Gerald T. Seidler

Multielement spectrometer for efficient measurement of the momentum transfer dependence of inelastic x-ray scattering

Nonresonant x-ray Raman scattering (XRS) is the inelastic scattering of hard x rays from the K shell of low-Z elements or the less tightly bound shells of heavier elements. In the limit of low momentum transfer q, XRS is determined by the same transition matrix element as is measured by x-ray absorption spectroscopies. However, XRS at higher q can often access higher order multipole transitions which help separate the symmetry of various contributions to the local density of states. The main drawback of XRS is its low cross section—a problem that is compounded for a q-dependent study. To address this issue, we have constructed a multielement spectrometer to simultaneously measure XRS at ten different values of q. By means of example, we report new measurements of the XRS from the L- and K-edges of Mg. This instrument is now available to general users at the Advanced Photon Source as the lower energy resolution inelastic x-ray scattering (LERIX) spectrometer.

Effect of pore morphology on the electrochemical properties of electric double layer carbon cryogel supercapacitors

In this study, a group of carbon cryogels have been synthesized using resorcinol formaldehyde as precursors, and altered via catalysis and activation, to obtain varied nanostructures and pore size distributions. To understand the relation between structure and electrochemical properties, an alternate approach to de Levi’s cylindrical pore, transmission line method was utilized. Using electrochemical impedance spectroscopy, the capacitor can be studied as a dielectric system composed of a porous electrode and the electrolyte (tetraethylammonium tetrafluoroborate in propylene carbonate). The complex capacitance and power are used to study the behavior of the system below the relaxation frequency f0 (φ=−45°). Therefore, the relaxation of the capacitor system at the low frequency range, f<f0, may be used as a measure of pore/electrolyte interaction. The approach proposed here also allows for a direct experimental characterization of the capacitance and power at low frequencies, where small pores are likely to...

Orientation of phenylphosphonic acid self-assembled monolayers on a transparent conductive oxide: a combined NEXAFS, PM-IRRAS, and DFT study.

Self-assembled monolayers (SAMs) of dipolar phosphonic acids can tailor the interface between organic semiconductors and transparent conductive oxides. When used in optoelectronic devices such as organic light emitting diodes and solar cells, these SAMs can increase current density and photovoltaic performance. The molecular ordering and conformation adopted by the SAMs determine properties such as work function and wettability at these critical interfaces. We combine angle-dependent near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) to determine the molecular orientations of a model phenylphosphonic acid on indium zinc oxide, and correlate the resulting values with density functional theory (DFT). We find that the SAMs are surprisingly well-oriented, with the phenyl ring adopting a well-defined tilt angle of 12-16° from the surface normal. We find quantitative agreement between the two experimental techniques and density functional theory calculations. These results not only provide a detailed picture of the molecular structure of a technologically important class of SAMs, but also resolve a long-standing ambiguity regarding the vibrational-mode assignments for phosphonic acids on oxide surfaces, thus improving the utility of PM-IRRAS for future studies.

High multipole transitions in NIXS: Valence and hybridization in 4f systems

Momentum-transfer (q) dependent non-resonant inelastic X-ray scattering measurements were made at the N4, 5 edges for several rare-earth compounds. With increasing q, giant dipole resonances diminish, to be replaced by strong multiplet lines at lower energy transfer. These multiplets result from two different orders of multipole scattering and are distinct for systems with simple 4f0 and 4f1 initial states. A many-body theoretical treatment of the multiplets agrees well with the experimental data on ionic La and Ce phosphate reference compounds. Comparing measurements on CeO2 and CeRh3 to the theory and the phosphates indicates sensitivity to hybridization as observed by a broadening of 4f0-related multiplet features. We expect such strong, non-dipole features to be generic for NIXS from f-electron systems.

Surface Characterization of Polythiophene:Fullerene Blends on Different Electrodes Using Near Edge X-Ray Absorption Fine Structure

We study the top surface composition of blends of the conjugated polymer regioregular poly-3-hexylthiophene (P3HT) with the fullerene (6,6)-phenyl-C(61)-butyric acid methyl ester (PCBM), an important model system for organic photovoltaics (OPVs), using near-edge X-ray absorption fine structure spectroscopy (NEXAFS). We compare the ratio of P3HT to PCBM near the air/film interface that results from preparing blend films on two sets of substrates: (1) poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) coated indium tin oxide (ITO) as is commonly used in conventional OPV structures and (2) ZnO substrates that are either unmodified or modified with a C(60)-like self-assembled monolayer, similar to those that have been recently reported in inverted OPV structures. We find that the top surface (the film/air interface) is enriched in P3HT compared to the bulk, regardless of substrate or annealing conditions, indicating that changes in device performance due to substrate modification treatments should be attributed to the buried substrate/film interface and the bulk of the film rather than the exposed film/air interface.

Local electronic structure of dicarba-closo-dodecarboranes C2B10H12.

We report nonresonant inelastic X-ray scattering (NRIXS) measurement of core-shell excitations from both B 1s and C 1s initial states in all three isomers of the dicarba-closo-dodecarboranes C2B10H12. First, these data yield an experimental determination of the angular-momentum-projected final local density of states (l-DOS). We find low-energy resonances with distinctive local s- or p-type character, providing a more complete experimental characterization of bond hybridization than is available from dipole-transition limited techniques, such as X-ray absorption spectroscopies. This analysis is supported by independent density functional theory and real-space full multiple scattering calculation of the l-DOS which yield a clear distinction between tangential and radial contributions. Second, we investigate the isomer sensitivity of the NRIXS signal and compare and contrast these results with prior electron energy loss spectroscopy measurements. This work establishes NRIXS as a valuable tool for borane chemistry, not only for the unique spectroscopic capabilities of the technique but also through its compatibility with future studies in solution or in high-pressure environments. In addition, this work also establishes the real-space full multiple scattering approach as a useful alternative to traditional approaches for excited states calculations of aromatic polyhedral boranes and related systems.

Fine structure and chemical shifts in nonresonant inelastic x-ray scattering from Li-intercalated graphite

The authors report measurements of hard x-ray nonresonant inelastic x-ray scattering (IXS) from the Li and C 1s electrons of fully staged LiC6 Li-intercalated graphite prepared by both chemical and electrochemical methods. They find that the Li 1s orbital shifts to higher energies relative to Li metal. Relative to graphite, the C 1s IXS for LiC6 shows a shift for the σ-orbital threshold to lower energies, but no shift for the π* resonance. The findings provide bulk-sensitive evidence for substantial charge transfer from the Li intercalant to the carbon host and establish important groundwork for future in situ electrochemical studies.

A plastic miniature x-ray emission spectrometer based on the cylindrical von Hamos geometry

We present a short working distance miniature x-ray emission spectrometer (miniXES) based on the cylindrical von Hamos geometry. We describe the general design principles for the spectrometer and detail a specific implementation that covers Kβ and valence level emission from Fe. Large spatial and angular access to the sample region provides compatibility with environmental chambers, microprobe, and pump/probe measurements. The primary spectrometer structure and optic is plastic, printed using a 3-dimensional rapid-prototype machine. The spectrometer is inexpensive to construct and is portable; it can be quickly set up at any focused beamline with a tunable narrow bandwidth monochromator. The sample clearance is over 27 mm, providing compatibility with a variety of environment chambers. An overview is also given of the calibration and data processing procedures, which are implemented by a multiplatform user-friendly software package. Finally, representative measurements are presented. Background levels are below the level of the Kβ(2, 5) valence emission, the weakest diagram line in the system, and photometric analysis of count rates finds that the instrument is performing at the theoretical limit.

An extraction algorithm for core level excitations in non-resonant inelastic x-ray scattering spectra

Non-resonant inelastic X-ray scattering of core electrons is a prominent tool for studying site-selective, i.e. momentum-transfer-dependent, shallow absorption edges of liquids and samples under extreme conditions. A bottleneck of the analysis of such spectra is the appropriate subtraction of the underlying background owing to valence and core electron excitations. This background exhibits a strong momentum-transfer dependence ranging from plasmon and particle-hole pair excitations to Compton scattering of core and valence electrons. In this work an algorithm to extract the absorption edges of interest from the superimposed background for a wide range of momentum transfers is presented and discussed for two examples, silicon and the compound silicondioxide.

Covalency in Metal–Oxygen Multiple Bonds Evaluated Using Oxygen K-edge Spectroscopy and Electronic Structure Theory

Advancing theories of how metal-oxygen bonding influences metal oxo properties can expose new avenues for innovation in materials science, catalysis, and biochemistry. Historically, spectroscopic analyses of the transition metal MO(4)(x-) anions have formed the basis for new M-O bonding theories. Herein, relative changes in M-O orbital mixing in MO(4)(2-) (M = Cr, Mo, W) and MO(4)(-) (M = Mn, Tc, Re) are evaluated for the first time by nonresonant inelastic X-ray scattering, X-ray absorption spectroscopy using fluorescence and transmission (via a scanning transmission X-ray microscope), and time-dependent density functional theory. The results suggest that moving from Group 6 to Group 7 or down the triads increases M-O e* (π*) mixing; for example, it more than doubles in ReO(4)(-) relative to CrO(4)(2-). Mixing in the t(2)* orbitals (σ* + π*) remains relatively constant within the same Group, but increases on moving from Group 6 to Group 7. These unexpected changes in orbital energy and composition for formally isoelectronic tetraoxometalates are evaluated in terms of periodic trends in d orbital energy and radial extension.