Theory of Ca L2,3-edge XAS using a novel multichannel multiple-scattering method.

A new method for calculating X-ray absorption spectroscopy (XAS) at the L2,3 edges of Ca and transition metals is presented. It is based on the multichannel multiple-scattering theory by Natoli et al. [Phys. Rev. B, (1990), 42, 1944-1968] combined with the eigen-channel R-matrix formalism. Atomic multiplet-like effects, owing to the Coulomb interaction of photoelectrons and the 2p hole, are taken into account through a configuration interaction ansatz for the final-state wavefunction. The various multiplet states lead to a set of channels for the photoelectron wavefunction, which is calculated in multiple-scattering theory. The method is applied to Ca, an important element for biological applications of XAS. An L3:L2 branching ratio of 3:4 is found, in good agreement with experiment but in contrast to the statistical value 2:1 obtained in all one-electron approaches. By using a linear mixture between statically screened (approximately 90%) and unscreened (approximately 10%) core-hole potential, the line shape, too, agrees well with the experimental one

Full-Potential Multiple Scattering Theory with Space-Filling Cells for bound and continuum states

We present a rigorous derivation of a real space Full-Potential Multiple-Scattering-Theory (FP-MST), valid both for continuum and bound states, that is free from the drawbacks that up to now have impaired its development, in particular the need to use cell shape functions and rectangular matrices. In this connection we give a new scheme to generate local basis functions for the truncated potential cells that is simple, fast, efficient, valid for any shape of the cell and reduces to the minimum the number of spherical harmonics in the expansion of the scattering wave function. The method also avoids the need for saturating 'internal sums' due to the re-expansion of the spherical Hankel functions around another point in space (usually another cell center). Thus this approach, provides a straightforward extension of MST in the Muffin-Tin (MT) approximation, with only one truncation parameter given by the classical relation $l_{\rm max} = kR_b$, where $k$ is the excited (or ground state) electron wave vector and $R_b$ the radius of the bounding sphere of the scattering cell. It is shown that the theory converges absolutely in the $l_{\rm max} \to \infty$ limit. As a consequence it provides a firm ground to the use of FP-MST as a viable method for electronic structure calculations and makes possible the computation of x-ray spectroscopies, notably photo-electron diffraction, absorption and anomalous scattering among others, with the ease and versatility of the corresponding MT theory. Some numerical applications of the theory are presented, both for continuum and bound states.Comment: 48 pages, 6 figures, 2 table

X-ray absorption spectra of graphene and graphene oxide by full-potential multiple scattering calculations with self-consistent charge density

International audienceThe x-ray absorption near-edge structure of graphene, graphene oxide, and diamond is studied by the recently developed real-space full potential multiple scattering (FPMS) theory with space-filling cells. It is shown how accurate potentials for FPMS can be generated from self-consistent charge densities obtained with other schemes, especially the projector augmented wave method. Compared to standard multiple scattering calculations in the muffin-tin approximation, FPMS gives much better agreement with experiment. The effects of various structural modifications on the graphene spectra are well reproduced. (1) Stacking of graphene layers increases the peak intensity in the higher energy region. (2) The spectrum of the C atom located at the edge of a graphene sheet shows a prominent pre-edge structure. (3) Adsorption of oxygen gives rise to the so-called interlayer-state peak. Moreover, O K-edge spectra of graphene oxide are calculated for three types of bonding, C-OH, C-O-C, and C-O, and the proportions of these bondings at 800∘C are deduced by fitting them to the experimental spectru

The MXAN procedure: a new method for analysing the XANES spectra of metalloproteins to obtain structural quantitative information.

The first quantitative analyses are reported of the FeK-edge polarized X-ray absorption near-edge structure (XANES) of a single crystal of the iron protein carbonmonoxy-myoglobin (MbCO) and of its cryogenic photoproduct Mb*CO. The CO—Fe–heme local structure has been determined using a novel fitting procedure, namedMXAN, which is able to fit the XANES part (from the edge to about 200 eV) of experimental X-ray absorption data. This method is based on the comparison between the experimental spectrum and several theoretical spectra that are generated by changing the relevant geometrical parameters of the site around the absorbing atom. The theoretical spectra are derived in the framework of the full multiple-scattering approach. TheMXANprocedure is able to recover information about the symmetry and atomic distances, and the solution is found to be independent of the starting conditions. The extracted local structure of Mb*CO includes an Fe—CO distance of 3.08 (7) Å, with a tilting angle between the heme normal and the Fe—C vector of 37 (7)° and a bending angle between the Fe—C vector and the C—O bond of 31 (5)

Study of the Electronic Structure in Oxides Using Absorption and Resonant X-Ray Scattering

Resonant X-ray scattering (RXS) is a spectroscopy where both the power of site selective diffraction and the power of local absorption spectroscopy regarding atomic species are combined. By virtue of the dependence on the core level state energy and the three dimensional electronic structure of the intermediate state, this technique is specially suited to study charge, orbital or spin orderings and associated crystal distortions. In the case of charge ordering, we exploit the fact that atoms with closely related site symmetries but with small charge differences exhibit resonances at slightly different energies. The sensitivity of this effect allows for quantitative estimations of the charge disproportion. Opposite to fluorescence or absorption measurements, the power of diffraction relies on the capability of detecting differences that are smaller than the inverse lifetime of the core hole level. To account for the uncertainty of the crystallographic structure and the fact that the charge ordering must be disentangled from the associated atomic displacements, a complete methodology is proposed and applied to the low temperature phase of magnetite. Relative sensitivity on spin, toroidal and orbital ordering is also shown and compared in different transition metal oxide compounds, like V2O3 and GaFeO3

Angular correlation between photoelectrons and Auger electrons within scattering theory

International audienceIn this paper we present a single-particle scattering approach for the angular correlation between a photoelectron and the subsequent Auger electron from atomic targets. This method is proposed as an alternative approach with respect to the usual density matrix formalism, since it is more convenient for extension to the solid state case. Such an extension is required by the great progress made in the field of coincidence spectroscopy in condensed matter systems. We derived a tensor expression for the cross section and an equivalent expression in terms of convenient angular functions has been treated for the case of linearly polarized light. Numerical calculations are performed for the L3M2,3M2,3 transition in argon, in the single configuration Dirac-Fock scheme. Results are compared with experimental data for different final angular momentum states of the doubly charged ion and for different kinematical conditions

Quadrupolar XMCD at the Fe K -edge in Fe phthalocyanine film on Au: Insight into the magnetic ground state

Under the terms of the Creative Commons Attribution license.-- et al.The observation of an anomalous quadrupolar signal in x-ray magnetic circular dichroism (XMCD) at the Fe K-edge of iron phthalocyanine (FePc) films is reported. All ground states previously suggested for FePc are incompatible with the experimental data. Based on ab initio molecular orbital multiplet calculations of the isolated FePc molecule, we propose a model for the magnetic ground state of the FePc film that explains the XMCD data and reproduces the observed values of the orbital moments in the perpendicular and planar directions.The financial support of the Spanish financial agency MINECO MAT2011-23791 and MAT2014-53921-R, Aragonese DGA-IMANA E34 (co-funded by Fondo Social Europeo), and European Union FEDER funds is acknowledged. The research at UCSD was supported by the Office of Basic Energy Science, US Department of Energy, BES-DMS, funded by the Department of Energy Office of Basic Energy Science, DMR, under Grant No. DE FG03 87ER-45332.Peer Reviewe

PROGRESS IN SCF-SW-XALPHA AB INITIO XANES CALCULATIONS FOR CHROMIUM HEXACARBONYL BASED ON GENERAL NON-MUFFIN-TIN POTENTIALS

We describe progress towards the performance of SCF-SW-Xalpha calculations of photo-absorption cross-sections based on the theory of Natoli et al. for non-muffin-tin potentials. A crucial requirement is the accurate modelling of the electron-molecule potential using spherical harmonic expansions. We describe how this has been achieved and what difficulties are encountered. In the particular case of our model compound, chromium hexacarbonyl, we show what muffin-tin calculations produce and show that we may expect significant improvements from a non-muffin-tin calculation. Finally, we comment on the programming problems involved in these computations

Molecular tilting and columnar stacking of Fe phthalocyanine thin films on Au(111)

Scanning tunneling microscopy and x-ray absorption spectroscopic results at the Fe K edge of Fe phthalocyanine (FePc) thin films grown on Au substrates, together with theoretical calculations, allow us to refine the structure of the film. In particular, we show that the columnar stacking of the FePc molecules is different from that found in bulk ¿ and ß phases. Moreover, the molecules do not lay parallel to the surface of the substrate. These structural findings are relevant to understand magnetism of FePc films.The financial support of the Spanish financial agency MINECO MAT2011-2379 and MAT2014-53921-R, Aragonese DGA-IMANA E34 (co-funded by European Social Fund), as well as European Union FEDER funds is acknowledged. The sample preparation and initial structural characterization were supported by the Office of Basic Energy Science, U.S. Department of Energy, BES-DMS funded by the Department of Energy’s Office of Basic Energy Science, DMR under Grant No. DE FG03 87ER-45332 and NSF DMR 0847552.Peer Reviewe

Structural Studies Using X-ray Absorption Spectroscopy of Intermediates Formed by Reaction of Ozone with Halogeno(dodecaphenylporphyrinato)manganese(III) Derivatives

Difference EXAFS and XANES studies at the Mn K-edge are reported which shed light on the mechanisms of activation of the title compounds by ozone. The reaction of ozone with either the chloro- or b..