Partial densities of states from x-ray absorption and Auger electron spectroscopy: Use of core-hole memory.

Ag L 3 edge x-ray absorption and L 3 - M 4,5 M 4,5 Auger electron spectra have been measured and simulated for a variety of x-ray electric-field polarization and Auger electron emission directions. The theory relies on density-functional theory, use of the Bethe-Salpeter equation, atomic multiplet theory, and a simplified model for the Auger line shape and its dependence on photon energy. We also demonstrate that partial densities of states for d T 2g , d Eg , and s Ag symmetry partial-wave channels at the Ag site in the solid can be deduced from the experimental measurements with only atomic theoretical input, i.e., with no solid-state theory other than assuming a Fermi edge.

Fast, efficient, and accurate dielectric screening using a local real-space approach.

Various many-body perturbation theory techniques for calculating electron behavior rely on W, the screened Coulomb interaction. Computing W requires complete knowledge of the dielectric response of the electronic system, and the fidelity of the calculated dielectric response limits the reliability of predicted electronic and structural properties. As a simplification, calculations often begin with the random-phase approximation (RPA). However, even RPA calculations are costly and scale poorly, typically as N 4 (N representing the system size). A local approach has been shown to be efficient while maintaining accuracy for screening core-level excitations [Ultramicroscopy 106, 986 (2006)]. We extend this method to valence-level excitations. We present improvements to the accuracy and execution of this scheme, including reconstruction of the all-electron character of the pseudopotential-based wave functions, improved N 2 log N scaling, and a parallelized implementation. We discuss applications to Bethe-Salpeter equation calculations of core and valence spectroscopies.

Design, calibration, and application of a cryogenic low-background infrared radiometer for spectral irradiance and radiance measurements from 4 µm to 20 µm wavelength.

We have constructed, calibrated, and tested a cryogenic low-background infrared radiometer for both spectral radiance and irradiance measurements over the 4 µm to 20 µm wavelength range. The primary purpose of the Missile Defense Transfer Radiometer (MDXR) is to measure absolute irradiance or radiance from cryogenic infrared test chamber sources using a photoconductive Si:As Blocked Impurity Band (BIB) detector and a set of spectral filters. The MDXR also includes an absolute cryogenic radiometer (ACR) and a Fourier transform spectrometer (FTS). For irradiance measurements, the ACR is used to provide the primary power scale for the BIB detector in conjunction with spectral filters, while the FTS/BIB configuration derives its scale from an internal blackbody source. The two measurement scales show agreement for the irradiance of highly collimated (< 1 mrad) infrared beams from 10-13 W/µm/cm2 to 10-8 W/µm/cm2 within the combined relative uncertainties of 2.6 % (coverage factor k = 1.) We have also calibrated the radiometer for radiance measurements by using a large cavity fluid bath blackbody that overfills the spatial and angular extent of the radiometer entrance pupil. The radiometric calibration uncertainty analysis of the radiometer as well as its maintenance and stability are discussed.

A new model dielectric function for loss functions and electron damping.

Trends in the zeroth frequency moment of the imaginary part of the dielectric function are studied for a wide range of metals, semiconductors and insulators. These results are combined with estimates for the inverse-first moment (related by Kramers-Kronig relations to the static dielectric function) and knowledge of the first moment from the f-sum rule. Matching all three moments allows for construction of a model dielectric function that reasonably predicts the loss function at different values of momentum and lifetime damping effects on occupied and unoccupied electron states. This is demonstrated by comparing model results and results of detailed, first-principles calculations.

Invited Article: Refined analysis of synchrotron radiation for NIST's SURF III facility.

We have developed a new method for the exact calculation of synchrotron radiation for the National Institute of Standards and Technology Synchrotron Ultraviolet Radiation Facility, SURF III. Instead of using the Schwinger formula, which is only an approximation, we develop formulae based on Graf's addition theorem for Bessel functions and accurate asymptotic expansions for Hankel functions and Bessel functions. By measuring the radiation intensity profile at two distances from the storage ring, we also confirm an apparent vertical emittance that is consistent with the vertical betatron oscillations that are intentionally introduced to extend beam lifetime by spreading the electron beam spatially. Finally, we determine how much diffraction by beamline apertures enhances the spectral irradiance at an integrating sphere entrance port at the end station. This should eliminate small but treatable components of the uncertainty budget that one should consider when using SURF III or similar synchrotrons as standard, calculable sources of ultraviolet and other radiation.

Acceleration of diffraction calculations in cylindrically symmetrical optics.

We have significantly accelerated diffraction calculations using three independent acceleration devices. These innovations are restricted to cylindrically symmetrical systems. In the first case, we consider Wolf's formula for integrated flux in a circular region following diffraction of light from a point source by a circular aperture or a circular lens. Although the formula involves a double sum, we evaluate it with the effort of a single sum by use of fast Fourier transforms (FFTs) to perform convolutions. In the second case, we exploit properties of the Fresnel-Kirchhoff propagator in the Gaussian, paraxial optics approximation to achieve the propagation of a partial wave from one optical element to the next. Ordinarily, this would involve a double loop over the radial variables on each element, but we have reduced the computational cost by a factor approximately equal to the smaller number of radius values. In the third case, we reduce the number of partial waves, for which the propagation needs to be calculated, to determine the throughput of an optical system of interest in radiometry when at least one element is very small, such as a pinhole aperture. As a demonstration of the benefits of the second case, we analyze intricate diffraction effects that occur in a satellite-based solar radiometry instrument.

Imaging Catalytic Activation of CO2 on Cu2O (110): A First-Principles Study.

Balancing global energy needs against increasing greenhouse gas emissions requires new methods for efficient CO2 reduction. While photoreduction of CO2 is promising, the rational design of photocatalysts hinges on precise characterization of the surface catalytic reactions. Cu2O is a promising next-generation photocatalyst, but the atomic-scale description of the interaction between CO2 and the Cu2O surface is largely unknown, and detailed experimental measures are lacking. In this study, density-functional theory (DFT) calculations have been performed to identify the Cu2O (110) surface stoichiometry that favors CO2 reduction. To facilitate interpretation of scanning tunneling microscopy (STM) and X-ray absorption near-edge structures (XANES) measurements, which are useful for characterizing catalytic reactions, we present simulations based on DFT-derived surface morphologies with various adsorbate types. STM and XANES simulations were performed using the Tersoff-Hamann approximation and Bethe-Salpeter equation (BSE) approach, respectively. The results provide guidance for observation of CO2 reduction reaction on, and rational surface engineering of, Cu2O (110). They also demonstrate the effectiveness of computational image and spectroscopy modeling as a predictive tool for surface catalysis characterization.

Local atomic geometry and Ti 1s near-edge spectra in PbTiO3 and SrTiO3.

We study Ti 1s near-edge spectroscopy in PbTiO3 at various temperatures above and below its tetragonal-to-cubic phase transition, and in SrTiO3 at room temperature. Ab initio molecular dynamics (AIMD) runs on 80-atom supercells are used to determine the average internal coordinates and their fluctuations. We determine that one vector local order parameter is the dominant contributor to changes in spectral features: the displacement of the Ti ion with respect to its axial O neighbors in each Cartesian direction, as these displacements enhance the cross section for transitions to Eg-derived core-hole exciton levels. Using periodic five-atom structures whose relative Ti-O displacements match the root-mean-square values from the AIMD simulations, and core-hole Bethe-Salpeter equation (BSE) calculations, we quantitatively predict the respective Ti 1s near-edge spectra. Properly accounting for atomic fluctuations greatly improves the agreement between theoretical and experimental spectra. The evolution of relative strengths of spectral features vs temperature and electric field polarization vector are captured in considerable detail. This work shows that local structure can be characterized from first-principles sufficiently well to aid both the prediction and the interpretation of near-edge spectra.

Accurate X-Ray Spectral Predictions: An Advanced Self-Consistent-Field Approach Inspired by Many-Body Perturbation Theory.

Constrained-occupancy delta-self-consistent-field (ΔSCF) methods and many-body perturbation theories (MBPT) are two strategies for obtaining electronic excitations from first principles. Using the two distinct approaches, we study the O 1s core excitations that have become increasingly important for characterizing transition-metal oxides and understanding strong electronic correlation. The ΔSCF approach, in its current single-particle form, systematically underestimates the pre-edge intensity for chosen oxides, despite its success in weakly correlated systems. By contrast, the Bethe-Salpeter equation within MBPT predicts much better line shapes. This motivates one to reexamine the many-electron dynamics of x-ray excitations. We find that the single-particle ΔSCF approach can be rectified by explicitly calculating many-electron transition amplitudes, producing x-ray spectra in excellent agreement with experiments. This study paves the way to accurately predict x-ray near-edge spectral fingerprints for physics and materials science beyond the Bethe-Salpether equation.

Refined treatment of single-edge diffraction effects in radiometry.

This work treats diffraction corrections in radiometry for cases of point and extended sources in cylindrically symmetrical three-element systems. It considers diffraction effects for spectral power and total power in cases of Planck sources. It improves upon an earlier work by the author by giving a simpler rendering of leading terms in asymptotic expansions for diffraction effects and reliable estimates for the remainders. This work also demonstrates a framework for accelerating the treatment of extended sources and simplifying the calculation of diffraction effects over a range of wavelengths. This is especially important in the short-wavelength region, where dense sampling of wavelength values is in principle necessitated by the rapidly oscillatory behavior of diffraction effects as a function of wavelength. We demonstrate the methodology's efficacy in two radiometric applications.

Results of aperture area comparisons for exo-atmospheric total solar irradiance measurements.

Exo-atmospheric solar irradiance measurements made by the solar irradiance community since 1978 have incorporated limiting apertures with diameters measured by a number of metrology laboratories using a variety of techniques. Knowledge of the aperture area is a critical component in the conversion of radiant flux measurements to solar irradiance. A National Aeronautics and Space Administration (NASA) Earth Observing System (EOS) sponsored international comparison of aperture area measurements of limiting apertures provided by solar irradiance researchers was performed, the effort being executed by the National Institute of Standards and Technology (NIST) in coordination with the EOS Project Science Office. Apertures that had institutional heritage with historical solar irradiance measurements were measured using the absolute aperture measurement facility at NIST. The measurement technique employed noncontact video microscopy using high-accuracy translation stages. We have quantified the differences between the participating institutions' aperture area measurements and find no evidence to support the hypothesis that preflight aperture area measurements were the root cause of discrepancies in long-term total solar irradiance satellite measurements. Another result is the assessment of uncertainties assigned to methods used by participants. We find that uncertainties assigned to a participant's values may be underestimated.

Electronic structure of lithium battery interphase compounds: comparison between inelastic x-ray scattering measurements and theory.

In lithium ion batteries, decomposition of the electrolyte and its associated passivation of the electrode surface occurs at low potentials, resulting in an electronically insulating, but Li-ion conducting, solid electrolyte interphase (SEI). The products of the SEI and their chemical constituents/properties play an important role in the long-term stability and performance of the battery. Reactivity and the sub-keV core binding energies of lithium, carbon, oxygen, and fluorine species in the SEI present technical challenges in the spectroscopy of these compounds. Using an alternative approach, nonresonant inelastic x-ray scattering, we examine the near-edge spectra of bulk specimens of common SEI compounds, including LiF, Li(2)CO(3), LiOH, LiOH·H(2)O, and Li(2)O. By working at hard x-ray energies, we also experimentally differentiate the s- and p-symmetry components of lithium's unoccupied states using the evolution of its K edge with momentum transfer. We find good agreement with theoretical spectra calculated using a Bethe-Salpeter approach in all cases. These results provide an analytical and diagnostic foundation for better understanding of the makeup of SEIs and the mechanism of their formation.

Electronic structure of crystalline 4He at high pressures.

Using inelastic x-ray scattering techniques, we have succeeded in probing the high-pressure electronic structure of helium at 300 K. Helium has the widest known valence-conduction band gap of all materials a property whose high-pressure response has been inaccessible to direct measurements. We observed a rich electron excitation spectrum, including a cutoff edge above 23 eV, a sharp exciton peak showing linear volume dependence, and a series of excitations and continuum at 26 to 45 eV. We determined the electronic dispersion along the Γ-M direction over two Brillouin zones, and provided a quantitative picture of the helium exciton beyond the simplified Wannier-Frenkel description.

Numerical quantification of the vibronic broadening of the SrTiO3 Ti L-edge spectrum.

The 2p(5)3d(1) excited state of the Ti(4+) ion in SrTiO(3) couples to e(g) distortions of the local oxygen cage, leading to a Jahn-Teller vibronic broadening of the excited states. We quantify this contribution to the broadening of the spectral features of the Ti L edge of SrTiO(3) by solving a model Hamiltonian, taking parameters for the Hamiltonian from previous first-principles calculations. Evaluation of the model Hamiltonian indicates that vibronic coupling accounts for the majority of the broadening observed for the L(3) edge, but only a minority of the L(2)-edge spectral width. The calculations reveal that, with increasing temperature, the spectral features become increasingly asymmetric and the amount of vibronic broadening grows approximately linearly.

Local screening of a core hole: A real-space approach applied to hafnium oxide.

An approach to screening a core hole's potential in solids for purposes such as theoretical near-edge spectrum calculations is developed. In this approach, the core hole's unscreened potential is decomposed into a short-range part and a long-range part. The short-range part is screened using a real-space screening calculation, while the long-range part can be screened using a model dielectric function. Screening of the core hole is computed for 1s holes in LiF, MgO, Si, solid argon, diamond, and two structures of hafnium oxide. Most of the screening results obtained using the approach presented here are compared to similar results obtained using a traditional Fourier-space approach. Because the approach presented here is a real-space approach, it should be very practical for systems with large unit cells.

Straight-edge diffraction of Planck radiation.

The irradiance diffraction profile of a straight edge is given as a Taylor series in powers of the distance from the geometrical shadow boundary to any point in the profile for monochromatic radiation. The coefficients of the series, which are obtained as simple analytic expressions, are proportional to the real part of a complex number whose phase cycles through a complete period every eight terms in the series. Integration of this series over a Planck distribution of radiation yields the power series for the Planck profile; this derived series has a finite radius of convergence. The asymptotic series for the Planck profile far from the shadow boundary and beyond the radius of convergence of its power series is obtained by analytic continuation of the power series with the aid of a Barnes type of integral representation.

Diffraction corrections in radiometry: spectral and total power and asymptotic properties.

Wolf's result for integrated flux in the case of diffraction by a circular lens or aperture in the scalar, paraxial Fresnel approximation is considered anew. Compact integral formulas for pertinent infinite sums are derived, and the result's generalizations to extended sources and Planckian sources and asymptotic aspects at small wavelength and high temperature are all considered. Simplification of calculations for an actual absolute radiometer is demonstrated.

Diffraction effects on broadband radiation: formulation for computing total irradiance.

I present a formulation for treating diffraction effects on total irradiance in the case of a Planck source; earlier work generally depended on calculating diffraction effects on spectral irradiance followed by summation over spectral components. The formulation is derived and demonstrated for Fraunhofer diffraction by circular apertures, rectangular apertures and slits, and Fresnel diffraction by circular apertures. The prospects for treating other sources and optical systems are also discussed.

Intuitive diffraction model for multistaged optical systems.

A simplified framework is motivated in which many diffraction effects can be treated, especially in multistaged optical systems. The results should be especially helpful for short wavelengths and broad-band sources, for which numerical calculations can be most difficult.

Optimally Toothed Apertures for Reduced Diffraction.

We model diffraction errors found when using toothed apertures [L. P. Boivin, Reduction of diffraction errors in radiometry by means of toothed apertures, Appl. Opt. 17, 3323-3328 (1978)]. Using toothed (cf. circular) apertures minimizes diffraction by inducing destructive interference within the diffracted signal. Since diffraction effects can be quite complicated, their over-all reduction may help limit uncertainties in, say calibrations. Our analysis yields three principles to guide design of nonlimiting (baffle) apertures which minimize diffrac tion. We performed detailed diffraction calculations within scalar (Kirchoff) diffraction theory, using parallel-computing resources at the National Institute of Standards and Technology.