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At least 73 records · Page 4

Solid state 59 Co NMR study of a Np(VII) compound

Np(VII) compounds with [Co(NH 3 ) 6 ] 3+ cations were synthesized and structurally examined using powder X-ray diffraction. Multiple phases were observed, consisting of octahedral [Co(NH 3 ) 6 ] 3+ cations, discrete tetragonal bipyramidal [NpO 4 (OH) 2 ] 3− anions, and waters of hydration. Electric field gradient tensors at Co sites were measured by solid state 59 Co nuclear magnetic resonance (NMR) spectroscopy and compared with theoretical calculations. The relative contributions of the chemical shift and electric field tensors to the NMR lineshape were determined by recording spectra at field strengths of 7.04 and 11.74 Tesla. Further, the evolution of structure and morphology as a function of sample age and the effects on NMR spectral parameters has also been investigated. These results demonstrate the use of NMR at multiple fields to expand understanding of the stability and electronic structure of high valent neptunium compounds.

heptavalent neptunium↗

Evidence of electron microbunching in laser-driven modulated downramp injection and prospects for beam-driven implementation

Plasma accelerators can generate high-energy, high-brightness electron beams over centimeter-scale distances, offering novel pathways to compact x-ray free-electron lasers. Generating beams pre-bunched at the desired radiation wavelength would significantly enhance longitudinal coherence and reduce saturation length. Plasma density-modulated downramp injection offers an in-situ way to generate such beams with nanometer-scale bunching. Here we report the first experimental evidence of this mechanism in a laser-driven wakefield accelerator, showing that modulated density downramps generate modulated electron energy spectra absent in unmodulated cases. Particle-in-cell simulations reproduce these observations and reveal bunching factors of 0.05 at 0.4 μm, with a compression factor of approximately 7. Building on this demonstration, we propose a beam-driven implementation for FACET-II to generate multi-GeV beams pre-bunched at hundreds of nanometers wavelength, with sub-micrometer emittance, kiloampere peak current, and sub-percent slice energy spread. Two-stage magnetic compression enables tunable bunching from optical to extreme ultraviolet wavelengths while achieving peak currents exceeding 100 kA. Coherent transition radiation calculations confirm diagnostic feasibility. This approach offers a promising path towards compact, high-energy pre-bunched electron sources for advanced photon science applications.

electron microbunching↗

Affine Transformations to Enable Machine Learning for Semi-Quantitative EDS Analysis

Energy Dispersive X-ray Spectroscopy (EDS) is an essential technique for determining elemental concentrations and distributions within microstructures, critical for materials discovery, optimization, and qualification. However, most published EDS data is qualitative because current quantitative EDS analysis methods require extensive calibration and post-processing, limiting their practicality and widespread adoption. This work seeks to establish a framework for accelerated EDS characterization and spectrum analysis that can leverage ML to analyze correlations between various elemental compositions and resulting EDS spectra. The complex physics and data result in a high-dimensional problem that grows exponentially with the number of elements in the system and the complexity of the spectrum analysis. ML provides a way to compute and optimize the results of this highly dimensional problem in a flexible way to tailor it to the user’s specific needs and material system. However, the framework emphasizes transparency through a strictly mathematical affine transformation, so the analysis remains understandable and reviewable to facilitate adoption by the scientific community. While currently implemented methods are simplistic and unvalidated, further development and demonstration of this framework could enable high-throughput, accurate, and accessible EDS characterization.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

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↗

Magnetic and EPR Spectroscopic Studies of Thiolate Bridged Divalent Ni, Pd, and Pt Ions Capped with VO(N 2 S 2 ) Metalloligands

Reactions of the metallodithiolate complex VO(bme-dach) (hereafter abbreviated as V, where bme-dach = N,N ′-bis(2-mercaptoethyl)-1,4-diazacycloheptane) with [Pd II (CH 3 CN) 4 ](BF 4 ) 2 and [Pt II (CH 3 CN) 4 ](BF 4 ) 2 yield the V–M–V trimetallic compounds [VPdV](BF 4 ) 2 (2) and [VPtV](BF 4 ) 2 (3). Reaction of a similar metalloligand, VO(bme-daco) (hereafter abbreviated as V′ where bme-daco = N,N′-bis(2-mercaptoethyl)-1,5-diazacyclooctane) with [Ni II (CH 3 CN) 6 ](BF 4 ) 2 afforded the related salt [V′NiV′](BF 4 ) 2 (1). X-ray structural analyses revealed that cations in 1, 2, and 3 adopt a stairstep C 2h structure consisting of two terminal VO(N 2 S 2 ) moieties bridged via thiolate sulfur to the group 10 metal ions. Weak ferromagnetic superexchange coupling (J = 0.282 cm –1 for 1, 0.954 cm –1 for 2, and 1.372 cm –1 for 3) was observed between the two S = 1/2 V IV centers separated by distances in the range of 5.9–6.3 Å, with J values varying following the order Ni < Pd < Pt. Frozen-solution EPR spectra measured on the more soluble [BArF 24 ] − (BArF 24 – = tetrakis((3,5-trifluoromethyl)phenyl)borate) analogues revealed that the [VPtV] 2+ cation exhibits a 15-line hyperfine splitting of 225 MHz at g = 4 in parallel mode, confirming exchange coupling between the two 51 V, I = 7/2 nuclei. Density-functional theory (DFT) calculations indicate an S = 1 ground state for 1–3. These results demonstrate that the choice of paramagnetic metallodithiolate ligand and diamagnetic bridge in such trimetallic species influences the sign and magnitude of magnetic interactions.

anions↗

Revisiting the Anisotropic Complex Refractive Indices of Sodium Nitrate for Interpretation of the Reflectance Spectrum of Pressed Pellets

Reflectance spectroscopy is notoriously confounding in that the measured spectral response is highly dependent upon the morphology of the sample. Fortunately, all such perturbations are neatly encoded by the complex refractive index of the sample. Herein, we seek to quantitatively model the measured infrared reflectance spectrum of a specularly flat pressed pellet sample of the birefringent compound, sodium nitrate. Single crystals of sodium nitrate were synthesized via a slow evaporation process and spectroscopically analyzed using polarization-dependent infrared single-angle reflectance spectroscopy. The anisotropic complex refractive index was measured from 7500 to 300 cm-1 (1.33 to 33.33 µm). The deduced anisotropic optical constants were found to be consistent with those previously reported. Once measured and validated, the optical constants were applied to model the pressed pellet reflectance spectrum. It was evident that an average of the anisotropic refractive indices was insufficient to account for the measured pellet reflectance. In order to account for contributions of all possible microcrystalline orientations within the pellet, the Python package PYELLI was used to calculate a basis set of orientation-dependent reflection spectra spanning the distinct ? and ? Euler rotations of the uniaxial crystal. When the population of orientations was allowed to vary freely in a spectral fit analysis, the fit-deduced orientations were tightly clustered along f = 45º, hinting at residual anisotropy in the pressed pellet sample. Conversely, an equally valid spectral fit (with marginally worse fit metric) was obtained when the population was constrained to an isotropic distribution of orientations. Subsequent non-zero cross-polarization reflectance measurements likewise suggested anisotropy in the pellet. However, both grazing incidence wide-angle x-ray scattering and scanning electron microscopy measurements revealed that the microcrystal orientations at the surface of the pressed pellet sample were isotropically distributed (and that the average crystallite size was larger than ?/10). Application of the measured complex refractive indices for modeling the reflectance spectrum of the pressed pellet, and rectification of these seemingly contradictory observations will be discussed.

Wilhelm, Michael J.↗

Crystal Growth of Quaternary RE 2 EuSi 2 S 8 ( RE = Ce–Nd, Sm, Gd, Tb) Using Flux-Assisted Boron Chalcogen Mixture (BCM) Method: Investigation of Magnetic and Luminescence Properties

A series of quaternary rare-earth containing thiosilicates with the general formula RE 2 EuSi 2 S 8 (RE = Ce–Nd, Sm, Gd, Tb) has been synthesized via the flux-assisted boron chalcogen mixture (BCM) crystal growth method. High-quality single crystals were obtained, and their crystal structures were determined by single-crystal X-ray diffraction. The RE 2 EuSi 2 S 8 series crystallizes in the trigonal system, adopting the space group R-3c. Polycrystalline samples were employed for physical property measurements, including magnetic susceptibility measurements, UV–visible diffuse reflectance, and photoluminescent response. Magnetic data of RE 2 EuSi 2 S 8 ( RE = Ce, Nd, and Gd) were collected over the 2–300 K temperature range. The samples were paramagnetic behavior with negative Weiss constants (θ W = −11.05, −10.55, and −1.35 K respectively). Their thermal stability was investigated using thermogravimetric analysis (TGA). Optical band gaps, estimated from diffuse reflectance spectra, were determined to be 2.2(1) eV for Ce 2 EuSi 2 S 8 , 1.8(1) eV for Nd 2 EuSi 2 S 8 , and 1.7(1) eV for Gd 2 EuSi 2 S 8 respectively. Finally, photoluminescence measurements were collected on Ce 2 EuSi 2 S 8 and Tb 2 EuSi 2 S 8 single crystals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Uniform Whole Wafer Anisotropic Etching of Structural Ta Thin Films

Tantalum (Ta) has promise as a structural material for micromechanical sensors and actuators. Anisotropic etching of alpha (α) phase Ta is required for micromachining applications. Uniform thickness and etch across a full wafer are desirable features. An experimental investigation is conducted to study plasma etching rate and anisotropy in etching α -Ta in relation to pressure and gas flow ratio. A comparatively low toxicity gas, carbon tetrafluoride (CF4), and argon (Ar) are used. Spectrometry by optical emission spectrometry (OES) and residual gas analysis (RGA) are employed to characterize the plasma to gain insight into the etch mechanisms. At low flow, the etch rate is slow due to an inadequate supply of the etching gas, CF4. The etch rate is also slowed at high flow due to a reduced CF4 residence time. Flow and pressure conditions to achieve a good etch rate and vertical sidewalls are identified and explained by means of a full factorial experiment coupled with emission spectra. Finally, with these conditions, uniform etching of 2.5 μm thick α-Ta across a 4-inch wafer is demonstrated.

36 MATERIALS SCIENCE↗

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↗

Frustration-driven magnetic correlations in the spin-$\frac{5}{2}$ triangular lattice antiferromagnet RbFe⁢(HPO 3 ) 2

Here, a detailed study of the structural and magnetic properties of a spin-5/2 triangular lattice antiferromagnet RbFe⁢(HPO 3 ) 2 is presented using x-ray diffraction, magnetization, heat capacity, and 31 P nuclear magnetic resonance (NMR) experiments on a polycrystalline sample. The crystal structure features an equilateral triangular lattice of Fe 3+ ions. The thermodynamic measurements reveal the onset of a magnetic long-range order at 𝑇 N⁢1 ≃7.8K in zero field, followed by another low-temperature field-induced ordering at 𝑇 N⁢2 in higher fields. The transition at 𝑇 N⁢1 is further confirmed from the NMR spin lattice relaxation measurements. The value of the frustration ratio (𝑓≃7) implies moderate spin frustration in the compound. The 31 P NMR spectra exhibit two distinct spectral lines corresponding to two inequivalent phosphorus sites (P1 and P2), consistent with the crystal structure. The P1 site is strongly coupled with an isotropic hyperfine coupling of 𝐴$^{iso}_{hf}$ = 0.55⁢(2)⁢ T/𝜇 B while the P2 site is weakly coupled with 𝐴$^{iso}_{hf}$ = 0.25⁢(3)⁢ T/𝜇 B with the Fe 3+ ions. The magnetic susceptibility and NMR shift data are described well assuming a spin-5/2 isotropic triangular lattice antiferromagnetic model with an average exchange coupling of 𝐽/𝑘 B = 2.8⁢(2)⁢K. Below 𝑇 N⁢1 , the spectra evolve into a nearly rectangular powder pattern, indicating a commensurate antiferromagnetic type order. The 31 P spin-lattice relaxation rate well below 𝑇N⁢1 follows a 𝑇 3 temperature dependence, implying a two-magnon Raman scattering mechanism in the ordered state. Three well-defined phase regimes are clearly ascertained in the 𝐻−𝑇 phase diagram, reflecting a weak magnetic anisotropy in the compound.

Nagpal, V. [Indian Institute of Science Education ↗

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↗

Statistical White-Line Analysis in High-Throughput TXM-XANES for Chemical State Quantification

The transmission X-ray microscopy (TXM) based X-ray absorption near-edge structure (XANES) technique provides three-dimensional mapping of element-specific chemical states at nanometer-scale spatial resolution and micrometer-scale fields of view. However, compared to conventional volume-averaged XANES (VA-XANES) measurements, the inherently small voxel size in TXM-XANES leads to a lower signal-to-noise ratio, making full-spectrum analysis computationally demanding and less robust. Here, we present the structural and compositional conditions for a statistical white-line analysis framework under which chemical state information can be directly extracted from the white-line peak position in voxel spectra without the need for voxel-wise background subtraction or normalization, under well-defined structural and compositional conditions. The method is validated on layered oxide cathode materials, where low-order polynomial fitting accurately reproduces white-line features, and the extracted energy distributions correlate strongly with VA-XANES results. This statistical approach enables high-throughput, dose-efficient, and noise-robust chemical state quantification in TXM-XANES, offering broad applicability to functional materials requiring nanoscale oxidation-state mapping.

TXM↗

A new layered kagome strip structure Na 2 Co 3 (AsO 4 ) 2 (OH) 2 : static and dynamic magnetic properties

One-dimensional kagome strip chains share much of the same frustrated structural motif as two-dimensional kagome antiferromagnets, making them valuable for deepening our understanding of kagome lattice magnetism. In this paper, we report the hydrothermal synthesis and detailed structural and property characterization of Na 2 Co 3 (AsO 4 ) 2 (OH) 2 , a striped kagome system. The crystal structure was characterized using single crystal X-ray diffraction which reveals that Na 2 Co 3 (AsO 4 ) 2 (OH) 2 crystallizes in monoclinic crystal system C2/m. The structure features a one-dimensional kagome strip lattice built from Co 2+ ions and undergoes an antiferromagnetic transition at T N = 14 K. The magnetic ground state at zero field was characterized using neutron powder diffraction. Below the magnetic transition, Na 2 Co 3 (AsO 4 ) 2 (OH) 2 orders into an antiferromagnetic structure with a k-vector (0.5, 0.5, 0.5). In the proposed model, the Co1 moment is predominantly confined to the ac-plane while the Co2 moment is primarily aligned along the b-axis. Two flat bands were observed in the inelastic neutron spectra below the magnetic transition, 5 and 10 meV. Inelastic neutron spectra were modeled with a Heisenberg Hamiltonian including three nearest-neighbor exchange interactions (J 1 , J 2 , J 3 ) and strong single-ion anisotropy to stabilize the observed magnetic structure. Our study highlights the complexity of Co 2+ -based kagome strip magnetic lattice compound Na 2 Co 3 (AsO 4 ) 2 (OH) 2 which provides an excellent platform to broaden our understanding of the frustrated kagome magnetic lattice space.

Liurukara, Duminda S. [Oak Ridge National Laborato↗

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↗

Revealing Local Structures through Machine-Learning-Fused Multimodal Spectroscopy

Atomistic structures of materials offer valuable insights into their functionality. Determining these structures remains a fundamental challenge in materials science, especially for systems with defects. While both experimental and computational methods exist, each has limitations in resolving nanoscale structures. Core-level spectroscopies, such as X-ray absorption (XAS) or electron energy-loss spectroscopies (EELS), have been used to determine the local bonding environment and structure of materials. Recently, machine learning (ML) methods have been applied to extract structural and bonding information from XAS/EELS data. However, frameworks relying solely on a single data stream, defined as characterization data derived from a single element using one technique, are often insufficient because multiple local environments can yield similar spectral features, making it challenging to differentiate between competing structural hypotheses. Here, in this work, we address this challenge by integrating multimodal ab initio simulations, experimental data acquisition, and ML techniques for structure characterization. Our goal is to determine local structures and properties using EELS and XAS data from multiple elements and edges. To showcase our approach, we use various lithium nickel manganese cobalt (NMC) oxide compounds which are used for lithium ion batteries, including those with oxygen vacancies and antisite defects, as the sample material system. We successfully inferred local element content, ranging from lithium to transition metals, with quantitative agreement with experimental data. Beyond local element inference, we find that ML model based on multimodal spectroscopic data is able to determine whether local defects such as oxygen vacancy and antisites are present, a task which is impossible for single mode spectra or other experimental techniques. Furthermore, our framework is able to provide physical interpretability, bridging spectroscopy with the local atomic and electronic structures.

battery↗

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↗

Impact of external screening on the valence and core level photoelectron spectra of monolayer W⁢S 2

Transition metal dichalcogenides (TMDs) represent an emerging class of layered materials with applications in microelectronics, optoelectronics, photonics, and catalysis. The confinement of charge carriers within the highly anisotropic, quasi-two-dimensional geometry of one-layer (1L) TMDs leads to reduced, variable dielectric screening, giving rise to a quasiparticle band gap that is highly susceptible to the surrounding dielectric environment. Here, exploiting the contrasting external dielectric environments of gold-supported and suspended 1L W⁢S 2 , we show how the electronic states of W⁢S 2 under the effective and ineffective screening environments align at a junction made within the same sheet of material. Photoelectron spectra point to the close alignment of the charge neutrality levels of W⁢S 2 in both environments, and the breakdown of rigid shifts between the valence states and core levels with the core levels shifting more than twice as much as the valence states. Furthermore, the effectively screened W⁢S 2 exhibits a valence state with the photoemission linewidth twice as large as the ineffectively screened suspended W⁢S 2 , presumably originated from the locally varying W⁢S 2 -Au distance and substrate disorders. Collectively, these findings provide key insights into the electronic behavior of W⁢S 2 and its photoemission process with the electronic states renormalized according to the external screening environments.

Dielectric properties↗

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↗