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At least 127 records · Page 7

Improved Stability of Oxysulfide Solid-State Electrolytes in Li(G3)TFSI Solvate Ionic Liquid Electrolyte

The performance of all solid-state batteries is limited by poor interfacial contact between active material and solid-state electrolyte (SSE) particles. Semi-solid batteries utilize a secondary electrolyte phase to wet the SSE/AM interface to improve cell performance. Solvate ionic liquids (SILs) are one class of liquid electrolytes under consideration for use in semi-solid batteries. This paper focuses on the Li(G3)TFSI SIL consisting of the bis(trifluoromethanesulfonyl)imide (TFSI − ) anion coupled to a [Li(G3)] + solvate cation. Sulfide SSEs are normally subject to nucleophilic attack by trigylme (G3), however, strong coordination of Li + to G3 in the [Li(G3)] + solvate cation prevents this reaction from taking place. Consequently, the stability of sulfide SSE depends on the ideal 1:1 molar ratio of G3 to TFSI, which may be difficult to maintain. We studied the chemical stability of 70Li 2 S·(30-x)P 2 S 5 ·xP 2 O 5 (x = 0, 2, 5, 10) (oxy)sulfide solid-state electrolyte in Li(G3)TFSI SIL. By physical measurement, UV–vis spectroscopy, electrochemical evaluation, X-ray photoelectron spectroscopy, and first principles calculation it is shown that increased oxygen content improves the stability of SSE in various Li(G3) x TFSI (x = 1, 2, 3, 4) liquid electrolytes. The results suggest that an oxysulfide SSE + SIL semi-solid electrolyte is a good choice for future semi-solid battery designs.

Electrochemistry↗

The Role of Cooperative Interactions Among Surfaces, Solvents, and Reactive Intermediates on Catalysis at Liquid–Solid Interfaces (Final Report DE-SC0020224)

This project established quantitative links between inner‑sphere chemistry (active metal identity, coordination, and zeolite topology) and outer‑sphere organization (solvent identity, hydrogen‑bond networks, and pore condensation) that govern rates, activation barriers, and selectivities for alkene epoxidation and epoxide ring‑opening at solid–liquid and quasi‑liquid–solid interfaces. We deconvoluted contributions from covalent interactions at active sites and noncovalent, solvent‑mediated interactions within pores by pairing well‑defined metal substituted zeolites with controlled solvent environments. We then mapped those contributions onto measurable kinetics (ΔH‡, ΔS‡), adsorption thermodynamics (ITC), and in situ spectroscopy. The transferrable outcomes include a set of design rules that include the following understandings. First, tune silanol ((SiOH)x) density and pore topology to organize solvent networks that selectively stabilize transition states. Second, exploit activity‑coefficient‑normalized rates and adsorption– barrier correlations to diagnose when solvent reorganization rather than surface chemistry limits performance. Third, use partial pore condensation (e.g., acetonitrile, water but also generalizable to other solvents) to elicit liquid‑like stabilization effects even in nominally vapor‑phase reactors. Collectively, these results provide strategies to increase epoxidation rates, improve oxidant utilization (i.e., selectivities), and steer regioselectivity in zeolite‑based catalytic processes relevant to sustainable oxidation chemistry. These outcomes should be transferable to other classes of reactions that proceed in microporous materials and under confinement provided by organized solvents (e.g., electrochemical double layers).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Topaz, a Potential Volatile-Carrier in Cold Subduction Zone: Constraint from Synchrotron X-ray Diffraction and Raman Spectroscopy at High Temperature and High Pressure

The equation of state and stability of topaz at high-pressure/high-temperature conditions have been investigated by in situ synchrotron X-ray diffraction (XRD) and Raman spectroscopy in this study. No phase transition occurs on topaz over the experimental pressure–temperature ($P-T$) range. The pressure–volume data were fitted by the third-order Birch–Murnaghan equation of state (EoS) with the zero-pressure unit–cell volume V 0 = 343.86 (9) Å 3 , the zero-pressure bulk modulus K 0 = 172 (3) GPa, and its pressure derivative K’ 0 = 1.3 (4), while the obtained K 0 = 155 (2) GPa when fixed K’ 0 = 4. In the pressure range of 0–24.4 GPa, the vibration modes of in-plane bending OH-groups for topaz show non-linear changes with the increase in pressure, while the other vibration modes show linear changes. Moreover, the temperature–volume data were fitted by Fei’s thermal equation with the thermal expansion coefficient α 300 = 1.9 (1) × 10 –5 K –1 at 300 K. Finally, the $P-T$ stability of topaz was studied by a synchrotron-based single-crystal XRD at simultaneously high $P-T$ conditions up to ~10.9 GPa and 700 K, which shows that topaz may maintain a metastable state at depths above 370 km in the upper mantle along the coldest subducting slab geotherm. Thus, topaz may be a potential volatile-carrier in the cold subduction zone. It can carry hydrogen and fluorine elements into the deep upper mantle and further affect the geochemical behavior of the upper mantle.

36 MATERIALS SCIENCE↗

The Quest for High-Temperature Superconductivity in Nickelates under Ambient Pressure

Recently, superconductivity with Tc ≈ 80 K was discovered in La3Ni2O7 under extreme hydrostatic pressure (>14 GPa). For practical applications, we needed to stabilize this state at ambient pressure. It was proposed that this could be accomplished by substituting La with Ba. To put this hypothesis to the test, we used the state-of-the-art atomic-layer-by-layer molecular beam epitaxy (ALL-MBE) technique to synthesize (La1−xBax)3Ni2O7 films, varying x and the distribution of La (lanthanum) and Ba (barium). Regrettably, none of the compositions we explored could be stabilized epitaxially; the targeted compounds decomposed immediately into a mixture of other phases. So, this path to high-temperature superconductivity in nickelates at ambient pressure does not seem promising.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Interplay of superconducting, metallic, and crystalline states of composite fermions at 𝜈 = $\frac{1}{6}$ in wide quantum wells

Evidence for developing fractional quantum Hall effect (FQHE) at filling fraction 𝜈 = 1/6 and 1/8 was recently reported in wide GaAs quantum wells [Wang et al., Phys. Rev. Lett. 134, 046502 (2025)]. In this article, we theoretically investigate the nature of the state at 𝜈 = 1/6 as a function of the quantum well width and the density by considering composite-fermion (CF) crystals, CF Fermi sea, and various kinds of paired CF states. The 𝑓-wave paired state has the lowest energy among the paired CF states. However, for parameters of interest, the energies of the CF crystal, the CF Fermi liquid, and the 𝑓-wave paired CF state are too close to distinguish. We, therefore, predict that 𝑖𝑓 the FQHE at 𝜈 = 1/6 is experimentally confirmed, this state would be an 𝑓-wave paired state of CFs, which can be verified by measurement of its thermal Hall conductance. Exact diagonalization studies on clean systems with up to eight electrons show that the ground states at 𝜈 = 𝑛/(6⁢𝑛 ± 1) are incompressible for all widths and densities we have considered, and are well described by the corresponding Laughlin and Jain states. We propose a phase diagram for large quantum well widths and densities in which at zero disorder, incompressible FQHE states are stabilized at 𝜈 = 𝑛/(6⁢𝑛 ± 1) and 𝜈 = 1/6, but in between these fillings the CF crystal is stabilized. We also present a qualitative discussion on the effects of disorder and propose a schematic phase diagram based on it. With disorder, which creates a spatial variation in the filling factor, two regimes are identified: (i) for small disorder, when the incompressible states percolate at the special fillings, FQHE with quantized Hall plateaus and vanishing longitudinal resistance should occur; and (ii) for larger disorder, when the CF crystal percolates, the longitudinal resistance rises with decreasing temperature but the domains of FQHE liquid produce minima at the special filling factors. Here, experiments are consistent with the latter scenario. We also mention a possible connection of the phase diagram presented here to a puzzling behavior observed for the fractional quantum anomalous Hall effect in pentalayer graphene.

Composite fermions↗

Small-moment antiferromagnetic ordering in single-crystalline La 2 Ni 7

Single crystals of La 2 Ni 7 have been grown out of a binary, La-Ni melt. Temperature dependent, zero magnetic field, specific heat, electrical resistivity, and low field magnetization measurements indicate that there is a series of antiferromagnetic phase transitions at T 1 = 61.0 ± 0.2 K, T 2 = 56.5 ± 0.2 K and T 3 = 42.2 ± 0.2 K. The three specific heat anomalies found at these temperatures qualitatively have very small entropy changes associated with them and the anisotropic M(H) data saturate at ~ 0.12 μ B /Ni; both observations strongly suggesting the AFM order is associated with very small, itinerant, moments. Anisotropic, H ||c and H ⟂c , ρ(H) and M(H) isotherms as well as constant field, ρ(T) and M(T) sweeps manifest signatures of multiple phase lines and result in HT phase diagrams that are clearly anisotropic. Analysis of M(T) and M(H) data allow for the identification of the two lower temperature magnetically ordered states as antiferromagnetically ordered, with the moments aligned along the crystallographic c-axis, and the higher temperature, T 2 < T < T 1 , state as having a finite ferromagnetic component. In addition, the metamagnetic transition at low temperatures, for H applied along the crystallographic c-axis (H ||c ) appears to be a near classic example of a spin-flop transition, resulting in a field stabilized antiferromagnetic state with the moments ordered perpendicular to the c-axis. Finally, although the small moment ordering, and existence of multiple phase transitions in field and temperature, suggesting an energetic proximity of these states, could foretell a degree of pressure sensitivity, our measurements of R(T) for applied pressures up to 2.0 GPa indicate that there is very little pressure dependence of T 1 , T 2 and T 3 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

On Distributed Model-Free Reinforcement Learning Control with Stability Guarantee

Distributed learning can enable scalable and effective decision making in numerous complex cyber-physical systems such as smart transportation, robotics swarm, power systems, etc. However, the stability of the system is usually not guaranteed in most existing learning paradigms; and this limitation can hinder the wide deployment of machine learning in decision making of safety-critical systems. This paper presents a stability guaranteed distributed reinforcement learning (SGDRL) framework for interconnected linear subsystems, without knowing the subsystem models. While the learning process requires data from a peer-to-peer (p2p) communication architecture, the control implementation of each subsystem is only based on its local state. The stability of the interconnected subsystems will be ensured by a diagonally dominant eigenvalue condition, which will then be used in a model-free RL algorithm to learn the feedback control gains. The RL algorithm structure follows an off-policy iterative framework, with interleaved policy evaluation and policy update steps. We numerically validate our theoretical results by performing simulations on four interconnected sub-systems.

Mukherjee, Sayak↗

Effects of thin metal contacts on few-layer van der Waals ferrielectric CuInP 2 S 6

Out-of-plane polarized ferroelectric materials in a capacitive structure provide a key component for several technological applications. Furthermore, two-dimensional materials are expected to aid in the quest for both ultrathin and flexible electronics. Of the various two-dimensional ferroelectrics with out-of-plane polarization, CuInP 2 S 6 is special in that the Cu atoms are highly mobile and it has been shown to possess both low- and high-polarization states. Here, using density-functional-theory calculations, we explore the stabilization of the ferroelectric state for several prototypical metal contacts (Gr, Ni, Cu, Au, and Ag). In all cases, we find that the ferroelectric state can be stabilized at fewer layers than in the freestanding case. For all of the considered conventional metal contacts, we also find the existence of a quasi-ferroelectric state that stabilizes a polar phase for thicknesses greater than two layers of CIPS. In the cases of Au and Ag, interfacial alignment and strain can be used to stabilize ferroelectricity at the bilayer limit. Furthermore, we find that the strength of the interaction between the contact and CuInP 2 S 6 also leads to stabilization of the high-polarization state when ferroelectricity is stabilized. Lastly, energy-barrier calculations show that the system is still switchable in the presence of contact doping from the metal contacts.

2D materials↗

Stellarator fusion systems enabled by arrays of planar coils

We present an overview of a novel electromagnetic coil configuration for stellarators and its application to two near-term fusion systems. The novel coil configuration is the planar coil stellarator, able to implement precisely-quasisymmetric 3D magnetic fields using a set of planar, plasma-encircling coils and a set of planar, field-shaping coils situated on a surface surrounding the plasma. This configuration combines the stellarator’s advantages of steady-state operation, stability, low recirculating power fraction, and a mature physics basis, with the benefits of using simpler, planar coils which allow for a maintenance scheme leveraging large ports, and the ability to control magnets individually. The initial near-term use case considered is a steady state deuterium–deuterium stellarator neutron source, called Eos. The second near-term use case considered is a deuterium–tritium stellarator fusion pilot plant, called Helios, that would be approximately twice the linear dimension of the Eos design.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Nanobody-enabled monitoring of kappa opioid receptor states

Recent studies show that GPCRs rapidly interconvert between multiple states although our ability to interrogate, monitor and visualize them is limited by a relative lack of suitable tools. We previously reported two nanobodies (Nb39 and Nb6) that stabilize distinct ligand- and efficacy-delimited conformations of the kappa opioid receptor. Here, we demonstrate via X-ray crystallography a nanobody-targeted allosteric binding site by which Nb6 stabilizes a ligand-dependent inactive state. As Nb39 stabilizes an active-like state, we show how these two state-dependent nanobodies can provide real-time reporting of ligand stabilized states in cells in situ. Significantly, we demonstrate that chimeric GPCRs can be created with engineered nanobody binding sites to report ligand-stabilized states. Our results provide both insights regarding potential mechanisms for allosterically modulating KOR with nanobodies and a tool for reporting the real-time, in situ dynamic range of GPCR activity.

60 APPLIED LIFE SCIENCES↗

Electromagnon Signatures of a Metastable Multiferroic State

Magnetoelectric multiferroic materials, particularly type-II multiferroics where ferroelectric polarizations arise from magnetic order, offer significant potential for the simultaneous control of magnetic and electric properties. However, it remains an open question as to how the multiferroic ground states are stabilized on the free-energy landscape in the presence of intricate competition between the magnetoelectric coupling and thermal fluctuations. Here, in this work, by using terahertz time-domain spectroscopy in combination with an applied magnetic field, photoexcitation, and single-shot detection, we reveal the spectroscopic signatures of a magnetic-field-induced metastable multiferroic state in a hexaferrite. This state remains robust until thermal influences cause the sample to revert to the original paraelectric state. Our findings shed light on the emergence of metastable multiferroicity and its interplay with thermal dynamics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Experimental and Theoretical Study of the Electronic Structures of Lanthanide Indium Perovskites LnInO 3

Ternary lanthanide indium oxides LnInO 3 (Ln = La, Pr, Nd, Sm) were synthesized by high-temperature solid-state reaction and characterized by Xray powder diffraction. Rietveld refinement of the powder patterns showed the LnInO 3 materials to be orthorhombic perovskites belonging to the space group Pnma, based on almost-regular InO 6 octahedra and highly distorted LnO 12 polyhedra. Experimental structural data were compared with results from density functional theory (DFT) calculations employing a hybrid Hamiltonian. Valence region X-ray photoelectron and K-shell X-ray emission and absorption spectra of the LnInO 3 compounds were simulated with the aid of the DFT calculations. Photoionization of lanthanide 4f orbitals gives rise to a complex final-state multiplet structure in the valence region for the 4f n compounds PrInO 3 , NdInO 3 , and SmInO 3 , and the overall photoemission spectral profiles were shown to be a superposition of final-state 4f n-1 terms onto the cross-section weighted partial densities of states from the other orbitals. The occupied 4f states are stabilized in moving across the series Pr-Nd-Sm. Band gaps were measured using diffuse reflectance spectroscopy. These results demonstrated that the band gap of LaInO 3 is 4.32 eV, in agreement with DFT calculations. This is significantly larger than a band gap of 2.2 eV first proposed in 1967 and based on the idea that In 4d states lie above the top of the O 2p valence band. However, both DFT and X-ray spectroscopy show that In 4d is a shallow core level located well below the bottom of the valence band. Band gaps greater than 4 eV were observed for NdInO 3 and SmInO 3 , but a lower gap of 3.6 eV for PrInO 3 was shown to arise from the occupied Pr 4f states lying above the main O 2p valence band.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Charge order textures induced by non-linear couplings in a half-doped manganite

Abstract The self-organization of strongly interacting electrons into superlattice structures underlies the properties of many quantum materials. How these electrons arrange within the superlattice dictates what symmetries are broken and what ground states are stabilized. Here we show that cryogenic scanning transmission electron microscopy (cryo-STEM) enables direct mapping of local symmetries and order at the intra-unit-cell level in the model charge-ordered system Nd 1/2 Sr 1/2 MnO 3 . In addition to imaging the prototypical site-centered charge order, we discover the nanoscale coexistence of an exotic intermediate state which mixes site and bond order and breaks inversion symmetry. We further show that nonlinear coupling of distinct lattice modes controls the selection between competing ground states. The results demonstrate the importance of lattice coupling for understanding and manipulating the character of electronic self-organization and that cryo-STEM can reveal local order in strongly correlated systems at the atomic scale.

42 ENGINEERING↗

Canted antiferromagnetism and spin reorientation in corner-shared single chain quasi-one-dimensional Ba 2 ⁢FeSe 3

Here, we report the canted antiferromagnetic (AFM) structure together with a spin reorientation in a single chain quasi-one-dimensional (Q-1D) iron chalcogenide Ba 2⁢ FeSe 3 . Ba 2 ⁢FeSe 3 crystallizes in Pnma (No. 62) orthorhombic structure with linear single iron chains consisting of corner-shared distorted FeSe 4 tetrahedra along the 𝑏 axis. Ba 2 ⁢FeSe 3 is a narrow-gap semiconductor and orders AFM below 60 K. Modeling of neutron powder diffraction data reveals a canted AFM ground state of magnetic space group 𝑃⁢𝑎⁢21/𝑐 (BNS No. 14.80) with commensurate propagation vector 𝐤 =(0, $\frac{1}{2}$, 0), where the Fe ion spins are AFM aligned with up-down-up-down (↑−↓−↑−↓) sequence along the Q-1D chain direction of the 𝑏 axis. In the magnetically ordered state, the canting of magnetic moments reorients from the 𝑎⁢𝑐 plane to the 𝑎⁢𝑏 plane below 30 K, with a 10° tilting angle toward the 𝑎 axis, and the magnetic moment does not induce a net moment in either orientation. The density functional theory results indicate that an ↑−↓−↑−↓ AFM state is stabilized along the chain direction. In this work, we elucidate the unique canted AFM of the iron chalcogenide and pave the way for searching exotic physics in Q-1D Ba 2⁢ FeSe 3 .

Gao, Fei [Univ. of Texas at Dallas, Richardson, TX↗

Microscopic origin of ultranodal superconducting states in spin- 1 2 systems

Several unconventional superconductors show indications of zero-energy excitations in the superconducting state consistent with the existence of a so-called Bogoliubov-Fermi surface (BFS). In particular, FeSe isovalently substituted with S seems to acquire a nonzero density of states at zero energy at low temperatures as the system goes into the tetragonal phase, consistent with a previously proposed phenomenological theory assuming an anisotropic spin singlet pairing gap coexisting with a nonunitary interband triplet component. Here we search for a microscopic model that can support the coexistence of singlet pairing with other orders, including interband nonunitary triplet pairing with magnetization, and discuss several candidates that indeed stabilize ground states with BFS. We show that with proper choice of the coupling strength of the various orders in our model, spontaneous breaking of C 4 rotational symmetry is realized at low temperatures. This feature resembles the findings of recent angle-resolved photoemission experiments in Fe(Se,S) in the tetragonal phase.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Engineering phase-frustration-induced flat bands in an aza-triangulene covalent kagome lattice

π-Conjugated covalent organic frameworks provide a versatile molecular scaffold for the realization of designer quantum nanomaterials. Strong electron–electron correlation within these artificial lattices can give rise to exotic phases of matter. Their experimental realization, however, requires precise control over orbital symmetry, charge localization and band dispersion, all arising from the effective hybridization between molecular linkers and nodes. Here we present a modular strategy for constructing diatomic kagome lattices from aza-[3]triangulene nodes, in which a D 3h -symmetric ground state is stabilized through resonance contributions from a cumulenic linker. First-principles density functional theory and scanning tunnelling spectroscopy reveal that the hybridization of a sixfold-degenerate set of edge-localized Wannier functions in the unit cell gives rise to orbital-phase-frustration-induced non-trivial flat bands. These results establish a general design principle for engineering orbital interactions in organic lattices and open a pathway towards programmable covalent-organic-framework-based quantum materials with correlated electronic ground states.

conjugated polymers↗

Thermal equation of state for zoisite: Implications for the transportation of water into the upper mantle and the high-velocity anomaly in the Farallon plate

Seismic tomography studies have revealed a high-velocity anomaly at depths between 100 km and 300 km in the Farallon plate. However, the reasons for the high-velocity anomaly continue to be debated. An analysis of the mineral proportions of eclogites exhumed from the Farallon plate shows that the average amount of zoisite in eclogite is ∼16.0 vol%. Therefore, the presence of zoisite eclogite needs to be considered to explain the high-velocity anomaly of the Farallon plate. However, the thermal equation of state and stability of zoisite have not been fully investigated under high pressure−temperature (P-T) conditions. We investigated the high-pressure and high-temperature behavior of natural zoisite utilizing synchrotron single crystal-X-ray diffraction (XRD). The results indicate that zoisite is metastable up to 24.8 GPa and 700 K. We obtained the ambient unit-cell volume V0 = 901.26(3) Å3 by synchrotron single crystal-XRD measurement. We also fitted the pressure-volume-temperature data to a high-temperature Birch-Murnaghan equation of state and obtained the zero-pressure bulk modulus K0 = 134.7(8) GPa, the temperature derivative of the bulk modulus (∂K/∂T)P = −0.011(4) GPa/K, and the thermal expansion coefficients α0V = 1.9(7) × 10−5 K−1 and α1V = 3(2) × 10−8 K−2 when the pressure derivative of bulk modulus (K′0) is fixed at 4. By incorporating the results from previous studies, we calculated the density and bulk sound velocity profiles of zoisite eclogite along the Farallon plate geotherm. Finally, we infer that zoisite could carry water to depths of ∼300 km within cold subducting slabs and that the bulk sound velocity of typical zoisite eclogite with ∼61.0 vol% omphacite, ∼23.0 vol% garnet, and ∼16.0 vol% zoisite could cause the high-velocity anomalies at depths of 100−300 km in the Farallon plate.

Geology↗

Topological and magnetic properties of a noncollinear spin state on a honeycomb lattice in a magnetic field

Here, this paper studies the topological and magnetic properties of a noncollinear spin state on a honeycomb lattice that evolves from coplanar to ferromagnetic with a magnetic field applied along the z axis. The coplanar state is stabilized by nearest-neighbor ferromagnetic interactions, single-ion anisotropy along z, and DzyaloshinskiiMoriya interactions between next-nearest-neighbor sites. Below the critical field H$_c$ that aligns the spins, the magnetic unit cell contains six sites and the spin dynamics contains six magnon modes. Although the classical energy is degenerate with respect to the twist angle φ between nearest-neighbor spins, the dependence of the free energy on φ at low temperatures is dominated by the magnon zero-point energy, which contains extremum at φ = πl/3 for integer l. The only unique ground states GS(φ) have l = 0 or 1. For H < H$'_c$, the zero-point energy has minima at even l and the ground state is GS(0); for H$'_c$ < H < H$'_c$, the zero-point energy has minima at odd l and the ground state is GS(π/3). In GS(0), the magnon density of states exhibits five distinct topological phases with increasing field associated with the opening and closing of energy gaps between two or three magnonic bands. While the Berry curvature vanishes for the coplanar φ = 0 phase in zero field, the Berry curvature and Chern numbers exhibit signatures of the five topological phases below H$'_c$. Whereas the Berry curvature and Chern number are sensitive to changes in the magnon density of states within GS(π/3), the inelastic spectrum S(k,ω) is sensitive to changes in the intensity of the magnon modes in the different magnetic phases GS(0) and GS(π/3) rather than the five topological phases within GS(π/3).

Fishman, Randy S. [Oak Ridge National Laboratory (↗