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The treatment of electronic correlations in open-shell systems is among the most challenging problems of condensed matter theory. Current approximations are only partly successful. Ligand-field multiplet theory has been widely successful in describing intra-atomic correlation effects in x-ray spectra, but typically ignores itinerant states. The cumulant expansion for the one-electron Green's function has been successful in describing shake-up effects but ignores atomic multiplets. More complete methods, such as dynamic mean-field theory can be computationally demanding. Here, we show that separating the dynamic Coulomb interactions into local and longer-range parts with ab initio parameters yields a combined multiplet-plus-cumulant approach that accounts for both local atomic multiplets and satellite excitations. The approach is illustrated in transition metal oxides and explains the multiplet peaks, charge-transfer satellites, and distributed background features observed in XPS experiment.

Many-body excitations in X-ray photoemission spectra have been difficult to simulate from first principles. We have recently developed a cumulant-based one-electron Green's function method using the real-time coupled-cluster-singles equation-of-motion approach (RT-EOM-CCS) that provides a general framework for treating these problems. Here we extend this approach to include double excitations in the ground-state energy and in the coupled cluster amplitudes, which have been implemented using subroutines generated by the Tensor Contraction Engine (TCE). As in the case of the singles approximation, RT-EOM-CCSD yields a nonperturbative cumulant form of the Green's function in terms of the time-dependent cluster amplitudes, adding nonlinear corrections to the traditional cumulant forms. The extended approach is applied to the core-hole spectral function for small molecular systems. We find that, when core-optimized basis sets are used, the doubles contributions reduce the mean absolute errors in the core binding energies of the 10 e systems from 0.8 to 0.3 eV. They also significantly improve the quasiparticle-satellite gap by reducing its overestimation from about 3-5 to about 0-1 eV in CH 4 , NH 3 , and H 2 O, and also improving the overall shape of the satellite features. Finally, we demonstrate the application of the new implementation to the larger, classical XPS ESCA series of molecules and show that the singles approximation can be paired with a modest basis set to study carbon speciation.

The real-space Green's function code FEFF has been extensively developed and used for calculations of X-ray and related spectra, including X-ray absorption (XAS), X-ray emission (XES), inelastic X-ray scattering, and electron energy-loss spectra. The code is particularly useful for the analysis and interpretation of the XAS fine-structure (EXAFS) and the near-edge structure (XANES) in materials throughout the periodic table. Nevertheless, many applications, such as non-equilibrium systems, and the analysis of ultra-fast pump-probe experiments, require extensions of the code including finite-temperature and auxiliary calculations of structure and vibrational properties. To enable these extensions, we have developed in tandem a new version FEFF10 and new FEFF-based workflows for the Corvus workflow manager, which allow users to easily augment the capabilities of FEFF10 via auxiliary codes. This coupling facilitates simplified input and automated calculations of spectra based on advanced theoretical techniques. The approach is illustrated with examples of high-temperature behavior, vibrational properties, many-body excitations in XAS, super-heavy materials, and fits of calculated spectra to experiment.

Green's function methods provide a robust, general framework within many-body theory for treating electron correlation in both excited states and x-ray spectra. Conventional methods using the Dyson equation or the cumulant expansion are typically based on the GW self-energy approximation. In order to extend this approximation in molecular systems, a non-perturbative real-time coupled-cluster cumulant Green's function approach has been introduced, where the cumulant is obtained as the solution to a system of coupled first order, non-linear differential equations. This approach naturally includes non-linear corrections to conventional cumulant Green's function techniques where the cumulant is linear in the GW self-energy. The method yields the spectral function for the core Green's function, which is directly related to the x-ray photoemission spectra (XPS) of molecular systems. The approach also yields very good results for binding energies and satellite excitations. The x-ray absorption spectrum (XAS) is then calculated using a convolution of the core spectral function and an effective, one-body XAS. Here this approach is extended to include the full coupled-cluster-singles (CCS) core Green's function by including the complete form of the non-linear contributions to the cumulant as well as all single, double, and triple cluster excitations in the CC amplitude equations. This approach naturally builds in orthogonality and shake-up effects analogous to those in the Mahan-Noizeres-de Dominicis edge singularity corrections that enhance the XAS near the edge. The method is illustrated for the XPS and XAS of NH 3 ., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Vila, Kas, Rehr, Kowalski and Peng.)

Interaction effects can change materials properties in intriguing ways, and they have, in general, a huge impact on electronic spectra. In particular, satellites in photoemission spectra are pure many-body effects, and their study is of increasing interest in both experiment and theory. However, the intrinsic spectral function is only a part of a measured spectrum, and it is notoriously difficult to extract this information, even for simple metals. Our joint experimental and theoretical study of the prototypical simple metal aluminum demonstrates how intrinsic satellite spectra can be extracted from measured data using angular resolution in photoemission. A nondispersing satellite is detected and explained by electron-electron interactions and the thermal motion of the atoms. Additional nondispersing intensity comes from the inelastic scattering of the outgoing photoelectron. The ideal intrinsic spectral function, instead, has satellites that disperse both in energy and in shape. Theory and the information extracted from experiment describe these features with very good agreement., Competing Interests: The authors declare no competing interest.

Green's function methods within many-body perturbation theory provide a general framework for treating electronic correlations in excited states and spectra. Here, we develop the cumulant form of the one-electron Green's function using a real-time coupled-cluster equation-of-motion approach, in an extension of our previous study (Rehr J.; et al. J. Chem. Phys. 2020, 152, 174113). The approach yields a nonperturbative expression for the cumulant in terms of the solution to a set of coupled first-order, nonlinear differential equations. The method thereby adds nonlinear corrections to traditional cumulant methods, which are linear in the self-energy. The approach is applied to the core-hole Green's function and is illustrated for a number of small molecular systems. For these systems, we find that the nonlinear contributions yield significant improvements, both for quasiparticle properties such as core-level binding energies and for inelastic losses that correspond to satellites observed in photoemission spectra.

Electron-core hole interactions are critical for proper interpretation of core-level spectroscopies commonly used as analytical tools in materials science. Here we utilize resonant Auger-electron spectroscopy to uniquely identify exciton, shake, and charge-transfer processes that result from the sudden creation of the core hole in both x-ray-absorption and photoemission spectra. These effects are captured for the transition-metal compounds SrTiO 3 and MoS 2 by fully ab initio , combined real-time cumulant, and Bethe-Salpeter equation approaches to account for core hole dynamics and screening. Atomic charges and excited-state electron-density fluctuations reflect materials' solid-state electronic structure, loss of translational symmetry around the core hole, and breakdown of the sudden approximation. They also demonstrate competition between long- and short-range screening in a solid.

First-principles, real-time-cumulant, and Bethe-Salpeter-equation calculations fully capture the detailed satellite structure that occurs in response to the sudden creation of the core hole in both photoemission and x-ray absorption spectra of the transition-metal compounds SrTiO 3 and rutile TiO 2 . Analysis of the excited-state, real-space charge-density fluctuations betrays the physical nature of these many electron excitations that are shown to reflect the materials' solid-state electronic structure and chemical bonding. This first-principles development of the cumulant-based core hole spectral function is generally applicable to other systems and should become a standard tool for all similar spectroscopic analysis going beyond the quasiparticle physics of the photoelectric effect.

We present a combined equation of motion coupled-cluster cumulant Green's function approach for calculating and understanding intrinsic inelastic losses in core level x-ray absorption spectra (XAS) and x-ray photoemission spectra. The method is based on a factorization of the transition amplitude in the time domain, which leads to a convolution of an effective one-body absorption spectrum and the core-hole spectral function. The spectral function characterizes intrinsic losses in terms of shake-up excitations and satellites using a cumulant representation of the core-hole Green's function that simplifies the interpretation. The one-body spectrum also includes orthogonality corrections that enhance the XAS at the edge.

Corvus, a Python-based package designed for managing workflows of physical simulations that utilize multiple scientific software packages, is presented. Corvus can be run as an executable script with an input file and automatically generated or custom workflows, or interactively, in order to build custom workflows with a set of Corvus-specific tools. Several prototypical examples are presented that link density functional, vibrational and X-ray spectroscopy software packages and are of interest to the synchrotron community. These examples highlight the simplification of complex spectroscopy calculations that were previously limited to expert users, and demonstrate the flexibility of the Corvus infrastructure to tackle more general problems in other research areas.

A theory program intended for use with extended X-ray-absorption fine structure (EXAFS) spectroscopy and based on the popular FEFF8 is presented. It provides an application programming interface designed to make it easy to integrate high-quality theory into EXAFS analysis software. This new code is then used to examine the impact of self-consistent scattering potentials on EXAFS data analysis by methodical testing of theoretical fitting standards against a curated suite of measured EXAFS data. For each data set, the results of a fit are compared using a well characterized structural model and theoretical fitting standards computed both with and without self-consistent potentials. It is demonstrated that the use of self-consistent potentials has scant impact on the results of the EXAFS analysis.

We present a finite-temperature extension of the retarded cumulant Green's function for calculations of exited-state, correlation, and thermodynamic properties of electronic systems. The method incorporates a cumulant to leading order in the screened Coulomb interaction W, and improves on the GW approximation of many-body perturbation theory. Results for the homogeneous electron gas are presented for a wide range of densities and temperatures, from cool to warm dense matter regimes, which reveal several hitherto unexpected properties. For example, correlation effects remain strong at high T while the exchange-correlation energy becomes small; also the spectral function broadens and damping increases with temperature, blurring the usual quasiparticle picture. These effects are evident, e.g., in Compton scattering which exhibits many-body corrections that persist at normal densities and intermediate T. The approach also yields exchange-correlation energies and potentials in good agreement with existing methods.

We present calculated valence and C 1s near-edge excitation spectra of solid C 60 and experimental results measured with high-resolution electron energy-loss spectroscopy. The near-edge calculations are carried out using three different methods: solution of the Bethe-Salpeter equation (BSE) as implemented in the OCEAN suite (Obtaining Core Excitations with ab initio methods and the NIST BSE solver), the excited-electron core-hole approach (XCH), and the constrained-occupancy method using the Stockholm-Berlin core-excitation code, StoBe. The three methods give similar results and are in good agreement with experiment, though the BSE results are the most accurate. The BSE formalism is also used to carry out valence level calculations using the NIST Bethe-Salpeter Equation solver (NBSE). Theoretical results include self-energy corrections to the band gap and band widths, lifetime-damping effects, and Debye-Waller effects in the core-excitation case. A comparison of spectral features to those observed experimentally illustrates the sensitivity of certain features to computational details, such as self-energy corrections to the band structure and core-hole screening.

One of the big challenges of theoretical condensed-matter physics is the description, understanding, and prediction of the effects of the Coulomb interaction on materials properties. In electronic spectra, the Coulomb interaction causes a renormalization of energies and change of spectral weight. Most importantly, it can lead to new structures, often called satellites. These can be linked to the coupling of excitations, also termed dynamical effects. State-of-the-art methods in the framework of many-body perturbation theory, in particular, the widely used GW approximation, often fail to describe satellite spectra. Instead, approaches based on a picture of electron-boson coupling such as the cumulant expansion are promising for the description of plasmon satellites. In this work, we give a unified derivation of the GW approximation and the cumulant expansion for the one-body Green's function. Using the example of bulk sodium, we compare the resulting spectral functions both in the valence and in the core region, and we discuss the dispersion of quasi-particles and satellites. We show that self-consistency is crucial to obtain meaningful results, in particular, at large binding energies. Very good agreement with experiment is obtained when the intrinsic spectral function is corrected for extrinsic and interference effects. Finally, we sketch how one can approach the problem in the case of the two-body Green's function, and we discuss the cancellation of various dynamical effects that occur in that case.

We show how the classic approach of Nozières and di Domenicis for treating the edge singularity in x-ray absorption and emission can be generalized to treat the more complex case of the resonant inelastic x-ray scattering (RIXS) process, including effects of the intermediate states involved therein in the presence of the core hole. We solve our lattice model essentially exactly (numerically) to obtain a novel form of edge singularity at the RIXS threshold energy. Our RIXS spectrum naturally includes both the well and poorly screened spectral components and their dispersions and allows its separation into pair and multiple-pair excitations.

We investigate the origin and physical effects of "dynamic structural disorder" (DSD) in supported nano-scale catalysts. DSD refers to the intrinsic fluctuating, inhomogeneous structure of such nano-scale systems. In contrast to bulk materials, nano-scale systems exhibit substantial fluctuations in structure, charge, temperature, and other quantities, as well as large surface effects. The DSD is driven largely by the stochastic librational motion of the center of mass and fluxional bonding at the nanoparticle surface due to thermal coupling with the substrate. Our approach for calculating and understanding DSD is based on a combination of real-time density functional theory/molecular dynamics simulations, transient coupled-oscillator models, and statistical mechanics. This approach treats thermal and dynamic effects over multiple time-scales, and includes bond-stretching and -bending vibrations, and transient tethering to the substrate at longer ps time-scales. Potential effects on the catalytic properties of these clusters are briefly explored. Model calculations of molecule-cluster interactions and molecular dissociation reaction paths are presented in which the reactant molecules are adsorbed on the surface of dynamically sampled clusters. This model suggests that DSD can affect both the prefactors and distribution of energy barriers in reaction rates, and thus can significantly affect catalytic activity at the nano-scale.

X-ray photoemission spectroscopy is used in a great variety of research fields; one observable is the sample's stoichiometry. The stoichiometry can be deduced based on the expectation that the ionization cross sections for innershell orbitals are independent of the molecular composition. Here we used chlorine-substituted ethanes in the gas phase to investigate the apparent carbon stoichiometry. We observe a nonstoichiometric ratio for a wide range of photon energies, the ratio exhibits x-ray-absorption fine structure spectroscopy (EXAFS)-like oscillations and hundreds of eV above the C1s ionization approaches a value far from 1. These effects can be accounted for by considering the scattering of the outgoing photoelectron, which we model by multiple-scattering EXAFS calculations, and by considering the effects of losses due to monopole shakeup and shakeoff and to intramolecular inelastic scattering processes.

Osteoporosis represents a major public health problem and increases patient morbidity through its association with fragility fractures. Among the different treatments proposed, strontium-based drugs have been shown to increase bone mass in postmenopausal osteoporosis patients and to reduce fracture risk. While the localization of Sr(2+) cations in the bone matrix has been extensively studied, little is known regarding the status of Sr(2+) cations in natural biological apatite. In this investigation the local environment of Sr(2+) cations has been investigated through XANES (X-ray absorption near-edge structure) spectroscopy in a set of pathological and physiological apatites. To assess the localization of Sr(2+) cations in these biological apatites, numerical simulations using the ab initio FEFF9 X-ray spectroscopy program have been performed. The complete set of data show that the XANES part of the absorption spectra may be used as a fingerprint to determine the localization of Sr(2+) cations versus the mineral part of calcifications. More precisely, it appears that a relationship exists between some features present in the XANES part and a Sr(2+)/Ca(2+) substitution process in site (I) of crystal apatite. Regarding the data, further experiments are needed to confirm a possible link between the relationship between the preparation mode of the calcification (cellular activity for physiological calcification and precipitation for the pathological one) and the adsorption mode of Sr(2+) cations (simple adsorption or insertion). Is it possible to draw a line between life and chemistry through the localization of Sr in apatite? The question is open for discussion. A better structural description of these physiological and pathological calcifications will help to develop specific therapies targeting the demineralization process in the case of osteoporosis.

We present a hybrid approach for Bethe-Salpeter equation (BSE) calculations of core excitation spectra, including x-ray absorption (XAS), electron energy loss spectra (EELS), and nonresonant inelastic x-ray scattering (NRIXS). The method is based on ab initio wave functions from the plane-wave pseudopotential code ABINIT; atomic core-level states and projector augmented wave (PAW) transition matrix elements; the NIST core-level BSE solver; and a many-pole self-energy model to account for final-state broadening and self-energy shifts. Multiplet effects are also approximately accounted for. The approach is implemented using an interface dubbed OCEAN (Obtaining Core Excitations using ABINIT and NBSE). To demonstrate the utility of the code we present results for the K edges in LiF as probed by XAS and NRIXS, the K edges of KCl as probed by XAS, the Ti L 2,3 edge in SrTiO 3 as probed by XAS, and the Mg L 2,3 edge in MgO as probed by XAS. These results are compared with experiment and with other theoretical approaches.

Conventional Kohn-Sham band-structure methods for calculating deep-core x-ray spectra typically neglect photoelectron self-energy effects, which give rise to an energy-dependent shift and broadening of the spectra. Here an a posteriori procedure is introduced to correct for these effects. The method is based on ab initio calculations of the GW self-energy using a many-pole model and a calculation of the dielectric function in the long wavelength limit using either the FEFF8 real-space Green's function code, or the AI2NBSE interface between the National Institute of Standards and Technology (NIST) Bethe-Salpeter equation solver (NBSE) and the ABINIT pseudopotential code. As an example the method is applied to core level x-ray spectra of LiF and MgAl 2 O 4 calculated using (respectively) OCEAN, an extension of the AI2NBSE code for core level excitations, and the PARATEC pseudopotential code with the core-hole treated using a super-cell. The method satisfactorily explains the discrepancy between experiment and calculations.

New theoretical and experimental investigations of the occupied and unoccupied local electronic densities of states (DOS) are reported for alpha-Li(3)N. Band-structure and density-functional theory calculations confirm the absence of covalent bonding character. However, real-space full-multiple-scattering (RSFMS) calculations of the occupied local DOS find less extreme nominal valences than have previously been proposed. Nonresonant inelastic x-ray scattering, RSFMS calculations, and calculations based on the Bethe-Salpeter equation are used to characterize the unoccupied electronic final states local to both the Li and N sites. There is a good agreement between experiment and theory. Throughout the Li 1s near-edge region, both experiment and theory find strong similarities in the s-and p-type components of the unoccupied local final DOS projected onto an orbital angular momentum basis (l-DOS). An unexpected, significant correspondence exists between the near-edge spectra for the Li 1s and N 1s initial states. We argue that both spectra are sampling essentially the same final DOS due to the combination of long core-hole lifetimes, long photoelectron lifetimes, and the fact that orbital angular momentum is the same for all relevant initial states. Such considerations may be generally applicable for low atomic number compounds.

We present ab initio calculations of frequency-dependent linear and nonlinear optical responses based on real-time time-dependent density functional theory for arbitrary photonic molecules. This approach is based on an extension of an approach previously implemented for a linear response using the electronic structure program SIESTA. Instead of calculating excited quantum states, which can be a bottleneck in frequency-space calculations, the response of large molecular systems to time-varying electric fields is calculated in real time. This method is based on the finite field approach generalized to the dynamic case. To speed the nonlinear calculations, our approach uses Gaussian enveloped quasimonochromatic external fields. We thereby obtain the frequency-dependent second harmonic generation beta(-2omega;omega,omega), the dc nonlinear rectification beta(0;-omega,omega), and the electro-optic effect beta(-omega;omega,0). The method is applied to nanoscale photonic nonlinear optical molecules, including p-nitroaniline and the FTC chromophore, i.e., 2-[3-Cyano-4-(2-{5-[2-(4-diethylamino-phenyl)-vinyl]-thiophen-2-yl}-vinyl)-5,5-dimethyl-5H-furan-2-ylidene]-malononitrile, and yields results in good agreement with experiment.

We discuss the application of the ab initio program FEFF8 to calculations of electron energy-loss spectroscopy (EELS), focusing in particular on core-loss spectra. FEFF8 is based on a self-consistent, real space multiple scattering formalism. We focus on issues relevant to practical simulations, including the construction of well-converged potentials, the treatment of inelastic losses and exchange-correlation potentials and the core-hole. We also discuss how to account for experimental conditions, for example, sample orientation and finite temperature effects such as Debye-Waller factors. Finally we discuss the interpretation of the spectra in terms of electronic structure and local projected density of states (LDOS). As an explicit example, we illustrate various features of the code by application to the ionization edges of GaN.

Modern analysis of X-ray absorption fine structure (XAFS) is usually based on a traditional least-squares fitting procedure. Here an alternative Bayes-Turchin method is discussed which has a number of advantages. In particular the method takes advantage of a priori estimates of the model parameters and their uncertainties and avoids the restriction on the size of the model parameter space or the necessity for Fourier filtering. Thus the method permits the analysis of the full X-ray absorption spectra (XAS), including both XAFS and X-ray absorption near-edge spectra (XANES). The approach leads to a set of linear equations for the model parameters, which are regularized using the 'Turchin condition'. Also, the method naturally partitions parameter space into relevant and irrelevant subspaces which are spanned by the experimental data or the a priori information, respectively. Finally we discuss how the method can be applied to the analysis of XANES spectra based on fits of experimental data to full multiple-scattering calculations. An illustrative application yields reasonable results even for very short data ranges.

Extended x-ray absorption fine structure (EXAFS), using a laser-imploded target as a source, can yield the properties of laser-shocked metals on a nanosecond time scale. EXAFS measurements of vanadium shocked to approximately 0.4 Mbar yield the compression and temperature in good agreement with hydrodynamic simulations and shock-speed measurements. In laser-shocked titanium at the same pressure, the EXAPS modulation damping is much higher than is warranted by the predicted temperature increase. This is shown to be due to the alpha-Ti to omega-Ti crystal phase transformation, known to occur below approximately 0.1 Mbar for slower shock waves.

Time-resolved x-ray spectroscopy at the Si L edges is used to probe the electronic structure of an amorphous Si foil as it melts following absorption of an ultrafast laser pulse. Picosecond temporal resolution allows observation of the transient liquid phase before vaporization and before the liquid breaks up into droplets. The melting causes changes in the spectrum that match predictions of molecular dynamics and ab initio x-ray absorption codes.

A major goal of theoretical simulations of X-ray absorption fine structure (XAFS) is to provide calculations for the interpretation and analysis of experimental data in terms of geometrical and electronic information. The extended region or EXAFS (50-2000 eV above an absorption edge) contains geometric information about the pair distribution function, i.e. distances to the nearest neighbors and their orientation. The theory of EXAFS is now well understood and has been recently reviewed [Rehr & Albers (2000). Rev. Mod. Phys. 72, 621-654]. The near-edge region (0-50 eV above the edge) or X-ray absorption near-edge structure (XANES) probes the states just above the Fermi level, and contains important electronic information, e.g. the electronic density of states (DOS). This data can be used to obtain the number of electrons or holes in the electronic configuration and spin and orbital moments on a particular atom via sum rules. XANES calculations with our ab initio code FEFF8 [Ankudinov et al. (1998). Phys. Rev. B, 58, 7565-7576] usually give semi-quantitative agreement with experiment, and permits the interpretation of XANES in terms of DOS. However, fully quantitative calculations remain a challenge. Several effects still need to be considered to treat the XANES region. These include non-spherical parts of the scattering potential and many-body effects such as multi-electron excitations, core-hole effects and local field effects (screening of the X-ray field).

There has been dramatic progress over the past decade both in theory and in ab initio calculations of X-ray absorption fine structure. Significant progress has also been made in understanding X-ray absorption near-edge structure (XANES). This contribution briefly reviews the developments in this field leading up to the current state. One of the key advances has been the development of several ab initio codes such as FEFF, which permit an interpretation of the spectra in terms of geometrical and electronic properties of a material. Despite this progress, XANES calculations have remained challenging both to compute and to interpret. However, recent advances based on parallel Lanczos multiple-scattering algorithms have led to speed increases of typically two orders of magnitude, making fast calculations practicable. Improvements in the interpretation of near-edge structure have also been made. It is suggested that these developments can be advantageous in structural biology, e.g. in post-genomics studies of metalloproteins.

The interpretation of X-ray absorption spectra in terms of electronic structure has long been of interest. Hole counts derived from such spectra are often interpreted in terms of free-atom occupation numbers or Mülliken counts. It is shown here, however, that renormalized-atom (RA) and cellular counts are better choices to characterize the configuration of occupied electron states in molecules and condensed matter. A projection-operator approach is introduced to subtract delocalized states and to determine quantitatively such hole counts from X-ray absorption spectra. The described approach is based on multiple-scattering theory (MST) and on atomic calculations of a smooth transformation relating the X-ray absorption spectra to local projected densities of states (LDOS). Theoretical tests for the s and d electrons in transition metals show that the approach works well.

The sensitivity of Pt L-edge XANES to local geometric and electronic structure in various Pt(n) clusters is investigated using the ab initio self-consistent FEFF8 code. Calculations based on FEFF8 are found to be in good agreement with experiment. For pure Pt clusters the XANES can distinguish between 2- and 3-dimensional clusters. Self-consistency is important in determining the variation of XANES with cluster size. The effect of a support is also studied. In Pt-Cl(x) clusters the presence of a Cl-Pt bond leads to a "hybridization peak," i.e., a peak in the Cl d-density of states (d-DOS) mixed with Pt d-states. For Pt-H clusters hydrogen addition is well correlated with the growth of a broad shoulder on the white line. This change is attributed largely to AXAFS, i.e., to a corresponding change in the atomic background absorption.

The FEFF8 was used to calculate x-ray absorption spectra (XANES) and the local partial electron density of states (LDOS) for several sulfides: InPS4 (twice defective chalcopyrite), CdIn2S4 (normal spinel) and Tl3AsS3 (space group R3m). The calculated XANES are compared with experimental spectra. The self-consistent MT-potentials found for clusters of about 35 atoms were used to calculate XANES and LDOS for clusters of 87 atoms in the approach of full multiple scattering. In all cases the agreement of the simulated XANES and experimental ones is quite good. The theoretical LDOS agree well with the experimental x-ray emission K- and L2,3-spectra.

There has been dramatic progress over the past decade both in theory and in ab initio calculations of X-ray absorption fine structure (XAFS). Rapid progress is now being made in understanding X-ray absorption near-edge structure (XANES). This presentation reviews the developments in this field by many groups leading up to the current state of the art. These developments have led to several ab initio codes, such as FEFF, which yield results comparable to experimental results for XAFS, and permit an interpretation of the spectra in terms of geometrical and electronic properties of a material. The review begins with a summary of the key theoretical developments that are essential for achieving a quantitative agreement with experiment for XAFS. The same high-order multiple-scattering (MS) theory of XAFS can also give an approximate treatment of XANES, but this approach can fail close to an edge, where full MS calculations are often necessary. However, a fully quantitative treatment of XANES remains challenging, largely as a result of a number of many-body effects, e.g. the approximate treatment of the core-hole, multiplet effects, the photoelectron self energy and inelastic losses. Finally, natural extensions of the theory to other spectroscopies, such as anomalous X-ray scattering, DAFS (diffraction anomalous fine structure) and XMCD (X-ray magnetic circular dichroism) are briefly discussed. These developments are illustrated with a number of applications.

Hydrogen adsorption on Pt(6)H(n) clusters leads to striking changes in the Pt L(2,3) x-ray absorption spectra. These effects are interpreted using a self-consistent real space Green's function approach. Calculations show that they are due largely to changes in the atomic background contribution to x-ray absorption (i.e., atomic x-ray absorption fine structure) and to reduced Pt-Pt scattering at the edge, while Pt-H multiple scattering is relatively weak. The origin of both effects is traced to the change in the local Pt potential due to Pt-H bonding.

A quantitative analysis of the XAS spectra of the tetracyanonickelate complex [Ni(CN)4]2- has been carried out. The simultaneous study of the EXAFS and XANES regions yielded complementary information regarding the geometric and electronic structures of the complex. XANES spectra were modeled by applying recently developed self-consistent, full multiple-scattering algorithms in the FEFF8 code (version 8 x 34). XANES spectra for clusters of different sizes (from 9 to 125 atoms) were computed and compared with experimental spectra. This region of the spectra was proportional to a broadened Ni p-density of states diagram above the Fermi level. Although the main features of the XANES spectra were reasonably reproduced by computations, the weak dependence of the theoretical spectra on cluster size contrasts with the close similarity between the experimental spectra of the solid and solution systems. Because of the special geometry of the complex, calculations with polarized light parallel and perpendicular to the molecular plane were carried out, yielding a reasonable reproduction of the experimental data from another report for cluster sizes equal to or higher than 45 atoms. The highly symmetric square planar structure of the complex was found to be responsible for the unusual amplitude of the multiple-scattering (MS) contributions to the EXAFS spectra. Spectra in this region were fitted using the FEFFIT EXAFS analysis program, taking into account only the MS paths that simultaneously have both a high amplitude, as calculated with the ab initio code FEFF, and a small Debye-Waller factor, as estimated by the independent-vibration approximation model. Fitting results yielded very similar structures for the Ni2+ complex in the solid state and in solution, though the larger Debye-Waller factors found for the solid suggest higher static disorder in this state.