Cone-beam x-ray luminescence computed tomography based on x-ray absorption dosage

NASA Astrophysics Data System (ADS)

Liu, Tianshuai; Rong, Junyan; Gao, Peng; Zhang, Wenli; Liu, Wenlei; Zhang, Yuanke; Lu, Hongbing

2018-02-01

With the advances of x-ray excitable nanophosphors, x-ray luminescence computed tomography (XLCT) has become a promising hybrid imaging modality. In particular, a cone-beam XLCT (CB-XLCT) system has demonstrated its potential in in vivo imaging with the advantage of fast imaging speed over other XLCT systems. Currently, the imaging models of most XLCT systems assume that nanophosphors emit light based on the intensity distribution of x-ray within the object, not completely reflecting the nature of the x-ray excitation process. To improve the imaging quality of CB-XLCT, an imaging model that adopts an excitation model of nanophosphors based on x-ray absorption dosage is proposed in this study. To solve the ill-posed inverse problem, a reconstruction algorithm that combines the adaptive Tikhonov regularization method with the imaging model is implemented for CB-XLCT reconstruction. Numerical simulations and phantom experiments indicate that compared with the traditional forward model based on x-ray intensity, the proposed dose-based model could improve the image quality of CB-XLCT significantly in terms of target shape, localization accuracy, and image contrast. In addition, the proposed model behaves better in distinguishing closer targets, demonstrating its advantage in improving spatial resolution.

Cone-beam x-ray luminescence computed tomography based on x-ray absorption dosage.

PubMed

Liu, Tianshuai; Rong, Junyan; Gao, Peng; Zhang, Wenli; Liu, Wenlei; Zhang, Yuanke; Lu, Hongbing

2018-02-01

With the advances of x-ray excitable nanophosphors, x-ray luminescence computed tomography (XLCT) has become a promising hybrid imaging modality. In particular, a cone-beam XLCT (CB-XLCT) system has demonstrated its potential in in vivo imaging with the advantage of fast imaging speed over other XLCT systems. Currently, the imaging models of most XLCT systems assume that nanophosphors emit light based on the intensity distribution of x-ray within the object, not completely reflecting the nature of the x-ray excitation process. To improve the imaging quality of CB-XLCT, an imaging model that adopts an excitation model of nanophosphors based on x-ray absorption dosage is proposed in this study. To solve the ill-posed inverse problem, a reconstruction algorithm that combines the adaptive Tikhonov regularization method with the imaging model is implemented for CB-XLCT reconstruction. Numerical simulations and phantom experiments indicate that compared with the traditional forward model based on x-ray intensity, the proposed dose-based model could improve the image quality of CB-XLCT significantly in terms of target shape, localization accuracy, and image contrast. In addition, the proposed model behaves better in distinguishing closer targets, demonstrating its advantage in improving spatial resolution. (2018) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE).

X-ray absorption spectroscopic studies of the active sites of nickel- and copper-containing metalloproteins

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

Tan, Grace O.

1993-06-01

X-ray absorption spectroscopy (XAS) is a useful tool for obtaining structural and chemical information about the active sites of metalloproteins and metalloenzymes. Information may be obtained from both the edge region and the extended X-ray absorption fine structure (EXAFS) or post-edge region of the K-edge X-ray absorption spectrum of a metal center in a compound. The edge contains information about the valence electronic structure of the atom that absorbs the X-rays. It is possible in some systems to infer the redox state of the metal atom in question, as well as the geometry and nature of ligands connected to it,more » from the features in the edge in a straightforward manner. The EXAFS modulations, being produced by the backscattering of the ejected photoelectron from the atoms surrounding the metal atom, provide, when analyzed, information about the number and type of neighbouring atoms, and the distances at which they occur. In this thesis, analysis of both the edge and EXAFS regions has been used to gain information about the active sites of various metalloproteins. The metalloproteins studied were plastocyanin (Pc), laccase and nickel carbon monoxide dehydrogenase (Ni CODH). Studies of Cu(I)-imidazole compounds, related to the protein hemocyanin, are also reported here.« less

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 spectral studies of copper (II) mixed ligand complexes

NASA Astrophysics Data System (ADS)

Soni, B.; Dar, Davood Ah; Shrivastava, B. D.; Prasad, J.; Srivastava, K.

2014-09-01

X-ray absorption spectra at the K-edge of copper have been studied in two copper mixed ligand complexes, one having tetramethyethylenediamine (tmen) and the other having tetraethyethylenediamine (teen) as one of the ligands. The spectra have been recorded at BL-8 dispersive extended X-ray absorption fine structure (EXAFS) beamline at the 2.5 GeV INDUS- 2 synchrotron, RRCAT, Indore, India. The data obtained has been processed using the data analysis program Athena. The energy of the K-absorption edge, chemical shift, edge-width and shift of the principal absorption maximum in the complexes have been determined and discussed. The values of these parameters have been found to be approximately the same in both the complexes indicating that the two complexes possess similar chemical environment around the copper metal atom. The chemical shift has been utilized to estimate effective nuclear charge on the absorbing atom. The normalized EXAFS spectra have been Fourier transformed. The position of the first peak in the Fourier transform gives the value of first shell bond length, which is shorter than the actual bond length because of energy dependence of the phase factors in the sine function of the EXAFS equation. This distance is thus the phase- uncorrected bond length. Bond length has also been determined by Levy's, Lytle's and Lytle, Sayers and Stern's (LSS) methods. The results obtained from LSS and the Fourier transformation methods are comparable with each other, since both are phase uncorrected bond lengths.

X-ray absorption Studies of Zinc species in Centella asiatica

NASA Astrophysics Data System (ADS)

Dehipawala, Sunil; Cheung, Tak; Hogan, Clayton; Agoudavi, Yao; Dehipawala, Sumudu

2013-03-01

Zinc is a very important mineral present in a variety of vegetables. It is an essential element in cellular metabolism and several bodily functions. We used X-ray fluorescence, and X-ray Absorption near Edge structure(XANES) to study the amount of zinc present in several leafy vegetables as well as its chemical environment within the plant. Main absorption edge position of XANES is sensitive to the oxidation state of zinc and is useful when comparing the type of zinc present in different vegetables to the standard zinc present in supplements. Normalized main edge height is proportional to the amount of zinc present in the sample. Several leafy greens were used in this study, such as Spinacia oleracea, Basella alba, Brassica oleracea, Cardiospermum halicacabumand Centella asiatica. All of these plant leaves contained approximately the same amount of zinc in the leaf portion of the plant and a slightly lower amount in the stems, except Centella asiatica. Both leaves and stems of the plant Centella asiatica contained nearly two times the zinc compared to other plants. Further investigation of zinc's chemical environment within Centella asiatica could lead to a much more efficient dietary consumption of zinc. Use of the National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886

High energy X-ray phase and dark-field imaging using a random absorption mask.

PubMed

Wang, Hongchang; Kashyap, Yogesh; Cai, Biao; Sawhney, Kawal

2016-07-28

High energy X-ray imaging has unique advantage over conventional X-ray imaging, since it enables higher penetration into materials with significantly reduced radiation damage. However, the absorption contrast in high energy region is considerably low due to the reduced X-ray absorption cross section for most materials. Even though the X-ray phase and dark-field imaging techniques can provide substantially increased contrast and complementary information, fabricating dedicated optics for high energies still remain a challenge. To address this issue, we present an alternative X-ray imaging approach to produce transmission, phase and scattering signals at high X-ray energies by using a random absorption mask. Importantly, in addition to the synchrotron radiation source, this approach has been demonstrated for practical imaging application with a laboratory-based microfocus X-ray source. This new imaging method could be potentially useful for studying thick samples or heavy materials for advanced research in materials science.

X-Ray Attenuation and Absorption for Materials of Dosimetric Interest

National Institute of Standards and Technology Data Gateway

SRD 126 X-Ray Attenuation and Absorption for Materials of Dosimetric Interest (Web, free access)   Tables and graphs of the photon mass attenuation coefficient and the mass energy-absorption coefficient are presented for all of the elements Z = 1 to 92, and for 48 compounds and mixtures of radiological interest. The tables cover energies of the photon (x-ray, gamma ray, bremsstrahlung) from 1 keV to 20 MeV.

Absorption in X-ray spectra of high-redshift quasars

NASA Technical Reports Server (NTRS)

Elvis, Martin; Fiore, Fabrizio; Wilkes, Belinda; Mcdowell, Jonathan; Bechtold, Jill

1994-01-01

We present evidence that X-ray absorption is common in high-redshift quasars. We have studied six high-redshift (z approximately 3) quasars with the ROSAT Position Sensitive Proportional Counter (PSPC) of which four are in directions of low Galactic N(sub H). Three out of these four show excess absorption, while only three in approximately 50 z approximately less than 0.4 quasars do, indicating that such absorption must be common, but not ubiquitous, at high redshifts, and that the absorbers must lie at z greater than 0.4. The six quasars were: S5 0014+81, Q0420-388, PKS 0438-436, S4 0636+680. PKS 2000-330, PKS 2126-158, which have redshifts between 2.85 and 3.78. PKS 0438-436 and PKS 2126-158 show evidence for absorption above the local Galactic value at better than 99.999% confidence level. If the absorber is at the redshift of the quasar, then values of N(sub H) = (0.86(+0.49, -0.28)) x 10(exp 22) atoms/sq cm for PKS 0438-436, and N(sub H) = (1.45(+1.20, -0.64)) x 10(exp 22) atoms/ sq cm for PKS 2126-158, are implied, assuming solar abundances. The spectrum of S4 0636+680 also suggests the presence of a similarly large absorption column density at the 98% confidence level. This absorption reverses the trend for the most luminous active galactic nuclei (AGN) to have the least X-ray absorption, so a new mechanism is likely to be responsible. Intervening absorption due to damped Lyman(alpha) systems is a plausible cause. We also suggest, as an intrinsic model, that intracluster material, e.g., a cooling flow, around the quasar could account for both the X-ray spectrum and other properties of these quasars. All the quasars are radio-loud and three are gigahertz peaked (two of the three showing absorption). No excess absorption above the Galactic value is seen toward Q0420-388. This quasar has two damped Lyman(alpha) systems at z = 3.08. The limit on the X-ray column density implies a low ionization fraction, N(H I)/N(H) approximately greater than 4 x 10(exp -3) (3

Soft x-ray absorption spectra of ilmenite family.

PubMed

Agui, A; Mizumaki, M; Saitoh, Y; Matsushita, T; Nakatani, T; Fukaya, A; Torikai, E

2001-03-01

We have carried out soft x-ray absorption spectroscopy to study the electronic structure of ilmenite family, such as MnTiO3, FeTiO3, and CoTiO3 at the soft x-ray beamline, BL23SU, at the SPring-8. The Ti and M L2,3 absorption spectra of MTiO3 (M=Mn, Fe, and Co) show spectra of Ti4+ and M2+ electron configurations, respectively. Except the Fe L2,3 spectrum, those spectra were understood within the O(h) symmetry around the transition metal ions. The Fe L3-edge spectrum clearly shows a doublet peak at the L3 edge, which is attributed to Fe2+ state, moreover the very high-resolution the L-edge spectra of transition metals show fine structures. The spectra of those ilmenites are compared.

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

High Resolution Spectroscopy of X-ray Quasars: Searching for the X-ray Absorption from the Warm-Hot Intergalactic Medium

NASA Technical Reports Server (NTRS)

Fang, Taotao; Canizares, Claude R.; Marshall, Herman L.

2004-01-01

We present a survey of six low to moderate redshift quasars with Chandra and XMM-Newton. The primary goal is to search for the narrow X-ray absorption lines produced by highly ionized metals in the Warm-Hot Intergalactic Medium. All the X-ray spectra can be well fitted by a power law with neutral hydrogen absorption. Only one feature is detected at above 3-sigma level in all the spectra, which is consistent with statistic fluctuation. We discuss the implications in our understanding of the baryon content of the universe. We also discuss the implication of the non-detection of the local (z approx. 0) X-ray absorption.

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

Determination of total x-ray absorption coefficient using non-resonant x-ray emission

PubMed Central

Achkar, A. J.; Regier, T. Z.; Monkman, E. J.; Shen, K. M.; Hawthorn, D. G.

2011-01-01

An alternative measure of x-ray absorption spectroscopy (XAS) called inverse partial fluorescence yield (IPFY) has recently been developed that is both bulk sensitive and free of saturation effects. Here we show that the angle dependence of IPFY can provide a measure directly proportional to the total x-ray absorption coefficient, µ(E). In contrast, fluorescence yield (FY) and electron yield (EY) spectra are offset and/or distorted from µ(E) by an unknown and difficult to measure amount. Moreover, our measurement can determine µ(E) in absolute units with no free parameters by scaling to µ(E) at the non-resonant emission energy. We demonstrate this technique with measurements on NiO and NdGaO3. Determining µ(E) across edge-steps enables the use of XAS as a non-destructive measure of material composition. In NdGaO3, we also demonstrate the utility of IPFY for insulating samples, where neither EY or FY provide reliable spectra due to sample charging and self-absorption effects, respectively. PMID:22355697

Discovery of an X-ray Violently Variable Broad Absorption Line Quasar

NASA Technical Reports Server (NTRS)

Ghosh, Kajal K.; Gutierrez, Carlos M.; Punsly, Brian; Chevallier, Loic; Goncalves, Anabela C.

2006-01-01

In this letter, we report on a quasar that is violently variable in the X-rays, XVV. It is also a broad absorption line quasar (BALQSO) that exhibits both high ionization and low ionization UV absorption lines (LoBALQSO). It is very luminous in the X-rays (approximately 10(exp 46) ergs s(sup -l) over the entire X-ray band). Surprisingly, this does not over ionize the LoBAL outflow. The X-rays vary by a factor of two within minutes in the quasar rest frame, which is shorter than 1/30 of the light travel time across a scale length equal to the black hole radius. We concluded that the X-rays are produced in a relativistic jet beamed toward earth in which variations in the Doppler enhancement produce the XVV behavior.

Ultrafast time-resolved X-ray absorption spectroscopy of ferrioxalate photolysis with a laser plasma X-ray source and microcalorimeter array

DOE PAGES

O’Neil, Galen C.; Miaja-Avila, Luis; Joe, Young Il; ...

2017-02-17

The detailed pathways of photoactivity on ultrafast time scales are a topic of contemporary interest. Using a tabletop apparatus based on a laser plasma X-ray source and an array of cryogenic microcalorimeter X-ray detectors, we measured a transient X-ray absorption spectrum during the ferrioxalate photoreduction reaction. With these high-efficiency detectors, we observe the Fe K edge move to lower energies and the amplitude of the extended X-ray absorption fine structure reduce, consistent with a photoreduction mechanism in which electron transfer precedes disassociation. We provide quantitative limits on the Fe–O bond length change. Lastly, we review potential improvements to our measurementmore » technique, highlighting the future potential of tabletop X-ray science using microcalorimeter sensors.« less

Ultrafast time-resolved X-ray absorption spectroscopy of ferrioxalate photolysis with a laser plasma X-ray source and microcalorimeter array

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

O’Neil, Galen C.; Miaja-Avila, Luis; Joe, Young Il

The detailed pathways of photoactivity on ultrafast time scales are a topic of contemporary interest. Using a tabletop apparatus based on a laser plasma X-ray source and an array of cryogenic microcalorimeter X-ray detectors, we measured a transient X-ray absorption spectrum during the ferrioxalate photoreduction reaction. With these high-efficiency detectors, we observe the Fe K edge move to lower energies and the amplitude of the extended X-ray absorption fine structure reduce, consistent with a photoreduction mechanism in which electron transfer precedes disassociation. We provide quantitative limits on the Fe–O bond length change. Lastly, we review potential improvements to our measurementmore » technique, highlighting the future potential of tabletop X-ray science using microcalorimeter sensors.« 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

X-ray Absorption Study of Graphene Oxide and Transition Metal Oxide Nanocomposites.

PubMed

Gandhiraman, Ram P; Nordlund, Dennis; Javier, Cristina; Koehne, Jessica E; Chen, Bin; Meyyappan, M

2014-08-14

The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties as the graphene oxide transformation to reduced-graphene oxide is a key step in the synthesis of the electrode materials. Polarized behavior of the synchrotron X-rays and the angular dependency of the near-edge X-ray absorption fine structures (NEXAFS) have been utilized to study the orientation of the σ and π bonds of the graphene oxide and graphene oxide-metal oxide nanocomposites. The core-level transitions of individual metal oxides and that of the graphene oxide nanocomposite showed that the interaction of graphene oxide with the metal oxide nanostructures has not altered the electronic structure of either of them. As the restoration of the π network is important for good electrical conductivity, the C K edge NEXAFS spectra of reduced graphene oxide nanocomposites confirms the same through increased intensity of the sp 2 -derived unoccupied states π* band. A pronounced angular dependency of the reduced sample and the formation of excitonic peaks confirmed the formation of extended conjugated network.

Thermal expansion behavior study of Co nanowire array with in situ x-ray diffraction and x-ray absorption fine structure techniques

NASA Astrophysics Data System (ADS)

Mo, Guang; Cai, Quan; Jiang, Longsheng; Wang, Wei; Zhang, Kunhao; Cheng, Weidong; Xing, Xueqing; Chen, Zhongjun; Wu, Zhonghua

2008-10-01

In situ x-ray diffraction and x-ray absorption fine structure techniques were used to study the structural change of ordered Co nanowire array with temperature. The results show that the Co nanowires are polycrystalline with hexagonal close packed structure without phase change up until 700 °C. A nonlinear thermal expansion behavior has been found and can be well described by a quadratic equation with the first-order thermal expansion coefficient of 4.3×10-6/°C and the second-order thermal expansion coefficient of 5.9×10-9/°C. The mechanism of this nonlinear thermal expansion behavior is discussed.

X ray absorption by dark nebulae (HEAO-2 guest investigator program)

NASA Technical Reports Server (NTRS)

Sanders, W. T.

1991-01-01

A study is described of data obtained from the Imaging Proportional Counter (IPC) x ray detector aboard the HEAO-2 satellite (Einstein Observatory). The research project involved a search for absorption of diffuse low energy x ray background emission by galactic dark nebulae. The commonly accepted picture that the bulk of the C band emission originates locally, closer that a few hundred parsec, and the bulk of the M band emission originates farther away than a few hundred parsec, was tested. The idea was to look for evidence of absorption of the diffuse background radiation by nearby interstellar clouds.

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.

Thomson Thick X-Ray Absorption in a Broad Absorption Line Quasar, PG 0946+301.

PubMed

Mathur; Green; Arav; Brotherton; Crenshaw; deKool; Elvis; Goodrich; Hamann; Hines; Kashyap; Korista; Peterson; Shields; Shlosman; van Breugel W; Voit

2000-04-20

We present a deep ASCA observation of a broad absorption line quasar (BALQSO) PG 0946+301. The source was clearly detected in one of the gas imaging spectrometers, but not in any other detector. If BALQSOs have intrinsic X-ray spectra similar to normal radio-quiet quasars, our observations imply that there is Thomson thick X-ray absorption (NH greater, similar1024 cm-2) toward PG 0946+301. This is the largest column density estimated so far toward a BALQSO. The absorber must be at least partially ionized and may be responsible for attenuation in the optical and UV. If the Thomson optical depth toward BALQSOs is close to 1, as inferred here, then spectroscopy in hard X-rays with large telescopes like XMM would be feasible.

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.

Vanadium K-edge X-ray absorption spectroscopy of bromoperoxidase from Ascophyllum nodosum

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

Arber, J.M.; de Boer, E.; Garner, C.D.

Bromoperoxidase from Ascophyllum nodusum was the first vanadium-containing enzyme to be isolated. X-ray absorption spectra have now been collected in order to investigate the coordination of vanadium in the native, native plus bromide, native plus hydrogen peroxide, and dithionite-reduced forms of the enzyme. The edge and X-ray absorption near-edge structures show that, in the four samples studied, it is only on reduction of the native enzyme that the metal site is substantially altered. In addition, these data are consistent with the presence of vanadium(IV) in the reduced enzyme and vanadium(V) in the other samples. Extended X-ray absorption fine structure datamore » confirm that there are structural changes at the metal site on reduction of the native enzyme, notably a lengthening of the average inner-shell distance, and the presence of terminal oxygen together with histidine and oxygen-donating residues.« less

Weak Hard X-Ray Emission from Two Broad Absorption Line Quasars Observed with NuStar: Compton-Thick Absorption or Intrinsic X-Ray Weakness?

NASA Technical Reports Server (NTRS)

Luo, B.; Brandt, W. N.; Alexander, D. M.; Harrison, F. A.; Stern, D.; Bauer, F. E.; Boggs, S. E.; Christensen, F. E.; Comastri, A.; Craig, W. W..;

WEAK HARD X-RAY EMISSION FROM TWO BROAD ABSORPTION LINE QUASARS OBSERVED WITH NuSTAR: COMPTON-THICK ABSORPTION OR INTRINSIC X-RAY WEAKNESS?

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

Luo, B.; Brandt, W. N.; Alexander, D. M.

We present Nuclear Spectroscopic Telescope Array (NuSTAR) hard X-ray observations of two X-ray weak broad absorption line (BAL) quasars, PG 1004+130 (radio loud) and PG 1700+518 (radio quiet). Many BAL quasars appear X-ray weak, probably due to absorption by the shielding gas between the nucleus and the accretion-disk wind. The two targets are among the optically brightest BAL quasars, yet they are known to be significantly X-ray weak at rest-frame 2-10 keV (16-120 times fainter than typical quasars). We would expect to obtain Almost-Equal-To 400-600 hard X-ray ({approx}> 10 keV) photons with NuSTAR, provided that these photons are not significantlymore » absorbed (N{sub H} {approx}< 10{sup 24} cm{sup -2}). However, both BAL quasars are only detected in the softer NuSTAR bands (e.g., 4-20 keV) but not in its harder bands (e.g., 20-30 keV), suggesting that either the shielding gas is highly Compton-thick or the two targets are intrinsically X-ray weak. We constrain the column densities for both to be N{sub H} Almost-Equal-To 7 Multiplication-Sign 10{sup 24} cm{sup -2} if the weak hard X-ray emission is caused by obscuration from the shielding gas. We discuss a few possibilities for how PG 1004+130 could have Compton-thick shielding gas without strong Fe K{alpha} line emission; dilution from jet-linked X-ray emission is one likely explanation. We also discuss the intrinsic X-ray weakness scenario based on a coronal-quenching model relevant to the shielding gas and disk wind of BAL quasars. Motivated by our NuSTAR results, we perform a Chandra stacking analysis with the Large Bright Quasar Survey BAL quasar sample and place statistical constraints upon the fraction of intrinsically X-ray weak BAL quasars; this fraction is likely 17%-40%.« less

Search for correlated UV and x ray absorption of NGC 3516

NASA Technical Reports Server (NTRS)

Martin, Christopher; Halpern, Jules P.; Kolman, Michiel

1991-01-01

NGC 3516, a low-luminosity Seyfert galaxy, is one of a small fraction of Seyfert galaxies that exhibit broad absorption in a resonance line. In order to determine whether the UV and x ray absorption in NGC 3516 are related, 5 IUE observations were obtained, quasi-simultaneously with 4 Ginga observations. The results are presented and discussed. The following subject areas are covered: short-term UV variability; emission lines; galactic absorption lines; the C IV, N V, and Si IV absorption features; lower limit on the carbon column density; estimate of the distance from the absorber to the continuum source; variability in the continuum and absorption; a comparison with BAL QSO's; and the x ray-UV connection.

First-principles calculations of K-shell X-ray absorption spectra for warm dense nitrogen

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

Li, Zi; Zhang, Shen; Kang, Wei

2016-05-15

X-ray absorption spectrum is a powerful tool for atomic structure detection on warm dense matter. Here, we perform first-principles molecular dynamics and X-ray absorption spectrum calculations on warm dense nitrogen along a Hugoniot curve. From the molecular dynamics trajectory, the detailed atomic structures are examined for each thermodynamical condition. The K-shell X-ray absorption spectrum is calculated, and its changes with temperature and pressure along the Hugoniot curve are discussed. The warm dense nitrogen systems may contain isolated nitrogen atoms, N{sub 2} molecules, and nitrogen clusters, which show quite different contributions to the total X-ray spectrum due to their different electronmore » density of states. The changes of X-ray spectrum along the Hugoniot curve are caused by the different nitrogen structures induced by the temperature and the pressure. Some clear signatures on X-ray spectrum for different thermodynamical conditions are pointed out, which may provide useful data for future X-ray experiments.« less

Insights into the mechanism of X-ray-induced disulfide-bond cleavage in lysozyme crystals based on EPR, optical absorption and X-ray diffraction studies

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

Sutton, Kristin A.; Black, Paul J.; Mercer, Kermit R.

2013-12-01

Electron paramagnetic resonance (EPR) and online UV–visible absorption microspectrophotometry with X-ray crystallography have been used in a complementary manner to follow X-ray-induced disulfide-bond cleavage, to confirm a multi-track radiation-damage process and to develop a model of that process. Electron paramagnetic resonance (EPR) and online UV–visible absorption microspectrophotometry with X-ray crystallography have been used in a complementary manner to follow X-ray-induced disulfide-bond cleavage. Online UV–visible spectroscopy showed that upon X-irradiation, disulfide radicalization appeared to saturate at an absorbed dose of approximately 0.5–0.8 MGy, in contrast to the saturating dose of ∼0.2 MGy observed using EPR at much lower dose rates. Themore » observations suggest that a multi-track model involving product formation owing to the interaction of two separate tracks is a valid model for radiation damage in protein crystals. The saturation levels are remarkably consistent given the widely different experimental parameters and the range of total absorbed doses studied. The results indicate that even at the lowest doses used for structural investigations disulfide bonds are already radicalized. Multi-track considerations offer the first step in a comprehensive model of radiation damage that could potentially lead to a combined computational and experimental approach to identifying when damage is likely to be present, to quantitate it and to provide the ability to recover the native unperturbed structure.« less

Detection of absorption lines in the spectra of X-ray bursts from X1608-52

NASA Astrophysics Data System (ADS)

Nakamura, Norio; Inoue, Hajime; Tanaka, Yasuo

X-ray bursts from X 1608-52 were observed with the gas scintillation proportional counters on the Tenma satellite. Absorption features were detected in the spectra of three bursts among 17 bursts observed. These absorption features are consistent with a common absorption line at 4.1 keV. The energy and the properties of the absorption lines of the X 1608-52 bursts are very similar to those observed from the X 1636-53 bursts by Waki et al. (1984). Near equality of the absorption-line energies for X 1636-53 and X 1608-52 would imply that mass and radius of the neutron stars in these two systems are very similar to each other.

X-ray two-photon absorption with high fluence XFEL pulses

DOE PAGES

Hoszowska, Joanna; Szlachetko, J.; Dousse, J. -Cl.; ...

2015-09-07

Here, we report on nonlinear interaction of solid Fe with intense femtosecond hard x-ray free-electron laser (XFEL) pulses. The experiment was performed at the CXI end-station of the Linac Coherent Light Source (LCLS) by means of high- resolution x-ray emission spectroscopy. The focused x-ray beam provided extreme fluence of ~10 5 photons/Å 2. Two-photon absorption leading to K-shell hollow atom formation and to single K-shell ionization of solid Fe was investigated.

Ultrafast absorption of intense x rays by nitrogen molecules

NASA Astrophysics Data System (ADS)

Buth, Christian; Liu, Ji-Cai; Chen, Mau Hsiung; Cryan, James P.; Fang, Li; Glownia, James M.; Hoener, Matthias; Coffee, Ryan N.; Berrah, Nora

2012-06-01

We devise a theoretical description for the response of nitrogen molecules (N2) to ultrashort and intense x rays from the free electron laser Linac Coherent Light Source (LCLS). We set out from a rate-equation description for the x-ray absorption by a nitrogen atom. The equations are formulated using all one-x-ray-photon absorption cross sections and the Auger and radiative decay widths of multiply-ionized nitrogen atoms. Cross sections are obtained with a one-electron theory and decay widths are determined from ab initio computations using the Dirac-Hartree-Slater (DHS) method. We also calculate all binding and transition energies of nitrogen atoms in all charge states with the DHS method as the difference of two self-consistent field (SCF) calculations (ΔSCF method). To describe the interaction with N2, a detailed investigation of intense x-ray-induced ionization and molecular fragmentation are carried out. As a figure of merit, we calculate ion yields and the average charge state measured in recent experiments at the LCLS. We use a series of phenomenological models of increasing sophistication to unravel the mechanisms of the interaction of x rays with N2: a single atom, a symmetric-sharing model, and a fragmentation-matrix model are developed. The role of the formation and decay of single and double core holes, the metastable states of N_2^{2+}, and molecular fragmentation are explained.

X-ray absorption radiography for high pressure shock wave studies

NASA Astrophysics Data System (ADS)

Antonelli, L.; Atzeni, S.; Batani, D.; Baton, S. D.; Brambrink, E.; Forestier-Colleoni, P.; Koenig, M.; Le Bel, E.; Maheut, Y.; Nguyen-Bui, T.; Richetta, M.; Rousseaux, C.; Ribeyre, X.; Schiavi, A.; Trela, J.

2018-01-01

The study of laser compressed matter, both warm dense matter (WDM) and hot dense matter (HDM), is relevant to several research areas, including materials science, astrophysics, inertial confinement fusion. X-ray absorption radiography is a unique tool to diagnose compressed WDM and HDM. The application of radiography to shock-wave studies is presented and discussed. In addition to the standard Abel inversion to recover a density map from a transmission map, a procedure has been developed to generate synthetic radiographs using density maps produced by the hydrodynamics code DUED. This procedure takes into account both source-target geometry and source size (which plays a non negligible role in the interpretation of the data), and allows to reproduce transmission data with a good degree of accuracy.

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.

X-Ray Absorption Microspectroscopy with Electrostatic Force Microscopy and its Application to Chemical States Mapping

NASA Astrophysics Data System (ADS)

Ishii, M.; Rigopoulos, N.; Poolton, N. R. J.; Hamilton, B.

2007-02-01

A new technique named X-EFM that measures the x-ray absorption fine structure (XAFS) of nanometer objects was developed. In X-EFM, electrostatic force microscopy (EFM) is used as an x-ray absorption detector, and photoionization induced by x-ray absorption of surface electron trapping sites is detected by EFM. An EFM signal with respect to x-ray photon energy provides the XAFS spectra of the trapping sites. We adopted X-EFM to observe Si oxide thin films. An edge jump shift intrinsic to the X-EFM spectrum was found, and it was explained with a model where an electric field between the trapping site and probe deepens the energy level of the inner-shell. A scanning probe under x-rays with fixed photon energy provided the chemical state mapping on the surface.

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

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

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.

X-Ray Modeling of the Intrinsic Absorption in NGC 4151

NASA Astrophysics Data System (ADS)

Denes Couto, Jullianna; Kraemer, Steven; Turner, T. Jane; Crenshaw, D. Michael

2017-01-01

We have investigated the relationship between the long term X-ray spectral variability in the Seyfert 1.5 galaxy NGC 4151 and its intrinsic absorption, by comparing our 2014 simultaneous ultraviolet/X-Ray observations taken with Hubble STIS Echelle and Chandra HETGS with archival observations from Chandra, XMM-Newton and Suzaku. The observations were divided into "high" and "low" states, with the low states showing strong and unabsorbed extended emission at energies below 2 keV. Our X-ray model consists of a broken powerlaw, neutral reflection and the two dominant absorption components identified by Kraemer et al (2005), X-High and D+Ea, which are present in all epochs. The model fittings suggest that the absorbers are very stable, with the principal changes in the intrinsic absorption resulting from variations in the ionization state of the gas in response to the variable strength of the ionizing continuum. However, the low states show evidence of larger column densities in one or both of the absorbers. Among plausible explanations for the column increase, we discuss the possibility of an expanding/contracting X-ray corona. X-High is consistent with being part of a magnetohydrodynamic (MHD) wind, while D+Ea is possibly radiatively driven, which suggests that at a sufficiently large radial distance there could be a break point between MHD-dominated and radiatively driven outflows. Preliminary results on the analysis of the AGN mass outflow rates and kinematics of the ionized gas in the extended emission region of NGC 4151 will also be presented.

Oxygen, Neon, and Iron X-Ray Absorption in the Local Interstellar Medium

NASA Technical Reports Server (NTRS)

Gatuzz, Efrain; Garcia, Javier; Kallman, Timothy R.; Mendoza, Claudio

2016-01-01

We present a detailed study of X-ray absorption in the local interstellar medium by analyzing the X-ray spectra of 24 galactic sources obtained with the Chandra High Energy Transmission Grating Spectrometer and the XMM-Newton Reflection Grating Spectrometer. Methods. By modeling the continuum with a simple broken power-law and by implementing the new ISMabs X-ray absorption model, we have estimated the total H, O, Ne, and Fe column densities towards the observed sources. Results. We have determined the absorbing material distribution as a function of source distance and galactic latitude longitude. Conclusions. Direct estimates of the fractions of neutrally, singly, and doubly ionized species of O, Ne, and Fe reveal the dominance of the cold component, thus indicating an overall low degree of ionization. Our results are expected to be sensitive to the model used to describe the continuum in all sources.

High Resolution X-Ray Absorption Spectroscopy: Distribution of Matter in and around Galaxies

NASA Astrophysics Data System (ADS)

Schulz, Norbert; MIT/CAT Team

2015-10-01

The chemical evolution of the Universe embraces aspects that reachdeep into modern astrophysics and cosmology. We want to know how present and past matter is affected by various levels and types of nucleo-synthesis and stellar evolution. Three major categories were be identified: 1. The study of pre-mordial star formation including periods of super-massive black hole formation, 2. The embedded evolution of the intergalactic medium IGM, 3. The status and evolution of stars and the interstellar medium ISM in galaxies. Today a fourth category relates to our understanding of dark matter in relationwith these three categories. The X-ray band is particularly sensitive to K- and L-shell absorption and scattering from high abundant elements like C, N, O, Ne, Mg, Si, S,Ar, Ca, Fe, and Ni. Like the Lyman alpha forest in the optical band, absorbers in the IGM produce an X-ray line forest along the line of sight in the X-rayspectrum of a background quasar. Similary bright X-ray sources within galaxies and the Milky Way produce a continuum, which is being absorbed by elements invarious phases of the ISM. High resolution X-ray absorption surveys are possible with technologies ready for flight within decade. == high efficiency X-ray optics with optical performance 3== high resolution X-ray gratings with R 3000 for E 1.5 keV== X-ray micro-calorimeters with R 2000 for E 1.5 keV. The vision for the next decade needs to lead to means and strategies which allows us to perform such absorption surveys as effectively as surveys are now or in very near future quite common in astronomy pursued in other wave length bands such as optical, IR, and sub-mm.

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.

A wavelet analysis for the X-ray absorption spectra of molecules

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

Penfold, T. J.; Ecole polytechnique Federale de Lausanne, Laboratoire de chimie et biochimie computationnelles, ISIC, FSB-BCH, CH-1015 Lausanne; SwissFEL, Paul Scherrer Inst, CH-5232 Villigen

2013-01-07

We present a Wavelet transform analysis for the X-ray absorption spectra of molecules. In contrast to the traditionally used Fourier transform approach, this analysis yields a 2D correlation plot in both R- and k-space. As a consequence, it is possible to distinguish between different scattering pathways at the same distance from the absorbing atom and between the contributions of single and multiple scattering events, making an unambiguous assignment of the fine structure oscillations for complex systems possible. We apply this to two previously studied transition metal complexes, namely iron hexacyanide in both its ferric and ferrous form, and a rheniummore » diimine complex, [ReX(CO){sub 3}(bpy)], where X = Br, Cl, or ethyl pyridine (Etpy). Our results demonstrate the potential advantages of using this approach and they highlight the importance of multiple scattering, and specifically the focusing phenomenon to the extended X-ray absorption fine structure (EXAFS) spectra of these complexes. We also shed light on the low sensitivity of the EXAFS spectrum to the Re-X scattering pathway.« less

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.

Interstellar X-Ray Absorption Spectroscopy of the Crab Pulsar with the LETGS

NASA Technical Reports Server (NTRS)

Paerels, Frits; Weisskopf, Martin C.; Tennant, Allyn F.; ODell, Stephen L.; Swartz, Douglas A.; Kahn, Steven M.; Behar, Ehud; Becker, Werner; Whitaker, Ann F. (Technical Monitor)

2001-01-01

We study the interstellar X-ray absorption along the line of sight to the Crab Pulsar. The Crab was observed with the Low Energy Transmission Grating Spectrometer on the Chandra X-ray Observatory, and the pulsar, a point source, produces a full resolution spectrum. The continuum spectrum appears smooth, and we compare its parameters with other measurements of the pulsar spectrum. The spectrum clearly shows absorption edges due to interstellar Ne, Fe, and O. The O edge shows spectral structure that is probably due to O bound in molecules or dust. We search for near-edge structure (EXAFS) in the O absorption spectrum. The Fe L absorption spectrum is largely due to a set of unresolved discrete n=2-3 transitions in neutral or near-neutral Fe, and we analyze it using a new set of dedicated atomic structure calculations, which provide absolute cross sections. In addition to being interesting in its own right, the ISM absorption needs to be understood in quantitative detail in order to derive spectroscopic constraints on possible soft thermal radiation from the pulsar.

Modeling Broadband X-Ray Absorption of Massive Star Winds

NASA Technical Reports Server (NTRS)

Leutenegger, Maurice A.; Cohen,David H.; Zsargo, Janos; Martell, Erin M.; MacArthur, James P.; Owocki, Stanley P.; Gagne, Marc; Hillier, D. John

2010-01-01

We present a method for computing the net transition of X-rays emitted by shock-heated plasma distributed throughout a partially optically thick stellar wind from a massive star. We find the transmission by an exact integration of the formal solution, assuming the emitting plasma and absorbing plasma are mixed at a constant mass ratio above some minimum radius, below which there is assumed to be no emission. This model is more realistic than either the slab absorption associated with a corona at the base of the wind or the exospheric approximation that assumes all observed X-rays are emitted without attenuation from above the radius of optical depth unity. Our model is implemented in XSPEC as a pre-calculated table that can be coupled to a user-defined table of the wavelength dependent wind opacity. We provide a default wind opacity model that is more representative of real wind opacities than the commonly used neutral ISM tabulation. Preliminary modeling of Chandra grating data indicates that the X-ray hardness trend of OB stars with spectral subtype cars largely be understood as a wind absorption effect.

Vibrational effects in x-ray absorption and resonant inelastic x-ray scattering using a semiclassical scheme

NASA Astrophysics Data System (ADS)

Ljungberg, Mathias P.

2017-12-01

A method is presented for describing vibrational effects in x-ray absorption spectroscopy and resonant inelastic x-ray scattering (RIXS) using a combination of the classical Franck-Condon (FC) approximation and classical trajectories run on the core-excited state. The formulation of RIXS is an extension of the semiclassical Kramers-Heisenberg formalism of Ljungberg et al. [Phys. Rev. B 82, 245115 (2010), 10.1103/PhysRevB.82.245115] to the resonant case, retaining approximately the same computational cost. To overcome difficulties with connecting the absorption and emission processes in RIXS, the classical FC approximation is used for the absorption, which is seen to work well provided that a zero-point-energy correction is included. In the case of core-excited states with dissociative character, the method is capable of closely reproducing the main features for one-dimensional test systems, compared to the quantum-mechanical formulation. Due to the good accuracy combined with the relatively low computational cost, the method has great potential of being used for complex systems with many degrees of freedom, such as liquids and surface adsorbates.

Inelastic losses in X-ray absorption theory

NASA Astrophysics Data System (ADS)

Campbell, Luke Whalin

There is a surprising lack of many body effects observed in XAS (X-ray Absorption Spectroscopy) experiments. While collective excitations and other satellite effects account for between 20% and 40% of the spectral weight of the core hole and photoelectron excitation spectrum, the only commonly observed many body effect is a relatively structureless amplitude reduction to the fine structure, typically no more than a 10% effect. As a result, many particle effects are typically neglected in the XAS codes used to predict and interpret modern experiments. To compensate, the amplitude reduction factor is simply fitted to experimental data. In this work, a quasi-boson model is developed to treat the case of XAS, when the system has both a photoelectron and a core hole. We find that there is a strong interference between the extrinsic and intrinsic losses. The interference reduces the excitation amplitudes at low energies where the core hole and photo electron induced excitations tend to cancel. At high energies, the interference vanishes, and the theory reduces to the sudden approximation. The x-ray absorption spectrum including many-body excitations is represented by a convolution of the one-electron absorption spectrum with an energy dependent spectral function. The latter has an asymmetric quasiparticle peak and broad satellite structure. The net result is a phasor sum, which yields the many body amplitude reduction and phase shift of the fine structure oscillations (EXAFS), and possibly additional satellite structure. Calculations for several cases of interest are found to be in reasonable agreement with experiment. Edge singularity effects and deviations from the final state rule arising from this theory are also discussed. The ab initio XAS code FEFF has been extended for calculations of the many body amplitude reduction and phase shift in x-ray spectroscopies. A new broadened plasmon pole self energy is added. The dipole matrix elements are modified to include a

X-ray absorption spectra: Graphene, h-BN, and their alloy

NASA Astrophysics Data System (ADS)

Bhowmick, Somnath; Rusz, Jan; Eriksson, Olle

2013-04-01

Using first-principles density functional theory calculations, in conjunction with the Mahan-Nozières-de Dominicis theory, we calculate the x-ray absorption spectra of the alloys of graphene and monolayer hexagonal boron nitride on a Ni (111) substrate. The chemical neighborhood of the constituent atoms (B, C, and N) inside the alloy differs from that of the parent phases. In a systematic way, we capture the change in the K-edge spectral shape, depending on the chemical neighborhood of B, C, and N. Our work also reiterates the importance of the dynamical core-hole screening for a proper description of the x-ray absorption process in sp2-bonded layered materials.

X-ray absorption spectroscopy and neutron diffraction study of the perovskite-type rare-earth cobaltites

NASA Astrophysics Data System (ADS)

Sikolenko, V.; Efimova, E.; Franz, A.; Ritter, C.; Troyanchuk, I. O.; Karpinsky, D.; Zubavichus, Y.; Veligzhanin, A.; Tiutiunnikov, S. I.; Sazonov, A.; Efimov, V.

2018-05-01

Correlations between local and long-range structure distortions in the perovskite-type RE1-xSrxCoO3-δ (RE = La, Pr, Nd; x = 0.0 and 0.5) compounds have been studied at room temperature by extended X-ray absorption fine structure (EXAFS) at the Co K-edge and high-resolution neutron powder diffraction (NPD). The use of two complementary experimental techniques allowed us to explore the influence of the type of rare-earth element and strontium substitution on unusual behavior of static and dynamic features of both the Co-O bond lengths.

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.

Effect of X-ray irradiation on the optical absorption of СdSe1-xTex nanocrystals embedded in borosilicate glass

NASA Astrophysics Data System (ADS)

Prymak, M. V.; Azhniuk, Yu. M.; Solomon, A. M.; Krasilinets, V. M.; Lopushansky, V. V.; Bodnar, I. V.; Gomonnai, A. V.; Zahn, D. R. T.

2012-07-01

The effect of X-ray irradiation on the optical absorption spectra of CdSe1-xTex nanocrystals embedded in a borosilicate matrix is studied. The observed blue shift of the absorption edge and bleaching of the confinement-related features in the spectra are related to X-ray induced negative ionization of the nanocrystals with charge transfer across the nanocrystal/matrix interface. The radiation-induced changes are observed to recover after longer post-irradiation storage at room temperature.

Modern Progress and Modern Problems in High Resolution X-ray Absorption from the Cold Interstellar Medium

NASA Astrophysics Data System (ADS)

Corrales, Lia; Li, Haochuan; Heinz, Sebastian

2018-01-01

With accurate cross-sections and higher signal-to-noise, X-ray spectroscopy can directly measure Milky Way gas and dust-phase metal abundances with few underlying assumptions. The X-ray energy band is sensitive to absorption by all abundant interstellar metals — carbon, oxygen, neon, silicon, magnesium, and iron — whether they are in gas or dust form. High resolution X-ray spectra from Galactic X-ray point sources can be used to directly measure metal abundances from all phases of the interstellar medium (ISM) along singular sight lines. We show our progress for measuring the depth of photoelectric absorption edges from neutral ISM metals, using all the observations of bright Galactic X-ray binaries available in the Chandra HETG archive. The cross-sections we use take into account both the absorption and scattering effects by interstellar dust grains on the iron and silicate spectral features. However, there are many open problems for reconciling X-ray absorption spectroscopy with ISM observations in other wavelengths. We will review the state of the field, lab measurements needed, and ways in which the next generation of X-ray telescopes will contribute.

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.

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

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

Density Measurement for MORB Melts by X-ray Absorption Method

NASA Astrophysics Data System (ADS)

Sakamaki, T.; Urakawa, S.; Suzuki, A.; Ohtani, E.; Katayama, Y.

2006-12-01

Density of silicate melts at high pressure is one of the most important properties to understand magma migration in the planetary interior and the differentiation of the terrestrial planets. The density measurements of silicate melts have been carried out by several methods (shock compression experiments and sink-float method in static experiments, etc.). However, since these methods have difficulties in acquisition of data at a desired pressure and temperature, the density of the silicate melt have been measured under only a few conditions. Recently a new density measurement was developed by the X-ray absorption method. Advantage of this method is to measure density of liquids at a desired pressure and temperature. In the present study we measured the density of MORB melt by X-ray absorption method. Experiments were carried out at the BL22XU beamline at SPring-8. A DIA-type cubic anvil apparatus was used for generation of high pressure and temperature. We used tungsten carbide anvils with the top anvil sizes of 6 mm and 4 mm. The energy of monochromateized X-ray beam was 23 keV. The intensities of incident and transmitted X-ray were measured by ion chambers. The density of the melt was calculated on the basis of Beer-Lambert law. The starting material was a glass with the MORB composition. Experiments were made from 1 atm to 5 GPa, from 300 to 2000 K. We compared the density of MORB melt with the compression curve of the melt in previous works. The density measured by this study is lower than that expected from the compression curve determined at higher pressures by the sink-float method. Structural change of the MORB melt with increasing pressure might be attributed to this discrepancy.

Density Measurement for MORB Melts by X-ray Absorption Method

NASA Astrophysics Data System (ADS)

Sakamaki, T.; Urakawa, S.; Ohtani, E.; Suzuki, A.; Katayama, Y.

2005-12-01

Density of silicate melts at high pressure is one of the most important properties to understand magma migration in the planetary interior and the differentiation of the terrestrial planets. The density measurements of silicate melts have been carried out by several methods (shock compression experiments and sink-float method in static experiments, etc.). However, since these methods have difficulties in acquisition of data at a desired pressure and temperature, the density of the silicate melt have been measured under only a few conditions. Recently a new density measurement was developed by the X-ray absorption method. Advantage of this method is to measure density of liquids at a desired pressure and temperature. In the present study we measured the density of MORB melt by X-ray absorption method. Experiments were carried out at the BL22XU beamline at SPring-8. A DIA-type cubic anvil apparatus was used for generation of high pressure and temperature. We used tungsten carbide anvils with the edge-length of 6 mm. The energy of monochromateized X-ray beam was 23 keV. The intensities of incident and transmitted X-ray were measured by ion chambers. The density of the melt was calculated on the basis of Beer-Lambert law. The starting material was a glass with the MORB composition. Experiments were made from 1 atm to 4 GPa, from 300 to 2200 K. We compared the density of MORB melt with the compression curve of the melt in previous works. The density measured by this study is lower than that expected from the compression curve determined at higher pressures by the sink-float method. Structural change of the MORB melt with increasing pressure might be attributed to this discrepancy.

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

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

2013-07-01

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, M2,3-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, M2,3-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.

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

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.

Electronic structure and optical properties of CdSxSe1-x solid solution nanostructures from X-ray absorption near edge structure, X-ray excited optical luminescence, and density functional theory investigations

NASA Astrophysics Data System (ADS)

Murphy, M. W.; Yiu, Y. M.; Ward, M. J.; Liu, L.; Hu, Y.; Zapien, J. A.; Liu, Yingkai; Sham, T. K.

2014-11-01

The electronic structure and optical properties of a series of iso-electronic and iso-structural CdSxSe1-x solid solution nanostructures have been investigated using X-ray absorption near edge structure, extended X-ray absorption fine structure, and X-ray excited optical luminescence at various absorption edges of Cd, S, and Se. It is found that the system exhibits compositions, with variable local structure in-between that of CdS and CdSe accompanied by tunable optical band gap between that of CdS and CdSe. Theoretical calculation using density functional theory has been carried out to elucidate the observations. It is also found that luminescence induced by X-ray excitation shows new optical channels not observed previously with laser excitation. The implications of these observations are discussed.

X-ray absorption studies of gamma irradiated Nd doped phosphate glass

NASA Astrophysics Data System (ADS)

Rai, V. N.; Rajput, Parasmani; Jha, S. N.; Bhattacharyya, D.

2015-06-01

This paper presents the X-ray absorption near edge structure (XANES) studies of Nd doped phosphate glasses before and after gamma irradiation. The intensity and location of LIII edge white line peak of Nd changes depending on its concentration as well as on the ratio of O/Nd in the glass matrix. The decrease in the peak intensity of white line after gamma irradiation indicates towards reduction of Nd3+ to Nd2+ in the glass matrix, which increases with an increase in the doses of gamma irradiation. Similarity in the XANES spectra of Nd doped phosphate glasses and Nd2O3 suggests that coordination geometry around Nd3+ in glass samples may be identical to that of Nd2O3.

Soft X-Ray Absorption Spectroscopy of High-Abrasion-Furnace Carbon Black

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

Muramatsu, Yasuji; Harada, Ryusuke; Gullikson, Eric M.

2007-02-02

The soft x-ray absorption spectra of high-abrasion-furnace carbon black were measured to obtain local-structure/chemical-states information of the primary particles and/or crystallites. The soft x-ray absorption spectral features of carbon black represent broader {pi}* and {sigma}* peak structures compared to highly oriented pyrolytic graphite (HOPG). The subtracted spectra between the carbon black and HOPG, (carbon black) - (HOPG), show double-peak structures on both sides of the {pi}* peak. The lower-energy peak, denoted as the 'pre-peak', in the subtracted spectra and the {pi}*/{sigma}* peak intensity ratio in the absorption spectra clearly depend on the specific surface area by nitrogen adsorption (NSA). Therefore,more » it is concluded that the pre-peak intensity and the {pi}*/{sigma}* ratio reflect the local graphitic structure of carbon black.« less

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.

Morphology, stability, and X-ray absorption spectroscopic study of iron oxide (Hematite) nanoparticles prepared by micelle nanolithography

NASA Astrophysics Data System (ADS)

Bera, Anupam; Bhattacharya, Atanu; Tiwari, N.; Jha, S. N.; Bhattacharyya, D.

2018-03-01

Currently, considerable effort is being made towards synthesis and characterization of iron oxide nanoparticles. In this article, we report on the preparation and characterization of iron oxide nanoparticle (NP) arrays supported on natively oxidized Si(100) surface. The NPs are synthesized by reverse micelle nanolithography technique and are then deposited onto natively oxidized Si(100) surface via spin-coating. Plasma oxidation followed by high temperature annealing results in a unimodal size distribution of pseudohexagonally-ordered array of iron oxide NPs (with ∼14 nm mean diameter and ∼5 nm mean height). High temperature annealing does not fragment the NPs. Particles are sinter-resistant: the unimodal arrays are robust with respect to thermal treatment. X-ray absorption spectroscopy (XAS), including X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS), reveals that structure of the iron oxide particle resembles closely the hematite α-Fe2O3 structure. Furthermore, with the help of EXAFS spectra, we eliminate the possibility of γ-Fe2O3, Fe3O4, FeO and FeO(OH) structures for the NPs.

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).

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

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.

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

X-ray absorption spectroscopic studies on gold nanoparticles in mesoporous and microporous materials.

PubMed

Akolekar, Deepak B; Foran, Garry; Bhargava, Suresh K

2004-05-01

Au L(3)-edge X-ray absorption spectroscopic measurements were carried out over a series of mesoporous and microporous materials containing gold nanoparticles to investigate the effects of the host matrix and preparation methods on the properties of gold nanoparticles. The materials of structure type MCM-41, ZSM-5, SAPO-18 and LSX with varying framework composition containing low concentrations of gold nanoparticles were prepared and characterized. In these materials the size of the gold nanoparticles varied in the range approximately 1 to 4 nm. A series of gold nanoparticles within different mesoporous and microporous materials have been investigated using X-ray absorption fine structure (XANES, EXAFS) and other techniques. Information such as atomic distances, bonding and neighbouring environment obtained from XAFS measurements was useful in elucidating the nature and structure of gold nanoparticles on these catalytic materials. The influence of the high-temperature (823, 1113, 1273 K) treatment on gold nanoparticles inside the mesoporous matrix was investigated using the XAFS technique. The XAFS and XANES results confirm various characteristics of gold nanoparticles in these materials suitable for catalysis, fabrication of nanodevices and other applications.

Accurate predictions of iron redox state in silicate glasses: A multivariate approach using X-ray absorption spectroscopy

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

Dyar, M. Darby; McCanta, Molly; Breves, Elly

2016-03-01

Pre-edge features in the K absorption edge of X-ray absorption spectra are commonly used to predict Fe3+ valence state in silicate glasses. However, this study shows that using the entire spectral region from the pre-edge into the extended X-ray absorption fine-structure region provides more accurate results when combined with multivariate analysis techniques. The least absolute shrinkage and selection operator (lasso) regression technique yields %Fe3+ values that are accurate to ±3.6% absolute when the full spectral region is employed. This method can be used across a broad range of glass compositions, is easily automated, and is demonstrated to yield accurate resultsmore » from different synchrotrons. It will enable future studies involving X-ray mapping of redox gradients on standard thin sections at 1 × 1 μm pixel sizes.« less

Accurate predictions of iron redox state in silicate glasses: A multivariate approach using X-ray absorption spectroscopy

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

Dyar, M. Darby; McCanta, Molly; Breves, Elly

2016-03-01

Pre-edge features in the K absorption edge of X-ray absorption spectra are commonly used to predict Fe 3+ valence state in silicate glasses. However, this study shows that using the entire spectral region from the pre-edge into the extended X-ray absorption fine-structure region provides more accurate results when combined with multivariate analysis techniques. The least absolute shrinkage and selection operator (lasso) regression technique yields %Fe 3+ values that are accurate to ±3.6% absolute when the full spectral region is employed. This method can be used across a broad range of glass compositions, is easily automated, and is demonstrated to yieldmore » accurate results from different synchrotrons. It will enable future studies involving X-ray mapping of redox gradients on standard thin sections at 1 × 1 μm pixel sizes.« 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.

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...

Two-Photon Absorption of Soft X-Ray Free Electron Laser Radiation by Graphite Near the Carbon K-Absorption Edge

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

Christensen, Steven T; Lam, Royce K.; Raj, Sumana L.

We have examined the transmission of soft X-ray pulses from the FERMI free electron laser through carbon films of varying thickness, quantifying nonlinear effects of pulses above and below the carbon K-edge. At typical of soft X-ray free electron laser intensities, pulses exhibit linear absorption at photon energies above and below the K-edge, ~308 and ~260 eV, respectively; whereas two-photon absorption becomes significant slightly below the K-edge, ~284.2 eV. The measured two-photon absorption cross section at 284.18 eV (~6 x 10-48 cm4 s) is 7 orders of magnitude above what is expected from a simple theory based on hydrogen-like atomsmore » - a result of resonance effects.« less

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

THE BLAZAR EMISSION ENVIRONMENT: INSIGHT FROM SOFT X-RAY ABSORPTION

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

Furniss, A.; Williams, D. A.; Fumagalli, M.

Collecting experimental insight into the relativistic particle populations and emission mechanisms at work within TeV-emitting blazar jets, which are spatially unresolvable in most bands and have strong beaming factors, is a daunting task. New observational information has the potential to lead to major strides in understanding the acceleration site parameters. Detection of molecular carbon monoxide (CO) in TeV emitting blazars, however, implies the existence of intrinsic gas, a connection often found in photo-dissociated region models and numerical simulations. The existence of intrinsic gas within a blazar could provide a target photon field for Compton up-scattering of photons to TeV energiesmore » by relativistic particles. We investigate the possible existence of intrinsic gas within the three TeV emitting blazars RGB J0710+591, W Comae, and 1ES 1959+650 which have measurements or upper limits on molecular CO line luminosity using an independent technique that is based on the spectral analysis of soft X-rays. Evidence for X-ray absorption by additional gas beyond that measured within the Milky Way is searched for in Swift X-ray Telescope (XRT) data between 0.3 and 10 keV. Without complementary information from another measurement, additional absorption could be misinterpreted as an intrinsically curved X-ray spectrum since both models can frequently fit the soft X-ray data. After breaking this degeneracy, we do not find evidence for intrinsically curved spectra for any of the three blazars. Moreover, no evidence for intrinsic gas is evident for RGB J0710+591 and W Comae, while the 1ES 1959+650 XRT data support the existence of intrinsic gas with a column density of {approx}1 Multiplication-Sign 10{sup 21} cm{sup -2}.« 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

First in-flight synchrotron X-ray absorption and photoemission study of carbon soot nanoparticles

PubMed Central

Ouf, F.-X.; Parent, P.; Laffon, C.; Marhaba, I.; Ferry, D.; Marcillaud, B.; Antonsson, E.; Benkoula, S.; Liu, X.-J.; Nicolas, C.; Robert, E.; Patanen, M.; Barreda, F.-A.; Sublemontier, O.; Coppalle, A.; Yon, J.; Miserque, F.; Mostefaoui, T.; Regier, T. Z.; Mitchell, J.-B. A.; Miron, C.

2016-01-01

Many studies have been conducted on the environmental impacts of combustion generated aerosols. Due to their complex composition and morphology, their chemical reactivity is not well understood and new developments of analysis methods are needed. We report the first demonstration of in-flight X-ray based characterizations of freshly emitted soot particles, which is of paramount importance for understanding the role of one of the main anthropogenic particulate contributors to global climate change. Soot particles, produced by a burner for several air-to-fuel ratios, were injected through an aerodynamic lens, focusing them to a region where they interacted with synchrotron radiation. X-ray photoelectron spectroscopy and carbon K-edge near-edge X-ray absorption spectroscopy were performed and compared to those obtained for supported samples. A good agreement is found between these samples, although slight oxidation is observed for supported samples. Our experiments demonstrate that NEXAFS characterization of supported samples provides relevant information on soot composition, with limited effects of contamination or ageing under ambient storage conditions. The highly surface sensitive XPS experiments of airborne soot indicate that the oxidation is different at the surface as compared to the bulk probed by NEXAFS. We also report changes in soot’s work function obtained at different combustion conditions. PMID:27883014

First in-flight synchrotron X-ray absorption and photoemission study of carbon soot nanoparticles.

PubMed

Ouf, F-X; Parent, P; Laffon, C; Marhaba, I; Ferry, D; Marcillaud, B; Antonsson, E; Benkoula, S; Liu, X-J; Nicolas, C; Robert, E; Patanen, M; Barreda, F-A; Sublemontier, O; Coppalle, A; Yon, J; Miserque, F; Mostefaoui, T; Regier, T Z; Mitchell, J-B A; Miron, C

2016-11-24

Many studies have been conducted on the environmental impacts of combustion generated aerosols. Due to their complex composition and morphology, their chemical reactivity is not well understood and new developments of analysis methods are needed. We report the first demonstration of in-flight X-ray based characterizations of freshly emitted soot particles, which is of paramount importance for understanding the role of one of the main anthropogenic particulate contributors to global climate change. Soot particles, produced by a burner for several air-to-fuel ratios, were injected through an aerodynamic lens, focusing them to a region where they interacted with synchrotron radiation. X-ray photoelectron spectroscopy and carbon K-edge near-edge X-ray absorption spectroscopy were performed and compared to those obtained for supported samples. A good agreement is found between these samples, although slight oxidation is observed for supported samples. Our experiments demonstrate that NEXAFS characterization of supported samples provides relevant information on soot composition, with limited effects of contamination or ageing under ambient storage conditions. The highly surface sensitive XPS experiments of airborne soot indicate that the oxidation is different at the surface as compared to the bulk probed by NEXAFS. We also report changes in soot's work function obtained at different combustion conditions.

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

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

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

Unveiling the X-ray/UV properties of AGN winds using Broad and mini-Broad Absorption Line Quasars

NASA Astrophysics Data System (ADS)

Giustini, M.

2015-07-01

BAL/mini-BALs are observed in the UV spectra of ˜ 20-30% of optically selected AGN as broad absorption troughs blueshifted by several thousands km/s, indicative of powerful nuclear winds. They could be representative of the average AGN if their winds cover only 20-30% of the continuum source, and/or represent an evolutionary state analogous to the high-soft state of BHB, when the jet emission is quenched and strong X-ray absorbing equatorial disk winds are virtually ubiquitous. High-quality, possibly time-resolved X-ray/UV studies are crucial to assess the global amount and 'character' of absorption in BAL/mini-BAL QSOs and to constrain the physical mechanism responsible for the launch and acceleration of their winds, therefore placing them in the broader context of AGN geometry and evolution. I will review here the known X-ray properties of BAL/mini-BAL QSOs, and present new results from a comprehensive X-ray spectral analysis of all the Palomar-Green BAL/mini-BAL QSOs with available XMM-Newton observations, for a total of 51 pointings of 14 different sources. These will include the most recent results from a high-quality simultaneous XMM/HST observational campaign on the mini-BAL QSO PG 1126-041, that unveiled with stunning details the X-ray/UV connection in action in an AGN disk wind through correlated X-ray/UV absorption variability.

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.

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.

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.

Phase-dependent absorption features in X-ray spectra of X-ray Dim Isolated Neutron Stars

NASA Astrophysics Data System (ADS)

Borghese, A.; Rea, N.; Coti Zelati, F.; Turolla, R.; Tiengo, A.; Zane, S.

2017-12-01

A detailed phase-resolved spectroscopy of archival XMM-Newton observations of X-ray Dim Isolated Neutron Stars (XDINSs) led to the discovery of narrow and strongly phase-dependent absorption features in two of these sources. The first was discovered in the X-ray spectrum of RX J0720.4-3125, followed by a new possible candidate in RX J1308.6+2127. Both spectral lines have similar properties: they are detected for only ˜ 20% of the rotational cycle and appear to be stable over the timespan covered by the observations. We performed Monte Carlo simulations to test the significance of these phase-variable features and in both cases the outcome has confirmed the detection with a confidence level > 4.6σ. Because of the narrow width and the strong dependence on the pulsar rotational phase, the most likely interpretation for these spectral features is in terms of resonant proton cyclotron absorption scattering in a confined high-B structure close to the stellar surface. Within the framework of this interpretation, our results provide evidence for deviations from a pure dipole magnetic field on small scales for highly magnetized neutron stars and support the proposed scenario of XDINSs being aged magnetars, with a strong non-dipolar crustal B-field component.

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.

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.

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.

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

Simulation of X-ray transient absorption for following vibrations in coherently ionized F2 molecules

NASA Astrophysics Data System (ADS)

Dutoi, Anthony D.; Leone, Stephen R.

2017-01-01

Femtosecond and attosecond X-ray transient absorption experiments are becoming increasingly sophisticated tools for probing nuclear dynamics. In this work, we explore and develop theoretical tools needed for interpretation of such spectra,in order to characterize the vibrational coherences that result from ionizing a molecule in a strong IR field. Ab initio data for F2 is combined with simulations of nuclear dynamics, in order to simulate time-resolved X-ray absorption spectra for vibrational wavepackets after coherent ionization at 0 K and at finite temperature. Dihalogens pose rather difficult electronic structure problems, and the issues encountered in this work will be reflective of those encountered with any core-valence excitation simulation when a bond is breaking. The simulations reveal a strong dependence of the X-ray absorption maximum on the locations of the vibrational wave packets. A Fourier transform of the simulated signal shows features at the overtone frequencies of both the neutral and the cation, which reflect spatial interferences of the vibrational eigenstates. This provides a direct path for implementing ultrafast X-ray spectroscopic methods to visualize coherent nuclear dynamics.

A X-Ray Absorption Study of Transition Metal Oxides

NASA Astrophysics Data System (ADS)

Bunker, Grant Byrd

This work is an experimental and theoretical study of the x-ray absorption near-edge structure of selected 3d transition metal compounds. The goal is to understand the physical mechanisms of XANES, using the competing multiple scattering (MS) and single scattering formalisms of Durham et al, and of Muller and Schaich, respectively. Careful experimental measurements of the K edge absorption of Mn oxides and KMnO(,4) at 300(DEGREES)K, 140(DEGREES)K and 80(DEGREES)K were made. These materials were chosen because they exhibit a variety of structures and oxidation states. Computer simulations of the XANES using the formalisms above were also performed. The experimental results show that atoms beyond the first coordination shell significantly affect the XANES near and above the edge; in particular the temperature dependent XANES and the "white line" in MnO establish this. We conclude that XANES, like EXAFS, is primarily sensitive to geometrical structure, except within about 1 Rydberg of the Fermi level. Two types of MS are distinguished: type 1 (forward scattering) is important in both XANES and EXAFS regions; type 2 (large angle scattering) is important only at and below the edge. MS of the photoelectron among the first shell Oxygen atoms in KMnO(,4) is observed experimentally, and found to become negligible above (DBLTURN) 1 Rydberg past the edge. The sharp features in XANES are primarily due to scattering from distant atoms, rather than localized states, except below the edge. This is supported by the observation that (alpha)-Mn(,2)O(,3) and Mn(,3)O(,4) spectra are nearly identical; their structures are the same, but the average oxidation states are different. We find the bond length strongly affects the edge position and the intensity of the 3d absorption in tetrahedrally coordinated transition metals. Other new results are the first shell EXAFS amplitude in MnO shows an anomalous energy dependence, which apparently cannot be explained by current theory. A new

Solvation structure of the halides from x-ray absorption spectroscopy

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

Antalek, Matthew; Hedman, Britt; Sarangi, Ritimukta, E-mail: ritis@slac.stanford.edu

2016-07-28

Three-dimensional models for the aqueous solvation structures of chloride, bromide, and iodide are reported. K-edge extended X-ray absorption fine structure (EXAFS) and Minuit X-ray absorption near edge (MXAN) analyses found well-defined single shell solvation spheres for bromide and iodide. However, dissolved chloride proved structurally distinct, with two solvation shells needed to explain its strikingly different X-ray absorption near edge structure (XANES) spectrum. Final solvation models were as follows: iodide, 8 water molecules at 3.60 ± 0.13 Å and bromide, 8 water molecules at 3.40 ± 0.14 Å, while chloride solvation included 7 water molecules at 3.15 ± 0.10 Å, andmore » a second shell of 7 water molecules at 4.14 ± 0.30 Å. Each of the three derived solvation shells is approximately uniformly disposed about the halides, with no global asymmetry. Time-dependent density functional theory calculations simulating the chloride XANES spectra following from alternative solvation spheres revealed surprising sensitivity of the electronic state to 6-, 7-, or 8-coordination, implying a strongly bounded phase space for the correct structure during an MXAN fit. MXAN analysis further showed that the asymmetric solvation predicted from molecular dynamics simulations using halide polarization can play no significant part in bulk solvation. Classical molecular dynamics used to explore chloride solvation found a 7-water solvation shell at 3.12 (−0.04/+0.3) Å, supporting the experimental result. These experiments provide the first fully three-dimensional structures presenting to atomic resolution the aqueous solvation spheres of the larger halide ions.« less

X-ray absorption fine structure and x-ray diffraction studies of crystallographic grains in nanocrystalline FePd:Cu thin films

NASA Astrophysics Data System (ADS)

Krupinski, M.; Perzanowski, M.; Polit, A.; Zabila, Y.; Zarzycki, A.; Dobrowolska, A.; Marszalek, M.

2011-03-01

FePd alloys have recently attracted considerable attention as candidates for ultrahigh density magnetic storage media. In this paper we investigate FePd thin alloy film with a copper admixture composed of nanometer-sized grains. [Fe(0.9 nm)/Pd(1.1 nm)/Cu(d nm)]×5 multilayers were prepared by thermal deposition at room temperature in UHV conditions on Si(100) substrates covered by 100 nm SiO2. The thickness of the copper layer has been changed from 0 to 0.4 nm. After deposition, the multilayers were rapidly annealed at 600 °C in a nitrogen atmosphere, which resulted in the creation of the FePd:Cu alloy. The structure of alloy films obtained this way was determined by x-ray diffraction (XRD), glancing angle x-ray diffraction, and x-ray absorption fine structure (EXAFS). The measurements clearly showed that the L10 FePd:Cu nanocrystalline phase has been formed during the annealing process for all investigated copper compositions. This paper concentrates on the crystallographic grain features of FePd:Cu alloys and illustrates that the EXAFS technique, supported by XRD measurements, can help to extend the information about grain size and grain shape of poorly crystallized materials. We show that, using an appropriate model of the FePd:Cu grains, the comparison of EXAFS and XRD results gives a reasonable agreement.

Near-edge X-ray absorption spectra for metallic Cu and Mn

NASA Astrophysics Data System (ADS)

Greaves, G. N.; Durham, P. J.; Diakun, G.; Quinn, P.

1981-11-01

The measurement of X-ray absorption fine structure of metals- both in the extended region (EXAFS) as well as in the near edge region (XANES)-has been widely discussed (see refs 1-6 for Cu and refs 7-9 for Mn). The recent availability of intense X-ray fluxes from storage rings has usually been exploited for EXAFS leaving the XANES often with poorer resolution than earlier work performed on conventional sources (for example, compare the near edge structure for copper in ref. 1 with refs 3 or 6). In addition, whilst the theory and analysis of EXAFS is relatively well-established2,10, a theory for the strong scattering regime near to the absorption edge has only recently been developed11. We report here the first high resolution XANES spectra for Cu and Mn which were performed at the SRS storage ring at Daresbury. Although both metals have close-packed structures consisting of atoms of similar size their local atomic structure is different in detail. Significant differences are found in their respective XANES reflecting the senstivity of this region of the X-ray absorption fine structure to the local atomic structure. Spectra for the two metals have been analysed using the new multiple scattering formalism. This is a real space calculation and unlike a conventional band structure approach it does not require structural periodicity but works from the local arrangement of atoms.

X-Ray Absorption Near Edge Structure And Extended X-Ray Absorption Fine Structure Analysis of Standards And Biological Samples Containing Mixed Oxidation States of Chromium(III) And Chromium(VI)

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

Parsons, J.G.; Dokken, K.; Peralta-Videa, J.R.

For the first time a method has been developed for the extended X-ray absorption fine structure (EXAFS) data analyses of biological samples containing multiple oxidation states of chromium. In this study, the first shell coordination and interatomic distances based on the data analysis of known standards of potassium chromate (Cr(VI)) and chromium nitrate hexahydrate (Cr(III)) were investigated. The standards examined were mixtures of the following molar ratios of Cr(VI):Cr(III), 0:1, 0.25:0.75, 0.5:0.5, 0.75:0.25, and 1:0. It was determined from the calibration data that the fitting error associated with linear combination X-ray absorption near edge structure (LC-XANES) fittings was approximately {+-}10%more » of the total fitting. The peak height of the Cr(VI) pre-edge feature after normalization of the X-ray absorption (XAS) spectra was used to prepare a calibration curve. The EXAFS fittings of the standards were also investigated and fittings to lechuguilla biomass samples laden with different ratios of Cr(III) and Cr(VI) were performed as well. An excellent agreement between the XANES data and the data presented in the EXAFS spectra was observed. The EXFAS data also presented mean coordination numbers directly related to the ratios of the different chromium oxidation states in the sample. The chromium oxygen interactions had two different bond lengths at approximately 1.68 and 1.98 {angstrom} for the Cr(VI) and Cr(III) in the sample, respectively.« less

X-ray absorption studies of chlorine valence and local environments in borosilicate waste glasses

NASA Astrophysics Data System (ADS)

McKeown, David A.; Gan, Hao; Pegg, Ian L.; Stolte, W. C.; Demchenko, I. N.

2011-01-01

Chlorine (Cl) is a constituent of certain types of nuclear wastes and its presence can affect the physical and chemical properties of silicate melts and glasses developed for the immobilization of such wastes. Cl K-edge X-ray absorption spectra (XAS) were collected and analyzed to characterize the unknown Cl environments in borosilicate waste glass formulations, ranging in Cl-content from 0.23 to 0.94 wt.%. Both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data for the glasses show trends dependent on calcium (Ca) content. Near-edge data for the Ca-rich glasses are most similar to the Cl XANES of CaCl 2, where Cl - is coordinated to three Ca atoms, while the XANES for the Ca-poor glasses are more similar to the mineral davyne, where Cl is most commonly coordinated to two Ca in one site, as well as Cl and oxygen nearest-neighbors in other sites. With increasing Ca content in the glass, Cl XANES for the glasses approach that for CaCl 2, indicating more Ca nearest-neighbors around Cl. Reliable structural information obtained from the EXAFS data for the glasses is limited, however, to Cl sbnd Cl, Cl sbnd O, and Cl sbnd Na distances; Cl sbnd Ca contributions could not be fit to the glass data, due to the narrow k-space range available for analysis. Structural models that best fit the glass EXAFS data include Cl sbnd Cl, Cl sbnd O, and Cl sbnd Na correlations, where Cl sbnd O and Cl sbnd Na distances decrease by approximately 0.16 Å as glass Ca content increases. XAS for the glasses indicates Cl - is found in multiple sites where most Cl-sites have Ca neighbors, with oxygen, and possibly, Na second-nearest neighbors. EXAFS analyses suggest that Cl sbnd Cl environments may also exist in the glasses in minor amounts. These results are generally consistent with earlier findings for silicate glasses, where Cl - was associated with Ca 2+ and Na + in network modifier sites.

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.

Complex X-ray Absorption and the Fe K(alpha) Profile in NGC 3516

NASA Technical Reports Server (NTRS)

Turner, T. J.; Kraemer, S. B.; George, I. M.; Reeves, J. N.; Botorff, M. C.

2004-01-01

We present data from simultaneous Chandra, XMM-Newton and BeppoSAX observations of the Seyfert 1 galaxy NGC 3516, taken during 2001 April and November. We have investigated the nature of the very flat observed X-ray spectrum. Chandra grating data show the presence of X-ray absorption lines, revealing two distinct components of the absorbing gas, one which is consistent with our previous model of the UV/X-ray absorber while the other, which is outflowing at a velocity of approximately 1100 kilometers per second, has a larger column density and is much more highly ionized. The broad-band spectral characteristics of the X-ray continuum observed with XMM during 2001 April, reveal the presence of a third layer of absorption consisting of a very large column (approximately 2.5 x 10(exp 23) per square centimeter) of highly ionized gas with a covering fraction approximately 50%. This low covering fraction suggests that the absorber lies within a few 1t-days of the X-ray source and/or is filamentary in structure. Interestingly, these absorbers are not in thermal equilibrium with one another. The two new components are too highly ionized to be radiatively accelerated, which we suggest is evidence for a hydromagnetic origin for the outflow. Applying our model to the November dataset, we can account for the spectral variability primarily by a drop in the ionization states of the absorbers, as expected by the change in the continuum flux. When this complex absorption is accounted for we find the underlying continuum to be typical of Seyfert 1 galaxies. The spectral curvature attributed to the high column absorber, in turn, reduces estimates of the flux and extent of any broad Fe emission line from the accretion disk.

Two-photon absorption of soft X-ray free electron laser radiation by graphite near the carbon K-absorption edge

NASA Astrophysics Data System (ADS)

Lam, Royce K.; Raj, Sumana L.; Pascal, Tod A.; Pemmaraju, C. D.; Foglia, Laura; Simoncig, Alberto; Fabris, Nicola; Miotti, Paolo; Hull, Christopher J.; Rizzuto, Anthony M.; Smith, Jacob W.; Mincigrucci, Riccardo; Masciovecchio, Claudio; Gessini, Alessandro; De Ninno, Giovanni; Diviacco, Bruno; Roussel, Eleonore; Spampinati, Simone; Penco, Giuseppe; Di Mitri, Simone; Trovò, Mauro; Danailov, Miltcho B.; Christensen, Steven T.; Sokaras, Dimosthenis; Weng, Tsu-Chien; Coreno, Marcello; Poletto, Luca; Drisdell, Walter S.; Prendergast, David; Giannessi, Luca; Principi, Emiliano; Nordlund, Dennis; Saykally, Richard J.; Schwartz, Craig P.

2018-07-01

We have examined the transmission of soft X-ray pulses from the FERMI free electron laser through carbon films of varying thickness, quantifying nonlinear effects of pulses above and below the carbon K-edge. At typical of soft X-ray free electron laser intensities, pulses exhibit linear absorption at photon energies above and below the K-edge, ∼308 and ∼260 eV, respectively; whereas two-photon absorption becomes significant slightly below the K-edge, ∼284.2 eV. The measured two-photon absorption cross section at 284.18 eV (∼6 × 10-48 cm4 s) is 7 orders of magnitude above what is expected from a simple theory based on hydrogen-like atoms - a result of resonance effects.

Bandpass x-ray diode and x-ray multiplier detector

DOEpatents

Wang, C.L.

1982-09-27

An absorption-edge of an x-ray absorption filter and a quantum jump of a photocathode determine the bandpass characteristics of an x-ray diode detector. An anode, which collects the photoelectrons emitted by the photocathode, has enhanced amplification provided by photoelectron-multiplying means which include dynodes or a microchannel-plate electron-multiplier. Suppression of undesired high frequency response for a bandpass x-ray diode is provided by subtracting a signal representative of energies above the passband from a signal representative of the overall response of the bandpass diode.

Randic and Schultz molecular topological indices and their correlation with some X-ray absorption parameters

NASA Astrophysics Data System (ADS)

Khatri, Sunil; Kekre, Pravin A.; Mishra, Ashutosh

2016-10-01

The properties of a molecular system are affected by the topology of molecule. Therefore many studies have been made where the various physic-chemical properties are correlated with the topological indices. These studies have shown a very good correlation demonstrating the utility of the graph theoretical approach. It is, therefore, very natural to expect that the various physical properties obtained by the X-ray absorption spectra may also show correlation with the topological indices. Some complexes were used to establish correlation between topological indices and some X-ray absorption parameters like chemical shift. The chemical shift is on the higher energy side of the metal edge in these complexes. The result obtained in these studies shows that the topological indices of organic molecule acting as a legands can be used for estimating edge shift theoretically.

In Situ Density Measurement of Basaltic Melts at High Pressure by X-ray Absorption Method

NASA Astrophysics Data System (ADS)

Ando, R.; Ohtani, E.; Suzuki, A.; Urakawa, S.; Katayama, Y.

2004-12-01

Density of silicate melt at high pressure is one of the most important properties to understand magma migration in the planetary interior. However, because of experimental difficulties, the density of magma at high pressure is poorly known. Katayama et al. (1996) recently developed a new in situ density measurement method for metallic melts, based on the density dependency of X-ray absorption in the sample. In this study, we tried to measure the density of basaltic melt by this absorption method. When X-ray is transmitted to the sample, the intensity of the transmitted X-ray beam (I) is expressed as follows; I=I0exp(-μ ρ t), where I0 is the intensity of incident X-ray beam, μ is the mass absorption coefficient, ρ is the density of the sample, and t is the thickness of the sample. If t and μ are known, we can determine the density of the sample by measuring I and I0. This is the principle of the absorption method for density measurement. In this study, in order to determine t, we used a single crystalline diamond cylinder as a sample capsule, diamond is less compressive and less deformable so that even at high pressure t (thickness of the sample at the point x) is expressed as follows; t = 2*(R02-x2)1/2, R0 is the inner radius of cylinder at the ambient condition, and x is distance from a center of the capsule. And diamond also shows less absorption so that this make it possible to measure the density of silicate melt with smaller absorption coefficient than metallic melts. In order to know the μ of the sample, we measured both densities (ρ ) and absorptions (I/I0) for some glasses and crystals with same composition of the sample at the ambient condition, and calculated as fallows; μ =ln(I/I0)/ρ . Experiments were made at the beamline (BL22XU) of SPring-8. For generation of high pressure and high temperature, we used DIA-type cubic anvil apparatus (SMAP180) there. We used tungsten carbide anvils with the edge-length of 6 mm. The energy of monochromatic X-ray

Emission and absorption x-ray edges of Li

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

Callcott, T A; Arakawa, E T; Ederer, D L

1977-01-01

Measurements of the K X-ray absorption and emission edges of Li are reported. They were made with the same spectrometer at the NBS storage ring and serve to establish a 0.1 eV separation between the edges with no possibility of instrument calibration error. These results are compared with recent theories of Almbladh and Mahan describing the effects of incomplete phonon relaxation about the core hole. It is concluded that these theories give a satisfactory explanation of the data.

X-ray absorption spectroscopy of aluminum z-pinch plasma with tungsten backlighter planar wire array source.

PubMed

Osborne, G C; Kantsyrev, V L; Safronova, A S; Esaulov, A A; Weller, M E; Shrestha, I; Shlyaptseva, V V; Ouart, N D

2012-10-01

Absorption features from K-shell aluminum z-pinch plasmas have recently been studied on Zebra, the 1.7 MA pulse power generator at the Nevada Terawatt Facility. In particular, tungsten plasma has been used as a semi-backlighter source in the generation of aluminum K-shell absorption spectra by placing a single Al wire at or near the end of a single planar W array. All spectroscopic experimental results were recorded using a time-integrated, spatially resolved convex potassium hydrogen phthalate (KAP) crystal spectrometer. Other diagnostics used to study these plasmas included x-ray detectors, optical imaging, laser shadowgraphy, and time-gated and time-integrated x-ray pinhole imagers. Through comparisons with previous publications, Al K-shell absorption lines are shown to be from much lower electron temperature (∼10-40 eV) plasmas than emission spectra (∼350-500 eV).

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

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

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.

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.

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.

Observing heme doming in myoglobin with femtosecond X-ray absorption spectroscopy

DOE PAGES

Levantino, M.; Lemke, H. T.; Schirò, G.; ...

2015-07-01

We report time-resolved X-ray absorption measurements after photolysis of carbonmonoxy myoglobin performed at the LCLS X-ray free electron laser with nearly 100 fs (FWHM) time resolution. Data at the Fe K-edge reveal that the photoinduced structural changes at the heme occur in two steps, with a faster (~70 fs) relaxation preceding a slower (~400 fs) one. We tentatively attribute the first relaxation to a structural rearrangement induced by photolysis involving essentially only the heme chromophore and the second relaxation to a residual Fe motion out of the heme plane that is coupled to the displacement of myoglobin F-helix.

Atomic-scale distortion of optically activated Sm dopants identified with site-selective X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Ishii, Masashi; Crowe, Iain F.; Halsall, Matthew P.; Hamilton, Bruce; Hu, Yongfeng; Sham, Tsun-Kong; Harako, Susumu; Zhao, Xin-Wei; Komuro, Shuji

2013-10-01

The local structure of luminescent Sm dopants was investigated using an X-ray absorption fine-structure technique with X-ray-excited optical luminescence. Because this technique evaluates X-ray absorption from luminescence, only optically active sites are analyzed. The Sm L3 near-edge spectrum contains split 5d states and a shake-up transition that are specific to luminescent Sm. Theoretical calculations using cluster models identified an atomic-scale distortion that can reproduce the split 5d states. The model with C4v local symmetry and compressive bond length of Sm-O of a six-fold oxygen (SmO6) cluster is most consistent with the experimental results.

UV-Visible Absorption Spectroscopy Enhanced X-ray Crystallography at Synchrotron and X-ray Free Electron Laser Sources.

PubMed

Cohen, Aina E; Doukov, Tzanko; Soltis, Michael S

2016-01-01

This review describes the use of single crystal UV-Visible Absorption micro-Spectrophotometry (UV-Vis AS) to enhance the design and execution of X-ray crystallography experiments for structural investigations of reaction intermediates of redox active and photosensitive proteins. Considerations for UV-Vis AS measurements at the synchrotron and associated instrumentation are described. UV-Vis AS is useful to verify the intermediate state of an enzyme and to monitor the progression of reactions within crystals. Radiation induced redox changes within protein crystals may be monitored to devise effective diffraction data collection strategies. An overview of the specific effects of radiation damage on macromolecular crystals is presented along with data collection strategies that minimize these effects by combining data from multiple crystals used at the synchrotron and with the X-ray free electron laser.

Transport Measurements and Synchrotron-Based X-Ray Absorption Spectroscopy of Iron Silicon Germanide Grown by Molecular Beam Epitaxy

NASA Astrophysics Data System (ADS)

Elmarhoumi, Nader; Cottier, Ryan; Merchan, Greg; Roy, Amitava; Lohn, Chris; Geisler, Heike; Ventrice, Carl, Jr.; Golding, Terry

2009-03-01

Some of the iron-based metal silicide and germanide phases have been predicted to be direct band gap semiconductors. Therefore, they show promise for use as optoelectronic materials. We have used synchrotron-based x-ray absorption spectroscopy to study the structure of iron silicon germanide films grown by molecular beam epitaxy. A series of Fe(Si1-xGex)2 thin films (2000 -- 8000å) with a nominal Ge concentration of up to x = 0.04 have been grown. X-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS) measurements have been performed on the films. The nearest neighbor co-ordination corresponding to the β-FeSi2 phase of iron silicide provides the best fit with the EXAFS data. Temperature dependent (20 < T < 350 K) magneto transport measurements were done on the Fe(Si1-xGex)2 thin films via Van Der Paw (VDP) Hall configuration using a 0.5-1T magnetic field and a current of 10-200 μA through indium ohmic contacts, the Hall coefficient was calculated. Results suggest semiconducting behavior of the films which is consistent with the EXAFS results.

First-Principles Predictions of Near-Edge X-ray Absorption Fine Structure Spectra of Semiconducting Polymers

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

Su, Gregory M.; Patel, Shrayesh N.; Pemmaraju, C. D.

The electronic structure and molecular orientation of semiconducting polymers in thin films determine their ability to transport charge. Methods based on near-edge X-ray absorption fine structure (NEXAFS) spectroscopy can be used to probe both the electronic structure and microstructure of semiconducting polymers in both crystalline and amorphous films. However, it can be challenging to interpret NEXAFS spectra on the basis of experimental data alone, and accurate, predictive calculations are needed to complement experiments. Here, we show that first-principles density functional theory (DFT) can be used to model NEXAFS spectra of semiconducting polymers and to identify the nature of transitions inmore » complicated NEXAFS spectra. Core-level X-ray absorption spectra of a set of semiconducting polymers were calculated using the excited electron and core-hole (XCH) approach based on constrained-occupancy DFT. A comparison of calculations on model oligomers and periodic structures with experimental data revealed the requirements for accurate prediction of NEXAFS spectra of both conjugated homopolymers and donor–acceptor polymers. The NEXAFS spectra predicted by the XCH approach were applied to study molecular orientation in donor–acceptor polymers using experimental spectra and revealed the complexity of using carbon edge spectra in systems with large monomeric units. The XCH approach has sufficient accuracy in predicting experimental NEXAFS spectra of polymers that it should be considered for design and analysis of measurements using soft X-ray techniques, such as resonant soft X-ray scattering and scanning transmission X-ray microscopy.« less

X-Ray Absorption Toward the Einstein Ring Source PKS 1830-211

NASA Technical Reports Server (NTRS)

Mathur, Smita; Nair, Sunita

1997-01-01

PKS 1830-211 is an unusually radio-loud gravitationally lensed quasar. In the radio spectrum, the system appears as two compact, dominant features surrounded by relatively extended radio emission that forms an Einstein ring. As the line of sight to it passes close to our Galactic center, PKS 1830-211 has not been detected in wave bands other than the radio and X-ray so far. Here we present X-ray data of PKS 1830-211 observed with ROSAT Position Sensitive Proportional Counter. The X-ray spectrum shows that absorption in excess of the Galactic contribution is highly likely, which at the redshift of the lensing galaxy (z(sub t)=0.886) corresponds to N(sub H)=3.5((sup 0.6)(sub -0.5))x10(exp 22) atoms sq cm. The effective optical extinction is large, A(sub V)(observed) is greater than or approximately 5.8. When corrected for this additional extinction, the two-point optical to X-ray slope alpha(sub ox) of PKS 1830-211 lies just within the observed range of quasars. It is argued here that both compact images must be covered by the X-ray absorber(s) that we infer to be the lensing galaxy (galaxies). The dust-to-gas ratio along the line of sight within the lensing galaxy is likely to be somewhat larger than for our Galaxy.

Insights into the mechanism of X-ray-induced disulfide-bond cleavage in lysozyme crystals based on EPR, optical absorption and X-ray diffraction studies.

PubMed

Sutton, Kristin A; Black, Paul J; Mercer, Kermit R; Garman, Elspeth F; Owen, Robin L; Snell, Edward H; Bernhard, William A

2013-12-01

Electron paramagnetic resonance (EPR) and online UV-visible absorption microspectrophotometry with X-ray crystallography have been used in a complementary manner to follow X-ray-induced disulfide-bond cleavage. Online UV-visible spectroscopy showed that upon X-irradiation, disulfide radicalization appeared to saturate at an absorbed dose of approximately 0.5-0.8 MGy, in contrast to the saturating dose of ∼0.2 MGy observed using EPR at much lower dose rates. The observations suggest that a multi-track model involving product formation owing to the interaction of two separate tracks is a valid model for radiation damage in protein crystals. The saturation levels are remarkably consistent given the widely different experimental parameters and the range of total absorbed doses studied. The results indicate that even at the lowest doses used for structural investigations disulfide bonds are already radicalized. Multi-track considerations offer the first step in a comprehensive model of radiation damage that could potentially lead to a combined computational and experimental approach to identifying when damage is likely to be present, to quantitate it and to provide the ability to recover the native unperturbed structure.

Insights into the mechanism of X-ray-induced disulfide-bond cleavage in lysozyme crystals based on EPR, optical absorption and X-ray diffraction studies

PubMed Central

Sutton, Kristin A.; Black, Paul J.; Mercer, Kermit R.; Garman, Elspeth F.; Owen, Robin L.; Snell, Edward H.; Bernhard, William A.

2013-01-01

Electron paramagnetic resonance (EPR) and online UV–visible absorption microspectrophotometry with X-ray crystallography have been used in a complementary manner to follow X-ray-induced disulfide-bond cleavage. Online UV–visible spectroscopy showed that upon X-irradiation, disulfide radicalization appeared to saturate at an absorbed dose of approximately 0.5–0.8 MGy, in contrast to the saturating dose of ∼0.2 MGy observed using EPR at much lower dose rates. The observations suggest that a multi-track model involving product formation owing to the interaction of two separate tracks is a valid model for radiation damage in protein crystals. The saturation levels are remarkably consistent given the widely different experimental parameters and the range of total absorbed doses studied. The results indicate that even at the lowest doses used for structural investigations disulfide bonds are already radicalized. Multi-track considerations offer the first step in a comprehensive model of radiation damage that could potentially lead to a combined computational and experimental approach to identifying when damage is likely to be present, to quantitate it and to provide the ability to recover the native unperturbed structure. PMID:24311579

An x-ray absorption study of the iron site in bacterial photosynthetic reaction centers.

PubMed Central

Bunker, G; Stern, E A; Blankenship, R E; Parson, W W

1982-01-01

Measurements were made of the extended x-ray absorption fine structure (EXAFS) of the iron site in photosynthetic reaction centers from the bacterium Rhodopseudomonas sphaeroides. Forms with two quinones, two quinones with added o-phenanthroline, and one quinone were studied. Only the two forms containing two quinones maintained their integrity and were analyzed. The spectra show directly that the added o-phenanthroline does not chelate the iron atom. Further analysis indicates that the iron is octahedrally coordinated by nitrogen and/or oxygen atoms located at various distances, with the average value of about 2.14 A. The analysis suggests that most of the ligands are nitrogens and that three of the nitrogen ligands belong to histidine rings. This interpretation accounts for several unusual features of the EXAFS spectrum. We speculate that the quinones are bound to the histidine rings in some manner. Qualitative features of the absorption edge spectra also are discussed and are related to the Fe-ligand distance. PMID:6977382

Automated generation and ensemble-learned matching of X-ray absorption spectra

NASA Astrophysics Data System (ADS)

Zheng, Chen; Mathew, Kiran; Chen, Chi; Chen, Yiming; Tang, Hanmei; Dozier, Alan; Kas, Joshua J.; Vila, Fernando D.; Rehr, John J.; Piper, Louis F. J.; Persson, Kristin A.; Ong, Shyue Ping

2018-12-01

X-ray absorption spectroscopy (XAS) is a widely used materials characterization technique to determine oxidation states, coordination environment, and other local atomic structure information. Analysis of XAS relies on comparison of measured spectra to reliable reference spectra. However, existing databases of XAS spectra are highly limited both in terms of the number of reference spectra available as well as the breadth of chemistry coverage. In this work, we report the development of XASdb, a large database of computed reference XAS, and an Ensemble-Learned Spectra IdEntification (ELSIE) algorithm for the matching of spectra. XASdb currently hosts more than 800,000 K-edge X-ray absorption near-edge spectra (XANES) for over 40,000 materials from the open-science Materials Project database. We discuss a high-throughput automation framework for FEFF calculations, built on robust, rigorously benchmarked parameters. FEFF is a computer program uses a real-space Green's function approach to calculate X-ray absorption spectra. We will demonstrate that the ELSIE algorithm, which combines 33 weak "learners" comprising a set of preprocessing steps and a similarity metric, can achieve up to 84.2% accuracy in identifying the correct oxidation state and coordination environment of a test set of 19 K-edge XANES spectra encompassing a diverse range of chemistries and crystal structures. The XASdb with the ELSIE algorithm has been integrated into a web application in the Materials Project, providing an important new public resource for the analysis of XAS to all materials researchers. Finally, the ELSIE algorithm itself has been made available as part of veidt, an open source machine-learning library for materials science.

Quantitative X-ray fluorescence computed tomography for low-Z samples using an iterative absorption correction algorithm

NASA Astrophysics Data System (ADS)

Huang, Rong; Limburg, Karin; Rohtla, Mehis

2017-05-01

X-ray fluorescence computed tomography is often used to measure trace element distributions within low-Z samples, using algorithms capable of X-ray absorption correction when sample self-absorption is not negligible. Its reconstruction is more complicated compared to transmission tomography, and therefore not widely used. We describe in this paper a very practical iterative method that uses widely available transmission tomography reconstruction software for fluorescence tomography. With this method, sample self-absorption can be corrected not only for the absorption within the measured layer but also for the absorption by material beyond that layer. By combining tomography with analysis for scanning X-ray fluorescence microscopy, absolute concentrations of trace elements can be obtained. By using widely shared software, we not only minimized the coding, took advantage of computing efficiency of fast Fourier transform in transmission tomography software, but also thereby accessed well-developed data processing tools coming with well-known and reliable software packages. The convergence of the iterations was also carefully studied for fluorescence of different attenuation lengths. As an example, fish eye lenses could provide valuable information about fish life-history and endured environmental conditions. Given the lens's spherical shape and sometimes the short distance from sample to detector for detecting low concentration trace elements, its tomography data are affected by absorption related to material beyond the measured layer but can be reconstructed well with our method. Fish eye lens tomography results are compared with sliced lens 2D fluorescence mapping with good agreement, and with tomography providing better spatial resolution.

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.

Bond-length relaxation in crystalline Si1-xGex alloys: An extended x-ray-absorption fine-structure study

NASA Astrophysics Data System (ADS)

Kajiyama, Hiroshi; Muramatsu, Shin-Ichi; Shimada, Toshikazu; Nishino, Yoichi

1992-06-01

Extended x-ray-absorption fine-structure spectra for crystalline Si1-xGex alloys, measured at the K edge of Ge at room temperature, are analyzed with a curve-fitting method based on the spherical-wave approximation. The Ge-Ge and Ge-Si bond lengths, coordination numbers of Ge and Si atoms around a Ge atom, and Debye-Waller factors of Ge and Si atoms are obtained. It is shown that Ge-Ge and Ge-Si bonds relax completely, for all Ge concentrations of their study, while the lattice constant varies monotonically, following Vegard's law. As noted by Bragg and later by Pauling and Huggins, the Ge-Ge and Ge-Si bond lengths are close to the sum of their constituent-element atomic radii: nearly 2.45 Å for Ge-Ge bonds and 2.40 Å for Ge-Si bonds. A study on the coordination around a Ge atom in the alloys revealed that Ge and Si atoms mix randomly throughout the compositional range studied.

Characterization of CuHal-intercalated carbon nanotubes with x-ray absorption spectroscopy combined with x-ray photoelectron and resonant photoemission spectroscopies

NASA Astrophysics Data System (ADS)

Brzhezinskaya, M.; Generalov, A.; Vinogdradov, A.; Eliseev, A.

2013-04-01

Encapsulated single-walled carbon nanotubes (SWCNTs) with inner channels filled by different compounds present the new class of composite materials. Such CNTs give opportunity to form 1D nanocrystals as well as quantum nanowires with new physical and chemical properties inside the tubes. The present study is aimed to characterize the possible chemical interaction between CuHal (Hal=I, Cl, Br) and SWCNTs in CuHal@SWCNTs and electronic structure of the latter using high-resolution near edge X-ray absorption fine structure (NEXAFS) spectroscopy combined with high-resolution X-ray photoelectron spectroscopy and resonant photoemission spectroscopy. The present study has shown that there is a chemical interaction between the filler and π-electron subsystem of CNTs which is accompanied by changes of the atomic and electronic structure of the filler during the encapsulating it inside CNTs.

An X-ray absorption spectroscopy study of the inversion degree in zinc ferrite nanocrystals dispersed on a highly porous silica aerogel matrix.

PubMed

Carta, D; Marras, C; Loche, D; Mountjoy, G; Ahmed, S I; Corrias, A

2013-02-07

The structural properties of zinc ferrite nanoparticles with spinel structure dispersed in a highly porous SiO(2) aerogel matrix were compared with a bulk zinc ferrite sample. In particular, the details of the cation distribution between the octahedral (B) and tetrahedral (A) sites of the spinel structure were determined using X-ray absorption spectroscopy. The analysis of both the X-ray absorption near edge structure and the extended X-ray absorption fine structure indicates that the degree of inversion of the zinc ferrite spinel structures varies with particle size. In particular, in the bulk microcrystalline sample, Zn(2+) ions are at the tetrahedral sites and trivalent Fe(3+) ions occupy octahedral sites (normal spinel). When particle size decreases, Zn(2+) ions are transferred to octahedral sites and the degree of inversion is found to increase as the nanoparticle size decreases. This is the first time that a variation of the degree of inversion with particle size is observed in ferrite nanoparticles grown within an aerogel matrix.

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.

The 16th International Conference on X-ray Absorption Fine Structure (XAFS16)

NASA Astrophysics Data System (ADS)

Grunwaldt, J.-D.; Hagelstein, M.; Rothe, J.

2016-05-01

This preface of the proceedings volume of the 16th International Conference on X- ray Absorption Fine Structure (XAFS16) gives a glance on the five days of cutting-edge X-ray science which were held in Karlsruhe, Germany, August 23 - 28, 2015. In addition, several satellite meetings took place in Hamburg, Berlin and Stuttgart, a Sino-German workshop, three data analysis tutorials as well as special symposia on industrial catalysis and XFELs were held at the conference venue.

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.

Are There Intrinsically X-Ray Quiet Quasars

NASA Technical Reports Server (NTRS)

Gallagher, S. C.; Brandt, W. N.; Laor, A.; Elvis, Martin; Mathur, S.; Wills, Beverly J.; Iyomoto, N.; White, Nicholas (Technical Monitor)

2000-01-01

Recent ROSAT studies have identified a significant population of Active Galactic Nuclei (AGN) that are notably faint in soft X-rays relative to their optical fluxes. Are these AGN intrinsically X-ray weak or are they just highly absorbed? Brandt, Laor & Wills have systematically examined the optical and UV spectral properties of a well-defined sample of these soft X-ray weak (SXW) AGN drawn from the Boroson & Green sample of all the Palomar Green AGN 00 with z < 0.5. We present ASCA observations of three of these SXW AGN: PG 1011-040, PG 1535+547 (Mrk 486), and PG 2112+059. In general, our ASCA observations support the intrinsic absorption scenario for explaining soft X-ray weakness; both PG 1535+547 and PG 2112+059 show significant column densities (NH is approximately 10(exp 22) - 10(exp 23)/sq cm) of absorbing gas. Interestingly, PG 1011-040 shows no spectral evidence for X-ray absorption. The weak X-ray emission may result from very strong absorption of a partially covered source, or this AGN may be intrinsically X-ray weak. PG 2112+059 is a Broad Absorption Line (BAL) QSO, and we find it to have the highest X-ray flux known of this class. It shows a typical power-law X-ray continuum above 3 keV; this is the first direct evidence that BAL QSOs indeed have normal X-ray continua underlying their intrinsic absorption. Finally, marked variability between the ROSAT and ASCA observations of PG 1535+547 and PG 2112+059 suggests that the soft X-ray weak designation may be transient, and multi-epoch 0.1-10.0 KeV X-ray observations are required to constrain variability of the absorber and continuum.

Microanalysis of iron oxidation state in iron oxides using X Ray Absorption Near Edge Structure (XANES)

NASA Technical Reports Server (NTRS)

Sutton, S. R.; Delaney, J.; Bajt, S.; Rivers, M. L.; Smith, J. V.

1993-01-01

An exploratory application of x ray absorption near edge structure (XANES) analysis using the synchrotron x ray microprobe was undertaken to obtain Fe XANES spectra on individual sub-millimeter grains in conventional polished sections. The experiments concentrated on determinations of Fe valence in a suite of iron oxide minerals for which independent estimates of the iron speciation could be made by electron microprobe analysis and x ray diffraction.

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.

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

Quasar Absorption Studies

NASA Technical Reports Server (NTRS)

Mushotzky, Richard (Technical Monitor); Elvis, Martin

2004-01-01

The aim of the proposal is to investigate the absorption properties of a sample of inter-mediate redshift quasars. The main goals of the project are: Measure the redshift and the column density of the X-ray absorbers; test the correlation between absorption and redshift suggested by ROSAT and ASCA data; constrain the absorber ionization status and metallicity; constrain the absorber dust content and composition through the comparison between the amount of X-ray absorption and optical dust extinction. Unanticipated low energy cut-offs where discovered in ROSAT spectra of quasars and confirmed by ASCA, BeppoSAX and Chandra. In most cases it was not possible to constrain adequately the redshift of the absorber from the X-ray data alone. Two possibilities remain open: a) absorption at the quasar redshift; and b) intervening absorption. The evidences in favour of intrinsic absorption are all indirect. Sensitive XMM observations can discriminate between these different scenarios. If the absorption is at the quasar redshift we can study whether the quasar environment evolves with the Cosmic time.

Cation distribution in NiZn-ferrite films via extended x-ray absorption fine structure

NASA Astrophysics Data System (ADS)

Harris, V. G.; Koon, N. C.; Williams, C. M.; Zhang, Q.; Abe, M.; Kirkland, J. P.

1996-04-01

We have applied extended x-ray absorption fine structure (EXAFS) spectroscopy to study the cation distribution in a series of spin-sprayed NiZn-ferrite films. A least-squares fitting of experimental EXAFS data with theoretical, multiple-scattering, EXAFS data allowed the quantitative determination of site distributions for all transition metal cations.

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.

The differential absorption hard x-ray spectrometer at the Z facility

DOE PAGES

Bell, Kate S.; Coverdale, Christine A.; Ampleford, David J.; ...

2017-08-03

The Differential Absorption Hard X-ray (DAHX) spectrometer is a diagnostic developed to measure time-resolved radiation between 60 keV and 2 MeV at the Z Facility. It consists of an array of 7 Si PIN diodes in a tungsten housing that provides collimation and coarse spectral resolution through differential filters. DAHX is a revitalization of the Hard X-Ray Spectrometer (HXRS) that was fielded on Z prior to refurbishment in 2006. DAHX has been tailored to the present radiation environment in Z to provide information on the power, spectral shape, and time profile of the hard emission by plasma radiation sources drivenmore » by the Z Machine.« less

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.

X-ray absorption and reflection as probes of the GaN conduction bands: Theory and experiments

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

Lambrecht, W.R.L.; Rashkeev, S.N.; Segall, B.

1997-04-01

X-ray absorption measurements are a well-known probe of the unoccupied states in a material. The same information can be obtained by using glancing angle X-ray reflectivity. In spite of several existing band structure calculations of the group III nitrides and previous optical studies in UV range, a direct probe of their conduction band densities of states is of interest. The authors performed a joint experimental and theoretical investigation using both of these experimental techniques for wurtzite GaN.

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.

X-ray absorption spectroscopy study of annealing process on Sr1-xLaxCuO2 electron-doped cuprate thin films

NASA Astrophysics Data System (ADS)

Galdi, A.; Orgiani, P.; Sacco, C.; Gobaut, B.; Torelli, P.; Aruta, C.; Brookes, N. B.; Minola, M.; Harter, J. W.; Shen, K. M.; Schlom, D. G.; Maritato, L.

2018-03-01

The superconducting properties of Sr1-xLaxCuO2 thin films are strongly affected by sample preparation procedures, including the annealing step, which are not always well controlled. We have studied the evolution of Cu L2,3 and O K edge x-ray absorption spectra (XAS) of Sr1-xLaxCuO2 thin films as a function of reducing annealing, both qualitatively and quantitatively. By using linearly polarized radiation, we are able to identify the signatures of the presence of apical oxygen in the as-grown sample and its gradual removal as a function of duration of 350 °C Ar annealing performed on the same sample. Even though the as-grown sample appears to be hole doped, we cannot identify the signature of the Zhang-Rice singlet in the O K XAS, and it is extremely unlikely that the interstitial excess oxygen can give rise to a superconducting or even a metallic ground state. XAS and x-ray linear dichroism analyses are, therefore, shown to be valuable tools to improving the control over the annealing process of electron doped superconductors.

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

The origin of luminescence from di[4-(4-diphenylaminophenyl)phenyl]sulfone (DAPSF), a blue light emitter: an X-ray excited optical luminescence (XEOL) and X-ray absorption near edge structure (XANES) study.

PubMed

Zhang, Duo; Zhang, Hui; Zhang, Xiaohong; Sham, Tsun-Kong; Hu, Yongfeng; Sun, Xuhui

2016-03-07

The electronic structure and optical properties of di[4-(4-diphenylaminophenyl)phenyl]sulfone (denoted as DAPSF), a highly efficient fluorophor, have been investigated using X-ray excited optical luminescence (XEOL) and X-ray absorption near edge structure (XANES) spectroscopy at excitation energies across the C, N, O K-edges and the sulfur K-edge. The results indicate that the blue luminescence is mainly related to the sulfur functional group.

Incorporation of Cadmium and Nickel into Ferrite Spinel Solid Solution: X-ray Diffraction and X-ray Absorption Fine Structure Analyses.

PubMed

Su, Minhua; Liao, Changzhong; Chan, Tingshan; Shih, Kaimin; Xiao, Tangfu; Chen, Diyun; Kong, Lingjun; Song, Gang

2018-01-16

The feasibility of incorporating Cd and Ni in hematite was studied by investigating the interaction mechanism for the formation of Cd x Ni 1-x Fe 2 O 4 solid solutions (CNFs) from CdO, NiO, and α-Fe 2 O 3 . X-ray diffraction results showed that the CNFs crystallized into spinel structures with increasing lattice parameters as the Cd content in the precursors was increased. Cd 2+ ions were found to occupy the tetrahedral sites, as evidenced by Rietveld refinement and extended X-ray absorption fine structure analyses. The incorporation of Cd and Ni into ferrite spinel solid solution strongly relied on the processing parameters. The incorporation of Cd and Ni into the CNFs was greater at high x values (0.7 < x ≤ 1.0) than at low x values (0.0 ≤ x ≤ 0.7). A feasible treatment technique based on the investigated mechanism of CNF formation was developed, involving thermal treatment of waste sludge containing Cd and Ni. Both of these metals in the waste sludge were successfully incorporated into a ferrite spinel solid solution, and the concentrations of leached Cd and Ni from this solid solution were substantially reduced, stabilizing at low levels. This research offers a highly promising approach for treating the Cd and Ni content frequently encountered in electronic waste and its treatment residues.

An X-ray absorption spectroscopic study of the metal site preference in Al1-xGaxFeO3

NASA Astrophysics Data System (ADS)

Walker, James D. S.; Grosvenor, Andrew P.

2013-01-01

Magnetoelectric materials have potential for being introduced into next generation technologies, especially memory devices. The AFeO3 (Pna21; A=Al, Ga) system has received attention to better understand the origins of magnetoelectric coupling. The magnetoelectric properties this system exhibits depend on the amount of anti-site disorder present, which is affected by the composition and the method of synthesis. In this study, Al1-xGaxFeO3 was synthesized by the ceramic method and studied by X-ray absorption spectroscopy. Al L2,3-, Ga K-, and Fe K-edge spectra were collected to examine how the average metal coordination number changes with composition. Examination of XANES spectra from Al1-xGaxFeO3 indicate that with increasing Ga content, Al increasingly occupies octahedral sites while Ga displays a preference for occupying the tetrahedral site. The Fe K-edge spectra indicate that more Fe is present in the tetrahedral site in AlFeO3 than in GaFeO3, implying more anti-site disorder is present in AlFeO3.

Low-temperature adsorption of H2S on Ni(001) studied by near-edge- and surface-extended-x-ray-absorption fine structure

NASA Astrophysics Data System (ADS)

McGrath, R.; MacDowell, A. A.; Hashizume, T.; Sette, F.; Citrin, P. H.

1989-11-01

The adsorption of H2S on Ni(001) has been studied with surface-extended x-ray-absorption fine structure and near-edge x-ray-absorption fine structure (NEXAFS) using the AT&T Bell Laboratories X15B beamline at the National Synchrotron Light Source. At 95 K and full saturation coverage, ~0.45 monolayer (ML) of S atoms in fourfold-hollow sites are produced, characteristic of room-temperature adsorption, accompanied by ~0.05 ML of oriented molecular H2S. Both these atomic and molecular chemisorbed species are buried under ~0.9 ML of disordered physisorbed H2S. No evidence for HS is found. Above 190 K the two molecular H2S phases desorb, leaving only dissociated S. These findings differ from previously reported interpretations of data obtained with high-resolution electron-energy-loss spectroscopy. They also exemplify the utility of NEXAFS for identifying and quantifying atomic and molecular surface species even when their difference involves only H and the two species coexist.

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

Experimental and theoretical comparison of the O K-edge nonresonant inelastic X-ray scattering and X-ray absorption spectra of NaReO4.

PubMed

Bradley, Joseph A; Yang, Ping; Batista, Enrique R; Boland, Kevin S; Burns, Carol J; Clark, David L; Conradson, Steven D; Kozimor, Stosh A; Martin, Richard L; Seidler, Gerald T; Scott, Brian L; Shuh, David K; Tyliszczak, Tolek; Wilkerson, Marianne P; Wolfsberg, Laura E

2010-10-06

Accurate X-ray absorption spectra (XAS) of first row atoms, e.g., O, are notoriously difficult to obtain due to the extreme sensitivity of the measurement to surface contamination, self-absorption, and saturation affects. Herein, we describe a comprehensive approach for determining reliable O K-edge XAS data for ReO(4)(1-) and provide methodology for obtaining trustworthy and quantitative data on nonconducting molecular systems, even in the presence of surface contamination. This involves comparing spectra measured by nonresonant inelastic X-ray scattering (NRIXS), a bulk-sensitive technique that is not prone to X-ray self-absorption and provides exact peak intensities, with XAS spectra obtained by three different detection modes, namely total electron yield (TEY), fluorescence yield (FY), and scanning transmission X-ray microscopy (STXM). For ReO(4)(1-), TEY measurements were heavily influenced by surface contamination, while the FY and STXM data agree well with the bulk NRIXS analysis. These spectra all showed two intense pre-edge features indicative of the covalent interaction between the Re 5d and O 2p orbitals. Density functional theory calculations were used to assign these two peaks as O 1s excitations to the e and t(2) molecular orbitals that result from Re 5d and O 2p covalent mixing in T(d) symmetry. Electronic structure calculations were used to determine the amount of O 2p character (%) in these molecular orbitals. Time dependent-density functional theory (TD-DFT) was also used to calculate the energies and intensities of the pre-edge transitions. Overall, under these experimental conditions, this analysis suggests that NRIXS, STXM, and FY operate cooperatively, providing a sound basis for validation of bulk-like excitation spectra and, in combination with electronic structure calculations, suggest that NaReO(4) may serve as a well-defined O K-edge energy and intensity standard for future O K-edge XAS studies.

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.

Enhancement of X-ray dose absorption for medical applications

NASA Astrophysics Data System (ADS)

Lim, Sara; Nahar, S.; Pradhan, A.; Barth, R.

2013-05-01

A promising technique for cancer treatment is radiation therapy with high-Z (HZ) nanomoities acting as radio-sensitizers attached to tumor cells and irradiated with X-rays. But the efficacy of radiosenstization is highly energy dependent. We study the physical effects in using platinum (Pt) as the radio-sensitizing agent, coupled with commonly employed broadband x-ray sources with mean energies around 100 keV, as opposed to MeV energies produced by clinical linear accelerators (LINAC) used in radiation therapy. Numerical calculations, in vitro, and in vivo studies of F98 rat glioma (brain cancer) demonstrate that irradiation from a medium energy X-ray (MEX) 160 kV source is far more effective than from a high energy x-ray (HEX) 6 MV LINAC. We define a parameter to quantify photoionization by an x-ray source, which thereby provides a measure of subsequent Auger decays. The platinum (Z = 78) results are also relevant to ongoing studies on x-ray interaction with gold (Z = 79) nanoparticles, widely studied as an HZ contrast agent. The present study should be of additional interest for a combined radiation plus chemotherapy treatment since Pt compounds such cis-Pt and carbo-Pt are commonly used in chemotherapy.

Studying Dust Scattering Halos with Galactic X-ray Binaries

NASA Astrophysics Data System (ADS)

Beeler, Doreen; Corrales, Lia; Heinz, Sebastian

2018-01-01

Dust is an important part of the interstellar medium (ISM) and contributes to the formation of stars and planets. Since the advent of modern X-ray telescopes, Galactic X-ray point sources have permitted a closer look at all phases of the ISM. Interstellar metals from oxygen to iron — in both gas and dust form — are responsible for absorption and scattering of X-ray light. Dust scatters the light in a forward direction and creates a diffuse halo image surrounding many bright Galactic X-ray binaries. We use all the bright X-ray point sources available in the Chandra HETG archive to study dust scattering halos from the local ISM. We have described a data analysis pipeline using a combination of the data reduction software CIAO and Python. We compare our results from Chandra HETG and ACIS-I observations of a well studied dust scattering halo around GX 13+1, in order to characterize any systematic errors associated with the HETG data set. We describe how our data products will be used to measure ISM scaling relations for X-ray extinction, dust abundance, and dust-to-metal ratios.

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

A liquid-He cryostat for structural and thermal disorder studies by X-ray absorption.

PubMed

Bouamrane, F; Ribbens, M; Fonda, E; Adjouri, C; Traverse, A

2003-07-01

A new device operating from 4.2 to 300 K is now installed on the hard X-ray station of the DCI ring in LURE in order to measure absorption coefficients. This liquid-He bath device has three optical windows. One allows the incident beam to impinge on the sample, one located at 180 degrees with respect to the sample allows transmitted beams to be detected, and another located at 90 degrees is used to detect emitted photons. Total electron yield detection mode is also possible thanks to a specific sample holder equipped with an electrode that collects the charges created by the emitted electrons in the He gas brought from the He bath around the sample. The performance of the cryostat is described by measurements of the absorption coefficients versus the temperature for Cu and Co foils. For comparison, the absorption coefficient is also measured for Cu clusters. As expected from dimension effects, the Debye temperature obtained for the clusters is lower than that of bulk Cu.

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.

Fluorescence x-ray absorption fine structure studies of Fe-Ni-S and Fe-Ni-Si melts to 1600 K

NASA Astrophysics Data System (ADS)

Manghnani, M. H.; Hong, X.; Balogh, J.; Amulele, G.; Sekar, M.; Newville, M.

2008-04-01

We report NiK -edge fluorescence x-ray absorption fine structure spectra (XAFS) for Fe0.75Ni0.05S0.20 and Fe0.75Ni0.05Si0.20 ternary alloys from room temperature up to 1600 K. A high-temperature furnace designed for these studies incorporates two x-ray transparent windows and enables both a vertical orientation of the molten sample and a wide opening angle, so that XAFS can be measured in the fluorescence mode with a detector at 90° with respect to the incident x-ray beam. An analysis of the Ni XAFS data for these two alloys indicates different local structural environments for Ni in Fe0.75Ni0.05S0.20 and Fe0.75Ni0.05Si0.20 melts, with more Ni-Si coordination than Ni-S coordination persisting from room temperature through melting. These results suggest that light elements such as S and Si may impact the structural and chemical properties of Fe-Ni alloys with a composition similar to the earth’s core.

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

High temperature extended x-ray absorption fine structure study of multiferroic BiFeO3

NASA Astrophysics Data System (ADS)

Raghavendra Reddy, V.; Meneghini, Carlo; Kothari, Deepti; Gupta, Ajay; Aquilanti, Giuliana

2012-08-01

Local atomic structure modifications around Fe atoms in polycrystalline multiferroic BiFeO3 are studied by Fe K edge x-ray absorption spectroscopy as a function of temperature across the Néel temperature (TN = 643 K) in order to reveal local structure modifications related to the magnetic transition. This work demonstrates that on crossing TN the local structure around Fe shows peculiar changes: the Fe-O bond lengths get shorter, the ligand symmetry increases and the Fe-O bond length disorder (σ2) deviates from Debye behaviour. These results suggest that the structural transition at the ferroelectric Curie temperature (TC = 1103 K) is anticipated by early local rearrangement of the structure starting already at TN.

Single shot near edge x-ray absorption fine structure spectroscopy in the laboratory

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

Mantouvalou, I., E-mail: ioanna.mantouvalou@tu-berlin.de; Witte, K.; Martyanov, W.

With the help of adapted off-axis reflection zone plates, near edge X-ray absorption fine structure spectra at the C and N K-absorption edge have been recorded using a single 1.2 ns long soft X-ray pulse. The transmission experiments were performed with a laser-produced plasma source in the laboratory rendering time resolved measurements feasible independent on large scale facilities. A resolving power of E/ΔE ∼ 950 at the respective edges could be demonstrated. A comparison of single shot spectra with those collected with longer measuring time proves that all features of the used reference samples (silicon nitrate and polyimide) can be resolved in 1.2 ns.more » Hence, investigations of radiation sensitive biological specimen become possible due to the high efficiency of the optical elements enabling low dose experiments.« 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 Absorption Spectroscopy Characterization of Electrochemical Processes in Renewable Energy Storage and Conversion Devices

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

Farmand, Maryam

2013-05-19

The development of better energy conversion and storage devices, such as fuel cells and batteries, is crucial for reduction of our global carbon footprint and improving the quality of the air we breathe. However, both of these technologies face important challenges. The development of lower cost and better electrode materials, which are more durable and allow more control over the electrochemical reactions occurring at the electrode/electrolyte interface, is perhaps most important for meeting these challenges. Hence, full characterization of the electrochemical processes that occur at the electrodes is vital for intelligent design of more energy efficient electrodes. X-ray absorption spectroscopymore » (XAS) is a short-range order, element specific technique that can be utilized to probe the processes occurring at operating electrode surfaces, as well for studying the amorphous materials and nano-particles making up the electrodes. It has been increasingly used in recent years to study fuel cell catalysts through application of the and #916; and mgr; XANES technique, in combination with the more traditional X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) techniques. The and #916; and mgr; XANES data analysis technique, previously developed and applied to heterogeneous catalysts and fuel cell electrocatalysts by the GWU group, was extended in this work to provide for the first time space resolved adsorbate coverages on both electrodes of a direct methanol fuel cell. Even more importantly, the and #916; and mgr; technique was applied for the first time to battery relevant materials, where bulk properties such as the oxidation state and local geometry of a cathode are followed.« less

Isotope effects in liquid water probed by transmission mode x-ray absorption spectroscopy at the oxygen K-edge.

PubMed

Schreck, Simon; Wernet, Philippe

2016-09-14

The effects of isotope substitution in liquid water are probed by x-ray absorption spectroscopy at the O K-edge as measured in transmission mode. Confirming earlier x-ray Raman scattering experiments, the D2O spectrum is found to be blue shifted with respect to H2O, and the D2O spectrum to be less broadened. Following the earlier interpretations of UV and x-ray Raman spectra, the shift is related to the difference in ground-state zero-point energies between D2O and H2O, while the difference in broadening is related to the difference in ground-state vibrational zero-point distributions. We demonstrate that the transmission-mode measurements allow for determining the spectral shapes with unprecedented accuracy. Owing in addition to the increased spectral resolution and signal to noise ratio compared to the earlier measurements, the new data enable the stringent determination of blue shift and broadening in the O K-edge x-ray absorption spectrum of liquid water upon isotope substitution. The results are compared to UV absorption data, and it is discussed to which extent they reflect the differences in zero-point energies and vibrational zero-point distributions in the ground-states of the liquids. The influence of the shape of the final-state potential, inclusion of the Franck-Condon structure, and differences between liquid H2O and D2O resulting from different hydrogen-bond environments in the liquids are addressed. The differences between the O K-edge absorption spectra of water from our transmission-mode measurements and from the state-of-the-art x-ray Raman scattering experiments are discussed in addition. The experimentally extracted values of blue shift and broadening are proposed to serve as a test for calculations of ground-state zero-point energies and vibrational zero-point distributions in liquid H2O and D2O. This clearly motivates the need for new calculations of the O K-edge x-ray absorption spectrum of liquid water.

PROBING X-RAY ABSORPTION AND OPTICAL EXTINCTION IN THE INTERSTELLAR MEDIUM USING CHANDRA OBSERVATIONS OF SUPERNOVA REMNANTS

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

Foight, Dillon R.; Slane, Patrick O.; Güver, Tolga

We present a comprehensive study of interstellar X-ray extinction using the extensive Chandra supernova remnant (SNR) archive and use our results to refine the empirical relation between the hydrogen column density and optical extinction. In our analysis, we make use of the large, uniform data sample to assess various systematic uncertainties in the measurement of the interstellar X-ray absorption. Specifically, we address systematic uncertainties that originate from (i) the emission models used to fit SNR spectra; (ii) the spatial variations within individual remnants; (iii) the physical conditions of the remnant such as composition, temperature, and non-equilibrium regions; and (iv) themore » model used for the absorption of X-rays in the interstellar medium. Using a Bayesian framework to quantify these systematic uncertainties, and combining the resulting hydrogen column density measurements with the measurements of optical extinction toward the same remnants, we find the empirical relation N {sub H} = (2.87 ± 0.12) × 10{sup 21} A {sub V} cm{sup 2}, which is significantly higher than the previous measurements.« less

A nearly on-axis spectroscopic system for simultaneously measuring UV-visible absorption and X-ray diffraction in the SPring-8 structural genomics beamline.

PubMed

Sakaguchi, Miyuki; Kimura, Tetsunari; Nishida, Takuma; Tosha, Takehiko; Sugimoto, Hiroshi; Yamaguchi, Yoshihiro; Yanagisawa, Sachiko; Ueno, Go; Murakami, Hironori; Ago, Hideo; Yamamoto, Masaki; Ogura, Takashi; Shiro, Yoshitsugu; Kubo, Minoru

2016-01-01

UV-visible absorption spectroscopy is useful for probing the electronic and structural changes of protein active sites, and thus the on-line combination of X-ray diffraction and spectroscopic analysis is increasingly being applied. Herein, a novel absorption spectrometer was developed at SPring-8 BL26B2 with a nearly on-axis geometry between the X-ray and optical axes. A small prism mirror was placed near the X-ray beamstop to pass the light only 2° off the X-ray beam, enabling spectroscopic analysis of the X-ray-exposed volume of a crystal during X-ray diffraction data collection. The spectrometer was applied to NO reductase, a heme enzyme that catalyzes NO reduction to N2O. Radiation damage to the heme was monitored in real time during X-ray irradiation by evaluating the absorption spectral changes. Moreover, NO binding to the heme was probed via caged NO photolysis with UV light, demonstrating the extended capability of the spectrometer for intermediate analysis.

Microwave-assisted synthesis of water-soluble, fluorescent gold nanoclusters capped with small organic molecules and a revealing fluorescence and X-ray absorption study

NASA Astrophysics Data System (ADS)

Helmbrecht, C.; Lützenkirchen-Hecht, D.; Frank, W.

2015-03-01

Colourless solutions of blue light-emitting, water-soluble gold nanoclusters (AuNC) were synthesized from gold colloids under microwave irradiation using small organic molecules as ligands. Stabilized by 1,3,5-triaza-7-phosphaadamantane (TPA) or l-glutamine (GLU), fluorescence quantum yields up to 5% were obtained. AuNC are considered to be very promising for biological labelling, optoelectronic devices and light-emitting materials but the structure-property relationships have still not been fully clarified. To expand the knowledge about the AuNC apart from their fluorescent properties they were studied by X-ray absorption spectroscopy elucidating the oxidation state of the nanoclusters' gold atoms. Based on curve fitting of the XANES spectra in comparison to several gold references, optically transparent fluorescent AuNC are predicted to be ligand-stabilized Au5+ species. Additionally, their near edge structure compared with analogous results of polynuclear clusters known from the literature discloses an increasing intensity of the feature close to the absorption edge with decreasing cluster size. As a result, a linear relationship between the cluster size and the X-ray absorption coefficient can be established for the first time.Colourless solutions of blue light-emitting, water-soluble gold nanoclusters (AuNC) were synthesized from gold colloids under microwave irradiation using small organic molecules as ligands. Stabilized by 1,3,5-triaza-7-phosphaadamantane (TPA) or l-glutamine (GLU), fluorescence quantum yields up to 5% were obtained. AuNC are considered to be very promising for biological labelling, optoelectronic devices and light-emitting materials but the structure-property relationships have still not been fully clarified. To expand the knowledge about the AuNC apart from their fluorescent properties they were studied by X-ray absorption spectroscopy elucidating the oxidation state of the nanoclusters' gold atoms. Based on curve fitting of the XANES

Interference between extrinsic and intrinsic losses in x-ray absorption fine structure

NASA Astrophysics Data System (ADS)

Campbell, L.; Hedin, L.; Rehr, J. J.; Bardyszewski, W.

2002-02-01

The interference between extrinsic and intrinsic losses in x-ray absorption fine structure (XAFS) is treated within a Green's-function formalism, without explicit reference to final states. The approach makes use of a quasiboson representation of excitations and perturbation theory in the interaction potential between electrons and quasibosons. These losses lead to an asymmetric broadening of the main quasiparticle peak plus an energy-dependent satellite in the spectral function. The x-ray absorption spectra (XAS) is then given by a convolution of an effective spectral function over a one-electron cross section. It is shown that extrinsic and intrinsic losses tend to cancel near excitation thresholds, and correspondingly, the strength in the main peak increases. At high energies, the theory crosses over to the sudden approximation. These results thus explain the observed weakness of multielectron excitations in XAS. The approach is applied to estimate the many-body corrections to XAFS, beyond the usual mean-free path, using a phasor summation over the spectral function. The asymmetry of the spectral function gives rise to an additional many-body phase shift in the XAFS formula.

The Frequency of Intrinsic X-Ray Weakness among Broad Absorption Line Quasars

NASA Astrophysics Data System (ADS)

Liu, Hezhen; Luo, B.; Brandt, W. N.; Gallagher, S. C.; Garmire, G. P.

2018-06-01

We present combined ≈14–37 ks Chandra observations of seven z = 1.6–2.7 broad absorption line (BAL) quasars selected from the Large Bright Quasar Survey (LBQS). These seven objects are high-ionization BAL (HiBAL) quasars, and they were undetected in the Chandra hard band (2–8 keV) in previous observations. The stacking analyses of previous Chandra observations suggested that these seven objects likely contain some candidates for intrinsically X-ray weak BAL quasars. With the new Chandra observations, six targets are detected. We calculate their effective power-law photon indices and hard-band flux weakness, and find that two objects, LBQS 1203+1530 and LBQS 1442–0011, show soft/steep spectral shapes ({{{Γ }}}eff}={2.2}-0.9+0.9 and {1.9}-0.8+0.9) and significant X-ray weakness in the hard band (by factors of ≈15 and 12). We conclude that the two HiBAL quasars are good candidates for intrinsically X-ray weak BAL quasars. The mid-infrared-to-ultraviolet spectral energy distributions of the two candidates are consistent with those of typical quasars. We constrain the fraction of intrinsically X-ray weak active galactic nuclei (AGNs) among HiBAL quasars to be ≈7%–10% (2/29–3/29), and we estimate it is ≈6%–23% (2/35–8/35) among the general BAL quasar population. Such a fraction is considerably larger than that among non-BAL quasars, and we suggest that intrinsically X-ray weak quasars are preferentially observed as BAL quasars. Intrinsically X-ray weak AGNs likely comprise a small minority of the luminous type 1 AGN population, and they should not affect significantly the completeness of these AGNs found in deep X-ray surveys.

Application of x-ray absorption fine structure (XAFS) to local-order analysis in Fe-Cr maghemite-like materials

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

Montero-Cabrera, M. E., E-mail: elena.montero@cimav.edu.mx; Fuentes-Cobas, L. E.; Macías-Ríos, E.

2015-07-23

The maghemite-like oxide system γ-Fe{sub 2-x}Cr{sub x}O{sub 3} (x=0.75, 1 and 1.25) was studied by X-ray absorption fine structure (XAFS) and by synchrotron radiation X-ray diffraction (XRD). Measurements were performed at the Stanford Synchrotron Radiation Lightsource at room temperature, at beamlines 2-1, 2-3 and 4-3. High-resolution XRD patterns were processed by means of the Rietveld method. In cases of atoms being neighbors in the Periodic Table, the order/disorder degree of the considered solutions is indiscernible by “normal” (absence of “anomalous scattering”) diffraction experiments. Thus, maghemite-like materials were investigated by XAFS in both Fe and Cr K-edges to clarify, via short-rangemore » structure characterization, the local ordering of the investigated system. Athena and Artemis graphic user interfaces for IFEFFIT and FEFF8.4 codes were employed for XAFS spectra interpretation. Pre-edge decomposition and theoretical modeling of X-ray absorption near edge structure (XANES) transitions were performed. By analysis of the Cr K-edge XANES, it has been confirmed that Cr is located in an octahedral environment. Fitting of the extended X-ray absorption fine structure (EXAFS) spectra was performed under the consideration that the central atom of Fe is allowed to occupy octa- and tetrahedral positions, while Cr occupies only octahedral ones. Coordination number of neighboring atoms, interatomic distances and their quadratic deviation average were determined for x=1, by fitting simultaneously the EXAFS spectra of both Fe and Cr K-edges. The results of fitting the experimental spectra with theoretical standards showed that the cation vacancies tend to follow a regular pattern within the structure of the iron-chromium maghemite (FeCrO{sub 3})« 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

Microscopic nonlinear relativistic quantum theory of absorption of powerful x-ray radiation in plasma.

PubMed

Avetissian, H K; Ghazaryan, A G; Matevosyan, H H; Mkrtchian, G F

2015-10-01

The microscopic quantum theory of plasma nonlinear interaction with the coherent shortwave electromagnetic radiation of arbitrary intensity is developed. The Liouville-von Neumann equation for the density matrix is solved analytically considering a wave field exactly and a scattering potential of plasma ions as a perturbation. With the help of this solution we calculate the nonlinear inverse-bremsstrahlung absorption rate for a grand canonical ensemble of electrons. The latter is studied in Maxwellian, as well as in degenerate quantum plasma for x-ray lasers at superhigh intensities and it is shown that one can achieve the efficient absorption coefficient in these cases.

X-RAYS FROM A RADIO-LOUD COMPACT BROAD ABSORPTION LINE QUASAR 1045+352 AND THE NATURE OF OUTFLOWS IN RADIO-LOUD BROAD ABSORPTION LINE QUASARS

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

Kunert-Bajraszewska, Magdalena; Katarzynski, Krzysztof; Siemiginowska, Aneta

2009-11-10

We present new results on X-ray properties of radio-loud broad absorption line (BAL) quasars and focus on broadband spectral properties of a high-ionization BAL (HiBAL) compact steep spectrum (CSS) radio-loud quasar 1045+352. This HiBAL quasar has a very complex radio morphology indicating either strong interactions between a radio jet and the surrounding interstellar medium or a possible re-start of the jet activity. We detected 1045+352 quasar in a short 5 ksec Chandra ACIS-S observation. We applied theoretical models to explain spectral energy distribution of 1045+352 and argue that non-thermal, inverse-Compton (IC) emission from the innermost parts of the radio jetmore » can account for a large fraction of the observed X-ray emission. In our analysis, we also consider a scenario in which the observed X-ray emission from radio-loud BAL quasars can be a sum of IC jet X-ray emission and optically thin corona X-ray emission. We compiled a sample of radio-loud BAL quasars that were observed in X-rays to date and report no correlation between their X-ray and radio luminosity. However, the radio-loud BAL quasars show a large range of X-ray luminosities and absorption columns. This is consistent with the results obtained earlier for radio-quiet BAL quasars and may indicate an orientation effect in BAL quasars or more complex dependence between X-ray emission, radio emission, and an orientation based on the radio morphology.« less

Telescope for x ray and gamma ray studies in astrophysics

NASA Technical Reports Server (NTRS)

Weaver, W. D.; Desai, Upendra D.

1993-01-01

Imaging of x-rays has been achieved by various methods in astrophysics, nuclear physics, medicine, and material science. A new method for imaging x-ray and gamma-ray sources avoids the limitations of previously used imaging devices. Images are formed in optical wavelengths by using mirrors or lenses to reflect and refract the incoming photons. High energy x-ray and gamma-ray photons cannot be reflected except at grazing angles and pass through lenses without being refracted. Therefore, different methods must be used to image x-ray and gamma-ray sources. Techniques using total absorption, or shadow casting, can provide images in x-rays and gamma-rays. This new method uses a coder made of a pair of Fresnel zone plates and a detector consisting of a matrix of CsI scintillators and photodiodes. The Fresnel zone plates produce Moire patterns when illuminated by an off-axis source. These Moire patterns are deconvolved using a stepped sine wave fitting or an inverse Fourier transform. This type of coder provides the capability of an instantaneous image with sub-arcminute resolution while using a detector with only a coarse position-sensitivity. A matrix of the CsI/photodiode detector elements provides the necessary coarse position-sensitivity. The CsI/photodiode detector also allows good energy resolution. This imaging system provides advantages over previously used imaging devices in both performance and efficiency.

Synchrotron X-ray studies of the keel of the short-spined sea urchin Lytechinus variegatus: absorption microtomography (microCT) and small beam diffraction mapping.

PubMed

Stock, S R; Barss, J; Dahl, T; Veis, A; Almer, J D; Carlo, F

2003-05-01

In sea urchin teeth, the keel plays an important structural role, and this paper reports results of microstructural characterization of the keel of Lytechinus variegatus using two noninvasive synchrotron x-ray techniques: x-ray absorption microtomography (microCT) and x-ray diffraction mapping. MicroCT with 14 keV x-rays mapped the spatial distribution of mineral at the 1.3 microm level in a millimeter-sized fragment of a mature portion of the keel. Two rows of low absorption channels (i.e., primary channels) slightly less than 10 microm in diameter were found running linearly from the flange to the base of the keel and parallel to its sides. The primary channels paralleled the oral edge of the keel, and the microCT slices revealed a planar secondary channel leading from each primary channel to the side of the keel. The primary and secondary channels were more or less coplanar and may correspond to the soft tissue between plates of the carinar process. Transmission x-ray diffraction with 80.8 keV x-rays and a 0.1 mm beam mapped the distribution of calcite crystal orientations and the composition Ca(1-x)Mg(x)CO(3) of the calcite. Unlike the variable Mg concentration and highly curved prisms found in the keel of Paracentrotus lividus, a constant Mg content (x = 0.13) and relatively little prism curvature was found in the keel of Lytechinus variegatus.

Alternative difference analysis scheme combining R-space EXAFS fit with global optimization XANES fit for X-ray transient absorption spectroscopy.

PubMed

Zhan, Fei; Tao, Ye; Zhao, Haifeng

2017-07-01

Time-resolved X-ray absorption spectroscopy (TR-XAS), based on the laser-pump/X-ray-probe method, is powerful in capturing the change of the geometrical and electronic structure of the absorbing atom upon excitation. TR-XAS data analysis is generally performed on the laser-on minus laser-off difference spectrum. Here, a new analysis scheme is presented for the TR-XAS difference fitting in both the extended X-ray absorption fine-structure (EXAFS) and the X-ray absorption near-edge structure (XANES) regions. R-space EXAFS difference fitting could quickly provide the main quantitative structure change of the first shell. The XANES fitting part introduces a global non-derivative optimization algorithm and optimizes the local structure change in a flexible way where both the core XAS calculation package and the search method in the fitting shell are changeable. The scheme was applied to the TR-XAS difference analysis of Fe(phen) 3 spin crossover complex and yielded reliable distance change and excitation population.

Correction of absorption-edge artifacts in polychromatic X-ray tomography in a scanning electron microscope for 3D microelectronics

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

Laloum, D., E-mail: david.laloum@cea.fr; CEA, LETI, MINATEC Campus, 17 rue des Martyrs, 38054 Grenoble Cedex 9; STMicroelectronics, 850 rue Jean Monnet, 38926 Crolles

2015-01-15

X-ray tomography is widely used in materials science. However, X-ray scanners are often based on polychromatic radiation that creates artifacts such as dark streaks. We show this artifact is not always due to beam hardening. It may appear when scanning samples with high-Z elements inside a low-Z matrix because of the high-Z element absorption edge: X-rays whose energy is above this edge are strongly absorbed, violating the exponential decay assumption for reconstruction algorithms and generating dark streaks. A method is proposed to limit the absorption edge effect and is applied on a microelectronic case to suppress dark streaks between interconnections.

Fast Time-Dependent Density Functional Theory Calculations of the X-ray Absorption Spectroscopy of Large Systems.

PubMed

Besley, Nicholas A

2016-10-11

The computational cost of calculations of K-edge X-ray absorption spectra using time-dependent density functional (TDDFT) within the Tamm-Dancoff approximation is significantly reduced through the introduction of a severe integral screening procedure that includes only integrals that involve the core s basis function of the absorbing atom(s) coupled with a reduced quality numerical quadrature for integrals associated with the exchange and correlation functionals. The memory required for the calculations is reduced through construction of the TDDFT matrix within the absorbing core orbitals excitation space and exploiting further truncation of the virtual orbital space. The resulting method, denoted fTDDFTs, leads to much faster calculations and makes the study of large systems tractable. The capability of the method is demonstrated through calculations of the X-ray absorption spectra at the carbon K-edge of chlorophyll a, C 60 and C 70 .

An X-ray spectral study of colliding wind binaries

NASA Astrophysics Data System (ADS)

Sugawara, Yasuharu; Maeda, Yoshitomo; Tsuboi, Yohko

2012-03-01

We present results of spectral studies of two Wolf-Rayet colliding wind binaries (WR 140 and WR 30a), using the data obtained by the Suzaku and XMM-Newton satellites. WR 140 is one of the best known examples of a Wolf-Rayet star. We executed the Suzaku X-ray observations at four different epochs around periastron passage in Jan. 2009 to understand the W-R stellar wind as well as the wind-wind collision shocks. We detected hard X-ray excess in the HXD band (> 10 keV) for the first time from a W-R binary. The emission measure of the dominant, high temperature component is not inversely proportional to the distance between the two stars. WR 30a is the rare WO-type W-R binary. We executed XMM-Newton observations and detected X-ray emission for the first time. The broad-band spectrum was well-fitted with double-absorption model. The hard X-ray emission was heavily absorbed. This can be interpreted that the hard X-ray emitting plasma exist near WO star.

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.

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

C IV absorption-line variability in X-ray-bright broad absorption-line quasi-stellar objects

NASA Astrophysics Data System (ADS)

Joshi, Ravi; Chand, Hum; Srianand, Raghunathan; Majumdar, Jhilik

2014-07-01

We report the kinematic shift and strength variability of the C IV broad absorption-line (BAL) trough in two high-ionization X-ray-bright quasi-stellar objects (QSOs): SDSS J085551+375752 (at zem ˜ 1.936) and SDSS J091127+055054 (at zem ˜ 2.793). Both these QSOs have shown a combination of profile shifts and the appearance and disappearance of absorption components belonging to a single BAL trough. The observed average kinematic shift of the whole BAL profile resulted in an average deceleration of ˜-0.7 ± 0.1, -2.0 ± 0.1 cm s-2 over rest-frame time-spans of 3.11 and 2.34 yr for SDSS J085551+375752 and SDSS J091127+055054, respectively. To our knowledge, these are the largest kinematic shifts known, exceeding by factors of about 2.8 and 7.8 the highest deceleration reported in the literature; this makes both objects potential candidates to investigate outflows using multiwavelength monitoring of their line and continuum variability. We explore various possible mechanisms to understand the observed profile variations. Outflow models involving many small self-shielded clouds, probably moving in a curved path, provide the simplest explanation for the C IV BAL strength and velocity variations, along with the X-ray-bright nature of these sources.

On the relation of optical obscuration and X-ray absorption in Seyfert galaxies

NASA Astrophysics Data System (ADS)

Burtscher, L.; Davies, R. I.; Graciá-Carpio, J.; Koss, M. J.; Lin, M.-Y.; Lutz, D.; Nandra, P.; Netzer, H.; Orban de Xivry, G.; Ricci, C.; Rosario, D. J.; Veilleux, S.; Contursi, A.; Genzel, R.; Schnorr-Müller, A.; Sternberg, A.; Sturm, E.; Tacconi, L. J.

2016-02-01

The optical classification of a Seyfert galaxy and whether it is considered X-ray absorbed are often used interchangeably. There are many borderline cases, however, and also numerous examples where the optical and X-ray classifications appear to be in disagreement. In this article we revisit the relation between optical obscuration and X-ray absorption in active galactic nuclei (AGNs). We make use of our "dust colour" method to derive the optical obscuration AV, and consistently estimated X-ray absorbing columns using 0.3-150 keV spectral energy distributions. We also take into account the variable nature of the neutral gas column NH and derive the Seyfert subclasses of all our objects in a consistent way. We show in a sample of 25 local, hard-X-ray detected Seyfert galaxies (log LX/ (erg / s) ≈ 41.5-43.5) that there can actually be a good agreement between optical and X-ray classification. If Seyfert types 1.8 and 1.9 are considered unobscured, the threshold between X-ray unabsorbed and absorbed should be chosen at a column NH = 1022.3 cm-2 to be consistent with the optical classification. We find that NH is related to AV and that the NH/AV ratio is approximately Galactic or higher in all sources, as indicated previously. However, in several objects we also see that deviations from the Galactic ratio are only due to a variable X-ray column, showing that (1) deviations from the Galactic NH/AV can be simply explained by dust-free neutral gas within the broad-line region in some sources; that (2) the dust properties in AGNs can be similar to Galactic dust and that (3) the dust colour method is a robust way to estimate the optical extinction towards the sublimation radius in all but the most obscured AGNs.

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.

Dynamical Study of Femtosecond-Laser-Ablated Liquid-Aluminum Nanoparticles Using Spatiotemporally Resolved X-Ray-Absorption Fine-Structure Spectroscopy

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

Oguri, Katsuya; Okano, Yasuaki; Nishikawa, Tadashi

2007-10-19

We study the temperature evolution of aluminum nanoparticles generated by femtosecond laser ablation with spatiotemporally resolved x-ray-absorption fine-structure spectroscopy. We successfully identify the nanoparticles based on the L-edge absorption fine structure of the ablation plume in combination with the dependence of the edge structure on the irradiation intensity and the expansion velocity of the plume. In particular, we show that the lattice temperature of the nanoparticles is estimated from the L-edge slope, and that its spatial dependence reflects the cooling of the nanoparticles during plume expansion. The results reveal that the emitted nanoparticles travel in a vacuum as a condensedmore » liquid phase with a lattice temperature of about 2500 to 4200 K in the early stage of plume expansion.« less

An X-ray Absorption Fine Structure study of Au adsorbed onto the non-metabolizing cells of two soil bacterial species

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

Song, Zhen; Kenney, Janice P.L.; Fein, Jeremy B.

2015-02-09

Gram-positive and Gram-negative bacterial cells can remove Au from Au(III)-chloride solutions, and the extent of removal is strongly pH dependent. In order to determine the removal mechanisms, X-ray Absorption Fine Structure (XAFS) spectroscopy experiments were conducted on non-metabolizing biomass of Bacillus subtilis and Pseudomonas putida with fixed Au(III) concentrations over a range of bacterial concentrations and pH values. X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) data on both bacterial species indicate that more than 90% of the Au atoms on the bacterial cell walls were reduced to Au(I). In contrast to what has beenmore » observed for Au(III) interaction with metabolizing bacterial cells, no Au(0) or Au-Au nearest neighbors were observed in our experimental systems. All of the removed Au was present as adsorbed bacterial surface complexes. For both species, the XAFS data suggest that although Au-chloride-hydroxide aqueous complexes dominate the speciation of Au in solution, Au on the bacterial cell wall is characterized predominantly by binding of Au atoms to sulfhydryl functional groups and amine and/or carboxyl functional groups, and the relative importance of the sulfhydryl groups increases with increasing pH and with decreasing Au loading. The XAFS data for both microorganism species suggest that adsorption is the first step in the formation of Au nanoparticles by bacteria, and the results enhance our ability to account for the behavior of Au in bacteria-bearing geologic systems.« less

An X-ray Absorption Fine Structure study of Au adsorbed onto the non-metabolizing cells of two soil bacterial species

NASA Astrophysics Data System (ADS)

Song, Zhen; Kenney, Janice P. L.; Fein, Jeremy B.; Bunker, Bruce A.

2012-06-01

Gram-positive and Gram-negative bacterial cells can remove Au from Au(III)-chloride solutions, and the extent of removal is strongly pH dependent. In order to determine the removal mechanisms, X-ray Absorption Fine Structure (XAFS) spectroscopy experiments were conducted on non-metabolizing biomass of Bacillus subtilis and Pseudomonas putida with fixed Au(III) concentrations over a range of bacterial concentrations and pH values. X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) data on both bacterial species indicate that more than 90% of the Au atoms on the bacterial cell walls were reduced to Au(I). In contrast to what has been observed for Au(III) interaction with metabolizing bacterial cells, no Au(0) or Au-Au nearest neighbors were observed in our experimental systems. All of the removed Au was present as adsorbed bacterial surface complexes. For both species, the XAFS data suggest that although Au-chloride-hydroxide aqueous complexes dominate the speciation of Au in solution, Au on the bacterial cell wall is characterized predominantly by binding of Au atoms to sulfhydryl functional groups and amine and/or carboxyl functional groups, and the relative importance of the sulfhydryl groups increases with increasing pH and with decreasing Au loading. The XAFS data for both microorganism species suggest that adsorption is the first step in the formation of Au nanoparticles by bacteria, and the results enhance our ability to account for the behavior of Au in bacteria-bearing geologic systems.

Long-Range Chemical Sensitivity in the Sulfur K-Edge X-ray Absorption Spectra of Substituted Thiophenes

PubMed Central

2015-01-01

Thiophenes are the simplest aromatic sulfur-containing compounds and are stable and widespread in fossil fuels. Regulation of sulfur levels in fuels and emissions has become and continues to be ever more stringent as part of governments’ efforts to address negative environmental impacts of sulfur dioxide. In turn, more effective removal methods are continually being sought. In a chemical sense, thiophenes are somewhat obdurate and hence their removal from fossil fuels poses problems for the industrial chemist. Sulfur K-edge X-ray absorption spectroscopy provides key information on thiophenic components in fuels. Here we present a systematic study of the spectroscopic sensitivity to chemical modifications of the thiophene system. We conclude that while the utility of sulfur K-edge X-ray absorption spectra in understanding the chemical composition of sulfur-containing fossil fuels has already been demonstrated, care must be exercised in interpreting these spectra because the assumption of an invariant spectrum for thiophenic forms may not always be valid. PMID:25116792

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.

Combining Sequential Extractions and X-ray Absorption Spectroscopy for Quantitative and Qualitative Zinc Speciation in Soil

NASA Astrophysics Data System (ADS)

Bauer, Tatiana; Minkina, Tatiana; Batukaev, Abdulmalik; Nevidomskaya, Dina; Burachevskaya, Marina; Tsitsuashvili, Viktoriya; Urazgildieva, Kamilya

2017-04-01

The combined use of X-ray absorption spectrometry and extractive fractionation is an effective approach for studying the interaction of metal ions with soil compounds and identifying the phases-carriers of metals in soil and their stable fixation. These studies were carried out using the technique of X-ray absorption spectroscopy and chemical extractive fractionation. In a model experiment the samples taken in Calcic Chernozem were artificially contaminated with higher portion of Zn(NO3)2 (2000 mg/kg). The metal were incubated in soil samples for 2 year. The samples of soil mineral and organic phases (calcite, kaolinite, bentonite, humic acids) were saturated with Zn2+ from a solution of nitrate salts of metal. The total content of Zn in soil and soil various phases was determined using the X-ray fluorescence method. Extended X-ray absorption fine structure (EXAFS) Zn was measured at the Structural Materials Science beamline of the Kurchatov Center for Synchrotron Radiation. Sequential fractionation of Zn in soil conducted by Tessier method (Tessier et al., 1979) which determining 5 fractions of metals in soil: exchangeable, bound to Fe-Mn oxide, bound to carbonate, bound to the organic matter, and bound to silicate (residual). This methodology has so far more than 4000 citations (Web of Science), which demonstrates the popularity of this approach. Much Zn compounds are contained in uncontaminated soils in stable primary and secondary silicates inherited from the parental rocks (67% of the total concentrations in all fractions), which is a regional trait of soils in the fore-Caucasian plain. Extracted fractionation of metal compounds in soil samples, artificially contaminated with Zn salts, indicates the priority holding of Zn2+ ions by silicates, carbonates and Fe-Mn oxides. The Zn content significantly increases in the exchangeable fraction. Atomic structure study of the soil various phases saturated with Zn2+ ion by using (XANES) X-ray absorption spectroscopy

High energy neutrino absorption and its effects on stars in close X-ray binaries

NASA Technical Reports Server (NTRS)

Gaisser, T. K.; Stecker, F. W.

1986-01-01

The physics and astrophysics of high energy neutrino production and interactions in close X-ray binary systems are studied. These studies were stimulated by recent observations of ultrahigh energy gamma-rays and possibly other ultrahigh energy particles coming from the directions of Cygnus X-3 and other binary systems and possessing the periodicity characteristics of these systems. Systems in which a compact object, such as a neutron star, is a strong source of high energy particles which, in turn, produce photons, neutronos and other secondary particles by interactions in the atmosphere of the companion star were considered. The highest energy neutrinos are absorbed deep in the companion and the associated energy deposition may be large enough to effect its structure or lead to its ultimate disruption. This neutrino heating was evaluated, starting with a detailed numerical calculation of the hadronic cascade induced in the atmosphere of the companion star. For some theoretical models, the resulting energy deposition from neutrino absorption may be so great as to disrupt the companion star over an astronomically small timescale of the order of 10,000 years. Even if the energy deposition is smaller, it may still be high enough to alter the system substantially, perhaps leading to quenching of high energy signals from the source. Given the cosmic ray luminosities required to produce the observed gamma rays from cygnus X-3 and LMX X-4, such a situation may occur in these sources.

Alternative difference analysis scheme combining R -space EXAFS fit with global optimization XANES fit for X-ray transient absorption spectroscopy

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

Zhan, Fei; Tao, Ye; Zhao, Haifeng

Time-resolved X-ray absorption spectroscopy (TR-XAS), based on the laser-pump/X-ray-probe method, is powerful in capturing the change of the geometrical and electronic structure of the absorbing atom upon excitation. TR-XAS data analysis is generally performed on the laser-on minus laser-off difference spectrum. Here, a new analysis scheme is presented for the TR-XAS difference fitting in both the extended X-ray absorption fine-structure (EXAFS) and the X-ray absorption near-edge structure (XANES) regions.R-space EXAFS difference fitting could quickly provide the main quantitative structure change of the first shell. The XANES fitting part introduces a global non-derivative optimization algorithm and optimizes the local structure changemore » in a flexible way where both the core XAS calculation package and the search method in the fitting shell are changeable. The scheme was applied to the TR-XAS difference analysis of Fe(phen) 3spin crossover complex and yielded reliable distance change and excitation population.« less

Study on Coloration Mechanism of Chinese Ancient Ceramics by X-ray Absorption Near-edge Structure

NASA Astrophysics Data System (ADS)

Peng, Y. H.; Xie, Z.; He, J. F.; Liu, Q. H.; Pan, Z. Y.; Cheng, W. R.; Wei, S. Q.

2013-04-01

The Fe K-edge X-ray absorption near-edge structure (XANES) spectra of a series of ceramic shards were measured by fluorescence mode to reveal the color-generating techniques of Chinese porcelain. The analysis disclosed relationships among the chemical form of the iron, the firing conditions and the colors of the ceramics. The results indicate that the coloration for different ceramics depend on the valence states of iron as the main color element in glaze and the proportion of Fe2+ and Fe3+ was attributed to the baking technology. The findings provide important information for archaeologist on the coloration researches.

Wind-embedded shocks in FASTWIND: X-ray emission and K-shell absorption

NASA Astrophysics Data System (ADS)

Carneiro, L. P.; Puls, J.; Sundqvist, J. O.; Hoffmann, T. L.

2017-11-01

EUV and X-ray radiation emitted from wind-embedded shocks can affect the ionization balance in the outer atmospheres of massive stars, and can also be the mechanism responsible for producing highly ionized atoms detected in the wind UV spectra. To investigate these processes, we implemented the emission from wind-embedded shocks and related physics into our atmosphere/spectrum synthesis code FASTWIND. We also account for the high energy absorption of the cool wind, by adding important K-shell opacities. Various tests justfying our approach have been described by Carneiro+(2016, A&A 590, A88). In particular, we studied the impact of X-ray emission on the ionization balance of important elements. In almost all the cases, the lower ionization stages (O iv, N iv, P v) are depleted and the higher stages (N v, O v, O vi) become enhanced. Moreover, also He lines (in particular He ii 1640 and He ii 4686) can be affected as well. Finally, we carried out an extensive discussion of the high-energy mass absorption coefficient, κν, regarding its spatial variation and dependence on T eff. We found that (i) the approximation of a radially constant κν can be justified for r >= 1.2R * and λ <= 18 Å, and also for many models at longer wavelengths. (ii) In order to estimate the actual value of this quantity, however, the He ii background needs to be considered from detailed modeling.

Nanoparticle-enhanced x-ray therapy for cancer

NASA Astrophysics Data System (ADS)

Letfullin, Renat R.; Rice, Colin E. W.; George, Thomas F.

2016-03-01

Photothermal therapies of nanophotohyperthermia and nanophotothermolysis utilize the light absorptive properties of nanoparticles to create heat and free radicals in a small localized region. Conjugating nanoparticles with various biomolecules allows for targeted delivery to specific tissues or even specific cells, cancerous cells being of particular interest. Previous studies have investigated nanoparticles at visible and infrared wavelengths where surface plasmon resonance leads to unique absorption characteristics. However, issues such as poor penetration depth of the visible light through biological tissues limits the effectiveness of delivery by noninvasive means. In other news, various nanoparticles have been investigated as contrast agents for traditional X-ray procedures, utilizing the strong absorption characteristics of the nanoparticles to enhance contrast of the detected X-ray image. Using X-rays to power photothermal therapies has three main advantages over visiblespectra wavelengths: the high penetration depth of X-rays through biological media makes noninvasive treatments very feasible; the high energy of individual photons means nanoparticles can be heated to desired temperatures with lower beam intensities, or activated to produce the free radicals; and X-ray sources are already common throughout the medical industry, making future implementation on existing equipment possible. This paper uses Lorenz-Mie theory to investigate the light absorption properties of various size gold nanoparticles over photon energies in the 1-100 keV range. These absorption values are then plugged into a thermal model to determine the temperatures reached by the nanoparticles for X-ray exposures of differing time and intensity. The results of these simulations are discussed in relation to the effective implementation of nanophotohyperthermia and nanophotothermolysis treatments.

Extragalactic Hard X-ray Surveys: From INTEGRAL to Simbol-X

NASA Astrophysics Data System (ADS)

Paltani, S.; Dwelly, T.; Walter, R.; McHardy, I. M.; Courvoisier, T. J.-L.

2009-05-01

We present some results of the deepest extragalactic survey performed by the INTEGRAL satellite. The fraction of very absorbed AGN is quite large. The sharp decrease in the absorption fraction with X-ray luminosity observed at lower-energy X-rays is not observed. The current lack of truly Compton-thick objects, with an upper limit of 14% to the size of this population, is just compatible with recent modeling of the cosmic X-ray background. We also study the prospects for a future hard X-ray serendipitous survey with Simbol-X. We show that Simbol-X will easily detect a large number of serendipitous AGN, allowing us to study the evolution of AGN up to redshifts about 2, opening the door to the cosmological study of hard X-ray selected AGN, which is barely possible with existing satellites like Swift and INTEGRAL.

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.

Applications of Hard X-ray Full-Field Transmission X-ray Microscopy at SSRL

NASA Astrophysics Data System (ADS)

Liu, Y.; Andrews, J. C.; Meirer, F.; Mehta, A.; Gil, S. Carrasco; Sciau, P.; Mester, Z.; Pianetta, P.

2011-09-01

State-of-the-art hard x-ray full-field transmission x-ray microscopy (TXM) at beamline 6-2C of Stanford Synchrotron Radiation Lightsource has been applied to various research fields including biological, environmental, and material studies. With the capability of imaging a 32-micron field-of-view at 30-nm resolution using both absorption mode and Zernike phase contrast, the 3D morphology of yeast cells grown in gold-rich media was investigated. Quantitative evaluation of the absorption coefficient was performed for mercury nanoparticles in alfalfa roots exposed to mercury. Combining XANES and TXM, we also performed XANES-imaging on an ancient pottery sample from the Roman pottery workshop at LaGraufesenque (Aveyron).

Hybridized orbital states in spin-orbit coupled 3 d -5 d double perovskites studied by x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Lee, Min-Cheol; Lee, Sanghyun; Won, C. J.; Lee, K. D.; Hur, N.; Chen, Jeng-Lung; Cho, Deok-Yong; Noh, T. W.

2018-03-01

We investigated the orbital hybridization mechanism in 3 d -5 d double perovskites (DPs) of La2CoIrO6 and La2CoPtO6 using x-ray absorption spectroscopy. It is clearly evidenced by O K -edge and Co K -edge x-ray absorption spectra that the Co 3 d orbitals hybridize not only with the half-filled Ir/Pt jeff states but also with the fully empty (unpolarized) Ir/Pt eg states in both DPs. The Co 3 d eg-Ir 5 d eg hybridization cannot contribute to the ferrimagnetic long-range order in La2CoIrO6 established by spin-selective Co 3 d t2 g-Ir 5 d jeff hybridization through the intermediate oxygen p state but could serve as an origin of paramagnetism. The strengths of such orbital hybridizations were found to be almost invariant to temperature, even far above the Curie temperature, implying persistent paramagnetism against the antiferromagnetic ordering in the spin-orbit entangled 3 d -5 d DPs.

Fabrication of 200 nanometer period centimeter area hard x-ray absorption gratings by multilayer deposition

PubMed Central

Lynch, S K; Liu, C; Morgan, N Y; Xiao, X; Gomella, A A; Mazilu, D; Bennett, E E; Assoufid, L; de Carlo, F; Wen, H

2012-01-01

We describe the design and fabrication trials of x-ray absorption gratings of 200 nm period and up to 100:1 depth-to-period ratios for full-field hard x-ray imaging applications. Hard x-ray phase-contrast imaging relies on gratings of ultra-small periods and sufficient depth to achieve high sensitivity. Current grating designs utilize lithographic processes to produce periodic vertical structures, where grating periods below 2.0 μm are difficult due to the extreme aspect ratios of the structures. In our design, multiple bilayers of x-ray transparent and opaque materials are deposited on a staircase substrate, and mostly on the floor surfaces of the steps only. When illuminated by an x-ray beam horizontally, the multilayer stack on each step functions as a micro-grating whose grating period is the thickness of a bilayer. The array of micro-gratings over the length of the staircase works as a single grating over a large area when continuity conditions are met. Since the layers can be nanometers thick and many microns wide, this design allows sub-micron grating periods and sufficient grating depth to modulate hard x-rays. We present the details of the fabrication process and diffraction profiles and contact radiography images showing successful intensity modulation of a 25 keV x-ray beam. PMID:23066175

Accurate Modeling of X-ray Extinction by Interstellar Grains

NASA Astrophysics Data System (ADS)

Hoffman, John; Draine, B. T.

2016-02-01

Interstellar abundance determinations from fits to X-ray absorption edges often rely on the incorrect assumption that scattering is insignificant and can be ignored. We show instead that scattering contributes significantly to the attenuation of X-rays for realistic dust grain size distributions and substantially modifies the spectrum near absorption edges of elements present in grains. The dust attenuation modules used in major X-ray spectral fitting programs do not take this into account. We show that the consequences of neglecting scattering on the determination of interstellar elemental abundances are modest; however, scattering (along with uncertainties in the grain size distribution) must be taken into account when near-edge extinction fine structure is used to infer dust mineralogy. We advertise the benefits and accuracy of anomalous diffraction theory for both X-ray halo analysis and near edge absorption studies. We present an open source Fortran suite, General Geometry Anomalous Diffraction Theory (GGADT), that calculates X-ray absorption, scattering, and differential scattering cross sections for grains of arbitrary geometry and composition.

ACCURATE MODELING OF X-RAY EXTINCTION BY INTERSTELLAR GRAINS

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

Hoffman, John; Draine, B. T., E-mail: jah5@astro.princeton.edu, E-mail: draine@astro.princeton.edu

Interstellar abundance determinations from fits to X-ray absorption edges often rely on the incorrect assumption that scattering is insignificant and can be ignored. We show instead that scattering contributes significantly to the attenuation of X-rays for realistic dust grain size distributions and substantially modifies the spectrum near absorption edges of elements present in grains. The dust attenuation modules used in major X-ray spectral fitting programs do not take this into account. We show that the consequences of neglecting scattering on the determination of interstellar elemental abundances are modest; however, scattering (along with uncertainties in the grain size distribution) must bemore » taken into account when near-edge extinction fine structure is used to infer dust mineralogy. We advertise the benefits and accuracy of anomalous diffraction theory for both X-ray halo analysis and near edge absorption studies. We present an open source Fortran suite, General Geometry Anomalous Diffraction Theory (GGADT), that calculates X-ray absorption, scattering, and differential scattering cross sections for grains of arbitrary geometry and composition.« less

Resonant soft X-ray scattering on protein solutions

NASA Astrophysics Data System (ADS)

Ye, Dan; Le, Thinh; Wang, Cheng; Zwart, Peter; Gomez, Esther; Gomez, Enrique

Protein structure is crucial for biological function, such that characterizing protein folding and packing is important for the design of therapeutics and enzymes. We propose resonant soft X-ray scattering (RSOXS) as an approach to study proteins and other biological assemblies in solution. Calculations of the scattering contrast suggest that soft X-ray scattering is more sensitive than hard X-ray scattering, because of contrast generated at the absorption edges of constituent elements such as carbon, nitrogen and oxygen. We have examined the structure of bovine serum albumin (BSA) in solution by RSOXS. We find that by varying incident X-ray energies, we are able to achieve higher scattering contrast near the absorption edge. From our RSOXS scattering result we are able to reconstruct the structure of BSA in 3D. These RSOXS results also agree with hard X-ray experiments, including crystallographic data. Our study demonstrates the potential of RSOXS for studying protein structure in solution.

Characterization and speciation of mercury-bearing mine wastes using X-ray absorption spectroscopy

USGS Publications Warehouse

Kim, C.S.; Brown, Gordon E.; Rytuba, J.J.

2000-01-01

Mining of mercury deposits located in the California Coast Range has resulted in the release of mercury to the local environment and water supplies. The solubility, transport, and potential bioavailability of mercury are controlled by its chemical speciation, which can be directly determined for samples with total mercury concentrations greater than 100 mg kg-1 (ppm) using X-ray absorption spectroscopy (XAS). This technique has the additional benefits of being non-destructive to the sample, element-specific, relatively sensitive at low concentrations, and requiring minimal sample preparation. In this study, Hg L(III)-edge extended X-ray absorption fine structure (EXAFS) spectra were collected for several mercury mine tailings (calcines) in the California Coast Range. Total mercury concentrations of samples analyzed ranged from 230 to 1060 ppm. Speciation data (mercury phases present and relative abundances) were obtained by comparing the spectra from heterogeneous, roasted (calcined) mine tailings samples with a spectral database of mercury minerals and sorbed mercury complexes. Speciation analyses were also conducted on known mixtures of pure mercury minerals in order to assess the quantitative accuracy of the technique. While some calcine samples were found to consist exclusively of mercuric sulfide, others contain additional, more soluble mercury phases, indicating a greater potential for the release of mercury into solution. Also, a correlation was observed between samples from hot-spring mercury deposits, in which chloride levels are elevated, and the presence of mercury-chloride species as detected by the speciation analysis. The speciation results demonstrate the ability of XAS to identify multiple mercury phases in a heterogeneous sample, with a quantitative accuracy of ??25% for the mercury-containing phases considered. Use of this technique, in conjunction with standard microanalytical techniques such as X-ray diffraction and electron probe microanalysis

Liquid helium cryostat with internal fluorescence detection for x-ray absorption studies in the 2-6 keV energy region

NASA Astrophysics Data System (ADS)

McFarlane Holman, Karen L.; Latimer, Matthew J.; Yachandra, Vittal K.

2004-06-01

X-ray absorption spectroscopy (XAS) in the intermediate x-ray region (2-6 keV) for dilute biological samples has been limited because of detector/flux limitations and inadequate cryogenic instrumentation. We have designed and constructed a new tailpiece/sample chamber for a commercially available liquid helium cooled cryostat which overcomes difficulties related to low fluorescence signals by using thin window materials and incorporating an internal photodiode detector. With the apparatus, XAS data at the Cl, S, and Ca K edges have been collected on frozen solutions and biological samples at temperatures down to 60 K. A separate chamber has been incorporated for collecting room-temperature spectra of standard compounds (for energy calibration purposes) which prevents contamination of the cryostat chamber and allows the sample to remain undisturbed, both important concerns for studying dilute and radiation-sensitive samples.

Pt and Ru X-ray absorption spectroscopy of PtRu anode catalysts in operating direct methanol fuel cells.

PubMed

Stoupin, Stanislav; Chung, Eun-Hyuk; Chattopadhyay, Soma; Segre, Carlo U; Smotkin, Eugene S

2006-05-25

In situ X-ray absorption spectroscopy, ex situ X-ray fluorescence, and X-ray powder diffraction enabled detailed core analysis of phase segregated nanostructured PtRu anode catalysts in an operating direct methanol fuel cell (DMFC). No change in the core structures of the phase segregated catalyst was observed as the potential traversed the current onset potential of the DMFC. The methodology was exemplified using a Johnson Matthey unsupported PtRu (1:1) anode catalyst incorporated into a DMFC membrane electrode assembly. During DMFC operation the catalyst is essentially metallic with half of the Ru incorporated into a face-centered cubic (FCC) Pt alloy lattice and the remaining half in an amorphous phase. The extended X-ray absorption fine structure (EXAFS) analysis suggests that the FCC lattice is not fully disordered. The EXAFS indicates that the Ru-O bond lengths were significantly shorter than those reported for Ru-O of ruthenium oxides, suggesting that the phases in which the Ru resides in the catalysts are not similar to oxides.

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

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...

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.

Operando X-ray absorption and EPR evidence for a single electron redox process in copper catalysis

DOE PAGES

Lu, Qingquan; Zhang, Jian; Peng, Pan; ...

2015-05-26

An unprecedented single electron redox process in copper catalysis is confirmed using operando X-ray absorption and EPR spectroscopies. The oxidation state of the copper species in the interaction between Cu(II) and a sulfinic acid at room temperature, and the accurate characterization of the formed Cu(I) are clearly shown using operando X-ray absorption and EPR evidence. Further investigation of anion effects on Cu(II) discloses that bromine ions can dramatically increase the rate of the redox process. Moreover, it is proven that the sulfinic acids are converted into sulfonyl radicals, which can be trapped by 2-arylacrylic acids and various valuable β-keto sulfonesmore » are synthesized with good to excellent yields under mild conditions.« less

Detailed transient heme structures of Mb-CO in solution after CO dissociation: an X-ray transient absorption spectroscopic study.

PubMed

Stickrath, Andrew B; Mara, Michael W; Lockard, Jenny V; Harpham, Michael R; Huang, Jier; Zhang, Xiaoyi; Attenkofer, Klaus; Chen, Lin X

2013-04-25

Although understanding the structural dynamics associated with ligand photodissociation is necessary in order to correlate structure and function in biological systems, few techniques are capable of measuring the ultrafast dynamics of these systems in solution-phase at room temperature. We present here a detailed X-ray transient absorption (XTA) study of the photodissociation of CO-bound myoglobin (Fe(II)CO-Mb) in room-temperature aqueous buffer solution with a time resolution of 80 ps, along with a general procedure for handling biological samples under the harsh experimental conditions that transient X-ray experiments entail. The XTA spectra of (Fe(II)CO-Mb) exhibit significant XANES and XAFS alterations following 527 nm excitation, which remain unchanged for >47 μs. These spectral changes indicate loss of the CO ligand, resulting in a five-coordinate, domed heme, and significant energetic reorganization of the 3d orbitals of the Fe center. With the current experimental setup, each X-ray pulse in the pulse train, separated by ~153 ns, can be separately discriminated, yielding snapshots of the myoglobin evolution over time. These methods can be easily applied to other biological systems, allowing for simultaneous structural and electronic measurements of any biological system with both ultrafast and slow time resolutions, effectively mapping out all of the samples' relevant physiological processes.

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

Simulation of Near-Edge X-ray Absorption Fine Structure with Time-Dependent Equation-of-Motion Coupled-Cluster Theory.

PubMed

Nascimento, Daniel R; DePrince, A Eugene

2017-07-06

An explicitly time-dependent (TD) approach to equation-of-motion (EOM) coupled-cluster theory with single and double excitations (CCSD) is implemented for simulating near-edge X-ray absorption fine structure in molecular systems. The TD-EOM-CCSD absorption line shape function is given by the Fourier transform of the CCSD dipole autocorrelation function. We represent this transform by its Padé approximant, which provides converged spectra in much shorter simulation times than are required by the Fourier form. The result is a powerful framework for the blackbox simulation of broadband absorption spectra. K-edge X-ray absorption spectra for carbon, nitrogen, and oxygen in several small molecules are obtained from the real part of the absorption line shape function and are compared with experiment. The computed and experimentally obtained spectra are in good agreement; the mean unsigned error in the predicted peak positions is only 1.2 eV. We also explore the spectral signatures of protonation in these molecules.

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.

Self-interaction-corrected time-dependent density-functional-theory calculations of x-ray-absorption spectra

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

Tu, Guangde; Rinkevicius, Zilvinas; Vahtras, Olav

We outline an approach within time-dependent density functional theory that predicts x-ray spectra on an absolute scale. The approach rests on a recent formulation of the resonant-convergent first-order polarization propagator [P. Norman et al., J. Chem. Phys. 123, 194103 (2005)] and corrects for the self-interaction energy of the core orbital. This polarization propagator approach makes it possible to directly calculate the x-ray absorption cross section at a particular frequency without explicitly addressing the excited-state spectrum. The self-interaction correction for the employed density functional accounts for an energy shift of the spectrum, and fully correlated absolute-scale x-ray spectra are thereby obtainedmore » based solely on optimization of the electronic ground state. The procedure is benchmarked against experimental spectra of a set of small organic molecules at the carbon, nitrogen, and oxygen K edges.« less

Site partitioning of Cr3+ in the trichroic alexandrite BeAl2O4:Cr3+ crystal: contribution from x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Bordage, Amélie; Rossano, Stéphanie; Horn, Adolf Heinrich; Fuchs, Yves

2012-06-01

X-ray absorption spectroscopy measurements at the Cr K-edge of a trichroic crystal of alexandrite BeAl2O4:Cr3+ for different orientations of the crystal with respect to the polarization and direction of the x-ray incident beam have been performed. Analysis of the experimental spectra with the help of first-principles calculations of x-ray absorption spectra allowed us to estimate the proportion of chromium Cr3+ cations among the two different octahedral sites of the alexandrite structure (70% in the Cs site-30% in the Ci site). The methodology presented in this work opens up new possibilities in the field of mineralogy for the study of complex minerals containing several sites potentially occupied by several transition elements or for solid solutions.

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 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.

A Comprehensive X-Ray Absorption Model for Atomic Oxygen

NASA Technical Reports Server (NTRS)

Gorczyca, T. W.; Bautista, M. A.; Hasoglu, M. F.; Garcia, J.; Gatuzz, E.; Kaastra, J. S.; Kallman, T. R.; Manson, S. T.; Mendoza, C.; Raassen, A. J. J.;

TWO DISTINCT-ABSORPTION X-RAY COMPONENTS FROM TYPE IIn SUPERNOVAE: EVIDENCE FOR ASPHERICITY IN THE CIRCUMSTELLAR MEDIUM

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

Katsuda, Satoru; Tsuboi, Yohko; Maeda, Keiichi

2016-12-01

We present multi-epoch X-ray spectral observations of three Type IIn supernovae (SNe), SN 2005kd, SN 2006jd, and SN 2010jl, acquired with Chandra , XMM-Newton , Suzaku , and Swift . Previous extensive X-ray studies of SN 2010jl have revealed that X-ray spectra are dominated by thermal emission, which likely arises from a hot plasma heated by a forward shock propagating into a massive circumstellar medium (CSM). Interestingly, an additional soft X-ray component was required to reproduce the spectra at a period of ∼1–2 years after the SN explosion. Although this component is likely associated with the SN, its origin remained an open question. Wemore » find a similar, additional soft X-ray component from the other two SNe IIn as well. Given this finding, we present a new interpretation for the origin of this component; it is thermal emission from a forward shock essentially identical to the hard X-ray component, but directly reaches us from a void of the dense CSM. Namely, the hard and soft components are responsible for the heavily and moderately absorbed components, respectively. The co-existence of the two components with distinct absorptions as well as the delayed emergence of the moderately absorbed X-ray component could be evidence for asphericity of the CSM. We show that the X-ray spectral evolution can be qualitatively explained by considering a torus-like geometry for the dense CSM. Based on our X-ray spectral analyses, we estimate the radius of the torus-like CSM to be on the order of ∼5 × 10{sup 16} cm.« less

Optically detected X-ray absorption spectroscopy measurements as a means of monitoring corrosion layers on copper.

PubMed

Dowsett, Mark G; Adriaens, Annemie; Jones, Gareth K C; Poolton, Nigel; Fiddy, Steven; Nikitenko, Sergé

2008-11-15

XANES and EXAFS information is conventionally measured in transmission through the energy-dependent absorption of X-rays or by observing X-ray fluorescence, but secondary fluorescence processes, such as the emission of electrons and optical photons (e.g., 200-1000 nm), can also be used as a carrier of the XAS signatures, providing complementary information such as improved surface specificity. Where the near-visible photons have a shorter range in a material, the data will be more surface specific. Moreover, optical radiation may escape more readily than X-rays through liquid in an environmental cell. Here, we describe a first test of optically detected X-ray absorption spectroscopy (ODXAS) for monitoring electrochemical treatments on copper-based alloys, for example, heritage metals. Artificially made corrosion products deposited on a copper substrate were analyzed in air and in a 1% (w/v) sodium sesquicarbonate solution to simulate typical conservation methods for copper-based objects recovered from marine environments. The measurements were made on stations 7.1 and 9.2 MF (SRS Daresbury, UK) using the mobile luminescence end station (MoLES), supplemented by XAS measurements taken on DUBBLE (BM26 A) at the ESRF. The ODXAS spectra usually contain fine structure similar to that of XAS spectra measured in X-ray fluorescence. Importantly, for the compounds examined, the ODXAS is significantly more surface specific, and >98% characteristic of thin surface layers of 0.5-1.5-microm thickness in cases where X-ray measurements are dominated by the substrate. However, EXAFS and XANES from broadband optical measurements are superimposed on a high background due to other optical emission modes. This produces statistical fluctuations up to double what would be expected from normal counting statistics because the data retain the absolute statistical fluctuation in the original raw count, while losing up to 70% of their magnitude when background is removed. The problem may be

A simple heat-pipe cell for X-ray absorption spectrometry of potassium vapor

NASA Astrophysics Data System (ADS)

Pres̆eren, R.; Kodre, A.; Arc̆on, I.; Padez̆nik Gomils̆ek, J.; Hribar, M.

1999-01-01

The construction and operation of a simple high-temperature X-ray absorption cell for potassium vapor is described. The principle of "spectroscopic heat pipe" is exploited to separate kapton windows, indispensable for good transmission in the low-energy region, from the hot and aggressive vapor. High-resolution spectrum of the K-edge region of atomic potassium reveals fingerprints of multielectron photoexcitations.

Reactivity of Chromium(III) Nutritional Supplements in Biological Media: An X-Ray Absorption Spectroscopic Study

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

Nguyen, A.; Mulyani, I.; Levina, A.

2009-05-22

Chromium(III) nutritional supplements are widely used due to their purported ability to enhance glucose metabolism, despite growing evidence on low activity and the potential genotoxicity of these compounds. Reactivities of Cr(III) complexes used in nutritional formulations, including [Cr3O(OCOEt)6(OH2)3]+ (A), [Cr(pic)3] (pic) = 2-pyridinecarboxylato(-) (B), and trans-[CrCl2(OH2)4]+ (CrCl3 {center_dot} 6H2O; C), in a range of natural and simulated biological media (artificial digestion systems, blood and its components, cell culture media, and intact L6 rat skeletal muscle cells) were studied by X-ray absorption near-edge structure (XANES) spectroscopy. The XANES spectroscopic data were processed by multiple linear-regression analyses with the use of amore » library of model Cr(III) compounds, and the results were corroborated by the results of X-ray absorption fine structure spectroscopy and electrospray mass spectrometry. Complexes A and B underwent extensive ligand-exchange reactions under conditions of combined gastric and intestinal digestion (in the presence of a semisynthetic meal, 3 h at 310 K), as well as in blood serum and in a cell culture medium (1-24 h at 310 K), with the formation of Cr(III) complexes with hydroxo and amino acid/protein ligands. Reactions of compounds A-C with cultured muscle cells led to similar ligand-exchange products, with at least part of Cr(III) bound to the surface of the cells. The reactions of B with serum greatly enhanced its propensity to be converted to Cr(VI) by biological oxidants (H2O2 or glucose oxidase system), which is proposed to be a major cause of both the insulin-enhancing activity and toxicity of Cr(III) compounds (Mulyani, I.; Levina, A.; Lay, P. A. Angew. Chem. Int. Ed. 2004, 43, 4504-4507). This finding enhances the current concern over the safety of consumption of large doses of Cr(III) supplements, particularly [Cr(pic)3].« less

X-ray microscope for solidification studies

NASA Technical Reports Server (NTRS)

Kaukler, William

1995-01-01

This report covers the second 6 month period for the year March 1, 1994 to February 28, 1995. The material outlined in this semi-annual report continues from the previous semi-annual report. The Fein Focus Inc. x-ray source was delivered in September and coincides with the beginning of the second 6 month effort. As a result, and as outlined in the statement of work, this period was dedicated to the evaluation, testing and calibration of the x-ray source. In addition, in this period the modeling effort was continued and extended by the Tiger series of Monte-Carlo simulation programs for photon and electron interactions with materials obtained from the Oak Ridge RISC Library. Some further calculations were also made with the absorption model.

X-ray microscope for solidification studies

NASA Astrophysics Data System (ADS)

Kaukler, William

1995-02-01

This report covers the second 6 month period for the year March 1, 1994 to February 28, 1995. The material outlined in this semi-annual report continues from the previous semi-annual report. The Fein Focus Inc. x-ray source was delivered in September and coincides with the beginning of the second 6 month effort. As a result, and as outlined in the statement of work, this period was dedicated to the evaluation, testing and calibration of the x-ray source. In addition, in this period the modeling effort was continued and extended by the Tiger series of Monte-Carlo simulation programs for photon and electron interactions with materials obtained from the Oak Ridge RISC Library. Some further calculations were also made with the absorption model.

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

X-Ray Absorbed, Broad-Lined, Red AGN and the Cosmic X-Ray Background

NASA Technical Reports Server (NTRS)

Mushotzky, Richard (Technical Monitor); Wilkes, Belinda

2005-01-01

We have obtained XMM spectra for five red, 2MASS AGN, selected from a sample observed by Chandra to be X-ray bright and to cover a range of hardness ratios. Our results confirm the presence of substantial absorbing material in three sources which have optical classifications ranging from Type 1 to Type 2, with an intrinsically flat (hard) power law continuum indicated in the other two. The presence of both X-ray absorption and broad optical emission lines with the usual strength suggests either a small (nuclear) absorber or a favored viewing angle so as to cover the X-ray source but not the broad emission line region (BELR). A soft excess is detected in all three Type 1 sources. We speculate that this soft X-ray emission may arise in an extended region of ionized gas, perhaps linked with the polarized (scattered) light which is a feature of these sources. The spectral complexity revealed by XMM emphasizes the limitations of the low S/N Chandra data. Overall, the new XMM results strengthen our conclusions (Wilkes et al. 2002) that the observed X-ray continua of red AGN are unusually hard at energies greater than 2 keV. Whether due to substantial line-of-sight absorption or to an intrinsically hard or reflection-dominated spectrum, these 'red' AGN have an observed spectral form consistent with contributing significantly to the missing had absorbed population of the Cosmic X-ray Background (CXRB). When absorption and or reflection is taken into account, all these AGN have power law slopes typical of broad-line (Type 1) AGN (Gamma approximately 1.9). This appears to resolve the spectral paradox which for so long has existed between the CXRB and the AGN thought to be the dominant contributors. It also suggests two scenarios whereby Type 1 AGN/QSOs may be responsible for a significant fraction of the CXRB at energies above 2 keV: 1) X-ray absorbed AGN/QSOs with visible broad emission lines; 2) AGN/QSOs with complex spectra whose hardness greater than 2 keV is not

Enabling liquid solvent structure analysis using hard x-ray absorption spectroscopy with a transferrable microfluidic reactor

DOE PAGES

Zheng, Jian; Zhang, Wei; Wang, Feng; ...

2018-04-11

In this study, a vacuum compatible microfluidic device, system for analysis at the liquid vacuum interface, is integrated to hard x-ray absorption spectroscopy to obtain the local structure of K 3[Fe(CN) 6] in aqueous solutions with three concentrations of 0.5 M, 0.05 M, and 0.005 M. The solutions were sealed in a microchannel 500 µm wide and 300 µm deep in a portable microfluidic device. The Fe K-edge x-ray absorption spectra indicate a presence of Fe(III) in the complex in water, with an octahedral geometry coordinated with 6 C atoms in the first shell with a distance of ~1.92 Åmore » and 6 N atoms in the second shell with a distance of ~3.10 Å. Varying the concentration has no observable influence on the structure of K 3[Fe(CN) 6]. Our results demonstrate the feasibility of using microfluidic based liquid cells in large synchrotron facilities. Using portable microfludic reactors provides a viable approach to enable multifaceted measurements of liquids in the future.« less

Enabling liquid solvent structure analysis using hard x-ray absorption spectroscopy with a transferrable microfluidic reactor

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

Zheng, Jian; Zhang, Wei; Wang, Feng

In this study, a vacuum compatible microfluidic device, system for analysis at the liquid vacuum interface, is integrated to hard x-ray absorption spectroscopy to obtain the local structure of K 3[Fe(CN) 6] in aqueous solutions with three concentrations of 0.5 M, 0.05 M, and 0.005 M. The solutions were sealed in a microchannel 500 µm wide and 300 µm deep in a portable microfluidic device. The Fe K-edge x-ray absorption spectra indicate a presence of Fe(III) in the complex in water, with an octahedral geometry coordinated with 6 C atoms in the first shell with a distance of ~1.92 Åmore » and 6 N atoms in the second shell with a distance of ~3.10 Å. Varying the concentration has no observable influence on the structure of K 3[Fe(CN) 6]. Our results demonstrate the feasibility of using microfluidic based liquid cells in large synchrotron facilities. Using portable microfludic reactors provides a viable approach to enable multifaceted measurements of liquids in the future.« 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.

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

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

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.

Biotransformations of anticancer ruthenium(III) complexes: an X-ray absorption spectroscopic study.

PubMed

Levina, Aviva; Aitken, Jade B; Gwee, Yee Yen; Lim, Zhi Jun; Liu, Mimi; Singharay, Anannya Mitra; Wong, Pok Fai; Lay, Peter A

2013-03-11

An anti-metastatic drug, NAMI-A ((ImH)[Ru(III) Cl4 (Im)(dmso)]; Im=imidazole, dmso=S-bound dimethylsulfoxide), and a cytotoxic drug, KP1019 ((IndH)[Ru(III) Cl4 (Ind)2 ]; Ind=indazole), are two Ru-based anticancer drugs in human clinical trials. Their reactivities under biologically relevant conditions, including aqueous buffers, protein solutions or gels (e.g, albumin, transferrin and collagen), undiluted blood serum, cell-culture medium and human liver (HepG2) cancer cells, were studied by Ru K-edge X-ray absorption spectroscopy (XAS). These XAS data were fitted from linear combinations of spectra of well-characterised Ru compounds. The absence of XAS data from the parent drugs in these fits points to profound changes in the coordination environments of Ru(III) . The fits point to the presence of Ru(IV/III) clusters and binding of Ru(III) to S-donor groups, amine/imine and carboxylato groups of proteins. Cellular uptake of KP1019 is approximately 20-fold higher than that of NAMI-A under the same conditions, but it diminishes drastically after the decomposition of KP1019 in cell-culture media, which indicate that the parent complex is taken in by cells through passive diffusion. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

TH-AB-209-07: High Resolution X-Ray-Induced Acoustic Computed Tomography

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

Xiang, L; Tang, S; Ahmad, M

Purpose: X-ray radiographic absorption imaging is an invaluable tool in medical diagnostics, biology and materials science. However, the use of conventional CT is limited by two factors: the detection sensitivity to weak absorption material and the radiation dose from CT scanning. The purpose of this study is to explore X-ray induced acoustic computed tomography (XACT), a new imaging modality, which combines X-ray absorption contrast and high ultrasonic resolution to address these challenges. Methods: First, theoretical models was built to analyze the XACT sensitivity to X-ray absorption and calculate the minimal radiation dose in XACT imaging. Then, an XACT system comprisedmore » of an ultrashort X-ray pulse, a low noise ultrasound detector and a signal acquisition system was built to evaluate the X-ray induced acoustic signal generation. A piece of chicken bone and a phantom with two golden fiducial markers were exposed to 270 kVp X-ray source with 60 ns exposure time, and the X-ray induced acoustic signal was received by a 2.25MHz ultrasound transducer in 200 positions. XACT images were reconstructed by a filtered back-projection algorithm. Results: The theoretical analysis shows that X-ray induced acoustic signals have 100% relative sensitivity to X-ray absorption, but not to X-ray scattering. Applying this innovative technology to breast imaging, we can reduce radiation dose by a factor of 50 compared with newly FDA approved breast CT. The reconstructed images of chicken bone and golden fiducial marker phantom reveal that the spatial resolution of the built XACT system is 350µm. Conclusion: In XACT, the imaging sensitivity to X-ray absorption is improved and the imaging dose is dramatically reduced by using ultrashort pulsed X-ray. Taking advantage of the high ultrasonic resolution, we can also perform 3D imaging with a single X-ray pulse. This new modality has the potential to revolutionize x-ray imaging applications in medicine and biology.« less

Enhancement of X-ray dose absorption for medical applications

NASA Astrophysics Data System (ADS)

Lim, Sara; Montenegro, Maximiliano; Nahar, Sultana; Pradhan, Anil; Barth, Rolf; Nakkula, Robin; Bell, Erica; Yu, Yan

2012-06-01

Interaction of high-Z (HZ) elements with X-rays occurs efficiently at specific resonant energies. Cross sections for photoionization rapidly decrease after the K-edge; higher energy X-rays are mostly Compton-scattered. These features restrict the energy range for the use of HZ moities for radiosensitization in cancer therapy. Conventional X-ray sources such as linear accelerators (LINAC) used in radiotherapy emit a broad spectrum up to MeV energies. We explore the dichotomy between X-ray radiotherapy in two ranges: (i) E < 100 keV including HZ sensitization, and (ii) E > 100 keV where sensitization is inefficient. We perform Monte Carlo numerical simulations of tumor tissue embedded with platinum compounds and gold nanoparticles and compute radiation dose enhancement factors (DEF) upon irradiation with 100 kV, 170 kV and 6 MV sources. Our results demonstrate that the DEF peak below 100 keV and fall sharply above 200 keV to very small values. Therefore most of the X-ray output from LINACs up to the MeV range is utilized very inefficiently. We also describe experimental studies for implementation of option (i) using Pt and Au reagents and selected cancer cell lines. Resultant radiation exposure to patients could be greatly reduced, yet still result in increased tumoricidal ability.

Small scale H I structure and the soft X-ray background

NASA Technical Reports Server (NTRS)

Jahoda, K.; Mccammon, D.; Lockman, F. J.

1986-01-01

The observed anticorrelation between diffuse soft X-ray flux and H I column density has been explained as absorption of soft X-rays produced in a hot galactic halo, assuming that the neutral interstellar material is sufficiently clumped to reduce the soft X-ray absorption cross section by a factor of two to three. A 21 cm emission line study of H I column density variations at intermediate and high galactic latitudes to 10' spatial resolution has been done. The results confirm conclusions from preliminary work at coarser resolution, and in combination with other data appear to rule out the hypothesis that clumping of neutral interstellar matter on any angular scale significantly reduces X-ray absorption cross sections in the 0.13 - 0.28 keV energy range. It is concluded therefore that the observed anticorrelation is not primarily a consequence of absorption of soft X-rays produced in a hot galactic halo.

Combined Mössbauer spectroscopic, multi-edge X-ray absorption spectroscopic, and density functional theoretical study of the radical SAM enzyme spore photoproduct lyase.

PubMed

Silver, Sunshine C; Gardenghi, David J; Naik, Sunil G; Shepard, Eric M; Huynh, Boi Hanh; Szilagyi, Robert K; Broderick, Joan B

2014-03-01

Spore photoproduct lyase (SPL), a member of the radical S-adenosyl-L-methionine (SAM) superfamily, catalyzes the direct reversal of the spore photoproduct, a thymine dimer specific to bacterial spores, to two thymines. SPL requires SAM and a redox-active [4Fe-4S] cluster for catalysis. Mössbauer analysis of anaerobically purified SPL indicates the presence of a mixture of cluster states with the majority (40 %) as [2Fe-2S](2+) clusters and a smaller amount (15 %) as [4Fe-4S](2+) clusters. On reduction, the cluster content changes to primarily (60 %) [4Fe-4S](+). The speciation information from Mössbauer data allowed us to deconvolute iron and sulfur K-edge X-ray absorption spectra to uncover electronic (X-ray absorption near-edge structure, XANES) and geometric (extended X-ray absorption fine structure, EXAFS) structural features of the Fe-S clusters, and their interactions with SAM. The iron K-edge EXAFS data provide evidence for elongation of a [2Fe-2S] rhomb of the [4Fe-4S] cluster on binding SAM on the basis of an Fe···Fe scatterer at 3.0 Å. The XANES spectra of reduced SPL in the absence and presence of SAM overlay one another, indicating that SAM is not undergoing reductive cleavage. The X-ray absorption spectroscopy data for SPL samples and data for model complexes from the literature allowed the deconvolution of contributions from [2Fe-2S] and [4Fe-4S] clusters to the sulfur K-edge XANES spectra. The analysis of pre-edge features revealed electronic changes in the Fe-S clusters as a function of the presence of SAM. The spectroscopic findings were further corroborated by density functional theory calculations that provided insights into structural and electronic perturbations that can be correlated by considering the role of SAM as a catalyst or substrate.

X-ray diffraction and X-ray K absorption near edge studies of copper (II) complexes with amino acids

NASA Astrophysics Data System (ADS)

Sharma, P. K.; Mishra, Ashutosh; Malviya, Varsha; Kame, Rashmi; Malviya, P. K.

2017-05-01

Synthesis of copper (II) complexes [CuL1L2X].nH2O, where n=1, 2,3 (X=Cl,Br,NO3) (L1is 2,2’-bipyridine and L2 is L-tyrosine) by the chemical root method. The XRD data for the samples have been recorded. EXAFS spectra have also been recorded at the K-edge of Cu using the dispersive beam line BL-8 at 2.5 Gev Indus-2 Synchrotron radiation source at RRCAT, Indore, India. XRD and EXAFS data have been analysed using the computer software. X-ray diffraction studies of all complexes indicate their crystalline nature. Lattice parameter, bond length, particle size have been determined from XRD data.

BIOCHEMICAL STUDY OF THE RADIOSENSITIVITY OF THE SMALL INTESTINE TO X RAYS. I. ABSORPTION OF LIPIDS (in French)

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

Maisin, J.R.; Dulcino, J.; Verly, W.

1963-01-01

The first results of a study on the absorption of fats during acute gastro-intestinal syndrome, occurring after irradiation, are reported. Three- month old C/sup +/ mice were exposed on the stomach with x-ray doses of 600, 1500, and 2500 r. The third day after irradiation the mice received either by stomach tube or injection in the duodenum a diet containing glyceryl-tri- (palmitate-1-C /sup 14/) or H/sup 3/-palmitic acid giving an activity equal to 0.5 mu c C/sup 14/ or 1 mu c H/sup 3/. The mice were sacrificed at different moments after administration of the diet. The results are givenmore » graphically and discussed. It was shown that the decrease in the absorption of fats, given by stomach tube, to mice receiving an abdominal irradiation of 1500 and 2500 r is essentially caused by gastric retention. In effect, when the fats are introduced directly in the duodenum, the absorption decrease observed in the irradiated mouse is not significant. There is no significant modification in the absorption of fats 13 months after irradiation with 600 r, whether they are given by stomach tube or duodenum injection. (J.S.R.)« less

X-ray absorption near-edge spectroscopy in bioinorganic chemistry: Application to M–O2 systems

PubMed Central

Sarangi, Ritimukta

2012-01-01

Metal K-edge X-ray absorption spectroscopy (XAS) has been extensively applied to bioinorganic chemistry to obtain geometric structure information on metalloprotein and biomimetic model complex active sites by analyzing the higher energy extended X-ray absorption fine structure (EXAFS) region of the spectrum. In recent years, focus has been on developing methodologies to interpret the lower energy K-pre-edge and rising-edge regions (XANES) and using it for electronic structure determination in complex bioinorganic systems. In this review, the evolution and progress of 3d-transition metal K-pre-edge and rising-edge methodology development is presented with particular focus on applications to bioinorganic systems. Applications to biomimetic transition metal–O2 intermediates (M = Fe, Co, Ni and Cu) are reviewed, which demonstrate the power of the method as an electronic structure determination technique and its impact in understanding the role of supporting ligands in tuning the electronic configuration of transition metal–O2 systems. PMID:23525635

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).

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.

X-ray phase-contrast imaging

NASA Astrophysics Data System (ADS)

Endrizzi, Marco

2018-01-01

X-ray imaging is a standard tool for the non-destructive inspection of the internal structure of samples. It finds application in a vast diversity of fields: medicine, biology, many engineering disciplines, palaeontology and earth sciences are just few examples. The fundamental principle underpinning the image formation have remained the same for over a century: the X-rays traversing the sample are subjected to different amount of absorption in different parts of the sample. By means of phase-sensitive techniques it is possible to generate contrast also in relation to the phase shifts imparted by the sample and to extend the capabilities of X-ray imaging to those details that lack enough absorption contrast to be visualised in conventional radiography. A general overview of X-ray phase contrast imaging techniques is presented in this review, along with more recent advances in this fast evolving field and some examples of applications.

MULTI-WAVELENGTH STUDIES OF SPECTACULAR RAM PRESSURE STRIPPING OF A GALAXY: DISCOVERY OF AN X-RAY ABSORPTION FEATURE

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

Gu, Liyi; Makishima, Kazuo; Yagi, Masafumi

We report the detection of an X-ray absorption feature near the galaxy M86 in the Virgo cluster. The absorber has a column density of 2-3 × 10{sup 20} cm{sup –2}, and its position coincides with the peak of an intracluster H I cloud which was removed from the galaxy NGC 4388 presumably by ram pressure. These results indicate that the H I cloud is located in front of M86 along the line-of-sight, and suggest that the stripping was primarily created by an interaction between NGC 4388 and the hot plasmas of the Virgo cluster, not the M86 halo. By calculatingmore » an X-ray temperature map, we further detected an X-ray counterpart of the H I cloud up to ≈3' south of M86. It has a temperature of 0.89 keV and a mass of ∼4.5 × 10{sup 8} M {sub ☉}, exceeding the estimated H I gas mass. The high hot-to-cold gas ratio in the cloud indicates a significant evaporation of the H I gas, probably by thermal conduction from the hotter cluster plasma with a sub-Spitzer rate.« less

X-Ray Absorption, Nuclear Infrared Emission, and Dust Covering Factors of AGNs: Testing Unification Schemes

NASA Astrophysics Data System (ADS)

Mateos, S.; Carrera, F. J.; Alonso-Herrero, A.; Hernán-Caballero, A.; Barcons, X.; Asensio Ramos, A.; Watson, M. G.; Blain, A.; Caccianiga, A.; Ballo, L.; Braito, V.; Ramos Almeida, C.

2016-03-01

We present the distributions of the geometrical covering factors of the dusty tori (f2) of active galactic nuclei (AGNs) using an X-ray selected complete sample of 227 AGNs drawn from the Bright Ultra-hard XMM-Newton Survey. The AGNs have z from 0.05 to 1.7, 2-10 keV luminosities between 1042 and 1046 erg s-1, and Compton-thin X-ray absorption. Employing data from UKIDSS, 2MASS, and the Wide-field Infrared Survey Explorer in a previous work, we determined the rest-frame 1-20 μm continuum emission from the torus, which we model here with the clumpy torus models of Nenkova et al. Optically classified type 1 and type 2 AGNs are intrinsically different, with type 2 AGNs having, on average, tori with higher f2 than type 1 AGNs. Nevertheless, ˜20% of type 1 AGNs have tori with large covering factors, while ˜23%-28% of type 2 AGNs have tori with small covering factors. Low f2 are preferred at high AGN luminosities, as postulated by simple receding torus models, although for type 2 AGNs the effect is certainly small. f2 increases with the X-ray column density, which implies that dust extinction and X-ray absorption take place in material that share an overall geometry and most likely belong to the same structure, the putative torus. Based on our results, the viewing angle, AGN luminosity, and also f2 determine the optical appearance of an AGN and control the shape of the rest-frame ˜1-20 μm nuclear continuum emission. Thus, the torus geometrical covering factor is a key ingredient of unification schemes.

Orientational behavior of thin films of poly(3-methylthiophene) on platinium: A FTIR and near edge x-ray absorption fine structure (NEXAFS) study

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

Yang, X.Q.; Chen, J.; Hale, P.D.

1988-01-01

Near edge x-ray absorption fine structure (NEXAFS) and infrared reflection-absorption spectroscopy (IRRAS) have been used to study the orientational behavior of thin films of poly(3-methylthiophene) electrochemically polymerized on a platinum surface. Clear orientational effects, with the thiophene rings predominantly oriented parallel to the platinum surface, were observed when the thickness of the polymer films were within a few hundred /angstrom/A. It was found that more highly ordered films were produced at lower polymerization potential (1.4V vs SCE) than at higher potential (1.8V vs SCE). 5 refs., 4 figs., 2 tabs.

X-ray absorption spectroscopy and imaging of heterogeneous hydrothermal mixtures using a diamond microreactor cell

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

Fulton, John L.; Darab, John G.; Hoffmann, Markus M.

2001-04-01

Hydrothermal synthesis is an important route to novel materials. Hydrothermal chemistry is also an important aspect of geochemistry and a variety of waste remediation technologies. There is a significant lack of information about the speciation of inorganic compounds under hydrothermal conditions. For these reasons we describe a high-temperature, high-pressure cell that allows one to acquire both x-ray absorption fine structure (XAFS) spectra and x-ray transmission and absorption images of heterogeneous hydrothermal mixtures. We demonstrate the utility of the method by measuring the Cu(I) speciation in a solution containing both solid and dissolved Cu phases at temperatures up to 325{sup o}C.more » X-ray imaging of the various hydrothermal phases allows micro-XAFS to be collected from different phases within the heterogeneous mixture. The complete structural characterization of a soluble bichloro-cuprous species was determined. In situ XAFS measurements were used to define the oxidation state and the first-shell coordination structure. The Cu--Cl distance was determined to be 2.12 Aa for the CuCl{sub 2}{sup -} species and the complete loss of tightly bound waters of hydration in the first shell was observed. The microreactor cell described here can be used to test thermodynamic models of solubility and redox chemistry of a variety of different hydrothermal mixtures.« less

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

Molybdenum X-Ray Absorption Edges from 200 – 20,000 eV, The Benefits of Soft X-Ray Spectroscopy for Chemical Speciation

PubMed Central

George, Simon J.; Drury, Owen B.; Fu, Juxia; Friedrich, Stephan; Doonan, Christian J.; George, Graham N.; White, Jonathan M.; Young, Charles G.; Cramer, Stephen P.

2009-01-01

We have surveyed the chemical utility of the near-edge structure of molybdenum x-ray absorption edges from the hard x-ray K-edge at 20,000 eV down to the soft x-ray M4,5-edges at ~230 eV. We compared, for each edge, the spectra of two tetrahedral anions, MoO4 and MoS42-. We used three criteria for assessing near-edge structure of each edge: (i) the ratio of the observed chemical shift between MoO42- and MoS42- and the linewidth, (ii) the chemical information from analysis of the near-edge structure and (iii) the ease of measurement using fluorescence detection. Not surprisingly, the K-edge was by far the easiest to measure, but it contained the least information. The L2,3-edges, although harder to measure, had benefits with regard to selection rules and chemical speciation in that they had both a greater chemical shift as well as detailed lineshapes which could be theoretically analyzed in terms of Mo ligand field, symmetry, and covalency. The soft x-ray M2,3-edges were perhaps the least useful, in that they were difficult to measure using fluorescence detection and had very similar information content to the corresponding L2,3-edges. Interestingly, the soft x-ray, low energy (~230 eV) M4,5-edges had greatest potential chemical sensitivity and using our high resolution superconducting tunnel junction (STJ) fluorescence detector they appear to be straightforward to measure. The spectra were amenable to analysis using both the TT-multiplet approach and FEFF. The results using FEFF indicate that the sharp near-edge peaks arise from 3d → 5p transitions, while the broad edge structure has predominately 3d → 4f character. A proper understanding of the dependence of these soft x-ray spectra on ligand field and site geometry is necessary before a complete assessment of the utility of the Mo M4,5-edges can be made. This work includes crystallographic characterization of sodium tetrathiomolybdate. PMID:19041140

X-ray data booklet. Revision

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

Vaughan, D.

A compilation of data is presented. Included are properties of the elements, electron binding energies, characteristic x-ray energies, fluorescence yields for K and L shells, Auger energies, energy levels for hydrogen-, helium-, and neonlike ions, scattering factors and mass absorption coefficients, and transmission bands of selected filters. Also included are selected reprints on scattering processes, x-ray sources, optics, x-ray detectors, and synchrotron radiation facilities. (WRF)

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.

Joint reconstruction of x-ray fluorescence and transmission tomography

DOE PAGES

Di, Zichao; Chen, Si; Hong, Young Pyo; ...

2017-05-30

X-ray fluorescence tomography is based on the detection of fluorescence x-ray photons produced following x-ray absorption while a specimen is rotated; it provides information on the 3D distribution of selected elements within a sample. One limitation in the quality of sample recovery is the separation of elemental signals due to the finite energy resolution of the detector. Another limitation is the effect of self-absorption, which can lead to inaccurate results with dense samples. To recover a higher quality elemental map, we combine x-ray fluorescence detection with a second data modality: conventional x-ray transmission tomography using absorption. By using these combinedmore » signals in a nonlinear optimization-based approach, we demonstrate the benefit of our algorithm on real experimental data and obtain an improved quantitative reconstruction of the spatial distribution of dominant elements in the sample. Furthermore, compared with single-modality inversion based on x-ray fluorescence alone, this joint inversion approach reduces ill-posedness and should result in improved elemental quantification and better correction of self-absorption.« less

Joint reconstruction of x-ray fluorescence and transmission tomography

PubMed Central

Di, Zichao Wendy; Chen, Si; Hong, Young Pyo; Jacobsen, Chris; Leyffer, Sven; Wild, Stefan M.

2017-01-01

X-ray fluorescence tomography is based on the detection of fluorescence x-ray photons produced following x-ray absorption while a specimen is rotated; it provides information on the 3D distribution of selected elements within a sample. One limitation in the quality of sample recovery is the separation of elemental signals due to the finite energy resolution of the detector. Another limitation is the effect of self-absorption, which can lead to inaccurate results with dense samples. To recover a higher quality elemental map, we combine x-ray fluorescence detection with a second data modality: conventional x-ray transmission tomography using absorption. By using these combined signals in a nonlinear optimization-based approach, we demonstrate the benefit of our algorithm on real experimental data and obtain an improved quantitative reconstruction of the spatial distribution of dominant elements in the sample. Compared with single-modality inversion based on x-ray fluorescence alone, this joint inversion approach reduces ill-posedness and should result in improved elemental quantification and better correction of self-absorption. PMID:28788848

RefleX: X-ray absorption and reflection in active galactic nuclei for arbitrary geometries

NASA Astrophysics Data System (ADS)

Paltani, S.; Ricci, C.

2017-11-01

Reprocessed X-ray radiation carries important information about the structure and physical characteristics of the material surrounding the supermassive black hole (SMBH) in active galactic nuclei (AGN). We report here on a newly developed simulation platform, RefleX, which allows to reproduce absorption and reflection by quasi-arbitrary geometries. We show here the reliability of our approach by comparing the results of our simulations with existing spectral models such as pexrav, MYTorus and BNTorus. RefleX implements both Compton scattering on free electrons and Rayleigh scattering and Compton scattering on bound electrons. We show the effect of bound-electron corrections on a torus geometry simulated like in MYTorus. We release with this paper the RefleX executable, as well as RXTorus, a model that assumes absorption and reflection from a torus with a varying ratio of the minor to major axis of the torus. To allow major flexibility RXTorus is also distributed in three components: absorbed primary emission, scattered radiation and fluorescent lines. RXTorus is provided for different values of the abundance, and with (atomic configuration) or without (free-electron configuration) taking into account Rayleigh scattering and bound electrons. We apply the RXTorus model in both configurations on the XMM-Newton and NuSTAR spectrum of the Compton-thick AGN NGC 424 and find that the models are able to reproduce very well the observations, but that the assumption on the bound or free state of the electrons has significant consequences on the fit parameters. RefleX executable, user manual and example models are available at http://www.astro.unige.ch/reflex. A copy of the RefleX executable is also 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/607/A31

Dynamical core-hole screening in the x-ray absorption spectra of hydrogenated carbon nanotubes and graphene

NASA Astrophysics Data System (ADS)

Wessely, O.; Katsnelson, M. I.; Nilsson, A.; Nikitin, A.; Ogasawara, H.; Odelius, M.; Sanyal, B.; Eriksson, O.

2007-10-01

We have calculated the electronic structure and the x-ray absorption (XA) spectrum of a hydrogenated single graphite plane, in order to simulate recent experimental results on hydrogenated single wall carbon nanotubes (SWCNT) as well as hydrogenated graphene. We find that the presence of H induces a substantial component of sp3 bonding and as a result the π and π* components to the electronic structure vanish. We have calculated a theoretical x-ray absorption spectrum using a multiband version of the Mahan-Nozières-De Dominicis theory. By making a fitting of the XA signal of C atoms that have H attached to them and C atoms without H in the vicinity we obtain a good representation of the experimental data and we can draw the conclusion that in the experiments [A. Nikitin , Phys. Rev. Lett. 95, 225507 (2005)] some 35-50 % H have been absorbed in the SWCNT.

Extended X-ray Absorption Fine Structure Study of Bond Constraints in Ge-Sb-Te Alloys

DTIC Science & Technology

2011-02-07

Ray Absorption Spectroscopy, or EXAFS. Using the spectroscopic capabilities provided by the MCAT line at the Advanced Photon Source at Argonne...Absorption Spectroscopy, or EXAFS. Using the spectroscopic capabilities provided by the MCAT line at the Advanced Photon Source at Argonne National

Oxidation Induced Doping of Nanoparticles Revealed by in Situ X-ray Absorption Studies.

PubMed

Kwon, Soon Gu; Chattopadhyay, Soma; Koo, Bonil; Dos Santos Claro, Paula Cecilia; Shibata, Tomohiro; Requejo, Félix G; Giovanetti, Lisandro J; Liu, Yuzi; Johnson, Christopher; Prakapenka, Vitali; Lee, Byeongdu; Shevchenko, Elena V

2016-06-08

Doping is a well-known approach to modulate the electronic and optical properties of nanoparticles (NPs). However, doping at nanoscale is still very challenging, and the reasons for that are not well understood. We studied the formation and doping process of iron and iron oxide NPs in real time by in situ synchrotron X-ray absorption spectroscopy. Our study revealed that the mass flow of the iron triggered by oxidation is responsible for the internalization of the dopant (molybdenum) adsorbed at the surface of the host iron NPs. The oxidation induced doping allows controlling the doping levels by varying the amount of dopant precursor. Our in situ studies also revealed that the dopant precursor substantially changes the reaction kinetics of formation of iron and iron oxide NPs. Thus, in the presence of dopant precursor we observed significantly faster decomposition rate of iron precursors and substantially higher stability of iron NPs against oxidation. The same doping mechanism and higher stability of host metal NPs against oxidation was observed for cobalt-based systems. Since the internalization of the adsorbed dopant at the surface of the host NPs is driven by the mass transport of the host, this mechanism can be potentially applied to introduce dopants into different oxidized forms of metal and metal alloy NPs providing the extra degree of compositional control in material design.

X-ray K-edge absorption spectra of Fe minerals and model compounds: II. EXAFS

NASA Astrophysics Data System (ADS)

Waychunas, Glenn A.; Brown, Gordon E.; Apted, Michael J.

1986-01-01

K-edge extended X-ray absorption fine structure (EXAFS) spectra of Fe in varying environments in a suite of well-characterized silicate and oxide minerals were collected using synchrotron radiation and analyzed using single scattering approximation theory to yield nearest neighbor Fe-O distances and coordination numbers. The partial inverse character of synthetic hercynite spinal was verified in this way. Comparison of the results from all samples with structural data from X-ray diffraction crystal structure refinements indicates that EXAFS-derived first neighbor distances are generally accurate to ±0.02 Å using only theoretically generated phase information, and may be improved over this if similar model compounds are used to determine EXAFS phase functions. Coordination numbers are accurate to ±20 percent and can be similarly improved using model compound EXAFS amplitude information. However, in particular cases the EXAFS-derived distances may be shortened, and the coordination number reduced, by the effects of static and thermal disorder or by partial overlap of the longer Fe-O first neighbor distances with second neighbor distances in the EXAFS structure function. In the former case the total information available in the EXAFS is limited by the disorder, while in the latter case more accurate results can in principle be obtained by multiple neighbor EXAFS analysis. The EXAFS and XANES spectra of Fe in Nain, Labrador osumulite and Lakeview, Oregon plagioclase are also analyzed as an example of the application of X-ray absorption spectroscopy to metal ion site occupation determination in minerals.

Current and Future X-ray Studies of High-Redshift AGNs and the First Supermassive Black Holes

NASA Astrophysics Data System (ADS)

Brandt, Niel

2016-01-01

X-ray observations of high-redshift AGNs at z = 4-7 have played a critical role in understanding the physical processes at work inthese objects as well as their basic demographics. Since 2000, Chandra and XMM-Newton have provided new X-ray detections for more than 120 such objects, and well-defined samples of z > 4 AGNs now allow reliable X-ray population studies. Once luminosity effectsare considered, the basic X-ray continuum properties of most high-redshift AGNs appear remarkably similar to those of local AGNs, although there are some notable apparent exceptions (e.g., highly radio-loud quasars). Furthermore, the X-ray absorption found in some objects has been used as a diagnostic of outflowing winds and circumnuclear material. Demographically, the X-ray data now support an exponential decline in the number density of luminous AGNs above z ~ 3, and quantitative space-density comparisons for optically selected and X-ray selected quasars indicate basic statistical agreement.The current X-ray discoveries point the way toward the future breakthroughs that will be possible with, e.g., Athena and the X-raySurveyor. These missions will execute powerful blank-field surveys to elucidate the demographics of the first growing supermassive black holes (SMBHs), including highly obscured systems, up to z ~ 10. They will also carry out complementary X-ray spectroscopic and variability investigations of high-redshift AGNs by targeting the most-luminous z = 7-10 quasars found in wide-field surveys by, e.g., Euclid, LSST, and WFIRST. X-ray spectroscopic and variability studies of the X-ray continuum and reflection signatures will help determine Eddington ratios and disk/corona properties; measuring these will clarify how the first quasars grew so quickly. Furthermore, absorption line/edge studies will reveal how outflows from the first SMBHs influenced the growth of the first galaxies. I will suggest some efficient observational strategies for Athena and the X-ray Surveyor.

Interlaced X-ray diffraction computed tomography

PubMed Central

Vamvakeros, Antonios; Jacques, Simon D. M.; Di Michiel, Marco; Senecal, Pierre; Middelkoop, Vesna; Cernik, Robert J.; Beale, Andrew M.

2016-01-01

An X-ray diffraction computed tomography data-collection strategy that allows, post experiment, a choice between temporal and spatial resolution is reported. This strategy enables time-resolved studies on comparatively short timescales, or alternatively allows for improved spatial resolution if the system under study, or components within it, appear to be unchanging. The application of the method for studying an Mn–Na–W/SiO2 fixed-bed reactor in situ is demonstrated. Additionally, the opportunities to improve the data-collection strategy further, enabling post-collection tuning between statistical, temporal and spatial resolutions, are discussed. In principle, the interlaced scanning approach can also be applied to other pencil-beam tomographic techniques, like X-ray fluorescence computed tomography, X-ray absorption fine structure computed tomography, pair distribution function computed tomography and tomographic scanning transmission X-ray microscopy. PMID:27047305

Spectral studies of cosmic X-ray sources

NASA Astrophysics Data System (ADS)

Blissett, R. J.

1980-01-01

The conventional "indirect" method of reduction and data analysis of spectral data from non-dispersive X-ray detectors, by the fitting of assumed spectral models, is examined. The limitations of this procedure are presented, and alternative schemes are considered in which the derived spectra are not biased to an astrophysical source model. A new method is developed in detail to directly restore incident photon spectra from the detected count histograms. This Spectral Restoration Technique allows an increase in resolution, to a degree dependent on the statistical precision of the data. This is illustrated by numerical simulations. Proportional counter data from Ariel 5 are analysed using this technique. The results obtained for the sources Cas A and the Crab Nebula are consistent with previous analyses and show that increases in resolution of up to a factor three are possible in practice. The source Cyg X-3 is closely examined. Complex spectral variability is found, with the continuum and iron-line emission modulated with the 4.8 hour period of the source. The data suggest multi-component emission in the source. Comparing separate Ariel 5 observations and published data from other experiments, a correlation between the spectral shape and source intensity is evident. The source behaviour is discussed with reference to proposed source models. Data acquired by the low-energy detectors on-board HEAO-1 are analysed using the Spectral Restoration Technique. This treatment explicitly demonstrates the existence of oxygen K-absorption edges in the soft X-ray spectra of the Crab Nebula and Sco X-1. These results are considered with reference to current theories of the interstellar medium. The thesis commences with a review of cosmic X-ray sources and the mechanisms responsible for their spectral signatures, and continues with a discussion of the instruments appropriate for spectral studies in X-ray astronomy.

ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectropscopy using IFEFFIT

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

Ravel, B.; Newville, M.; UC)

2010-07-20

A software package for the analysis of X-ray absorption spectroscopy (XAS) data is presented. This package is based on the IFEFFIT library of numerical and XAS algorithms and is written in the Perl programming language using the Perl/Tk graphics toolkit. The programs described here are: (i) ATHENA, a program for XAS data processing, (ii) ARTEMIS, a program for EXAFS data analysis using theoretical standards from FEFF and (iii) HEPHAESTUS, a collection of beamline utilities based on tables of atomic absorption data. These programs enable high-quality data analysis that is accessible to novices while still powerful enough to meet the demandsmore » of an expert practitioner. The programs run on all major computer platforms and are freely available under the terms of a free software license.« less

Measuring the Dust Grains and Distance to X Persei Via Its X-ray Halo

NASA Astrophysics Data System (ADS)

Smith, Randall

2006-09-01

We propose to observe the X-ray halo of the high mass X-ray binary pulsar X Per to measure interstellar dust grains along the line of sight (LOS) and to determine the distance to X Per. The X-ray halo is formed by scattering from grains along the LOS, which for X Per appear to be concentrated in one molecular cloud. Unlike many other X-ray halo observations, this low-absorption high-latitude sightline is well-characterized from absorption spectroscopy done with HST, Copernicus, and FUSE. This halo observation will measure the distance to the cloud and the dust size distribution in it. We will also be able to determine the distance to X Per by measuring the time delayed pulses in the X-ray halo.

X-RAY ABSORPTION, NUCLEAR INFRARED EMISSION, AND DUST COVERING FACTORS OF AGNs: TESTING UNIFICATION SCHEMES

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

Mateos, S.; Carrera, F. J.; Alonso-Herrero, A.

2016-03-10

We present the distributions of the geometrical covering factors of the dusty tori (f{sub 2}) of active galactic nuclei (AGNs) using an X-ray selected complete sample of 227 AGNs drawn from the Bright Ultra-hard XMM-Newton Survey. The AGNs have z from 0.05 to 1.7, 2–10 keV luminosities between 10{sup 42} and 10{sup 46} erg s{sup −1}, and Compton-thin X-ray absorption. Employing data from UKIDSS, 2MASS, and the Wide-field Infrared Survey Explorer in a previous work, we determined the rest-frame 1–20 μm continuum emission from the torus, which we model here with the clumpy torus models of Nenkova et al. Opticallymore » classified type 1 and type 2 AGNs are intrinsically different, with type 2 AGNs having, on average, tori with higher f{sub 2} than type 1 AGNs. Nevertheless, ∼20% of type 1 AGNs have tori with large covering factors, while ∼23%–28% of type 2 AGNs have tori with small covering factors. Low f{sub 2} are preferred at high AGN luminosities, as postulated by simple receding torus models, although for type 2 AGNs the effect is certainly small. f{sub 2} increases with the X-ray column density, which implies that dust extinction and X-ray absorption take place in material that share an overall geometry and most likely belong to the same structure, the putative torus. Based on our results, the viewing angle, AGN luminosity, and also f{sub 2} determine the optical appearance of an AGN and control the shape of the rest-frame ∼1–20 μm nuclear continuum emission. Thus, the torus geometrical covering factor is a key ingredient of unification schemes.« 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.

High Resolution X-ray-Induced Acoustic Tomography

PubMed Central

Xiang, Liangzhong; Tang, Shanshan; Ahmad, Moiz; Xing, Lei

2016-01-01

Absorption based CT imaging has been an invaluable tool in medical diagnosis, biology, and materials science. However, CT requires a large set of projection data and high radiation dose to achieve superior image quality. In this letter, we report a new imaging modality, X-ray Induced Acoustic Tomography (XACT), which takes advantages of high sensitivity to X-ray absorption and high ultrasonic resolution in a single modality. A single projection X-ray exposure is sufficient to generate acoustic signals in 3D space because the X-ray generated acoustic waves are of a spherical nature and propagate in all directions from their point of generation. We demonstrate the successful reconstruction of gold fiducial markers with a spatial resolution of about 350 μm. XACT reveals a new imaging mechanism and provides uncharted opportunities for structural determination with X-ray. PMID:27189746

Backscatter of hard X-rays in the solar atmosphere. [Calculating the reflectance of solar x ray emission

NASA Technical Reports Server (NTRS)

Bai, T.; Ramaty, R.

1977-01-01

The solar photosphere backscatters a substantial fraction of the hard X rays from solar flares incident upon it. This reflection was studied using a Monte Carlo simulation which takes into account Compton scattering and photo-electric absorption. Both isotropic and anisotropic X ray sources are considered. The bremsstrahlung from an anisotropic distribution of electrons are evaluated. By taking the reflection into account, the inconsistency is removed between recent observational data regarding the center-to-limb variation of solar X ray emission and the predictions of models in which accelerated electrons are moving down toward the photosphere.

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.

X-ray absorption microtomography (microCT) and small beam diffraction mapping of sea urchin teeth.

PubMed

Stock, S R; Barss, J; Dahl, T; Veis, A; Almer, J D

2002-07-01

Two noninvasive X-ray techniques, laboratory X-ray absorption microtomography (microCT) and X-ray diffraction mapping, were used to study teeth of the sea urchin Lytechinus variegatus. MicroCT revealed low attenuation regions at near the tooth's stone part and along the carinar process-central prism boundary; this latter observation appears to be novel. The expected variation of Mg fraction x in the mineral phase (calcite, Ca(1-x)Mg(x)CO(3)) cannot account for all of the linear attenuation coefficient decrease in the two zones: this suggested that soft tissue is localized there. Transmission diffraction mapping (synchrotron X-radiation, 80.8 keV, 0.1 x 0.1mm(2) beam area, 0.1mm translation grid, image plate area detector) simultaneously probed variations in 3-D and showed that the crystal elements of the "T"-shaped tooth were very highly aligned. Diffraction patterns from the keel (adaxial web) and from the abaxial flange (containing primary plates and the stone part) differed markedly. The flange contained two populations of identically oriented crystal elements with lattice parameters corresponding to x=0.13 and x=0.32. The keel produced one set of diffraction spots corresponding to the lower x. The compositions were more or less equivalent to those determined by others for camarodont teeth, and the high Mg phase is expected to be disks of secondary mineral epitaxially related to the underlying primary mineral element. Lattice parameter gradients were not noted in the keel or flange. Taken together, the microCT and diffraction results indicated that there was a band of relatively high protein content, of up to approximately 0.25 volume fraction, in the central part of the flange and paralleling its adaxial and abaxial faces. X-ray microCT and microdiffraction data used in conjunction with protein distribution data will be crucial for understanding the properties of various biocomposites and their mechanical functions.

Dynamical Core-Hole Screening in the X-Ray Absorption Spectra of Hydrogenated Carbon Nanotubes And Graphene

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

Wessely, O.; /Uppsala U. /Imperial Coll., London; Katsnelson, M.I.

2009-04-30

We have calculated the electronic structure and the x-ray absorption (XA) spectrum of a hydrogenated single graphite plane, in order to simulate recent experimental results on hydrogenated single wall carbon nanotubes (SWCNT) as well as hydrogenated graphene. We find that the presence of H induces a substantial component of sp{sup 3} bonding and as a result the {pi} and {pi}* components to the electronic structure vanish. We have calculated a theoretical x-ray absorption spectrum using a multiband version of the Mahan-Nozieres-De Dominicis theory. By making a fitting of the XA signal of C atoms that have H attached to themmore » and C atoms without H in the vicinity we obtain a good representation of the experimental data and we can draw the conclusion that in the experiments [A. Nikitin et al., Phys. Rev. Lett. 95, 225507 (2005)] some 35-50 % H have been absorbed in the SWCNT.« less

Quantitative X-ray Differential Interference Contrast Microscopy

NASA Astrophysics Data System (ADS)

Nakamura, Takashi

. A new illumination apparatus required for the transfer function analysis under partially coherent illumination is also proposed. Such a characterization is essential for a proper selection of DIC optics for various transparent samples under study. Finally, optical elements used for x-ray DIC microscopy are highly absorptive and high brilliance x-ray sources such as synchrotrons are generally needed for image contrast. To extend the use of x-ray DIC microscopy to a wider variety of applications, a high efficiency large numerical aperture optical element consisting of high reflective Bragg reflectors is proposed. Using Bragg reflectors, which have 70% ˜99% reflectivity at extreme ultraviolet and soft x-rays for all angles of glancing incidence, the first order focusing efficiency is expected to increase by ˜ 8 times compared to that of a typical Fresnel zone-plate. This thesis contributes to current nanoscale x-ray phase contrast imaging research and provides new insights for biological, material, and magnetic sciences

Cerium LIII-edge x-ray absorption study of the CexFe4-yCoySb12 skutterudites

NASA Astrophysics Data System (ADS)

Grandjean, Fernande; Long, Gary J.; Cortes, Robert; Morelli, Donald T.; Meisner, Gregory P.

2000-11-01

The cerium LIII-edge x-ray absorption near-edge spectra of the CexFe4-yCoySb12 compounds have been obtained at 295 K and unambiguously indicate that cerium is in the 4f1 electronic ground state for all values of 0.22<=x<=0.98 and 0.0<=y<=3.5. This stable trivalent state of cerium is in agreement with the proposed (CeFe4Sb12)1-α(□Co4Sb12)α, solid solution structure, in which the cerium atoms are always surrounded by twelve antimony first neighbors and six iron second neighbors, the observed magnetic properties of CeFe4Sb12 and Ce0.9Fe3CoSb12, and the electronic structure of CeFe4Sb12 obtained from band-structure calculations.

Soft X-ray spectral observations of quasars and high X-ray luminosity Seyfert galaxies

NASA Technical Reports Server (NTRS)

Petre, R.; Mushotzky, R. F.; Krolik, J. H.; Holt, S. S.

1983-01-01

Results of the analysis of 28 Einstein SSS observations of 15 high X-ray luminosity (L(x) 10 to the 435 power erg/s) quasars and Seyfert type 1 nuclei are presented. The 0.75-4.5 keV spectra are in general well fit by a simple model consisting of a power law plus absorption by cold gas. The averager spectral index alpha is 0.66 + or - .36, consistent with alpha for the spectrum of these objects above 2 keV. In all but one case, no evidence was found for intrinsic absorption, with an upper limit of 2 x 10 to the 21st power/sq cm. Neither was evidence found for partial covering of the active nucleus by dense, cold matter (N(H) 10 to the 22nd power/sq cm; the average upper limit on the partial covering fraction is 0.5. There is no obvious correlation between spectral index and 0175-4.5 keV X-ray luminosity (which ranges from 3 x 10 to the 43rd to 47th powers erg/s or with other source properties. The lack of intrinsic X-ray absorption allows us to place constraints on the density and temperature of the broad-line emission region, and narrow line emission region, and the intergalactic medium.

Redox chemistry of a binary transition metal oxide (AB2O4): a study of the Cu(2+)/Cu(0) and Fe(3+)/Fe(0) interconversions observed upon lithiation in a CuFe2O4 battery using X-ray absorption spectroscopy.

PubMed

Cama, Christina A; Pelliccione, Christopher J; Brady, Alexander B; Li, Jing; Stach, Eric A; Wang, Jiajun; Wang, Jun; Takeuchi, Esther S; Takeuchi, Kenneth J; Marschilok, Amy C

2016-06-22

Copper ferrite, CuFe2O4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe2O4. A phase pure tetragonal CuFe2O4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. Ex situ X-ray absorption spectroscopy (XAS) measurements were used to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(ii) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(iii) cations to octahedral positions previously occupied by copper(ii). Upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(iii) was achieved. The results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.

ASCA Observation of the Dipping X-Ray Source X1916-053

NASA Technical Reports Server (NTRS)

Ko, Yuan-Kuen; Makai, Koji; Smale, Alan P.; White, Nick E.

1997-01-01

We present the results of timing and spectral studies of the dipping X-ray source X1916-053, observed by ASCA during its Performance Verification phase. The detected dipping activity is consistent with previous observations, with a period of 3008s and an intermittent secondary dip observed roughly 0.4 out of phase with the primary dip. The energy spectra of different intensity states are fitted with a power law with partial covering fraction absorption and interstellar absorption. The increase in the hardness ratio during the primary and secondary dips, and the increase in the covering fraction and column density with decreasing X-ray intensity, all imply that the dipping is caused by the photo-absorbing materials which have been suggested to be where the accreted flow hits the outer edge of the disk materials. The spectra at all intensity levels show no apparent evidence for Fe or Ne emission lines. This may be due to the low metal abundance in the accretion flow. Alternatively, the X-ray luminosity of the central source may be too weak to excite emission lines, which are assumed to be produced by X-ray photoionization of the disk materials.

Imaging efficiency of an X-ray contrast agent-incorporated polymeric microparticle.

PubMed

Ahn, Sungsook; Jung, Sung Yong; Lee, Jin Pyung; Lee, Sang Joon

2011-01-01

Biocompatible polymeric encapsulants have been widely used as a delivery vehicle for a variety of drugs and imaging agents. In this study, X-ray contrast agent (iopamidol) is encapsulated into a polymeric microparticle (polyvinyl alcohol) as a particulate flow tracer in synchrotron X-ray imaging system. The physical properties of the designed microparticles are investigated and correlated with enhancement in the imaging efficiency by experimental observation and theoretical interpretation. The X-ray absorption ability of the designed microparticle is assessed by Beer-Lambert-Bouguer law. Particle size, either in dried state or in solvent, primarily dominates the X-ray absorption ability under the given condition, thus affecting imaging efficiency of the designed X-ray contrast flow tracers. Copyright © 2011 John Wiley & Sons, Ltd.

Structure of nanocrystalline calcium silicate hydrates: insights from X-ray diffraction, synchrotron X-ray absorption and nuclear magnetic resonance.

PubMed

Grangeon, Sylvain; Claret, Francis; Roosz, Cédric; Sato, Tsutomu; Gaboreau, Stéphane; Linard, Yannick

2016-06-01

The structure of nanocrystalline calcium silicate hydrates (C-S-H) having Ca/Si ratios ranging between 0.57 ± 0.05 and 1.47 ± 0.04 was studied using an electron probe micro-analyser, powder X-ray diffraction, 29 Si magic angle spinning NMR, and Fourier-transform infrared and synchrotron X-ray absorption spectroscopies. All samples can be described as nanocrystalline and defective tobermorite. At low Ca/Si ratio, the Si chains are defect free and the Si Q 3 and Q 2 environments account, respectively, for up to 40.2 ± 1.5% and 55.6 ± 3.0% of the total Si, with part of the Q 3 Si being attributable to remnants of the synthesis reactant. As the Ca/Si ratio increases up to 0.87 ± 0.02, the Si Q 3 environment decreases down to 0 and is preferentially replaced by the Q 2 environment, which reaches 87.9 ± 2.0%. At higher ratios, Q 2 decreases down to 32.0 ± 7.6% for Ca/Si = 1.38 ± 0.03 and is replaced by the Q 1 environment, which peaks at 68.1 ± 3.8%. The combination of X-ray diffraction and NMR allowed capturing the depolymerization of Si chains as well as a two-step variation in the layer-to-layer distance. This latter first increases from ∼11.3 Å (for samples having a Ca/Si ratio <∼0.6) up to 12.25 Å at Ca/Si = 0.87 ± 0.02, probably as a result of a weaker layer-to-layer connectivity, and then decreases down to 11 Å when the Ca/Si ratio reaches 1.38 ± 0.03. The decrease in layer-to-layer distance results from the incorporation of interlayer Ca that may form a Ca(OH) 2 -like structure, nanocrystalline and intermixed with C-S-H layers, at high Ca/Si ratios.

Structure of nanocrystalline calcium silicate hydrates: insights from X-ray diffraction, synchrotron X-ray absorption and nuclear magnetic resonance

PubMed Central

Grangeon, Sylvain; Claret, Francis; Roosz, Cédric; Sato, Tsutomu; Gaboreau, Stéphane; Linard, Yannick

2016-01-01

The structure of nanocrystalline calcium silicate hydrates (C–S–H) having Ca/Si ratios ranging between 0.57 ± 0.05 and 1.47 ± 0.04 was studied using an electron probe micro-analyser, powder X-ray diffraction, 29Si magic angle spinning NMR, and Fourier-transform infrared and synchrotron X-ray absorption spectroscopies. All samples can be described as nanocrystalline and defective tobermorite. At low Ca/Si ratio, the Si chains are defect free and the Si Q 3 and Q 2 environments account, respectively, for up to 40.2 ± 1.5% and 55.6 ± 3.0% of the total Si, with part of the Q 3 Si being attributable to remnants of the synthesis reactant. As the Ca/Si ratio increases up to 0.87 ± 0.02, the Si Q 3 environment decreases down to 0 and is preferentially replaced by the Q 2 environment, which reaches 87.9 ± 2.0%. At higher ratios, Q 2 decreases down to 32.0 ± 7.6% for Ca/Si = 1.38 ± 0.03 and is replaced by the Q 1 environment, which peaks at 68.1 ± 3.8%. The combination of X-ray diffraction and NMR allowed capturing the depolymerization of Si chains as well as a two-step variation in the layer-to-layer distance. This latter first increases from ∼11.3 Å (for samples having a Ca/Si ratio <∼0.6) up to 12.25 Å at Ca/Si = 0.87 ± 0.02, probably as a result of a weaker layer-to-layer connectivity, and then decreases down to 11 Å when the Ca/Si ratio reaches 1.38 ± 0.03. The decrease in layer-to-layer distance results from the incorporation of interlayer Ca that may form a Ca(OH)2-like structure, nanocrystalline and intermixed with C–S–H layers, at high Ca/Si ratios. PMID:27275135

Nondestructive Evaluation of Advanced Materials with X-ray Phase Mapping

NASA Technical Reports Server (NTRS)

Hu, Zhengwei

2005-01-01

X-ray radiation has been widely used for imaging applications since Rontgen first discovered X-rays over a century ago. Its large penetration depth makes it ideal for the nondestructive visualization of the internal structure and/or defects of materials unobtainable otherwise. Currently used nondestructive evaluation (NDE) tools, X-ray radiography and tomography, are absorption-based, and work well in heavy-element materials where density or composition variations due to internal structure or defects are high enough to produce appreciable absorption contrast. However, in many cases where materials are light-weight and/or composites that have similar mass absorption coefficients, the conventional absorption-based X-ray methods for NDE become less useful. Indeed, the light-weight and ultra-high-strength requirements for the most advanced materials used or developed for current flight mission and future space exploration pose a great challenge to the standard NDE tools in that the absorption contrast arising from the internal structure of these materials is often too weak to be resolved. In this presentation, a solution to the problem, the use of phase information of X-rays for phase contrast X-ray imaging, will be discussed, along with a comparison between the absorption-based and phase-contrast imaging methods. Latest results on phase contrast X-ray imaging of lightweight Space Shuttle foam in 2D and 3D will be presented, demonstrating new opportunities to solve the challenging issues encountered in advanced materials development and processing.

Reduced chromium in olivine grains from lunar basalt 15555 - X-ray Absorption Near Edge Structure (XANES)

NASA Technical Reports Server (NTRS)

Sutton, S. R.; Jones, K. W.; Gordon, B.; Rivers, M. L.; Bajt, S.; Smith, J. V.

1993-01-01

The oxidation state of Cr in 200-micron regions within individual lunar olivine and pyroxene grains from lunar basalt 15555 was inferred using X-ray Absorption Near Edge Structure (XANES). Reference materials had previously been studied by optical absorption spectroscopy and included Cr-bearing borosilicate glasses synthesized under controlled oxygen fugacity and Cr-doped olivines. The energy dependence of XANES spectral features defined by these reference materials indicated that Cr is predominantly divalent in the lunar olivine and trivalent in the pyroxene. These results, coupled with the apparent f(02)-independence of partitioning coefficients for Cr into olivine, imply that the source magma was dominated by divalent Cr at the time of olivine crystallization.

Americium characterization by X-ray fluorescence and absorption spectroscopy in plutonium uranium mixed oxide

NASA Astrophysics Data System (ADS)

Degueldre, Claude; Cozzo, Cedric; Martin, Matthias; Grolimund, Daniel; Mieszczynski, Cyprian

2013-06-01

Plutonium uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regard to their environment and the coolant. In this work the study of the atomic structure and next-neighbour environment of Am in the (Pu,U)O2 lattice in an irradiated (60 MW d kg-1) MOX sample was performed employing micro-X-ray fluorescence (µ-XRF) and micro-X-ray absorption fine structure (µ-XAFS) spectroscopy. The chemical bonds, valences and stoichiometry of Am (˜0.66 wt%) are determined from the experimental data gained for the irradiated fuel material examined in its peripheral zone (rim) of the fuel. In the irradiated sample Am builds up as Am3+ species within an [AmO8]13- coordination environment (e.g. >90%) and no (<10%) Am(IV) or (V) can be detected in the rim zone. The occurrence of americium dioxide is avoided by the redox buffering activity of the uranium dioxide matrix.

X-ray studies of quasars with the Einstein Observatory

NASA Technical Reports Server (NTRS)

Tananbaum, H.; Branduardi, G.; Fabbiano, G.; Feigelson, E.; Giacconi, R.; Henry, J. P.; Avni, Y.; Elvis, M.; Pye, J. P.; Soltan, A.

1979-01-01

Results of an investigation of the X-ray properties of quasars conducted using the Einstein Observatory (HEAO 2) are reported. The positions, fluxes and luminosities of 35 known quasars were observed by the Einstein high-resolution imaging detector and the imaging proportional counter. Assuming optical redshifts as valid distance indicators, 0.5-4.5 keV X-ray luminosities ranging from 10 to the 43rd to 10 to the 47 ergs/sec are obtained, with evidence of very little cold gas absorption. Flux variability on a time scale of less than 10,000 sec is observed for the quasar OX 169, which implies a mass between 8 x 10 to the 5th and 2 x 10 to the 8th solar masses for the black hole assumed to be responsible for the emission. Preliminary results of the quasar survey also indicate that quasars contribute significantly to the diffuse X-ray background.

Design, Fabrication and Testing of Multilayer Coated X-Ray Optics for the Water Window Imaging X-Ray Microscope

NASA Technical Reports Server (NTRS)

Spencer, Dwight C.

1996-01-01

Hoover et. al. built and tested two imaging Schwarzschild multilayer microscopes. These instruments were constructed as prototypes for the "Water Window Imaging X-Ray Microscope," which is a doubly reflecting, multilayer x-ray microscope configured to operate within the "water window." The "water window" is the narrow region of the x-ray spectrum between the K absorption edges of oxygen (lamda = 23.3 Angstroms) and of carbon (lamda = 43.62 Angstroms), where water is relatively highly transmissive and carbon is highly absorptive. This property of these materials, thus permits the use of high resolution multilayer x-ray microscopes for producing high contrast images of carbon-based structures within the aqueous physiological environments of living cells. We report the design, fabrication and testing of multilayer optics that operate in this regime.

X-ray Properties of an Unbiased Hard X-ray Detected Sample of AGN

NASA Technical Reports Server (NTRS)

Winter, Lisa M.; Mushotzky, Richard F.; Tueller, Jack; Markwardt, Craig

2007-01-01

The SWIFT gamma ray observatory's Burst Alert Telescope (BAT) has detected a sample of active galactic nuclei (AGN) based solely on their hard X-ray flux (14-195keV). In this paper, we present for the first time XMM-Newton X-ray spectra for 22 BAT AGXs with no previously analyzed X-ray spectra. If our sources are a representative sample of the BAT AGN, as we claim, our results present for the first time global X-ray properties of an unbiased towards absorption (n(sub H) < 3 x 10(exp 25)/sq cm), local (< z >= 0.03), AGN sample. We find 9/22 low absorption (n(sub H) < 10(exp 23)/sq cm), simple power law model sources, where 4 of these sources have a statistically significant soft component. Among these sources, we find the presence of a warm absorber statistically significant for only one Seyfert 1 source, contrasting with the ASCA results of Reynolds (1997) and George et al. (1998), who find signatures of warm absorption in half or more of their Seyfert 1 samples at similar redshifts. Additionally, the remaining sources (13122) have more complex spectra, well-fit by an absorbed power law at E > 2.0 keV. Five of the complex sources (NGC 612, ESO 362-G018, MRK 417, ESO 506-G027, and NGC 6860) are classified as Compton-thick candidates. Further, we find four more sources (SWIFT J0641.3+3257, SWIFT J0911.2+4533, SWIFT J1200.8+0650, and NGC 4992) with properties consistent with the hidden/buried AGN reported by Ueda et al. (2007). Finally, we include a comparison of the XMM EPIC spectra with available SWIFT X-ray Telescope (XRT) observations. From these comparisons, we find 6/16 sources with varying column densities, 6/16 sources with varying power law indices, and 13/16 sources with varying fluxes, over periods of hours to months. Flux and power law index are correlated for objects where both parameters vary.

Improved Modeling of Midlatitude D-Region Ionospheric Absorption of High Frequency Radio Signals During Solar X-Ray Flares

DTIC Science & Technology

2009-06-01

a physics-based model which calculates mid - latitude ionospheric electron and ion density profiles for prediction of HF propagation and absorption...greatest in the summer due to longer periods of daylight and ionization. For times not close to sunrise or sunset, mid - latitude ionospheric ...IMPROVED MODELING OF MIDLATITUDE D-REGION IONOSPHERIC ABSORPTION OF HIGH FREQUENCY RADIO SIGNALS DURING SOLAR X-RAY FLARES 1

Probing the CZTS/CdS heterojunction utilizing photoelectrochemistry and x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Turnbull, Matthew J.; Vaccarello, Daniel; Wong, Jonathan; Yiu, Yun Mui; Sham, Tsun-Kong; Ding, Zhifeng

2018-04-01

The importance of renewable resources is becoming more and more influential on research due to the depletion of fossil fuels. Cost-effective ways of harvesting solar energy should also be at the forefront of these investigations. Cu2ZnSnS4 (CZTS) solar cells are well within the frame of these goals, and a thorough understanding of how they are made and processed synthetically is crucial. The CZTS/CdS heterojunction was examined using photoelectrochemistry and synchrotron radiation (SR) spectroscopy. These tools provided physical insights into this interface that was formed by the electrophoretic deposition of CZTS nanocrystals and chemical bath deposition (CBD) of CdS for the respective films. It was discovered that CBD induced a change in the local and long range environment of the Zn in the CZTS lattice, which was detrimental to the photoresponse. X-ray absorption near-edge structures and extended X-ray absorption fine structures (EXAFSs) of the junction showed that this change was at an atomic level and was associated with the coordination of oxygen to zinc. This was confirmed through FEFF fitting of the EXAFS and through IR spectroscopy. It was found that this change in both photoresponse and the Zn coordination can be reversed with the use of low temperature annealing. Investigating CZTS through SR techniques provides detailed structural information of minor changes from the zinc perspective.

Revealing the electronic ground state of ReNiO3 combining Ni-L3 x-ray absorption and resonant inelastic x-ray scattering

NASA Astrophysics Data System (ADS)

Bisogni, Valentina; Catalano, Sara; Green, Robert; Gibert, Marta; Scherwitzl, Raoul; Huang, Yaobo; Balandesh, Shadi; Strocov, Vladimir N.; Zubko, Pavlo; Sawatzky, George; Triscone, Jean-Marc; Schmitt, Thorsten

Rare-earth nickelates ReNiO3 attract a lot of interest thanks to their intriguing physical properties like sharp metal to insulator transition, unusual magnetic order and expected superconductivity in nickelate-based heterostructures. Full understanding of these materials, however, is hampered by the difficulties in describing their electronic ground state (GS). Taking a NdNiO3 thin film as a representative example, we reveal with x-ray absorption and resonant inelastic x-ray scattering unusual coexistence of bound and continuum excitations, providing strong evidence for abundant O 2p holes in the GS of these materials. Using an Anderson impurity model interpretation, we show that these distinct spectral signatures arise from a Ni 3d8 configuration along with holes in the O 2p valence band, confirming suggestions that these materials exhibit a negative charge-transfer energy, with O 2p states extending across the Fermi level.

Determination of Cu Environments in the Cyanobacterium Anabaena flos-aquae by X-Ray Absorption Spectroscopy

PubMed Central

Kretschmer, X. C.; Meitzner, G.; Gardea-Torresdey, J. L.; Webb, R.

2004-01-01

Whole cells and peptidoglycan isolated from cell walls of the cyanobacterium Anabaena flos-aquae were lyophilized and used at pH 2 and pH 5 in Cu(II) binding studies. X-ray absorption spectra measured at the Cu K-edge were used to determine the oxidation states and chemical environments of Cu species in the whole-cell and peptidoglycan samples. In the whole-cell samples, most of the Cu retained at both pH values was coordinated by phosphate ligands. The whole-cell fractions contained significant concentrations of Cu(I) as well as Cu(II). An X-ray absorption near-edge spectrum analysis suggested that Cu(I) was coordinated by amine and thiol ligands. An analysis of the peptidoglycan fractions found that more Cu was adsorbed by the peptidoglycan fraction prepared at pH 5, due to increased chelation by amine and carboxyl ligands. The peptidoglycan fractions, also referred to as the cell wall fractions, contained little or no Cu(I). The Cu loading level was 30 times higher in the cell wall sample prepared at pH 5 than in the sample prepared at pH 2. Amine and bidentate carboxyl ligands had similar relative levels of importance in cell wall peptidoglycan samples prepared at both pH values, but phosphate coordination was insignificant. PMID:14766554

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

X-ray absorption in insulators with non-Hermitian real-time time-dependent density functional theory.

PubMed

Fernando, Ranelka G; Balhoff, Mary C; Lopata, Kenneth

2015-02-10

Non-Hermitian real-time time-dependent density functional theory was used to compute the Si L-edge X-ray absorption spectrum of α-quartz using an embedded finite cluster model and atom-centered basis sets. Using tuned range-separated functionals and molecular orbital-based imaginary absorbing potentials, the excited states spanning the pre-edge to ∼20 eV above the ionization edge were obtained in good agreement with experimental data. This approach is generalizable to TDDFT studies of core-level spectroscopy and dynamics in a wide range of materials.

Arsenite Oxidation by a Poorly-Crystalline Manganese Oxide 2. Results from X-ray Absorption Spectroscopy and X-ray Diffraction

PubMed Central

Lafferty, Brandon J.; Ginder-Vogel, Matthew; Zhu, Mengqiang; Livi, Kenneth J. T.; Sparks, Donald L.

2010-01-01

Arsenite (AsIII) oxidation by manganese oxides (Mn-oxides) serves to detoxify and, under many conditions, immobilize arsenic (As) by forming arsenate (AsV). AsIII oxidation by MnIV-oxides can be quite complex, involving many simultaneous forward reactions and subsequent back reactions. During AsIII oxidation by Mn-oxides, a reduction in oxidation rate is often observed, which is attributed to Mn-oxide surface passivation. X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) data show that MnII sorption on a poorly-crystalline hexagonal birnessite (δ-MnO2) is important in passivation early during reaction with AsIII. Also, it appears that MnIII in the δ-MnO2 structure is formed by conproportionation of sorbed MnII and MnIV in the mineral structure. The content of MnIII within the δ-MnO2 structure appears to increase as the reaction proceeds. Binding of AsV to δ-MnO2 also changes as MnIII becomes more prominent in the δ-MnO2 structure. The data presented indicate that AsIII oxidation and AsV sorption by poorly-crystalline δ-MnO2 is greatly affected by Mn oxidation state in the δ-MnO2 structure. PMID:20977204

The active site structure of tetanus neurotoxin resolved by multiple scattering analysis in X-Ray absorption spectroscopy.

PubMed Central

Meneghini, C; Morante, S

1998-01-01

A detailed study of the x-ray absorption spectrum of tetanus neurotoxin in the K-edge EXAFS region of the zinc absorber is presented that allows the complete identification of the amino acid residues coordinated to the zinc active site. A very satisfactory interpretation of the experimental data can be given if multiple scattering contributions are included in the analysis. Comparing the absorption spectrum of tetanus neurotoxin to that of two other structurally similar zinc-endopeptidases, thermolysin and astacin, in which the zinc coordination mode is known from crystallographic data, we conclude that in tetanus neurotoxin, besides a water molecule, zinc is coordinated to two histidines and a tyrosine. PMID:9746536

X-Ray Continua of Broad Absorption Line Quasars

NASA Technical Reports Server (NTRS)

Mathur, S.

1999-01-01

The targets for this program, PG1416-129 and LBQS 2212-1759 were known to be Broad Absorption Line Quasars (BALQSOs). BALQSOs are highly absorbed in soft X-rays. Good high energy response of Rossi-XTE made them ideal targets for observation. We observed LBQS 2212-1759 with PCA. We have now analyzed the data and found that the source was not detected. Since our target was expected to be faint, reliable estimate of background was very important. With the release of new FTOOLS (version 4.1) we were able to do so. We also analyzed a well known bright object and verified our results with the published data. This gave us confidence in the non-detection of our target LBQS 2212-1759. We are currently investigating the implications of this non-detection. Due to some scheduling problems, our second target PG1416-129 was not observed in A01. It was observed on 06/26/98. This target was detected with RXTE. We are now working on the spectral analysis with XSPEC.

X-ray Absorption Fine Structure (XAFS) Studies of Oxide Glasses—A 45-Year Overview

PubMed Central

Zanotto, Edgar Dutra

2018-01-01

X-ray Absorption Fine Structure (XAFS) spectroscopy has been widely used to characterize the short-range order of glassy materials since the theoretical basis was established 45 years ago. Soon after the technique became accessible, mainly due to the existence of Synchrotron laboratories, a wide range of glassy materials was characterized. Silicate glasses have been the most studied because they are easy to prepare, they have commercial value and are similar to natural glasses, but borate, germanate, phosphate, tellurite and other less frequent oxide glasses have also been studied. In this manuscript, we review reported advances in the structural characterization of oxide-based glasses using this technique. A focus is on structural characterization of transition metal ions, especially Ti, Fe, and Ni, and their role in different properties of synthetic oxide-based glasses, as well as their important function in the formation of natural glasses and magmas, and in nucleation and crystallization. We also give some examples of XAFS applications for structural characterization of glasses submitted to high pressure, glasses used to store radioactive waste and medieval glasses. This updated, comprehensive review will likely serve as a useful guide to clarify the details of the short-range structure of oxide glasses. PMID:29382102

Finite temperature effects on the X-ray absorption spectra of energy related materials

NASA Astrophysics Data System (ADS)

Pascal, Tod; Prendergast, David

2014-03-01

We elucidate the role of room-temperature-induced instantaneous structural distortions in the Li K-edge X-ray absorption spectra (XAS) of crystalline LiF, Li2SO4, Li2O, Li3N and Li2CO3 using high resolution X-ray Raman spectroscopy (XRS) measurements and first-principles density functional theory calculations within the eXcited electron and Core Hole (XCH) approach. Based on thermodynamic sampling via ab-initio molecular dynamics (MD) simulations, we find calculated XAS in much better agreement with experiment than those computed using the rigid crystal structure alone. We show that local instantaneous distortion of the atomic lattice perturbs the symmetry of the Li 1 s core-excited-state electronic structure, broadening spectral line-shapes and, in some cases, producing additional spectral features. This work was conducted within the Batteries for Advanced Transportation Technologies (BATT) Program, supported by the U.S. Department of Energy Vehicle Technologies Program under Contract No. DE-AC02-05CH11231.

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.

Grazing incidence X-ray absorption characterization of amorphous Zn-Sn-O thin film

NASA Astrophysics Data System (ADS)

Moffitt, S. L.; Ma, Q.; Buchholz, D. B.; Chang, R. P. H.; Bedzyk, M. J.; Mason, T. O.

2016-05-01

We report a surface structure study of an amorphous Zn-Sn-O (a-ZTO) transparent conducting film using the grazing incidence X-ray absorption spectroscopy technique. By setting the measuring angles far below the critical angle at which the total external reflection occurs, the details of the surface structure of a film or bulk can be successfully accessed. The results show that unlike in the film where Zn is severely under coordinated (N < 4), it is fully coordinated (N = 4) near the surface while the coordination number around Sn is slightly smaller near the surface than in the film. Despite a 30% Zn doping, the local structure in the film is rutile-like.

Ab Initio Theory of Dynamical Core-Hole Screening in Graphite from X-Ray Absorption Spectra

NASA Astrophysics Data System (ADS)

Wessely, O.; Katsnelson, M. I.; Eriksson, O.

2005-04-01

We have implemented the effect of dynamical core-hole screening, as given by Mahan, Nozières, and De Dominicis, in a first-principles based method and applied the theory to the x-ray absorption (XA) spectrum of graphite. It turns out that two of the conspicuous peaks of graphite are well described, both regarding the position, shape, and relative intensity, whereas one peak is absent in the theory. Only by incorporation of both excitonic and delocalized processes can a full account of the experimental spectrum be obtained theoretically, and we interpret the XA spectrum in graphite to be the result of a well screened and a poor screened process, much in the same way as is done for core level x-ray photoelectron spectroscopy.

The Soft X-ray View of Ultra Fast Outflows

NASA Astrophysics Data System (ADS)

Reeves, J.; Braito, V.; Nardini, E.; Matzeu, G.; Lobban, A.; Costa, M.; Pounds, K.; Tombesi, F.; Behar, E.

2017-10-01

The recent large XMM-Newton programmes on the nearby quasars PDS 456 and PG 1211+143 have revealed prototype ultra fast outflows in the iron K band through highly blue shifted absorption lines. The wind velocities are in excess of 0.1c and are likely to make a significant contribution to the host galaxy feedback. Here we present evidence for the signature of the fast wind in the soft X-ray band from these luminous quasars, focusing on the spectroscopy with the RGS. In PDS 456, the RGS spectra reveal the presence of soft X-ray broad absorption line profiles, which suggests that PDS 456 is an X-ray equivalent to the BAL quasars, with outflow velocities reaching 0.2c. In PG 1211, the soft X-ray RGS spectra show a complex of several highly blue shifted absorption lines over a wide range of ionisation and reveal outflowing components with velocities between 0.06-0.17c. For both quasars, the soft X-ray absorption is highly variable, even on timescales of days and is most prominent when the quasar flux is low. Overall the results imply the presence of a soft X-ray component of the ultra fast outflows, which we attribute to a clumpy or inhomogeneous phase of the disk wind.

Creation of X-Ray Transparency of Matter by Stimulated Elastic Forward Scattering.

PubMed

Stöhr, J; Scherz, A

2015-09-04

X-ray absorption by matter has long been described by the famous Beer-Lambert law. Here, we show how this fundamental law needs to be modified for high-intensity coherent x-ray pulses, now available at x-ray free electron lasers, due to the onset of stimulated elastic forward scattering. We present an analytical expression for the modified polarization-dependent Beer-Lambert law for the case of resonant core-to-valence electronic transitions and incident transform limited x-ray pulses. Upon transmission through a solid, the resonant absorption and dichroic contrasts are found to vanish with increasing x-ray intensity, with the stimulation threshold lowered by orders of magnitude through a resonant superradiantlike effect. Our results have broad implications for the study of matter with x-ray lasers.

Creation of X-Ray Transparency of Matter by Stimulated Elastic Forward Scattering

NASA Astrophysics Data System (ADS)

Stöhr, J.; Scherz, A.

2015-09-01

X-ray absorption by matter has long been described by the famous Beer-Lambert law. Here, we show how this fundamental law needs to be modified for high-intensity coherent x-ray pulses, now available at x-ray free electron lasers, due to the onset of stimulated elastic forward scattering. We present an analytical expression for the modified polarization-dependent Beer-Lambert law for the case of resonant core-to-valence electronic transitions and incident transform limited x-ray pulses. Upon transmission through a solid, the resonant absorption and dichroic contrasts are found to vanish with increasing x-ray intensity, with the stimulation threshold lowered by orders of magnitude through a resonant superradiantlike effect. Our results have broad implications for the study of matter with x-ray lasers.

A Highly Sensitive X-ray Imaging Modality for Hepatocellular Carcinoma Detection in Vitro

PubMed Central

Rand, Danielle; Walsh, Edward G.; Derdak, Zoltan; Wands, Jack R.; Rose-Petruck, Christoph

2015-01-01

Innovations that improve sensitivity and reduce cost are of paramount importance in diagnostic imaging. The novel x-ray imaging modality called Spatial Frequency Heterodyne Imaging (SFHI) is based on a linear arrangement of x-ray source, tissue, and x-ray detector, much like that of a conventional x-ray imaging apparatus. However, SFHI rests on a complete paradigm reversal compared to conventional x-ray absorption-based radiology: while scattered x-rays are carefully rejected in absorption-based x-ray radiology to enhance the image contrast, SFHI forms images exclusively from x-rays scattered by the tissue. In this study we use numerical processing to produce x-ray scatter images of Hepatocellular Carcinoma (HCC) labeled with a nanoparticle contrast agent. We subsequently compare the sensitivity of SFHI in this application to that of both conventional x-ray imaging and Magnetic Resonance Imaging (MRI). Although SFHI is still in the early stages of its development, our results show that the sensitivity of SFHI is an order of magnitude greater than that of absorption-based x-ray imaging and approximately equal to that of MRI. As x-ray imaging modalities typically have lower installation and service costs compared to MRI, SFHI could become a cost effective alternative to MRI, particularly in areas of the world with inadequate availability of MRI facilities. PMID:25559398

A highly sensitive x-ray imaging modality for hepatocellular carcinoma detection in vitro

DOE PAGES

Rand, Danielle; Walsh, Edward G.; Derdak, Zoltan; ...

2015-01-05

Innovations that improve sensitivity and reduce cost are of paramount importance in diagnostic imaging. The novel x-ray imaging modality called Spatial Frequency Heterodyne Imaging (SFHI) is based on a linear arrangement of x-ray source, tissue, and x-ray detector, much like that of a conventional x-ray imaging apparatus. However, SFHI rests on a complete paradigm reversal compared to conventional x-ray absorption-based radiology: while scattered x-rays are carefully rejected in absorption-based x-ray radiology to enhance the image contrast, SFHI forms images exclusively from x-rays scattered by the tissue. Here in this study we use numerical processing to produce x-ray scatter images ofmore » Hepatocellular Carcinoma (HCC) labeled with a nanoparticle contrast agent. We subsequently compare the sensitivity of SFHI in this application to that of both conventional x-ray imaging and Magnetic Resonance Imaging (MRI). Although SFHI is still in the early stages of its development, our results show that the sensitivity of SFHI is an order of magnitude greater than that of absorption-based x-ray imaging and approximately equal to that of MRI. Lastly, as x-ray imaging modalities typically have lower installation and service costs compared to MRI, SFHI could become a cost effective alternative to MRI, particularly in areas of the world with inadequate availability of MRI facilities.« less

A highly sensitive x-ray imaging modality for hepatocellular carcinoma detection in vitro

NASA Astrophysics Data System (ADS)

Rand, Danielle; Walsh, Edward G.; Derdak, Zoltan; Wands, Jack R.; Rose-Petruck, Christoph

2015-01-01

Innovations that improve sensitivity and reduce cost are of paramount importance in diagnostic imaging. The novel x-ray imaging modality called spatial frequency heterodyne imaging (SFHI) is based on a linear arrangement of x-ray source, tissue, and x-ray detector, much like that of a conventional x-ray imaging apparatus. However, SFHI rests on a complete paradigm reversal compared to conventional x-ray absorption-based radiology: while scattered x-rays are carefully rejected in absorption-based x-ray radiology to enhance the image contrast, SFHI forms images exclusively from x-rays scattered by the tissue. In this study we use numerical processing to produce x-ray scatter images of hepatocellular carcinoma labeled with a nanoparticle contrast agent. We subsequently compare the sensitivity of SFHI in this application to that of both conventional x-ray imaging and magnetic resonance imaging (MRI). Although SFHI is still in the early stages of its development, our results show that the sensitivity of SFHI is an order of magnitude greater than that of absorption-based x-ray imaging and approximately equal to that of MRI. As x-ray imaging modalities typically have lower installation and service costs compared to MRI, SFHI could become a cost effective alternative to MRI, particularly in areas of the world with inadequate availability of MRI facilities.

First-principles X-ray absorption dose calculation for time-dependent mass and optical density.

PubMed

Berejnov, Viatcheslav; Rubinstein, Boris; Melo, Lis G A; Hitchcock, Adam P

2018-05-01

A dose integral of time-dependent X-ray absorption under conditions of variable photon energy and changing sample mass is derived from first principles starting with the Beer-Lambert (BL) absorption model. For a given photon energy the BL dose integral D(e, t) reduces to the product of an effective time integral T(t) and a dose rate R(e). Two approximations of the time-dependent optical density, i.e. exponential A(t) = c + aexp(-bt) for first-order kinetics and hyperbolic A(t) = c + a/(b + t) for second-order kinetics, were considered for BL dose evaluation. For both models three methods of evaluating the effective time integral are considered: analytical integration, approximation by a function, and calculation of the asymptotic behaviour at large times. Data for poly(methyl methacrylate) and perfluorosulfonic acid polymers measured by scanning transmission soft X-ray microscopy were used to test the BL dose calculation. It was found that a previous method to calculate time-dependent dose underestimates the dose in mass loss situations, depending on the applied exposure time. All these methods here show that the BL dose is proportional to the exposure time D(e, t) ≃ K(e)t.

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.

Polarization Dependent X-ray Absorption Spectroscopy of the TiO2 Polymorphs Anatase (001) and Rutile (001)

NASA Astrophysics Data System (ADS)

Ederer, D. L.; Ruzycki, N.; Schuler, T.; Zhang, G. P.; Callcott, T. A.; Nachimuthu, P.; Perera, R. C. C.

2002-03-01

Polarization Dependent X-ray Absorption Spectroscopy of the TiO2 Polymorphs Anatase (001) and Rutile (001) N. Ruzycki^a, T. Schuler^a, D.L. Ederer^a, T. A. Callcott^, G. P. Zhang^b, P. Nachimuthu^c,d, and R.C.C. Perera^c a-Tulane University, Department of Physics, New Orleans, LA, 70118 b- Univesity of Tennessee, Department of Physics and Astronomy, Knoxville, TN, 37996 c- Center for X-ray Optics, Lawrence Berkeley Laboratory, Berkeley, CA, d- Department of Chemistry, University of Nevada Las Vegas, Las Vegas NV, 89154 TiO2 is a useful industrial catalyst and has applications in gas sensing and photoelectric devices. All structures consist of octrahedrally-coordinated Ti atoms and three-fold coordinated O atoms. Anatase and rutile differ mainly in the amount of distortion in the octahedra. Because Soft X-ray Absorption Spectroscoy (SXAS) is sensitive to the ligand field, these small differences are reflected the spectra. In the experiment the electronic polarization vector was varied angulary along the equatorial and the longitudnal axes of the sixfold coordinated titanium atoms. This study showed a strong polarization dependence at the oxygen K-edge for rutile (001) and the anatase (001) in the t_2g and eg region for the equatorial bonds. The Titanium L-edge showed a smaller polarization dependence. There was no polarization dependence in the longitudinal direction for anatase (001) or rutile (001) in either the oxygen K-edge or the Ti-L edge. These data are compared with calculations of polarization-dependent matrix elements of the transitions.

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

Variable X-Ray Absorption in the Mini-BAL QSO PG 1126-041

NASA Technical Reports Server (NTRS)

Giustini, M.; Cappi, M.; Chartas, G.; Dadina, M.; Eracleous, M.; Ponti, G.; Proga, D.; Tombesi, F.; Vignali, C.; Palumbo, G. G. C.

2011-01-01

Context. X-ray studies of AGN with powerful nuclear winds are important to constrain the physics of the inner accretion/ejection flow around SMBH, and to understand the impact of such winds on the AGN environment. Aims. Our main scientific goal is to constrain the properties of a variable outflowing absorber that is thought to be launched near the SMBH of the mini-BAL QSO PG 1126-041 using a multi-epoch observational campaign performed with XMM-Newton. Methods. We performed temporally resolved X-ray spectroscopy and simultaneous UV and X-ray photometry on the most complete set of observations and on the deepest X-ray exposure of a mini-BAL QSO to date. Results. We found complex X-ray spectral variability on time scales of both months and hours, best reproduced by means of variable massive ionized absorbers along the line of sight. As a consequence, the observed optical-to-X-ray spectral index is found to be variable with time. In the highest signal-to-noise observation we detected highly ionized X-ray absorbing material outflowing much faster (u(sub X) approx. 16 500 km/s) than the UV absorbing one (u(sub uv) approx. 5,000 km/s). This highly ionized absorber is found to be variable on very short (a few kiloseconds) time scales. Conclusions. Our findings are qualitatively consistent with line driven accretion disk winds scenarios. Our observations have opened the time-resolved X-ray spectral analysis field for mini-BAL QSOs; only with future deep studies will we be able to map the dynamics of the inner flow and understand the physics of AGN winds and their impact on the environment.

Redox chemistry of a binary transition metal oxide (AB 2 O 4 ): a study of the Cu 2+ /Cu 0 and Fe 3+ /Fe 0 interconversions observed upon lithiation in a CuFe 2 O 4 battery using X-ray absorption spectroscopy

DOE PAGES

Cama, Christina A.; Pelliccione, Christopher J.; Brady, Alexander B.; ...

2016-06-06

Copper ferrite, CuFe 2 O 4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe 2 O 4. A phase pure tetragonal CuFe 2 O 4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. We used ex situ X-ray absorption spectroscopy (XAS) measurements to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structuremore » (XANES), extended X-ray absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(II) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(III) cations to octahedral positions previously occupied by copper(II). Then, upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(III) was achieved. Our results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.« less

Comparison of the Manganese Cluster in Oxygen-Evolving Photosystem II with Distorted Cubane Manganese Compounds through X-ray Absorption Spectroscopy

PubMed Central

Cinco, Roehl M.; Rompel, Annette; Visser, Hendrik; Aromí, Guillem; Christou, George; Sauer, Kenneth; Klein, Melvin P.; Yachandra, Vittal K.

2014-01-01

X-ray absorption spectroscopy has been employed to assess the degree of similarity between the oxygen-evolving complex (OEC) in photosystem II (PS II) and a family of synthetic manganese complexes containing the distorted cubane [Mn4O3X] core (X = benzoate, acetate, methoxide, hydroxide, azide, fluoride, chloride, or bromide). These [Mn4(μ3-O)3(μ3-X)] cubanes possess C3v symmetry except for the X = benzoate species, which is slightly more distorted with only Cs symmetry. In addition, Mn4O3Cl complexes containing three or six terminal Cl ligands at three of the Mn were included in this study. The Mn K-edge X-ray absorption near edge structure (XANES) from the oxygen-ligated complexes begin to resemble general features of the PS II (S1 state) spectrum, although the second derivatives are distinct from those in PS II. The extended X-ray absorption fine structure (EXAFS) of these Mn compounds also displays superficial resemblance to that of PS II, but major differences emerge on closer examination of the phases and amplitudes. The most obvious distinction is the smaller magnitude of the Fourier transform (FT) of the PS II EXAFS compared to the FTs from the distorted cubanes. Curve fitting of the Mn EXAFS spectra verifies the known core structures of the Mn cubanes, and shows that the number of the crucial 2.7 and 3.3 Å Mn–Mn distances differs from that observed in the OEC. The EXAFS method detects small changes in the core structures as X is varied in this series, and serves to exclude the distorted cubane of C3v symmetry as a topological model for the Mn catalytic cluster of the OEC. Instead, the method shows that even more distortion of the cubane framework, altering the ratio of the Mn–Mn distances, is required to resemble the Mn cluster in PS II. PMID:11671305

Melting of iron determined by X-ray absorption spectroscopy to 100 GPa

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

Aquilanti, Giuliana; Trapananti, Angela; Karandikar, Amol

2015-09-14

There is a long-standing controversy over the melting curve of Fe at high pressure as determined from static laser heated diamond anvil cell and dynamic compression studies. X-ray absorption spectroscopy measurements are used here as a criterion to detect melting under pressure. Confronted with a diversity of obtained melting curves, this technique, used at such pressure and temperature conditions, is eligible to be at the forefront to probe Earth's deep interior. Furthermore, the experiment reported here holds promise for addressing important issues related to the structure and phase diagram of compressed melts, such as the existence of structural complexity (polyamorphism)more » in the liquid phase or the extent of icosahedral ordering whose investigation has been limited until now to ambient conditions.« less

The X-ray Absorber in the X-ray Transient NLS1 WPVS 007

NASA Astrophysics Data System (ADS)

Grupe, Dirk

This proposal is for a funding request for an approved XMM-Newton observations of the X-ray transient Narrow-Line Seyfert 1 galaxy WPVS 007. The request is for 4 month of salary for the PI for one year in order to do the data analysis, publish the results, and attend an international AGN meeting. XMM will observe WPVS 007 in June 2010 simultaneously with HST, Chandra, and Swift. The goal is to establish a tight connection between the UV broad absorption line troughs found in FUSE observations and the strong partial covering absorber feature found by Swift. WPVS 007 showed a dramatic transformation into a Broad Absorption line QSO like AGN between a 1996 HST observation and a 2003 FUSE observation. Several Swift monitoring observations have suggested that the absorber may have started to disappear. Therefore it is crucial for our HST COS UV spectroscopy to know what the status of the X-ray absorber is. The XMM observation will provide a well-exposed X-ray spectrum even if WPVS 007 will be in a low flux state. This spectrum will enable us to put constraints on the absorption column density and covering fraction of the partial covering absorber.

Surface modification study of borate materials from B K-edge X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Kasrai, Masoud; Fleet, Michael E.; Muthupari, Swaminathan; Li, D.; Bancroft, G. M.

The B K-edge X-ray absorption near-edge structure (XANES) spectra of two borates with tetrahedrally-coordinated B [[4]B; natural danburite (CaB2Si2O8) and synthetic boron phosphate (BPO4)] have been recorded in total electron yield (TEY) and fluorescence yield (FY) modes to investigate the surface and bulk structure of these materials. The TEY XANES measurement shows that danburite is susceptible to surface damage involving conversion of [4]B sites to [3]B sites by reaction with moisture and/or mechanical abrasion (grinding, polishing, etc.). The bulk of the mineral is essentially unaffected. Commercial boron phosphate powder exhibits more extensive surface and bulk damage, which increases with air exposure but is recovered on heating at 650°C. In contrast to ELNES, the XANES technique is not affected by beam damage and when collected in the FY mode is capable of yielding meaningful information on the coordination and intermediate-range structure of B in borate and borosilicate materials.

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.

Intensity-dependent resonant transmission of x-rays in solid-density aluminum plasma

NASA Astrophysics Data System (ADS)

Cho, M. S.; Chung, H.-K.; Cho, B. I.

2018-05-01

X-ray free-electron lasers (XFELs) provide unique opportunities to generate and investigate dense plasmas. The absorption and transmission properties of x-ray photons in dense plasmas are important in characterizing the state of the plasmas. Experimental evidence shows that the transmission of x-ray photons through dense plasmas depends greatly on the incident XFEL intensity. Here, we present a detailed analysis of intensity-dependent x-ray transmission in solid-density aluminum using collisional-radiative population kinetics calculations. Reverse saturable absorption (RSA), i.e., an increase in x-ray absorption with intensity has been observed for photon energies below the K-absorption edge and in the intensity range of 1016-1017 W/cm2 for XFEL photons with 1487 eV. At higher intensities, a transition from RSA to saturable absorption (SA) is predicted; thus, the x-ray absorption decreases with intensity above a threshold value. For XFEL photon energies of 1501 eV and 1515 eV, the transition from RSA to SA occurs at XFEL intensities between 1017-1018 W/cm2. Electron temperatures are predicted to be in the range of 30-50 eV for the given experimental conditions. Detailed population kinetics of the charge states explains the intensity-dependent absorption of x-ray photons and the fast modulation of XFEL pulses for both RSA and SA.

Simulation tools for analyzer-based x-ray phase contrast imaging system with a conventional x-ray source

NASA Astrophysics Data System (ADS)

Caudevilla, Oriol; Zhou, Wei; Stoupin, Stanislav; Verman, Boris; Brankov, J. G.

2016-09-01

Analyzer-based X-ray phase contrast imaging (ABI) belongs to a broader family of phase-contrast (PC) X-ray imaging modalities. Unlike the conventional X-ray radiography, which measures only X-ray absorption, in PC imaging one can also measures the X-rays deflection induced by the object refractive properties. It has been shown that refraction imaging provides better contrast when imaging the soft tissue, which is of great interest in medical imaging applications. In this paper, we introduce a simulation tool specifically designed to simulate the analyzer-based X-ray phase contrast imaging system with a conventional polychromatic X-ray source. By utilizing ray tracing and basic physical principles of diffraction theory our simulation tool can predicting the X-ray beam profile shape, the energy content, the total throughput (photon count) at the detector. In addition we can evaluate imaging system point-spread function for various system configurations.

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.

Evolution of silver nanoparticles in the rat lung investigated by X-ray absorption spectroscopy

DOE PAGES

Davidson, R. Andrew; Anderson, Donald S.; Van Winkle, Laura S.; ...

2014-12-16

Following a 6-h inhalation exposure to aerosolized 20 and 110 nm diameter silver nanoparticles, lung tissues from rats were investigated with X-ray absorption spectroscopy, which can identify the chemical state of silver species. Lung tissues were processed immediately after sacrifice of the animals at 0, 1, 3, and 7 days post exposure and the samples were stored in an inert and low-temperature environment until measured. We found that it is critical to follow a proper processing, storage and measurement protocol; otherwise only silver oxides are detected after inhalation even for the larger nanoparticles. The results of X-ray absorption spectroscopy measurementsmore » taken in air at 85 K suggest that the dominating silver species in all the postexposure lung tissues were metallic silver, not silver oxide, or solvated silver cations. The results further indicate that the silver nanoparticles in the tissues were transformed from the original nanoparticles to other forms of metallic silver nanomaterials and the rate of this transformation depended on the size of the original nanoparticles. Furthermore, we found that 20 nm diameter silver nanoparticles were significantly modified after aerosolization and 6-h inhalation/deposition, whereas larger, 110 nm diameter nanoparticles were largely unchanged. Over the seven-day postexposure period the smaller 20 nm silver nanoparticles underwent less change in the lung tissue than the larger 110 nm silver nanoparticles. In contrast, silica-coated gold nanoparticles did not undergo any modification processes and remained as the initial nanoparticles throughout the 7-day study period.« less

Evolution of silver nanoparticles in the rat lung investigated by X-ray absorption spectroscopy

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

Davidson, R. Andrew; Anderson, Donald S.; Van Winkle, Laura S.

Following a 6-h inhalation exposure to aerosolized 20 and 110 nm diameter silver nanoparticles, lung tissues from rats were investigated with X-ray absorption spectroscopy, which can identify the chemical state of silver species. Lung tissues were processed immediately after sacrifice of the animals at 0, 1, 3, and 7 days post exposure and the samples were stored in an inert and low-temperature environment until measured. We found that it is critical to follow a proper processing, storage and measurement protocol; otherwise only silver oxides are detected after inhalation even for the larger nanoparticles. The results of X-ray absorption spectroscopy measurementsmore » taken in air at 85 K suggest that the dominating silver species in all the postexposure lung tissues were metallic silver, not silver oxide, or solvated silver cations. The results further indicate that the silver nanoparticles in the tissues were transformed from the original nanoparticles to other forms of metallic silver nanomaterials and the rate of this transformation depended on the size of the original nanoparticles. Furthermore, we found that 20 nm diameter silver nanoparticles were significantly modified after aerosolization and 6-h inhalation/deposition, whereas larger, 110 nm diameter nanoparticles were largely unchanged. Over the seven-day postexposure period the smaller 20 nm silver nanoparticles underwent less change in the lung tissue than the larger 110 nm silver nanoparticles. In contrast, silica-coated gold nanoparticles did not undergo any modification processes and remained as the initial nanoparticles throughout the 7-day study period.« less

The X-ray absorption spectrum of 4U1700-37 and its implications for the stellar wind of the companion HD153919

NASA Technical Reports Server (NTRS)

White, N. E.; Kallman, T. R.; Swank, J. H.

1982-01-01

The first high resolution non-dispersive 2-60 KeV X-ray spectra of 4U1700-37 is presented. The continuum is typical of that found from X-ray pulsars; that is a flat power law between 2 and 10 keV and, beyond 10 keV, an exponential decay of characteristic energy varying between 10 and 20 keV. No X-ray pulsations were detected between 160 ms and 6 min with an amplitude greater than approximately 2%. The absorption measured at binary phases approximately 0.72 is comparable to that expected from the stellar wind of the primary. The gravitational capture of material in the wind is found to be more than enough to power the X-ray source. The increase in the average absorption after phi o approximately 0.5 is confirmed. The minimum level of adsorption is a factor of 2 or 3 lower than that reported by previous observers, which may be related to a factor of approximately 10 decline in the average X-ray luminosity over the same interval. Short term approximately 50% variations in adsorption are seen for the first time which appear to be loosely correlated with approximately 10 min flickering activity in the X-ray flux. These most likely originate from inhomogeneities in the stellar wind of the primary.

The X-ray emitting galaxy Cen-A

NASA Technical Reports Server (NTRS)

Mushotzky, R. F.; Sercemitsos, P. J.; Becker, R. H.; Boldt, E. A.; Holt, S. S.

1977-01-01

OSO-8 X-ray observations of Cen-A in 1975 and 1976 are reported. The source spectrum is well fit in both years by a power law of number index 1.62 and absorption due to 1.3 x 10 to the 23rd power at/sq cm. The total flux varied by a factor 2 between 1975 and 1976. In 1976 there were approximately 40% flux variations on a time scale of days. The 6.4 keV Fe fluorescent line and the 7.1 keV absorption edge were measured implying Fe/H approximately equals .000016. Simultaneous radio measurements show variation in phase with X-ray variability. Models considering radio, milimeter, IR and X-ray data show that all the data can be accounted for by a model in which the X-rays are due to a synchrotron self-Compton source embedded in a cold H(2) cloud.

Enabling liquid solvent structure analysis using hard x-ray absorption spectroscopy with a transferrable microfluidic reactor

NASA Astrophysics Data System (ADS)

Zheng, Jian; Zhang, Wei; Wang, Feng; Yu, Xiao-Ying

2018-05-01

In this paper, a vacuum compatible microfluidic device, system for analysis at the liquid vacuum interface, is integrated to hard x-ray absorption spectroscopy to obtain the local structure of K3[Fe(CN)6] in aqueous solutions with three concentrations of 0.5 M, 0.05 M, and 0.005 M. The solutions were sealed in a microchannel 500 µm wide and 300 µm deep in a portable microfluidic device. The Fe K-edge x-ray absorption spectra indicate a presence of Fe(III) in the complex in water, with an octahedral geometry coordinated with 6 C atoms in the first shell with a distance of ~1.92 Å and 6 N atoms in the second shell with a distance of ~3.10 Å. Varying the concentration has no observable influence on the structure of K3[Fe(CN)6]. Our results demonstrate the feasibility of using microfluidic based liquid cells in large synchrotron facilities. Using portable microfludic reactors provides a viable approach to enable multifaceted measurements of liquids in the future.

Enabling liquid solvent structure analysis using hard x-ray absorption spectroscopy with a transferrable microfluidic reactor.

PubMed

Zheng, Jian; Zhang, Wei; Wang, Feng; Yu, Xiao-Ying

2018-05-10

In this paper, a vacuum compatible microfluidic device, system for analysis at the liquid vacuum interface, is integrated to hard x-ray absorption spectroscopy to obtain the local structure of K 3 [Fe(CN) 6 ] in aqueous solutions with three concentrations of 0.5 M, 0.05 M, and 0.005 M. The solutions were sealed in a microchannel 500 µm wide and 300 µm deep in a portable microfluidic device. The Fe K-edge x-ray absorption spectra indicate a presence of Fe(III) in the complex in water, with an octahedral geometry coordinated with 6 C atoms in the first shell with a distance of ~1.92 Å and 6 N atoms in the second shell with a distance of ~3.10 Å. Varying the concentration has no observable influence on the structure of K 3 [Fe(CN) 6 ]. Our results demonstrate the feasibility of using microfluidic based liquid cells in large synchrotron facilities. Using portable microfludic reactors provides a viable approach to enable multifaceted measurements of liquids in the future.

Enabling liquid solvent structure analysis using hard x-ray absorption spectroscopy with a transferrable microfluidic reactor

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

Zheng, Jian; Zhang, Wei; Wang, Feng

In this paper, a vacuum compatible microfluidic device, System for Analysis at the Liquid Vacuum Interface (SALVI), is integrated to hard x-ray absorption spectroscopy (XAS) to obtain the local structure of K3[Fe(CN)6] in aqueous solutions with three concentrations of 0.5 M, 0.05 M, and 0.005 M. The solutions were sealed in a microchannel of 500 μm wide and 300 µm deep in a portable microfluidic device. The Fe K-edge x-ray absorption spectra show that the complex in water is Fe(III). The complex is present with octahedral geometry coordinated with 6 C atoms in the first shell with a distance ofmore » ~1.92 Å and 6 N atoms in the second shell with a distance of ~3.10 Å. Varying the concentration has no observable influence on the structure of K3[Fe(CN)6]. Our results demonstrate the feasibility of using microfluidic based liquid cells in large synchrotron facilities and it is a viable approach to enable multifaceted measurements of liquids in the future.« less

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.

K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites

DOE PAGES

Baker, Michael L.; Mara, Michael W.; Yan, James J.; ...

2017-02-09

Continual advancements in the development of synchrotron radiation sources have resulted in X-ray based spectroscopic techniques capable of probing the electronic and structural properties of numerous systems. This review gives an overview of the application of metal K-edge and L-edge X-ray absorption spectroscopy (XAS), as well as Kα resonant inelastic X-ray scattering (RIXS), to the study of electronic structure in transition metal sites with emphasis on experimentally quantifying 3d orbital covalency. The specific sensitivities of K-edge XAS, L-edge XAS, and RIXS are discussed emphasizing the complementary nature of the methods. L-edge XAS and RIXS are sensitive to mixing between 3dmore » orbitals and ligand valence orbitals, and to the differential orbital covalency (DOC), that is, the difference in the covalencies for different symmetry sets of the d orbitals. Both L-edge XAS and RIXS are highly sensitive to and enable separation of σ and π donor bonding and π back bonding contributions to bonding. Applying ligand field multiplet simulations, including charge transfer via valence bond configuration interactions, DOC can be obtained for direct comparison with density functional theory calculations and to understand chemical trends. Here, the application of RIXS as a probe of frontier molecular orbitals in a heme enzyme demonstrates the potential of this method for the study of metal sites in highly covalent coordination sites in bioinorganic chemistry.« less

K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites

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

Baker, Michael L.; Mara, Michael W.; Yan, James J.

Continual advancements in the development of synchrotron radiation sources have resulted in X-ray based spectroscopic techniques capable of probing the electronic and structural properties of numerous systems. This review gives an overview of the application of metal K-edge and L-edge X-ray absorption spectroscopy (XAS), as well as Kα resonant inelastic X-ray scattering (RIXS), to the study of electronic structure in transition metal sites with emphasis on experimentally quantifying 3d orbital covalency. The specific sensitivities of K-edge XAS, L-edge XAS, and RIXS are discussed emphasizing the complementary nature of the methods. L-edge XAS and RIXS are sensitive to mixing between 3dmore » orbitals and ligand valence orbitals, and to the differential orbital covalency (DOC), that is, the difference in the covalencies for different symmetry sets of the d orbitals. Both L-edge XAS and RIXS are highly sensitive to and enable separation of σ and π donor bonding and π back bonding contributions to bonding. Applying ligand field multiplet simulations, including charge transfer via valence bond configuration interactions, DOC can be obtained for direct comparison with density functional theory calculations and to understand chemical trends. Here, the application of RIXS as a probe of frontier molecular orbitals in a heme enzyme demonstrates the potential of this method for the study of metal sites in highly covalent coordination sites in bioinorganic chemistry.« less

Applications of x ray absorption fine structure to the in situ study of the effect of cobalt in nickel hydrous oxide electrodes for fuel cells and rechargeable batteries

NASA Technical Reports Server (NTRS)

Kim, Sunghyun; Tryk, Donald A.; Scherson, Daniel A.; Antonio, Mark R.

1993-01-01

Electronic and structural aspects of composite nickel-cobalt hydrous oxides have been examined in alkaline solutions using in situ X-ray absorption fine structure (XAFS). The results obtained have indicated that cobalt in this material is present as cobaltic ions regardless of the oxidation state of nickel in the lattice. Furthermore, careful analysis of the Co K-edge Extended X-ray absorption fine structure data reveals that the co-electrodeposition procedure generates a single phase, mixed metal hydrous oxide, in which cobaltic ions occupy nickel sites in the NiO2 sheet-like layers and not two intermixed phases each consisting of a single metal hydrous oxide.

Quick-scanning x-ray absorption spectroscopy system with a servo-motor-driven channel-cut monochromator with a temporal resolution of 10 ms.

PubMed

Nonaka, T; Dohmae, K; Araki, T; Hayashi, Y; Hirose, Y; Uruga, T; Yamazaki, H; Mochizuki, T; Tanida, H; Goto, S

2012-08-01

We have developed a quick-scanning x-ray absorption fine structure (QXAFS) system and installed it at the recently constructed synchrotron radiation beamline BL33XU at the SPring-8. Rapid acquisition of high-quality QXAFS data was realized by combining a servo-motor-driven Si channel-cut monochromator with a tapered undulator. Two tandemly aligned monochromators with channel-cut Si(111) and Si(220) crystals covered energy ranges of 4.0-28.2 keV and 6.6-46.0 keV, respectively. The system allows the users to adjust instantly the energy ranges of scans, the starting angles of oscillations, and the frequencies. The channel-cut crystals are cooled with liquid nitrogen to enable them to withstand the high heat load from the undulator radiation. Deformation of the reflecting planes is reduced by clamping each crystal with two cooling blocks. Performance tests at the Cu K-edge demonstrated sufficiently high data quality for x-ray absorption near-edge structure and extended x-ray absorption fine-structure analyses with temporal resolutions of up to 10 and 25 ms, respectively.

Probing the evolution of palladium species in Pd@MOF catalysts during the Heck coupling reaction: An operando X-ray absorption spectroscopy study.

PubMed

Yuan, Ning; Pascanu, Vlad; Huang, Zhehao; Valiente, Alejandro; Heidenreich, Niclas; Leubner, Sebastian; Inge, A Ken; Gaar, Jakob; Stock, Norbert; Persson, Ingmar; Martin-Matute, Belen; Zou, Xiaodong

2018-06-11

The mechanism of the Heck C-C coupling reaction catalyzed by Pd@MOFs has been investigated using operando X-ray absorption spectroscopy (XAS) and powder X-ray diffraction (PXRD) combined with transmission electron microscopy (TEM) analysis and nuclear magnetic resonance ( 1 H NMR) kinetic studies. A custom-made reaction cell was used allowing operando PXRD and XAS data collection using high-energy synchrotron radiation. By analyzing the XAS data in combination with ex situ studies, the evolution of the palladium species is followed from the as-synthesized to its deactivated form. An adaptive reaction mechanism is pro-posed. Mononuclear Pd(II) complexes are found to be the dominant active species at the beginning of the reaction, which then gradually transform into Pd nanoclusters with 13-20 Pd atoms on average in later catalytic turnovers. Consumption of available reagent and substrate leads to coordination of Cl - ions to their surfaces, which causes the poisoning of the active sites. By understanding the deactivation process, it was possible to tune the reaction conditions and prolong the lifetime of the catalyst.

A high pressure La K-edge X-ray absorption fine structure spectroscopy investigation of La1/3NbO3

NASA Astrophysics Data System (ADS)

Marini, C.; Joseph, B.; Noked, O.; Shuker, R.; Kennedy, B. J.; Mathon, O.; Pascarelli, S.; Sterer, E.

2018-01-01

La K-edge X-ray absorption spectroscopy has been used to elucidate the changes in the local electronic and lattice structure that occur in the A-site deficient double perovskite La?NbO? up to 6 GPa. The pressure evolution of the oxygen dodecahedrum around the A-site has been examined. XANES (X-ray absorption near edge structure) data show modifications ascribed to the increase of bands overlapping as a consequence of the bond distance contraction, which has been directly probed by EXAFS (extended x-ray absorption fine structure) spectra. The La-O Debye Waller factors (DWFs) tend to increase whereas the La-Nb bond DWFs show only a tendency to decrease indicating the robustness of the crystal lattice structure, even in presence of the oxygen disordering. This permits the system to reverse back to its original conditions in this pressure range as evident from the measurements upon pressure release. The present results have been interpreted in the light of charge transfer related to the two-step reduction mechanism acting at the Nb site (with niobium ions passing from Nb? to Nb?) which also results in the elongation of the Nb-O bond distances in the octahedra, in agreement with the Nb K-edge results reported earlier.

Study of Super- and Subsonic Ionization Fronts in Low-Density, Soft X-Ray-Irradiated Foam Targets

NASA Astrophysics Data System (ADS)

Willi, O.; Barringer, L.; Vickers, C.; Hoarty, D.

2000-04-01

The transition from super- to subsonic propagation of an ionization front has been studied in X-ray irradiated, low-density foam targets using soft X-ray imaging and point projection absorption spectroscopy. The foams were doped with chlorine and irradiated with an intense pulse of soft X-ray radiation with a temperature up to 120 eV produced by laser heating a burnthrough converter foil. The cylindrical foam targets were radiographed side-on allowing the change in the chlorine ionization and hence the front to be observed. From the absolute target transmission the density profile was obtained. Comparison of experimental absorption spectra with simulated ones allowed the temperature of the heated material to be inferred for the first time without reliance on detailed hydrodynamic simulations to interpret the data. The experimental observations were compared to radiation hydrodynamic simulations.

Cr/B 4C multilayer mirrors: Study of interfaces and X-ray reflectance

DOE PAGES

Burcklen, C.; Soufli, R.; Gullikson, E.; ...

2016-03-24

Here, we present an experimental study of the effect of layer interfaces on the x-ray reflectance in Cr/B 4C multilayer interference coatings with layer thicknesses ranging from 0.7 nm to 5.4 nm. The multilayers were deposited by magnetron sputtering and by ion beam sputtering. Grazing incidence x-ray reflectometry, soft x-ray reflectometry, and transmission electron microscopy reveal asymmetric multilayer structures with a larger B 4C-on-Cr interface, which we modeled with a 1–1.5 nm thick interfacial layer. Reflectance measurements in the vicinity of the Cr L 2,3 absorption edge demonstrate fine structure that is not predicted by simulations using the currently tabulatedmore » refractive index (optical constants) values for Cr.« less

The origin of blueshifted absorption features in the X-ray spectrum of PG 1211+143: outflow or disc

NASA Astrophysics Data System (ADS)

Gallo, L. C.; Fabian, A. C.

2013-07-01

In some radio-quiet active galactic nuclei (AGN), high-energy absorption features in the X-ray spectra have been interpreted as ultrafast outflows (UFOs) - highly ionized material (e.g. Fe XXV and Fe XXVI) ejected at mildly relativistic velocities. In some cases, these outflows can carry energy in excess of the binding energy of the host galaxy. Needless to say, these features demand our attention as they are strong signatures of AGN feedback and will influence galaxy evolution. For the same reason, alternative models need to be discussed and refuted or confirmed. Gallo and Fabian proposed that some of these features could arise from resonance absorption of the reflected spectrum in a layer of ionized material located above and corotating with the accretion disc. Therefore, the absorbing medium would be subjected to similar blurring effects as seen in the disc. A priori, the existence of such plasma above the disc is as plausible as a fast wind. In this work, we highlight the ambiguity by demonstrating that the absorption model can describe the ˜7.6 keV absorption feature (and possibly other features) in the quasar PG 1211+143, an AGN that is often described as a classic example of a UFO. In this model, the 2-10 keV spectrum would be largely reflection dominated (as opposed to power law dominated in the wind models) and the resonance absorption would be originating in a layer between about 6 and 60 gravitational radii. The studies of such features constitute a cornerstone for future X-ray observatories like Astro-H and Athena+. Should our model prove correct, or at least important in some cases, then absorption will provide another diagnostic tool with which to probe the inner accretion flow with future missions.

Elucidating the Nature of the Excited State of a Heteroleptic Copper Photosensitizer by using Time-Resolved X-ray Absorption Spectroscopy.

PubMed

Moonshiram, Dooshaye; Garrido-Barros, Pablo; Gimbert-Suriñach, Carolina; Picón, Antonio; Liu, Cunming; Zhang, Xiaoyi; Karnahl, Michael; Llobet, Antoni

2018-04-25

We report the light-induced electronic and geometric changes taking place within a heteroleptic Cu I photosensitizer, namely [(xant)Cu(Me 2 phenPh 2 )]PF 6 (xant=xantphos, Me 2 phenPh 2 =bathocuproine), by time-resolved X-ray absorption spectroscopy in the ps-μs time regime. Time-resolved X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analysis enabled the elucidation of the electronic and structural configuration of the copper center in the excited state as well as its decay dynamics in different solvent conditions with and without triethylamine acting as a sacrificial electron donor. A three-fold decrease in the decay lifetime of the excited state is observed in the presence of triethylamine, showing the feasibility of the reductive quenching pathway in the latter case. A prominent pre-edge feature is observed in the XANES spectrum of the excited state upon metal to charge ligand transfer transition, showing an increased hybridization of the 3d states with the ligand p orbitals in the tetrahedron around the Cu center. EXAFS and density functional theory illustrate a significant shortening of the Cu-N and an elongation of the Cu-P bonds together with a decrease in the torsional angle between the xantphos and bathocuproine ligand. This study provides mechanistic time-resolved understanding for the development of improved heteroleptic Cu I photosensitizers, which can be used for the light-driven production of hydrogen from water. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Complete Hard X-Ray Surveys, AGN Luminosity Functions and the X-Ray Background

NASA Technical Reports Server (NTRS)

Tueller, Jack

2011-01-01

AGN are believed to make up most of the Cosmic X-Ray Background (CXB) above a few keV, but this background cannot be fully resolved at energies less than 10 keV due to absorption. The Swift/BAT and INTEGRAL missions are performing the first complete hard x-ray surveys with minimal bias due to absorption. The most recent results for both missions will be presented. Although the fraction of the CXB resolved by these surveys is small, it is possible to derive unbiased number counts and luminosity functions for AGN in the local universe. The survey energy range from 15-150 keV contains the important reflection and cutoff spectral features dominate the shape of the AGN contribution to the CXB. Average spectral characteristics of survey detected AGN will be presented and compared with model distributions. The numbers of hard x-ray blazars detected in these surveys are finally sufficient to estimate this important component's contribution the cosmic background. Constraints on CXB models and their significance will be discussed.

Revealing electronic structure changes in Chevrel phase cathodes upon Mg insertion using X-ray absorption spectroscopy

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

Wan, Liwen F.; Wright, Joshua; Perdue, Brian R.

Following previous work predicting the electronic response of the Chevrel phase Mo6S8 upon Mg insertion (Thole et al., Phys. Chem. Chem. Phys., 2015, 17, 22548), we provide the experimental proof, evident in X-ray absorption spectroscopy, to illustrate the charge compensation mechanism of the Chevrel phase compound during Mg insertion and de-insertion processes.

Mechanism of selenite removal by a mixed adsorbent based on Fe-Mn hydrous oxides studied using X-ray absorption spectroscopy.

PubMed

Chubar, Natalia; Gerda, Vasyl; Szlachta, Małgorzata

2014-11-18

Selenium cycling in the environment is greatly controlled by various minerals, including Mn and Fe hydrous oxides. At the same time, such hydrous oxides are the main inorganic ion exchangers suitable (on the basis of their chemical nature) to sorb (toxic) anions, separating them from water solutions. The mechanism of selenite adsorption by the new mixed adsorbent composed of a few (amorphous and crystalline) phases [maghemite, MnCO3, and X-ray amorphous Fe(III) and Mn(III) hydrous oxides] was studied by extended X-ray absorption fine structure (EXAFS) spectroscopy [supported by Fourier transform infrared (FTIR) and X-ray diffraction (XRD) data]. The complexity of the porous adsorbent, especially the presence of the amorphous phases of Fe(III) and Mn(III) hydrous oxides, is the main reason for its high selenite removal performance demonstrated by batch and column adsorption studies shown in the previous work. Selenite was bound to the material via inner-sphere complexation (via oxygen) to the adsorption sites of the amorphous Fe(III) and Mn(III) oxides. This anion was attracted via bidentate binuclear corner-sharing coordination between SeO3(2-) trigonal pyramids and both FeO6 and MnO6 octahedra; however, the adsorption sites of Fe(III) hydrous oxides played a leading role in selenite removal. The contribution of the adsorption sites of Mn(III) oxide increased as the pH decreased from 8 to 6. Because most minerals have a complex structure (they are seldom based on individual substances) of various crystallinity, this work is equally relevant to environmental science and environmental technology because it shows how various solid phases control cycling of chemical elements in the environment.

X-ray absorption fine structure (XAFS) analysis of titanium-implanted soft tissue.

PubMed

Uo, Motohiro; Asakura, Kiyotaka; Yokoyama, Atsuro; Ishikawa, Makoto; Tamura, Kazuchika; Totsuka, Yasunori; Akasaka, Tsukasa; Watari, Fumio

2007-03-01

Tissues contacting Ti dental implants were subjected to X-ray absorption fine structure (XAFS) analysis to examine the chemical state of Ti transferred from the placed implant into the surrounding tissue. Nine tissues that contacted pure Ti cover screws for several months were excised in a second surgery whereby healing abutments were set. Six tissues that surrounded implants retrieved due to their failure were also excised. Ti distributions in the excised specimens were confirmed by X-ray scanning analytical microscopy (XSAM), and the specimens were subjected to fluorescence XAFS analysis to determine the chemical states of the low concentrations of Ti in the tissues surrounding Ti dental implants. Ti mostly existed in the metallic state and was considered to be debris derived from the abrasion of implant pieces during implant surgery. Oxidized forms of Ti, such as anatase and rutile, were also detected in a few specimens-and existed in either a pure state or mixed state with metallic Ti. It was concluded that the existence of Ti in the tissue did not cause implant failure. Moreover, the usefulness of XAFS for analysis of the chemical states of rarely contained elements in biological tissue was demonstrated.

Theoretical X-ray production cross sections at incident photon energies across Li (i=1-3) absorption edges of Br

NASA Astrophysics Data System (ADS)

Puri, Sanjiv

2015-08-01

The X-ray production (XRP) cross sections, σLk (k = l, η, α, β6, β1, β3, β4, β9,10, γ1,5, γ2,3) have been evaluated at incident photon energies across the Li(i=1-3) absorption edge energies of 35Br using theoretical data sets of different physical parameters, namely, the Li(i=1-3) sub-shell the X-ray emission rates based on the Dirac-Fock (DF) model, the fluorescence and Coster Kronig yields based on the Dirac-Hartree-Slater (DHS) model, and two sets of the photoionisation cross sections based on the relativistic Hartree-Fock-Slater (RHFS) model and the Dirac-Fock (DF) model, in order to highlight the importance of electron exchange effects at photon energies in vicinity of absorption edge energies.

Plutonium-uranium mixed oxide characterization by coupling micro-X-ray diffraction and absorption investigations

NASA Astrophysics Data System (ADS)

Degueldre, C.; Martin, M.; Kuri, G.; Grolimund, D.; Borca, C.

2011-09-01

Plutonium-uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The potential differences of metal redox state and microstructural developments of the matrix before and after irradiation are commonly analysed by electron probe microanalysis. In this work the structure and next-neighbor atomic environments of Pu and U oxide features within unirradiated homogeneous MOX and irradiated (60 MW d kg -1) MOX samples was analysed by micro-X-ray fluorescence (μ-XRF), micro-X-ray diffraction (μ-XRD) and micro-X-ray absorption fine structure (μ-XAFS) spectroscopy. The grain properties, chemical bonding, valences and stoichiometry of Pu and U are determined from the experimental data gained for the unirradiated as well as for irradiated fuel material examined in the center of the fuel as well as in its peripheral zone (rim). The formation of sub-grains is observed as well as their development from the center to the rim (polygonization). In the irradiated sample Pu remains tetravalent (>95%) and no (<5%) Pu(V) or Pu(VI) can be detected while the fuel could undergo slight oxidation in the rim zone. Any slight potential plutonium oxidation is buffered by the uranium dioxide matrix while locally fuel cladding interaction could also affect the redox of the fuel.

Electronic structure change of NiS2- x Se x in the metal-insulator transition probed by X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Jeong, Jinwon; Park, Kyung Ja; Cho, En-Jin; Noh, Han-Jin; Kim, Sung Baek; Kim, Hyeong-Do

2018-01-01

The electronic structure change of NiS2- x Se x as a function of Se concentration x has been studied by Ni L-edge X-ray absorption spectroscopy (XAS). The XAS spectra show distinct features in Ni L 3 edge, indicating whether the system is insulating or metallic. These features can be semi-quantitatively explained within the framework of the configurational interaction cluster model (CICM). In the S-rich region, relatively large charge-transfer energy (Δ 5 eV) from ligand p to Ni 3 d states and a little small p- d hybridization strength ( V pdσ 1.1 eV) can reproduce the experimental spectra in the CICM calculation, and vice versa in the Se-rich region. Our analysis result is consistent with the Zaanen-Sawatzky-Allen scheme that the systems in S-rich side ( x ≤ 0.5) are a charge transfer insulator. However, it also requires that the Δ value must change abruptly in spite of the small change of x near x = 0.5. As a possible microscopic origin, we propose a percolation scenario where a long range connection of Ni[(S,Se)2]6 octahedra with Se-Se dimers plays a key role to gap closure.

Absorption dips at low X-ray energies in Cygnus X-1. [observed with Copernicus satellite

NASA Technical Reports Server (NTRS)

Murdin, P. G.

1976-01-01

Absorbing material in Cygnus X-1 jitters near the line joining the two stars, out of the orbital plane is described. Three looks with the Copernicus satellite at Cygnus X-1 have produced four examples of absorption dips (decreases in the 2 to 7 keV flux from Cygnus X-1 with an increase of spectral hardness consistent with photoelectric absorption).

Iodate in calcite and vaterite: Insights from synchrotron X-ray absorption spectroscopy and first-principles calculations

NASA Astrophysics Data System (ADS)

Podder, J.; Lin, J.; Sun, W.; Botis, S. M.; Tse, J.; Chen, N.; Hu, Y.; Li, D.; Seaman, J.; Pan, Y.

2017-02-01

Calcium carbonates such as calcite are the dominant hosts of inorganic iodine in nature and are potentially important for the retention and removal of radioactive iodine isotopes (129I and 131I) in contaminated water. However, little is known about the structural environment of iodine in carbonates. In this study, iodate (IO3-) doped calcite and vaterite have been synthesized using the gel-diffusion method at three NaIO3 concentrations (0.002; 0.004; 0.008 M) and a pH value of 9.0, under ambient temperature and pressure. Inductively coupled plasma mass spectrometry (ICP-MS) analyses show that iodine is preferentially incorporated into calcite over vaterite. Synchrotron iodine K-edge X-ray absorption near-edge structure (XANES) spectra confirm that IO3- is the dominant iodine species in synthetic calcite and vaterite. Analyses of iodine K-edge extended X-ray absorption fine structure (EXAFS) data, complemented by periodic first-principles calculations at the density functional theory (DFT) levels, demonstrate that the I5+ ion of the IO3- group in calcite and vaterite is bonded by three and two additional O atoms (i.e., coordination numbers = 6 and 5), respectively, and is incorporated via the charged coupled substitution I5+ + Na+ ↔ C4+ + Ca2+, with the Na+ cation at a nearest Ca2+ site being the most energetically favorable configuration.

Role of defects in BiFeO₃ multiferroic films and their local electronic structure by x-ray absorption spectroscopy

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

Ravalia, Ashish; Vagadia, Megha; Solanki, P. S.

2014-10-21

Present study reports the role of defects in the electrical transport in BiFeO₃ (BFO) multiferroic films and its local electronic structure investigated by near-edge X-ray absorption fine structure. Defects created by high energy 200 MeV Ag⁺¹⁵ ion irradiation with a fluence of ∼5 × 10¹¹ ions/cm² results in the increase in structural strain and reduction in the mobility of charge carriers and enhancement in resistive (I-V) and polarization (P-E) switching behaviour. At higher fluence of ∼5 × 10¹² ions/cm², there is a release in the structural strain due to local annealing effect, resulting in an increase in the mobility of charge carriers, which are releasedmore » from oxygen vacancies and hence suppression in resistive and polarization switching. Near-edge X-ray absorption fine structure studies at Fe L₃,₂- and O K-edges show a significant change in the spectral features suggesting the modifications in the local electronic structure responsible for changes in the intrinsic magnetic moment and electrical transport properties of BFO.« less

High quality x-ray absorption spectroscopy measurements with long energy range at high pressure using diamond anvil cell.

PubMed

Hong, Xinguo; Newville, Matthew; Prakapenka, Vitali B; Rivers, Mark L; Sutton, Stephen R

2009-07-01

We describe an approach for acquiring high quality x-ray absorption fine structure (XAFS) spectroscopy spectra with wide energy range at high pressure using diamond anvil cell (DAC). Overcoming the serious interference of diamond Bragg peaks is essential for combining XAFS and DAC techniques in high pressure research, yet an effective method to obtain accurate XAFS spectrum free from DAC induced glitches has been lacking. It was found that these glitches, whose energy positions are very sensitive to the relative orientation between DAC and incident x-ray beam, can be effectively eliminated using an iterative algorithm based on repeated measurements over a small angular range of DAC orientation, e.g., within +/-3 degrees relative to the x-ray beam direction. Demonstration XAFS spectra are reported for rutile-type GeO2 recorded by traditional ambient pressure and high pressure DAC methods, showing similar quality at 440 eV above the absorption edge. Accurate XAFS spectra of GeO2 glass were obtained at high pressure up to 53 GPa, providing important insight into the structural polymorphism of GeO2 glass at high pressure. This method is expected be applicable for in situ XAFS measurements using a diamond anvil cell up to ultrahigh pressures.

High quality x-ray absorption spectroscopy measurements with long energy range at high pressure using diamond anvil cell

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

Hong, X.; Newville, M.; Prakapenka, V.B.

We describe an approach for acquiring high quality x-ray absorption fine structure (XAFS) spectroscopy spectra with wide energy range at high pressure using diamond anvil cell (DAC). Overcoming the serious interference of diamond Bragg peaks is essential for combining XAFS and DAC techniques in high pressure research, yet an effective method to obtain accurate XAFS spectrum free from DAC induced glitches has been lacking. It was found that these glitches, whose energy positions are very sensitive to the relative orientation between DAC and incident x-ray beam, can be effectively eliminated using an iterative algorithm based on repeated measurements over amore » small angular range of DAC orientation, e.g., within {+-}3{sup o} relative to the x-ray beam direction. Demonstration XAFS spectra are reported for rutile-type GeO{sub 2} recorded by traditional ambient pressure and high pressure DAC methods, showing similar quality at 440 eV above the absorption edge. Accurate XAFS spectra of GeO{sub 2} glass were obtained at high pressure up to 53 GPa, providing important insight into the structural polymorphism of GeO{sub 2} glass at high pressure. This method is expected be applicable for in situ XAFS measurements using a diamond anvil cell up to ultrahigh pressures.« less

Extended X-ray Absorption Fine Structure (EXAFS) Analysis of Vitreous Rare Earth Sodium Phosphates

NASA Astrophysics Data System (ADS)

Yoo, Changhyeon; Marasinghe, Kanishka; Segre, Carlo; Shibata, Tomohiro

2015-03-01

The local structure around rare-earth ions (RE3+) in rare-earth ultraphosphate (REUP) glasses has been studied using RE LIII edge (RE = Nd, Er, Dy, and Eu) and K edge (RE = Nd, Pr, Dy, and Eu) extended X-ray absorption fine structure (EXAFS) spectroscopy. (RE2O3)x (Na2O)y(P2O5) 1 - x - y glasses in the compositional range 0 <= x <= 0.14 and x + y = 0.3 and 0.4 were studied. RE-oxygen (RE-O) coordination number decreases from ~ 10 to ~ 7.5 with increasing RE-content for Nd, Pr, Eu, and Dy. For Er, RE-O coordination number increases from ~ 8.7 to ~ 10 with increasing RE-content. For the first oxygen shell, the RE-O distance ranges between 2.41-2.43 Å, 2.44-2.46 Å, 2.24-2.26 Å, 2.28-2.32 Å, and 2.32-2.36 Å for Nd, Pr, Er, Dy, and EU glasses, respectively. Second shell around RE ions consists of phosphorus atoms, with RE-P distance about 3.0-3.5 Å and coordination number ranging from 1 to 3. The third shell primarily contains oxygen and is at a distance about 4.0-4.1 Å from RE ions.

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.

Ionized absorbers, ionized emitters, and the X-ray spectrum of active galactic nuclei

NASA Technical Reports Server (NTRS)

Netzer, Hagai

1993-01-01

Broad absorption features are common in the X-ray spectrum of low-luminosity AGNs. The features have been modeled by leaky neutral absorbers or by highly ionized gas that completely occult the continuum source. Such models are incomplete since they do not take into account all the physical processes in the gas. In particular, no previous model included the X-ray emission by the ionized absorbing gas and the reflection of the continuum source radiation. The present work discusses the emission, absorption, and reflection properties of photoionized gases with emphasis on conditions thought to prevail in AGNs. It shows that such gas is likely to produce intense X-ray line and continuum radiation and to reflect a sizable fraction of the nonstellar continuum at all energies. If such gas is indeed responsible for the observed X-ray absorption, then absorption edges are much weaker than commonly assumed, and some residual X-ray continuum is likely to be observed even if the line of sight is completely blocked. Moreover, X-ray emission features may show up in sources not showing X-ray absorption. This has immense consequences for medium-resolution X-ray missions, such as BBXRT and Astro-D, and for the planned high-resolution experiments on board XMM and AXAF.

Establishing nonlinearity thresholds with ultraintense X-ray pulses

NASA Astrophysics Data System (ADS)

Szlachetko, Jakub; Hoszowska, Joanna; Dousse, Jean-Claude; Nachtegaal, Maarten; Błachucki, Wojciech; Kayser, Yves; Sà, Jacinto; Messerschmidt, Marc; Boutet, Sebastien; Williams, Garth J.; David, Christian; Smolentsev, Grigory; van Bokhoven, Jeroen A.; Patterson, Bruce D.; Penfold, Thomas J.; Knopp, Gregor; Pajek, Marek; Abela, Rafael; Milne, Christopher J.

2016-09-01

X-ray techniques have evolved over decades to become highly refined tools for a broad range of investigations. Importantly, these approaches rely on X-ray measurements that depend linearly on the number of incident X-ray photons. The advent of X-ray free electron lasers (XFELs) is opening the ability to reach extremely high photon numbers within ultrashort X-ray pulse durations and is leading to a paradigm shift in our ability to explore nonlinear X-ray signals. However, the enormous increase in X-ray peak power is a double-edged sword with new and exciting methods being developed but at the same time well-established techniques proving unreliable. Consequently, accurate knowledge about the threshold for nonlinear X-ray signals is essential. Herein we report an X-ray spectroscopic study that reveals important details on the thresholds for nonlinear X-ray interactions. By varying both the incident X-ray intensity and photon energy, we establish the regimes at which the simplest nonlinear process, two-photon X-ray absorption (TPA), can be observed. From these measurements we can extract the probability of this process as a function of photon energy and confirm both the nature and sub-femtosecond lifetime of the virtual intermediate electronic state.

Establishing nonlinearity thresholds with ultraintense X-ray pulses

DOE PAGES

Szlachetko, Jakub; Hoszowska, Joanna; Dousse, Jean-Claude; ...

2016-09-13

X-ray techniques have evolved over decades to become highly refined tools for a broad range of investigations. Importantly, these approaches rely on X-ray measurements that depend linearly on the number of incident X-ray photons. The advent of X-ray free electron lasers (XFELs) is opening the ability to reach extremely high photon numbers within ultrashort X-ray pulse durations and is leading to a paradigm shift in our ability to explore nonlinear X-ray signals. However, the enormous increase in X-ray peak power is a double-edged sword with new and exciting methods being developed but at the same time well-established techniques proving unreliable.more » Consequently, accurate knowledge about the threshold for nonlinear X-ray signals is essential. Here in this paper we report an X-ray spectroscopic study that reveals important details on the thresholds for nonlinear X-ray interactions. By varying both the incident X-ray intensity and photon energy, we establish the regimes at which the simplest nonlinear process, two-photon X-ray absorption (TPA), can be observed. From these measurements we can extract the probability of this process as a function of photon energy and confirm both the nature and sub-femtosecond lifetime of the virtual intermediate electronic state.« less

Relationship between x-ray emission and absorption spectroscopy and the local H-bond environment in water

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

Zhovtobriukh, Iurii; Besley, Nicholas A.; Fransson, Thomas

Here, the connection between specific features in the water X-ray absorption spectrum and X-ray emission spectrum (XES) and the local H-bond coordination is studied based on structures obtained from path-integral molecular dynamics simulations using either the opt-PBE-vdW density functional or the MB-pol force field. Computing the XES spectrum using all molecules in a snapshot results in only one peak in the lone-pair (1b 1) region, while the experiment shows two peaks separated by 0.8-0.9 eV. Different H-bond configurations were classified based on the local structure index (LSI) and a geometrical H-bond cone criterion. We find that tetrahedrally coordinated molecules characterizedmore » by high LSI values and two strong donated and two strong accepted H-bonds contribute to the low energy 1b 1 emission peak and to the post-edge region in absorption. Molecules with the asymmetric H-bond environment with one strong accepted H-bond and one strong donated H-bond and low LSI values give rise to the high energy 1b 1 peak in the emission spectrum and mainly contribute to the pre-edge and main-edge in the absorption spectrum. The 1b 1 peak splitting can be increased to 0.62 eV by imposing constraints on the H-bond length, i.e., for very tetrahedral structures short H-bonds (less than 2.68 Å) and for very asymmetric structures elongated H-bonds (longer than 2.8 Å). Such structures are present, but underrepresented, in the simulations which give more of an average of the two extremes.« less

Relationship between x-ray emission and absorption spectroscopy and the local H-bond environment in water

DOE PAGES

Zhovtobriukh, Iurii; Besley, Nicholas A.; Fransson, Thomas; ...

2018-04-14

Here, the connection between specific features in the water X-ray absorption spectrum and X-ray emission spectrum (XES) and the local H-bond coordination is studied based on structures obtained from path-integral molecular dynamics simulations using either the opt-PBE-vdW density functional or the MB-pol force field. Computing the XES spectrum using all molecules in a snapshot results in only one peak in the lone-pair (1b 1) region, while the experiment shows two peaks separated by 0.8-0.9 eV. Different H-bond configurations were classified based on the local structure index (LSI) and a geometrical H-bond cone criterion. We find that tetrahedrally coordinated molecules characterizedmore » by high LSI values and two strong donated and two strong accepted H-bonds contribute to the low energy 1b 1 emission peak and to the post-edge region in absorption. Molecules with the asymmetric H-bond environment with one strong accepted H-bond and one strong donated H-bond and low LSI values give rise to the high energy 1b 1 peak in the emission spectrum and mainly contribute to the pre-edge and main-edge in the absorption spectrum. The 1b 1 peak splitting can be increased to 0.62 eV by imposing constraints on the H-bond length, i.e., for very tetrahedral structures short H-bonds (less than 2.68 Å) and for very asymmetric structures elongated H-bonds (longer than 2.8 Å). Such structures are present, but underrepresented, in the simulations which give more of an average of the two extremes.« less

Mammographic x-ray unit kilovoltage test tool based on k-edge absorption effect.

PubMed

Napolitano, Mary E; Trueblood, Jon H; Hertel, Nolan E; David, George

2002-09-01

A simple tool to determine the peak kilovoltage (kVp) of a mammographic x-ray unit has been designed. Tool design is based on comparing the effect of k-edge discontinuity of the attenuation coefficient for a series of element filters. Compatibility with the mammography accreditation phantom (MAP) to obtain a single quality control film is a second design objective. When the attenuation of a series of sequential elements is studied simultaneously, differences in the absorption characteristics due to the k-edge discontinuities are more evident. Specifically, when the incident photon energy is higher than the k-edge energy of a number of the elements and lower than the remainder, an inflection may be seen in the resulting attenuation data. The maximum energy of the incident photon spectra may be determined based on this inflection point for a series of element filters. Monte Carlo photon transport analysis was used to estimate the photon transmission probabilities for each of the sequential k-edge filter elements. The photon transmission corresponds directly to optical density recorded on mammographic x-ray film. To observe the inflection, the element filters chosen must have k-edge energies that span a range greater than the expected range of the end point energies to be determined. For the design, incident x-ray spectra ranging from 25 to 40 kVp were assumed to be from a molybdenum target. Over this range, the k-edge energy changes by approximately 1.5 keV between sequential elements. For this design 21 elements spanning an energy range from 20 to 50 keV were chosen. Optimum filter element thicknesses were calculated to maximize attenuation differences at the k-edge while maintaining optical densities between 0.10 and 3.00. Calculated relative transmission data show that the kVp could be determined to within +/-1 kV. To obtain experimental data, a phantom was constructed containing 21 different elements placed in an acrylic holder. MAP images were used to determine

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

Transmission X-ray microscopy for full-field nano-imaging of biomaterials

PubMed Central

ANDREWS, JOY C; MEIRER, FLORIAN; LIU, YIJIN; MESTER, ZOLTAN; PIANETTA, PIERO

2010-01-01

Imaging of cellular structure and extended tissue in biological materials requires nanometer resolution and good sample penetration, which can be provided by current full-field transmission X-ray microscopic techniques in the soft and hard X-ray regions. The various capabilities of full-field transmission X-ray microscopy (TXM) include 3D tomography, Zernike phase contrast, quantification of absorption, and chemical identification via X-ray fluorescence and X-ray absorption near edge structure (XANES) imaging. These techniques are discussed and compared in light of results from imaging of biological materials including microorganisms, bone and mineralized tissue and plants, with a focus on hard X-ray TXM at ≤ 40 nm resolution. PMID:20734414

Transmission X-ray microscopy for full-field nano imaging of biomaterials.

PubMed

Andrews, Joy C; Meirer, Florian; Liu, Yijin; Mester, Zoltan; Pianetta, Piero

2011-07-01

Imaging of cellular structure and extended tissue in biological materials requires nanometer resolution and good sample penetration, which can be provided by current full-field transmission X-ray microscopic techniques in the soft and hard X-ray regions. The various capabilities of full-field transmission X-ray microscopy (TXM) include 3D tomography, Zernike phase contrast, quantification of absorption, and chemical identification via X-ray fluorescence and X-ray absorption near edge structure imaging. These techniques are discussed and compared in light of results from the imaging of biological materials including microorganisms, bone and mineralized tissue, and plants, with a focus on hard X-ray TXM at ≤ 40-nm resolution. Copyright © 2010 Wiley-Liss, Inc.

X-ray Absorption Spectroscopy Systematics at the Tungsten L-Edge

PubMed Central

2015-01-01

A series of mononuclear six-coordinate tungsten compounds spanning formal oxidation states from 0 to +VI, largely in a ligand environment of inert chloride and/or phosphine, was interrogated by tungsten L-edge X-ray absorption spectroscopy. The L-edge spectra of this compound set, comprised of [W0(PMe3)6], [WIICl2(PMePh2)4], [WIIICl2(dppe)2][PF6] (dppe = 1,2-bis(diphenylphosphino)ethane), [WIVCl4(PMePh2)2], [WV(NPh)Cl3(PMe3)2], and [WVICl6], correlate with formal oxidation state and have usefulness as references for the interpretation of the L-edge spectra of tungsten compounds with redox-active ligands and ambiguous electronic structure descriptions. The utility of these spectra arises from the combined correlation of the estimated branching ratio of the L3,2-edges and the L1 rising-edge energy with metal Zeff, thereby permitting an assessment of effective metal oxidation state. An application of these reference spectra is illustrated by their use as backdrop for the L-edge X-ray absorption spectra of [WIV(mdt)2(CO)2] and [WIV(mdt)2(CN)2]2– (mdt2– = 1,2-dimethylethene-1,2-dithiolate), which shows that both compounds are effectively WIV species even though the mdt ligands exist at different redox levels in the two compounds. Use of metal L-edge XAS to assess a compound of uncertain formulation requires: (1) Placement of that data within the context of spectra offered by unambiguous calibrant compounds, preferably with the same coordination number and similar metal ligand distances. Such spectra assist in defining upper and/or lower limits for metal Zeff in the species of interest. (2) Evaluation of that data in conjunction with information from other physical methods, especially ligand K-edge XAS. (3) Increased care in interpretation if strong π-acceptor ligands, particularly CO, or π-donor ligands are present. The electron-withdrawing/donating nature of these ligand types, combined with relatively short metal–ligand distances, exaggerate the difference

Extended x-ray absorption fine structure study of phase transitions in the piezoelectric perovskite K0.5Na0.5NbO3

NASA Astrophysics Data System (ADS)

Kodre, A.; Tellier, J.; Arčon, I.; Malič, B.; Kosec, M.

2009-06-01

Following an x-ray diffraction study of phase transitions of the piezoelectric perovskite K0.5Na0.5NbO3 the structural changes of the material are studied using extended x-ray absorption fine structure analysis, whereby the neighborhood of Nb atom is determined in the temperature range of monoclinic, tetragonal, and cubic phases. Within the entire range Nb atom is displaced from the center of the octahedron of its immediate oxygen neighbors, as witnessed by the splitting of Nb-O distance. The model shows high prevalence of the displacement in the (111) crystallographic direction of the simple perovskite cell. The corresponding splitting of the Nb-Nb distance is negligible. There is no observable disalignment of the linear Nb-O-Nb bonds from the ideal cubic arrangement, judging from the intensity of the focusing of the photoelectron wave on the Nb-Nb scattering path by the interposed oxygen atom. As a general result, the phase transitions are found as an effect of the long-range order, while the placement of the atoms in the immediate vicinity remains largely unaffected.

The X-ray emitting galaxy Centaurus A

NASA Technical Reports Server (NTRS)

Mushotzky, R. F.; Serlemitsos, P. J.; Boldt, E. A.; Holt, S. S.; Becker, R. H.

1978-01-01

OSO-8 X-ray observations of Cen A in 1975 and 1976 are reported. The source spectrum can be well fitted in both years by a power law of number index 1.66 and absorption due to 1.3 by 10 to the 23rd power atoms/sq cm. The total flux varied by a factor of 2 between 1975 and 1976. In 1976 there were flux variations of approximately 40% on a time scale of days. Measurements of the 6.4-keV Fe fluorescent line and the 7.1-keV absorption edge imply Fe/H of approximately 0.000016. Simultaneous radio measurements show variation in phase with X-ray variability. Consideration of radio, millimeter, infrared, and X-ray data shows that all the data can be accounted for by a model in which the X-rays are due to a synchrotron self-Compton source embedded in a cold H2 cloud.

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.

X-Rays form the Vela-Puppis Complex

NASA Technical Reports Server (NTRS)