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Building artificial neurons and synapses is key to achieving the promise of energy efficiency and acceleration envisioned for brain-inspired information processing. Emulating the spiking behavior of biological neurons in physical materials requires precise programming of conductance nonlinearities. Strong correlated solid-state compounds exhibit pronounced nonlinearities such as metal-insulator transitions arising from dynamic electron-electron and electron-lattice interactions. However, a detailed understanding of atomic rearrangements and their implications for electronic structure remains obscure. In this work, we unveil discontinuous conductance switching from an antiferromagnetic insulator to a paramagnetic metal in ε-Cu 0.9 V 2 O 5 . Distinctively, fashioning nonlinear dynamical oscillators from entire millimeter-sized crystals allows us to map the structural transformations underpinning conductance switching at an atomistic scale using single-crystal X-ray diffraction. We observe superlattice ordering of Cu ions between [V 4 O 10 ] layers at low temperatures, a direct result of interchain Cu-ion migration and intrachain reorganization. The resulting charge and spin ordering along the vanadium oxide framework stabilizes an insulating state. Using X-ray absorption and emission spectroscopies, assigned with the aid of electronic structure calculations and measurements of partially and completely decuprated samples, we find that Cu 3 d and V 3 d orbitals are closely overlapped near the Fermi level. The filling and overlap of these states, specifically the narrowing/broadening of V 3 d xy states near the Fermi level, mediate conductance switching upon Cu-ion rearrangement. Understanding the mechanisms of conductance nonlinearities in terms of ion motion along specific trajectories can enable the atomistic design of neuromorphic active elements through strategies such as cointercalation and site-selective modification.

The stabilization and enhanced performance of lithium metal batteries (LMBs) depend on the formation and evolution of the Solid Electrolyte Interphase (SEI) layer as a critical component for regulating the Li metal electrodeposition processes. This study employs a first-principles kinetic Monte Carlo (kMC) model to simulate the SEI formation and Li + electrodeposition processes on a lithium metal anode, integrating both the electrochemical electrolyte reduction reactions and the diffusion events giving place to the SEI aggregation processes during battery charge and discharge processes. The model replicates the competitive interactions between organic and inorganic SEI components, emphasizing the influence of the cycling regime. Results indicate that grain boundaries within the SEI facilitate faster lithium-ion transport compared to crystalline regions, crucial for improving the performance and stability of LMBs. The findings underscore the importance of dynamic SEI modeling for further development of next-generation high-energy-density batteries., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Lithium metal batteries (LMB) have high energy densities and are crucial for clean energy solutions. The characterization of the lithium metal interphase is fundamentally and practically important but technically challenging. Taking advantage of synchrotron X-ray, which has the unique capability of analyzing crystalline/amorphous phases quantitatively with statistical significance, we study the composition and dynamics of the LMB interphase for a newly developed important LMB electrolyte that is based on fluorinated ether. Pair distribution function analysis revealed the sequential roles of the anion and solvent in interphase formation during cycling. The relative ratio between Li 2 O and LiF first increases and then decreases during cycling, suggesting suppressed Li 2 O formation in both initial and long extended cycles. Theoretical studies revealed that in initial cycles, this is due to the energy barriers in many-electron transfer. In long extended cycles, the anion decomposition product Li 2 O encourages solvent decomposition by facilitating solvent adsorption on Li 2 O which is followed by concurrent depletion of both. This work highlights the important role of Li 2 O in transitioning from an anion-derived interphase to a solvent-derived one.

Advances in sulfurized-polyacrylonitrile (SPAN)-based cathode materials promise safer and more efficient lithium-sulfur (Li-S) battery performance. To elucidate electrolyte-cathode interfacial electrochemistry and polysulfide (PS) dissolution, we emulate discharge SPAN reactions via ab initio molecular dynamics (AIMD) simulations. Plausible structures and their lithiation profiles are cross-validated via Raman/IR spectroscopy and density functional theory (DFT). Lithium bis(fluorosulfonyl)imide (LiFSI) plays versatile roles in the Li-SPAN cell electrochemistry, primarily as the major source in forming the cathode-electrolyte interphase (CEI), further verified via X-ray photoelectron spectroscopy and AIMD. Besides being a charge carrier and CEI composer, LiFSI mediates the PS generation processes in SPAN electrochemical lithiation. Analysis of AIMD trajectories during progressive lithiation reveals that, compared to carbonates, ether solvents enable stronger solvation and chemical stabilization for both salt and SPAN structures. Differentiated CEI formation and electrochemical lithiation decomposition pathways and products are profoundly associated with the intrinsic nature of lithium bonding with oxygen and sulfur., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The 5/6s 2 lone-pair electrons of p-block cations in their lower oxidation states are a versatile electronic and geometric structure motif that can underpin lattice anharmonicity and often engender electronic and structural instabilities that underpin the function of active elements in nonlinear optics, thermochromics, thermoelectrics, neuromorphic computing, and photocatalysis. In contrast to periodic solids where lone-pair-bearing cations are part of the structural framework, installing lone-pair-bearing cations in the interstitial sites of intercalation hosts provides a means of a systematically modulating electronic structure through the choice of the group and the period of the inserted cation while preserving the overall framework connectivity. The extent of stereochemical activity and the energy positioning of lone-pair-derived mid-gap states depend on the cation identity, stoichiometry, and strength of anion hybridization. V 2 O 5 polymorphs are versatile insertion hosts that can accommodate a broad range of s-, p-, and d-block cations. However, the insertion of lone-pair-bearing cations remains largely underexplored. In this article, we examine the implications of varying the 6s 2 cations situated in interlayer sites between condensed [V 4 O 10 ] n double layers. Systematic modulations of lattice distortions, electronic structure, and magnetic ordering are observed with increasing strength of stereochemical activity from group 12 to group 14 cations. We compare and contrast p-block-layered M x V 2 O 5 (M = Hg, Tl, and Pb) compounds and map the significance of local off-centering arising from the stereochemical activity of lone-pair cations to the emergence of filled antibonding lone-pair 6s 2 -O 2p-hybridized mid-gap states mediated by second-order Jahn-Teller distortions. Crystallographic studies of cation coordination environments and the resulting modulation of V-V interactions have been used in conjunction with variable-energy hard X-ray photoelectron spectroscopy measurements, first-principles electronic structure calculations, and crystal orbital Hamilton population analyses to decipher the origins of stereochemical activity. Magnetic susceptibility measurements reveal antiferromagnetic signatures for all the three compounds. However, the differences in V-V interactions significantly affect the energy balance of the superexchange interactions, resulting in an ordering temperature of 160 and 260 K for Hg 0.5 V 2 O 5 and δ-Tl 0.5 V 2 O 5 , respectively, as compared to 7 K for δ-Pb 0.5 V 2 O 5 . In δ-Pb 0.5 V 2 O 5 , the strong stereochemical activity of electron lone pairs and the resulting electrostatic repulsions enforce superlattice ordering, which strongly modifies the electronic localization patterns along the [V 4 O 10 ] slabs, resulting in disrupted magnetic ordering and an anomalously low ordering temperature. The results demonstrate a versatile strategy for toggling the stereochemical activity of electron lone pairs to modify the electronic structure near the Fermi level and to mediate superexchange interactions., Competing Interests: The authors declare no competing financial interest., (© 2023 American Chemical Society.)

Carbon ( 13 C) and oxygen ( 18 O) isotopes in carbonates form clumped isotope species inversely correlated with temperature, providing a valuable paleothermometer for sedimentary carbonates and fossils. However, this signal resets ("reorders") with increasing temperature after burial. Research on reordering kinetics has characterized reordering rates and hypothesized the effects of impurities and trapped water, but the atomistic mechanism remains obscure. This work studies carbonate-clumped isotope reordering in calcite via first-principles simulations. We developed an atomistic view of the isotope exchange reaction between carbonate pairs in calcite, discovering a preferred configuration and elucidating how Mg 2+ substitution and Ca 2+ vacancies lower the free energy of activation (Δ A ‡ ) compared to pristine calcite. Regarding water-assisted isotopic exchange, the H + -O coordination distorts the transition state configuration and reduces Δ A ‡ . We proposed a water-mediated exchange mechanism showing the lowest Δ A ‡ involving a reaction pathway with a hydroxylated four-coordinated carbon atom, confirming that internal water facilitates clumped isotope reordering.

Building a sustainable human habitat on the Moon requires advances in excavation, paving, and additive manufacturing to construct landing pads, surface transportation arteries, resilient shelters, and scientific outposts. Construction of infrastructure elements on the lunar surface necessitates exploration of the interfacial reactivity of locally sourced regolith and the adaptation of Earth-based construction techniques. Various crosslinking frameworks and sintering methods have been proposed as a means of consolidating lunar regolith into load-bearing structures but each have challenges related to incomplete understanding of reaction chemistry, excessive thermal budgets, and lack of universal applicability to different mineral components of regolith. We describe here a versatile experimental and computational study of the consolidation of a regolith simulant through formation of siloxane networks enmeshing mineral particles by surface dissolution-precipitation and polycondensation reactions. Furthermore, by tailoring the rheological properties of the formulation an additive manufacturing feedstock can be developed for the construction of lunar infrastructure., Competing Interests: The authors declare no competing interests., (© 2023 The Author(s).)

Like no other sulfur host material, polyacrylonitrile-derived sulfurized carbon (SPAN) promises improved electrochemical performance for lithium-sulfur batteries, based on its compatibility with carbonate solvents and ability to prevent self-discharge and shuttle effect. However, a complete understanding of the SPAN's lithiation mechanism is still missing because its structural features vary widely with synthesis conditions, and its electrochemical performance deviates from elemental sulfur. This study continues our research on the elucidation of the SPAN's structural characteristics and lithiation mechanisms via computational approaches. Our models reproduce most experimental data regarding carbon's graphitization level and conjugated ordering, sulfur-carbon covalent bonding, sulfur loading, and elemental composition. Our simulations emulate the discharge voltage observed in experiments for the first discharge, which reveals that sulfur follows multiple reduction pathways based on its interaction with the carbon backbone. Sulfur reduction takes place above 1.0 V vs Li/Li + mostly in the SPAN-like material, with no long-chain lithium polysulfide formation. Below 1.0 V vs Li/Li + , the backbone's electrochemical activity occurs via multiple C-Li and N-Li interactions, mostly with edge carbon atoms and pyridinic nitrogen. Moreover, we identify Li + binding sites throughout the graphitized backbone that might lead to prohibited energy costs for Li + deintercalation, which may explain the irreversible capacity loss between the first and second discharges. This work improves understanding of lithiation mechanisms in sulfurized carbon, which is useful for rationally designing SPAN synthesis pathways tailored to increase sulfur loading and enhanced electrochemical performance.

We aim at elucidating the mechanism of the trimethyl aluminum (TMA) decomposition on oxidized nickel (NiO) and metallic nickel (Ni) facets in the absence of a source of hydroxyl groups. This TMA decomposition mechanism constitutes the earliest stage of growth of Al 2 O 3 coatings with the atomic layer decomposition (ALD) method, which stabilizes nickel catalysts in energy-intensive processes such as the dry reforming of methane. Our first-principles calculations suggest thermodynamic favorability for the TMA decomposition on metallic nickel compared to oxidized nickel. Moreover, the decomposition of TMA on metallic nickel showed almost no differences in terms of energy barriers between flat and stepped surfaces. Regarding the impact of the CH 3 radicals formed after TMA decomposition, we calculated stronger adsorption on metallic nickel facets than on oxidized nickel, and these adsorption energies are comparable to the adsorption energies calculated in earlier works on Al 2 O 3 ALD growth on palladium surfaces. These results lead us to believe in the growth of porous Al 2 O 3 coatings triggered by CH 3 contamination rather than due to preferential TMA decomposition on stepped and/or defective facets. The CH 3 radicals are likely to be thermally stable at temperatures used during Al 2 O 3 ALD processes, partially passivating the surface towards further TMA decomposition.

A newly designed sulfur/graphene computational model emulates the electrochemical behavior of a Li-S battery cathode, promoting the S-C interaction through the edges of graphene sheets. A random mixture of eight-membered sulfur rings mixed with small graphene sheets is simulated at 64 wt %sulfur loading. Structural stabilization and sulfur reduction calculations are performed with classical reactive molecular dynamics. This methodology allowed the collective behavior of the sulfur and graphene structures to be accounted for. The sulfur encapsulation induces ring opening and the sulfur phase evolves into a distribution of small chain-like structures interacting with C through the graphene edges. This new arrangement of the sulfur phase not only leads to a less pronounced volume expansion during sulfur reduction but also to a different discharge voltage profile, in qualitative agreement with earlier reports on sulfur encapsulation in microporous carbon structures. The Li 2 S phase grows around ensembles of parallel graphene nanosheets during sulfur reduction. No diffusion of sulfur or lithium between graphene nanosheets is observed, and extended Li 2 S domains bridging the space between carbon ensembles are suppressed. The results emphasize the importance of morphology on the electrochemical performance of the composite material. The sulfur/graphene model outlined here provides new understanding of the graphene effects on the sulfur reduction behavior and the role that van der Waals interactions may play in promoting formation of multilayer graphene ensembles and small Li 2 S domains during sulfur reduction., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)