Joshua J. Kas

Parameter-free calculations of X-ray spectra with FEFF9

We briefly review our implementation of the real-space Greens function (RSGF) approach for calculations of X-ray spectra, focusing on recently developed parameter free models for dominant many-body effects. Although the RSGF approach has been widely used both for near edge (XANES) and extended (EXAFS) ranges, previous implementations relied on semi-phenomenological methods, e.g., the plasmon-pole model for the self-energy, the final-state rule for screened core hole effects, and the correlated Debye model for vibrational damping. Here we describe how these approximations can be replaced by efficient ab initio models including a many-pole model of the self-energy, inelastic losses and multiple-electron excitations; a linear response approach for the core hole; and a Lanczos approach for Debye-Waller effects. We also discuss the implementation of these models and software improvements within the FEFF9 code, together with a number of examples.

Bethe-Salpeter equation calculations of core excitation spectra

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 L2,3 edge in SrTiO3 as probed by XAS, and the Mg L2,3 edge in MgO as probed by XAS. These results are compared with experiment and with other theoretical approaches.

Valence Electron Photoemission Spectrum of Semiconductors: Ab Initio Description of Multiple Satellites

The experimental valence band photoemission spectrum of semiconductors exhibits multiple satellites that cannot be described by the GW approximation for the self-energy in the framework of many-body perturbation theory. Taking silicon as a prototypical example, we compare experimental high energy photoemission spectra with GW calculations and analyze the origin of the GW failure. We then propose an approximation to the functional differential equation that determines the exact one-body Greens function, whose solution has an exponential form. This yields a calculated spectrum, including cross sections, secondary electrons, and an estimate for extrinsic and interference effects, in excellent agreement with experiment. Our result can be recast as a dynamical vertex correction beyond GW, giving hints for further developments.

Many-pole model of inelastic losses in x-ray absorption spectra

Inelastic losses are crucial to a quantitative analysis of x-ray absorption spectra. However, current treatments are semi-phenomenological in nature. Here a first-principles, many-pole generalization of the plasmon-pole model is developed for improved calculations of inelastic losses. The method is based on the GW approximation for the self-energy and real space multiple scattering calculations of the dielectric function for a given system. The model retains the efficiency of the plasmonpole model and is applicable both to periodic and aperiodic materials over a wide energy range. The same many-pole model is applied to extended GW calculations of the quasiparticle spectral function. This yields estimates of multi-electron excitation effects, e.g., the many-body amplitude factor S 2 0 due to intrinsic losses. Illustrative calculations are compared with other GW calculations of the self-energy, the inelastic mean free path, and experimental x-ray absorption spectra.

Theoretical optical and x-ray spectra of liquid and solid H2O

Theoretical optical and x-ray spectra of model structures of water and ice are calculated using a many-body perturbation theory, Bethe-Salpeter equation (BSE) approach implemented in the valence- and core-excitation codes ai2nbse and ocean. These codes use ab initio density functional theory wave functions from a plane-wave, pseudopotential code, quasiparticle self-energy corrections, and a BSE treatment of particle-hole interactions. This approach improves upon independent-particle methods through the inclusion of a complex, energy-dependent self-energy and screened particle-hole interactions to account for inelastic losses and excitonic effects. These many-body effects are found to be crucial for quantitative calculations of ice and water spectra.

Ab initio calculations of electron inelastic mean free paths and stopping powers

A method is presented for first-principles calculations of inelastic mean free paths and stopping powers in condensed matter over a broad energy range. The method is based on {\it ab initio} calculations of the dielectric function in the long wavelength limit using a real-space Greens function formalism, together with extensions to finite momentum transfer. From these results we obtain the loss function and related quantities such as optical-oscillator strengths and mean excitation energies. From a many-pole representation of the dielectric function we then obtain the electron self-energy and inelastic mean free paths (IMFP). Finally using our calculated dielectric function and the optical-data model of Fernandez-Varea {\it et al}., we obtain collision stopping powers (CSP) and penetration ranges. The results are consistent with semi-empirical approaches and with experiment.

X-ray-Raman-scattering-based EXAFS beyond the dipole limit.

X-ray Raman scattering (XRS) provides a bulk-sensitive method of measuring the extended X-ray absorption fine structure (EXAFS) of soft X-ray absorption edges. Accurate measurements and data analysis procedures for the determination of XRS-EXAFS of polycrystalline diamond are described. The contributions of various angular-momentum components beyond the dipole limit to the atomic background and the EXAFS oscillations are incorporated using self-consistent real-space multiple-scattering calculations. The properly extracted XRS-EXAFS oscillations are in good agreement with calculations and earlier soft X-ray EXAFS results. It is shown, however, that under certain conditions multiple-scattering contributions to XRS-EXAFS deviate from those in standard EXAFS, leading to noticeable changes in the real-space signal at higher momentum transfers owing to non-dipole contributions. These results pave the way for the accurate application of XRS-EXAFS to previously inaccessible light-element systems.

Deconvolving instrumental and intrinsic broadening in core-shell x-ray spectroscopies

Intrinsic and experimental mechanisms frequently lead to broadening of spectral features in core-shell spectroscopies. For example, intrinsic broadening occurs in x-ray absorption spectroscopy XAS measurements of heavy elements where the core-hole lifetime is very short. On the other hand, nonresonant x-ray Raman scattering XRS and other energy loss measurements are more limited by instrumental resolution. Here, we demonstrate that the Richardson-Lucy RL iterative algorithm provides a robust method for deconvolving instrumental and intrinsic resolutions from typical XAS and XRS data. For the K-edge XAS of Ag, we find nearly complete removal of 9.3 eV full width at half maximum broadening from the combined effects of the short core-hole lifetime and instrumental resolution. We are also able to remove nearly all instrumental broadening in an XRS measurement of diamond, with the resulting improved spectrum comparing favorably with prior soft x-ray XAS measurements. We present a practical methodology for implementing the RL algorithm in these problems, emphasizing the importance of testing for stability of the deconvolution process against noise amplification, perturbations in the initial spectra, and uncertainties in the core-hole lifetime.

Dynamical effects in electron spectroscopy

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 Greens 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 Greens function, and we discuss the cancellation of various dynamical effects that occur in that case.

Polarization Dependent High Energy Resolution X-ray Absorption Study of Dicesium Uranyl Tetrachloride

Dicesium uranyl tetrachloride (Cs2UO2Cl4) has been a model compound for experimental and theoretical studies of electronic structure of U(VI) in the form of UO2(2+) (uranyl ion) for decades. We have obtained angle-resolved electronic structure information for oriented Cs2UO2Cl4 crystal, specifically relative energies of 5f and 6d valence orbitals probed with extraordinary energy resolution by polarization dependent high energy resolution X-ray absorption near edge structure (PD-HR-XANES) and compare these with predictions from quantum chemical Amsterdam density functional theory (ADF) and ab initio real space multiple-scattering Greens function based FEFF codes. The obtained results have fundamental value but also demonstrate an experimental approach, which offers great potential to benchmark and drive improvement in theoretical calculations of electronic structures of actinide elements.