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At least 433 records · Page 24

Proximity Magnetism in Mn(Bi,Sb) 2 Te 4 –(Bi,Sb) 2 Te 3 /MnTe Natural Heterostructures

Magnetic topological insulators and their heterostructures provide significant opportunities to couple band topology with a nontrivial spin configuration for enhanced spintronic device performance, as well as designing magnetoelectric systems and functionalities. We find that Mn interdiffusion from MnTe when interfaced with (Bi,Sb) 2 Te 3 stabilizes as self-organized Mn(Bi,Sb) 2 Te 4 septuple lamellae among alternating (Bi,Sb) 2 Te 3 quintuple layers, as observed using scanning transmission electron microscopy and depth-sensitive polarized neutron reflectometry. We further demonstrate a valuable combination of magnetic and topological orders in these naturally formed Mn(Bi,Sb) 2 Te 4 –(Bi,Sb) 2 Te 3 heterostructures, which are exchange-coupled with MnTe. Magnetotransport experiments and quantum magnetism simulations reveal that, above its own Néel temperature T N ∼ 20 K, Mn(Bi,Sb) 2 Te 4 mediates the exchange field leading to an anomalous Hall effect at the (Bi,Sb) 2 Te 3 /MnTe interface, with an enhanced interfacial T N exceeding 200 K, approaching that of the bulk MnTe. This magnetic interface, in turn, allows a robust and deterministic spin–orbit torque switching without an external magnetic field at a low critical current density of 3 × 10 5 A cm –2 . The antiferromagnetically coupled architecture of Mn(Bi,Sb) 2 Te 4 –(Bi,Sb) 2 Te 3 /MnTe, featuring magnetic and topological proximity effects across a chalcogenide backbone, is rich in fundamental interface physics and holds the potential for practical applications in spintronics.

magnetic topological insulator↗

Integrating Ultra-Coarse-Grained Protein Models into Accessible Workflows for Multiscale Molecular Dynamics

To capture protein conformational transitions using molecular dynamics (MD), several simulation resolutions covering different spatial and temporal scales are typically needed. All-atom (AA) simulations provide fine resolution, but are computationally infeasible for large systems over longer durations. Coarse-grained (CG) and ultra-coarse-grained (UCG) models have a lower resolution and computational cost while still being able to conserve essential protein features. Prior work on a Multiscale Machinelearned Modeling Infrastructure (MuMMI) combined both AA and CG simulations to study RAS-RAF protein interactions, leveraging CG models for longer time scales and using AA to investigate unusual conformations in greater detail. However, MuMMI is still resource-intensive, and this study aims to maximize exploration of the protein conformational space while reducing computational cost. In this paper, we build on prior work that integrates UCG models based on heterogeneous elastic network modeling (hENM) into the MuMMI workflow. We demonstrate that UCG models enable accurate sampling of protein conformations, focusing on simulating RAS-RAF protein interactions. Using higher-resolution CG Martini simulation data, we can automatically refine intramolecular interactions in UCG models. We present a scalable Python package that uses fluctuations observed in higher-resolution CG Martini simulations to estimate bond coefficients of the UCG model. We built novel machine learning-based backmapping methods to recover more detailed CG Martini structures from UCG structures, using diffusion models to learn the mapping between scales. Finally, we present UCG-mini-MuMMI, an accessible and less compute-intensive version of MuMMI as a resource for the scientific community. Incorporating UCG models into MD studies is applicable to a broad range of systems and proteins, and our study offers insights into the advantages and limitations of these methods.

Chemical structure↗

Surface Chemistry and Particle Morphology Changes in Pine Biomass under Indirect Thermal Gradients: Implications for Feed Screw Design

The conversion of biomass feedstocks into fuels and chemicals using fast pyrolysis is a promising approach to renewable energy. Feed screws that convey biomass to pyrolysis reactors, however, often encounter plugging. Indirect heating of the feed screw occurs due to contact with the pyrolysis chamber, resulting in a heating gradient ranging from ambient temperature (22 °C) to reactor temperature (500 °C). Given that major cell wall macromolecules, such as lignin, cellulose, and hemicellulose, begin to produce bio-oils and volatile resin acid compounds within this temperature gradient, we hypothesized that indirect heating during feed screw conveyance is sufficient to cause premature degradation of biomass. We characterized this degradation by observing increases in surface roughness, changes in overall particle morphology, and the production and deposition of bio-oils on biomass particle surfaces. Correlative analysis between optical in situ hot-stage microscopy, confocal Raman spectroscopy, and SEM analysis revealed that heating at temperatures as low as 375 °C caused significant increases in surface roughness, with large fissures forming between and within cell walls. Additionally, droplets of bio-oil were observed on particles, especially in the bark and cambium samples. This work suggests that these phenomena contribute to particle agglomeration, leading to feed screw plugging, and that engineering a solution to cool the feed screw could prevent particle agglomeration and reduce plugging incidents, thereby increasing biomass processing efficiency.

09 BIOMASS FUELS↗

Along the Channel Gradients Impact on the Spatioactivity of Gas Diffusion Electrodes at High Conversions during CO 2 Electroreduction

Results of a 2-D transport model for a gas diffusion electrode performing CO 2 reduction to CO with a flowing catholyte are presented, including the concentration gradients along the flow cell, spatial distribution of the current density and local pH in the catalyst layer. The model predicts that both the concentration of CO 2 and the buffer electrolyte gradually diminish along the channels for a parallel flow of gas and electrolyte as a result of electrochemical conversion and nonelectrochemical consumption. At high single-pass conversions, significant concentration gradients exist along the flow channels leading to large local variations in the current density (>150 mA/cm 2 ), which becomes prominent when compared to ohmic losses. In addition, concentration overpotentials change dramatically with CO 2 flow rate, which results in significant differences in outlet concentrations at high conversions. The outlet concentration of CO attains a maximum of 80% along with 5% CO 2 and 15% H 2 , although the maximum single-pass conversion is limited to below 60% due to homogeneous consumption by the electrolyte. Fundamental and practical implications of our findings on electrochemical CO 2 reduction are discussed with a focus on the trade-off between high current density operation and high single-pass conversion efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing Heterogeneous Charge Distributions at the α-Al 2 O 3 (0001)/H 2 O Interface

Unlike metal or semiconductor electrodes, the surface charge resulting from the protonation or deprotonation of insulating mineral oxides is highly localized and heterogeneous in nature. In this work the Stark active C≡N stretch of potassium thiocyanate is used as a molecular probe of the heterogeneity of the interfacial electrostatic potential at the α-Al 2 O 3 (0001)/H 2 O interface. Vibrational sum frequency generation (vSFG) measurements performed in the OH stretching region suggest that thiocyanate species organize interfacial water similarly to halide ions. Changes in the electrostatic potential are then tracked via Stark shifts of the vibrational frequency of the thiocyanate stretch. Our vSFG measurements show that we can simultaneously measure the vSFG response of SCN – ions experiencing charged and neutral surface sites. We assign local potentials of +308 and -154 mV to positively and negatively charged aluminol groups that are present at pH = 4 and pH = 10, respectively. Thiocyanate anions at positively charged surface sites and negatively charged surface sites and those participating in contact ion pairing adopt similar orientations and are oppositely oriented relative to thiocyanate ions near neutral surface sites. All four species followed Langmuir adsorption isotherms. Density functional theory–molecular dynamics (DFT-MD) simulations of SCN – near the neutral α-Al 2 O 3 (0001)/H 2 O interface show that the vSFG response in the C≡N stretch region originates from a SCN–H–O–Al complex, suggesting the surface site specificity of these experiments. To our knowledge this is the first spectroscopic measurement of local potentials associated with a heterogeneously charged surface. The ability to probe the evolution of local charges in situ could provide vital insight into many industrial, electrochemical, and geochemically relevant interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photochemical C( sp )–C( sp 2 ) Bond Activation in Phosphaalkynes: A New Route to Reactive Terminal Cyaphido Complexes L n M–C≡P

The photochemical activation of the C(sp)–C(sp 2 ) bond in Pt(0)-η 2 -aryl-phosphaalkyne complexes leads selectively to coordination compounds of the type L n Pt(aryl)(C≡P). The oxidative addition reaction is a novel, clean, and atom-economic route for the synthesis of reactive terminal Pt(II)-cyaphido complexes, which can undergo [3 + 2] cycloaddition reactions with organic azides, yielding the corresponding Pt(II)-triazaphospholato complexes. The C–C bond cleavage reaction is thermodynamically uphill. Upon heating, the reverse and quantitative reductive elimination toward the Pt(0)-phosphaalkyne-π-complex is observed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Watching Excited State Dynamics with Optical and X-ray Probes: The Excited State Dynamics of Aquocobalamin and Hydroxocobalamin

Femtosecond time-resolved X-ray absorption (XANES) at the Co K-edge, X-ray emission (XES) in the Co Kβ and valence-to-core regions, and broadband UV–vis transient absorption are combined to probe the femtosecond to picosecond sequential atomic and electronic dynamics following photoexcitation of two vitamin B12 compounds, hydroxocobalamin and aquocobalamin. Polarized XANES difference spectra allow identification of sequential structural evolution involving first the equatorial and then the axial ligands, with the latter showing rapid coherent bond elongation to the outer turning point of the excited state potential followed by recoil to a relaxed excited state structure. Time-resolved XES, especially in the valence-to-core region, along with polarized optical transient absorption suggests that the recoil results in the formation of a metal-centered excited state with a lifetime of 2–5 ps. In conclusion, this combination of methods provides a uniquely powerful tool to probe the electronic and structural dynamics of photoactive transition-metal complexes and will be applicable to a wide variety of systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Indolo[2,3- b ]quinoxaline as a Low Reduction Potential and High Stability Anolyte Scaffold for Nonaqueous Redox Flow Batteries

Redox flow batteries (RFBs) are a promising stationary energy storage technology for leveling power supply from intermittent renewable energy sources with demand. A central objective for the development of practical, scalable RFBs is to identify affordable and high-performance redox-active molecules as storage materials. Herein, we report the design, synthesis, and evaluation of a new organic scaffold, indolo[2,3-b]quinoxaline, for highly stable, low-reduction potential, and high-solubility anolytes for nonaqueous redox flow batteries (NARFBs). The mixture of 2- and 3-(tert-butyl)-6-(2-methoxyethyl)-6H-indolo[2,3-b]quinoxaline exhibits a low reduction potential (-2.01 V vs Fc/Fc + ), high solubility (>2.7 M in acetonitrile), and remarkable stability (99.86% capacity retention over 49.5 h (202 cycles) of H-cell cycling). This anolyte was paired with N-(2-(2-methoxyethoxy)-ethyl)phenothiazine (MEEPT) to achieve a 2.3 V all-organic NARFB exhibiting 95.8% capacity retention over 75.1 h (120 cycles) of cycling.

25 ENERGY STORAGE↗

Chemical Kinetic Method for Active-Site Quantification in Fe-N-C Catalysts and Correlation with Molecular Probe and Spectroscopic Site-Counting Methods

Mononuclear Fe ions ligated by nitrogen (FeN x ) dispersed on nitrogen-doped carbon (Fe-N-C) serve as active centers for electrocatalytic O 2 reduction and thermocatalytic aerobic oxidations. Despite their promise as replacements for precious metals in a variety of practical applications, such as fuel cells, the discovery of new Fe-N-C catalysts has relied primarily on empirical approaches. In this context, the development of quantitative structure–reactivity relationships and benchmarking of catalysts prepared by different synthetic routes and by different laboratories would be facilitated by the broader adoption of methods to quantify atomically dispersed FeN x active centers. In the present study, we develop a kinetic probe reaction method that uses the aerobic oxidation of a model hydroquinone substrate to quantify the density of FeN x centers in Fe- N-C catalysts. The kinetic method is compared with low-temperature Mössbauer spectroscopy, CO pulse chemisorption, and electrochemical reductive stripping of NO derived from NO 2 – on a suite of Fe-N-C catalysts prepared by diverse routes and featuring either the exclusive presence of Fe as FeN x sites or the coexistence of aggregated Fe species in addition to FeN x . The FeN x site densities derived from the kinetic method correlate well with those obtained from CO pulse chemisorption and Mössbauer spectroscopy. The broad survey of Fe-N-C materials also reveals the presence of outliers and challenges associated with each site quantification approach. Furthermore, the kinetic method developed here does not require pretreatments that may alter active-site distributions nor specialized equipment beyond reaction vessels and analytical instrumentation (e.g., NMR).

36 MATERIALS SCIENCE↗

Characterization of Deformational Isomerization Potential and Interconversion Dynamics with Ultrafast X-ray Solution Scattering

Dimeric complexes composed of d 8 square planar metal centers and rigid bridging ligands provide model systems to understand the interplay between attractive dispersion forces and steric strain in order to assist the development of reliable methods to model metal dimer complexes more broadly. [Ir 2 (dimen) 4 ] 2+ (dimen = para-diisocyanomenthane) presents a unique case study for such phenomena, as distortions of the optimal structure of a ligand with limited conformational flexibility counteract the attractive dispersive forces from the metal and ligand to yield a complex with two ground state deformational isomers. Here, in this work, we use ultrafast X-ray solution scattering (XSS) and optical transient absorption spectroscopy (OTAS) to reveal the nature of the equilibrium distribution and the exchange rate between the deformational isomers. The two ground state isomers have spectrally distinct electronic excitations that enable the selective excitation of one isomer or the other using a femtosecond duration pulse of visible light. We then track the dynamics of the nonequilibrium depletion of the electronic ground state population—often termed the ground state hole—with ultrafast XSS and OTAS, revealing a restoration of the ground state equilibrium in 2.3 ps. This combined experimental and theoretical study provides a critical test of various density functional approximations in the description of bridged d 8 –d 8 metal complexes. The results show that density functional theory calculations can reproduce the primary experimental observations if dispersion interactions are added, and a hybrid functional, which includes exact exchange, is used.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Time-Resolved X-ray Emission Spectroscopy and Synthetic High-Spin Model Complexes Resolve Ambiguities in Excited-State Assignments of Transition-Metal Chromophores: A Case Study of Fe-Amido Complexes

To fully harness the potential of abundant metal coordination complex photosensitizers, a detailed understanding of the molecular properties that dictate and control the electronic excited-state population dynamics initiated by light absorption is critical. In the absence of detectable luminescence, optical transient absorption (TA) spectroscopy is the most widely employed method for interpreting electron redistribution in such excited states, particularly for those with a charge-transfer character. The assignment of excited-state TA spectral features often relies on spectroelectrochemical measurements, where the transient absorption spectrum generated by a metal-to-ligand charge-transfer (MLCT) electronic excited state, for instance, can be approximated using steady-state spectra generated by electrochemical ligand reduction and metal oxidation and accounting for the loss of absorptions by the electronic ground state. However, the reliability of this approach can be clouded when multiple electronic configurations have similar optical signatures. Using a case study of Fe(II) complexes supported by benzannulated diarylamido ligands, we highlight an example of such an ambiguity and show how time-resolved X-ray emission spectroscopy (XES) measurements can reliably assign excited states from the perspective of the metal, particularly in conjunction with accurate synthetic models of ligand-field electronic excited states, leading to a reinterpretation of the long-lived excited state as a ligand-field metal-centered quintet state. Furthermore, a detailed analysis of the XES data on the long-lived excited state is presented, along with a discussion of the ultrafast dynamics following the photoexcitation of low-spin Fe(II)-N amido complexes using a high-spin ground-state analogue as a spectral model for the 5 T 2 excited state.

14 SOLAR ENERGY↗

Regioisomeric Engineering for Multicharge and Spin Stabilization in Two-Electron Organic Catholytes

Developing multicharge and spin stabilization strategies is fundamental to enhancing the lifetime of functional organic materials, particularly for long-term energy storage in multiredox organic redox flow batteries. Current approaches are limited to the incorporation of electronic substituents to increase or decrease the overall electron density or bulky substituents to sterically shield reactive sites. With the aim to further expand the molecular toolbox for charge and spin stabilization, we introduce regioisomerism as a scaffold-diversifying design element that considers the collective and cumulative electronic and steric contributions from all of the substituents based on their relative regioisomeric arrangements. Through a systematic study of regioisomers of near-planar aromatic cyclic triindoles and nonplanar nonaromatic cyclic tetraindoles, we demonstrate that this regioisomeric engineering strategy significantly enhances the H-cell cycling stability in the above two new classes of 2e – catholytes, even when current strategies failed to stabilize the multicharged species. Density functional theory calculations reveal that the strategy operates by redistributing the charge and spin densities while highlighting the role of aromaticity in charge stabilization. The most stable 2e – catholyte candidate was paired with a viologen derivative anolyte to achieve a proof-of-concept all-organic flow battery with 1.26–1.49 V, 98% capacity retention, and only 0.0117% fade/h and 0.00563% fade/cycle over 400 cycles (192 h), which is the highest capacity retention ever reported over 400 cycles in a multielectron all-organic flow battery setup. We anticipate regioisomeric engineering to be a promising strategy complementary to conventional electronic and steric approaches for multicharge and spin stabilization in other functional organic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Excited State Covalency, Dynamics, and Photochemistry of Square Planar Ni-Thiolate Complexes Revealed by Ultrafast X-ray Absorption

Highly covalent Ni bis(dithiolene) and related complexes provide an ideal platform for investigating the effects of metal–ligand orbital hybridization on excited state character and dynamics. In particular, we focus on the ligand field excited states that dominate the photophysics of first-row transition metal complexes. Here, we investigate if they can be significantly delocalized off the metal center, possibly yielding photochemical reactivity more similar to charge transfer excited states than metal-centered ligand field excited states. Here [Ni(mpo) 2 ] (mpo = 2-mercaptopyridine- N-oxide) provides a representative example for the larger chemical class and is an active electro- and photo-catalyst for proton reduction. A detailed characterization of the excited state electronic structure, dynamics, and photochemistry of [Ni(mpo) 2 ] is presented based on ultrafast transient X- ray absorption spectroscopy at the Ni and S 1s core absorption K-edges. By comparing the ultrafast Ni K-edge absorption to ab initio calculations, we identify an excited state relaxation mechanism where an initial ligand-to-metal charge transfer excitation results in both excited state electron transfer (generating a catalytically relevant reduced photoproduct [Ni(mpo) 2 ] − ) and relaxation to a pseudo-tetrahedral triplet ligand field excited state. From the ultrafast S K-edge absorption, the ligand field excited state is found to be highly delocalized onto the thiolate ligands and a tetrahedral structural distortion is shown to substantially influence the degree of delocalization. The results identify a significant structural coordinate to target when aiming to control the excited state covalency in square planar complexes.

Lim, Hyeongtaek [SLAC National Accelerator Laborat↗

Orientation-Driven Chirality Funnels in Chiral Low-Dimensional Lead-Halide Perovskite Heterostructures

Chiral hybrid metal-halide perovskites show low-symmetry crystal structures, large Rashba splitting, spin-filtering, and strong chiroptical activity. Circular dichroism and circularly polarized photoluminescence have been investigated in chiral perovskites with increasingly distorted chiral structures. Here, we report the fabrication of chiral (R/S)-EBAPbI3 (EBA = α-ethylbenzylamine) single crystals, which possess highly distorted octahedral structures with a high angle variance value of ∼68 degree2. Using control in the fabrication conditions, we transfer chiral single crystals to thin films and achieve different crystal orientation preferences that induce tunable chiroptical properties to their heterostructures with PbI2 nanodomains, which we characterize with in situ X-ray diffraction and grazing-incidence wide-angle X-ray scattering measurements. Using transient chiroptical spectroscopies, we resolve photoexcited charge carrier dynamics and chirality transfer processes in such heterostructures down to cryogenic temperatures. We observe rapid carrier transfer along the in-plane (002) facets in chiral perovskite phases to PbI2 nanostructures within the initial few picoseconds, while carrier transfer along the out-of-plane (002) facets occurs at a slower rate. This fast transfer process leads to high photoluminescence intensities and large degrees of circular polarization in the emission from PbI2 nanodomains at cryogenic temperatures. Our findings report a multidimensional chiral-achiral heterostructure which takes advantage of controllable chirality transfer and offers new routes for future spintronic and chiroptical applications.

Liu, Shangpu↗

Pursuing Heteroleptic Ligand Design Principles for Photoactive Fe Complexes with Ultrafast X-ray Emission and Variable-Temperature Optical Spectroscopies

Understanding the key parameters that govern the photophysical and photochemical properties of transition metal complexes is essential for the development of efficient photosensitizers for photocatalytic applications. Achieving this objective necessitates clear and detailed investigations of their electronic excited states, for which time-resolved metal Kβ X-ray emission spectroscopy (XES) has proven highly effective. Here, we present a time-resolved Fe Kβ XES study of a heteroleptic Fe(II) polypyridyl carbene complex, [Fe(phen) 2 (C 4 H 10 N 4 )] 2+ (1; phen = 1,10-phenanthroline), utilizing both the valence-to-core and Kβ mainline spectral regions, complemented by variable-temperature transient optical absorption (VT-TA) spectroscopy. Detailed analysis of the time-resolved Kβ XES data, supported by density functional theory (DFT) calculations and an Eyring analysis of the VT-TA data, reveals parallel excited state relaxation dynamics that support an assignment of the long-lived excited state to a triplet metal-centered state. Placing these results in the context of prior studies of heteroleptic Fe(II) polypyridyl cyanide complexes motivated a series of DFT calculations to investigate the effects of ligand structural flexibility and arrangement. These calculations reinforce the experimentally derived conclusion that constraining structural flexibility with multidentate ligands significantly impacts the excited state relaxation dynamics. Furthermore, our study emphasizes that the arrangement of strong field ligands in heteroleptic complexes substantially affects the energy of Jahn–Teller active triplet metal-centered states in low-spin d 6 metal complexes. Together, these findings provide synthetic design principles for extending metal-to-ligand charge transfer excited state lifetimes of heteroleptic Fe complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Flat Analyzer Polycapillary Spectrometer for X-ray Absorption Spectroscopy of Dilute Transition Metals at X-ray-Free Electron Lasers

X-ray absorption spectroscopy (XAS) coupled with highly intense pulses from an X-ray-free electron laser (XFEL) can be used to track ultrafast chemical dynamics. Nonetheless, measurements for dilute samples (≤1 mM) have been exceptionally challenging, as scattering background signals dominate over the sample’s X-ray fluorescence. We show that femtosecond time-resolved XAS measurements of sub-millimolar transition metal solutions are now possible at the Linac Coherent Light Source (LCLS) using a high-throughput polycapillary XAS spectrometer, designed, developed, and commissioned at LCLS and the Stanford Synchrotron Radiation Lightsource (SSRL). The instrument integrates three polycapillary optics that collect and collimate X-ray fluorescence emitted from the interaction point with a high solid angle. X-ray collimated fluorescence is then selectively diffracted by coupled graphite analyzer crystals. As a result, the contribution of scattered photons is suppressed. Experiments at the Pt L 3 -edge on 0.1 mM aqueous K 2 PtCl 6 (delivered via a 100 μm liquid jet) were successfully performed in the laser pump X-ray probe configuration at the LCLS XCS and XPP instruments. We report the transient spectra of hexachloroplatinate within the first 10 ps after a 266 nm photoexcitation. We observed a short-lived reduced intermediate (≈2 ps). The polycapillary X-ray spectrometer at LCLS now enables the efficient study of the dynamics of ultradilute transition metals in solution. This capability opens the door to investigating plasmonic systems, photocatalysts, enzymes, and other scarce and dilute samples.

LCLS↗