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At least 91 records · Page 5

Is Deprotonation of the Oxygen-Evolving Complex of Photosystem II during the S 1 → S 2 Transition Suppressed by Proton Quantum Delocalization?

We address the protonation state of the water-derived ligands in the oxygen-evolving complex (OEC) of photosystem II (PSII), prepared in the S 2 state of the Kok cycle. We perform quantum mechanics/molecular mechanics calculations of isotropic proton hyperfine coupling constants, with direct comparisons to experimental data from two-dimensional hyperfine sublevel correlation (HYSCORE) spectroscopy and extended X-ray absorption fine structure (EXAFS). We find a low-barrier hydrogen bond with significant delocalization of the proton shared by the water-derived ligand, W1, and the aspartic acid residue D1–D61 of the D1 polypeptide. The lowering of the zero-point energy of a shared proton due to quantum delocalization precludes its release to the lumen during the S 1 → S 2 transition. Retention of the proton facilitates the shuttling of a proton during the isomerization of the tetranuclear manganese–calcium–oxo (Mn 4 Ca–oxo) cluster, from the “open” to “closed” conformation, a step suggested to be necessary for oxygen evolution from previous studies. Our findings suggest that quantum-delocalized protons, stabilized by low-barrier hydrogen bonds in model catalytic systems, can facilitate the accumulation of multiple oxidizing equivalents at low overpotentials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Co doping on the structure and physicochemical properties of hausmannite (Mn 3 O 4 ) and its transformation during aging

Hausmannite is a common low-valence manganese oxide mineral with a distorted spinel structure in surficial sediments. Although natural Mn oxides often contain various transition metal (TM) impurities, few studies have addressed the substitution mechanisms of TMs, such as cobalt (Co), with hausmannite and induced changes in the mineral physicochemical properties. In this study, Co-doped hausmannites with final Co/Mn molar ratios of 0.05 and 0.11 were synthesized and characterized by wet chemical analysis, powder X-ray diffraction (XRD), Fourier transformed infrared spectra (FTIR), high resolution transmission electron microscope (HRTEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure spectroscopy (XAFS). Co-doped samples have larger crystallite sizes and smaller specific surface areas than those of the hausmannite without Co. The Co cations exist in a mixed-valence of +3 and + 2. Powder XRD and acid dissolution experiments indicate that Co incorporates into the mineral structures, and increases the mineral structural stability. Co K-edge extended X-ray adsorption fine structure (EXAFS) analysis demonstrates that Co likely substitutes for lattice Mn(III). After aging at room temperature for three years, 14.1 ± 1.9% of pure hausmannite is transformed to manganite while only 2.6 ± 0.7% of manganite appears in the aged Co-doped sample with an initial Co/Mn molar ratio of 0.10. Finally, these results provide new insights into the incorporation mechanisms of TMs into low valence Mn oxides, and the stability of these minerals in natural environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mixed-strategy approach to band-edge analysis and modeling in semiconductors

In semiconductor physics, the Urbach rule describes an exponential dependence of the UV-Vis absorption coefficient on photon energy at the band edge. The rule is so ubiquitously applied that a single common mechanism, variability in the local potential, is generally considered to be the cause of exponential band edges. Variability in the local potential may be caused by alloy inhomogeneity, structural defects, impurities, thermal excitation, or any other mechanism that interrupts ideal crystallinity and creates disorder. A crucial point of the Urbach rule is its development for band edges which approach linearity when plotted on a logarithmic scale. The rule was not developed in the context of nonlinear band edges with complex fine structure. Even so, this model has been applied extensively to band edges with such features. Using differential analysis and deconvolution, we develop an analytical technique capable of separating the components responsible for the fine structure observed. This approach reduces challenging signal-artifact convolution problems to a simple linear combination. Furthermore, we develop a model that can be applied to the nonlinear band-edge signals extracted. In this work, we show that in the limiting case of linearity, our model is consistent with and produces the same results as the linear Urbach model. Our model is capable of bypassing “tailing” as an indirect measure of the spread in the local potential and gives a direct measure of this quantity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Probing fundamental constant oscillation in the Galactic Center with S-Star Spectroscopy

Astrophysical spectroscopy provides a powerful probe of spacetime variations of fundamental constants, as atomic and ionic emission and absorption lines depend sensitively on the fine-structure constant. In particular, coherent temporal oscillations induced by an ultralight scalar background produce characteristic, time-resolved signatures that can be robustly disentangled from intrinsic variability. In the Galactic Center, such scalar backgrounds can be substantially enhanced, either through the formation of dense scalar clouds powered by black hole rotational energy extraction or as ultralight scalar dark matter forming a soliton-like core. These scalar configurations generically induce oscillations of the fine-structure constant, with periods set by the scalar mass and spatial profiles determined by the scalar wavefunction and its coupling to the electromagnetic sector. We show that precise, time-resolved spectroscopy of S-stars orbiting the supermassive black hole Sgr A^* provides a sensitive test of these effects, enabling constraints on quadratic scalar-photon couplings in the exceptionally high boson-density environment of the Galactic Center.

Bai, Zhaoyu [Weizmann Inst.] (ORCID:00000002075815↗

Unveiling the Mechanism of Mn Dissolution Through a Dynamic Cathode‐Electrolyte Interphase on LiMn2O4

Abstract Understanding the formation and evolution of the cathode‐electrolyte interphase (CEI), which forms at the interface between the cathode and electrolyte, is crucial for revealing degradation mechanisms in cathode materials, especially for developing strategies to stabilize the interphase in the strongly oxidizing conditions that evolve at high operating voltages in next‐generation Li‐ion batteries. However, The present understanding of the CEI is challenged by its complex and dynamic nature. In this work, near‐edge X‐ray absorption fine structure spectroscopy, electrochemical characterization, and reactive molecular dynamics simulations are combined to reveal a mechanism for CEI formation and evolution above model LiMn 2 O 4 (LMO) thin‐film electrodes in contact with conventional carbonate‐based electrolytes. It is found that Mn dissolution from LMO can be understood in terms of repetitive Mn 3 O 4 formation and dissolution behavior during cycling, which is closely connected to electrolyte decomposition and a key aspect of the CEI formation and growth. The behavior of the CEI in this model system offers detailed insight into the dynamic chemistry of the interphase, underscoring the important role of electrolyte composition and cathode surface structure in interphase degradation.

Ou, Wenhan↗

Circular dichroism in hard X-ray photoelectron diffraction observed by time-of-flight momentum microscopy

X-ray photoelectron diffraction (XPD) is a powerful technique that yields detailed structural information of solids and thin films that complements electronic structure measurements. Among the strongholds of XPD we can identify dopant sites, track structural phase transitions, and perform holographic reconstruction. High-resolution imaging of k ll -distributions (momentum microscopy) presents a new approach to core-level photoemission. It yields full-field k x -k y XPD patterns with unprecedented acquisition speed and richness in details. Here, we show that beyond the pure diffraction information, XPD patterns exhibit pronounced circular dichroism in the angular distribution (CDAD) with asymmetries up to 80%, alongside with rapid variations on a small k ll -scale (0.1 Å -1 ). Measurements with circularly-polarized hard X-rays (hν = 6 keV) for a number of core levels, including Si, Ge, Mo and W, prove that core-level CDAD is a general phenomenon that is independent of atomic number. The fine structure in CDAD is more pronounced compared to the corresponding intensity patterns. Additionally, they obey the same symmetry rules as found for atomic and molecular species, and valence bands. Further, the CD is antisymmetric with respect to the mirror planes of the crystal, whose signatures are sharp zero lines. Calculations using both the Bloch-wave approach and one-step photoemission reveal the origin of the fine structure that represents the signature of Kikuchi diffraction. To disentangle the roles of photoexcitation and diffraction, XPD has been implemented into the Munich SPRKKR package to unify the one-step model of photoemission and multiple scattering theory.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

In situ x-ray absorption investigations of a heterogenized molecular catalyst and its interaction with a carbon nanotube support

A highly active heterogenized molecular CO 2 reduction catalyst on a conductive carbon support is investigated to identify if its improved catalytic activity can be attributed to strong electronic interactions between catalyst and support. The molecular structure and electronic character of a [Re +1 (tBu-bpy)(CO) 3 Cl] (tBu-bpy = 4,4'-tert-butyl-2,2'-bipyridine) catalyst deposited on multiwalled carbon nanotubes are characterized using Re L 3 -edge x-ray absorption spectroscopy under electrochemical conditions and compared to the homogeneous catalyst. The Re oxidation state is characterized from the near-edge absorption region, while structural changes of the catalyst are assessed from the extended x-ray absorption fine structure under reducing conditions. Chloride ligand dissociation and a Re-centered reduction are both observed under applied reducing potential. The results confirm weak coupling of [Re(tBu-bpy)(CO) 3 Cl] with the support, since the supported catalyst exhibits the same oxidation changes as the homogeneous case. However, these results do not preclude strong interactions between a reduced catalyst intermediate and the support, preliminarily investigated here using quantum mechanical calculations. Thus, our results suggest that complicated linkage schemes and strong electronic interactions with the initial catalyst species are not required to improve the activity of heterogenized molecular catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Brightening of Dark States in CsPbBr 3 Quantum Dots Caused by Light–Induced Magnetism

Lead halide perovskite quantum dots (QDs) have shown great potential for optoelectronic and quantum photonic applications. Although controversy remains about the electronic fine structures of bulk perovskites due to the strong spin-orbit coupling affecting the conduction bands, compelling evidence indicates that the ground states of perovskite QDs remain dark, limiting their applications in optoelectronic devices. In this study, it is demonstrated that photoexcitation can induce large intrinsic magnetic fields in Mn-doped CsPbBr 3 perovskite QDs. Equivalent to applying an external magnetic field, the light-induced field causes giant Zeeman splitting to the bright triplet states and brightens the dark singlet ground state, thus effectively rendering a partially bright ground state in the doped QDs. These findings here may contribute to the understanding of the electronic fine structures in perovskite QDs and demonstrate a potential approach for creating semiconductor nanostructures that can serve as bright light sources.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Alpha-alpha scattering in the Multiverse

We investigate the phase shifts of low-energy α-α scattering under variations of the fundamental parameters of the Standard Model, namely the light quark mass, the electromagnetic fine-structure constant as well as the QCD θ-angle. As a first step, we recalculate α-α scattering in our Universe utilizing various improvements in the adiabatic projection method, which leads to an improved, parameter-free prediction of the S- and D-wave phase shifts for laboratory energies below 10 MeV. We find that positive shifts in the pion mass have a small effect on the S-wave phase shift, whereas lowering the pion mass adds some repulsion in the two-alpha system. The effect on the D-wave phase shift turns out to be more pronounced as signaled by the D-wave resonance parameters. Variations of the fine-structure constant have almost no effect on the low-energy α-α phase shifts. We further show that up-to-and-including next-to-leading order in the chiral expansion, variations of these phase shifts with respect to the QCD θ-angle can be expressed in terms of the θ-dependent pion mass.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

In situ EXAFS study of Sr adsorption on TiO 2 (110) under high ionic strength wastewater conditions

In order to provide important details concerning the adsorption reactions of Sr, batch reactions and a set of both ex situ and in situ Grazing Incidence X-ray Absorption Fine Structure (GIXAFS) adsorption experiments were completed on powdered TiO 2 and on rutile(110), both reacted with either SrCl 2 or SrCO 3 solutions. TiO 2 sorption capacity for strontium (Sr) ranges from 550 ppm (SrCl 2 solutions, second order kinetics) to 1400 ppm (SrCO 3 solutions, first order kinetics), respectively, and is rapid. Sr adsorption decreased as a function of chloride concentration but significantly increased as carbonate concentrations increased. In the presence of carbonate, the ability of TiO 2 to remove Sr from the solution increases by a factor of ~4 due to rapid epitaxial surface precipitation of an SrCO 3 thin film, which registers itself on the rutile(110) surface as a strontianite-like phase (d-spacing 2.8 Å). Extended X-ray Absorption Fine Structure (EXAFS) results suggest the initial attachment is via tetradental inner-sphere Sr adsorption. Moreover, adsorbates from concentrated SrCl 2 solutions contain carbonate and hydroxyl species, which results in both inner- and outer-sphere adsorbates and explains the reduced Sr adsorption in these systems. These results not only provide new insights into Sr kinetics and adsorption on TiO 2 but also provide valuable information concerning potential improvements in effluent water treatment models and are pertinent in developing treatment methods for rutile-coated structural materials within nuclear power plants.

54 ENVIRONMENTAL SCIENCES↗

Improved quasiparticle self-consistent electronic band structure and excitons in β – LiGaO 2

The band structure of β–LiGaO 2 is calculated using the quasiparticle self-consistent QSGWˆ method where the screened Coulomb interaction Wˆ is evaluated including electron-hole interaction ladder diagrams and G is the one-electron Green's function. Improved convergence compared to previous calculations leads to a significantly larger band gap of about 7.0 eV. However, exciton binding energies are found to be large and lead to an exciton gap of about 6.0 eV if also a zero-point-motion correction of about –0.4 eV is included. Furthermore, these results are in excellent agreement with recent experimental results on the onset of absorption. Besides the excitons observed thus far, the calculations indicate the existence of a Rydberg-like series of exciton excited states, which is however modified from the classical Wannier exciton model by the anisotropies of the material and the more complex mixing of Bloch states in the excitons resulting from the Bethe-Salpeter equation. The exciton fine structure and the exciton wave functions are visualized and analyzed in various ways.

36 MATERIALS SCIENCE↗

Nitrate-To-Ammonia Electroconversion at Neutral pH on Polycrystalline Vanadium Sulfide Derived from Vanadium Disulfide

The electrochemical nitrate reduction reaction (NO3RR) offers a pathway to produce NH3 for fuel and fertilizer from waste NO3-. In this work, a polycrystalline vanadium sulfide (VSx), which is derived from solvothermally grown and annealed VS2, is shown to exhibit excellent NO3RR activity (2.3 +- 0.6 mg.cm-2 geo..h-1 @ -0.92 VRHE) and Faradaic efficiency to NH4+ (69 +- 6% at -0.69 VRHE) in buffered neutral pH electrolyte containing 0.1 M NO3-. A variety of characterization techniques are leveraged to support the VSx assignment, including X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, selected area electron diffraction, and X-ray diffraction measurements. The VS2 annealing step reduces the oxide character and generates VSx, which, based on the improved NO3RR activity, results in the creation of active sites for NO3- binding. To help shed light on NO3RR on VSx, VS2 is used as a model system, and a grand-canonical density functional theory (GC-DFT) investigation of VS2 shows strong evidence that S vacancies are active sites for NO3RR, where NO3- outcompetes H+ for adsorption at the S-vacancy sites. Moreover, GC-DFT results highlight a thermodynamically favorable reaction to generate NH4+ in an aqueous electrolyte at relevant cathodic potentials. As an annealed material, VSx may contain undersaturated V sites, which show an electronic structure similar to the theoretically calculated S-vacancy site of VS2, and these sites may contribute to the observed increase in NO3RR activity and selectivity for NH4+ on VSx versus unannealed VS2. Finally, kinetic isotope effect measurements suggest that the kinetic rate-limiting step of the NO3RR on VSx is not proton-coupled, indicating it may be the first electron transfer to adsorbed NO3*.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalytic Water Electrolysis by Co–Cu–W Mixed Metal Oxides: Insights from X-ray Absorption Spectroelectrochemistry

Mixed metal oxides (MMOs) are a promising class of electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Despite their importance for sustainable energy schemes, our understanding of relevant reaction pathways, catalytically active sites, and synergistic effects is rather limited. Here, we applied synchrotron-based X-ray absorption spectroscopy (XAS) to explore the evolution of the amorphous Co–Cu–W MMO electrocatalyst, shown previously to be an efficient bifunctional OER and HER catalyst for water splitting. Ex situ XAS measurements provided structural environments and the oxidation state of the metals involved, revealing Co 2+ (octahedral), Cu + / 2+ (tetrahedral/square-planar), and W 6+ (octahedral) centers. Operando XAS investigations, including X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), elucidated the dynamic structural transformations of Co, Cu, and W metal centers during the OER and HER. The experimental results indicate that Co 3+ and Cu 0 are the active catalytic sites involved in the OER and HER, respectively, while Cu 2+ and W 6+ play crucial roles as structure stabilizers, suggesting strong synergistic interactions within the Co–Cu–W MMO system. In conclusion, these results, combined with the Tafel slope analysis, revealed that the bottleneck intermediate during the OER is Co 3+ hydroperoxide, whose formation is accompanied by changes in the Cu–O bond lengths, pointing to a possible synergistic effect between Co and Cu ions. Our study reveals important structural effects taking place during MMO-driven OER/HER electrocatalysis and provides essential experimental insights into the complex catalytic mechanism of emerging noble-metal-free MMO electrocatalysts for full water splitting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deciphering the Solvent Effect for the Solvation Structure of Ca 2+ in Polar Molecular Liquids

Although the crystal structures for many inorganic compounds are readily available, researchers are still working hard to understand the relations between the structures and chemical properties of solutions because most of the chemical reactions take place in solutions. A huge amount of effort has been put toward modeling the ion solvation structure from the perspectives of both experiments and theories. In this study, the solvation structures of Ca 2+ ions in aqueous and alcoholic solutions at different concentrations were carefully evaluated by Ca K-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses. Further, density functional theory (DFT) calculations were also performed to correlate the results with the experimental data and then further extended to other similar systems. It was found that the number of coordinating solvent molecules decreases with increasing Ca 2+ concentration and increasing solvent molecule sizes. From the EXAFS data, it was observed that the first solvation shell of Ca 2+ splits into two Ca-O distances in a methanol solution and the counter ion Cl - might also be within the first shell at high concentrations. For the first time, the effects of solvents with different polarities and sizes on the ion solvation environment were systematically evaluated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In Situ Determination of Speciation and Local Structure of NaCl–SrCl 2 and LiF–ZrF 4 Molten Salts

Understanding the local environment of the metal atoms in salt melts is important for modeling the properties of melts and predicting their behavior and thus helping enable the development of technologies such as molten salt reactors and solar-thermal power systems and new approaches to recycling rare-earth metals. Toward that end, we have developed an in situ approach for measuring the coordination of metals in molten salt coupling X-ray absorption spectroscopy (XAS) and Raman spectroscopy. Our approach was demonstrated for two salt mixtures (1.9 and 5 mol % SrCl 2 in NaCl, 0.8 and 5 mol % ZrF 4 in LiF) at up to 1100 °C. Near-edge (X-ray absorption near-edge structure, XANES) and extended X-ray absorption fine structure (EXAFS) spectra were measured. The EXAFS response was modeled using ab initio FEFF calculations. Strontium’s first shell is observed to be coordinated with chlorine (Sr 2+ –Cl – ) and zirconium’s first shell is coordinated by fluorine (Zr 4+ –F – ), both having coordination numbers that decrease with increasing temperature. Multiple zirconium complexes are believed to be present in the melt, which may interfere and distort the EXAFS spectra and result in an anomalously low zirconium first shell coordination number. Finally, the use of boron nitride (BN) powder as a salt diluent for XAFS measurements was found to not interfere with measurements and thus can be used for investigations of such systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of oxidation on the release of multiple metals from industrially polluted sediments and synchrotron-based evidence of Cu–S dynamic association

Disposal operations for industrially polluted sediments are usually accompanied by disturbance and resuspension, which can induce metal remobilization and secondary pollution. Evaluating the risk of metal release under various redox conditions is fundamental for predicting contaminant mobilization and guiding remediation measures. An abandoned oxidation pond, Yanjia Lake, China, was selected as a typical industrially polluted site. Re-suspension experiments were carried out by mixing polluted sediments with lake water under oxic or anoxic conditions, then investigating the effect of oxidation conditions on the release of multiple metals. Metal concentrations and aqueous chemistry in the overlying water were monitored. Synchrotron-based methods, including X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), were used to characterize oxidation states and coordination conditions of metals in sediments. The release of metals, including Cr, Co, Ni, Cu, Zn, Se, Mo, Sn, Cd, and Pb, was enhanced under oxic vs. anoxic conditions. The XANES analysis revealed that elevated Cr and Zn concentrations under oxic conditions likely resulted from the oxidation of Cr(III) and oxidizing dissolution of ZnS, respectively. K-edge Cu XANES, S XANES, and Cu EXAFS analyses reconstructed the Cu–S association, indicating that S-related oxidation promoted Cu release and Cu–O partly replaced Cu–S in the sediment after a 7-day oxic treatment. The release of most metals was promoted under oxic conditions, resulting from the oxidation of sulfides and metals as indicated by aqueous and synchrotron-based evidence. The risk of secondary pollution is greatly enhanced under oxic conditions, which suggests that measures should be taken to minimize the redox disturbance during sediment remediation. This information can guide the management of sediments in Yanjia Lake and other contaminated sites with similar properties.

54 ENVIRONMENTAL SCIENCES↗

Temporal Ni K-Edge X-ray Absorption Spectroscopy Study Reveals the Kinetics of the Ni Redox Behavior of the Iron-Nickel Oxide Bimetallic OER Catalyst

Operando X-ray absorption spectroscopy (XAS) can be utilized to probe the phase and structural changes of FeNiOx and similar transition metal oxide electrocatalysts during electrocatalytic reactions. However, capturing the temporal changes occurring in the operando chemistry of electrocatalysts has been little studied. Here, in this work, we successfully capture the time-resolved changes at the Ni K-edge for both the X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) regions of an aqueous phase synthesized FeNiO x bimetallic nanoparticle electrocatalyst. During a stepped voltage experiment, the temporal change in the Ni K-edge was observed as the applied voltage was stepped from 0.7 to 0.8 V versus the silver/silver chloride reference electrode, and the change observed is associated with the Ni redox transition from the 2+ to 3+/4+ oxidation state. Individual XAS spectra were obtained in 90 s, and a total of 9 scans post voltage step showed a unique transition from a hydroxide to an oxyhydroxide phase. The shift in absorption edge energy position and the changes in spectral shape for individual scans explain the typically observed broadening of the Ni K-edge XANES spectrum during time-averaged operando XAS, and a kinetic analysis revealed a first-order observed rate constant, |k obs |, of 0.00426 s –1 and a half-life (t 1/2 ) of 163 s. Multivariate curve resolution-alternating least squares analysis followed by linear combination fitting analysis for time-averaged versus time-resolved Ni K-edge changes upon voltage step show distinct differences in estimated contributions from Ni 2+ oxide/hydroxide phases. Detailed EXAFS modeling shows the phase transition from hydroxide to oxyhydroxide on top of the unchanged metallic core.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗