arXiv subjects

G. T. Seidler

Publications and source records attributed to G. T. Seidler.

15 recordsLinked to original sources

arXiv2019

Pressure Effects on the 4f Electronic Structure of Light Lanthanides

Using the satellite structure of the $L_{\gamma1}$ line in non-resonant x-ray emission spectra, we probe the high-pressure evolution of the bare 4f signature of the early light lanthanides at ambient temperature. For Ce and Pr the satellite peak experiences a sudden reduction concurrent with their respective volume collapse (VC) transitions. These new experimental results are supported by calculations using state-of-the-art extended atomic structure codes for Ce and Pr, and also for Nd, which does not exhibit a VC. Our work suggests that changes to the 4f occupation are more consistently associated with evolution of the satellite than is the reduction of the 4f moment. Indeed, we show that in the case of Ce, mixing of a higher atomic angular momentum state, driven by the increased hybridization, acts to obscure the expected satellite reduction. These measurements emphasize the importance of a unified study of a full set of microscopic observables to obtain the most discerning test of the underlying, fundamental f-electron phenomena at high pressures.

cond-mat.str-el↗

arXiv2018

Ferromagnetic Quantum Critical Point in CePd$_2$P$_2$ with Pd $\rightarrow$ Ni Substitution

An investigation of the structural, thermodynamic, and electronic transport properties of the isoelectronic chemical substitution series Ce(Pd$_{1-x}$Ni$_x$)$_2$P$_2$ is reported, where a possible ferromagnetic quantum critical point is uncovered in the temperature - concentration ($T-x$) phase diagram. This behavior results from the simultaneous contraction of the unit cell volume, which tunes the relative strengths of the Kondo and RKKY interactions, and the introduction of disorder through alloying. Near the critical region at $x_{\rm{cr}}$ $\approx$ 0.7, the rate of contraction of the unit cell volume strengthens, indicating that the cerium $f$-valence crosses over from trivalent to a non-integer value. Consistent with this picture, x-ray absorption spectroscopy measurements reveal that while CePd$_2$P$_2$ has a purely trivalent cerium $f$-state, CeNi$_2$P$_2$ has a small ($<$ 10 \%) tetravalent contribution. In a broad region around $x_{\rm{cr}}$, there is a breakdown of Fermi liquid temperature dependences, signaling the influence of quantum critical fluctuations and disorder effects. Measurements of clean CePd$_2$P$_2$ furthermore show that applied pressure has a similar initial effect to alloying on the ferromagnetic order. From these results, CePd$_2$P$_2$ emerges as a keystone system to test theories such as the Belitz-Kirkpatrick-Vojta model for ferromagnetic quantum criticality, where distinct behaviors are expected in the dirty and clean limits.

cond-mat.str-el↗

arXiv2017

Benchmark Results and Theoretical Treatments for Valence-to-Core X-ray Emission Spectroscopy in Transition Metal Compounds

We report measurement of the valence-to-core (VTC) region of the K-shell x-ray emission spectra from several Zn and Fe inorganic compounds, and their critical comparison with several existing theoretical treatments. We find generally good agreement between the respective theories and experiment, and in particular find an important admixture of dipole and quadrupole character for Zn materials that is much weaker in Fe-based systems. These results on materials whose simple crystal structures should not, a prior, pose deep challenges to theory, will prove useful in guiding the further development of DFT and time-dependent DFT methods for VTC-XES predictions and their comparison to experiment.

cond-mat.mtrl-sci↗

arXiv2014

A Laboratory-based Hard X-ray Monochromator for High-Resolution X-ray Emission Spectroscopy and X-ray Absorption Near Edge Structure Measurements

We report the development of a laboratory-based Rowland-circle monochromator that incorporates a low poer x-ray (bremsstrahlung) tube source, a spherically-bent crystal analyzer (SBCA), and an energy-resolving solid-state detector. This relatively inexpensive, introductory level instrument achieves 1-eV energy resolution for photon energies of 5 keV to 10 keV while also dmeonstrating a net efficiency previously seen only in laboratory monochromators having much coarser energy resolution. Despite the use of only a compact, air-cooled 10 W x-ray tube, we find count rates for nonresonant x-ray emission spectroscopy (XES) comparable to those achived at monochromatized spectroscopy beamlines at synchrotron light sources. For x-ray absorption near edge structure (XANES), the monochromatized flux is small (due to the use of a low-powered x-ray generator) but still useful for routine transmission-mode studies of concentrated samples. These results indicate that upgrading to a standard commercial high-powered line-focused x-ray tube or rotating anode x-ray generator would result in monochromatized fluxes of order 10^6 to 10^7 photons/s with no loss in energy resolution. This work establishes core technical capabilities for a rejuvenation of laboratory-based x-ray spectroscopies that could have special relevance for contemporary research on catalytic or electrical energy storage systems using transition-metal, lanthanide, or noble-metal active species.

cond-mat.mtrl-sci↗

arXiv2013

Photometric study of single-shot energy-dispersive X-ray diffraction at a laser plasma facility

The low repetition rates and possible shot-to-shot variations in laser-plasma studies place a high value on single-shot diagnostics. For example, white-beam scattering methods based on broadband backlighter x-ray sources are used to determine changes in the structure of laser-shocked crystalline materials by the evolution of coincidences of reciprocal lattice vectors and kinematically-allowed momentum transfers. Here, we demonstrate that white-beam techniques can be extended to strongly-disordered dense plasma and warm dense matter (WDM) systems where reciprocal space is only weakly structured and spectroscopic detection is consequently needed to determine the static structure factor and thus the ion-ion radial distribution function. Specifically, we report a photometric study of energy-dispersive diffraction (ED-XRD) for structural measurement of high energy density systems at large-scale laser facilities such as OMEGA and the National Ignition Facility. We find that structural information can be obtained in single-shot ED-XRD experiments using established backlighter and spectrometer technologies.

physics.plasm-ph↗

arXiv2010

A Comparative Study of the Valence Electronic Excitations of N_2 by Inelastic X-ray and Electron Scattering

Bound state, valence electronic excitation spectra of N_2 are probed by nonresonant inelastic x-ray and electron scattering. Within the usual theoretical treatments, dynamical structure factors derived from the two probes should be identical. However, we find strong disagreements outside the dipole scattering limit, even at high probe energies. This suggests an unexpectedly important contribution from intra-molecular multiple scattering of the probe electron from core electrons or the nucleus. These effects should grow progressively stronger as the atomic number of the target species increases.

physics.atom-ph↗

arXiv2010

Probing Electronic Correlations in Actinide Materials Using Multipolar Transitions

We report nonresonant inelastic x-ray scattering from the semi-core 5d levels of several actinide compounds. Dipole-forbidden, high-multipole features form a rich bound-state spectrum dependent on valence electron configuration and spin-orbit and Coulomb interactions. Cross-material comparisons, together with the anomalously high Coulomb screening required for agreement between atomic multiplet theory and experiment, demonstrate sensitivity to the neighboring electronic environment, such as is needed to address long-standing questions of electronic localization and bonding in 5f compounds.

cond-mat.str-el↗

arXiv2010

Coexistence of Bound and Virtual-bound States in Shallow-core to Valence Spectroscopies

We develop the theory for shallow-core to valence excitations when the multiplet spread is larger than the core-hole attraction, e.g., if the core and valence orbitals have the same principal quantum number. This results in a cross-over from bound to virtual-bound excited states with increasing energy and in large differences between dipole and high-order multipole transitions, as observed in inelastic x-ray scattering. The theory is important to obtain ground state information from x-ray spectroscopies of strongly correlated transition metal, rare-earth and actinide systems.

cond-mat.str-el↗

arXiv2008

A Short Working Distance Multiple Crystal X-ray Spectrometer

For x-ray spot sizes of a few tens of microns or smaller, a mm-sized flat analyzer crystal placed ~ 1 cm from the sample will exhibit high energy resolution while subtending a collection solid angle comparable to that of a typical spherically bent crystal analyzer (SBCA) at much larger working distances. Based on this observation and a non-focusing geometry for the analyzer optic, we have constructed and tested a short working distance (SWD) multicrystal x-ray spectrometer. This prototype instrument has a maximum effective collection solid angle of 0.14 sr, comparable to that of 17 SBCA at 1 meter working distance. We find good agreement with prior work for measurements of the Mn K_beta x-ray emission and resonant inelastic x-ray scattering (RIXS) for MnO and also for measurements of the x-ray absorption near-edge structure for Dy metal using Lalpha2 partial-fluorescence yield detection. We discuss future applications at third- and fourth-generation light sources. For concentrated samples, the extremely large collection angle of SWD spectrometers will permit collection of high-resolution x-ray emission spectra with a single pulse of the Linac Coherent Light Source.

cond-mat.mtrl-sci↗

arXiv2008

Intermediate-Range Order in Water Ices

We report measurements of the non-resonant inelastic x-ray scattering (NRIXS) from the O 1s orbitals in ice Ih, and also report calculations of the corresponding spectra for ice Ih and several other phases of water ice. We find that the intermediate-energy fine structure may be calculated well using an ab initio real-space full multiple scattering approach, and that it provides a strong fingerprint of the intermediate-range order for some ice phases. These results have important consequences for future NRIXS measurements of high-pressure phases of ice and also may call into question the assumption that the wavefunctions for final states within a few eV of the absorption edge are strongly localized.

cond-mat.mtrl-sci↗

arXiv2008

The local electronic structure of alpha-Li3N

New theoretical and experimental investigation of the occupied and unoccupied local electronic density of states (DOS) are reported for alpha-Li3N. 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 finds less extreme nominal valences than have previously been proposed. Nonresonant inelastic x-ray scattering (NRIXS), 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 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 density of states 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 density of states 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 generically applicable for low atomic number compounds.

cond-mat.mtrl-sci↗

arXiv2007

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 4f^0 and 4f^1 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 4f^0-related multiplet features. We expect such strong, nondipole features to be generic for NIXS from f-electron systems.

cond-mat.str-el↗

arXiv2007

Exciton spectroscopy of hexagonal boron nitride using non-resonant x-ray Raman scattering

We report non-resonant x-ray Raman scattering (XRS) measurements from hexagonal boron nitride for transferred momentum from 2 to 9 $\mathrmÅ^{-1}$ along directions both in and out of the basal plane. A symmetry-based argument, together with real-space full multiple scattering calculations of the projected density of states in the spherical harmonics basis, reveals that a strong pre-edge feature is a dominantly $Y_{10}$-type Frenkel exciton with no other \textit{s}-, \textit{p}-, or \textit{d}- components. This conclusion is supported by a second, independent calculation of the \textbf{q}-dependent XRS cross-section based on the Bethe-Salpeter equation.

cond-mat.mtrl-sci↗

arXiv2007

Deconvolving Instrumental and Intrinsic Broadening in Excited State X-ray Spectroscopies

Intrinsic and experimental mechanisms frequently lead to broadening of spectral features in excited-state 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 FWHM 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 to 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.

cond-mat.mtrl-sci↗

arXiv2006

Background Proportional Enhancement of the Extended Fine Structure in Nonresonant Inelastic X-ray Scattering

We report new measurements and calculations of the non-resonant inelastic x-ray scattering (NRIXS) from Mg and Al for a wide range of momentum transfers, q. Extended oscillations in the dynamic structure factor S(q,w) due to scattering from the 2p and 2s orbitals (i.e. L-edges) are observed out to more than 150 eV past the binding energy. These results are discussed in context of the recently proposed representation of S(q,w) for core shells as an atomic background modulated by interference between different photoelectron scattering paths, in analogy to the standard treatment of extended x-ray absorption fine structure. In agreement with this representation, we find a strong increase in the atomic background with increasing q with a concomitant enhancement in the amplitude of the extended fine structure. This effect should be generic and hence may enable improved measurement of the extended fine structure in a wide range of materials containing low-Z elements.

cond-mat.mtrl-sci↗