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All sourcesNASA NTRSDOE OSTI
NASA NTRS1994

X-Ray Absorption Spectroscopy in High Temperature Oxidation of Metals and Alloys

An experimental technique is described that allows for the joint study of the kinetics and of the oxide structure during the high temperature oxidation of metal surfaces. Oxygen is supplied at the metal through an electrochemical oxygen pump and the oxygen pressure, at the metal surface, is measured during oxidation by a YSZ (yttria stabilized zirconia) oxygen sensor. XAS (x-ray absorption spectroscopy) is performed in fluorescence mode at the cation K edge and after each oxidation step. An appropriate analysis of the XAS spectra could provide information on both the oxidation kinetics and oxide structure. Experimental data on the high temperature oxidation of nickel, cobalt, and Fe(64%)Ni(36%) alloy, at low oxygen pressure, are reported and analyzed according to the proposed data reduction. These results indicate the presented technique to be particularly suitable for studying the hot corrosion of oxide film too thick for common surface spectroscopy (AUGER, ESCA) and too thin for conventional thermogravimetric technique.

Daniele Gozzi↗
DOE OSTI2015

A novel synthesis of tin oxide thin films by the sol-gel process for optoelectronic applications

A novel and simple chemical method based on sol-gel processing was proposed to deposit metastable orthorhombic tin oxide (SnOx) thin films on glass substrates at room temperature. The resultant samples are labeled according to the solvents used: ethanol (SnO-EtOH), isopropanol (SnO-IPA) and methanol (SnO-MeOH). The variations in the structural, morphological and optical properties of the thin films deposited using different solvents were characterized by X-ray diffraction, atomic force microscopy, Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, UV-vis spectroscopy and photoluminescence (PL) analysis. The XRD patterns confirm that all the films, irrespective of the solvents used for preparation, were polycrystalline in nature and contained a mixed phases of tin (II) oxide and tin (IV) oxide in a metastable orthorhombic crystal structure. FTIR spectra confirmed the presence of Sn=O and Sn-O in all of the samples. PL spectra showed a violet emission band centered at 380 nm (3.25 eV) for all of the solvents. The UV-vis spectra indicated a maximum absorption band shown at 332 nm and the highest average transmittance around 97% was observed for the SnO-IPA and SnO-MeOH thin film samples. The AFM results show variations in the grain size with solvent. The structural and optical properties of the SnO thin films indicate that this method of fabricating tin oxide is promising and that future work is warranted to analyze the electrical properties of the films in order to determine the viability of these films for various transparent conducting oxide applications.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Surface plasmon resonance induced Er{sup 3+} photoluminescence enhancement in tellurite glass

The melt quenching method is used to prepare tellurite glasses co-activated with erbium ions and silver nanoparticles (Ag NPs). The glass samples are characterized by x-ray diffraction, UV-vis-NIR absorption, transmission electron microscopy (TEM) imaging, and photoluminescence spectroscopy. The XRD pattern shows no sharp peak indicating an amorphous nature of the glasses. The presence of Ag NPs is confirmed from TEM micrograph. The absorption spectra reveal not only the peaks due to Er{sup 3+} ions, but also the surface plasmon resonance band of silver NPs in the 510–535 nm range. The J-O model has been applied to the room temperature absorption intensities of Er{sup 3+} (4f{sup 11}) transitions to establish the so-called J-O intensity parameters: Ω{sub 2}, Ω{sub 4}, and Ω{sub 6}. The intensity parameters are used to determine the radiative decay rates (emission probabilities of transitions) and branching ratios of the Er{sup 3+} transitions from the excited state J manifolds to the lower-lying J' manifolds. Intensified of 1.53 μm band is obtained for the sample containing 0.5 mol. % of AgNO{sub 3} (Ag0.5 glass) using for excitation a laser operating at 980 nm. The simultaneous influence of the Ag NPs → Er{sup 3+} energy transfer and the contribution of the intensified local field effect due to the silver NPs give origin to the enhancement of both the Photoluminescence (PL) intensity and the PL lifetime relative to the {sup 4}I{sub 13/2} → {sup 4}I{sub 15/2} transition, whereas the quenching is ascribed to the energy transfer from Er{sup 3+} ions to silver NPs. Based on the analysis of the temperature dependence of the PL intensity and decay time, we identified a weak back transfer process from Er to the glass host that makes the quenching of the PL intensity weak. Large magnitudes of calculated emission cross-section (σ{sub e}), effective bandwidth (Δλ{sub eff}), and bandwidth quality factor (FWHM × σ{sub e}) relatives to {sup 4}I{sub 13/2} → {sup 4}I{sub 15/2} transition in Er doped Ag0.5 glass have been shown. They indicate that this glass sample has good prospect as a gain medium applied for 1.53 μm band broad and high-gain erbium-doped fiber amplifiers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

Aliovalent gallium dopants remove Ti 3+ defects and improve photocatalytic and photoelectrochemical water oxidation properties of LaTiO 2 N

LaTiO 2 N is a promising semiconductor for the water splitting reaction due to its 2.1 eV band gap and stability against corrosion. However, its solar energy conversion is limited by Ti 3+ recombination defects introduced during ammonolysis. Here we show for the first time that Ti 3+ defects in LaTiO 2 N can be suppressed with incorporation of 2, 5, and 10% aliovalent gallium (Ga 3+ ) dopants during synthesis via the layered La 2 Ti 2 O 7 intermediate. Electron paramagnetic resonance (EPR) spectroscopy on the solid powders confirms a reduction in the Ti 3+ donor density from 2.97 × 10 17 cm −3 for the non-doped material to ∼6.24 × 10 16 cm −3 for 5% Ga-doped LaTiO 2 N. The remaining Ti 3+ defects are concentrated near the LaTiO 2 N surface, according to X-ray photoelectron spectroscopy. The defect reduction shifts the optical absorption edge from 2.02 to 2.09 eV and eliminates a broad absorption band at 1050 nm from the optical absorption spectra. It also removes a 1.0–1.7 eV sub-band gap photovoltage signal from surface photovoltage spectra. This suggests that empty Ti 3+ d-orbitals are located 1.0–1.7 eV above the LaTiO 2 N valence band edge. Removing these recombination states with increasing Ga 3+ content enhances the photoconversion efficiency of LaTiO 2 N during water oxidation. The optimized 2 wt% CoO x -loaded 5% Ga-doped LaTi O2 N material has a 16% AQE (400 nm) for O 2 production from aqueous silver nitrate solution and a ∼2.1 mA cm −2 water oxidation photocurrent at 1.23 V under 100 mW cm −2 Xe arc lamp illumination. The water oxidation photocurrent is stable during a 50 min test, and the Faraday efficiency for O 2 generation is 97%, confirming short-term corrosion stability of LaTiO 2 N. Altogether, these results provide a better understanding of the distribution, concentration, and impact of Ti 3+ defects on the optical, photovoltage, and photoelectrochemical properties of LaTiO 2 N. In combination with other defect control strategies, aliovalent Ga 3+ doping can help bring the solar energy conversion efficiency of LaTiO 2 N closer to the theoretical limit.

Wang, Li [University of California, Davis, CA (Uni↗
DOE OSTI2015

Local electronic states of Fe{sub 4}N films revealed by x-ray absorption spectroscopy and x-ray magnetic circular dichroism

We performed x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) measurements at Fe L{sub 2,3} and N K-edges for Fe{sub 4}N epitaxial films grown by molecular beam epitaxy. In order to clarify the element specific local electronic structure of Fe{sub 4}N, we compared experimentally obtained XAS and XMCD spectra with those simulated by a combination of a first-principles calculation and Fermi's golden rule. We revealed that the shoulders observed at Fe L{sub 2,3}-edges in the XAS and XMCD spectra were due to the electric dipole transition from the Fe 2p core-level to the hybridization state generated by σ* anti-bonding between the orbitals of N 2p at the body-centered site and Fe 3d on the face-centered (II) sites. Thus, the observed shoulders were attributed to the local electronic structure of Fe atoms at II sites. As to the N K-edge, the line shape of the obtained spectra was explained by the dipole transition from the N 1s core-level to the hybridization state formed by π* and σ* anti-bondings between the Fe 3d and N 2p orbitals. This hybridization plays an important role in featuring the electronic structures and physical properties of Fe{sub 4}N.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

Electron-Deficient Phenazines: Synthesis, Structures, Redox, and Optoelectronic Properties in the Gas Phase, in Solution, and in the Solid State

High-temperature gas-phase reactions of 1,4-C4F8I2 with phenazine (PHNZ) afforded new thermally- and air-stable derivatives with cyclo-C4F8 substituents, viz. 1,2-PHNZ(C4F8), 2,3-PHNZ(C4F8), 1,2:6,7-PHNZ(C4F8)2, 1,2:7,8-PHNZ(C4F8)2, and 1,2:8,9-PHNZ(C4F8)2. Reactions in the presence of Cu powder resulted in reductive-defluorination/aromatization of some of the cyclo-C4F8 substituents to produce 2,3-PHNZ(C4F4), 2,3-PHNZ(C4HF3), and 1,2:6,7-PHNZ(C4F8)(C4F4), which are formally tri- or tetrafluoro derivatives of benzo[a]phenazine. Single-crystal X-ray diffraction structures of these compounds demonstrate the planarity of 2,3-PHNZ(C4F4) and 2,3-PHNZ(C4HF3) and ordered p-stacking in 1,2-PHNZ(C4HF3), 1,2-PHNZ(C4F4), 1,2-PHNZ(C4F8), and 2,3-PHNZ(C4F8). Low-temperature gas-phase photoelectron spectra of the PHNZ(C4F8)1,2 compounds show that they are strong electron acceptors, with the three PHNZ(C4F8)2 isomers having electron affinities exceeding that of C60. Cyclic voltammetry in acetonitrile show that the five PHNZ(C4F8)1,2 compounds exhibit reversible one-electron reductions with large positive shifts in their reduction potentials relative to unsubstituted PHNZ. Spectroelectrochemical absorption and EPR spectra of PHNZ(C4F8)1,2- • anion radicals and extensive DFT calculations revealed the significant role that the different substitution patterns have on determining the optoelectronic properties of the PHNZ(C4F8)1,2 derivatives and PHNZ(C4F8)1,2- • anion radicals. Time-resolved microwave conductivity measurements and photoluminescence spectra of blends of the PHNZ(C4F8)1,2 derivatives with the donor poly(3-hexylthiophene) (P3HT) were recorded to assess the possible use of the new compounds in optoelectronic devices.

Balser, Sebastian↗
DOE OSTI2026

Optimizing Porous Transport Layer Porosity for Proton Exchange Membrane Water Electrolysis

An empirical model is presented that describes anode-side losses related to porous transport layer (PTL) morphology in proton exchange membrane water electrolysis (PEMWE). The model is based on an advanced voltage breakdown analysis that links various overpotentials to PTL morphology. Custom Ti PTLs, spanning uncommonly low porosities (22 - 31%), were fabricated and analyzed with X-ray CT to obtain pore and particle size distributions. Particle size distributions were consistent across samples with an average particle diameter of 12.0?..mu..m, whereas average pore diameters ranged from 6.0 to 7.0?..mu..m. The PTLs were tested in standard PEMWE cell assemblies with anode catalyst loadings of 0.1 mgIr cm-2 to obtain polarization curves, electrochemical impedance spectra, and augmented Tafel analysis. The PTL-dependent anode side losses were deconvoluted and assigned to excess utilization, concentration, ion transport resistance, and electrical contact resistance overpotentials. The data and model reveal an optimal 20 - 28% PTL porosity region where utilization and contact resistance overpotentials are minimized without triggering concentration and ion transport losses related to water deprivation. The optimal PTL porosity depends on the operating current density and is demonstrated at realistic PEMWE water flow rates to establish PTL design guidance for operation at scale.

08 HYDROGEN↗
DOE OSTI2024

Lanthanum-Promoted Electrocatalyst for the Oxygen Evolution Reaction: Unique Catalyst or Oxide Deconstruction?

A conventional performance metric for electrocatalysts that promote the oxygen evolution reaction (OER) is the current density at a given overpotential. However, the assumption that increased current density at lower overpotentials indicates superior catalyst design is precarious for OER catalysts in the working environment, as the crystalline lattice is prone to deconstruction and amorphization, thus greatly increasing the concentration of catalytic active sites. We show this to be the case for La 3+ incorporation into Co 3 O 4 . Powder X-ray diffraction (PXRD), Raman spectroscopy and extended X-ray absorption fine structure (EXAFS) reveal smaller domain sizes with decreased long-range order and increased amorphization for La-modified Co 3 O 4 . This lattice deconstruction is exacerbated under the conditions of OER as indicated by operando spectroscopies. The overpotential for OER decreases with increasing La 3+ concentration, with maximum activity achieved at 17% La incorporation. HRTEM images and electron diffraction patterns clearly show the formation of an amorphous overlayer during OER catalysis that is accelerated with La 3+ addition. O 1s XPS spectra after OER show the loss of lattice-oxide and an increase in peak intensities associated with hydroxylated or defective O-atom environments, consistent with Co(O) x (OH) y species in an amorphous overlayer. Furthermore, our results suggest that improved catalytic activity of oxides incorporated with La 3+ ions (and likely other metal ions) is due to an increase in the number of terminal octahedral Co(O) x (OH) y edge sites upon Co 3 O 4 lattice deconstruction, rather than enhanced intrinsic catalysis.

Catalysts↗
DOE OSTI2015

A multiwavelength study of the relativistic tidal disruption candidate swift J2058.4+0516 at late times

We report a multiwavelength (X-ray, ultraviolet/optical/infrared (UVOIR), radio) analysis of the relativistic tidal disruption event (TDE) candidate Sw J2058+05 from 3 months to 3 yr post-discovery in order to study its properties and compare its behavior with that of Sw J1644+57. Our main results are as follows: (1) The long-term X-ray light curve of Sw J2058+05 shows a remarkably similar trend to that of Sw J1644+57. After a prolonged power-law decay, the X-ray flux drops off rapidly by a factor of ≳160 within a span of Δt/t⩽0.95 . Associating this sudden decline with the transition from super-Eddington to sub-Eddington accretion, we estimate the black hole mass to be in the range of 10{sup 4–6} M{sub ⊙}. (2) We detect rapid (≲500 s) X-ray variability before the drop-off, suggesting that, even at late times, the X-rays originate from close to the black hole (ruling out a forward-shock origin). (3) We confirm using Hubble Space Telescope and Very Long Baseline Array astrometry that the location of the source coincides with the galaxy’s center to within ≲400 pc (in projection). (4) We modeled Sw J2058+05's UVOIR spectral energy distribution with a single-temperature blackbody and find that while the radius remains more or less constant at a value of 63.4 ± 4.5 AU (∼10{sup 15} cm) at all times during the outburst, the blackbody temperature drops significantly from ∼30,000 K at early times to a value of ∼15,000 K at late times (before the X-ray drop-off). Our results strengthen Sw J2058+05's interpretation as a TDE similar to Sw J1644+57.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

Removal of Ca 2+ from the Oxygen-Evolving Complex in Photosystem II Has Minimal Effect on the Mn 4 O 5 Core Structure: A Polarized Mn X-ray Absorption Spectroscopy Study

We studied Ca 2+ -depleted and Ca 2+ -reconstituted spinach photosystem II using polarized X-ray absorption spectroscopy of oriented PS II preparations to investigate the structural and functional role of the Ca 2+ ion in the Mn 4 O 5 Ca cluster of the oxygen-evolving complex (OEC). Samples were prepared by low pH/citrate treatment as one-dimensionally ordered membrane layers and poised in the Ca 2+ -depleted S 1 (S 1 ') and S 2 (S 2 ') states, the S 2 'Y Z • state, at which point the catalytic cycle of water oxidation is inhibited, and the Ca 2+ -reconstituted S 1 state. Polarized Mn K-edge XANES and EXAFS spectra exhibit pronounced dichroism. Polarized EXAFS data of all states of Ca 2+ -depleted PS II investigated show only minor changes in distances and orientations of the Mn-Mn vectors compared to the Ca 2+ -containing OEC, which may be attributed to some loss of rigidity of the core structure. Thus, removal of the Ca 2+ ion does not lead to fundamental distortion or rearrangement of the tetranuclear Mn cluster, which indicates that the Ca 2+ ion in the OEC is not critical for structural maintenance of the cluster, at least in the S 1 and S 2 states, but fulfills a crucial catalytic function in the mechanism of the water oxidation reaction. On the basis of this structural information, reasons for the inhibitory effect of Ca 2+ removal are discussed, attributing to the Ca 2+ ion a fundamental role in organizing the surrounding (substrate) water framework and in proton-coupled electron transfer to Y Z • (D1-Tyr161).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Synthesis and Properties of Bulk Mg 3 WN 4 in a Wurtzite-Derived Structure

Experimental synthesis of theoretically predicted materials with controlled elemental coordination environments can lead to the realization of useful properties, such as facile ion transport or ferroelectric switching. Among such materials are ternary nitrides in the Mg−W−N composition space, where several stable and metastable compounds have been predicted and synthesized recently in bulk and film forms. Here, we report for the first time on the bulk synthesis of Mg 3 WN 4 in a wurtzite-derived crystal structure via a solid-state metathesis reaction. In situ synchrotron powder X-ray diffraction shows how the ion exchange proceeds from Li 6 WN 4 + MgCl 2 precursors to Mg 3 WN 4 + LiCl products, with the reaction starting slowly near 380 °C and completing by 600 °C, including the presence of a competing disordered rocksalt-derived phase (Mg,W)N above 440 °C. The follow-up ex situ powder synthesis at 400 °C for 0.5 h with 10% excess MgCl 2 reveals the cation-ordered nature of the wurtzite-derived Mg 3 WN 4 structure with polar symmetry confirmed by second-harmonic generation measurements. Optical absorption spectra, chemical composition analysis, and electron microscopy imaging suggest that bulk Mg 3 WN 4 obtained via metathesis reaction is prone to defect formation. Overall, this study shows that selective ex situ synthesis of the phase-pure ternary nitrides, informed by in situ measurements, is possible by carefully controlling the thermal budget of the reaction and paves the way toward property characterization of the Mg 3 WN 4 wurtzite-derived material.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Fast and accurate calculation of EXAFS Debye-Waller factors in U⁢O2 using the dynamical matrix method

Theoretical modeling of bonding dynamics in metal oxides is required for predicting their thermal conductivity, catalytic activity, and mechanical properties. A primary challenge is the scarcity of experimental methods for validating theoretical predictions of these atomic-scale dynamics. This work presents a workflow that uses experimental extended x-ray absorption fine structure (EXAFS) data collected at high temperatures to validate an interatomic force field for uranium dioxide (UO2), an important model material. The validated force field is then used to drive computationally intensive molecular dynamics (MD) simulations and as input for the much faster dynamical matrix Debye-Waller (DMDW) method. The predicted values of the Debye-Waller factors from the DMDW calculations are in good agreement with those obtained from the MD simulations, with residual pair-specific differences attributable to quantum zero-point motion at low temperatures and lattice anharmonicity at high temperatures. We further show that theoretical EXAFS spectra constructed directly from DMDW-derived Debye-Waller factors reproduce the experimental data (at relatively low temperatures) with accuracy comparable to full MD-EXAFS, providing an additional validation of the choice of the potential. This study establishes a validated, rapid computational pathway for modeling bond dynamics, naturally incorporating quantum nuclear\\\\r\\\\nstatistics absent in classical simulations, which are essential for the mechanistic understanding of complex oxide materials.

58 GEOSCIENCES↗
DOE OSTI2026

Directional dependence of equilibrated TLD-400 chips in multiple radiation fields

Fielding of thermoluminescent dosimeters (TLDs) for measurement of photon radiation dose in experiments is the standard practice for γ-irradiation facilities, pulsed power x-ray facilities, and reactor facilities at Sandia National Laboratories (SNL). Due to the high-dose experimental conditions and the mixed ( 1 n, γ) fields in these facilities, SNL radiation metrologists have historically used CaF 2 :Mn TLDs (also known as TLD-400). Recent inquiries to the radiation metrology staff have raised concerns that the aluminum-equilibrated TLD-400 chips may exhibit a directionally dependent response. The metrologists were asked whether the dose measured by the chip may be impacted by the angle of incidence on the equilibrated TLD. To provide a thorough answer to this query, a set of adjoint Monte Carlo radiation transport calculations was performed for three different equilibrated TLDs as well as bare TLD chips using the Integrated Tiger Series (ITS) code. The key feature of the adjoint calculations performed in this study is that each photon escaping the modeled geometry was tallied into angular bins to provide information on both the energy and angular dependence of the equilibrated chip. After the adjoint Monte Carlo calculations were completed, the resulting energy-dependent response function for each angular bin was convolved with multiple photon energy spectra representing various radiation facilities at SNL. The radiation facilities selected for analysis span a range of photon energies from approximately 1 keV up to approximately 20 MeV. Thus, the presented results are applicable to a wide variety of radiation facilities around the world. Although the bare TLD-400 chip was expected to display the largest variation due to the photon angle of impact on the dosimeter, the dosimeter with the thinnest aluminum equilibrator (SNL thin equilibrated TLD-400) was determined to have the biggest differential between the impact angle with the maximum dose ( D max ) and the impact angle with the minimum dose ( D min ). However, the SNL normal equilibrated TLD-400 chip demonstrated a dramatic reduction in that differential between maximum and minimum dose angles. The reduction in this differential is one of the dominant factors in experimenters’ choice to field these dosimeters at SNL radiation facilities. The results from the PNNL (Hanford) energy-flattening field capsule are consistent with the previous publications. The differential dose responses due to the photon impact angle indicate that experimenters should strive to field their TLD-400 dosimeters in a consistent manner to avoid additional uncertainty in the measurements based on dosimeter orientation.

Adjoint radiation transport↗
DOE OSTI2015

Supernova remnant KESTEVEN 27: Interaction with a neighbor Hi cloud viewed by Fermi

We report on the likely detection of γ-ray emission from the supernova remnant (SNR) Kesteven 27 (Kes 27). We analyze 5.7 yr Fermi Large Area Telescope data of the SNR region and find an unresolved source at a position consistent with the radio brightness peak and the X-ray knot of Kes 27, which is located in the eastern region of the SNR and caused by its interaction with a nearby Hi cloud. The source’s emission is best fit with a power-law spectrum with a photon index of 2.5 ± 0.1 and a >0.2 GeV luminosity of 5.8×10{sup 34} erg s{sup −1} assuming a distance of 4.3 kpc, as derived from radio observations of the nearby Hi cloud. Comparing the properties of the source with that of other SNRs that are known to be interacting with nearby high-density clouds, we discuss the origin of the source’s emission. The spectral energy distribution of the source can be described by a hadronic model that considers the interaction of energetic protons escaping from the shock front of Kes 27 with a high-density cloud.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2026

4-Electron Oxygen Reduction Reaction (ORR) with Iron Phthalocyanine (FePc) Functionalized Nanowire Templated-3D Fuzzy Graphene (NT-3DFG)

Iron phthalocyanine (FePc) is a promising alternative to platinum-based catalysts for sustainable energy devices; however, the plane-symmetry of Fe-N 4 sites, random aggregation, and poor conductivity of FePc present major barriers for their application as oxygen reduction reaction (ORR) electrocatalysts. Here, we report the synergistic effects of FePc electrocatalysts supported by a nanowire-templated three-dimensional fuzzy graphene (FePc@NT-3DFG) substrate. The in situ functionalized oxygen groups (iFOGs) at the edge of NT-3DFG localize Fe active sites in FePc under alkaline ORR conditions. With a uniform FePc distribution through many single layers of graphene, the NT-3DFG substrates improve O 2 adsorption and catalytic activity while stabilizing the electrochemical activity during reactions. The FePc@NT-3DFG catalyst exhibits fast ORR kinetics with an extremely low Tafel slope of 28.3 ± 2.7 mV dec −1 , a higher half-wave potential of 0.911 ± 0.004 V (vs RHE), and notable long-term stability at 0.5 V (vs RHE) of 96.0 ± 0.4% retention after 30 h. Surface chemistry spectra validate electronic configuration modification of Fe at the iFOGs. Density functional theory calculations indicate that the extra layers of graphene improve oxygen adsorption. Moreover, additional exploration of other transition metal phthalocyanines supports the effects of iFOGs through the transition toward 4e − ORR. This work offers an expanded strategy for active site modification through edge-based graphene substrates for 4e − ORR.

X-ray absorption spectroscopy↗
DOE OSTI2015

Sub-mm jet properties of the X-ray binary Swift J1745–26

We present the results of our observations of the early stages of the 2012–2013 outburst of the transient black hole X-ray binary (BHXRB), Swift J1745–26, with the Very Large Array, Submillimeter Array, and James Clerk Maxwell telescope (SCUBA–2). Our data mark the first multiple-band mm and sub-mm observations of a BHXRB. During our observations the system was in the hard accretion state producing a steady, compact jet. The unique combination of radio and mm/sub-mm data allows us to directly measure the spectral indices in and between the radio and mm/sub-mm regimes, including the first mm/sub-mm spectral index measured for a BHXRB. Spectral fitting revealed that both the mm (230 GHz) and sub-mm (350 GHz) measurements are consistent with extrapolations of an inverted power law from contemporaneous radio data (1–30 GHz). This indicates that, as standard jet models predict, a power law extending up to mm/sub-mm frequencies can adequately describe the spectrum, and suggests that the mechanism driving spectral inversion could be responsible for the high mm/sub-mm fluxes (compared to radio fluxes) observed in outbursting BHXRBs. While this power law is also consistent with contemporaneous optical data, the optical data could arise from either jet emission with a jet spectral break frequency of ν{sub break}≳1×10{sup 14} Hz or the combination of jet emission with a lower jet spectral break frequency of ν{sub break}≳2×10{sup 11} Hz and accretion disk emission. Our analysis solidifies the importance of the mm/sub-mm regime in bridging the crucial gap between radio and IR frequencies in the jet spectrum, and justifies the need to explore this regime further.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2026

Electron–Ion Covariance Reveals Geometry-Resolved Inner-Shell Spectra in CS 2 Photodissociation

The chemical shifts of inner-shell atomic orbitals are highly sensitive to chemical bonding and molecular structure. In evolving systems, however, the spectra of distinct molecular species and geometries overlap, obscuring the underlying chemical dynamics. Here we demonstrate the use of electron–ion covariance analysis to combine the structural sensitivity of Coulomb explosion imaging with inner-shell spectroscopy, yielding geometry-specific spectra of transient and product species. We apply this approach to the excited state dynamics of CS 2 probed by ionization above the S 2p edge. Electron–ion covariance with time- and momentum-selected S + and S 2+ ions isolates distinct S 2p photoelectron spectra for ground-state CS 2 , bent photoexcited CS 2 , the CS photoproduct, and bare atomic sulfur ─ species whose spectra overlap strongly in the channel-averaged measurement. Clear chemical shifts are observed in the covariance photoelectron spectrum for each of these species, all of which are consistent with high-level calculations. Here, by extracting the atomic S contribution to the photoelectron spectrum in a finely time-resolved manner we can disentangle this contribution to the overall time-resolved photoelectron spectrum as the photodissociation proceeds. These results demonstrate the promise of electron–ion covariance as a general approach to geometry-resolved inner-shell spectroscopy, opening a route to tracking structural evolution through chemical shifts in complex photoexcited molecules.

Ionization↗