X-ray absorption near edge structure in some Mn compounds

The shapes of the manganese K-absorption edge in the compounds MnSO₄H₂O, MnF₂, MnCO₃, MnO and MnS have been studied using a Cauchois type X-ray spectrograph. Three peaks A, B and C observed in the main edges have been assigned the electronic transitions ls → 3d, ls → 4s and ls → 4p respectively. The transitions have been explained on the basis of the Z + 1 analogy. It has also been shown that the 3d → 4s and 4s → 4p orbital separations depend on the partial charge of an ion in its compound.     

X-ray absorption near edge structure (XANES) for KCl

The cluster calculations of K and L_2,3 edge XANES of K and Cl in KCl within the multiple scattering theory formalism using nonlocal HF potentials with abd without consideration of core hole field were performed. For K spectra the influence of the core hole potential is rather weak and the results are similar to those obtained with Xα potentials. For L_2,3 spectra, particularly for that of K⁺, core hole field leads to a radical redistribution of oscillator strength caused mainly by the spatial rearrangement of d like states. Calculated XANES curves show good over-all agreement with the experimental spectra (the L_2,3 absorption of K⁺ in KCl was measured using the synchrotron radiation of the USSR Academy of Sciences storage ring VEPP-2M in Novosibirsk).     

X-ray absorption near edge structure in solid Kr and KrF2

X-ray absorption near edge structure (XANES) spectra of gaseous Kr, solid Kr and solid KrF₂ have been obtained and compared to differentiate between continuum resonances near the edge and bound state transitions. By comparing experimental and ab initio (MSW-Xα) calculated spectra the influence of environment as well as molecular bonding on XANES is demonstrated.     

Study of metglas 2605 CO by extended and near edge X-ray absorption fine structure

Extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) studies of the transition metal sites in Metglas 2605 CO (Fe₆₇Co₁₈B₁₄Si₁) illustrate differences in the two sites. The average transition metal distance, obtained by standard EXAFS analysis, is larger for iron than for cobalt sites in this material. The XANES for Co and Fe are nearly identical except for a shift of the Co fine structure to high energy relative to that of Fe; the sign and magnitude of this shift is commensurate with the EXAFS results. Finally, there was no detected polarization dependence of the EXAFS, indicating that the structural manifestations of the magnetic anisotropy in this material are smaller than the detection limits of these experiments.     

Xanes (X-ray absorption near edge structure) of V in vanadium-iron phosphate glasses

The X-ray Absorption Near-Edge Structure (XANES) of V in vanadium-iron glasses (50P₂O₅ + (50?x)FeO + xV₂O₅) have been measured. The effective charge of V ions in glasses has been determined. At low V₂O₅ concentration (x ～ 5) only V⁴⁺ with 6-fold coordination is present on the contrary a static mixed valence state (V⁴⁺, V⁵⁺) has been found at high concentrations 20?x?50. The results explain the electron hopping conductivity effects at high V₂O₅ concentration (x ～ 50) involving V⁴⁺ ? V⁵⁺ pairs and at low V₂O₅ concentration (x?10) involving V⁴⁺ ? Fe³⁺ pairs.     

Local coordination geometry around Cu and Cu ions in silicate glasses: an X-ray absorption near edge structure investigation

We present an X-ray absorption near edge structure (XANES) study on Cu⁺ and Cu²⁺ ions in silicate glasses at the Cu K-edge, aimed to determine the geometry of the local structure around the metal. This study is based on the comparison between experimental data and theoretical calculations made in the framework of multiple scattering theory. The XANES signals relative to several clusters are simulated on the basis of known crystalline structures involving Cu⁺ and Cu²⁺ ions in silicate matrices. Concerning the Cu²⁺ in glass, the simulations suggest the presence of a square coordination of oxygen atoms around the absorber, with a possible presence of metal ions in the second shell. As for the Cu⁺ ions, the metal clustering is excluded and a linear O-Cu-O coordination is evidenced. Received 30 April 1999     

Analysis of the X-ray absorption fine structure near the TiL 2, 3 edge in free titanium nanoclusters

A theoretical analysis is made of the experimental TiL _{2, 3} X-ray absorption near edge structure (XANES) spectra of free titanium nanoclusters containing 15–55 or 100–120 atoms. Good agreement between experimental and simulated data is obtained using the time-dependent local density approximation.     

X-ray absorption near edge structures (XANES) in simple and complex Mn compounds

The X-ray Absorption Near Edge Structures (XANES) of Mn compounds at the Mn K-edge have been measured with high resolution at the Frascati Synchrotron Radiation Facility “PULS”. Molecular effects, such as “shape resonances”, have been identified in molecular complexes. Experimental evidence of solid state (or long-range order) effects have been found in spectra of simple oxides.The application of XANES for determining the local structure and chemical bonding of Mn ion in unknown compounds is discussed.     

Atomic chemisorption on simple metals: Chemical trends and core-hole relaxation effects

We have obtained essentially exact numerical solutions for a simple model of atomic chemisorption on simple metals. The approximations constituting the model are the semi-infinite jellium simulation of the metal substrate and the self-consistent local density theory of exchange and correlation. The solutions provide a detailed picture of the electronic charge making up the chemisorption bond. The variation of this picture with the valence of the adatom exhibits in a direct and microscopic way the roles of electronegativity, charge transfer, and covalency. Predicted bond energies, bond lengths, and dipole moments are consistent with measurements and independent theoretical considerations.     

Theoretical study of electronic structure, chemical bonding, and X-ray absorption near edge spectroscopy in niobium and niobium monoxide

In this work, we calculate band structures, the density of state and chemical bonding of the metallic niobium (Nb) and its mono-oxide (NbO) crystals in their solid states using the Density Functional Theory and X-ray Absorption Near Edge Spectroscopy. The electronic properties of Nb and NbO are investigated using the Finite Difference Method. These theoretical results are found in good agreement with the most recent experimental data. Our calculations reveal that the NbO crystal behaves like a superconductor.     

X-ray absorption near edge structure and crystallographic studies of the mixed valence oxide SrRu0.8Ni0.2O3

Neutron diffraction methods are used to refine the structure of SrRu(0.8)Ni(0.2)O(3) at room temperature and 4 K. X-ray absorption measurements at the Ru L-edge demonstrate that partial oxidation of the Ru(4+) to Ru(5+) occurs upon introducing Ni into the SrRuO(3) structure to form SrRu(0.8)Ni(0.2)O(3). Whilst the diffraction measurements show that SrRu(0.8)Ni(0.2)O(3) is isostructural with SrRuO(3), the Ni doped compound exhibits an unusual first order orthorhombic-cubic phase transition near 670 K as revealed by x-ray diffraction. The Curie temperature in SrRu(0.8)Ni(0.2)O(3) is lower than that found in SrRuO(3) as a consequence of local distortions reducing the p-d hybridization.     

X-ray absorption near the edge structure and x-ray photoelectron spectroscopy studies on pyrite prepared by thermally sulfurizing iron films

This paper reports how pyrite films were prepared by thermal sulfurization of magnetron sputtered iron films and characterized by x-ray absorption near edge structure spectra and x-ray photoelectron spectroscopy on a 4B9B beam line at the Beijing Synchrotron Radiation Facility. The band gap of the pyrite agrees well with the optical band gap obtained by a spectrophotometer. The octahedral symmetry of pyrite leads to the splitting of the d orbit into t_{\rm 2g} and e_{\rm g} levels. The high spin and low spin states were analysed through the difference of electron exchange interaction and the orbital crystal field. Only when the crystal field splitting is higher than 1.5 eV, the two weak peaks above the white lines can appear, and this was approved by experiments in the present work.     

X-ray microanalysis near an absorption edge using synchrotron radiation: How to obtain quantitative results

X-ray absorption microanalysis by contact microscopy with synchrotron radiation potentially offers the advantages of high resolution and large fields. However, difficulties appear when quantitative results are required, due in particular to the image detectors that are used. The degree of confidence in quantitative results is examined for photographic detectors. Computer processing is performed taking into account several factors such as the recording process, emulsion response, alignment of image pairs for subtraction, presence of harmonics in the synchrotron beam. As an example we show the analysis of nickel in 20 μm thick polymetallic nodule section on an area of 5.1 × 5.1 mm².     

Evaluation of hydrogen chemisorption in nanostructured carbon films by near edge X-ray absorption spectroscopy

We have developed a method for the quantitative evaluation of the chemisorbed fraction of hydrogen in nanostructured carbon films using Near Edge X-ray Absorption Spectroscopy (NEXAFS). In the carbon K-edge spectrum the peak related to carbon bonded to hydrogen is assumed to be correlated with the amount of hydrogen bonded to carbon. This assumption is supported by a comparative analysis of gas-phase hydrocarbons obtained via Electron Energy Loss Spectroscopy (EELS). We applied the method to nanostructured carbon (ns-C) films synthesized by supersonic cluster beam deposition. The evaluated quantity of chemisorbed hydrogen in different samples exposed to molecular hydrogen (pressure of 0.12 MPa, for 3 hours at room temperature) is ∼1.5 wt.%.     

Influence of the geometric structure on the V L3 near edge X-ray absorption fine structure from vanadium phosphorus oxide catalysts

We present the V L₃ near edge X-ray absorption fine structure (NEXAFS) of a vanadium phosphorus oxide (VPO) catalyst. The spectrum is related to the V3d–O2p hybridised unoccupied states. The overall peak position at the V L₃-absorption edge is determined by the formal oxidation state of the absorbing vanadium atom. Details of the absorption fine structure are influenced by the geometric structure of the compound. Empirically we found a linear relationship between the energy position of several absorption resonances and the V–O bond length of the participating atoms. This allows identification of the contribution of specific V–O bonds to the near edge X-ray absorption fine structure. The bond length/resonance position relationship will be discussed under consideration of relations between geometric structure and NEXAFS features observed in X-ray absorption experiments and theory.     

Ab initio theory of dynamical core-hole screening in graphite from x-ray absorption spectra

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.     

Lead speciation of PM2.5 collected from Greater Cairo,Egypt and Zarqa,Jordan: An energy dispersive X-ray fluorescence and X-ray absorption near edge structure study

Fine aerosol particles with an aerodynamic diameter equal or less than 2.5 μm (PM_2.5) have been collected from two sites (residential and industrial) in Greater Cairo, Egypt and one site in Zarqa, Jordan. Based on the elemental quantitative analysis of PM_2.5 using energy dispersive X-ray fluorescence with Mo secondary target, Pb concentrations increased remarkably during winter season regardless of the sampling location. Moreover, it reached the maximum concentration at the industrial location of Greater Cairo, Egypt, and it equals 415 ± 485 ng/m³. The remarkable high standard deviation is due to the significant variation of Pb concentration from time to time during that winter season. Depending on the energy dispersive X-ray fluorescence results, specific PM_2.5 samples that have the highest concentration of Pb (two samples/location) have been selected for the X-ray absorption near edge structure measurements to estimate the oxidation state of Pb species. The X-ray absorption near edge structure measurements including 13 Pb references have been carried out at Pb-L₃ absorption edge (13.039 keV) using fluorescence mode. It was shown that PM_2.5 contains divalent and tetravalent lead in both industrial site in Greater Cairo, Egypt and urban site of Zarqa, Jordan although that of a residential area of Greater Cairo-Egypt is almost divalent lead.     

Evidence of SiO at the Si-oxide interface by surface soft X-ray absorption near edge spectroscopy

Using synchrotron radiation a new surface sensitive spectroscopy has been applied to determine the local structure of the first surface oxide layer formed on the Si(111) surface. The Surface Soft X-ray Absorption (SSXA) spectra have been measured. From the analysis of the X-ray Absorption Near Edge Structures (XANES) we have extracted structural information. We have first determined that bulk amorphous SiO has a characteristic microsopic structure, which cannot be described by the random alloy or microcrystalline (Si + SiO₂) mixture models. The oxide layer formed on the Si(111) surface by ground-state molecular excitation in ultra high vacuum at temperatures (～700°C) approaching the oxide dissociation point has this unique SiO local structure. Such SiO layer not formed at room temperature is expected to be present in the SiSiO₂ interface grown at high temperature. An electronic transition to empty states at the SiSiO₂ interface has been observed.     

Smoothing of K edge X-ray fine structure in alloys of transition metals with aluminium

Measurements of the transition metal K-edge fine structure have been made for a number of fcc and bcc random solid solution alloys containing aluminum. In each case, structures corresponding to unoccupied p states lose contrast as the aluminum content increases. The spectra are compared with theoretical band structures calculated by us using the average-t-matrix method.     

C 1s near edge X-ray absorption fine structure (NEXAFS) of substituted benzoic acids—A theoretical and experimental study

Ab initio calculations are performed to explain the discrete transitions in experimental C 1s-NEXAFS (near edge X-ray absorption fine structure) spectra of various benzoic acid derivates. Transition energies and oscillator strengths of the contributing C 1s–π^* excitations are computed using the ADC(2) (second-order algebraic-diagrammatic construction) method. This method is demonstrated to be well suited for the finite electronic systems represented by these simple organic acids. There is good agreement between experiment and theory reproducing all the relevant spectral features. Some transitions can only be assigned based on a theoretical foundation. Remaining discrepancies between experimental and computed spectra are discussed.