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At least 145 records · Page 8

Probabilistic Damage Characterization Using the Computationally-Efficient Bayesian Approach

This work presents a computationally-ecient approach for damage determination that quanti es uncertainty in the provided diagnosis. Given strain sensor data that are polluted with measurement errors, Bayesian inference is used to estimate the location, size, and orientation of damage. This approach uses Bayes' Theorem to combine any prior knowledge an analyst may have about the nature of the damage with information provided implicitly by the strain sensor data to form a posterior probability distribution over possible damage states. The unknown damage parameters are then estimated based on samples drawn numerically from this distribution using a Markov Chain Monte Carlo (MCMC) sampling algorithm. Several modi cations are made to the traditional Bayesian inference approach to provide signi cant computational speedup. First, an ecient surrogate model is constructed using sparse grid interpolation to replace a costly nite element model that must otherwise be evaluated for each sample drawn with MCMC. Next, the standard Bayesian posterior distribution is modi ed using a weighted likelihood formulation, which is shown to improve the convergence of the sampling process. Finally, a robust MCMC algorithm, Delayed Rejection Adaptive Metropolis (DRAM), is adopted to sample the probability distribution more eciently. Numerical examples demonstrate that the proposed framework e ectively provides damage estimates with uncertainty quanti cation and can yield orders of magnitude speedup over standard Bayesian approaches.

Warner, James E.↗

Comparative Study of Neutral and Cationic Sn 2 H 2 : Toward Laboratory Detection of the Cation

Group 14 M 2 H 2 isomers (M = Si, Ge, Sn, and Pb) have attracted interest due to their radically differing electronic structures from acetylene. To better understand the Sn–H interactions of the neutral and cationic Sn 2 H 2 structures, we present the most rigorous study of these systems to date. CCSD(T)/cc-pwCVTZ harmonic frequencies are presented as the first predictions for the neutral and cationic species to date. CCSDT(Q)/CBS relative energies are reported using the focal point approach, confirming the butterfly isomer as the global minimum on the potential energy surface for both the neutral and cationic species. In all, there exist 7 minima and 15 transition states. NBO analysis is also performed to elucidate the changes in bond order going from neutral to cation across all isomers of Sn 2 H 2 . Our results provide insights into the important Sn–H interaction and provide guidance for future work that may detect Sn 2 H$^{+}_{2}$ in the laboratory for the first time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chirality Transfer to the Magnetic Sublattice in the Hybrid Perovskite (R)-/(S)-3-Fluoropyrrolidinium Copper(II) Chloride

Incorporating chiral organic cations into organic–inorganic hybrid materials has been shown to enable the inorganic sublattice to display chiroptical properties. We report a new two-dimensional magnetic (S = 1/2) chiral metal halide perovskite, (R)- and (S)-(C 4 H 9 FN) 2 CuCl 4 (where (C 4 H 9 FN) + is 3-fluoropyrrolidinium), which consists of Cu–Cl inorganic layers separated by (C 4 H 9 FN) + organic cations. The presence of the chiral (C 4 H 9 FN) + organic cation induces the formation of chiral magnetic order, even though the inorganic sublattice itself is nearly structurally centrosymmetric. We also report the racemic variant, containing an equal amount of (R)- and (S)- cations, which shows no evidence of chiral magnetic order. When the magnetic susceptibility is measured perpendicular to the inorganic Cu–Cl layer propagation direction, an antiferromagnetic phase transition at Néel temperature T N = 2.23 K is observed in both the chiral and racemic materials, and the existence of the magnetic phase transition is supported by specific heat capacity measurements. Field-induced magnetic chirality is observed through the existence of a second-order magnetoelectric effect in the chiral variant, while no magnetoelectric signal is observed for the racemic material, indicating the absence of magnetic chirality. Our findings demonstrate that materials exhibiting chiral magnetic order can be created through the incorporation of a chiral cation into an organic–inorganic hybrid magnetic material, potentially allowing for the design of tailored materials that combine chiral magnetism with other desirable optical and electronic properties that come from structural chirality.

Cations↗

The influence of various cations on the catalytic properties of clays

The polymerization of alanine adenylate in the presence of the sodium form of various clays was studied, and hectorite was found to cause more polymerization than nontronite and montmorillonite (in that order) although the differences were not great. The effect on polymerization of presaturating montmorillonite with different cations was determined. Hectorite, with increased basicity of the interspatial planes, allows polymerization of lysine, which montmorillonite does not. The general trend is that, for the same amino acid, higher degrees of polymerization are obtained when the cation in the octahedral lattice of the clay is divalent rather than trivalent. With the exchangeable cations the order is reversed, for a reason that is explained. The main role of clays in the polymerization mechanism of amino acids is concentration and neutralization of charges.

Paecht-Horowitz, M.↗

Coordination of copper within a crystalline carbon nitride and its catalytic reduction of CO 2

Inherently disordered structures of carbon nitrides have hindered an atomic level tunability and understanding of their catalytic reactivity. Starting from a crystalline carbon nitride, poly(triazine imide) or PTI/LiCl, the coordination of copper cations to its intralayer N-triazine groups was investigated using molten salt reactions. The reaction of PTI/LiCl within CuCl or eutectic KCl/CuCl 2 molten salt mixtures at 280 to 450 °C could be used to yield three partially disordered and ordered structures, wherein the Cu cations are found to coordinate within the intralayer cavities. Local structural differences and the copper content, i.e., whether full or partial occupancy of the intralayer cavity occurs, were found to be dependent on the reaction temperature and Cu-containing salt. Crystallites of Cu-coordinated PTI were also found to electrophoretically deposit from aqueous particle suspensions onto either graphite or FTO electrodes. As a result, electrocatalytic current densities for the reduction of CO 2 and H 2 O reached as high as ∼10 to 50 mA cm −2 , and remained stable for >2 days. Selectivity for the reduction of CO 2 to CO vs. H 2 increases for thinner crystals as well as for when two Cu cations coordinate within the intralayer cavities of PTI. Mechanistic calculations have also revealed the electrocatalytic activity for CO 2 reduction requires a smaller thermodynamic driving force with two neighboring Cu atoms per cavity as compared to a single Cu atom. These results thus establish a useful synthetic pathway to metal-coordination in a crystalline carbon nitride and show great potential for mediating stable CO 2 reduction at sizable current densities.

Chemistry↗

Modeling phase transformations in Mn-rich disordered rocksalt cathodes with machine-learning interatomic potentials

Mn-rich disordered rocksalt (DRX) cathode materials exhibit a phase transformation from a disordered to a partially disordered spinel-like structure (δ-phase) during electrochemical cycling. Here, in this computational study, we use charge-informed molecular dynamics with a fine-tuned CHGNet foundation potential to investigate the phase transformation in LixMn 0.8 Ti 0.1 O 1.9 F 0.1 . Our results indicate that transition metal migration occurs and reorders to form the spinel-like ordering in an FCC anion framework. The transformed structure contains a higher concentration of nontransition metal (0-TM) face-sharing channels, which are known to improve Li transport kinetics. Analysis of the Mn valence distribution suggests that the appearance of tetrahedral Mn 2+ is a consequence of spinel-like ordering, rather than the trigger for cation migration as previously suggested. Calculated equilibrium intercalation voltage profiles demonstrate that the δ-phase, unlike the ordered spinel, exhibits solid-solution signatures at low voltage. A higher Li capacity is obtained than in the DRX phase. This study provides atomic insights into solid-state phase transformation and its relation to experimental electrochemistry, highlighting the potential of machine-learning interatomic potentials for understanding complex oxide materials.

Zhong, Peichen [University of California, Berkeley↗

Identifying point defects and ordering in the high-entropy layered oxide Li 1.5 MO 3-δ (M=Mn, Al, Fe, Co, Ni) for energy storage applications

High-entropy layered oxides (HELOs) represent a very promising class of next-generation battery cathodes, combining the well-studied properties of layered cathode materials such as LiCoO 2 with the chemical tunability and stability of high-entropy materials. HELO materials often form particles with complex defects and domain structures, complicating accurate characterization of structure and cation mixing. Understanding disorder and order in HELO materials is necessary for understanding their performance and utility as cathodes. Here we demonstrate the characterization of the HELO Li 1.5 MO 3-δ (M = Mn, Al, Fe, Co, Ni), wherein X-ray powder diffraction, transmission electron microscopy imaging, and electron diffraction patterns are analyzed to reveal the presence of ordering in the HELO, with imaging and diffraction simulation employed to compare experimental results to atomic modeling. Finally, without rigorous characterization at the atomic scale, important features such as defect ordering can be easily overlooked and therefore remain unconsidered when interpreting experimental results.

36 MATERIALS SCIENCE↗

Butterfly, Vinylidene-Like, Monobridged and Trans Structures of Si 2 H 2 + : Comparison to the Well-Characterized Neutral Si 2 H 2

This paper investigates four of the constitutional isomers of Si 2 H 2 + , namely the butterfly, vinylidene-like, monobridged, and trans structures. These isomer geometries were all studied using the CCSD(T) method with basis sets as large as cc-pV5Z. Higher level methods CCSDT and CCSDT(Q) were used for final energetics. It is found that the butterfly isomer has the lowest energy, followed by vinylidene-like and monobridged structures; the trans structure has the highest energy of the four. All structures were compared with their neutral counterparts. Partial charges are computed and it is found that all isomers share the positive charge between the silicon atoms. NBO analysis shows that the cation Si-Si bond order is reduced by 0.5 relative to the neutral versions of the same isomer in the case of the butterfly, vinylidene-like, and monobridged; and reduced by 0.6 for the trans isomer. Vibrational frequencies, infrared intensities, and dipole moments are predicted to encourage the spectroscopic identification of Si 2 H 2 + .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Density functional modeling of the binding energies between aluminosilicate oligomers and different metal cations

Interactions between negatively charged aluminosilicate species and positively charged metal cations are critical to many important engineering processes and applications, including sustainable cements and aluminosilicate glasses. In an effort to probe these interactions, here we have calculated the pair-wise interaction energies (i.e., binding energies) between aluminosilicate dimer/trimer and 17 different metal cations M n+ (M n+ = Li + , Na + , K + , Cu + , Cu 2+ , Co 2+ , Zn 2+ , Ni 2+ , Mg 2+ , Ca 2+ , Ti 2+ , Fe 2+ , Fe 3+ , Co 3+ , Cr 3+ , Ti 4+ and Cr 6+ ) using a density functional theory (DFT) approach. Analysis of the DFT-optimized structural representations for the clusters (dimer/trimer + M n+ ) shows that their structural attributes (e.g., interatomic distances) are generally consistent with literature observations on aluminosilicate glasses. The DFT-derived binding energies are seen to vary considerably depending on the type of cations (i.e., charge and ionic radii) and aluminosilicate species (i.e., dimer or trimer). A survey of the literature reveals that the difference in the calculated binding energies between different M n+ can be used to explain many literature observations associated with the impact of metal cations on materials properties (e.g., glass corrosion, mineral dissolution, and ionic transport). Analysis of all the DFT-derived binding energies reveals that the correlation between these energy values and the ionic potential and field strength of the metal cations are well captured by 2nd order polynomial functions ( R 2 values of 0.99–1.00 are achieved for regressions). Given that the ionic potential and field strength of a given metal cation can be readily estimated using well-tabulated ionic radii available in the literature, these simple polynomial functions would enable rapid estimation of the binding energies of a much wider range of cations with the aluminosilicate dimer/trimer, providing guidance on the design and optimization of sustainable cements and aluminosilicate glasses and their associated applications. Finally, the limitations associated with using these simple model systems to model complex interactions are also discussed.

Gong, Kai↗

AL4GAP: Active learning workflow for generating DFT-SCAN accurate machine-learning potentials for combinatorial molten salt mixtures

Machine learning interatomic potentials have emerged as a powerful tool for bypassing the spatiotemporal limitations of ab initio simulations, but major challenges remain in their efficient parameterization. We present AL4GAP, an ensemble active learning software workflow for generating multicomposition Gaussian approximation potentials (GAP) for arbitrary molten salt mixtures. The workflow capabilities include: (1) setting up user-defined combinatorial chemical spaces of charge neutral mixtures of arbitrary molten mixtures spanning 11 cations (Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba and two heavy species, Nd, and Th) and 4 anions (F, Cl, Br, and I), (2) configurational sampling using low-cost empirical parameterizations, (3) active learning for down-selecting configurational samples for single point density functional theory calculations at the level of Strongly Constrained and Appropriately Normed (SCAN) exchange-correlation functional, and (4) Bayesian optimization for hyperparameter tuning of two-body and many-body GAP models. Here, we apply the AL4GAP workflow to showcase high throughput generation of five independent GAP models for multicomposition binary-mixture melts, each of increasing complexity with respect to charge valency and electronic structure, namely: LiCl–KCl, NaCl–CaCl 2 , KCl–NdCl 3 , CaCl 2 –NdCl 3 , and KCl–ThCl 4 . Our results indicate that GAP models can accurately predict structure for diverse molten salt mixture with density functional theory (DFT)-SCAN accuracy, capturing the intermediate range ordering characteristic of the multivalent cationic melts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure of triple perovskite BaSr 2 MgTa 2 O 9 revisited

An experimental investigation of the structure and crystal-chemistry of the triple perovskite BaSr 2 MgTa 2 O 9 is reported. Polycrystalline BaSr 2 MgTa 2 O 9 was synthesized via solid-state reaction and its structure quantitatively probed at 10 and 300 ​K using neutron diffraction. Monoclinic (A2/m, a 0 $\bar{b}$ – $b$ – ) and trigonal structural models (P$\bar{3}$c1, a – a – a – ) were fit to diffraction data. The former was found to correctly reproduce experimental intensities, while the latter failed to do so. This difference is attributed to the ability of the monoclinic model to accurately reflect octahedral tilting. BaSr 2 MgTa 2 O 9 features corner-sharing MgO 6 and TaO 6 octahedra with barium and strontium cations occupying cubooctahedral holes. Barium and strontium are disordered over the A site, whereas B site cations magnesium and tantalum are ordered. Finally, chemical substitution of strontium for barium in Ba 3 MgTa 2 O 9 induces tilting of MgO 6 and TaO 6 octahedra in two directions and geometric distortions of MgO 6 octahedra.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

2D Homologous Series SrFM n BiS n +2 (M = Pb, Ag 0.5 Bi 0.5 ; n = 0, 1) and Commensurately Modulated Sr 2 F 2 Bi 2/3 S 2

In this work, we report three new mixed-anion two-dimensional (2D) compounds: SrFPbBiS 3 , SrFAg 0.5 Bi 1.5 S 3 , and Sr 2 F 2 Bi 2/3 S 2 . Their structures as well as the parent compound SrFBiS 2 were refined using single-crystal X-ray diffraction data, with the sequence of SrFBiS 2 , SrFPbBiS 3 , and SrFAg 0.5 Bi 1.5 S 3 defining the new homologous series SrFM n BiS n+2 (M = Pb, Ag 0.5 Bi 0.5 ; n= 0, 1). Sr 2 F 2 Bi 2/3 S 2 has a different structure, which is modulated with a q vector of 1/3b* and was refined in superspace group X2/m(0 β 0)00 as well as in the 1x3x1 superstructure with space group C2/m (with similar results). Sr 2 F 2 Bi 2/3 S 2 features hexagonal layers of alternating [Sr 2 F 2 ] 2+ and [Bi 2/3 S 2 ] 2- , and the modulated structure arises from the unique ordering pattern of Sr 2+ cations. SrFPbBiS 3 , SrFAg 0.5 Bi 1.5 S 3 , and Sr 2 F 2 Bi 2/3 S 2 are semiconductors with band gaps of 1.31, 1.21, and 1.85 eV, respectively. The latter compound exhibits room temperature red photoluminescence at ~ 700 nm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interplay Between Metastability and Mechanically Induced Structural Instability in CsPbBr 3 Photovoltaic Perovskite

An atomic-level understanding of the underlying structural metastability is still absent in halide perovskite photovoltaic systems. Focusing on the model material CsPbBr 3 , the impact of mechanically induced atomic structure alteration is elucidated through structural modeling and X-ray diffraction measurements. Sudden Cs–Br bond breaking drives the system metastability, where the first-order transition arises from cation-halide bond strain relief by severing the corner connectivity of the PbBr 6 units. The pressure–volume and entropy terms govern the Gibbs free-energy landscape in halide perovskites. In conclusion, metastability is revealed as a critical factor limiting the performance of lead halide perovskites under extreme but natural environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improved methods for separation of Cobalt, Manganese, Nickel, Lithium from Waste Lithium-ion Battery Scrap

Improved methods for separation of Cobalt, Manganese, Nickel, Lithium from Waste Lithium-ion Battery Scrap Mark L. Strauss1, John Klaehn1 Luis Diaz Aldana1, Tedd Lister1 Idaho National Laboratory1, Biological and Chemical Processing Department, Idaho Falls, Idaho 83415 ABSTRACT The current methods for the separation of Co, Mn, Ni, Li require that the leach solution have a pH between 2-4 in order to use many Cyanex cationic exchange products. Using a unique buffer solution for the reagent combined with the leachate of innovative electrochemical leaching process for lithium batteries demonstrates the separation is possible without a large of pH modification as other commercial hydrometallugical separation process. This research demonstrates a process that is more environmentally sustainable because the reagent consumption may be less. The corresponding McCable-Thiele diagrams and number of theoretical stages were determined to achieve a 80-90% purity of cobalt, manganese, nickel and lithium.

42 ENGINEERING↗

Reducing the Cation Exchange Capacity of Lithium Clay to Form Better Dispersed Polymer-Clay Nanocomposites

Polymer-clay nanocomposites have exhibited superior strength and thermo- oxidative properties as compared to pure polymers for use in air and space craft; however, there has often been difficulty completely dispersing the clay within the matrices of the polymer. In order to improve this process, the cation exchange capacity of lithium clay is first lowered using twenty-four hour heat treatments of no heat, 130 C, 150 C, or 170 C to fixate the lithium ions within the clay layers so that they are unexchangeable. Generally, higher temperatures have generated lower cation exchange capacities. An ion exchange involving dodecylamine, octadecylamine, or dimethyl benzidine (DMBZ) is then employed to actually expand the clay galleries. X-ray diffraction and transmission electron microscopy can be used to determine whether the clay has been successfully exfoliated. Finally, resins of DMBZ with clay are then pressed into disks for characterization using dynamic mechanical analyzer and oven- aging techniques in order to evaluate their glass transition, modulus strength, and thermal-oxidative stability in comparison to neat DMBZ. In the future, they may also be tested as composites for flexural and laminar shear strength.

Liang, Maggie↗

Charge order driven multiferroic behavior in Sr 4 Fe 6 O 12 : An ab-initio study

Here, in this paper, we report the structural, electronic, and ferroelectric properties of the layered mixed-valent transition-metal compound Sr 4 ⁢ Fe 6 ⁢O 12 (SFO). We demonstrate how SFO undergoes a phase transition from a high-temperature (𝑇) centrosymmetric tetragonal phase (𝑃⁢4 2 /𝑚⁢𝑛⁢𝑚) to a low-𝑇 polar orthorhombic phase (𝑃⁢𝑚⁢𝑛⁢2 1 ). The transition is primarily driven by charge ordering at tetrahedral Fe-layer creating Fe 3+ and Fe 2+ cations between two edge-sharing tetrahedra. This charge ordering induces electronic polarization, which is remarkably larger (3.5 times) in magnitude than ionic polarization and oppositely directed, giving a net polarization of 0.05 C/m 2 which is comparable to the state-of-the-art rare-earth nickelets and manganite perovskites. The direction of structural distortion, governed by the polar mode irrep $Γ^−_5$, depends sensitively on the type of magnetic ordering in the Fe-octahedral layer. Consequently, both the ionic and electronic polarization directions are influenced by magnetic ordering, suggesting the potential for multiferroic behavior with strong magnetoelectric coupling in this material.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Influence of Cation Size on the Local Atomic Structure and Electronic Properties of Ta Perovskite Oxynitrides

Partial anion substitution in transition metal oxides provides rich opportunities to control and tune physical and chemical properties, for example, combining the merits of oxides and nitrides. In addition, the possibility of resulting anion sublattice order provides a means to target polar and chiral structures based on a wide array of accessible structural archetypes by design. Here, in this work, we investigate the local structures of a family of perovskite tantalum oxynitrides—ATaO 2 N (A = Ba, Sr, and Ca)—using a combination of experimental and theoretical approaches including neutron total scattering, density functional theory (DFT), and ab initio molecular dynamics (AIMD) simulations. We present the first experimental study of chemical short-range order (CSRO) in CaTaO 2 N, confirming local cis N ordering of the anion sub-lattice. Our systematic exploration of a local structure across the A cation size series (from the larger Ba to the smaller Ca) reveals a perovskite motif increasingly distorted with respect to long-range average structures. DFT and AIMD simulations support the observed trends. Overall, structures with cis ordering of the nitrogen anions in each TaO 4 N 2 octahedron are favored over those with trans ordering. With diminishing A cation size, local cis ordering and Ta off-centering play decreasing roles in overall lattice stability, overshadowed by the stabilizing effects of octahedral tilting. The influence of these factors on local dipole formation and frustrated dipole ordering are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗