462 research outputs found
XAFS spectroscopy. I. Extracting the fine structure from the absorption spectra
Three independent techniques are used to separate fine structure from the
absorption spectra, the background function in which is approximated by (i)
smoothing spline. We propose a new reliable criterion for determination of
smoothing parameter and the method for raising of stability with respect to
k_min variation; (ii) interpolation spline with the varied knots; (iii) the
line obtained from bayesian smoothing. This methods considers various prior
information and includes a natural way to determine the errors of XAFS
extraction. Particular attention has been given to the estimation of
uncertainties in XAFS data. Experimental noise is shown to be essentially
smaller than the errors of the background approximation, and it is the latter
that determines the variances of structural parameters in subsequent fitting.Comment: 16 pages, 7 figures, for freeware XAFS analysis program, see
http://www.crosswinds.net/~klmn/viper.htm
Step by step capping and strain state of GaN/AlN quantum dots studied by grazing incidence diffraction anomalous fine structure
The investigation of small size embedded nanostructures, by a combination of
complementary anomalous diffraction techniques, is reported. GaN Quantum Dots
(QDs), grown by molecular beam epitaxy in a modified Stranski-Krastanow mode,
are studied in terms of strain and local environment, as a function of the AlN
cap layer thickness, by means of grazing incidence anomalous diffraction. That
is, the X-ray photons energy is tuned across the Ga absorption K-edge which
makes diffraction chemically selective. Measurement of \textit{hkl}-scans,
close to the AlN (30-30) Bragg reflection, at several energies across the Ga
K-edge, allows the extraction of the Ga partial structure factor, from which
the in-plane strain of GaN QDs is deduced. From the fixed-Q energy-dependent
diffracted intensity spectra, measured for diffraction-selected iso-strain
regions corresponding to the average in-plane strain state of the QDs,
quantitative information regarding composition and the out-of-plane strain has
been obtained. We recover the in-plane and out-of-plane strains in the dots.
The comparison to the biaxial elastic strain in a pseudomorphic layer indicates
a tendency to an over-strained regime.Comment: submitted to PR
Deconvolution problems in x-ray absorption fine structure
A Bayesian method application to the deconvolution of EXAFS spectra is
considered. It is shown that for purposes of EXAFS spectroscopy, from the
infinitely large number of Bayesian solutions it is possible to determine an
optimal range of solutions, any one from which is appropriate. Since this
removes the requirement for the uniqueness of solution, it becomes possible to
exclude the instrumental broadening and the lifetime broadening from EXAFS
spectra. In addition, we propose several approaches to the determination of
optimal Bayesian regularization parameter. The Bayesian deconvolution is
compared with the deconvolution which uses the Fourier transform and optimal
Wiener filtering. It is shown that XPS spectra could be in principle used for
extraction of a one-electron absorptance. The amplitude correction factors
obtained after deconvolution are considered and discussed.Comment: 6 two-column pages, 5 eps figures; submitted to J. Phys.: Appl. Phy
X-ray Absorption Fine Structure in Embedded Atoms
Oscillatory structure is found in the atomic background absorption in
x-ray-absorption fine structure (XAFS). This atomic-XAFS or AXAFS arises from
scattering within an embedded atom, and is analogous to the Ramsauer-Townsend
effect. Calculations and measurements confirm the existence of AXAFS and show
that it can dominate contributions such as multi-electron excitations. The
structure is sensitive to chemical effects and thus provides a new probe of
bonding and exchange effects on the scattering potential.Comment: 4 pages plus 2 postscript figures, REVTEX 3.
Geometric, electronic, and magnetic structure of CoFeSi: Curie temperature and magnetic moment measurements and calculations
In this work a simple concept was used for a systematic search for new
materials with high spin polarization. It is based on two semi-empirical
models. Firstly, the Slater-Pauling rule was used for estimation of the
magnetic moment. This model is well supported by electronic structure
calculations. The second model was found particularly for Co based Heusler
compounds when comparing their magnetic properties. It turned out that these
compounds exhibit seemingly a linear dependence of the Curie temperature as
function of the magnetic moment. Stimulated by these models, CoFeSi was
revisited. The compound was investigated in detail concerning its geometrical
and magnetic structure by means of X-ray diffraction, X-ray absorption and
M\"o\ss bauer spectroscopies as well as high and low temperature magnetometry.
The measurements revealed that it is, currently, the material with the highest
magnetic moment () and Curie-temperature (1100K) in the classes of
Heusler compounds as well as half-metallic ferromagnets. The experimental
findings are supported by detailed electronic structure calculations
EXAFS study of lead-free relaxor ferroelectric BaTi(1-x)Zr(x)O3 at the Zr K-edge
Extended X-ray absorption fine structure (EXAFS) experiments at the Zr K-edge
were carried out on perovskite relaxor ferroelectrics BaTi(1-x)Zr(x)O3 (BTZ) (x
= 0.25, 0.30, 0.35), and on BaZrO3 for comparison. Structural information up to
4.5 A around the Zr atoms is obtained, revealing that the local structure
differs notably from the average Pm-3m cubic structure deduced from X-ray
diffraction. In particular, our results show that the distance between Zr atoms
and their first oxygen neighbors is independent of the Zr substitution rate x
and equal to that measured in BaZrO3, while the X-ray cubic cell parameter
increases linearly with x. Furthermore, we show that the Zr atoms tend to
segregate in Zr-rich regions. We propose that the relaxor behavior in BTZ is
linked to random elastic fields generated by this particular chemical
arrangement, rather than to random electric fields as is the case in most
relaxors.Comment: 13 pages, 12 figures, 4 tables. Submitted to Phys. Rev.
Ice-VII inclusions in diamonds: Evidence for aqueous fluid in Earth’s deep mantle
Water-rich regions in Earth’s deeper mantle are suspected to play a key role in the global water budget and the mobility of heat-generating elements. We show that ice-VII occurs as inclusions in natural diamond and serves as an indicator for such water-rich regions. Ice-VII, the residue of aqueous fluid present during growth of diamond, crystallizes upon ascent of the host diamonds but remains at pressures as high as 24 gigapascals; it is now recognized as a mineral by the International Mineralogical Association. In particular, ice-VII in diamonds points toward fluid-rich locations in the upper transition zone and around the 660-kilometer boundary
Identifying HIV care enrollees at-risk for cannabis use disorder
Increased scientific attention given to cannabis in the United States has particular relevance for its domestic HIV care population, given that evidence exists for both cannabis as a therapeutic agent and cannabis use disorder (CUD) as a barrier to antiretroviral medication adherence. It is critical to identify relative risk for CUD among demographic subgroups of HIV patients, as this will inform detection and intervention efforts. A Center For AIDS Research Network of Integrated Clinical Systems cohort (N = 10,652) of HIV-positive adults linked to care at seven United State sites was examined for this purpose. Based on a patient-report instrument with validated diagnostic threshold for CUD, the prevalence of recent cannabis use and corresponding conditional probabilities for CUD were calculated for the aggregate sample and demographic subgroups. Generalized estimating equations then tested models directly examining patient demographic indices as predictors of CUD, while controlling for history and geography. Conditional probability of CUD among cannabis-using patients was 49%, with the highest conditional probabilities among demographic subgroups of young adults and those with non-specified sexual orientation (67–69%) and the lowest conditional probability among females and those 50+ years of age (42% apiece). Similarly, youthful age and male gender emerged as robust multivariate model predictors of CUD. In the context of increasingly lenient policies for use of cannabis as a therapeutic agent for chronic conditions like HIV/AIDS, current study findings offer needed direction in terms of specifying targeted patient groups in HIV care on whom resources for enhanced surveillance and intervention efforts will be most impactful
Molybdenum oxide on Fe2O3 Core-Shell catalysts: Probing the nature of the structural motifs responsible for methanol oxidation catalysis
A series of MoOx-modified Fe2O3 catalysts have been prepared in an attempt to make core–shell oxidic materials of the type MoOx/Fe2O3. It is conclusively shown that for three monolayers of Mo dosed, the Mo stays in the surface region, even after annealing to high temperature. It is only when the material is annealed above 400 °C that it reacts with the iron oxide. We show by a combination of methods, and especially by XAFS, that at temperatures above 400 °C, most of the Mo converts to Fe2(MoO4)3, with Mo in a tetrahedral structure, whereas below that temperature, nanocrystalline MoO3 is present in the sample; however, the active catalysts have an octahedral MoOx layer at the surface even after calcination to 600 °C. This surface layer appears to be present at all temperatures between 300 and 600 °C, and it is the nanoparticles of MoO3 that are present at the lower temperature that react to form ferric molybdate, which underlies this surface layer. It is the MoOx layer on the Fe2(MoO4)3 underlayer that makes the surface active and selective for formaldehyde synthesis, whereas the iron oxide surface itself is a combustor. The material is both activated and improved in selectivity due to the dominance of the methoxy species on the Mo-doped material, as opposed to the much more stable formate, which is the main intermediate on Fe2O3
Structure and Morphology of Silver Nanoparticles on the (111) Surface of Cerium Oxide
The structure of Ag nanoparticles of different size, supported on the cerium oxide (111) surface, was investigated by X-ray absorption fine structure at the Ag K-edge. The results of the data analysis in the near and extended energy range are interpreted with the help of the results obtained by X-ray photoelectron spectroscopy and scanning tunneling microscopy measurements and allow to obtain a detailed atomic scale description of the model system investigated. The Ag nanoparticles have an average size of a few tens of angstroms, which increases with increasing deposited Ag amount. The nanoparticles show a slight tendency to nucleate at the step edges between different cerium oxide layers and they have a face centered cubic structure with an Ag-Ag interatomic distance contracted by 3-4% with respect to the bulk value. The interatomic distance contraction is mainly ascribed to dimensionality induced effects, while epitaxial effects have a minor role. The presence of Ag-O bonds at the interface between the nanoparticles and the supporting oxide is also detected. The Ag-O interatomic distance decreases with decreasing nanoparticle size
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