen edge. While these oxygen K-edge results agree with previous soft X-ray absorption studies on LiBF 4 salt concentration in propylene carbonate, carbon K-edge spectra reveal a shift in energy, which can be explained with differing ionic conductivities of the electrolyte solutions.

What can be Learned from X-ray Spectroscopy Concerning Hot Gas in Local Bubble and Charge Exchange Processes?

NASA Technical Reports Server (NTRS)

Snowden, Steve

2007-01-01

What can be learned from x-ray spectroscopy in observing hot gas in local bubble and charge exchange processes depends on spectral resolution, instrumental grasp, instrumental energy band, signal-to-nose, field of view, angular resolution and observatory location. Early attempts at x-ray spectroscopy include ROSAT; more recently, astronomers have used diffuse x-ray spectrometers, XMM Newton, sounding rocket calorimeters, and Suzaku. Future observations are expected with calorimeters on the Spectrum Roentgen Gamma mission, and the Solar Wind Charge Exchange (SWCX). The Geospheric SWCX may provide remote sensing of the solar wind and magnetosheath and remote observations of solar CMEs moving outward from the sun.

Application of ultra-small-angle X-ray scattering / X-ray photon correlation spectroscopy to relate equilibrium or non-equilibrium dynamics to microstructure

NASA Astrophysics Data System (ADS)

Allen, Andrew; Zhang, Fan; Levine, Lyle; Ilavsky, Jan

2013-03-01

Ultra-small-angle X-ray scattering (USAXS) can probe microstructures over the nanometer-to-micrometer scale range. Through use of a small instrument entrance slit, X-ray photon correlation spectroscopy (XPCS) exploits the partial coherence of an X-ray synchrotron undulator beam to provide unprecedented sensitivity to the dynamics of microstructural change. In USAXS/XPCS studies, the dynamics of local structures in a scale range of 100 nm to 1000 nm can be related to an overall hierarchical microstructure extending from 1 nm to more than 1000 nm. Using a point-detection scintillator mode, the equilibrium dynamics at ambient temperature of small particles (which move more slowly than nanoparticles) in aqueous suspension have been quantified directly for the first time. Using a USAXS-XPCS scanning mode for non-equilibrium dynamics incipient processes within dental composites have been elucidated, prior to effects becoming detectable using any other technique. Use of the Advanced Photon Source, an Office of Science User Facility operated for the United States Department of Energy (U.S. DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357.

EUV Spectroscopy of High-redshift X-ray Objects

NASA Astrophysics Data System (ADS)

Kowalski, Michael Paul; Wolff, M. T.; Wood, K. S.; Barbee, T. W., Jr.

2010-03-01

As astronomical observations are pushed to cosmological distances (z>3) the spectral energy distributions of X-ray objects, AGNs for example, will have their maxima redshifted into the EUV waveband ( 90-912 Å/0.1-0.01 keV). Consequently, a wealth of spectral diagnostics, provided by, for example, the Fe L-shell complex ( 60-6 Å/0.2-2.0 keV) and the O VII/VIII lines ( 20 Å/0.5 keV), will be lost to X-ray instruments operating at traditional ( 0.5-10 keV) and higher X-ray energies. There are precedents in other wavebands. For example, HST evolutionary studies will become largely the province of JWST. Despite the successes of EUVE, the ROSAT WFC, and the Chandra LETG, the EUV continues to be unappreciated and under-utilized, partly because of a preconception that absorption by neutral galactic Hydrogen in the ISM prevents any useful extragalactic measurements at all EUV wavelengths and, until recently, by a lack of a suitable enabling technology. Thus, if future planned X-ray missions (e.g., IXO, Gen-X) are optimized again for traditional X-ray energies, their performance (effective area, resolving power) will be cut off at ultrasoft X-ray energies or at best be radically reduced in the EUV. This opens up a critical gap in performance located right at short EUV wavelengths, where the critical X-ray spectral transitions occur in high-z objects. However, normal-incidence multilayer-grating technology, which performs best precisely at such wavelengths, together with advanced nano-laminate fabrication techniques have been developed and are now mature to the point where advanced EUV instrument designs with performance complementary to IXO and Gen-X are practical. Such EUV instruments could be flown either independently or as secondary instruments on these X-ray missions. We present here a critical examination of the limits placed on extragalactic EUV measurements by ISM absorption, the range where high-z measurements are practical, and the requirements this imposes on

Optical Metrology for the Segmented Optics on the Constellation-X Spectroscopy X-Ray Telescope

NASA Technical Reports Server (NTRS)

Content, David; Colella, David; Fleetwood, Charles; Hadjimichael, Theo; Lehan, John; McMann, Joseph; Reid, Paul; Saha, Timo; Wright, Geraldine; Zhang, William

2004-01-01

We present the metrology requirements and metrology implementation necessary to prove out the reflector technology for the Constellation X(C-X) spectroscopy X-ray telescope (SXT). This segmented, 1.6m diameter highly nested Wolter-1 telescope presents many metrology and alignment challenges. In particular, these mirrors have a stringent imaging error budget as compared to their intrinsic stiffness; This is required for Constellation-X to have sufficient effective area with the weight requirement. This has implications for the metrology that can be used. A variety of contract and noncontact optical profiling and interferometric methods are combined to test the formed glass substrates before replication and the replicated reflector segments.The reflectors are tested both stand-alone and in-situ in an alignment tower.Some of these methods have not been used on prior X-ray telescopes and some are feasible only because of the segmented approach used on the SXT. Methods discussed include high precision coordinate measurement machines using very low force or optical probe axial interferometric profiling azimuthal circularity profiling and use of advanced null optics such as conical computer generated hologram (CGHs).

X-ray Emission Spectroscopy of Biomimetic Mn Coordination Complexes.

PubMed

Jensen, Scott C; Davis, Katherine M; Sullivan, Brendan; Hartzler, Daniel A; Seidler, Gerald T; Casa, Diego M; Kasman, Elina; Colmer, Hannah E; Massie, Allyssa A; Jackson, Timothy A; Pushkar, Yulia

2017-06-15

Understanding the function of Mn ions in biological and chemical redox catalysis requires precise knowledge of their electronic structure. X-ray emission spectroscopy (XES) is an emerging technique with a growing application to biological and biomimetic systems. Here, we report an improved, cost-effective spectrometer used to analyze two biomimetic coordination compounds, [Mn IV (OH) 2 (Me 2 EBC)] 2+ and [Mn IV (O)(OH)(Me 2 EBC)] + , the second of which contains a key Mn IV ═O structural fragment. Despite having the same formal oxidation state (Mn IV ) and tetradentate ligands, XES spectra from these two compounds demonstrate different electronic structures. Experimental measurements and DFT calculations yield different localized spin densities for the two complexes resulting from Mn IV -OH conversion to Mn IV ═O. The relevance of the observed spectroscopic changes is discussed for applications in analyzing complex biological systems such as photosystem II. A model of the S 3 intermediate state of photosystem II containing a Mn IV ═O fragment is compared to recent time-resolved X-ray diffraction data of the same state.

Clocking Femtosecond Collisional Dynamics via Resonant X-Ray Spectroscopy

DOE PAGES

van den Berg, Q. Y.; Fernandez-Tello, E. V.; Burian, T.; ...

2018-02-01

Electron-ion collisional dynamics is of fundamental importance in determining plasma transport properties, nonequilibrium plasma evolution, and electron damage in diffraction imaging applications using bright x-ray free-electron lasers (FELs). Here in this paper, we describe the first experimental measurements of ultrafast electron impact collisional ionization dynamics using resonant core-hole spectroscopy in a solid-density magnesium plasma, created and diagnosed with the Linac Coherent Light Source x-ray FEL. By resonantly pumping the 1s → 2p transition in highly charged ions within an optically thin plasma, we have measured how off-resonance charge states are populated via collisional processes on femtosecond time scales. We presentmore » a collisional cross section model that matches our results and demonstrates how the cross sections are enhanced by dense-plasma effects including continuum lowering. Nonlocal thermodynamic equilibrium collisional radiative simulations show excellent agreement with the experimental results and provide new insight on collisional ionization and three-body-recombination processes in the dense-plasma regime.« less

Chemical order in the glassy As/sub x/S/sub 1-//sub x/ system: An x-ray-absorption spectroscopy study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, C.Y.; Paesler, M.A.; Sayers, D.E.

1989-05-15

We have examined chemical ordering in the glassy As/sub x/S/sub 1-//sub x/ system by determining the effect of composition on the local structure of these chalcogenide glasses using x-ray-absorption spectroscopy. Structural changes associated with composition indicate that with increasing S content, the S-rich glasses on the As site have a similar local structure to crystalline As/sub 2/S/sub 3/ (orpiment), but the As-S-As linkages are replaced by As-S-S linkages at higher S concentration. In As-rich glasses a breakdown of the local AsS/sub 3/ configuration is evident and the formation of As-As bonds is observed. Further comparison between As-rich alloys and crystallinemore » As/sub 4/S/sub 4/ (realgar) suggests that a significant fraction of disordered As/sub 4/S/sub 4/ molecular fragments is contained in the As-rich region.« less

X-ray absorption spectroscopy investigations on oxidized Ni/Au contacts to p-GaN.

PubMed

Jan, J C; Asokan, K; Chiou, J W; Pong, W F; Tseng, P K; Chen, L C; Chen, F R; Lee, J F; Wu, J S; Lin, H J; Chen, C T

2001-03-01

X-ray absorption spectroscopy was used to investigate the electronic structure of as-deposited and oxidized Ni/Au contacts to p-GaN and to elucidate the mechanism responsible for low impedance. X-ray absorption near edge spectra of Ni K- and L3,2-edges clearly indicate formation of NiO on the sample surface after annealing. The reason for low impedance may be attributed to increase in hole concentration and existence of p-NiO layer on the surface.

The effect of Sr and Bi on the Si(100) surface oxidation - Auger electron spectroscopy, low energy electron diffraction, and X-ray photoelectron spectroscopy study

NASA Technical Reports Server (NTRS)

Fan, W. C.; Mesarwi, A.; Ignatiev, A.

1990-01-01

The effect of Sr and Bi on the oxidation of the Si(100) surface has been studied by Auger electron spectroscopy, low electron diffraction, and X-ray photoelectron spectroscopy. A dramatic enhancement, by a factor of 10, of the Si oxidation has been observed for Si(100) with a Sr overlayer. The SR-enhanced Si oxidation has been studied as a function of O2 exposure and Sr coverage. In contrast to the oxidation promotion of Sr on Si, it has been also observed that a Bi overlayer on Si(100) reduced Si oxidation significantly. Sr adsorption on the Si(100) with a Bi overlayer enhances Si oxidation only at Sr coverage of greater than 0.3 ML.

AEGIS: An Astrophysics Experiment for Grating and Imaging Spectroscopy---a Soft X-ray, High-resolution Spectrometer

NASA Astrophysics Data System (ADS)

Huenemoerder, David; Bautz, M. W.; Davis, J. E.; Heilmann, R. K.; Houck, J. C.; Marshall, H. L.; Neilsen, J.; Nicastro, F.; Nowak, M. A.; Schattenburg, M. L.; Schulz, N. S.; Smith, R. K.; Wolk, S.; AEGIS Team

2012-01-01

AEGIS is a concept for a high-resolution soft X-ray spectroscopic observatory developed in response to NASA's request for definitions of the next X-ray astronomy mission. At a small fraction of the cost of the once-planned International X-ray Observatory (IXO), AEGIS has capabilities that surpass IXO grating spectrometer requirements, and which are far superior to those of existing soft X-ray spectrometers. AEGIS incorporates innovative technology in X-ray optics, diffraction gratings and detectors. The mirror uses high area-to-mass ratio segmented glass architecture developed for IXO, but with smaller aperture and larger graze angles optimized for high-throughput grating spectroscopy with low mass and cost. The unique Critical Angle Transmission gratings combine low mass and relaxed figure and alignment tolerances of Chandra transmission gratings but with high diffraction efficiency and resolving power of blazed reflection gratings. With more than an order of magnitude better performance over Chandra and XMM grating spectrometers, AEGIS can obtain high quality spectra of bright AGN in a few hours rather than 10 days. Such high resolving power allows detailed kinematic studies of galactic outflows, hot gas in galactic haloes, and stellar accretion flows. Absorption line spectroscopy will be used to study large scale structure, cosmic feedback, and growth of black holes in thousands of sources to great distances. AEGIS will enable powerful multi-wavelength investigations, for example with Hubble/COS in the UV to characterize the intergalactic medium. AEGIS will be the first observatory with sufficient resolution below 1 keV to resolve thermally-broadened lines in hot ( 10 MK) plasmas. Here we describe key science investigations enable by Aegis, its scientific payload and mission plan. Acknowledgements: Support was provided in part by: NASA SAO contract SV3-73016 to MIT for the Chandra X-ray Center and Science Instruments; NASA grant NNX08AI62G; and the MKI

The X-ray Astronomy Recovery Mission

NASA Astrophysics Data System (ADS)

Tashiro, M.; Kelley, R.

2017-10-01

On 25 March 2016, the Japanese 6th X-ray astronomical satellite ASTRO-H (Hitomi), launched on February 17, lost communication after a series of mishap in its attitude control system. In response to the mishap the X-ray astronomy community and JAXA analyzed the direct and root cause of the mishap and investigated possibility of a recovery mission with the international collaborator NASA and ESA. Thanks to great effort of scientists, agencies, and governments, the X-ray Astronomy Recovery Mission (XARM) are proposed. The recovery mission is planned to resume high resolution X-ray spectroscopy with imaging realized by Hitomi under the international collaboration in the shortest time possible, simply by focusing one of the main science goals of Hitomi Resolving astrophysical problems by precise high-resolution X-ray spectroscopy'. XARM will carry a 6 x 6 pixelized X-ray micro-calorimeter on the focal plane of an X-ray mirror assembly, and an aligned X-ray CCD camera covering the same energy band and wider field of view, but no hard X-ray or soft gamma-ray instruments are onboard. In this paper, we introduce the science objectives, mission concept, and schedule of XARM.

Revealing hole trapping in zinc oxide nanoparticles by time-resolved X-ray spectroscopy

DOE PAGES

Penfold, Thomas J.; Szlachetko, Jakub; Santomauro, Fabio G.; ...

2018-02-02

Nanostructures of transition metal oxides (TMO), such as ZnO, have attracted considerable interest for solar-energy conversion and photocatalysis. For the latter, trapping of charge carriers has an essential role. The probing of electron trapping in the conduction band of room temperature photoexcited TMOs has recently become possible owing to the emergence of time-resolved element-sensitive methods, such as X-ray spectroscopy. However, because the valence band of TMOs is dominated by the oxygen 2p orbitals,holes have so far escaped observation. Herein we use a novel dispersive X-ray emission spectrometer combined with X-ray absorption spectroscopy to directly probe the charge carrier relaxation andmore » trapping pro-cesses in ZnO nanoparticles after above band-gap photoexcitation. Here, our results, supported by simulations, demonstrate that within our temporal resolution of 80 ps, photo-excited holes are trapped at singly charged oxygen vacancies, turning them into doubly charged vacancies, which causes an outward displacement by approximately 15% of the four surrounding Zn atoms away from the central vacancy. These traps recombine radiatively with the delocalised electrons of the conduction band yielding the commonly observed green luminescence. This identification of the hole traps and their evolution provides new insight for future developments of TMO-based nanodevices.« less

Revealing hole trapping in zinc oxide nanoparticles by time-resolved X-ray spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Penfold, Thomas J.; Szlachetko, Jakub; Santomauro, Fabio G.

Nanostructures of transition metal oxides (TMO), such as ZnO, have attracted considerable interest for solar-energy conversion and photocatalysis. For the latter, trapping of charge carriers has an essential role. The probing of electron trapping in the conduction band of room temperature photoexcited TMOs has recently become possible owing to the emergence of time-resolved element-sensitive methods, such as X-ray spectroscopy. However, because the valence band of TMOs is dominated by the oxygen 2p orbitals,holes have so far escaped observation. Herein we use a novel dispersive X-ray emission spectrometer combined with X-ray absorption spectroscopy to directly probe the charge carrier relaxation andmore » trapping pro-cesses in ZnO nanoparticles after above band-gap photoexcitation. Here, our results, supported by simulations, demonstrate that within our temporal resolution of 80 ps, photo-excited holes are trapped at singly charged oxygen vacancies, turning them into doubly charged vacancies, which causes an outward displacement by approximately 15% of the four surrounding Zn atoms away from the central vacancy. These traps recombine radiatively with the delocalised electrons of the conduction band yielding the commonly observed green luminescence. This identification of the hole traps and their evolution provides new insight for future developments of TMO-based nanodevices.« less

New Optimizations of Microcalorimeter Arrays for High-Resolution Imaging X-ray Spectroscopy

NASA Astrophysics Data System (ADS)

Kilbourne, Caroline

We propose to continue our successful research program in developing arrays of superconducting transition-edge sensors (TES) for x-ray astrophysics. Our standard 0.3 mm TES pixel achieves better than 2.5-eV resolution, and we now make 32x32 arrays of such pixels. We have also achieved better than 1-eV resolution in smaller pixels, and promising performance in a range of position-sensitive designs. We propose to continue to advance the designs of both the single-pixel and position-sensitive microcalorimeters so that we can produce arrays suitable for several x-ray spectroscopy observatories presently in formulation. We will also investigate various array and pixel optimizations such as would be needed for large arrays for surveys, large- pixel arrays for diffuse soft x-ray measurements, or sub-arrays of fast pixels optimized for neutron-star burst spectroscopy. In addition, we will develop fabrication processes for integrating sub-arrays with very different pixel designs into a monolithic focal-plane array to simplify the design of the focal-plane assembly and make feasible new detector configurations such as the one currently baselined for AXSIO. Through a series of measurements on test devices, we have improved our understanding of the weak-link physics governing the observed resistive transitions in TES detectors. We propose to build on that work and ultimately use the results to improve the immunity of the detector to environmental magnetic fields, as well as its fundamental performance, in each of the targeted optimizations we are developing.

Identification of Uranyl Minerals Using Oxygen K-Edge X Ray Absorption Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ward, Jesse D.; Bowden, Mark E.; Resch, Charles T.

2016-03-01

Uranium analysis is consistently needed throughout the fuel cycle, from mining to fuel fabrication to environmental monitoring. Although most of the world’s uranium is immobilized as pitchblende or uraninite, there exists a plethora of secondary uranium minerals, nearly all of which contain the uranyl cation. Analysis of uranyl compounds can provide clues as to a sample’s facility of origin and chemical history. X-ray absorption spectroscopy is one technique that could enhance our ability to identify uranium minerals. Although there is limited chemical information to be gained from the uranium X-ray absorption edges, recent studies have successfully used ligand NEXAFS tomore » study the physical chemistry of various uranium compounds. This study extends the use of ligand NEXAFS to analyze a suite of uranium minerals. We find that major classes of uranyl compounds (carbonate, oxyhydroxide, silicate, and phosphate) exhibit characteristic lineshapes in the oxygen K-edge absorption spectra. As a result, this work establishes a library of reference spectra that can be used to classify unknown uranyl minerals.« less

X-ray Absorption Spectroscopy Characterization of a Li/S Cell

DOE PAGES

Ye, Yifan; Kawase, Ayako; Song, Min-Kyu; ...

2016-01-11

The X-ray absorption spectroscopy technique has been applied to study different stages of the lithium/sulfur (Li/S) cell life cycle. We investigated how speciation of S in Li/S cathodes changes upon the introduction of CTAB (cetyltrimethylammonium bromide, CH 3(CH 2) 15N+(CH 3) 3Br₋) and with charge/discharge cycling. The introduction of CTAB changes the synthesis reaction pathway dramatically due to the interaction of CTAB with the terminal S atoms of the polysulfide ions in the Na 2S x solution. For the cycled Li/S cell, the loss of electrochemically active sulfur and the accumulation of a compact blocking insulating layer of unexpected sulfurmore » reaction products on the cathode surface during the charge/discharge processes make the capacity decay. Lastly, a modified coin cell and a vacuum-compatible three-electrode electro-chemical cell have been introduced for further in-situ/in-operando studies.« less

X-ray photoelectron spectroscopy study of chemically-etched Nd-Ce-Cu-O surfaces

NASA Technical Reports Server (NTRS)

Vasquez, R. P.; Gupta, A.; Kussmaul, A.

1991-01-01

Acetic acid, Br2, and HCl solutions are investigated for removing insulating species from Nd(1.85)Ce(0.15)CuO(4-delta) (NCCO) thin film surfaces. X-ray photoelectron spectroscopy (XPS) shows that the HCl etch is most effective, yielding O 1s spectra comparable to those obtained from samples cleaned in vacuum and a clear Fermi edge in the valence band region. Reduction and oxidation reversibly induces and eliminates, respectively, Fermi level states for undoped samples, but has no clearly observable effect on the XPS spectra for doped samples. Reactivity to air is much less for NCCO compared to hole superconductors, which is attributed to the lack of reactive alkaline earth elements in NCCO.

X-ray Raman spectroscopic study of benzene at high pressure.

PubMed

Pravica, Michael; Grubor-Urosevic, Ognjen; Hu, Michael; Chow, Paul; Yulga, Brian; Liermann, Peter

2007-10-11

We have used X-ray Raman spectroscopy (XRS) to study benzene up to approximately 20 GPa in a diamond anvil cell at ambient temperature. The experiments were performed at the High-Pressure Collaborative Access Team's 16 ID-D undulator beamline at the Advanced Photon Source. Scanned monochromatic X-rays near 10 keV were used to probe the carbon X-ray edge near 284 eV via inelastic scattering. The diamond cell axis was oriented perpendicular to the X-ray beam axis to prevent carbon signal contamination from the diamonds. Beryllium gaskets confined the sample because of their high transmission throughput in this geometry. Spectral alterations with pressure indicate bonding changes that occur with pressure because of phase changes (liquid: phase I, II, III, and III') and possibly due to changes in the hybridization of the bonds. Changes in the XRS spectra were especially evident in the data taken when the sample was in phase III', which may be related to a rate process observed in earlier shock wave studies.

X-ray Emission Line Spectroscopy of Nearby Galaxies

NASA Astrophysics Data System (ADS)

Wang, Daniel

What are the origins of the diffuse soft X-ray emission from non-AGN galaxies? Preliminary analysis of XMM-Newton RGS spectra shows that a substantial fraction of the emission cannot arise from optically-thin thermal plasma, as commonly assumed, and may originate in charge exchange at the interface with neutral gas. We request the support for a comprehensive observing, data analysis, and modeling program to spectroscopically determine the origins of the emission. First, we will use our scheduled XMM-Newton AO-10 368 ks observations of the nearest compact elliptical galaxy M32 to obtain the first spectroscopic calibration of the cumulative soft X-ray emission from the old stellar population and will develop a spectral model for the charge exchange, as well as analysis tools to measure the spatial and kinematic properties of the X-ray line- emitting plasma. Second, we will characterize the truly diffuse emission from the hot plasma and/or its interplay with the neutral gas in a sample of galactic spheroids and active star forming/starburst regions in nearby galaxies observed by XMM-Newton. In particular, we will map out the spatial distributions of key emission lines and measure (or tightly constrain) the kinematics of hot plasma outflows for a few X-ray-emitting regions with high-quality RGS data. For galaxies with insufficient counting statistics in individual emission lines, we will conduct a spectral stacking analysis to constrain the average properties of the X-ray-emitting plasma. We will use the results of these X-ray spectroscopic analyses, together with complementary X-ray CCD imaging/spectral data and observations in other wavelength bands, to test the models of the emission. In addition to the charge exchange, alternative scenarios such as resonance scattering and relic AGN photo-ionization will also be examined for suitable regions. These studies are important to the understanding of the relationship between the diffuse soft X-ray emission and various

Saccharose solid matrix embedded proteins: a new method for sample preparation for X-ray absorption spectroscopy.

PubMed

Ascone, I; Sabatucci, A; Bubacco, L; Di Muro, P; Salvato, B

2000-01-01

In this study, solid samples of hemoglobin and hemocyanin have been prepared by embedding the proteins into a saccharose-based matrix. These materials have been developed specifically for specimens for X-ray absorption spectroscopy (XAS). The preservation of protein conformation and active site organization was tested, making comparisons between the solid and the corresponding liquid samples, using resonance Raman, infra red, fluorescence and XAS. The XAS spectra of irradiated solid and liquid samples were then compared, and the preservation of biological activity of the proteins during both preparation procedure and X-ray irradiation was assessed. In all cases, the measurements clearly demonstrate that protein solid samples are both structurally and functionally quite well preserved, much better than those in the liquid state. The saccharose matrix provides an excellent protection against X-ray damages, allowing for longer exposure to the X-ray beam. Moreover, the demonstrated long-term stability of samples permits their preparation and storage in optimal conditions, allowing for the repetition of data collection with the same sample in several experimental sessions. The very high protein concentration that can be reached results in a significantly better signal-to-noise ratio, particularly useful for high molecular weight proteins with a low metal-to-protein ratio. On the bases of the above-mentioned results, we propose the new method as a standard procedure for the preparation of biological samples to be used for XAS spectroscopy.

Identifying anthropogenic uranium compounds using soft X-ray near-edge absorption spectroscopy

NASA Astrophysics Data System (ADS)

Ward, Jesse D.; Bowden, Mark; Tom Resch, C.; Eiden, Gregory C.; Pemmaraju, C. D.; Prendergast, David; Duffin, Andrew M.

2017-01-01

Uranium ores mined for industrial use are typically acid-leached to produce yellowcake and then converted into uranium halides for enrichment and purification. These anthropogenic chemical forms of uranium are distinct from their mineral counterparts. The purpose of this study is to use soft X-ray absorption spectroscopy to characterize several common anthropogenic uranium compounds important to the nuclear fuel cycle. Chemical analyses of these compounds are important for process and environmental monitoring. X-ray absorption techniques have several advantages in this regard, including element-specificity, chemical sensitivity, and high spectral resolution. Oxygen K-edge spectra were collected for uranyl nitrate, uranyl fluoride, and uranyl chloride, and fluorine K-edge spectra were collected for uranyl fluoride and uranium tetrafluoride. Interpretation of the data is aided by comparisons to calculated spectra. The effect of hydration state on the sample, a potential complication in interpreting oxygen K-edge spectra, is discussed. These compounds have unique spectral signatures that can be used to identify unknown samples.

Identifying anthropogenic uranium compounds using soft X-ray near-edge absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ward, Jesse D.; Bowden, Mark; Tom Resch, C.

2017-01-01

Uranium ores mined for industrial use are typically acid-leached to produce yellowcake and then converted into uranium halides for enrichment and purification. These anthropogenic chemical forms of uranium are distinct from their mineral counterparts. The purpose of this study is to use soft X-ray absorption spectroscopy to characterize several common anthropogenic uranium compounds important to the nuclear fuel cycle. Non-destructive chemical analyses of these compounds is important for process and environmental monitoring and X-ray absorption techniques have several advantages in this regard, including element-specificity, chemical sensitivity, and high spectral resolution. Oxygen K-edge spectra were collected for uranyl nitrate, uranyl fluoride,more » and uranyl chloride, and fluorine K-edge spectra were collected for uranyl fluoride and uranium tetrafluoride. Interpretation of the data is aided by comparisons to calculated spectra. These compounds have unique spectral signatures that can be used to identify unknown samples.« less

High-rate x-ray spectroscopy in mammography with a CdTe detector: a digital pulse processing approach.

PubMed

Abbene, L; Gerardi, G; Principato, F; Del Sordo, S; Ienzi, R; Raso, G

2010-12-01

Direct measurement of mammographic x-ray spectra under clinical conditions is a difficult task due to the high fluence rate of the x-ray beams as well as the limits in the development of high resolution detection systems in a high counting rate environment. In this work we present a detection system, based on a CdTe detector and an innovative digital pulse processing (DPP) system, for high-rate x-ray spectroscopy in mammography. The DPP system performs a digital pile-up inspection and a digital pulse height analysis of the detector signals, digitized through a 14-bit, 100 MHz digitizer, for x-ray spectroscopy even at high photon counting rates. We investigated on the response of the digital detection system both at low (150 cps) and at high photon counting rates (up to 500 kcps) by using monoenergetic x-ray sources and a nonclinical molybdenum anode x-ray tube. Clinical molybdenum x-ray spectrum measurements were also performed by using a pinhole collimator and a custom alignment device. The detection system shows excellent performance up to 512 kcps with an energy resolution of 4.08% FWHM at 22.1 keV. Despite the high photon counting rate (up to 453 kcps), the molybdenum x-ray spectra, measured under clinical conditions, are characterized by a low number of pile-up events. The agreement between the attenuation curves and the half value layer values, obtained from the measured spectra, simulated spectra, and from the exposure values directly measured with an ionization chamber, also shows the accuracy of the measurements. These results make the proposed detection system a very attractive tool for both laboratory research and advanced quality controls in mammography.

Monitoring Ultrafast Chemical Dynamics by Time-Domain X-ray Photo- and Auger-Electron Spectroscopy.

PubMed

Gessner, Oliver; Gühr, Markus

2016-01-19

photocatalytic activity have been performed based on the combination of strong light absorption in dye molecules with charge separation and transport in adjacent semiconductor nanostructures. However, a fundamental understanding of the enabling and limiting dynamics on critical atomic length- and time scales is often still lacking. Femtosecond time-resolved X-ray photoelectron spectroscopy is employed to gain a better understanding of a short-lived intermediate that may be linked to the unexpectedly limited performance of ZnO based dye-sensitized solar cells by delaying the generation of free charge carriers. The transient spectra strongly suggest that photoexcited dye molecules attached to ZnO nanocrystals inject their charges into the substrate within less than 1 ps but the electrons are then temporarily trapped at the surface of the semiconductor in direct vicinity of the injecting molecules. The experiments are extended to monitor the electronic response of the semiconductor substrate to the collective injection from a monolayer of dye molecules and the subsequent electron-ion recombination dynamics. The results indicate some qualitative similarities but quantitative differences between the recombination dynamics at molecule-semiconductor interfaces and previously studied bulk-surface electron-hole recombination dynamics in photoexcited semiconductors.

The aquatic hyphomycete Heliscus lugdunensis protects its hyphae tip cells from cadmium: A micro X-ray fluorescence and X-ray absorption near edge structure spectroscopy study

NASA Astrophysics Data System (ADS)

Isaure, Marie-Pierre; Leyh, Benjamin; Salomé, Murielle; Krauss, Gerd-Joachim; Schaumlöffel, Dirk; Dobritzsch, Dirk

2017-11-01

Aquatic fungi can be used to evaluate the functioning of natural ecosystems. Heliscus lugdunensis is an early colonizer of allochthone leafs. Since this aquatic hyphomycete is able to develop in metal contaminated habitats and tolerates cadmium, it appears to be a good candidate to investigate adaptation to metal pollution. This study aimed at examining the sequestration of Cd in the hyphae of H. lugdunensis, and particularly the role of the tip cells. For that, H. lugdunensis growth was evaluated under various Cd concentrations, and a combination of synchrotron micro X-ray fluorescence and X-ray absorption near edge structure spectroscopy was carried out to determine the compartments of Cd accumulation and the Cd chemical species, respectively. Results showed that the hyphal tip cells were depleted in Cd, and that the metal was stored in older cells. Cd was mainly associated with sulfur ligands and to a lesser extent bound to phosphates and carboxyl/hydroxyl groups from cell wall and/or organic acids. Finally, the aquatic fungus was able to maintain the tip cell as a functional system, thus allowing the colonization of contaminated environments.

Local Structure Determination of Carbon/Nickel Ferrite Composite Nanofibers Probed by X-ray Absorption Spectroscopy.

PubMed

Nilmoung, Sukunya; Kidkhunthod, Pinit; Maensiri, Santi

2015-11-01

Carbon/NiFe2O4 composite nanofibers have been successfully prepared by electrospinning method using a various concentration solution of Ni and Fe nitrates dispersed into polyacrylonitride (PAN) solution in N,N' dimethylformamide. The phase and mophology of PAN/NiFe2O4 composite samples were characterized and investigated by X-ray diffraction and scanning electron microscopy. The magnetic properties of the prepared samples were measured at ambient temperature by a vibrating sample magnetometer. It is found that all composite samples exhibit ferromagnetism. This could be local-structurally explained by the existed oxidation states of Ni2+ and Fe3+ in the samples. Moreover, local environments around Ni and Fe ions could be revealed by X-ray absorption spectroscopy (XAS) measurement including X-ray absorption near edge structure (XANES) and Extended X-ray absorption fine structure (EXAFS).

CONTIN XPCS: Software for Inverse Transform Analysis of X-Ray Photon Correlation Spectroscopy Dynamics

PubMed Central

Narayanan, Suresh; Zhang, Fan; Kuzmenko, Ivan; Ilavsky, Jan

2018-01-01

X-ray photon correlation spectroscopy (XPCS) and dynamic light scattering (DLS) both reveal dynamics using coherent scattering, but X-rays permit investigating of dynamics in a much more diverse array of materials. Heterogeneous dynamics occur in many such materials, and we showed how classic tools employed in analysis of heterogeneous DLS dynamics extend to XPCS, revealing additional information that conventional Kohlrausch exponential fitting obscures. This work presents the software implementation of inverse transform analysis of XPCS data called CONTIN XPCS, an extension of traditional CONTIN that accommodates dynamics encountered in equilibrium XPCS measurements. PMID:29875507

CONTIN XPCS: Software for Inverse Transform Analysis of X-Ray Photon Correlation Spectroscopy Dynamics.

PubMed

Andrews, Ross N; Narayanan, Suresh; Zhang, Fan; Kuzmenko, Ivan; Ilavsky, Jan

2018-02-01

X-ray photon correlation spectroscopy (XPCS) and dynamic light scattering (DLS) both reveal dynamics using coherent scattering, but X-rays permit investigating of dynamics in a much more diverse array of materials. Heterogeneous dynamics occur in many such materials, and we showed how classic tools employed in analysis of heterogeneous DLS dynamics extend to XPCS, revealing additional information that conventional Kohlrausch exponential fitting obscures. This work presents the software implementation of inverse transform analysis of XPCS data called CONTIN XPCS, an extension of traditional CONTIN that accommodates dynamics encountered in equilibrium XPCS measurements.

Report on the 18th International Conference on X-ray and Inner-Shell Processes (X99).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gemmell, D. S.; Physics

2000-01-01

The 18th conference of the series served as a forum for discussing fundamental issues in the field of x-ray and inner-shell processes and their application in various disciplines of science and technology. Special emphasis was given to the opportunities offered by modern synchrotron x-ray sources. The program included plenary talks, progress reports and poster presentations relating to new developments in the field of x-ray and inner-shell processes. The range of topics included: X-ray interactions with atoms, molecules, clusters, surfaces and solids; Decay processes for inner-shell vacancies; X-ray absorption and emission spectroscopy - Photoionization processes; Phenomena associated with highly charged ionsmore » and collisions with energetic particles; Electron-spin and -momentum spectroscopy; X-ray scattering and spectroscopy in the study of magnetic systems; Applications in materials science, biology, geosciences, and other disciplines; Elastic and inelastic x-ray scattering processes in atoms and molecules; Threshold phenomena (post-collision interaction, resonant Raman processes, etc.); Nuclear absorption and scattering of x-rays; 'Fourth-generation' x-ray sources; Processes exploiting the polarization and coherence properties of x-ray beams; Developments in experimental techniques (x-ray optics, temporal techniques, detectors); Microscopy, spectromicroscopy, and various imaging techniques; Non-linear processes and x-ray lasers; Ionization and excitation induced by charged particles and by x-rays; and Exotic atoms (including 'hollow' atoms and atoms that contain 'exotic' particles).« less

Charge and Spin-State Characterization of Cobalt Bis( o-dioxolene) Valence Tautomers Using Co Kβ X-ray Emission and L-Edge X-ray Absorption Spectroscopies

DOE PAGES

Liang, H. Winnie; Kroll, Thomas; Nordlund, Dennis; ...

2016-12-30

The valence tautomeric states of Co(phen)(3,5-DBQ) 2 and Co(tmeda)(3,5-DBQ) 2, where 3,5-DBQ is either the semiquinone (SQ –) or catecholate (Cat 2–) form of 3,5-di- tert-butyl-1,2-benzoquinone, have been examined by a series of cobalt-specific X-ray spectroscopies. In this work, we have utilized the sensitivity of 1s3p X-ray emission spectroscopy (Kβ XES) to the oxidation and spin states of 3d transition-metal ions to determine the cobalt-specific electronic structure of valence tautomers. A comparison of their Kβ XES spectra with the spectra of cobalt coordination complexes with known oxidation and spin states demonstrates that the low-temperature valence tautomer can be described asmore » a low-spin Co III configuration and the high-temperature valence tautomer as a high-spin Co II configuration. This conclusion is further supported by Co L-edge X-ray absorption spectroscopy (L-edge XAS) of the high-temperature valence tautomers and ligand-field atomic-multiplet calculations of the Kβ XES and L-edge XAS spectra. In conclusion, the nature and strength of the magnetic exchange interaction between the cobalt center and SQ – in cobalt valence tautomers is discussed in view of the effective spin at the Co site from Kβ XES and the molecular spin moment from magnetic susceptibility measurements.« less

Charge and Spin-State Characterization of Cobalt Bis( o-dioxolene) Valence Tautomers Using Co Kβ X-ray Emission and L-Edge X-ray Absorption Spectroscopies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang, H. Winnie; Kroll, Thomas; Nordlund, Dennis

The valence tautomeric states of Co(phen)(3,5-DBQ) 2 and Co(tmeda)(3,5-DBQ) 2, where 3,5-DBQ is either the semiquinone (SQ –) or catecholate (Cat 2–) form of 3,5-di- tert-butyl-1,2-benzoquinone, have been examined by a series of cobalt-specific X-ray spectroscopies. In this work, we have utilized the sensitivity of 1s3p X-ray emission spectroscopy (Kβ XES) to the oxidation and spin states of 3d transition-metal ions to determine the cobalt-specific electronic structure of valence tautomers. A comparison of their Kβ XES spectra with the spectra of cobalt coordination complexes with known oxidation and spin states demonstrates that the low-temperature valence tautomer can be described asmore » a low-spin Co III configuration and the high-temperature valence tautomer as a high-spin Co II configuration. This conclusion is further supported by Co L-edge X-ray absorption spectroscopy (L-edge XAS) of the high-temperature valence tautomers and ligand-field atomic-multiplet calculations of the Kβ XES and L-edge XAS spectra. In conclusion, the nature and strength of the magnetic exchange interaction between the cobalt center and SQ – in cobalt valence tautomers is discussed in view of the effective spin at the Co site from Kβ XES and the molecular spin moment from magnetic susceptibility measurements.« less

Incorporation of Trace Elements in Ancient and Modern Human Bone: An X-Ray Absorption Spectroscopy Study

NASA Astrophysics Data System (ADS)

Pingitore, N. E.; Cruz-Jimenez, G.; Price, T. D.

2001-12-01

X-ray absorption spectroscopy (XAS) affords the opportunity to probe the atomic environment of trace elements in human bone. We are using XAS to investigate the mode(s) of incorporation of Sr, Zn, Pb, and Ba in both modern and ancient (and thus possibly altered) human and animal bone. Because burial and diagenesis may add trace elements to bone, we performed XAS analysis on samples of pristine contemporary and ancient, buried human and animal bone. We assume that deposition of these elements during burial occurs by processes distinct from those in vivo, and this will be reflected in their atomic environments. Archaeologists measure strontium in human and animal bone as a guide to diet. Carnivores show lower Sr/Ca ratios than their herbivore prey due to discrimination against Sr relative to Ca up the food chain. In an initial sample suite no difference was observed between modern and buried bone. Analysis of additional buried samples, using a more sensitive detector, revealed significant differences in the distance to the second and third neighbors of the Sr in some of the buried samples. Distances to the first neighbor, oxygen, were similar in all samples. Zinc is also used in paleo-diet studies. Initial x-ray absorption spectroscopy of a limited suite of bones did not reveal any differences between modern and buried samples. This may reflect the limited number of samples examined or the low levels of Zn in typical aqueous solutions in soils. Signals from barium and lead were too low to record useful XAS spectra. Additional samples will be studied for Zn, Ba, and Pb. We conducted our XAS experiments on beam lines 4-1 and 4-3 at the Stanford Synchrotron Radiation Laboratory. Data were collected in the fluorescence mode, using a Lytle detector and appropriate filter, and a solid state, 13-element Ge-detector.

Monitoring long-range electron transfer pathways in proteins by stimulated attosecond broadband X-ray Raman spectroscopy

DOE PAGES

Zhang, Yu; Biggs, Jason D.; Govind, Niranjan; ...

2014-10-09

In this study, long-range electron transfer (ET) plays a key role in many biological energy conversion and synthesis processes. We show that nonlinear spectroscopy with attosecond X-ray pulses provides a real time movie of the evolving oxidation states and electron densities around atoms, and can probe these processes with high spatial and temporal resolution. This is demonstrated in a simulation study of the stimulated X-ray Raman (SXRS) signals in Re-modified azurin, which had long served as a benchmark for long-range ET in proteins. Nonlinear SXRS signals are sensitive to the local electronic structure and should offer a novel window formore » long-range ET.« less

Crystallography with online optical and X-ray absorption spectroscopies demonstrates an ordered mechanism in copper nitrite reductase.

PubMed

Hough, Michael A; Antonyuk, Svetlana V; Strange, Richard W; Eady, Robert R; Hasnain, S Samar

2008-04-25

Nitrite reductases are key enzymes that perform the first committed step in the denitrification process and reduce nitrite to nitric oxide. In copper nitrite reductases, an electron is delivered from the type 1 copper (T1Cu) centre to the type 2 copper (T2Cu) centre where catalysis occurs. Despite significant structural and mechanistic studies, it remains controversial whether the substrates, nitrite, electron and proton are utilised in an ordered or random manner. We have used crystallography, together with online X-ray absorption spectroscopy and optical spectroscopy, to show that X-rays rapidly and selectively photoreduce the T1Cu centre, but that the T2Cu centre does not photoreduce directly over a typical crystallographic data collection time. Furthermore, internal electron transfer between the T1Cu and T2Cu centres does not occur, and the T2Cu centre remains oxidised. These data unambiguously demonstrate an 'ordered' mechanism in which electron transfer is gated by binding of nitrite to the T2Cu. Furthermore, the use of online multiple spectroscopic techniques shows their value in assessing radiation-induced redox changes at different metal sites and demonstrates the importance of ensuring the correct status of redox centres in a crystal structure determination. Here, optical spectroscopy has shown a very high sensitivity for detecting the change in T1Cu redox state, while X-ray absorption spectroscopy has reported on the redox status of the T2Cu site, as this centre has no detectable optical absorption.

Counting-loss correction for X-ray spectroscopy using unit impulse pulse shaping.

PubMed

Hong, Xu; Zhou, Jianbin; Ni, Shijun; Ma, Yingjie; Yao, Jianfeng; Zhou, Wei; Liu, Yi; Wang, Min

2018-03-01

High-precision measurement of X-ray spectra is affected by the statistical fluctuation of the X-ray beam under low-counting-rate conditions. It is also limited by counting loss resulting from the dead-time of the system and pile-up pulse effects, especially in a high-counting-rate environment. In this paper a detection system based on a FAST-SDD detector and a new kind of unit impulse pulse-shaping method is presented, for counting-loss correction in X-ray spectroscopy. The unit impulse pulse-shaping method is evolved by inverse deviation of the pulse from a reset-type preamplifier and a C-R shaper. It is applied to obtain the true incoming rate of the system based on a general fast-slow channel processing model. The pulses in the fast channel are shaped to unit impulse pulse shape which possesses small width and no undershoot. The counting rate in the fast channel is corrected by evaluating the dead-time of the fast channel before it is used to correct the counting loss in the slow channel.

X-ray Fluorescence Spectroscopy: the Potential of Astrophysics-developed Techniques

NASA Astrophysics Data System (ADS)

Elvis, M.; Allen, B.; Hong, J.; Grindlay, J.; Kraft, R.; Binzel, R. P.; Masterton, R.

2012-12-01

X-ray fluorescence from the surface of airless bodies has been studied since the Apollo X-ray fluorescence experiment mapped parts of the lunar surface in 1971-1972. That experiment used a collimated proportional counter with a resolving power of ~1 and a beam size of ~1degree. Filters separated only Mg, Al and SI lines. We review progress in X-ray detectors and imaging for astrophysics and show how these advances enable much more powerful use of X-ray fluorescence for the study of airless bodies. Astrophysics X-ray instrumentation has developed enormously since 1972. Low noise, high quantum efficiency, X-ray CCDs have flown on ASCA, XMM-Newton, the Chandra X-ray Observatory, Swift and Suzaku, and are the workhorses of X-ray astronomy. They normally span 0.5 to ~8 keV with an energy resolution of ~100 eV. New developments in silicon based detectors, especially individual pixel addressable devices, such as CMOS detectors, can withstand many orders of magnitude more radiation than conventional CCDs before degradation. The capability of high read rates provides dynamic range and temporal resolution. Additionally, the rapid read rates minimize shot noise from thermal dark current and optical light. CMOS detectors can therefore run at warmer temperatures and with ultra-thin optical blocking filters. Thin OBFs mean near unity quantum efficiency below 1 keV, thus maximizing response at the C and O lines.such as CMOS detectors, promise advances. X-ray imaging has advanced similarly far. Two types of imager are now available: specular reflection and coded apertures. X-ray mirrors have been flown on the Einstein Observatory, XMM-Newton, Chandra and others. However, as X-ray reflection only occurs at small (~1degree) incidence angles, which then requires long focal lengths (meters), mirrors are not usually practical for planetary missions. Moreover the field of view of X-ray mirrors is comparable to the incident angle, so can only image relatively small regions. More useful

X-ray emission spectroscopy of biomimetic Mn coordination complexes

DOE PAGES

Jensen, Scott C.; Davis, Katherine M.; Sullivan,

2017-05-19

Understanding the function of Mn ions in biological and chemical redox catalysis requires precise knowledge of their electronic structure. X-ray emission spectroscopy (XES) is an emerging technique with a growing application to biological and biomimetic systems. Here, we report an improved, cost-effective spectrometer used to analyze two biomimetic coordination compounds, [Mn IV(OH) 2(Me 2EBC)] 2+ and [Mn IV(O)(OH)(Me 2EBC)] +, the second of which contains a key Mn IV=O structural fragment. Despite having the same formal oxidation state (Mn IV) and tetradentate ligands, XES spectra from these two compounds demonstrate different electronic structures. Experimental measurements and DFT calculations yield differentmore » localized spin densities for the two complexes resulting from Mn IV–OH conversion to Mn IV=O. The relevance of the observed spectroscopic changes is discussed for applications in analyzing complex biological systems such as photosystem II. In conclusion, a model of the S 3 intermediate state of photosystem II containing a Mn IV=O fragment is compared to recent time-resolved X-ray diffraction data of the same state.« less

Monte Carlo simulation of X-ray imaging and spectroscopy experiments using quadric geometry and variance reduction techniques

NASA Astrophysics Data System (ADS)

Golosio, Bruno; Schoonjans, Tom; Brunetti, Antonio; Oliva, Piernicola; Masala, Giovanni Luca

2014-03-01

The simulation of X-ray imaging experiments is often performed using deterministic codes, which can be relatively fast and easy to use. However, such codes are generally not suitable for the simulation of even slightly more complex experimental conditions, involving, for instance, first-order or higher-order scattering, X-ray fluorescence emissions, or more complex geometries, particularly for experiments that combine spatial resolution with spectral information. In such cases, simulations are often performed using codes based on the Monte Carlo method. In a simple Monte Carlo approach, the interaction position of an X-ray photon and the state of the photon after an interaction are obtained simply according to the theoretical probability distributions. This approach may be quite inefficient because the final channels of interest may include only a limited region of space or photons produced by a rare interaction, e.g., fluorescent emission from elements with very low concentrations. In the field of X-ray fluorescence spectroscopy, this problem has been solved by combining the Monte Carlo method with variance reduction techniques, which can reduce the computation time by several orders of magnitude. In this work, we present a C++ code for the general simulation of X-ray imaging and spectroscopy experiments, based on the application of the Monte Carlo method in combination with variance reduction techniques, with a description of sample geometry based on quadric surfaces. We describe the benefits of the object-oriented approach in terms of code maintenance, the flexibility of the program for the simulation of different experimental conditions and the possibility of easily adding new modules. Sample applications in the fields of X-ray imaging and X-ray spectroscopy are discussed. Catalogue identifier: AERO_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AERO_v1_0.html Program obtainable from: CPC Program Library, Queen’s University, Belfast, N. Ireland

Electronic structure of cobalt doped CdSe quantum dots using soft X-ray spectroscopy

DOE PAGES

Wright, Joshua T.; Su, Dong; van Buuren, Tony; ...

2014-08-21

Here, the electronic structure and magnetic properties of cobalt doped CdSe quantum dots (QDs) are studied using electron microscopy, soft X-ray spectroscopy, and magnetometry. Magnetometry measurements suggest these QDs are superparamagnetic, contrary to a spin-glass state observed in the bulk analogue. Electron microscopy shows well formed QDs, but with cobalt existing as doped into the QD and as unreacted species not contained in the QD. X-ray absorption measurements at the Co L3-edge suggest that changes in spectra features as a function of particle size can be described considering combination of a cobalt ion in a tetrahedral crystal field and anmore » octahedrally coordinated (impurity) phase. With decreasing particle sizes, the impurity phase increases, suggesting that small QDs can be difficult to dope.« less

Near Edge X-Ray Absorption and X-Ray Photoelectron Diffraction Studies of the Structural Environment of Ge-Si Systems

NASA Astrophysics Data System (ADS)

Castrucci, P.; Gunnella, R.; Pinto, N.; Bernardini, R.; de Crescenzi, M.; Sacchi, M.

Near edge X-ray absorption spectroscopy (XAS), X-ray photoelectron diffraction (XPD) and Auger electron diffraction (AED) are powerful techniques for the qualitative study of the structural and electronic properties of several systems. The recent development of a multiple scattering approach to simulating experimental spectra opened a friendly way to the study of structural environments of solids and surfaces. This article reviews recent X-ray absorption experiments using synchrotron radiation which were performed at Ge L edges and core level electron diffraction measurements obtained using a traditional X-ray source from Ge core levels for ultrathin Ge films deposited on silicon substrates. Thermodynamics and surface reconstruction have been found to play a crucial role in the first stages of Ge growth on Si(001) and Si(111) surfaces. Both techniques show the occurrence of intermixing processes even for room-temperature-grown Ge/Si(001) samples and give a straightforward measurement of the overlayer tetragonal distortion. The effects of Sb as a surfactant on the Ge/Si(001) interface have also been investigated. In this case, evidence of layer-by-layer growth of the fully strained Ge overlayer with a reduced intermixing is obtained when one monolayer of Sb is predeposited on the surface.

New Worlds / New Horizons Science with an X-ray Astrophysics Probe

NASA Technical Reports Server (NTRS)

Smith, Randall K.; Bookbinder, Jay A.; Hornschemeier, Ann E.; Bandler, Simon; Brandt, W. N.; Hughes, John P.; McCammon, Dan; Matsumoto, Hironori; Mushotzky, Richard; Osten, Rachel A.;

Insights into electron and ion acceleration and transport from x-ray and gamma-ray imaging spectroscopy

NASA Astrophysics Data System (ADS)

Hurford, Gordon J.; Krucker, Samuel

The previous solar maximum has featured high resolution imaging/spectroscopy observations at hard x-ray and gamma-ray energies by the Reuven Ramaty High Energy Solar/Spectroscopic Imager (RHESSI). Highlights of these observations will be reviewed, along with their impli-cations for our understanding of ion and electron acceleration and transport processes. The results to date have included new insights into the location of the acceleration region and the thick target model, a new appreciation of the significance of x-ray albedo, observation of coronal gamma-ray sources and their implications for electron trapping, and indications of differences in the acceleration and transport between electrons and ions. The role of RHESSI's observational strengths and weaknesses in determining the character of its scientific results will also be discussed and used to identify what aspects of the acceleration and transport processes must await the next generation of instrumentation. The extent to which new instrumentation now under development, such as Solar Orbiter/STIX, GRIPS, and FOXSI, can address these open issues will be outlined.

Investigating the local structure of B-site cations in (1-x)BaTiO3-xBiScO3 and (1-x)PbTiO3-xBiScO3 using X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Blanchard, Peter E. R.; Grosvenor, Andrew P.

2018-05-01

The structural properties of (1-x)BaTiO3-xBiScO3 and (1-x)PbTiO3-xBiScO3 were investigated using powder X-ray diffraction and X-ray absorption spectroscopy. Diffraction measurements confirmed that substituting small amounts of BiScO3 into BaTiO3 initially stabilizes a cubic phase at x = 0.2 before impurity phases begin to form at x = 0.5. BiScO3 substitution also resulted in noticeable changes in the local coordination environment of Ti4+. X-ray absorption near-edge spectroscopy (XANES) analysis showed that replacing Ti4+ with Sc3+ results in an increase in the off-centre displacement of Ti4+ cations. Surprisingly, BiScO3 substitution has no effect on the displacement of the Ti4+ cation in the (1-x)PbTiO3-xBiScO3 solid solution.

Band gap states in nanocrystalline WO3 thin films studied by soft x-ray spectroscopy and optical spectrophotometry.

PubMed

Johansson, M B; Kristiansen, P T; Duda, L; Niklasson, G A; Österlund, L

2016-11-30

Nanocrystalline tungsten trioxide (WO3) thin films prepared by DC magnetron sputtering have been studied using soft x-ray spectroscopy and optical spectrophotometry. Resonant inelastic x-ray scattering (RIXS) measurements reveal band gap states in sub-stoichiometric γ-WO3-x with x  =  0.001-0.005. The energy positions of these states are in good agreement with recently reported density functional calculations. The results were compared with optical absorption measurements in the near infrared spectral region. An optical absorption peak at 0.74 eV is assigned to intervalence transfer of polarons between W sites. A less prominent peak at energies between 0.96 and 1.16 eV is assigned to electron excitation of oxygen vacancies. The latter results are supported by RIXS measurements, where an energy loss in this energy range was observed, and this suggests that electron transfer processes involving transitions from oxygen vacancy states can be observed in RIXS. Our results have implications for the interpretation of optical properties of WO3, and the optical transitions close to the band gap, which are important in photocatalytic and photoelectrochemical applications.

X ray spectra of X Per. [oso-8 observations

NASA Technical Reports Server (NTRS)

Becker, R. H.; Boldt, E. A.; Holt, S. S.; Pravdo, S. H.; Robinson-Saba, J.; Serlemitsos, P. J.; Swank, J. H.

1978-01-01

The cosmic X-ray spectroscopy experiment on OSO-8 observed X Per for twenty days during two observations in Feb. 1976 and Feb. 1977. The spectrum of X Per varies in phase with its 13.9 min period, hardening significantly at X-ray minimum. Unlike other X-ray binary pulsar spectra, X Per's spectra do not exhibit iron line emission or strong absorption features. The data show no evidence for a 22 hour periodicity in the X-ray intensity of X Per. These results indicate that the X-ray emission from X Per may be originating from a neutron star in a low density region far from the optically identified Be star.

REDSoX: Monte-Carlo ray-tracing for a soft x-ray spectroscopy polarimeter

NASA Astrophysics Data System (ADS)

Günther, Hans M.; Egan, Mark; Heilmann, Ralf K.; Heine, Sarah N. T.; Hellickson, Tim; Frost, Jason; Marshall, Herman L.; Schulz, Norbert S.; Theriault-Shay, Adam

2017-08-01

X-ray polarimetry offers a new window into the high-energy universe, yet there has been no instrument so far that could measure the polarization of soft X-rays (about 17-80 Å) from astrophysical sources. The Rocket Experiment Demonstration of a Soft X-ray Polarimeter (REDSoX Polarimeter) is a proposed sounding rocket experiment that uses a focusing optic and splits the beam into three channels. Each channel has a set of criticalangle transmission (CAT) gratings that disperse the x-rays onto a laterally graded multilayer (LGML) mirror, which preferentially reflects photons with a specific polarization angle. The three channels are oriented at 120 deg to each other and thus measure the three Stokes parameters: I, Q, and U. The period of the LGML changes with position. The main design challenge is to arrange the gratings so that they disperse the spectrum in such a way that all rays are dispersed onto the position on the multi-layer mirror where they satisfy the local Bragg condition despite arriving on the mirror at different angles due to the converging beam from the focusing optics. We present a polarimeteric Monte-Carlo ray-trace of this design to assess non-ideal effects from e.g. mirror scattering or the finite size of the grating facets. With mirror properties both simulated and measured in the lab for LGML mirrors of 80-200 layers we show that the reflectivity and the width of the Bragg-peak are sufficient to make this design work when non-ideal effects are included in the simulation. Our simulations give us an effective area curve, the modulation factor and the figure of merit for the REDSoX polarimeter. As an example, we simulate an observation of Mk 421 and show that we could easily detect a 20% linear polarization.

Gamma ray spectroscopy in astrophysics. [conferences

NASA Technical Reports Server (NTRS)

Cline, T. L. (Editor); Ramaty, R. (Editor)

1978-01-01

Experimental and theoretical aspects of gamma ray spectroscopy in high energy astrophysics are discussed. Line spectra from solar, stellar, planetary, and cosmic gamma rays are examined as well as HEAO investigations, the prospects of a gamma ray observatory, and follow-on X-ray experiments in space.

p-Type dopant incorporation and surface charge properties of catalyst-free GaN nanowires revealed by micro-Raman scattering and X-ray photoelectron spectroscopy.

PubMed

Wang, Q; Liu, X; Kibria, M G; Zhao, S; Nguyen, H P T; Li, K H; Mi, Z; Gonzalez, T; Andrews, M P

2014-09-07

Micro-Raman scattering and X-ray photoelectron spectroscopy were employed to investigate Mg-doped GaN nanowires. With the increase of Mg doping level, pronounced Mg-induced local vibrational modes were observed. The evolution of longitudinal optical phonon-plasmon coupled mode, together with detailed X-ray photoelectron spectroscopy studies, show that the near-surface region of nanowires can be transformed from weakly n-type to p-type with the increase of Mg doping.

High pressure in situ x-ray absorption spectroscopy cell for studying simultaneously the liquid phase and the solid-liquid interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grunwaldt, Jan-Dierk; Ramin, Michael; Rohr, Markus

2005-05-15

A high pressure in situ x-ray absorption spectroscopy cell with two different path lengths and path positions is presented for studying element-specifically both the liquid phase and the solid-liquid interface at pressures up to 250 bar and temperatures up to 220 deg. C. For this purpose, one x-ray path probes the bottom, while the other x-ray path penetrates through the middle of the in situ cell. The basic design of the cell resembles a 10 ml volume batch reactor, which is equipped with in- and outlet lines to dose compressed gases and liquids as well as a stirrer for goodmore » mixing. Due to the use of a polyetheretherketone inset it is also suitable for measurements under corrosive conditions. The characteristic features of the cell are illustrated using case studies from catalysis and solid state chemistry: (a) the ruthenium-catalyzed formylation of an amine in 'supercritical' carbon dioxide in the presence of hydrogen; (b) the cycloaddition of carbon dioxide to propylene oxide in the presence of a solid Zn-based catalyst, and (c) the solvothermal synthesis of MoO{sub 3} nanorods from MoO{sub 3}-2H{sub 2}O.« less

Soft x-ray absorption spectroscopy of metalloproteins and high-valent metal-complexes at room temperature using free-electron lasers

PubMed Central

Kubin, Markus; Kern, Jan; Gul, Sheraz; Kroll, Thomas; Chatterjee, Ruchira; Löchel, Heike; Fuller, Franklin D.; Sierra, Raymond G.; Quevedo, Wilson; Weniger, Christian; Rehanek, Jens; Firsov, Anatoly; Laksmono, Hartawan; Weninger, Clemens; Alonso-Mori, Roberto; Nordlund, Dennis L.; Lassalle-Kaiser, Benedikt; Glownia, James M.; Krzywinski, Jacek; Moeller, Stefan; Turner, Joshua J.; Minitti, Michael P.; Dakovski, Georgi L.; Koroidov, Sergey; Kawde, Anurag; Kanady, Jacob S.; Tsui, Emily Y.; Suseno, Sandy; Han, Zhiji; Hill, Ethan; Taguchi, Taketo; Borovik, Andrew S.; Agapie, Theodor; Messinger, Johannes; Erko, Alexei; Föhlisch, Alexander; Bergmann, Uwe; Mitzner, Rolf; Yachandra, Vittal K.; Yano, Junko; Wernet, Philippe

2017-01-01

X-ray absorption spectroscopy at the L-edge of 3d transition metals provides unique information on the local metal charge and spin states by directly probing 3d-derived molecular orbitals through 2p-3d transitions. However, this soft x-ray technique has been rarely used at synchrotron facilities for mechanistic studies of metalloenzymes due to the difficulties of x-ray-induced sample damage and strong background signals from light elements that can dominate the low metal signal. Here, we combine femtosecond soft x-ray pulses from a free-electron laser with a novel x-ray fluorescence-yield spectrometer to overcome these difficulties. We present L-edge absorption spectra of inorganic high-valent Mn complexes (Mn ∼ 6–15 mmol/l) with no visible effects of radiation damage. We also present the first L-edge absorption spectra of the oxygen evolving complex (Mn4CaO5) in Photosystem II (Mn < 1 mmol/l) at room temperature, measured under similar conditions. Our approach opens new ways to study metalloenzymes under functional conditions. PMID:28944255

Soft x-ray absorption spectroscopy of metalloproteins and high-valent metal-complexes at room temperature using free-electron lasers

DOE PAGES

Kubin, Markus; Kern, Jan; Gul, Sheraz; ...

2017-09-01

X-ray absorption spectroscopy at the L-edge of 3d transition metals provides unique information on the local metal charge and spin states by directly probing 3d-derived molecular orbitals through 2p-3d transitions. But, this soft x-ray technique has been rarely used at synchrotron facilities for mechanistic studies of metalloenzymes due to the difficulties of x-ray-induced sample damage and strong background signals from light elements that can dominate the low metal signal. Here, we combine femtosecond soft x-ray pulses from a free-electron laser with a novel x-ray fluorescence-yield spectrometer to overcome these difficulties. We present L-edge absorption spectra of inorganic high-valent Mn complexesmore » (Mn ~ 6-15 mmol/l) with no visible effects of radiation damage. We then present the first L-edge absorption spectra of the oxygen evolving complex (Mn 4 CaO 5 ) in Photosystem II (Mn < 1 mmol/l) at room temperature, measured under similar conditions. Our approach opens new ways to study metalloenzymes under functional conditions.« less

X-ray and optical spectroscopy of the massive young open cluster IC 1805

NASA Astrophysics Data System (ADS)

Rauw, G.; Nazé, Y.

2016-10-01

Context. Very young open clusters are ideal places to study the X-ray properties of a homogeneous population of early-type stars. In this respect, the IC 1805 open cluster is very interesting as it hosts the O4 If+ star HD 15570 thought to be in an evolutionary stage intermediate between a normal O-star and a Wolf-Rayet star. Aims: Such a star could provide a test for theoretical models aiming at explaining the empirical scaling relation between the X-ray and bolometric luminosities of O-type stars. Methods: We have observed IC 1805 with XMM-Newton and further collected optical spectroscopy of some of the O-star members of the cluster. Results: The optical spectra allow us to revisit the orbital solutions of BD+60° 497 and HD 15558, and provide the first evidence of binarity for BD+60° 498. X-ray emission from colliding winds does not appear to play an important role among the O-stars of IC 1805. Notably, the X-ray fluxes do not vary significantly between archival X-ray observations and our XMM-Newton pointing. The very fast rotator BD+60° 513, and to a lesser extent the O4 If+ star HD 15570 appear somewhat underluminous. Whilst the underluminosity of HD 15570 is only marginally significant, its amplitude is found to be compatible with theoretical expectations based on its stellar and wind properties. A number of other X-ray sources are detected in the field, and the brightest objects, many of which are likely low-mass pre-main sequence stars, are analyzed in detail. Based on observations collected with XMM-Newton, an ESA science mission with instruments and contributions directly funded by ESA member states and the USA (NASA), and with the TIGRE telescope (La Luz, Mexico).Table A.1 is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/594/A82

X-ray spectroscopy of the mixed morphology supernova remnant W 28 with XMM-Newton

NASA Astrophysics Data System (ADS)

Nakamura, Ryoko; Bamba, Aya; Ishida, Manabu; Yamazaki, Ryo; Tatematsu, Ken'ichi; Kohri, Kazunori; Pühlhofer, Gerd; Wagner, Stefan J.; Sawada, Makoto

2014-06-01

We report on spatially resolved X-ray spectroscopy of the north-eastern part of the mixed morphology supernova remnant (SNR) W 28 with XMM-Newton. The observed field of view includes a prominent and twisted shell emission forming the edge of this SNR as well as part of the center-filled X-ray emission brightening toward the south-west edge of the field of view. The shell region spectra are in general represented by an optically thin thermal plasma emission in collisional ionization equilibrium with a temperature of ˜ 0.3 keV and a density of ˜ 10 cm-3, which is much higher than the density obtained for inner parts. In contrast, we detected no significant X-ray flux from one of the TeV γ-ray peaks with an upper-limit flux of 2.1 × 10-14 erg cm-2 s-1 in the 2-10 keV band. The large flux ratio of TeV to X-ray, larger than 16, and the spatial coincidence of the molecular cloud and the TeV γ-ray emission site indicate that the TeV γ-ray of W 28 is π0-decay emission originating from collisions between accelerated protons and molecular cloud protons. Comparing the spectrum in the TeV band and the X-ray upper limit, we obtained a weak upper limit on the magnetic field strength B ≲ 1500 μG.

Revealing the electronic structure of LiC 6 by soft X-ray spectroscopy

DOE PAGES

Zhang, L.; Li, X.; Augustsson, A.; ...

2017-03-09

The electronic structure of LiC 6 has been investigated in this paper by soft X-ray absorption and emission spectroscopies. The results reveal that upon full lithiation of graphite, the Li 2s electrons are transferred into the carbon π* states in a near rigid-band behavior, resulting in the increased density of states near E F and the shift of σ* states to lower energies. Finally, in addition, the resonant inelastic X-ray scattering spectra of LiC 6 do not show strong dispersive features as that of graphite, indicating that the crystal momentum is not conserved during the scattering process due to themore » delocalization of electrons in the intermediate state.« less

Davisson-Germer Prize in Atomic or Surface Physics Talk: Soft X-Ray Studies of Surfaces, Interfaces and Thin Films: From Spectroscopy to Ultrafast Nanoscale Movies

NASA Astrophysics Data System (ADS)

Stöhr, Joachim

2011-03-01

My talk will review the development of soft x-ray spectroscopy and microscopy and its impact on our understanding of chemical bonding, magnetism and dynamics at surfaces and interfaces. I will first outline important soft x-ray spectroscopy and microscopy techniques that have been developed over the last 30 years and their key strengths such as elemental and chemical specificity, sensitivity to small atomic concentrations, separation of charge and spin properties, spatial resolution down to the nanometer scale, and temporal resolution down to the intrinsic femtosecond timescale of atomic and electronic motions. I will then present scientific breakthroughs based on soft x-ray studies in three selected areas: the nature of molecular bonding and reactivity on metal surfaces, the molecular origin of liquid crystal alignment on surfaces, and the microscopic origin of interface-mediated spin alignments in modern magnetic devices. My talk will also cover the use of soft x-rays for revealing the temporal evolution of electronic structure, addressing the key problem of ``function,'' down to the intrinsic femtosecond time scale of charge and spin configuration changes. As examples I will present the formation and breaking of chemical bonds in surface complexes and the motion of the magnetization in magnetic devices. Work supported by the Office of Basic Energy Science of the US Department of Energy.

Physics of Accretion in X-Ray Binaries

NASA Technical Reports Server (NTRS)

Vrtilek, Saeqa D.

2004-01-01

This project consists of several related investigations directed to the study of mass transfer processes in X-ray binaries. Models developed over several years incorporating highly detailed physics will be tested on a balanced mix of existing data and planned observations with both ground and space-based observatories. The extended time coverage of the observations and the existence of {\\it simultaneous} X-ray, ultraviolet, and optical observations will be particularly beneficial for studying the accretion flows. These investigations, which take as detailed a look at the accretion process in X-ray binaries as is now possible, test current models to their limits, and force us to extend them. We now have the ability to do simultaneous ultraviolet/X-ray/optical spectroscopy with HST, Chandra, XMM, and ground-based observatories. The rich spectroscopy that these Observations give us must be interpreted principally by reference to detailed models, the development of which is already well underway; tests of these essential interpretive tools are an important product of the proposed investigations.

The use of C-near edge X-ray absorption fine structure spectroscopy for the elaboration of chemistry in lignocellulosics

Treesearch

Lucian A. Lucia; Hiroki Nanko; Alan W. Rudie; Doug G. Mancosky; Sue Wirick

2006-01-01

The research presented elucidates the oxidation chemistry occurring in hydrogen peroxide bleached kraft pulp fibers by employing carbon near edge x-ray absorption fine structure spectroscopy (C-NEXAFS). C-NEXAFS is a soft x-ray technique that selectively interrogates atomic moieties using photoelectrons (Xrays) of variable energies. The X1A beam line at the National...

Effects of sulfation level on the desulfation behavior of pre-sulfated Pt BaO/Al2O3 lean NOx trap catalysts: a combined H2 Temperature-Programmed Reaction, in-situ sulfur K-edge X-ray Absorption Near-Edge Spectroscopy, X-ray Photoelectron Spectroscopy, and Time-Resolved X-ray Diffraction Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Do Heui; Szanyi, Janos; Kwak, Ja Hun

2009-04-03

Desulfation by hydrogen of pre-sulfated Pt(2wt%) BaO(20wt%)/Al2O3 with various sulfur loading (S/Ba = 0.12, 0.31 and 0.62) were investigated by combining H2 temperature programmed reaction (TPRX), x-ray photoelectron spectroscopy (XPS), in-situ sulfur K-edge x-ray absorption near-edge spectroscopy (XANES), and synchrotron time-resolved x-ray diffraction (TR-XRD) techniques. We find that the amount of H2S desorbed during the desulfation in the H2 TPRX experiments is not proportional to the amount of initial sulfur loading. The results of both in-situ sulfur K-edge XANES and TR-XRD show that at low sulfur loadings, sulfates were transformed to a BaS phase and remained in the catalyst, rathermore » than being removed as H2S. On the other hand, when the deposited sulfur level exceeded a certain threshold (at least S/Ba = 0.31) sulfates were reduced to form H2S, and the relative amount of the residual sulfide species in the catalyst was much less than at low sulfur loading. Unlike samples with high sulfur loading (e.g., S/Ba = 0.62), H2O did not promote the desulfation for the sample with S/Ba of 0.12, implying that the formed BaS species originating from the reduction of sulfates at low sulfur loading are more stable to hydrolysis. The results of this combined spectroscopy investigation provide clear evidence to show that sulfates at low sulfur loadings are less likely to be removed as H2S and have a greater tendency to be transformed to BaS on the material, leading to the conclusion that desulfation behavior of Pt BaO/Al2O3 lean NOx trap catalysts is markedly dependent on the sulfation levels.« less

The Physics of Accretion in X-Ray Binaries

NASA Technical Reports Server (NTRS)

Vrtilek, S.; Oliversen, Ronald (Technical Monitor)

2001-01-01

This project consists of several related investigations directed to the study of mass transfer processes in X-ray binaries. Models developed over several years incorporating highly detailed physics will be tested on a balanced mix of existing data and planned observations with both ground and space-based observatories. The extended time coverage of the observations and the existence of simultaneous X-ray, ultraviolet, and optical observations will be particularly beneficial for studying the accretion flows. These investigations, which take as detailed a look at the accretion process in X-ray binaries as is now possible, test current models to their limits, and force us to extend them. We now have the ability to do simultaneous ultraviolet/X-ray/optical spectroscopy with HST, Chandra, XMM, and ground-based observatories. The rich spectroscopy that these observations give us must be interpreted principally by reference to detailed models, the development of which is already well underway; tests of these essential interpretive tools are an important product of the proposed investigations.

Valence fluctuating compound α-YbAlB4 studied by 174Yb Mössbauer spectroscopy and X-ray diffraction using synchrotron radiation

NASA Astrophysics Data System (ADS)

Oura, Momoko; Ikeda, Shugo; Masuda, Ryo; Kobayashi, Yasuhiro; Seto, Makoto; Yoda, Yoshitaka; Hirao, Naohisa; Kawaguchi, Saori I.; Ohishi, Yasuo; Suzuki, Shintaro; Kuga, Kentaro; Nakatsuji, Satoru; Kobayashi, Hisao

2018-05-01

The structural properties and the Yb 4 f electronic state of the valence fluctuating α-YbAlB4 have been investigated by powder X-ray diffraction under pressure and 174Yb Mössbauer spectroscopy with magnetic fields at low temperature, respectively, using synchrotron radiation. Powder X-ray diffraction patterns showed that the crystal structure does not change up to p ∼ 18 GPa at 8 K and the volume decreases smoothly. However, the pressure dependence of the difference in the structure factor between the (060) and (061) diffraction lines changes at ∼ 3.4 GPa, indicating the change of atomic coordination parameters. The 174Yb Mössbauer spectroscopy measurements at 2 K with 10 and 50 kOe suggest that the electrical quadrupole interaction changes by applied magnetic fields.

Anionic and cationic redox and interfaces in batteries: Advances from soft X-ray absorption spectroscopy to resonant inelastic scattering

NASA Astrophysics Data System (ADS)

Yang, Wanli; Devereaux, Thomas P.

2018-06-01

Recent advances in battery science and technology have triggered both the challenges and opportunities on studying the materials and interfaces in batteries. Here, we review the recent demonstrations of soft X-ray spectroscopy for studying the interfaces and electrode materials. The focus of this review is on the recently developed mapping of resonant inelastic X-ray scattering (mRIXS) as a powerful probe of battery chemistry with superior sensitivity. Six different channels of soft X-ray absorption spectroscopy (sXAS) are introduced for different experimental purposes. Although conventional sXAS channels remain effective tools for quantitative analysis of the transition-metal states and surface chemistry, we elaborate the limitations of sXAS in both cationic and anionic redox studies. Particularly, based on experimental findings in various electrodes, we show that sXAS is unreliable for studying oxygen redox. We then demonstrate the mRIXS as a reliable technique for fingerprinting oxygen redox and summarize several crucial observations. We conclude that mRIXS is the tool-of-choice to study both the practical issue on reversibility of oxygen redox and the fundamental nature of bulk oxygen states. We hope this review clarifies the popular misunderstanding on oxygen sXAS results of oxide electrodes, and establishes a reliable technique for detecting oxygen redox through mRIXS.

Spectra of cosmic X-ray sources

NASA Technical Reports Server (NTRS)

Holt, S. S.; Mccray, R.

1982-01-01

X-ray measurements provide the most direct probes of astrophysical environments with temperatures exceeding one million K. Progress in experimental research utilizing dispersive techniques (e.g., Bragg and grating spectroscopy) is considerably slower than that in areas utilizing photometric techniques, because of the relative inefficiency of the former for the weak X-ray signals from celestial sources. As a result, the term "spectroscopy" as applied to X-ray astronomy has traditionally satisfied a much less restrictive definition (in terms of resolving power) than it has in other wavebands. Until quite recently, resolving powers of order unity were perfectly respectable, and still provide (in most cases) the most useful spectroscopic data. In the broadest sense, X-ray photometric measurements are spectroscopic, insofar as they represent samples of the overall electromagnetic continua of celestial objects.

Effects of Sulfation Level on the Desulfation Behavior of Presulfated Pt-BaO/Al2O3 Lean NOx Trap Catalysts: A Combined H2 Temperature-Programmed Reaction, in Situ Sulfur K-Edge X-ray Absorption Near-Edge Spectroscopy, X-ray Photoelectron Spectroscopy, and Time-Resolved X-ray Diffraction Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, D.H.; Hanson, J.; Szanyi, J.

2009-04-30

Desulfation by hydrogen of presulfated Pt (2 wt %)-BaO(20 wt %)/Al{sub 2}O{sub 3} with various sulfur loading (S/Ba = 0.12, 0.31, and 0.62) were investigated by combining H{sub 2} temperature programmed reaction (TPRX), X-ray photoelectron spectroscopy (XPS), in situ sulfur K-edge X-ray absorption near-edge spectroscopy (XANES), and synchrotron time-resolved X-ray diffraction (TR-XRD) techniques. We find that the amount of H{sub 2}S desorbed during the desulfation in the H{sub 2} TPRX experiments is not proportional to the amount of initial sulfur loading. The results of both in situ sulfur K-edge XANES and TR-XRD show that at low sulfur loadings, sulfates weremore » transformed to a BaS phase and remained in the catalyst rather than being removed as H{sub 2}S. On the other hand, when the deposited sulfur level exceeded a certain threshold (at least S/Ba = 0.31) sulfates were reduced to form H{sub 2}S, and the relative amount of the residual sulfide species in the catalyst was much less than at low sulfur loading. Unlike samples with high sulfur loading (e.g., S/Ba = 0.62), H{sub 2}O did not promote the desulfation for the sample with S/Ba of 0.12, implying that the formed BaS species originating from the reduction of sulfates at low sulfur loading are more stable to hydrolysis. The results of this combined spectroscopy investigation provide clear evidence to show that sulfates at low sulfur loadings are less likely to be removed as H{sub 2}S and have a greater tendency to be transformed to BaS on the material, leading to the conclusion that desulfation behavior of Pt-BaO/Al{sub 2}O{sub 3} lean NO{sub x} trap catalysts is markedly dependent on the sulfation levels.« less

Combining X-ray and neutron crystallography with spectroscopy.

PubMed

Kwon, Hanna; Smith, Oliver; Raven, Emma Lloyd; Moody, Peter C E

2017-02-01

X-ray protein crystallography has, through the determination of the three-dimensional structures of enzymes and their complexes, been essential to the understanding of biological chemistry. However, as X-rays are scattered by electrons, the technique has difficulty locating the presence and position of H atoms (and cannot locate H + ions), knowledge of which is often crucially important for the understanding of enzyme mechanism. Furthermore, X-ray irradiation, through photoelectronic effects, will perturb the redox state in the crystal. By using single-crystal spectrophotometry, reactions taking place in the crystal can be monitored, either to trap intermediates or follow photoreduction during X-ray data collection. By using neutron crystallography, the positions of H atoms can be located, as it is the nuclei rather than the electrons that scatter neutrons, and the scattering length is not determined by the atomic number. Combining the two techniques allows much greater insight into both reaction mechanism and X-ray-induced photoreduction.

X-ray photoelectron spectroscopy study of radiofrequency-sputtered refractory compound steel interfaces

NASA Technical Reports Server (NTRS)

Wheeler, D. R.; Brainard, W. A.

1978-01-01

Radiofrequency sputtering was used to deposit Mo2C, Mo2B5, and MoSi2 coatings on 440C steel substrates. Both sputter etched and preoxidized substrates were used, and the films were deposited with and without a substrate bias of -300 V. The composition of the coatings was measured as a function of depth by X-ray photoelectron spectroscopy combined with argon ion etching. In the interfacial region there was evidence that bias produced a graded interface in Mo2B5 but not in Mo2C. Oxides of iron and of all film constituents except carbon were presented in all cases but the iron oxide concentration was higher and the layer thicker on the preoxidized substrates. The film and iron oxides were mixed in the MoSi2 and Mo2C films but layered in the Mo2B5 film. The presence of mixed oxides correlates with enhanced film adhesion.

The Compton-thick AGN fraction from the deepest X-ray spectroscopy in the CDF-S

NASA Astrophysics Data System (ADS)

Corral, A.; Georgantopoulos, I.; Akylas, A.; Ranalli, P.

2017-10-01

Highly obscured AGN, especially Compton-thick (CT) AGN, likely play a key role in the galaxy-AGN co-evolution scenario. They would comprise the early stages of AGN activity, preceding the AGN-feedback/star-formation quenching phase, during which most of both the SMBH and galaxy growth take place. However, the actual CT fraction among the AGN population is still largely unconstrained. The most reliable way of confirming the obscured nature of an AGN by X-ray spectroscopy, but very deep observations are needed to extend local analyses to larger distances. We will present the X-ray spectral analysis of the deepest X-ray data obtained to date, the almost 7Ms observation of the Chandra Deep Field South. The unprecedented depth of this survey allow us to carry out reliable spectral analyses down to a flux limit of 10^{-16} erg cm^{-2} s^{-1} in the hard 2-8 keV band. Besides the new deeper X-ray data, our approach also includes the implementation of Bayesian inference in the determination of the CT fraction. Our results favor X-ray background synthesis models which postulate a moderate fraction (25%) of CT objects among the obscured AGN population.

X-Ray Spectroscopy of Ultra-Thin Oxide/Oxide Heteroepitaxial Films: A Case Study of Single-Nanometer VO2/TiO2

PubMed Central

Quackenbush, Nicholas F.; Paik, Hanjong; Woicik, Joseph C.; Arena, Dario A.; Schlom, Darrell G.; Piper, Louis F. J.

2015-01-01

Epitaxial ultra-thin oxide films can support large percent level strains well beyond their bulk counterparts, thereby enabling strain-engineering in oxides that can tailor various phenomena. At these reduced dimensions (typically < 10 nm), contributions from the substrate can dwarf the signal from the epilayer, making it difficult to distinguish the properties of the epilayer from the bulk. This is especially true for oxide on oxide systems. Here, we have employed a combination of hard X-ray photoelectron spectroscopy (HAXPES) and angular soft X-ray absorption spectroscopy (XAS) to study epitaxial VO2/TiO2 (100) films ranging from 7.5 to 1 nm. We observe a low-temperature (300 K) insulating phase with evidence of vanadium-vanadium (V-V) dimers and a high-temperature (400 K) metallic phase absent of V-V dimers irrespective of film thickness. Our results confirm that the metal insulator transition can exist at atomic dimensions and that biaxial strain can still be used to control the temperature of its transition when the interfaces are atomically sharp. More generally, our case study highlights the benefits of using non-destructive XAS and HAXPES to extract out information regarding the interfacial quality of the epilayers and spectroscopic signatures associated with exotic phenomena at these dimensions. PMID:28793516

X-Ray Spectroscopy of Ultra-Thin Oxide/Oxide Heteroepitaxial Films: A Case Study of Single-Nanometer VO2/TiO2.

PubMed

Quackenbush, Nicholas F; Paik, Hanjong; Woicik, Joseph C; Arena, Dario A; Schlom, Darrell G; Piper, Louis F J

2015-08-21

Epitaxial ultra-thin oxide films can support large percent level strains well beyond their bulk counterparts, thereby enabling strain-engineering in oxides that can tailor various phenomena. At these reduced dimensions (typically < 10 nm), contributions from the substrate can dwarf the signal from the epilayer, making it difficult to distinguish the properties of the epilayer from the bulk. This is especially true for oxide on oxide systems. Here, we have employed a combination of hard X-ray photoelectron spectroscopy (HAXPES) and angular soft X-ray absorption spectroscopy (XAS) to study epitaxial VO2/TiO2 (100) films ranging from 7.5 to 1 nm. We observe a low-temperature (300 K) insulating phase with evidence of vanadium-vanadium (V-V) dimers and a high-temperature (400 K) metallic phase absent of V-V dimers irrespective of film thickness. Our results confirm that the metal insulator transition can exist at atomic dimensions and that biaxial strain can still be used to control the temperature of its transition when the interfaces are atomically sharp. More generally, our case study highlights the benefits of using non-destructive XAS and HAXPES to extract out information regarding the interfacial quality of the epilayers and spectroscopic signatures associated with exotic phenomena at these dimensions.

X-ray Spectroscopy of Ultra-thin Oxide/oxide Heteroepitaxial Films: A Case Study of Single-nanometer VO2/TiO2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Quackenbush, Nicholas F.; Paik, Hanjong; Woicik, Joseph C.

2015-08-21

Epitaxial ultra-thin oxide films can support large percent level strains well beyond their bulk counterparts, thereby enabling strain-engineering in oxides that can tailor various phenomena. At these reduced dimensions (typically < 10 nm), contributions from the substrate can dwarf the signal from the epilayer, making it difficult to distinguish the properties of the epilayer from the bulk. This is especially true for oxide on oxide systems. Here, we have employed a combination of hard X-ray photoelectron spectroscopy (HAXPES) and angular soft X-ray absorption spectroscopy (XAS) to study epitaxial VO2/TiO2 (100) films ranging from 7.5 to 1 nm. We observe amore » low-temperature (300 K) insulating phase with evidence of vanadium-vanadium (V-V) dimers and a high-temperature (400 K) metallic phase absent of V-V dimers irrespective of film thickness. Results confirm that the metal insulator transition can exist at atomic dimensions and that biaxial strain can still be used to control the temperature of its transition when the interfaces are atomically sharp. Generally, our case study highlights the benefits of using non-destructive XAS and HAXPES to extract out information regarding the interfacial quality of the epilayers and spectroscopic signatures associated with exotic phenomena at these dimensions.« less

Synchrotron X-ray Analytical Techniques for Studying Materials Electrochemistry in Rechargeable Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Feng; Liu, Yijin; Yu, Xiqian

Rechargeable battery technologies have ignited major breakthroughs in contemporary society, including but not limited to revolutions in transportation, electronics, and grid energy storage. The remarkable development of rechargeable batteries is largely attributed to in-depth efforts to improve battery electrode and electrolyte materials. There are, however, still intimidating challenges of lower cost, longer cycle and calendar life, higher energy density, and better safety for large scale energy storage and vehicular applications. Further progress with rechargeable batteries may require new chemistries (lithium ion batteries and beyond) and better understanding of materials electrochemistry in the various battery technologies. In the past decade, advancementmore » of battery materials has been complemented by new analytical techniques that are capable of probing battery chemistries at various length and time scales. Synchrotron X-ray techniques stand out as one of the most effective methods that allows for nearly nondestructive probing of materials characteristics such as electronic and geometric structures with various depth sensitivities through spectroscopy, scattering, and imaging capabilities. This article begins with the discussion of various rechargeable batteries and associated important scientific questions in the field, followed by a review of synchrotron X-ray based analytical tools (scattering, spectroscopy and imaging) and their successful applications (ex situ, in situ, and in operando) in gaining fundamental insights into these scientific questions. Furthermore, electron microscopy and spectroscopy complement the detection length scales of synchrotron X-ray tools, and are also discussed towards the end. We highlight the importance of studying battery materials by combining analytical techniques with complementary length sensitivities, such as the combination of X-ray absorption spectroscopy and electron spectroscopy with spatial resolution

Synchrotron X-ray Analytical Techniques for Studying Materials Electrochemistry in Rechargeable Batteries

DOE PAGES

Lin, Feng; Liu, Yijin; Yu, Xiqian; ...

2017-08-30

Rechargeable battery technologies have ignited major breakthroughs in contemporary society, including but not limited to revolutions in transportation, electronics, and grid energy storage. The remarkable development of rechargeable batteries is largely attributed to in-depth efforts to improve battery electrode and electrolyte materials. There are, however, still intimidating challenges of lower cost, longer cycle and calendar life, higher energy density, and better safety for large scale energy storage and vehicular applications. Further progress with rechargeable batteries may require new chemistries (lithium ion batteries and beyond) and better understanding of materials electrochemistry in the various battery technologies. In the past decade, advancementmore » of battery materials has been complemented by new analytical techniques that are capable of probing battery chemistries at various length and time scales. Synchrotron X-ray techniques stand out as one of the most effective methods that allows for nearly nondestructive probing of materials characteristics such as electronic and geometric structures with various depth sensitivities through spectroscopy, scattering, and imaging capabilities. This article begins with the discussion of various rechargeable batteries and associated important scientific questions in the field, followed by a review of synchrotron X-ray based analytical tools (scattering, spectroscopy and imaging) and their successful applications (ex situ, in situ, and in operando) in gaining fundamental insights into these scientific questions. Furthermore, electron microscopy and spectroscopy complement the detection length scales of synchrotron X-ray tools, and are also discussed towards the end. We highlight the importance of studying battery materials by combining analytical techniques with complementary length sensitivities, such as the combination of X-ray absorption spectroscopy and electron spectroscopy with spatial resolution

Elemental content of enamel and dentin after bleaching of teeth (a comparative study between laser-induced breakdown spectroscopy and x-ray photoelectron spectroscopy)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Imam, H.; Ahmed, Doaa; Eldakrouri, Ashraf

2013-06-21

The elemental content of the superficial and inner enamel as well as that of dentin was analyzed using laser-induced breakdown spectroscopy (LIBS) and x-ray photoelectron spectroscopy (XPS) of bleached and unbleached tooth specimens. It is thus clear from the spectral analysis using both the LIBS and XPS technique that elemental changes (though insignificant within the scopes of this study) of variable intensities do occur on the surface of the enamel and extend deeper to reach dentin. The results of the LIBS revealed a slight reduction in the calcium levels in the bleached compared to the control specimens in all themore » different bleaching groups and in both enamel and dentin. The good correlation found between the LIBS and XPS results demonstrates the possibility of LIBS technique for detection of minor loss in calcium and phosphorus in enamel and dentin.« less

X-ray scattering study

NASA Technical Reports Server (NTRS)

Wriston, R. S.; Froechtenigt, J. F.

1972-01-01

A soft X-ray glancing incidence telescope mirror and a group of twelve optical flat samples were used to study the scattering of X-rays. The mirror was made of Kanigen coated beryllium and the images produced were severely limited by scattering of X-rays. The best resolution attained was about fifteen arc seconds. The telescope efficiency was found to be 0.0006. The X-ray beam reflected from the twelve optical flat samples was analyzed by means of a long vacuum system of special design for these tests. The scattering then decreased with increasing angle of incidence until a critical angle was passed. At larger angles the scattering increased again. The samples all scattered more at 44 A than at 8 A. Metal samples were found to have about the same scattering at 44 A but greater scattering at 8 A than glass samples.

X-ray Absorption and Emission Spectroscopy of CrIII (Hydr)Oxides: Analysis of the K-Pre-Edge Region

NASA Astrophysics Data System (ADS)

Frommer, Jakob; Nachtegaal, Maarten; Czekaj, Izabela; Weng, Tsu-Chien; Kretzschmar, Ruben

2009-10-01

Pre-edge spectral features below the main X-ray absorption K-edge of transition metals show a pronounced chemical sensitivity and are promising sources of structural information. Nevertheless, the use of pre-edge analysis in applied research is limited because of the lack of definite theoretical peak-assignments. The aim of this study was to determine the factors affecting the chromium K-pre-edge features in trivalent chromium-bearing oxides and oxyhydroxides. The selected phases varied in the degree of octahedral polymerization and the degree of iron-for-chromium substitution in the crystal structure. We investigated the pre-edge fine structure by means of high-energy-resolution fluorescence detected X-ray absorption spectroscopy and by 1s2p resonant X-ray emission spectroscopy. Multiplet theory and full multiple-scattering calculations were used to analyze the experimental data. We show that the chromium K-pre-edge contains localized and nonlocalized transitions. Contributions arising from nonlocalized metal-metal transitions are sensitive to the nearest metal type and to the linkage mode between neighboring metal octahedra. Analyzing these transitions opens up new opportunities for investigating the local coordination environment of chromium in poorly ordered solids of environmental relevance.

Cosmic X-ray physics

NASA Technical Reports Server (NTRS)

Mccammon, D.; Cox, D. P.; Kraushaar, W. L.; Sanders, W. T.

1985-01-01

A progress report of research activities carried out in the area of cosmic X-ray physics is presented. The Diffuse X-ray Spectrometer DXS which has been flown twice as a rocket payload is described. The observation times proved to be too small for meaningful X-ray data to be obtained. Data collection and reduction activities from the Ultra-Soft X-ray background (UXT) instrument are described. UXT consists of three mechanically-collimated X-ray gas proportional counters with window/filter combinations which allow measurements in three energy bands, Be (80-110 eV), B (90-187 eV), and O (e84-532 eV). The Be band measurements provide an important constraint on local absorption of X-rays from the hot component of the local interstellar medium. Work has also continued on the development of a calorimetric detector for high-resolution spectroscopy in the 0.1 keV - 8keV energy range.

In Situ X-ray Absorption Near-Edge Structure Spectroscopy of ZnO Nanowire Growth During Chemical Bath Deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

McPeak, Kevin M.; Becker, Matthew A.; Britton, Nathan G.

2010-12-03

Chemical bath deposition (CBD) offers a simple and inexpensive route to deposit semiconductor nanostructures, but lack of fundamental understanding and control of the underlying chemistry has limited its versatility. Here we report the first use of in situ X-ray absorption spectroscopy during CBD, enabling detailed investigation of both reaction mechanisms and kinetics of ZnO nanowire growth from zinc nitrate and hexamethylenetetramine (HMTA) precursors. Time-resolved X-ray absorption near-edge structure (XANES) spectra were used to quantify Zn(II) speciation in both solution and solid phases. ZnO crystallizes directly from [Zn(H{sub 2}O){sub 6}]{sup 2+} without long-lived intermediates. Using ZnO nanowire deposition as an example,more » this study establishes in situ XANES spectroscopy as an excellent quantitative tool to understand CBD of nanomaterials.« less

X-ray photoelectron spectroscopy study of the stability of Fomblin Z25 on the native oxide of aluminum

NASA Technical Reports Server (NTRS)

Herrera-Fierro, Pilar; Pepper, Stephen V.; Jones, William R.

1992-01-01

Thin films of Fomblin Z25, a perfluoropolyalkylether lubricant, were vapor deposited onto clean, oxidized aluminum, and onto sapphire surfaces, and their behavior at different temperatures was studied using X-ray photoelectron spectroscopy and temperature desorption spectroscopy (TDS). The interfacial fluid molecules decompose on the native oxide at room temperature, and continue to decompose at elevated temperatures, as previous studies had shown to occur on the clean metal. TDS indicated that different degradation mechanisms were operative for clean and oxidized aluminum. On sapphire substrates, no reaction was observed at room temperature. The native oxide of aluminum is neither passive nor protective towards Fomblin Z25. At higher temperatures (150 C), degradation of the polymer on sapphire produced a debris layer at the interface with a chemical composition similar to the one formed on aluminum oxide. Rubbing a Fomblin film on a single crystal sapphire also induced the decomposition of the lubricant in contact with the interface and the formation of a debris layer.

Magnetic x-ray dichroism in ultrathin epitaxial films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tobin, J.G.; Goodman, K.W.; Cummins, T.R.

1997-04-01

The authors have used Magnetic X-ray Linear Dichroism (MXLD) and Magnetic X-ray Circular Dichroism (MXCD) to study the magnetic properties of epitaxial overlayers in an elementally specific fashion. Both MXLD and MXCD Photoelectron Spectroscopy were performed in a high resolution mode at the Spectromicroscopy Facility of the ALS. Circular Polarization was obtained via the utilization of a novel phase retarder (soft x-ray quarter wave plate) based upon transmission through a multilayer film. The samples were low temperature Fe overlayers, magnetic alloy films of NiFe and CoNi, and Gd grown on Y. The authors results include a direct comparison of highmore » resolution angle resolved Photoelectron Spectroscopy performed in MXLD and MXCD modes as well as structural studies with photoelectron diffraction.« less

Research relative to high energy astrophysics. [large area modular array of reflectors, X-ray spectroscopy, and thermal control

NASA Technical Reports Server (NTRS)

Gorenstein, P.

1984-01-01

Various parameters which affect the design of the proposed large area modular array of reflectors (LAMAR) are considered, including thermal control, high resolution X-ray spectroscopy, pointing control, and mirror performance. The LAMAR instrument is to be a shuttle-launched X-ray observatory to carry out cosmic X-ray investigations. The capabilities of LAMAR are enumerated. Angular resolution performance of the mirror module prototype was measured to be 30 sec of ARC for 50% of the power. The LAMAR thermal pre-collimator design concepts and test configurations are discussed in detail.

Confocal depth-resolved fluorescence micro-X-ray absorption spectroscopy for the study of cultural heritage materials: a new mobile endstation at the Beijing Synchrotron Radiation Facility

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Guang; Chu, Shengqi; Sun, Tianxi

A confocal fluorescence endstation for depth-resolved micro-X-ray absorption spectroscopy is described. A polycapillary half-lens defines the incident beam path and a second polycapillary half-lens at 90° defines the probe sample volume. An automatic alignment program based on an evolutionary algorithm is employed to make the alignment procedure efficient. This depth-resolved system was examined on a general X-ray absorption spectroscopy (XAS) beamline at the Beijing Synchrotron Radiation Facility. Sacrificial red glaze (AD 1368–1644) china was studied to show the capability of the instrument. As a mobile endstation to be applied on multiple beamlines, the confocal system can improve the function andmore » flexibility of general XAS beamlines, and extend their capabilities to a wider user community.« less

The soft x-ray beamline at Frascati Labs

NASA Astrophysics Data System (ADS)

Cinque, Gianfelice; Burattini, Emilio; Grilli, Antonio; Dabagov, Sultan

2005-08-01

DAΦNE-Light is the Synchrotron Radiation laboratory at the Laboratori Nazionali di Frascati (LNF)1. Three beamlines were commissioned since spring 2003 to exploit parasitically the intense photon emission from DAΦNE, the 0.5 1 GeV storage ring routinely circulating over 1 A of electrons. The soft X-ray beamline utilizes a wiggler source and, by a double-crystal fixed-exit monochromator, it is operational in the distinguishing energy window 1.5 - 4 keV range to be extended from the "water window" toward 6 keV. At present, the research activity is focused on X-ray Absorption Spectroscopy (XAS): precisely, X-ray Absorption Near Edge Spectroscopy (XANES) on the inner electronic levels of light elements and transition metals from Al to Ge and both d- and f-shells of higher Z atoms. Preliminary tests of X-ray imaging have been performed in view of applying different focusing optics, namely policapillary systems in trasmission and/or bent mica diffractor in back-reflection, for X-ray microscopy and spectromicroscopy experiments. The use of polycapillary systems (lenses, halflenses, capillaries) for studying features of radiation transportation by such structures (X-ray channelling, focusing, bending, etc.) has been planned.

EUV spectroscopy of high-redshift x-ray objects

NASA Astrophysics Data System (ADS)

Kowalski, M. P.; Wolff, M. T.; Wood, K. S.; Barbee, T. W., Jr.; Barstow, M. A.

2010-07-01

As astronomical observations are pushed to cosmological distances (z>3) the spectral energy distributions of X-ray objects, AGN for example, will be redshifted into the EUV waveband. Consequently, a wealth of critical spectral diagnostics, provided by, for example, the Fe L-shell complex and the O VII/VIII lines, will be lost to future planned X-ray missions (e.g., IXO, Gen-X) if operated at traditional X-ray energies. This opens up a critical gap in performance located at short EUV wavelengths, where critical X-ray spectral transitions occur in high-z objects. However, normal-incidence multilayer-grating technology, which performs best precisely at such wavelengths, together with advanced nanolaminate replication techniques have been developed and are now mature to the point where advanced EUV instrument designs with performance complementary to IXO and Gen-X are practical. Such EUV instruments could be flown either independently or as secondary instruments on these X-ray missions. We present here a critical examination of the limits placed on extragalactic EUV measurements by ISM absorption, the range where high-z measurements are practical, and the requirements this imposes on next-generation instrument designs. We conclude with a discussion of a breakthrough technology, nanolaminate replication, which enables such instruments.

A sealable ultrathin window sample cell for the study of liquids by means of soft X-ray spectroscopy

NASA Astrophysics Data System (ADS)

Grötzsch, D.; Streeck, C.; Nietzold, C.; Malzer, W.; Mantouvalou, I.; Nutsch, A.; Dietrich, P.; Unger, W.; Beckhoff, B.; Kanngießer, B.

2017-12-01

A new sample cell concept for the analysis of liquids or solid-liquid interfaces using soft X-ray spectroscopy is presented, which enables the complete sealing of the cell as well as the transport into vacuum via, for example, a load-lock system. The cell uses pressure monitoring and active as well as passive pressure regulation systems, thereby facilitating the full control over the pressure during filling, sealing, evacuation, and measurement. The cell design and sample preparation as well as the crucial sealing procedure are explained in detail. As a first proof-of-principle experiment, successful nitrogen K-edge fluorescence yield near-edge X-ray absorption fine structure experiments of a biomolecular solution are presented. For this purpose, it is shown that the careful evaluation of all involved parameters, such as window type or photon flux, is desirable for optimizing the experimental result.

Characterization of Sb-doped Bi(2)UO(6) solid solutions by X-ray diffraction and X-ray absorption spectroscopy.

PubMed

Misra, N L; Yadav, A K; Dhara, Sangita; Mishra, S K; Phatak, Rohan; Poswal, A K; Jha, S N; Sinha, A K; Bhattacharyya, D

2013-01-01

The preparation and characterization of Sb-doped Bi(2)UO(6) solid solutions, in a limited composition range, is reported for the first time. The solid solutions were prepared by solid-state reactions of Bi(2)O(3), Sb(2)O(3) and U(3)O(8) in the required stoichiometry. The reaction products were characterized by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) measurements at the Bi and U L(3) edges. The XRD patterns indicate the precipitation of additional phases in the samples when Sb doping exceeds 4 at%. The chemical shifts of the Bi absorption edges in the samples, determined from the XANES spectra, show a systematic variation only up to 4 at% of Sb doping and support the results of XRD measurements. These observations are further supported by the local structure parameters obtained by analysis of the EXAFS spectra. The local structure of U is found to remain unchanged upon Sb doping indicating that Sb(+3) ions replace Bi(+3) during the doping of Bi(2)UO(6) by Sb.

X-ray spectroscopies studies of the 3d transition metal oxides and applications of photocatalysis

DOE PAGES

Ye, Yifan; Kapilashrami, Mukes; Chuang, Cheng-Hao; ...

2017-02-08

Some recent advances in synchrotron based x-ray spectroscopy enable materials scientists to emanate fingerprints on important materials properties, e.g., electronic, optical, structural, and magnetic properties, in real-time and under nearly real-world conditions. This characterization, then, in combination with optimized materials synthesis routes and tailored morphological properties could contribute greatly to the advances in solid-state electronics and renewable energy technologies. In connection to this, such perspective reflects the current materials research in the space of emerging energy technologies, namely photocatalysis, with a focus on transition metal oxides, mainly on the Fe 2O 3- and TiO 2-based materials.

Electronic structure measurements of metal-organic solar cell dyes using x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Johnson, Phillip S.

The focus of this thesis is twofold: to report the results of X-ray absorption studies of metal-organic dye molecules for dye-sensitized solar cells and to provide a basic training manual on X-ray absorption spectroscopy techniques and data analysis. The purpose of our research on solar cell dyes is to work toward an understanding of the factors influencing the electronic structure of the dye: the choice of the metal, its oxidation state, ligands, and cage structure. First we study the effect of replacing Ru in several common dye structures by Fe. First-principles calculations and X-ray absorption spectroscopy at the C 1s and N 1s edges are combined to investigate transition metal dyes in octahedral and square planar N cages. Octahedral molecules are found to have a downward shift in the N 1s-to-pi* transition energy and an upward shift in C 1s-to-pi* transition energy when Ru is replaced by Fe, explained by an extra transfer of negative charge from Fe to the N ligands compared to Ru. For the square planar molecules, the behavior is more complex because of the influence of axial ligands and oxidation state. Next the crystal field parameters for a series of phthalocyanine and porphyrins dyes are systematically determined using density functional calculations and atomic multiplet calculations with polarization-dependent X-ray absorption spectra. The polarization dependence of the spectra provides information on orbital symmetries which ensures the determination of the crystal field parameters is unique. A uniform downward scaling of the calculated crystal field parameters by 5-30% is found to be necessary to best fit the spectra. This work is a part of the ongoing effort to design and test new solar cell dyes. Replacing the rare metal Ru with abundant metals like Fe would be a significant advance for dye-sensitized solar cells. Understanding the effects of changing the metal centers in these dyes in terms of optical absorption, charge transfer, and electronic

Crystals for astronomical X-ray spectroscopy

NASA Technical Reports Server (NTRS)

Burek, A.

1976-01-01

Crystal spectrometric properties and the factors that affect their measurement are discussed. Theoretical and experimental results on KAP are summarized and theoretical results based on the dynamical theory of X-ray diffraction are given for the acid phthalates as well as for the commonly used planes of ADP, PET and EDDT. Anomalous dispersion is found to be important for understanding the details of crystal Bragg reflection properties at long X-ray wavelengths and some important effects are pointed out. The theory of anomalous dispersion is applied to explain the anomalous reflectivity exhibited by KAP at 23.3 A.

Spectroscopy of X-ray Photoionized Plasmas in the Laboratory

NASA Astrophysics Data System (ADS)

Liedahl, Duane A.; Loisel, Guillaume; Bailey, James E.; Nagayama, Taisuke; Hansen, Stephanie B.; Rochau, Gregory; Fontes, Christopher J.; Mancini, Roberto; Kallman, Timothy R.

2018-06-01

The physical processes operating in astrophysical plasmas --- heating, cooling, ionization, recombination, level population kinetics, and radiation transport --- are all accessible to observation in the laboratory. What distinguishes X-ray photoionized plasmas from the more common case of high-temperature collisionally-ionized plasmas is the elevated level of importance of the radiation/matter interaction. The advent of laboratory facilities with the capability to generate high-powered X-ray sources has provided the means by which to study this interaction, which is also fundamental to active galactic nuclei and other accretion-powered objects. We discuss recent and ongoing experiments, with an emphasis on X-ray spectroscopic measurements of silicon plasmas obtained at the Sandia Z Pulsed Power Facility.

Analysis of doping concentration and composition in wide bandgap AlGaN:Si by wavelength dispersive x-ray spectroscopy

NASA Astrophysics Data System (ADS)

Kusch, Gunnar; Mehnke, Frank; Enslin, Johannes; Edwards, Paul R.; Wernicke, Tim; Kneissl, Michael; Martin, Robert W.

2017-03-01

Detailed knowledge of the dopant concentration and composition of wide band gap Al x Ga{}1-x{{N}} layers is of crucial importance for the fabrication of ultra violet light emitting diodes. This paper demonstrates the capabilities of wavelength dispersive x-ray (WDX) spectroscopy in accurately determining these parameters and compares the results with those from high resolution x-ray diffraction (HR-XRD) and secondary ion mass spectrometry (SIMS). WDX spectroscopy has been carried out on different silicon-doped wide bandgap Al x Ga{}1-x{{N}} samples (x between 0.80 and 1). This study found a linear increase in the Si concentration with the SiH4/group-III ratio, measuring Si concentrations between 3× {10}18 cm-3 and 2.8× {10}19 cm-3, while no direct correlation between the AlN composition and the Si incorporation ratio was found. Comparison between the composition obtained by WDX and by HR-XRD showed very good agreement in the range investigated, while comparison of the donor concentration between WDX and SIMS found only partial agreement, which we attribute to a number of effects.

Effect of iron oxide reductive dissolution on the transformation and immobilization of arsenic in soils: New insights from X-ray photoelectron and X-ray absorption spectroscopy.

PubMed

Fan, Jian-Xin; Wang, Yu-Jun; Liu, Cun; Wang, Li-Hua; Yang, Ke; Zhou, Dong-Mei; Li, Wei; Sparks, Donald L

2014-08-30

The geochemical behavior and speciation of arsenic (As) in paddy soils is strongly controlled by soil redox conditions and the sequestration by soil iron oxyhydroxides. Hence, the effects of iron oxide reductive dissolution on the adsorption, transformation and precipitation of As(III) and As(V) in soils were investigated using batch experiments and synchrotron based techniques to gain a deeper understanding at both macroscopic and microscopic scales. The results of batch sorption experiments revealed that the sorption capacity of As(V) on anoxic soil was much higher than that on control soil. Synchrotron based X-ray fluorescence (μ-XRF) mapping studies indicated that As was heterogeneously distributed and was mainly associated with iron in the soil. X-ray absorption near edge structure (XANES), micro-X-ray absorption near edge structure (μ-XANES) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the primary speciation of As in the soil is As(V). These results further suggested that, when As(V) was introduced into the anoxic soil, the rapid coprecipitation of As(V) with ferric/ferrous ion prevented its reduction to As(III), and was the main mechanism controlling the immobilization of As. This research could improve the current understanding of soil As chemistry in paddy and wetland soils. Copyright © 2014 Elsevier B.V. All rights reserved.

Proton transfer mediated by the vibronic coupling in oxygen core ionized states of glyoxalmonoxime studied by infrared-X-ray pump-probe spectroscopy.

PubMed

Felicíssimo, V C; Guimarães, F F; Cesar, A; Gel'mukhanov, F; Agren, H

2006-11-30

The theory of IR-X-ray pump-probe spectroscopy beyond the Born-Oppenheimer approximation is developed and applied to the study of the dynamics of intramolecular proton transfer in glyoxalmonoxime leading to the formation of the tautomer 2-nitrosoethenol. Due to the IR pump pulses the molecule gains sufficient energy to promote a proton to a weakly bound well. A femtosecond X-ray pulse snapshots the wave packet route and, hence, the dynamics of the proton transfer. The glyoxalmonoxime molecule contains two chemically nonequivalent oxygen atoms that possess distinct roles in the hydrogen bond, a hydrogen donor and an acceptor. Core ionizations of these form two intersecting core-ionized states, the vibronic coupling between which along the OH stretching mode partially delocalizes the core hole, resulting in a hopping of the core hole from one site to another. This, in turn, affects the dynamics of the proton transfer in the core-ionized state. The quantum dynamical simulations of X-ray photoelectron spectra of glyoxalmonoxime driven by strong IR pulses demonstrate the general applicability of the technique for studies of intramolecular proton transfer in systems with vibronic coupling.

High resolution x-ray fluorescence spectroscopy - a new technique for site- and spin-selectivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Xin

1996-12-01

X-ray spectroscopy has long been used to elucidate electronic and structural information of molecules. One of the weaknesses of x-ray absorption is its sensitivity to all of the atoms of a particular element in a sample. Through out this thesis, a new technique for enhancing the site- and spin-selectivity of the x-ray absorption has been developed. By high resolution fluorescence detection, the chemical sensitivity of K emission spectra can be used to identify oxidation and spin states; it can also be used to facilitate site-selective X-ray Absorption Near Edge Structure (XANES) and site-selective Extended X-ray Absorption Fine Structure (EXAFS). Themore » spin polarization in K fluorescence could be used to generate spin selective XANES or spin-polarized EXAFS, which provides a new measure of the spin density, or the nature of magnetic neighboring atoms. Finally, dramatic line-sharpening effects by the combination of absorption and emission processes allow observation of structure that is normally unobservable. All these unique characters can enormously simplify a complex x-ray spectrum. Applications of this novel technique have generated information from various transition-metal model compounds to metalloproteins. The absorption and emission spectra by high resolution fluorescence detection are interdependent. The ligand field multiplet model has been used for the analysis of K{alpha} and K{beta} emission spectra. First demonstration on different chemical states of Fe compounds has shown the applicability of site selectivity and spin polarization. Different interatomic distances of the same element in different chemical forms have been detected using site-selective EXAFS.« less

Electronic structure and magnetic properties of the half-metallic ferrimagnet Mn2VAl probed by soft x-ray spectroscopies

NASA Astrophysics Data System (ADS)

Nagai, K.; Fujiwara, H.; Aratani, H.; Fujioka, S.; Yomosa, H.; Nakatani, Y.; Kiss, T.; Sekiyama, A.; Kuroda, F.; Fujii, H.; Oguchi, T.; Tanaka, A.; Miyawaki, J.; Harada, Y.; Takeda, Y.; Saitoh, Y.; Suga, S.; Umetsu, R. Y.

2018-01-01

We have studied the electronic structure of ferrimagnetic Mn2VAl single crystals by means of soft x-ray absorption spectroscopy (XAS), x-ray absorption magnetic circular dichroism (XMCD), and resonant soft x-ray inelastic scattering (RIXS). We have successfully observed the XMCD signals for all the constituent elements. The Mn L2 ,3 XAS and XMCD spectra are reproduced by spectral simulations based on density-functional theory, indicating the itinerant character of the Mn 3 d states. On the other hand, the V 3 d electrons are rather localized since the ionic model can qualitatively explain the V L2 ,3 XAS and XMCD spectra. This picture is consistent with local d d excitations revealed by the V L3 RIXS.

Covalency in lanthanides. An X-ray absorption spectroscopy and density functional theory study of LnCl6(x-) (x = 3, 2).

PubMed

Löble, Matthias W; Keith, Jason M; Altman, Alison B; Stieber, S Chantal E; Batista, Enrique R; Boland, Kevin S; Conradson, Steven D; Clark, David L; Lezama Pacheco, Juan; Kozimor, Stosh A; Martin, Richard L; Minasian, Stefan G; Olson, Angela C; Scott, Brian L; Shuh, David K; Tyliszczak, Tolek; Wilkerson, Marianne P; Zehnder, Ralph A

2015-02-25

Covalency in Ln-Cl bonds of Oh-LnCl6(x-) (x = 3 for Ln = Ce(III), Nd(III), Sm(III), Eu(III), Gd(III); x = 2 for Ln = Ce(IV)) anions has been investigated, primarily using Cl K-edge X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TDDFT); however, Ce L3,2-edge and M5,4-edge XAS were also used to characterize CeCl6(x-) (x = 2, 3). The M5,4-edge XAS spectra were modeled using configuration interaction calculations. The results were evaluated as a function of (1) the lanthanide (Ln) metal identity, which was varied across the series from Ce to Gd, and (2) the Ln oxidation state (when practical, i.e., formally Ce(III) and Ce(IV)). Pronounced mixing between the Cl 3p- and Ln 5d-orbitals (t2g* and eg*) was observed. Experimental results indicated that Ln 5d-orbital mixing decreased when moving across the lanthanide series. In contrast, oxidizing Ce(III) to Ce(IV) had little effect on Cl 3p and Ce 5d-orbital mixing. For LnCl6(3-) (formally Ln(III)), the 4f-orbitals participated only marginally in covalent bonding, which was consistent with historical descriptions. Surprisingly, there was a marked increase in Cl 3p- and Ce(IV) 4f-orbital mixing (t1u* + t2u*) in CeCl6(2-). This unexpected 4f- and 5d-orbital participation in covalent bonding is presented in the context of recent studies on both tetravalent transition metal and actinide hexahalides, MCl6(2-) (M = Ti, Zr, Hf, U).

Frontiers of X-Ray Astronomy

NASA Astrophysics Data System (ADS)

Fabian, Andrew C.; Pounds, Kenneth A.; Blandford, Roger D.

2004-07-01

Preface; 1. Forty years on from Aerobee 150: a personal perspective K. Pounds; 2. X-ray spectroscopy of astrophysical plasmas S. M. Kahn, E. Behar, A. Kinkhabwala and D. W. Savin; 3. X-rays from stars M. Gudel; 4. X-ray observations of accreting white-dwarf systems M. Cropper, G. Ramsay, C. Hellier, K. Mukai, C. Mauche and D. Pandel; 5. Accretion flows in X-ray binaries C. Done; 6. Recent X-ray observations of supernova remnants C. R. Canizares; 7. Luminous X-ray sources in spiral and star-forming galaxies M. Ward; 8. Cosmological constraints from Chandra observations of galaxy clusters S. W. Allen; 9. Clusters of galaxies: a cosmological probe R. Mushotzky; 10. Obscured active galactic nuclei: the hidden side of the X-ray Universe G. Matt; 11. The Chandra Deep Field-North Survey and the cosmic X-ray background W. N. Brandt, D. M. Alexander, F. E. Bauer and A. E. Hornschemeier; 12. Hunting the first black holes G. Hasinger; 13. X-ray astronomy in the new millennium: a summary R. D. Blandford.

X-ray irradiation of soda-lime glasses studied in situ with surface plasmon resonance spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Serrano, A.; Galvez, F.; Rodriguez de la Fuente, O.

2013-03-21

We present here a study of hard X-ray irradiation of soda-lime glasses performed in situ and in real time. For this purpose, we have used a Au thin film grown on glass and studied the excitation of its surface plasmon resonance (SPR) while irradiating the sample with X-rays, using a recently developed experimental setup at a synchrotron beamline [Serrano et al., Rev. Sci. Instrum. 83, 083101 (2012)]. The extreme sensitivity of the SPR to the features of the glass substrate allows probing the modifications caused by the X-rays. Irradiation induces color centers in the soda-lime glass, modifying its refractive index.more » Comparison of the experimental results with simulated data shows that both, the real and the imaginary parts of the refractive index of soda-lime glasses, change upon irradiation in time intervals of a few minutes. After X-ray irradiation, the effects are partially reversible. The defects responsible for these modifications are identified as non-bridging oxygen hole centers, which fade by recombination with electrons after irradiation. The kinetics of the defect formation and fading process are also studied in real time.« less

The Cambridge-Cambridge X-ray Serendipity Survey: I X-ray luminous galaxies

NASA Technical Reports Server (NTRS)

Boyle, B. J.; Mcmahon, R. G.; Wilkes, B. J.; Elvis, M.

1994-01-01

We report on the first results obtained from a new optical identification program of 123 faint X-ray sources with S(0.5-2 keV) greater than 2 x 10(exp -14) erg/s/sq cm serendipitously detected in ROSAT PSPC pointed observations. We have spectroscopically identified the optical counterparts to more than 100 sources in this survey. Although the majority of the sample (68 objects) are QSO's, we have also identified 12 narrow emission line galaxies which have extreme X-ray luminosities (10(exp 42) less than L(sub X) less than 10(exp 43.5) erg/s). Subsequent spectroscopy reveals them to be a mixture of star-burst galaxies and Seyfert 2 galaxies in approximately equal numbers. Combined with potentially similar objects identified in the Einstein Extended Medium Sensitivity Survey, these X-ray luminous galaxies exhibit a rate of cosmological evolution, L(sub X) varies as (1 + z)(exp 2.5 +/- 1.0), consistent with that derived for X-ray QSO's. This evolution, coupled with the steep slope determined for the faint end of the X-ray luminosity function (Phi(L(sub X)) varies as L(sub X)(exp -1.9)), implies that such objects could comprise 15-35% of the soft (1-2 keV) X-ray background.

Lu.sub.1-xI.sub.3:Ce.sub.x-a scintillator for gamma-ray spectroscopy and time-of-flight pet

DOEpatents

Shah, Kanai S [Newton, MA

2008-02-12

The present invention includes very fast scintillator materials including lutetium iodide doped with Cerium (Lu.sub.1-xI.sub.3:Ce.sub.x; LuI.sub.3:Ce). The LuI.sub.3 scintillator material has surprisingly good characteristics including high light output, high gamma-ray stopping efficiency, fast response, low cost, good proportionality, and minimal afterglow that the material is useful for gamma-ray spectroscopy, medical imaging, nuclear and high energy physics research, diffraction, non-destructive testing, nuclear treaty verification and safeguards, and geological exploration.

Towards simultaneous measurements of electronic and structural properties in ultra-fast x-ray free electron laser absorption spectroscopy experiments

NASA Astrophysics Data System (ADS)

Gaudin, J.; Fourment, C.; Cho, B. I.; Engelhorn, K.; Galtier, E.; Harmand, M.; Leguay, P. M.; Lee, H. J.; Nagler, B.; Nakatsutsumi, M.; Ozkan, C.; Störmer, M.; Toleikis, S.; Tschentscher, Th; Heimann, P. A.; Dorchies, F.

2014-04-01

The rapidly growing ultrafast science with X-ray lasers unveils atomic scale processes with unprecedented time resolution bringing the so called ``molecular movie'' within reach. X-ray absorption spectroscopy is one of the most powerful x-ray techniques providing both local atomic order and electronic structure when coupled with ad-hoc theory. Collecting absorption spectra within few x-ray pulses is possible only in a dispersive setup. We demonstrate ultrafast time-resolved measurements of the LIII-edge x-ray absorption near-edge spectra of irreversibly laser excited Molybdenum using an average of only few x-ray pulses with a signal to noise ratio limited only by the saturation level of the detector. The simplicity of the experimental set-up makes this technique versatile and applicable for a wide range of pump-probe experiments, particularly in the case of non-reversible processes.

X-ray Absorption Spectroscopy Characterization of a Li/S Cell

PubMed Central

Ye, Yifan; Kawase, Ayako; Song, Min-Kyu; Feng, Bingmei; Liu, Yi-Sheng; Marcus, Matthew A.; Feng, Jun; Cairns, Elton J.; Guo, Jinghua; Zhu, Junfa

2016-01-01

The X-ray absorption spectroscopy technique has been applied to study different stages of the lithium/sulfur (Li/S) cell life cycle. We have investigated how speciation of S in Li/S cathodes changes upon the introduction of CTAB (cetyltrimethylammonium bromide, CH3(CH2)15N+(CH3)3Br−) and with charge/discharge cycling. The introduction of CTAB changes the synthesis reaction pathway dramatically due to the interaction of CTAB with the terminal S atoms of the polysulfide ions in the Na2Sx solution. For the cycled Li/S cell, the loss of electrochemically active sulfur and the accumulation of a compact blocking insulating layer of unexpected sulfur reaction products on the cathode surface during the charge/discharge processes make the capacity decay. A modified coin cell and a vacuum-compatible three-electrode electro-chemical cell have been introduced for further in-situ/in-operando studies. PMID:28344271

ZnO Luminescence and scintillation studied via photoexcitation, X-ray excitation, and gamma-induced positron spectroscopy.

PubMed

Ji, J; Colosimo, A M; Anwand, W; Boatner, L A; Wagner, A; Stepanov, P S; Trinh, T T; Liedke, M O; Krause-Rehberg, R; Cowan, T E; Selim, F A

2016-08-23

The luminescence and scintillation properties of ZnO single crystals were studied by photoluminescence and X-ray-induced luminescence (XRIL) techniques. XRIL allowed a direct comparison to be made between the near-band emission (NBE) and trap emissions providing insight into the carrier recombination efficiency in the ZnO crystals. It also provided bulk luminescence measurements that were not affected by surface states. The origin of a green emission, the dominant trap emission in ZnO, was then investigated by gamma-induced positron spectroscopy (GIPS) - a unique defect spectroscopy method that enables positron lifetime measurements to be made for a sample without contributions from positron annihilation in the source materials. The measurements showed a single positron decay curve with a 175 ps lifetime component that was attributed to Zn vacancies passivated by hydrogen. Both oxygen vacancies and hydrogen-decorated Zn vacancies were suggested to contribute to the green emission. By combining scintillation measurements with XRIL, the fast scintillation in ZnO crystals was found to be strongly correlated with the ratio between the defect luminescence and NBE. This study reports the first application of GIPS to semiconductors, and it reveals the great benefits of the XRIL technique for the study of emission and scintillation properties of materials.

ZnO Luminescence and scintillation studied via photoexcitation, X-ray excitation, and gamma-induced positron spectroscopy

NASA Astrophysics Data System (ADS)

Ji, J.; Colosimo, A. M.; Anwand, W.; Boatner, L. A.; Wagner, A.; Stepanov, P. S.; Trinh, T. T.; Liedke, M. O.; Krause-Rehberg, R.; Cowan, T. E.; Selim, F. A.

2016-08-01

The luminescence and scintillation properties of ZnO single crystals were studied by photoluminescence and X-ray-induced luminescence (XRIL) techniques. XRIL allowed a direct comparison to be made between the near-band emission (NBE) and trap emissions providing insight into the carrier recombination efficiency in the ZnO crystals. It also provided bulk luminescence measurements that were not affected by surface states. The origin of a green emission, the dominant trap emission in ZnO, was then investigated by gamma-induced positron spectroscopy (GIPS) - a unique defect spectroscopy method that enables positron lifetime measurements to be made for a sample without contributions from positron annihilation in the source materials. The measurements showed a single positron decay curve with a 175 ps lifetime component that was attributed to Zn vacancies passivated by hydrogen. Both oxygen vacancies and hydrogen-decorated Zn vacancies were suggested to contribute to the green emission. By combining scintillation measurements with XRIL, the fast scintillation in ZnO crystals was found to be strongly correlated with the ratio between the defect luminescence and NBE. This study reports the first application of GIPS to semiconductors, and it reveals the great benefits of the XRIL technique for the study of emission and scintillation properties of materials.

ZnO Luminescence and scintillation studied via photoexcitation, X-ray excitation, and gamma-induced positron spectroscopy

PubMed Central

Ji, J.; Colosimo, A. M.; Anwand, W.; Boatner, L. A.; Wagner, A.; Stepanov, P. S.; Trinh, T. T.; Liedke, M. O.; Krause-Rehberg, R.; Cowan, T. E.; Selim, F. A.

2016-01-01

The luminescence and scintillation properties of ZnO single crystals were studied by photoluminescence and X-ray-induced luminescence (XRIL) techniques. XRIL allowed a direct comparison to be made between the near-band emission (NBE) and trap emissions providing insight into the carrier recombination efficiency in the ZnO crystals. It also provided bulk luminescence measurements that were not affected by surface states. The origin of a green emission, the dominant trap emission in ZnO, was then investigated by gamma-induced positron spectroscopy (GIPS) - a unique defect spectroscopy method that enables positron lifetime measurements to be made for a sample without contributions from positron annihilation in the source materials. The measurements showed a single positron decay curve with a 175 ps lifetime component that was attributed to Zn vacancies passivated by hydrogen. Both oxygen vacancies and hydrogen-decorated Zn vacancies were suggested to contribute to the green emission. By combining scintillation measurements with XRIL, the fast scintillation in ZnO crystals was found to be strongly correlated with the ratio between the defect luminescence and NBE. This study reports the first application of GIPS to semiconductors, and it reveals the great benefits of the XRIL technique for the study of emission and scintillation properties of materials. PMID:27550235

Combined use of infrared and hard X-ray microprobes for spectroscopy-based neuroanatomy

NASA Astrophysics Data System (ADS)

Surowka, A. D.; Ziomber, A.; Czyzycki, M.; Migliori, A.; Pieklo, L.; Kasper, K.; Szczerbowska-Boruchowska, M.

2018-05-01

Understanding the pathological triggers that affect the structural and physiological integrity of biochemical milieu of neurons is crucial to extend our knowledge on brain disorders, that are in many circumstances hardly treatable. Over recently, by using sophisticated hyperspectral micro-imaging modalities, it has been placed within our reach to get an insight into high fidelity histological details along with corresponding biochemical information in a label-free fashion, without using any additional chemical fixatives. However, in order to push forwards extensive application of these methods in the clinical arena, it is viable to make further iterations in novel data analysis protocols in order to boost their sensitivity. Therefore, in our study we proposed a new combined approach utilizing both benchtop Fourier transform infrared (FTIR) and synchrotron X-ray fluorescence (SR-XRF) micro-spectroscopies coupled with multivariate data clustering using the K-means algorithm for combined molecular and elemental micro-imaging, so that these complimentary analytical tools could be used for delineating between various brain structures based on their biochemical composition. By utilizing mid-IR transmission FTIR experiments, the biochemical composition in terms of lipids, proteins and phosphodiesters became accessible. In turn, the SR-XRF experiment was carried out at the advanced IAEA X-ray spectrometry station at Elettra Sincrotrone Trieste. By measuring in vacuum and by using the primary exciting X-ray beam, monochromatized to 10.5 keV, we took advantage of accessing the characteristic X-ray lines of a variety of elements ranging from carbon to zinc. Herein, we can report that the developed methodology has high specificity for label-free discriminating between lipid- and protein-rich brain tissue areas.

Probing solid catalysts under operating conditions: electrons or X-rays?

PubMed

Thomas, John Meurig; Hernandez-Garrido, Juan-Carlos

2009-01-01

Seeing is believing: In light of recent advances, the pros and cons of using electrons and X-rays for in situ studies of catalysts are analyzed: by using X-rays the structure of bound reactants at steady state are obtained from extended X-ray adsorption fine structure spectroscopy (EXAFS) data (see graph), thereby affording mechanistic insights.

Characterization of pentavalent and hexavalent americium complexes in nitric acid using X-ray absorption fine structure spectroscopy and first-principles modeling

DOE PAGES

Riddle, Catherine; Czerwinski, Kenneth; Kim, Eunja; ...

2016-01-18

We studied the speciation of pentavalent and hexavalent americium (Am) complexes in nitric acidicby X-ray absorption fine structure spectroscopy (XAFS), UV-visible spectroscopy, and density functional theory (DFT). Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) results were consistent with the presence of a mixture of AmO 2 + and AmO 2 2+ with only a small amount AmO 2 present. The resulting average bond distances we found were 1.71 Å for Am=O and 2.44 Å for Am-O. All-electron scalar relativistic calculations were also carried out using DFT to predict the equilibrium geometries and properties ofmore » the AmO 2 + and AmO 2 2+ aquo complexes. Calculated bond distances for the Am(VI) complex are in reasonable agreement with EXAFS data and the computed energy gaps between frontier molecular orbitals suggest a slightly higher kinetic stability and chemical hardness of Am(VI) compared to Am(V).« less

Overview of nanoscale NEXAFS performed with soft X-ray microscopes.

PubMed

Guttmann, Peter; Bittencourt, Carla

2015-01-01

Today, in material science nanoscale structures are becoming more and more important. Not only for the further miniaturization of semiconductor devices like carbon nanotube based transistors, but also for newly developed efficient energy storage devices, gas sensors or catalytic systems nanoscale and functionalized materials have to be analysed. Therefore, analytical tools like near-edge X-ray absorption fine structure (NEXAFS) spectroscopy has to be applied on single nanostructures. Scanning transmission X-ray microscopes (STXM) as well as full-field transmission X-ray microscopes (TXM) allow the required spatial resolution to study individual nanostructures. In the soft X-ray energy range only STXM was used so far for NEXAFS studies. Due to its unique setup, the TXM operated by the Helmholtz-Zentrum Berlin (HZB) at the electron storage ring BESSY II is the first one in the soft X-ray range which can be used for NEXAFS spectroscopy studies which will be shown in this review. Here we will give an overview of the different microscopes used for NEXAFS studies and describe their advantages and disadvantages for different samples.

Electronic structure of transition metal-cysteine complexes from X-ray absorption spectroscopy.

PubMed

Leung, Bonnie O; Jalilehvand, Farideh; Szilagyi, Robert K

2008-04-17

The electronic structures of HgII, NiII, CrIII, and MoV complexes with cysteine were investigated by sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy and density functional theory. The covalency in the metal-sulfur bond was determined by analyzing the intensities of the electric-dipole allowed pre-edge features appearing in the XANES spectra below the ionization threshold. Because of the well-defined structures of the selected cysteine complexes, the current work provides a reference set for further sulfur K-edge XAS studies of bioinorganic active sites with transition metal-sulfur bonds from cysteine residues as well as more complex coordination compounds with thiolate ligands.

Characterization of the LCLS “nanosecond two-bunch” mode for x-ray speckle visibility spectroscopy experiments

DOE PAGES

Sun, Yanwen; Zhu, Diling; Song, Sanghoon; ...

2017-05-23

The generation of two X-ray pulses with tunable nanosecond scale time separations has recently been demonstrated at the Linac Coherent Light Source using an accelerator based technique. This approach offers the opportunity to extend X-ray Photon Correlation Spectroscopy techniques to the yet unexplored regime of nanosecond timescales by means of X-ray Speckle Visibility Spectroscopy. As the two pulses originate from two independent Spontaneous Amplified Stimulated Emission processes, the beam properties fluctuate from pulse pair to pulse pair, but as well between the individual pulses within a pair. However, two-pulse XSVS experiments require the intensity of the individual pulses to bemore » either identical in the ideal case, or with a accurately known intensity ratio. We present the design and performances of a non-destructive intensity diagnostic based on measurement of scattering from a transparent target using a high-speed photo-detector. Individual pulses within a pulse pair with time delays as short as 0.7 ns can be resolved. Moreover, using small angle coherent scattering, we characterize the averaged spatial overlap of the focused pulse pairs. Furthermore, the multi-shot average-speckle contrasts from individual pulses and pulse pairs are compared.« less

X-ray photoelectron spectroscopy and atomic force microscopy characterization of the effects of etching Zn xCd 1- xTe surfaces

NASA Astrophysics Data System (ADS)

George, M. A.; Azoulay, M.; Jayatirtha, H. N.; Burger, A.; Collins, W. E.; Silberman, E.

1993-10-01

X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) was used for the first time to characterize the chemical composition of modified surfaces of Zn xCd 1- xTe single crystals. These surface treatments were selected for their relevance to device preparation procedures. The XPS peaks indicated an increase of the tellurium and a depletion of the cadmium concentrations upon etching in bromine methanol solution. AFM revealed the formation of pronounced Te inclusions. Higher x values correlated with a decrease in residual bromine left on the surface, while cut and polished samples had higher oxide concentrations and increased bromination of the surface than cleaved samples.

Broadband high resolution X-ray spectral analyzer

DOEpatents

Silver, Eric H.; Legros, Mark; Madden, Norm W.; Goulding, Fred; Landis, Don

1998-01-01

A broad bandwidth high resolution x-ray fluorescence spectrometer has a performance that is superior in many ways to those currently available. It consists of an array of 4 large area microcalorimeters with 95% quantum efficiency at 6 keV and it produces x-ray spectra between 0.2 keV and 7 keV with an energy resolution of 7 to 10 eV. The resolution is obtained at input count rates per array element of 10 to 50 Hz in real-time, with analog pulse processing and thermal pile-up rejection. This performance cannot be matched by currently available x-ray spectrometers. The detectors are incorporated into a compact and portable cryogenic refrigerator system that is ready for use in many analytical spectroscopy applications as a tool for x-ray microanalysis or in research applications such as laboratory and astrophysical x-ray and particle spectroscopy.

Broadband high resolution X-ray spectral analyzer

DOEpatents

Silver, E.H.; Legros, M.; Madden, N.W.; Goulding, F.; Landis, D.

1998-07-07

A broad bandwidth high resolution X-ray fluorescence spectrometer has a performance that is superior in many ways to those currently available. It consists of an array of 4 large area microcalorimeters with 95% quantum efficiency at 6 keV and it produces X-ray spectra between 0.2 keV and 7 keV with an energy resolution of 7 to 10 eV. The resolution is obtained at input count rates per array element of 10 to 50 Hz in real-time, with analog pulse processing and thermal pile-up rejection. This performance cannot be matched by currently available X-ray spectrometers. The detectors are incorporated into a compact and portable cryogenic refrigerator system that is ready for use in many analytical spectroscopy applications as a tool for X-ray microanalysis or in research applications such as laboratory and astrophysical X-ray and particle spectroscopy. 6 figs.

Hard X-ray and low-energy gamma-ray spectrometers

NASA Technical Reports Server (NTRS)

Gehrels, N.; Crannell, C. J.; Orwig, L. E.; Forrest, D. J.; Lin, R. P.; Starr, R.

1988-01-01

Basic principles of operation and characteristics of scintillation and semi-conductor detectors used for solar hard X-ray and gamma-ray spectrometers are presented. Scintillation materials such as NaI offer high stopping power for incident gamma rays, modest energy resolution, and relatively simple operation. They are, to date, the most often used detector in solar gamma-ray spectroscopy. The scintillator BGO has higher stopping power than NaI, but poorer energy resolution. The primary advantage of semi-conductor materials such as Ge is their high-energy resolution. Monte-Carlo simulations of the response of NaI and Ge detectors to model solar flare inputs show the benefit of high resoluton for studying spectral lines. No semi-conductor material besides Ge is currently available with adequate combined size and purity to make general-use hard X-ray and gamma-ray detectors for solar studies.

X-ray magnetic circular dichroism measured at the Fe K-edge with a reduced intrinsic broadening: x-ray absorption spectroscopy versus resonant inelastic x-ray scattering measurements

NASA Astrophysics Data System (ADS)

Juhin, Amélie; Sainctavit, Philippe; Ollefs, Katharina; Sikora, Marcin; Filipponi, Adriano; Glatzel, Pieter; Wilhelm, Fabrice; Rogalev, Andrei

2016-12-01

X-ray magnetic circular dichroism is measured at the Fe K pre-edge in yttrium iron garnet using two different procedures that allow reducing the intrinsic broadening due to the 1s corehole lifetime. First, deconvolution of XMCD data measured in total fluorescence yield (TFY) with an extremely high signal-to-noise ratio enables a factor of 2.4 to be gained in the XMCD intensity. Ligand field multiplet calculations performed with different values of intrinsic broadening show that deconvolving such high quality XMCD data is similar to reducing the lifetime broadening from a 1s corehole to a 2p corehole. Second, MCD is measured by resonant inelastic x-ray scattering spectroscopy as a function of incident energy and emission energy. Selection of a fixed emission energy, instead of using the TFY, allows enhancing the MCD intensity up to a factor of  ˜4.7. However, this significantly changes the spectral shape of the XMCD signal, which cannot be interpreted any more as an absorption spectrum.

Simulating Valence-to-Core X-ray Emission Spectroscopy of Transition Metal Complexes with Time-Dependent Density Functional Theory.

PubMed

Zhang, Yu; Mukamel, Shaul; Khalil, Munira; Govind, Niranjan

2015-12-08

Valence-to-core (VtC) X-ray emission spectroscopy (XES) has emerged as a powerful technique for the structural characterization of complex organometallic compounds in realistic environments. Since the spectrum represents electronic transitions from the ligand molecular orbitals to the core holes of the metal centers, the approach is more chemically sensitive to the metal-ligand bonding character compared with conventional X-ray absorption techniques. In this paper we study how linear-response time-dependent density functional theory (LR-TDDFT) can be harnessed to simulate K-edge VtC X-ray emission spectra reliably. LR-TDDFT allows one to go beyond the single-particle picture that has been extensively used to simulate VtC-XES. We consider seven low- and high-spin model complexes involving chromium, manganese, and iron transition metal centers. Our results are in good agreement with experiment.

Rapid Mapping of Lithiation Dynamics in Transition Metal Oxide Particles with Operando X-ray Absorption Spectroscopy.

PubMed

Nowack, Lea; Grolimund, Daniel; Samson, Vallerie; Marone, Federica; Wood, Vanessa

2016-02-24

Since the commercialization of lithium ion batteries (LIBs), layered transition metal oxides (LiMO2, where M = Co, Mn, Ni, or mixtures thereof) have been materials of choice for LIB cathodes. During cycling, the transition metals change their oxidation states, an effect that can be tracked by detecting energy shifts in the X-ray absorption near edge structure (XANES) spectrum. X-ray absorption spectroscopy (XAS) can therefore be used to visualize and quantify lithiation kinetics in transition metal oxide cathodes; however, in-situ measurements are often constrained by temporal resolution and X-ray dose, necessitating compromises in the electrochemistry cycling conditions used or the materials examined. We report a combined approach to reduce measurement time and X-ray exposure for operando XAS studies of lithium ion batteries. A highly discretized energy resolution coupled with advanced post-processing enables rapid yet reliable identification of the oxidation state. A full-field microscopy setup provides sub-particle resolution over a large area of battery electrode, enabling the oxidation state within many transition metal oxide particles to be tracked simultaneously. Here, we apply this approach to gain insights into the lithiation kinetics of a commercial, mixed-metal oxide cathode material, nickel cobalt aluminium oxide (NCA), during (dis)charge and its degradation during overcharge.

Rapid Mapping of Lithiation Dynamics in Transition Metal Oxide Particles with Operando X-ray Absorption Spectroscopy

PubMed Central

Nowack, Lea; Grolimund, Daniel; Samson, Vallerie; Marone, Federica; Wood, Vanessa

2016-01-01

Since the commercialization of lithium ion batteries (LIBs), layered transition metal oxides (LiMO2, where M = Co, Mn, Ni, or mixtures thereof) have been materials of choice for LIB cathodes. During cycling, the transition metals change their oxidation states, an effect that can be tracked by detecting energy shifts in the X-ray absorption near edge structure (XANES) spectrum. X-ray absorption spectroscopy (XAS) can therefore be used to visualize and quantify lithiation kinetics in transition metal oxide cathodes; however, in-situ measurements are often constrained by temporal resolution and X-ray dose, necessitating compromises in the electrochemistry cycling conditions used or the materials examined. We report a combined approach to reduce measurement time and X-ray exposure for operando XAS studies of lithium ion batteries. A highly discretized energy resolution coupled with advanced post-processing enables rapid yet reliable identification of the oxidation state. A full-field microscopy setup provides sub-particle resolution over a large area of battery electrode, enabling the oxidation state within many transition metal oxide particles to be tracked simultaneously. Here, we apply this approach to gain insights into the lithiation kinetics of a commercial, mixed-metal oxide cathode material, nickel cobalt aluminium oxide (NCA), during (dis)charge and its degradation during overcharge. PMID:26908198

Rapid Mapping of Lithiation Dynamics in Transition Metal Oxide Particles with Operando X-ray Absorption Spectroscopy

NASA Astrophysics Data System (ADS)

Nowack, Lea; Grolimund, Daniel; Samson, Vallerie; Marone, Federica; Wood, Vanessa

2016-02-01

Since the commercialization of lithium ion batteries (LIBs), layered transition metal oxides (LiMO2, where M = Co, Mn, Ni, or mixtures thereof) have been materials of choice for LIB cathodes. During cycling, the transition metals change their oxidation states, an effect that can be tracked by detecting energy shifts in the X-ray absorption near edge structure (XANES) spectrum. X-ray absorption spectroscopy (XAS) can therefore be used to visualize and quantify lithiation kinetics in transition metal oxide cathodes; however, in-situ measurements are often constrained by temporal resolution and X-ray dose, necessitating compromises in the electrochemistry cycling conditions used or the materials examined. We report a combined approach to reduce measurement time and X-ray exposure for operando XAS studies of lithium ion batteries. A highly discretized energy resolution coupled with advanced post-processing enables rapid yet reliable identification of the oxidation state. A full-field microscopy setup provides sub-particle resolution over a large area of battery electrode, enabling the oxidation state within many transition metal oxide particles to be tracked simultaneously. Here, we apply this approach to gain insights into the lithiation kinetics of a commercial, mixed-metal oxide cathode material, nickel cobalt aluminium oxide (NCA), during (dis)charge and its degradation during overcharge.

Synchrotron-based soft X-ray spectroscopic studies of the electronic structure of organic semiconducting molecules

NASA Astrophysics Data System (ADS)

Demasi, Alexander

Organic molecules have been the subject of many scientific studies due to their potential for use in a new generation of optoelectronic and semiconducting devices, such as organic photovoltaics and organic light emitting diodes. These studies are motivated by the fact that organic semiconductor devices have several advantages over traditional inorganic semiconductor devices. Unlike inorganic semiconductors, where the electronic properties are a result of the deliberate introduction of dopants to the material, the properties of organic semiconductors are often intrinsic to the molecules themselves. As a result, organic semiconductor devices are frequently less susceptible to contamination by impurities than their inorganic counterparts, which results in the relatively lower cost of producing such devices. Accurate experimental determination of the bulk and surface electronic structure of organic semiconductors is a prerequisite in developing a comprehensive understanding of such materials. The organic materials studied in this thesis were N,N-Ethylene-bis(1,1,1trifluoropentane-2,4-dioneiminato)-copper(ii) (abbreviated Cu-TFAC), aluminum tris-8hydroxyquinoline (A1g3), lithium quinolate (Liq), tetracyanoquinodimethane (TCNQ), and tetrafluorotetracyanoquinodimethane (F4TCNQ). The electronic structures of these materials were measured with several synchrotron-based x-ray spectroscopies. X-ray photoemission spectroscopy was used to measure the occupied total density of states and the core-level states of the aforementioned materials. X-ray absorption spectroscopy (XAS) was used to probe the element-specific unoccupied partial density of states (PDOS); its angle-resolved variant was used to measure the orientation of the molecules in a film and, in some circumstances, to gauge the extent of an organic film's crystallinity. Most notably, x-ray emission spectroscopy (XES) measures the element- specific occupied PDOS and, when aided by XAS, resonant XES can additionally be

Adaptive design of an X-ray magnetic circular dichroism spectroscopy experiment with Gaussian process modelling

NASA Astrophysics Data System (ADS)

Ueno, Tetsuro; Hino, Hideitsu; Hashimoto, Ai; Takeichi, Yasuo; Sawada, Masahiro; Ono, Kanta

2018-01-01

Spectroscopy is a widely used experimental technique, and enhancing its efficiency can have a strong impact on materials research. We propose an adaptive design for spectroscopy experiments that uses a machine learning technique to improve efficiency. We examined X-ray magnetic circular dichroism (XMCD) spectroscopy for the applicability of a machine learning technique to spectroscopy. An XMCD spectrum was predicted by Gaussian process modelling with learning of an experimental spectrum using a limited number of observed data points. Adaptive sampling of data points with maximum variance of the predicted spectrum successfully reduced the total data points for the evaluation of magnetic moments while providing the required accuracy. The present method reduces the time and cost for XMCD spectroscopy and has potential applicability to various spectroscopies.

X-Ray Photoelectron Spectroscopy Study of the Heating Effects on Pd/6H-SiC Schottky Structure

NASA Technical Reports Server (NTRS)

Chen, Liang-Yu; Hunter, Gary W.; Neudeck, Philip G.; Knight, Dak

1998-01-01

X-ray photoelectron spectroscopy is used to study the effects of heat treatment on the Pd/6H-SiC Schottky diode structure. After heating the structure at 425 C for 140 h, a very thin surface layer of PdO mixed with SiO(x) formed on the palladium surface of the Schottky structure. Heat treatment promoted interfacial diffusion and reaction which significantly broadened the interfacial region. In the interfacial region, the palladium concentration decreases with depth, and the interfacial products are Pd(x)Si (x = 1,2,3,4). In the high Pd concentration regions, Pd4Si is the major silicide component while gr and Pd2Si are major components in the low Pd concentration region. At the center of the interface, where the total palladium concentration equals that of silicon, the concentrations of palladium associated with various palladium silicides (Pd(x)Si, x= 1,2,3,4) are approximately equal. The surface passivation layer composed of PdO and SiO, may significantly affect the electronic and catalytic properties of the surface of the Schottky diode which plays a major role in gas detection. The electronic properties of the Schottky structure may be dominated by a (Pd+Pd(x)Si)/SiC interface. In order to stabilize the properties of the Schottky structure the surface and interface diffusion and reactions must be controlled.

Copper doped TiO2 nanoparticles characterized by X-ray absorption spectroscopy, total scattering, and powder diffraction--a benchmark structure-property study.

PubMed

Lock, Nina; Jensen, Ellen M L; Mi, Jianli; Mamakhel, Aref; Norén, Katarina; Qingbo, Meng; Iversen, Bo B

2013-07-14

Metal functionalized nanoparticles potentially have improved properties e.g. in catalytic applications, but their precise structures are often very challenging to determine. Here we report a structural benchmark study based on tetragonal anatase TiO2 nanoparticles containing 0-2 wt% copper. The particles were synthesized by continuous flow synthesis under supercritical water-isopropanol conditions. Size determination using synchrotron PXRD, TEM, and X-ray total scattering reveals 5-7 nm monodisperse particles. The precise dopant structure and thermal stability of the highly crystalline powders were characterized by X-ray absorption spectroscopy and multi-temperature synchrotron PXRD (300-1000 K). The combined evidence reveals that copper is present as a dopant on the particle surfaces, most likely in an amorphous oxide or hydroxide shell. UV-VIS spectroscopy shows that copper presence at concentrations higher than 0.3 wt% lowers the band gap energy. The particles are unaffected by heating to 600 K, while growth and partial transformation to rutile TiO2 occur at higher temperatures. Anisotropic unit cell behavior of anatase is observed as a consequence of the particle growth (a decreases and c increases).

X-Ray Calorimeter Arrays for Astrophysics

NASA Technical Reports Server (NTRS)

Kilbourne, Caroline A.

2009-01-01

High-resolution x-ray spectroscopy is a powerful tool for studying the evolving universe. The grating spectrometers on the XMM and Chandra satellites started a new era in x-ray astronomy, but there remains a need for instrumentation that can provide higher spectral resolution with high throughput in the Fe-K band (around 6 keV) and can enable imaging spectroscopy of extended sources, such as supernova remnants and galaxy clusters. The instrumentation needed is a broad-band imaging spectrometer - basically an x-ray camera that can distinguish tens of thousands of x-ray colors. The potential benefits to astrophysics of using a low-temperature calorimeter to determine the energy of an incident x-ray photon via measurement of a small change in temperature was first articulated by S. H. Moseley over two decades ago. In the time since, technological progress has been steady, though full realization in an orbiting x-ray telescope is still awaited. A low-temperature calorimeter can be characterized by the type of thermometer it uses, and three types presently dominate the field. The first two types are temperature-sensitive resistors - semiconductors in the metal-insulator transition and superconductors operated in the superconducting-normal transition. The third type uses a paramagnetic thermometer. These types can be considered the three generations of x-ray calorimeters; by now each has demonstrated a resolving power of 2000 at 6 keV, but only a semiconductor calorimeter system has been developed to spaceflight readiness. The Soft X-ray Spectrometer on Astro-H, expected to launch in 2013, will use an array of silicon thermistors with I-IgTe x-ray absorbers that will operate at 50 mK. Both the semiconductor and superconductor calorimeters have been implemented in small arrays, kilo-pixel arrays of the superconducting calorimeters are just now being produced, and it is anticipated that much larger arrays will require the non-dissipative advantage of magnetic thermometers.

Summary: Update to ASTM Guide E 1523 to Charge Control and Charge Referencing Techniques in X-ray Photoelectron Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baer, Donald R.

2005-04-22

An updated version of the ASTM guide E1523 to the methods to charge control and charge referencing techniques in x-ray photoelectron spectroscopy has been released by ASTM. The guide is meant to acquaint x-ray photoelectron spectroscopy (XPS) users with the various charge control and charge referencing techniques that are and have been used in the acquisition and interpretation of XPS data from surfaces of insulating specimens. The current guide has been expanded to include new references as well as recommendations for reporting information on charge control and charge referencing. The previous version of the document had been published in 1997.

Towards simultaneous measurements of electronic and structural properties in ultra-fast x-ray free electron laser absorption spectroscopy experiments

PubMed Central

Gaudin, J.; Fourment, C.; Cho, B. I.; Engelhorn, K.; Galtier, E.; Harmand, M.; Leguay, P. M.; Lee, H. J.; Nagler, B.; Nakatsutsumi, M.; Ozkan, C.; Störmer, M.; Toleikis, S.; Tschentscher, Th; Heimann, P. A.; Dorchies, F.

2014-01-01

The rapidly growing ultrafast science with X-ray lasers unveils atomic scale processes with unprecedented time resolution bringing the so called “molecular movie” within reach. X-ray absorption spectroscopy is one of the most powerful x-ray techniques providing both local atomic order and electronic structure when coupled with ad-hoc theory. Collecting absorption spectra within few x-ray pulses is possible only in a dispersive setup. We demonstrate ultrafast time-resolved measurements of the LIII-edge x-ray absorption near-edge spectra of irreversibly laser excited Molybdenum using an average of only few x-ray pulses with a signal to noise ratio limited only by the saturation level of the detector. The simplicity of the experimental set-up makes this technique versatile and applicable for a wide range of pump-probe experiments, particularly in the case of non-reversible processes. PMID:24740172

Towards simultaneous measurements of electronic and structural properties in ultra-fast x-ray free electron laser absorption spectroscopy experiments

DOE PAGES

Gaudin, J.; Fourment, C.; Cho, B. I.; ...

2014-04-17

The rapidly growing ultrafast science with X-ray lasers unveils atomic scale processes with unprecedented time resolution bringing the so called “molecular movie” within reach. X-ray absorption spectroscopy is one of the most powerful x-ray techniques providing both local atomic order and electronic structure when coupled with ad-hoc theory. Collecting absorption spectra within few x-ray pulses is possible only in a dispersive setup. We demonstrate ultrafast time-resolved measurements of the LIII-edge x-ray absorption near-edge spectra of irreversibly laser excited Molybdenum using an average of only few x-ray pulses with a signal to noise ratio limited only by the saturation level ofmore » the detector. The simplicity of the experimental set-up makes this technique versatile and applicable for a wide range of pump-probe experiments, particularly in the case of non-reversible processes.« less

Effect of Pressure on Valence and Structural Properties of YbFe 2 Ge 2 Heavy Fermion Compound—A Combined Inelastic X-ray Spectroscopy, X-ray Diffraction, and Theoretical Investigation

DOE PAGES

Kumar, Ravhi S.; Svane, Axel; Vaitheeswaran, Ganapathy; ...

2015-10-19

We measured the crystal structure and the Yb valence of the YbFe 2Ge 2 heavy fermion compound at room temperature and under high pressures using high-pressure powder X-ray diffraction and X-ray absorption spectroscopy via both partial fluorescence yield and resonant inelastic X-ray emission techniques. Moreover, the measurements are complemented by first-principles density functional theoretical calculations using the self-interaction corrected local spin density approximation investigating in particular the magnetic structure and the Yb valence. Finally, while the ThCr 2Si 2-type tetragonal (I4/mmm) structure is stable up to 53 GPa, the X-ray emission results show an increase of the Yb valence frommore » v = 2.72(2) at ambient pressure to v = 2.93(3) at ~9 GPa, where at low temperature a pressure-induced quantum critical state was reported.« less

Probing Transient Valence Orbital Changes with Picosecond Valence-to-Core X-ray Emission Spectroscopy

DOE PAGES

March, Anne Marie; Assefa, Tadesse A.; Boemer, Christina; ...

2017-01-17

Here we probe the dynamics of valence electrons in photoexcited [Fe(terpy) 2] 2+ in solution to gain deeper insight into the Fe-ligand bond changes. We use hard X-ray emission spectroscopy (XES), which combines element specificity and high penetration with sensitivity to orbital structure, making it a powerful technique for molecular studies in a wide variety of environments. A picosecond-time-resolved measurement of the complete Is X-ray emission spectrum captures the transient photoinduced changes and includes the weak valence-to-core (vtc) emission lines that correspond to transitions from occupied valence orbitals to the nascent core-hole. Vtc-XES offers particular insight into the molecular orbitalsmore » directly involved in the light-driven dynamics; a change in the metal-ligand orbital overlap results in an intensity reduction and a blue energy shift in agreement with our theoretical calculations and more subtle features at the highest energies reflect changes in the frontier orbital populations.« less

Probing Transient Valence Orbital Changes with Picosecond Valence-to-Core X-ray Emission Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

March, Anne Marie; Assefa, Tadesse A.; Boemer, Christina

Here we probe the dynamics of valence electrons in photoexcited [Fe(terpy) 2] 2+ in solution to gain deeper insight into the Fe-ligand bond changes. We use hard X-ray emission spectroscopy (XES), which combines element specificity and high penetration with sensitivity to orbital structure, making it a powerful technique for molecular studies in a wide variety of environments. A picosecond-time-resolved measurement of the complete Is X-ray emission spectrum captures the transient photoinduced changes and includes the weak valence-to-core (vtc) emission lines that correspond to transitions from occupied valence orbitals to the nascent core-hole. Vtc-XES offers particular insight into the molecular orbitalsmore » directly involved in the light-driven dynamics; a change in the metal-ligand orbital overlap results in an intensity reduction and a blue energy shift in agreement with our theoretical calculations and more subtle features at the highest energies reflect changes in the frontier orbital populations.« less

Elemental profiling of laser cladded multilayer coatings by laser induced breakdown spectroscopy and energy dispersive X-ray spectroscopy

NASA Astrophysics Data System (ADS)

Lednev, V. N.; Sdvizhenskii, P. A.; Filippov, M. N.; Grishin, M. Ya.; Filichkina, V. A.; Stavertiy, A. Ya.; Tretyakov, R. S.; Bunkin, A. F.; Pershin, S. M.

2017-09-01

Multilayer tungsten carbide wear resistant coatings were analyzed by laser induced breakdown spectroscopy (LIBS) and energy dispersive X-ray (EDX) spectroscopy. Coaxial laser cladding technique was utilized to produce tungsten carbide coating deposited on low alloy steel substrate with additional inconel 625 interlayer. EDX and LIBS techniques were used for elemental profiling of major components (Ni, W, C, Fe, etc.) in the coating. A good correlation between EDX and LIBS data was observed while LIBS provided additional information on light element distribution (carbon). A non-uniform distribution of tungsten carbide grains along coating depth was detected by both LIBS and EDX. In contrast, horizontal elemental profiling showed a uniform tungsten carbide particles distribution. Depth elemental profiling by layer-by-layer LIBS analysis was demonstrated to be an effective method for studying tungsten carbide grains distribution in wear resistant coating without any sample preparation.

X-ray diffraction, Raman, and photoacoustic studies of ZnTe nanocrystals

NASA Astrophysics Data System (ADS)

Ersching, K.; Campos, C. E. M.; de Lima, J. C.; Grandi, T. A.; Souza, S. M.; da Silva, D. L.; Pizani, P. S.

2009-06-01

Nanocrystalline ZnTe was prepared by mechanical alloying. X-ray diffraction (XRD), energy dispersive spectroscopy, Raman spectroscopy, and photoacoustic absorption spectroscopy techniques were used to study the structural, chemical, optical, and thermal properties of the as-milled powder. An annealing of the mechanical alloyed sample at 590 °C for 6 h was done to investigate the optical properties in a defect-free sample (close to bulk form). The main crystalline phase formed was the zinc-blende ZnTe, but residual trigonal tellurium and hexagonal ZnO phases were also observed for both as-milled and annealed samples. The structural parameters, phase fractions, average crystallite sizes, and microstrains of all crystalline phases were obtained from Rietveld analyses of the X-ray patterns. Raman results corroborate the XRD results, showing the longitudinal optical phonons of ZnTe (even at third order) and those modes of trigonal Te. Nonradiative surface recombination and thermal bending heat transfer mechanisms were proposed from photoacoustic analysis. An increase in effective thermal diffusivity coefficient was observed after annealing and the carrier diffusion coefficient, the surface recombination velocity, and the recombination time parameters remained the same.

X-ray photoelectron spectroscopy study of radiofrequency sputtered chromium bromide, molybdenum disilicide, and molybdenum disulfide coatings and their friction properties

NASA Technical Reports Server (NTRS)

Wheeler, D. R.; Brainard, W. A.

1977-01-01

Radiofrequency sputtered coatings of CRB2, MOSI2, and MOS2 were examined by X-ray photoelectron spectroscopy. The effects of sputtering target history, deposition time, RF power level, and substrate bias on film composition were studied. Friction tests were run on RF sputtered surfaces of 440-C steel to correlate XPS data with lubricating properties. Significant deviations from stoichiometry and high oxide levels for all three compounds were related to target outgassing. The effect of biasing on these two factors depended on the compound. Improved stoichiometry correlated well with good friction and wear properties.

X-Ray Photoelectron Spectroscopy of Stabilized Zirconia Films with Embedded Au Nanoparticles Formed under Irradiation with Gold Ions

NASA Astrophysics Data System (ADS)

Zubkov, S. Yu.; Antonov, I. N.; Gorshkov, O. N.; Kasatkin, A. P.; Kryukov, R. N.; Nikolichev, D. E.; Pavlov, D. A.; Shenina, M. E.

2018-03-01

Nanosized films of stabilized zirconia with Au nanoparticles formed by implanting Au ions are studied by X-ray photoelectron spectroscopy and transmission electron microscopy. The effect of irradiation of films with Au ions and postimplantation annealing on the distribution of chemical elements and zirconium- containing ZrO x compounds over the depth of the films is studied. Based on the data on the dimensional shift of the Au 4 f photoelectron line, the average value of the nanoparticle size is determined.

X-Ray Studies of Diffusion Dynamics in Nano-Confined Geometries

NASA Astrophysics Data System (ADS)

Boucheron, Leandra

Since their discovery in the late 1800s, x-rays have taken the stage as one of the most powerful research techniques for materials science. Their element-specific absorption has allowed for everyday applications in security and medical imaging, while their short wavelength has a tremendous ability to resolve materials on a molecular or even atomic level. In this dissertation, I will discuss basic properties of x-rays as well as how they are produced and detected. I will also present x-ray scattering and analysis techniques before moving onto a discussion of my research on diffusion in soft-matter systems. I provide a full alignment guide for a lab-based dynamic light scattering (DLS) goniometer system, which I used for some preliminary studies of systems. I proceed to discuss diffusion on the nanoscale in quasi-1D (nanopores) and quasi-2D (liquid surface) systems. The latter of these systems was the main focus of my dissertation research. I utilized x-ray photon correlation spectroscopy (XPCS) to study the diffusion and interparticle dynamics of iron oxide nanoparticles at the air-water interface. Autocorrelation analysis revealed that these particles show signatures of a jammed system under lateral compression. I present these results as well as a description of their interpretation and importance in the main text.

Investigation of the Structural Stability of Ion-Implanted Gd 2Ti 2-xSn xO 7 Pyrochlore-Type Oxides by Glancing Angle X-ray Absorption Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aluri, Esther Rani; Hayes, John R.; Walker, James D.S.

2016-03-24

Rare-earth titanate and stannate pyrochlore-type oxides have been investigated in the past for the sequestration of nuclear waste elements because of their resistance to radiation-induced structural damage. In order to enhance this property, it is necessary to understand the effect of radioactive decay of the incorporated actinide elements on the local chemical environment. In this study, Gd 2Ti 2–xSn xO 7 materials have been implanted with Au– ions to simulate radiation-induced structural damage. Glancing angle X-ray absorption near-edge spectroscopy (GA-XANES), glancing angle X-ray absorption fine structure (GA-EXAFS) analysis, and powder X-ray diffraction have been used to investigate changes in themore » local coordination environment of the metal atoms in the damaged surface layer. Examination of GA-XANES/EXAFS spectra from the implanted Gd 2Ti 2–xSn xO 7 materials collected at various glancing angles allowed for an investigation of how the local coordination environment around the absorbing atoms changed at different depths in the damaged surface layer. This study has shown the usefulness of GA-XANES to the examination of ion-implanted materials and has suggested that Gd 2Ti 2–xSn xO 7 becomes more susceptible to ion-beam-induced structural damage with increasing Sn concentration.« less

The superconducting high-resolution soft X-ray spectrometer at the advanced biological and environmental X-ray facility

NASA Astrophysics Data System (ADS)

Friedrich, S.; Drury, O. B.; George, S. J.; Cramer, S. P.

2007-11-01

We have built a 36-pixel superconducting tunnel junction X-ray spectrometer for chemical analysis of dilute samples in the soft X-ray band. It offers an energy resolution of ˜10-20 eV FWHM below 1 keV, a solid angle coverage of ˜10 -3, and can be operated at total rates of up to ˜10 6 counts/s. Here, we describe the spectrometer performance in speciation measurements by fluorescence-detected X-ray absorption spectroscopy at the Advanced Biological and Environmental X-ray facility at the ALS synchrotron.

Probing Chemical Bonding in Uranium Dioxide by Means of High-Resolution X-ray Absorption Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Butorin, Sergei M.; Modin, Anders; Vegelius, Johan R.

Here, a systematic X-ray absorption study at the U 3d, 4d, and 4f edges of UO 2 was performed, and the data were analyzed within framework of the Anderson impurity model. By applying the high-energy-resolution fluorescence-detection (HERFD) mode of X-ray absorption spectroscopy (XAS) at the U 3d 3/2 edge and conducting the XAS measurements at the shallower U 4f levels, fine details of the XAS spectra were resolved resulting from reduced core-hole lifetime broadening. This multiedge study enabled a far more effective analysis of the electronic structure at the U sites and characterization of the chemical bonding and degree ofmore » the 5f localization in UO 2. The results support the covalent character of UO 2 and do not agree with the suggestions of rather ionic bonding in this compound as expressed in some publications.« less

Probing Chemical Bonding in Uranium Dioxide by Means of High-Resolution X-ray Absorption Spectroscopy

DOE PAGES

Butorin, Sergei M.; Modin, Anders; Vegelius, Johan R.; ...

2016-11-30

Here, a systematic X-ray absorption study at the U 3d, 4d, and 4f edges of UO 2 was performed, and the data were analyzed within framework of the Anderson impurity model. By applying the high-energy-resolution fluorescence-detection (HERFD) mode of X-ray absorption spectroscopy (XAS) at the U 3d 3/2 edge and conducting the XAS measurements at the shallower U 4f levels, fine details of the XAS spectra were resolved resulting from reduced core-hole lifetime broadening. This multiedge study enabled a far more effective analysis of the electronic structure at the U sites and characterization of the chemical bonding and degree ofmore » the 5f localization in UO 2. The results support the covalent character of UO 2 and do not agree with the suggestions of rather ionic bonding in this compound as expressed in some publications.« less

Photo-Darkening Kinetics and Structural Anisotropic Modifications in the Chalcogenide Glass Arsenic Trisulfide: a Study of Kinetic X-Ray Absorption Spectroscopy

NASA Astrophysics Data System (ADS)

Lee, Jay Min

1990-08-01

The purpose of the study is to investigate the mechanisms involved with photo-induced atomic structural modifications in the chalcogenide glass As_2 S_3. This glass exhibits the reversible effects of photo-darkening followed by thermal bleaching. We observed the time behavior of photo-induced properties under the influence of linearly polarized band -gap light. In a macroscopic optical investigation, we monitor optical changes in the photo-darkening process, and in a local structural probe we study kinetic (or time -resolved dispersive) x-ray absorption spectroscopy. Our observations center on kinetic phenomena and structural modifications induced by polarized excitation of lone-pair orbitals in the chalcogenide glass. Experimental results include the following observations: (i) The polarity of the optically induced anisotropy is critically dependent on the intensity and the polarization of the band-gap irradiation beam. (ii) The near edge peak height in x-ray absorption spectra shows subtle but sensitive change during the photo-darkening process. (iii) Photon intensity dependent dichroic kinetics reflect a connection between the optically probed macroscopic property and the x-ray probed local anisotropic structure. Analysis of the x-ray absorption results includes a computer simulation of the polarized absorption spectra. These results suggest that specific structural units tend to orient themselves with respect to the photon polarization. A substantial part of the analysis involves a major effort in dealing with the x-ray kinetic data manipulation and the experimental difficulties caused by a synchrotron instability problem. Based on our observations, we propose a possible mechanism for the observed photo-structural modifications. Through a model of computer relaxed photo-darkening kinetics, we support the notion that a twisting of a specific intermediate range order structure is responsible for local directional variations and global network distortions. In the

X-Ray Weak Broad-Line Quasars: Absorption or Intrinsic X-Ray Weakness

NASA Technical Reports Server (NTRS)

Risaliti, Guido; Mushotzky, Richard F. (Technical Monitor)

2004-01-01

XMM observations of X-ray weak quasars have been performed during 2003. The data for all but the last observation are now available (there has been a delay of several months on the initial schedule, due to high background flares which contaminated the observations: as a consequence, most of them had to be rescheduled). We have reduced and analyzed these data, and obtained interesting preliminary scientific results. Out of the eight sources, 4 are confirmed to be extrimely X-ray weak, in agreement with the results of previous Chandra observations. 3 sources are confirmed to be highly variable both in flux (by factors 20-50) and in spectral properties (dramatic changes in spectral index). For both these groups of objects, an article is in preparation. Preliminary results have been presented at an international workshop on AGN surveys in December 2003, in Cozumel (Mexico). In order to further understand the nature of these X-ray weak quasars, we submitted proposals for spectroscopy at optical and infrared telescopes. We obtained time at the TNG 4 meter telescope for near-IR observations, and at the Hobby-Eberly Telescope for optical high-resolution spectroscopy. These observations will be performed in early 2004, and will complement the XMM data, in order to understand whether the X-ray weakness of these sources is an intrinsic property or is due to absorption by circumnuclear material.

High average power, highly brilliant laser-produced plasma source for soft X-ray spectroscopy.

PubMed

Mantouvalou, Ioanna; Witte, Katharina; Grötzsch, Daniel; Neitzel, Michael; Günther, Sabrina; Baumann, Jonas; Jung, Robert; Stiel, Holger; Kanngiesser, Birgit; Sandner, Wolfgang

2015-03-01

In this work, a novel laser-produced plasma source is presented which delivers pulsed broadband soft X-radiation in the range between 100 and 1200 eV. The source was designed in view of long operating hours, high stability, and cost effectiveness. It relies on a rotating and translating metal target and achieves high stability through an on-line monitoring device using a four quadrant extreme ultraviolet diode in a pinhole camera arrangement. The source can be operated with three different laser pulse durations and various target materials and is equipped with two beamlines for simultaneous experiments. Characterization measurements are presented with special emphasis on the source position and emission stability of the source. As a first application, a near edge X-ray absorption fine structure measurement on a thin polyimide foil shows the potential of the source for soft X-ray spectroscopy.

Comment on ?Spin crossover in (Mg,Fe)O: A M?ssbauer effect study with an alternative interpretation of x-ray emission spectroscopy data?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, J; Struzhkin, V V; Garriliuk, A

2006-05-23

Electronic spin-pairing transition of iron in magnesiow{umlt u}stite-(Mg,Fe)O has been recently studied with X-ray emission and M{umlt o}ssbauer spectroscopies under high pressures. While these studies reported a high-spin to low-spin transition of iron to occur at pressures above approximately 50 GPa, the width of the observed transition varies significantly. In particular, Kantor et al. reported that the transition in (Mg0.8,Fe0.2)O occurs over a pressure range of approximately 50 GPa in high-pressure M{umlt o}ssbauer measurements. To account for the discrepancy in the transition pressure, Kantor et al. reanalyzed the X-ray emission spectra by Lin et al. using a simple spectral decompositionmore » method and claimed that X-ray emission measurements are also consistent with a spin crossover of iron at high pressures. Here we show that the proposed fitting method is inadequate to describe the X-ray emission spectrum of the low-spin FeS2 and would give an erroneous satellite peak (K{sub beta}') intensity, leading to an artificial high-spin component and, consequently, to invalid conclusions regarding the width of the pressure-induced transition in magnesiow{umlt u}stite. Furthermore, we compare Kantor's M{umlt o}ssbauer data with other recent high-pressure M{umlt o}ssbauer studies and show that the width of the transition can be simply explained by different experimental conditions (sample thickness, diameter, and hydrostaticity).« less

Local X-ray magnetic circular dichroism study of Fe/Cu(111) using a tunneling smart tip

PubMed Central

DiLullo, Andrew; Shirato, Nozomi; Cummings, Marvin; Kersell, Heath; Chang, Hao; Rosenmann, Daniel; Miller, Dean; Freeland, John W.; Hla, Saw-Wai; Rose, Volker

2016-01-01

Localized spectroscopy with simultaneous topographic, elemental and magnetic information is presented. A synchrotron X-ray scanning tunneling microscope has been employed for the local study of the X-ray magnetic circular dichroism at the Fe L 2,3-edges of a thin iron film grown on Cu(111). Polarization-dependent X-ray absorption spectra have been obtained through a tunneling smart tip that serves as a photoelectron detector. In contrast to conventional spin-polarized scanning tunneling microscopy, X-ray excitations provide magnetic contrast even with a non-magnetic tip. Intensity variations in the photoexcited tip current point to chemical variations within a single magnetic Fe domain. PMID:26917146

Local X-ray magnetic circular dichroism study of Fe/Cu(111) using a tunneling smart tip

DOE PAGES

DiLullo, Andrew; Shirato, Nozomi; Cummings, Marvin; ...

2016-01-28

Localized spectroscopy with simultaneous topographic, elemental and magnetic information is presented. A synchrotron X-ray scanning tunneling microscope has been employed for the local study of the X-ray magnetic circular dichroism at the FeL 2,3-edges of a thin iron film grown on Cu(111). Polarization-dependent X-ray absorption spectra have been obtained through a tunneling smart tip that serves as a photoelectron detector. In contrast to conventional spin-polarized scanning tunneling microscopy, X-ray excitations provide magnetic contrast even with a non-magnetic tip. Intensity variations in the photoexcited tip current point to chemical variations within a single magnetic Fe domain.

Local X-ray magnetic circular dichroism study of Fe/Cu(111) using a tunneling smart tip.

PubMed

DiLullo, Andrew; Shirato, Nozomi; Cummings, Marvin; Kersell, Heath; Chang, Hao; Rosenmann, Daniel; Miller, Dean; Freeland, John W; Hla, Saw-Wai; Rose, Volker

2016-03-01

Localized spectroscopy with simultaneous topographic, elemental and magnetic information is presented. A synchrotron X-ray scanning tunneling microscope has been employed for the local study of the X-ray magnetic circular dichroism at the Fe L2,3-edges of a thin iron film grown on Cu(111). Polarization-dependent X-ray absorption spectra have been obtained through a tunneling smart tip that serves as a photoelectron detector. In contrast to conventional spin-polarized scanning tunneling microscopy, X-ray excitations provide magnetic contrast even with a non-magnetic tip. Intensity variations in the photoexcited tip current point to chemical variations within a single magnetic Fe domain.

GSFC Contributions to the NATO X-ray Astronomy Institute, Erice, July 1979. [X-ray spectra of supernova remants, galactic X-ray sources, active galactic nuclei, and clusters of galaxies

NASA Technical Reports Server (NTRS)

Holt, S. S.; Mushotzky, R. F.

1979-01-01

An overview of X-ray astronomical spectroscopy in general is presented and results obtained by HEAO 1 and 2 as well as earlier spacecraft are examined. Particular emphasis is given to the spectra of supernova remnants; galactic binary X-ray sources, cataclysmic variables, bulges, pulsars, and stars; the active nuclei of Seyfert 1 galaxy, BL Lac, and quasars; the diffuse X-ray background; and galactic clusters.

X-ray Weak Broad-line Qquasars: Absorption or Intrinsic X-ray Weakness

NASA Technical Reports Server (NTRS)

Mushotzky, Richard (Technical Monitor); Risaliti, Guida

2005-01-01

XMM observations of X-ray weak quasars have been performed during 2003 and 2004. The data for all the observations have become available in 2004 (there has been a delay of several months on the initial schedule, due to high background flares which contaminated the observations: as a consequence, most of them had to be rescheduled). We have reduced and analyzed all the data, and obtained interesting scientific results. Out of the eight sources, 4 are confirmed to be extremely X-ray weak, in agreement with the results of previous Chandra observations. 3 sources are confined to be highly variable both in flux (by factor 20-50) and in spectral properties (dramatic changes in spectral index). For both these groups of objects we are completing a publication: 1) For the X-ray weak sources, a paper is submitted with a complete analysis of the X-ray spectra both from Chandra and XMM-Newton, and a comparison with optical and near-IR photometry obtained from all-sky surveys. Possible models for the unusual spectral energy distribution of these sources are also presented. 2) For the variable sources, a paper is being finalized where the X-ray spectra obtained with XMM-Newton are compared with previous X-ray observations and with observations at other wavelengths. It is shown that these sources are high luminosity and extreme cases of the highly variable class of narrow-line Seyfert Is. In order to further understand the nature of these X-ray weak quasars, we submitted proposals for spectroscopy at optical and infrared telescopes. We obtained time at the TNG 4 meter telescope for near-IR observations and at the Hobby-Eberly Telescope for optical high-resolution spectroscopy. These observations have been performed in early 2004. They will complement the XMM data and will lead to understanding of whether the X-ray weakness of these sources is an intrinsic property or is due to absorption by circum-nuclear material. The infrared spectra of the variable sources have been already

Applications of “Tender” Energy (1-5 keV) X-ray Absorption Spectroscopy in Life Sciences

DOE Office of Scientific and Technical Information (OSTI.GOV)

Northrup, Paul; Leri, Alessandra; Tappero, Ryan

The “tender” energy range of 1 to 5 keV, between the energy ranges of most “hard” (>5 keV) and “soft” (<1 keV) synchrotron X-ray facilities, offers some unique opportunities for synchrotron-based X-ray absorption fine structure spectroscopy in life sciences. In particular the K absorption edges of Na through Ca offer opportunities to study local structure, speciation, and chemistry of many important biological compounds, structures and processes. This is an area of largely untapped science, in part due to a scarcity of optimized facilities. Such measurements also entail unique experimental challenges. Lastly, this brief review describes the technique, its experimental challenges,more » recent progress in development of microbeam measurement capabilities, and several highlights illustrating applications in life sciences.« less

Applications of “Tender” Energy (1-5 keV) X-ray Absorption Spectroscopy in Life Sciences

DOE PAGES

Northrup, Paul; Leri, Alessandra; Tappero, Ryan

2016-02-15

The “tender” energy range of 1 to 5 keV, between the energy ranges of most “hard” (>5 keV) and “soft” (<1 keV) synchrotron X-ray facilities, offers some unique opportunities for synchrotron-based X-ray absorption fine structure spectroscopy in life sciences. In particular the K absorption edges of Na through Ca offer opportunities to study local structure, speciation, and chemistry of many important biological compounds, structures and processes. This is an area of largely untapped science, in part due to a scarcity of optimized facilities. Such measurements also entail unique experimental challenges. Lastly, this brief review describes the technique, its experimental challenges,more » recent progress in development of microbeam measurement capabilities, and several highlights illustrating applications in life sciences.« less

Results from the X-ray polychromator on SMM

NASA Astrophysics Data System (ADS)

Culhane, J. L.; Acton, L. W.; Gabriel, A. H.

Observations of the soft X-ray emitting plasma by means of the X-Ray Polychromator (XRP) on the Solar Maximum Mission satellite are described. The scientific advances achieved by use of the XRP are in the areas of: (1) flare morphology, (2) spectroscopy and plasma diagnostics, (3) chromospheric evaporation and the physics of flare loops, (4) studies of the microwave emission mechanisms of active regions, (5) the fluorescent excitation of Fe II K-alpha radiation, (6) measurement of variations of calcium abundance for X-ray plasmas, and (7) soft X-ray observations of spray transients. The findings in each of these areas are discussed.

Results from the X-ray polychromator on SMM

NASA Technical Reports Server (NTRS)

Culhane, J. L.; Acton, L. W.; Gabriel, A. H.

1984-01-01

Observations of the soft X-ray emitting plasma by means of the X-Ray Polychromator (XRP) on the Solar Maximum Mission satellite are described. The scientific advances achieved by use of the XRP are in the areas of: (1) flare morphology, (2) spectroscopy and plasma diagnostics, (3) chromospheric evaporation and the physics of flare loops, (4) studies of the microwave emission mechanisms of active regions, (5) the fluorescent excitation of Fe II K-alpha radiation, (6) measurement of variations of calcium abundance for X-ray plasmas, and (7) soft X-ray observations of spray transients. The findings in each of these areas are discussed.

Disentangling atomic-layer-specific x-ray absorption spectra by Auger electron diffraction spectroscopy

NASA Astrophysics Data System (ADS)

Matsui, Fumihiko; Matsushita, Tomohiro; Kato, Yukako; Hashimoto, Mie; Daimon, Hiroshi

2009-11-01

In order to investigate the electronic and magnetic structures of each atomic layer at subsurface, we have proposed a new method, Auger electron diffraction spectroscopy, which is the combination of x-ray absorption spectroscopy (XAS) and Auger electron diffraction (AED) techniques. We have measured a series of Ni LMM AED patterns of the Ni film grown on Cu(001) surface for various thicknesses. Then we deduced a set of atomic-layer-specific AED patterns in a numerical way. Furthermore, we developed an algorithm to disentangle XANES spectra from different atomic layers using these atomic-layer-specific AED patterns. Surface and subsurface core level shift were determined for each atomic layer.

An X-ray photoelectron spectroscopy study of the thermal nitridation of SiO2/Si

NASA Technical Reports Server (NTRS)

Vasquez, R. P.; Madhukar, A.; Grunthaner, F. J.; Naiman, M. L.

1986-01-01

The dependence of the nitrogen distribution in thermally nitrided SiO2 films on the nitridation time and temperature has been studied by means of X-ray photoelectron spectroscopy (XPS). The photoelectron peak intensities were measured by fitting Voigt profiles to the XPS spectra and were used to calculate the film composition as a function of film depth, applying an analytical method described in detail. The times of appearance of the maxima in interfacial nitrogen concentration are shown for 800, 1000, and 1150 C, and the data are related to a kinetic model of Vasquez and Madhukar (1985), which considers the effect of interfacial strain on the nitridation kinetics. In addition, the intensity of a fluorine marker (from the HF used in the etching step) was found to correlate with the nitrogen concentration. It is postulated that the F bonds preferentially to defects. This hypothesis and the measured F intensities are consistent with the proposed strain-dependent energy of defect formation.

Experimental Results and Modeling of Low-Heat-Capacity TES Microcalorimeters for Soft-X-ray Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eckart, Megan E.; NASA Postdoctoral Program Fellow; Adams, Joseph S.

2009-12-16

Transition-edge-sensor (TES) X-ray microcalorimeters have mostly been targeted at mid-band energies from 0.05-10 keV and high energies to above 100 keV. However, many other optimizations are possible. Here we present results from devices optimized for soft X-ray applications. For spectroscopy below 1 keV, the X-ray stopping power and heat capacity (C) of the TES itself are high enough that we can omit a separate absorber. The resulting devices have low C and the best-achievable energy resolution should be under 1 eV. We are interested in pursuing such devices primarily for astrophysical applications and laboratory astrophysics at LLNL's Electron-Beam Ion Trap.more » To this end, we have studied arrays in which 'bare' TESs are interspersed with broad-band pixels that have absorbers. By extending the absorbers to cover the area where the leads contact the low-energy pixels, we have eliminated a significant source of non-Gaussian detector response. The bare devices are in a different regime from our typical devices in that C is ten times lower and the conductance to the bath is four times lower. We have explored this regime through simultaneous fitting of noise and impedance data. These data cannot be fit by the simple model we employ to describe our typical broad-band devices. In this contribution we present X-ray spectra and the results from modeling.« less

The New Peruvian Meteorite Carancas: Mössbauer Spectroscopy and X-Ray Diffraction Studies

NASA Astrophysics Data System (ADS)

Munayco, P.; Munayco, J.; Varela, M. E.; Scorzelli, R. B.

2013-02-01

The Carancas meteorite fell on 15 September 2007 approximately 10 km south of Desaguadero, near Lake Titicaca, Peru, producing bright lights, clouds of dust in the sky and intense detonations. The Carancas meteorite is classified as a H4-5 ordinary chondrite with shock stage S3 and a degree of weathering W0. The Carancas meteorite is characterized by well defined chondrules composed either of olivine or pyroxene. The Mössbauer spectra show an overlapping of paramagnetic and magnetic phases. The spectra show two quadrupole doublets associated to olivine and pyroxene; and two magnetic sextets, associated with the primary phases kamacite/taenite and Troilite (Fe2+). Metal particles were extracted from the bulk powdered samples exhibit only kamacite and small amounts of the intergrowth tetrataenite/antitaenite. X-Ray diffractogram shows the primary phases olivine, pyroxene, troilite, kamacite, diopside and albite. Iron oxides has not been detected by Mössbauer spectroscopy or XRD as can be expected for a meteorite immediately recovered after its fall.

NuSTAR Hard X-Ray Survey of the Galactic Center Region I: Hard X-Ray Morphology and Spectroscopy of the Diffuse Emission

NASA Astrophysics Data System (ADS)

Mori, Kaya; Hailey, Charles J.; Krivonos, Roman; Hong, Jaesub; Ponti, Gabriele; Bauer, Franz; Perez, Kerstin; Nynka, Melania; Zhang, Shuo; Tomsick, John A.; Alexander, David M.; Baganoff, Frederick K.; Barret, Didier; Barrière, Nicolas; Boggs, Steven E.; Canipe, Alicia M.; Christensen, Finn E.; Craig, William W.; Forster, Karl; Giommi, Paolo; Grefenstette, Brian W.; Grindlay, Jonathan E.; Harrison, Fiona A.; Hornstrup, Allan; Kitaguchi, Takao; Koglin, Jason E.; Luu, Vy; Madsen, Kristen K.; Mao, Peter H.; Miyasaka, Hiromasa; Perri, Matteo; Pivovaroff, Michael J.; Puccetti, Simonetta; Rana, Vikram; Stern, Daniel; Westergaard, Niels J.; Zhang, William W.; Zoglauer, Andreas

2015-12-01

We present the first sub-arcminute images of the Galactic Center above 10 keV, obtained with NuSTAR. NuSTAR resolves the hard X-ray source IGR J17456-2901 into non-thermal X-ray filaments, molecular clouds, point sources, and a previously unknown central component of hard X-ray emission (CHXE). NuSTAR detects four non-thermal X-ray filaments, extending the detection of their power-law spectra with Γ ˜ 1.3-2.3 up to ˜50 keV. A morphological and spectral study of the filaments suggests that their origin may be heterogeneous, where previous studies suggested a common origin in young pulsar wind nebulae (PWNe). NuSTAR detects non-thermal X-ray continuum emission spatially correlated with the 6.4 keV Fe Kα fluorescence line emission associated with two Sgr A molecular clouds: MC1 and the Bridge. Broadband X-ray spectral analysis with a Monte-Carlo based X-ray reflection model self-consistently determined their intrinsic column density (˜1023 cm-2), primary X-ray spectra (power-laws with Γ ˜ 2) and set a lower limit of the X-ray luminosity of Sgr A* flare illuminating the Sgr A clouds to LX ≳ 1038 erg s-1. Above ˜20 keV, hard X-ray emission in the central 10 pc region around Sgr A* consists of the candidate PWN G359.95-0.04 and the CHXE, possibly resulting from an unresolved population of massive CVs with white dwarf masses MWD ˜ 0.9 M⊙. Spectral energy distribution analysis suggests that G359.95-0.04 is likely the hard X-ray counterpart of the ultra-high gamma-ray source HESS J1745-290, strongly favoring a leptonic origin of the GC TeV emission.

X-ray photoemission study of NiS2-xSex (x=0.0 1.2)

NASA Astrophysics Data System (ADS)

Krishnakumar, S. R.; Sarma, D. D.

2003-10-01

Electronic structure of NiS2-xSex system has been investigated for various compositions (x) using x-ray photoemission spectroscopy. An analysis of the core-level as well as the valence-band spectra of NiS2 in conjunction with many-body cluster calculations provides a quantitative description of the electronic structure of this compound. With increasing Se content, the on-site Coulomb correlation strength (U) does not change, while the bandwidth W of the system increases, driving the system from a covalent insulating state to a pd-metallic state.

Understanding the effects of Cr doping in rutile TiO2 by DFT calculations and X-ray spectroscopy.

PubMed

Vásquez, G Cristian; Maestre, David; Cremades, Ana; Ramírez-Castellanos, Julio; Magnano, Elena; Nappini, Silvia; Karazhanov, Smagul Zh

2018-06-07

The effects of Cr on local environment and electronic structure of rutile TiO 2 are studied combining theoretical and experimental approaches. Neutral and negatively charged substitutional Cr impurities Cr Ti 0 and Cr Ti 1- as well as Cr-oxygen vacancy complex 2Cr Ti  + V O are studied by the density functional theory (DFT) within the generalized gradient approximation (GGA) of Perdew-Burke-Ernzerhof (PBE) functional. Experimental results based on X-Ray absorption spectroscopy (XAS) and X-Ray photoelectron spectroscopy (XPS) performed on Cr doped TiO 2 at the Synchrotron facility were compared to the theoretical results. It is shown that the electrons of the oxygen vacancy tend to be localized at the t 2g states of the Cr ions in order to reach the stable oxidation state of Cr 3+ . Effects of Cr on crystal field (CF) and structural distortions in the rutile TiO 2 cell were analyzed by the DFT calculations and XAS spectra revealing that the CF and tetragonal distortions in TiO 2 are very sensitive to the concentration of Cr.

Observational techniques for solar flare gamma-rays, hard X-rays, and neutrons

NASA Technical Reports Server (NTRS)

Lin, Robert P.

1989-01-01

The development of new instrumentation and techniques for solar hard X-ray, gamma ray and neutron observations from spacecraft and/or balloon-borne platforms is examined. The principal accomplishments are: (1) the development of a two segment germanium detector which is near ideal for solar hard X-ray and gamma ray spectroscopy; (2) the development of long duration balloon flight techniques and associated instrumentation; and (3) the development of innovative new position sensitive detectors for hard X-ray and gamma rays.

Band alignment of SiO2/(AlxGa1-x)2O3 (0 ≤ x ≤ 0.49) determined by X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Feng, Zhaoqing; Feng, Qian; Zhang, Jincheng; Li, Xiang; Li, Fuguo; Huang, Lu; Chen, Hong-Yan; Lu, Hong-Liang; Hao, Yue

2018-03-01

In this work, we report the investigation of the band alignment of SiO2/(AlxGa1-x)2O3 (0 ≤ x ≤ 0.49) utilizing the high resolution X-ray photoelectron spectroscopy (XPS) measurements. The single crystallinity and orientation of β-(AlxGa1-x)2O3 films grown on sapphire by pulsed laser deposition were studied with the high resolution X-ray diffraction. The Ga 2p3/2 and Si 2p core-level spectra as well as valence band spectra were used in the analysis of band alignment. As the mole fraction x of Al increases from 0 to 0.49, the bandgap and conduction band offset values of SiO2/(AlxGa1-x)2O3 increases from 4.9 to 5.6 eV and from 1.5 to 2.1 eV, respectively, while that of valence band offset decreases from 2.2 to 0.9 eV. From the results obtained, the energy band diagram of the studied SiO2/(AlxGa1-x)2O3 (0 ≤ x ≤ 0.49) interfaces is found to be of type I. Energy band lineups of SiO2/(AlxGa1-x)2O3 were thus determined which can be used as for Ga2O3 based power device technology.

X-ray absorption spectroscopy and X-ray photoelectron spectroscopy studies of CaSO 4:Dy thermoluminescent phosphors

NASA Astrophysics Data System (ADS)

Bakshi, A. K.; Jha, S. N.; Olivi, L.; Phase, D. M.; Kher, R. K.; Bhattacharyya, D.

2007-11-01

Extended X-ray absorption fine structure (EXAFS) measurements have been carried out on CaSO4:Dy phosphor samples at the Dy L3 edge with synchrotron radiation. Measurements were carried out on a set of samples which were subjected to post-preparation annealing at different temperatures and for different cycles. The EXAFS data have been analysed to find the Dy-S and Dy-O bond lengths in the neighbourhood of the Dy atoms in a CaSO4 matrix. The observations from EXAFS measurements were verified with XANES and XPS techniques. On the basis of these measurements, efforts were made to explain the loss of thermoluminescence sensitivity of CaSO4:Dy phosphors after repeated cycles of annealing at 400 °C in air for 1 h.

Microreactor Cells for High-Throughput X-ray Absorption Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beesley, Angela; Tsapatsaris, Nikolaos; Weiher, Norbert

2007-01-19

High-throughput experimentation has been applied to X-ray Absorption spectroscopy as a novel route for increasing research productivity in the catalysis community. Suitable instrumentation has been developed for the rapid determination of the local structure in the metal component of precursors for supported catalysts. An automated analytical workflow was implemented that is much faster than traditional individual spectrum analysis. It allows the generation of structural data in quasi-real time. We describe initial results obtained from the automated high throughput (HT) data reduction and analysis of a sample library implemented through the 96 well-plate industrial standard. The results show that a fullymore » automated HT-XAS technology based on existing industry standards is feasible and useful for the rapid elucidation of geometric and electronic structure of materials.« less

Infrared and X-Ray Spectroscopy of the Kes 75 Supernova Shell Characterizing the Dust and Gas Properties

NASA Technical Reports Server (NTRS)

Temim, Tea; Arendt, Richard G.; Dwek, Eli; Slane, Patrick

2012-01-01

We present deep Chandra observations and Spitzer Space Telescope infrared (IR) spectroscopy of the shell in the composite supernova remnant (SNR) Kes 75 (G29.7-0.3). The remnant is composed of a central pulsar wind nebula and a bright partial shell in the south that is visible at radio, IR, and X-ray wavelengths. The X-ray emission can be modeled by either a single thermal component with a temperature of approx 1.5 keV, or with two thermal components with temperatures of 1.5 and 0.2 keY. Previous studies suggest that the hot component may originate from reverse-shocked SN ejecta. However, our new analysis shows no definitive evidence for enhanced abundances of Si, S, Ar, Mg, and Fe, as expected from supernova (SN) ejecta, or for the IR spectral signatures characteristic of confirmed SN condensed dust, thus favoring a circumstellar or interstellar origin for the X-ray and IR emission. The X-ray and IR emission in the shell are spatially correlated, suggesting that the dust particles are collisionally heated by the X-ray emitting gas. The IR spectrum of the shell is dominated by continuum emission from dust with little, or no line emission. Modeling the IR spectrum shows that the dust is heated to a temperature of approx 140 K by a relatively dense, hot plasma, that also gives rise to the hot X-ray emission component. The density inferred from the IR emission is significantly higher than the density inferred from the X-ray models, suggesting a low filling factor for this X-ray emitting gas. The total mass of the warm dust component is at least 1.3 x 10(exp -2) Solar Mass, assuming no significant dust destruction has occurred in the shell. The IR data also reveal the presence of an additional plasma component with a cooler temperature, consistent with the 0.2 keV gas component. Our IR analysis therefore provides an independent verification of the cooler component of the X-ray emission. The complementary analyses of the X-ray and IR emission provide quantitative

Monte Carlo study of x-ray cross talk in a variable resolution x-ray detector

NASA Astrophysics Data System (ADS)

Melnyk, Roman; DiBianca, Frank A.

2003-06-01

A variable resolution x-ray (VRX) detector provides a great increase in the spatial resolution of a CT scanner. An important factor that limits the spatial resolution of the detector is x-ray cross-talk. A theoretical study of the x-ray cross-talk is presented in this paper. In the study, two types of the x-ray cross-talk were considered: inter-cell and inter-arm cross-talk. Both types of the x-ray cross-talk were simulated, using the Monte Carlo method, as functions of the detector field of view (FOV). The simulation was repeated for lead and tungsten separators between detector cells. The inter-cell x-ray cross-talk was maximum at the 34-36 cm FOV, but it was low at small and the maximum FOVs. The inter-arm x-ray cross-talk was high at small and medium FOVs, but it was greatly reduced when variable width collimators were placed on the front surfaces of the detector. The inter-cell, but not inter-arm, x-ray cross-talk was lower for tungsten than for lead separators. From the results, x-ray cross-talk in a VRX detector can be minimized by imaging all objects between 24 cm and 40 cm in diameter with the 40 cm FOV, using tungsten separators, and placing variable width collimators in front of the detector.

Molecular structure of hybrid imino-chalcone in the solid state: X-ray diffraction, spectroscopy study and third-order nonlinear optical properties

NASA Astrophysics Data System (ADS)

Custodio, J. M. F.; Santos, F. G.; Vaz, W. F.; Cunha, C. E. P.; Silveira, R. G.; Anjos, M. M.; Campos, C. E. M.; Oliveira, G. R.; Martins, F. T.; da Silva, C. C.; Valverde, C.; Baseia, B.; Napolitano, H. B.

2018-04-01

A comprehensive structural study of the compound (2E)-1-((E)-4-(4-methoxybenzylideneamino)phenyl)-3-(4-methoxyphenyl)prop-2-en-1-one was carried out in this work. Single crystal X-ray diffraction (SCXRD), X-ray powder diffraction (XRPD), NMR, Raman and Infrared spectroscopies, and DFT calculations were performed for characterization of this iminochalcone hybrid. Intermolecular interactions were described by Hirshfeld surface analysis derived from crystal structure. Reactivity and intramolecular charge transfer were investigated using the frontier molecular orbitals and molecular electrostatic potential. In addition, we have calculated the Nonlinear Optical Properties at the CAM-B3LYP/6-311+g(d) level of theory in the presence of different solvents (gas-phase, acetone, chloroform, dichloromethane, dimethyl sulfoxide, ethanol, methanol, and water), being found meaningful NLO parameters for our compound. At last, there is a good agreement between calculated and experimental IR spectrum, allowing the assignment of some of normal vibrational modes of the iminochalcone hybrid.

Preparation and characterization of polymer layer systems for validation of 3D Micro X-ray fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Schaumann, Ina; Malzer, Wolfgang; Mantouvalou, Ioanna; Lühl, Lars; Kanngießer, Birgit; Dargel, Rainer; Giese, Ulrich; Vogt, Carla

2009-04-01

For the validation of the quantification of the newly-developed method of 3D Micro X-ray fluorescence spectroscopy (3D Micro-XRF) samples with a low average Z matrix and minor high Z elements are best suited. In a light matrix the interferences by matrix effects are minimized so that organic polymers are appropriate as basis for analytes which are more easily detected by X-ray fluorescence spectroscopy. Polymer layer systems were assembled from single layers of ethylene-propylene-diene rubber (EPDM) filled with changing concentrations of silica and zinc oxide as inorganic additives. Layer thicknesses were in the range of 30-150 μm. Before the analysis with 3D Micro-XRF all layers have been characterized by scanning micro-XRF with regard to filler dispersion, by infrared microscopy and light microscopy in order to determine the layer thicknesses and by ICP-OES to verify the concentration of the X-ray sensitive elements in the layers. With the results obtained for stacked polymer systems the validity of the analytical quantification model for the determination of stratified materials by 3D Micro-XRF could be demonstrated.

Progress in the Development of Mo-Au Transition-Edge Sensors for X-Ray Spectroscopy

NASA Technical Reports Server (NTRS)

Stahle, Caroline K.; Brekosky, Regis P.; Figueroa-Feliciano, Enectali; Finkbeiner, Fred M.; Gygax, John D.; Li, Mary J.; Lindeman, Mark A..; Porter, F. Scott; Tralshawalaa, Nilesh

2000-01-01

X-ray microcalorimeters using transition-edge sensors (TES) show great promise for use in astronomical x-ray spectroscopy. We have obtained very high energy resolution (2.8 electronvolts at 1.5 kiloelectronvolts and 3.7 electronvolts at 3.3 kiloelectronvolts) in a large, isolated TES pixel using a Mo/Au proximity-effect bilayer on a silicon nitride membrane. We will discuss the performance and our characterization of that device. In order to be truly suitable for use behind an x-ray telescope, however, such devices need to be arrayed with a pixel size and focal-plane coverage commensurate with the telescope focal length and spatial resolution. Since this requires fitting the TES and its thermal link, a critical component of each calorimeter pixel, into a far more compact geometry than has previously been investigated, we must study the fundamental scaling laws in pixel optimization. We have designed a photolithography mask that will allow us to probe the range in thermal conductance that can be obtained by perforating the nitride membrane in a narrow perimeter around the sensor. This mask will also show the effects of reducing the TES area. Though we have not yet tested devices of the compact designs, we will present our progress in several of the key processing steps and discuss the parameter space of our intended investigations.

Drop-on-demand sample delivery for studying biocatalysts in action at X-ray free-electron lasers.

PubMed

Fuller, Franklin D; Gul, Sheraz; Chatterjee, Ruchira; Burgie, E Sethe; Young, Iris D; Lebrette, Hugo; Srinivas, Vivek; Brewster, Aaron S; Michels-Clark, Tara; Clinger, Jonathan A; Andi, Babak; Ibrahim, Mohamed; Pastor, Ernest; de Lichtenberg, Casper; Hussein, Rana; Pollock, Christopher J; Zhang, Miao; Stan, Claudiu A; Kroll, Thomas; Fransson, Thomas; Weninger, Clemens; Kubin, Markus; Aller, Pierre; Lassalle, Louise; Bräuer, Philipp; Miller, Mitchell D; Amin, Muhamed; Koroidov, Sergey; Roessler, Christian G; Allaire, Marc; Sierra, Raymond G; Docker, Peter T; Glownia, James M; Nelson, Silke; Koglin, Jason E; Zhu, Diling; Chollet, Matthieu; Song, Sanghoon; Lemke, Henrik; Liang, Mengning; Sokaras, Dimosthenis; Alonso-Mori, Roberto; Zouni, Athina; Messinger, Johannes; Bergmann, Uwe; Boal, Amie K; Bollinger, J Martin; Krebs, Carsten; Högbom, Martin; Phillips, George N; Vierstra, Richard D; Sauter, Nicholas K; Orville, Allen M; Kern, Jan; Yachandra, Vittal K; Yano, Junko

2017-04-01

X-ray crystallography at X-ray free-electron laser sources is a powerful method for studying macromolecules at biologically relevant temperatures. Moreover, when combined with complementary techniques like X-ray emission spectroscopy, both global structures and chemical properties of metalloenzymes can be obtained concurrently, providing insights into the interplay between the protein structure and dynamics and the chemistry at an active site. The implementation of such a multimodal approach can be compromised by conflicting requirements to optimize each individual method. In particular, the method used for sample delivery greatly affects the data quality. We present here a robust way of delivering controlled sample amounts on demand using acoustic droplet ejection coupled with a conveyor belt drive that is optimized for crystallography and spectroscopy measurements of photochemical and chemical reactions over a wide range of time scales. Studies with photosystem II, the phytochrome photoreceptor, and ribonucleotide reductase R2 illustrate the power and versatility of this method.

Drop-on-demand sample delivery for studying biocatalysts in action at X-ray free-electron lasers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fuller, Franklin D.; Gul, Sheraz; Chatterjee, Ruchira

X-ray crystallography at X-ray free-electron laser (XFEL) sources is a powerful method for studying macromolecules at biologically relevant temperatures. Moreover, when combined with complementary techniques like X-ray emission spectroscopy (XES), both global structures and chemical properties of metalloenzymes can be obtained concurrently, providing new insights into the interplay between the protein structure/dynamics and chemistry at an active site. However, implementing such a multimodal approach can be compromised by conflicting requirements to optimize each individual method. In particular, the method used for sample delivery greatly impacts the data quality. We present here a new, robust way of delivering controlled sample amountsmore » on demand using acoustic droplet ejection coupled with a conveyor belt drive that is optimized for crystallography and spectroscopy measurements of photochemical and chemical reactions over a wide range of time scales. Studies with photosystem II, the phytochrome photoreceptor, and ribonucleotide reductase R2 illustrate the power and versatility of this method.« less

Drop-on-demand sample delivery for studying biocatalysts in action at X-ray free-electron lasers

DOE PAGES

Fuller, Franklin D.; Gul, Sheraz; Chatterjee, Ruchira; ...

2017-02-27

X-ray crystallography at X-ray free-electron laser (XFEL) sources is a powerful method for studying macromolecules at biologically relevant temperatures. Moreover, when combined with complementary techniques like X-ray emission spectroscopy (XES), both global structures and chemical properties of metalloenzymes can be obtained concurrently, providing new insights into the interplay between the protein structure/dynamics and chemistry at an active site. However, implementing such a multimodal approach can be compromised by conflicting requirements to optimize each individual method. In particular, the method used for sample delivery greatly impacts the data quality. We present here a new, robust way of delivering controlled sample amountsmore » on demand using acoustic droplet ejection coupled with a conveyor belt drive that is optimized for crystallography and spectroscopy measurements of photochemical and chemical reactions over a wide range of time scales. Studies with photosystem II, the phytochrome photoreceptor, and ribonucleotide reductase R2 illustrate the power and versatility of this method.« less

X-ray And EUV Spectroscopy Of Highly Charged Tungsten Ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Biedermann, Christoph; Radtke, Rainer

2009-09-10

The Berlin EBIT has been established by the Max-Planck-Institut fuer Plasmaphysik to generate atomic physics data in support of research in the field of controlled nuclear fusion, by measuring the radiation from highly charged ions in the x-ray, extreme ultraviolet and visible spectral ranges and providing valuable diagnostics for high temperature plasmas. In future fusion devices, for example ITER, currently being constructed at Cadarache, France, the plasma facing components will be armored with high-Z materials, most likely tungsten, due to the favorable properties of this element. At the same time the tremendous radiation cooling of these high-Z materials represents amore » threat to fusion and obliges one to monitor carefully the radiation. With EBIT a selected ensemble of ions in specific charge states can be produced, stored and excited for spectroscopic investigations. Employing this technique, we have for example resolved the wide structure observed around 5 nm at the ASDEX Upgrade tokamak as originating from E1-transitions into the open 4d shell of tungsten ions in charge states 25+ to 37+ producing a band-like emission pattern. Further, these ions emit well-separated M1 lines in the EUV range around 65 nm suitable for plasma diagnostics. Kr-like to Cr-like tungsten ions (38+ to 50+) show strong soft-x-ray lines in the range 0.5 to 2 and 5 to 15 nm. Lines of even higher charged tungsten ions, up to Ne-like W{sup 64+}, abundant in the core plasma of present and future fusion test devices, have been investigated with high resolution Bragg-crystal spectroscopy at 0.13 nm. Recently, x-ray spectroscopic measurements of the dielectronic recombination LMn resonances of W{sup 60+} to W{sup 67+} ions have been preformed and compare well with atomic structure calculations.« less

NuSTAR HARD X-RAY SURVEY OF THE GALACTIC CENTER REGION. I. HARD X-RAY MORPHOLOGY AND SPECTROSCOPY OF THE DIFFUSE EMISSION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mori, Kaya; Hailey, Charles J.; Perez, Kerstin

2015-12-01

We present the first sub-arcminute images of the Galactic Center above 10 keV, obtained with NuSTAR. NuSTAR resolves the hard X-ray source IGR J17456–2901 into non-thermal X-ray filaments, molecular clouds, point sources, and a previously unknown central component of hard X-ray emission (CHXE). NuSTAR detects four non-thermal X-ray filaments, extending the detection of their power-law spectra with Γ ∼ 1.3–2.3 up to ∼50 keV. A morphological and spectral study of the filaments suggests that their origin may be heterogeneous, where previous studies suggested a common origin in young pulsar wind nebulae (PWNe). NuSTAR detects non-thermal X-ray continuum emission spatially correlated with the 6.4more » keV Fe Kα fluorescence line emission associated with two Sgr A molecular clouds: MC1 and the Bridge. Broadband X-ray spectral analysis with a Monte-Carlo based X-ray reflection model self-consistently determined their intrinsic column density (∼10{sup 23} cm{sup −2}), primary X-ray spectra (power-laws with Γ ∼ 2) and set a lower limit of the X-ray luminosity of Sgr A* flare illuminating the Sgr A clouds to L{sub X} ≳ 10{sup 38} erg s{sup −1}. Above ∼20 keV, hard X-ray emission in the central 10 pc region around Sgr A* consists of the candidate PWN G359.95–0.04 and the CHXE, possibly resulting from an unresolved population of massive CVs with white dwarf masses M{sub WD} ∼ 0.9 M{sub ⊙}. Spectral energy distribution analysis suggests that G359.95–0.04 is likely the hard X-ray counterpart of the ultra-high gamma-ray source HESS J1745–290, strongly favoring a leptonic origin of the GC TeV emission.« less

Determination of copper binding in Pseudomonas putida CZ1 by chemical modifications and X-ray absorption spectroscopy.

PubMed

Chen, XinCai; Shi, JiYan; Chen, YingXu; Xu, XiangHua; Chen, LiTao; Wang, Hui; Hu, TianDou

2007-03-01

Previously performed studies have shown that Pseudomonas putida CZ1 biomass can bind an appreciable amount of Cu(II) and Zn(II) ions from aqueous solutions. The mechanisms of Cu- and Zn-binding by P. putida CZ1 were ascertained by chemical modifications of the biomass followed by Fourier transform infrared and X-ray absorption spectroscopic analyses of the living or nonliving cells. A dramatic decrease in Cu(II)- and Zn(II)-binding resulted after acidic methanol esterification of the nonliving cells, indicating that carboxyl functional groups play an important role in the binding of metal to the biomaterial. X-ray absorption spectroscopy was used to determine the speciation of Cu ions bound by living and nonliving cells, as well as to elucidate which functional groups were involved in binding of the Cu ions. The X-ray absorption near-edge structure spectra analysis showed that the majority of the Cu was bound in both samples as Cu(II). The fitting results of Cu K-edge extended X-ray absorption fine structure spectra showed that N/O ligands dominated in living and nonliving cells. Therefore, by combining different techniques, our results indicate that carboxyl functional groups are the major ligands responsible for the metal binding in P. putida CZ1.

Comprehensive Experimental and Computational Spectroscopic Study of Hexacyanoferrate Complexes in Water: From Infrared to X-ray Wavelengths.

PubMed

Ross, Matthew; Andersen, Amity; Fox, Zachary W; Zhang, Yu; Hong, Kiryong; Lee, Jae-Hyuk; Cordones, Amy; March, Anne Marie; Doumy, Gilles; Southworth, Stephen H; Marcus, Matthew A; Schoenlein, Robert W; Mukamel, Shaul; Govind, Niranjan; Khalil, Munira

2018-05-17

We present a joint experimental and computational study of the hexacyanoferrate aqueous complexes at equilibrium in the 250 meV to 7.15 keV regime. The experiments and the computations include the vibrational spectroscopy of the cyanide ligands, the valence electronic absorption spectra, and Fe 1s core hole spectra using element-specific-resonant X-ray absorption and emission techniques. Density functional theory-based quantum mechanics/molecular mechanics molecular dynamics simulations are performed to generate explicit solute-solvent configurations, which serve as inputs for the spectroscopy calculations of the experiments spanning the IR to X-ray wavelengths. The spectroscopy simulations are performed at the same level of theory across this large energy window, which allows for a systematic comparison of the effects of explicit solute-solvent interactions in the vibrational, valence electronic, and core-level spectra of hexacyanoferrate complexes in water. Although the spectroscopy of hexacyanoferrate complexes in solution has been the subject of several studies, most of the previous works have focused on a narrow energy window and have not accounted for explicit solute-solvent interactions in their spectroscopy simulations. In this work, we focus our analysis on identifying how the local solvation environment around the hexacyanoferrate complexes influences the intensity and line shape of specific spectroscopic features in the UV/vis, X-ray absorption, and valence-to-core X-ray emission spectra. The identification of these features and their relationship to solute-solvent interactions is important because hexacyanoferrate complexes serve as model systems for understanding the photochemistry and photophysics of a large class of Fe(II) and Fe(III) complexes in solution.