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At least 289 records · Page 16

SHF: Symmetrical Hierarchical Forest with Pretrained Vision Transformer Encoder for High-Resolution Medical Segmentation

This paper presents a novel approach to addressing the long-sequence problem in high-resolution medical images for Vision Transformers (ViTs). Using smaller patches as tokens can enhance ViT performance, but quadratically increases computation and memory requirements. Therefore, the common practice for applying ViTs to high-resolution images is either to: (a) employ complex sub-quadratic attention schemes or (b) use large to medium-sized patches and rely on additional mechanisms within the model to capture the spatial hierarchy of details. We propose Symmetrical Hierarchical Forest (SHF), a lightweight approach that adaptively patches the input image to increase token information density and encode hierarchical spatial structures into the input embedding. We then apply a reverse depatching scheme to the output embeddings of the transformer encoder, eliminating the need for convolution-based decoders. Unlike previous methods that modify attention mechanisms or use a complex hierarchy of interacting models, SHF can be retrofitted to any ViT model to allow it to learn the hierarchical structure of details in high-resolution images without requiring architectural changes. Experimental results demonstrate significant gains in computational efficiency and performance: on the PAIP WSI dataset, we achieved a 3∼32×speedup or a 2.95%∼7.03% increase in accuracy (measured by Dice score) at a 64K2 resolution with the same computational budget, compared to state-of-the-art production models. On the 3D medical datasets BTCV and KiTS, training was 6×faster, with accuracy gains of 6.93% and 5.9%, respectively, compared to models without SHF.

Zhang, Enzhi [Hokkaido University, Japan]↗

Multi-scale imaging of high-pressure hydrogen induced damage in EPDM rubber using X-ray microcomputed tomography, helium-ion microscopy and transmission electron microscopy

Ethylene propylene diene (EPDM) rubber has gained increasing interest for use in hydrogen infrastructure due to its excellent sealing performance and low temperature properties. However, severe structural damage has been observed in EPDM O-rings after exposure to high-pressure hydrogen. The origination and propagation mechanisms of this damage are poorly understood. Here, to address this knowledge gap, multi-scale imaging leveraging X-ray micro-computed tomography (micro-CT), helium ion microscopy (HeIM), and transmission electron microscopy (TEM) were used in this work to study a series of sulfur-cured ethylene propylene diene (EPDM) rubber materials with varying additives that were exposed to different hydrogen environments. Micro-CT captured the substantial structural damage due to hydrogen exposure; it revealed an association between zinc oxide (ZnO) particles and damage initiation. Further studies by TEM and scanning TEM with energy dispersive X-ray spectroscopy (EDS) were focused on these particles at the micro-to nano-scale range. TEM indicated that hydrogen causes void formation at the interface between ZnO and the rubber matrix. HeIM enabled imaging of surface morphology of the material at high resolution pre- and post-hydrogen exposure while providing information on chemical composition and that cannot be captured by either micro-CT or TEM.

08 HYDROGEN↗

PDB-IHM: A System for Deposition, Curation, Validation, and Dissemination of Integrative Structures

Structures of many large biomolecular assemblies are now being determined using integrative approaches. In these approaches, information derived from multiple experimental and computational methods is combined to compute three-dimensional structures of multi-protein complexes and other macromolecular machines. A standalone prototype data resource for integrative structures called PDB-Dev was built, based on recommendations of the Integrative and Hybrid Methods (IHM) Task Force of the Worldwide Protein Data Bank (wwPDB). This effort included developing data standards and software tools for collecting, curating, validating, visualizing, archiving, and disseminating integrative structures that span diverse spatiotemporal scales and conformational states. Mechanisms have been created to validate integrative structures based on the experimental data underpinning them. Building upon this foundational framework, PDB-Dev has been further expanded to handle large dynamic macromolecular systems and integrative structures that combine, for example, experimental restraints with atomic coordinates computed by machine learning algorithms. Data standards and supporting tools have also been extended to capture information about biomolecular dynamics, such as conformational transitions and related kinetic data derived from biophysical methods. Recently, PDB-Dev was unified with the PDB archive and rebranded as PDB-IHM (pdb-ihm.org), further promoting FAIR (Findable, Accessible, Interoperable, and Reusable) principles of data stewardship for integrative structural biology.

IHMCIF↗

A Novel Manufacturing Process of Lightweight Automotive Seats (Integration of Additive Manufacturing and Reinforced Polymer Composite)

Lightweight automotive seats offer multiple benefits to original equipment manufacturers in terms of cost savings from various aspects, including less material usage, more integrated processes, and compliance with Corporate Average Fuel Economy Standards. Original equipment manufacturers have been focusing on innovative ways to produce light weight automotive seats. The commercially available automotive seats are currently made of multiple metal components combined through welding and fasteners. The use of additive manufacturing and composite structures is particularly useful for light weighting the automotive components. Additive manufacturing (AM) offers multiple advantages over traditional manufacturing processes such as freedom of design thereby enabling complex structural geometries, mass customization and waste minimization, and control over the fiber alignment through deposition in a predetermined pattern. Combining metal inserts with polymer composites through a novel manufacturing process allows design of lightweight and high-performance materials for automotive components. However, fabricating these metal polymer composite structures through traditional manufacturing processes limits their mechanical properties due to limited design freedom, lack of control over fiber orientation in composite parts, and poor interfacial bonding between the constituent materials. It is essential to develop a novel manufacturing process to enable high throughput production of lightweight automotive seats using metal and polymer composites. As such it is important to design the automotive seat suitable for manufacturing via this process and perform mechanical characterization on various subcomponents of the seat to ensure that the design and performance requirements provided by the auto manufacturer are met. The aim of this project is to develop a novel manufacturing technique to produce lightweight automotive seat by combining AM with conventional manufacturing processes. The car seat back panel will be designed via topology optimization and numerical simulations to minimize the overall weight while ensuring it meets all the performance requirements. The optimization of the seat back structure will be based on computational stress analysis to maximize the stiffness and minimize the weight. Materials currently used by Ford Motor Company will be adopted for a few subcomponents while the in-house composite materials will be used for the rest of the seat back. The composite and metallic materials will be tested to determine their mechanical properties as these are necessary for simulations. A novel manufacturing process will be developed to integrate AM metal inserts with discontinuous reinforced composite through large scale additive manufacturing and compression overmolding processes. The developed manufacturing technique will be used to fabricated various subcomponents suitable for the seat back design and mechanically tested to determine their properties. The manufacturing of the lightweight seat back design through this process involves integrated AM metal inserts with the composite structure for recliner connection. The manufacturing of the entire seat back which is lightweight through the novel manufacturing process will be discussed. The performance of the designed seat back will be investigated through numerical simulations and shown to meet all the requirements provided by the auto manufacturer. The final goal of developing a novel manufacturing process for lightweight automotive seats is met through design optimization of seat back, manufacturing of subcomponents, mechanical characterization, and validation through numerical simulations. The routes to achieve the final goal of the project and the depth in which they were investigated changed throughout the project due to personnel changes and the COVID-19 pandemic. The project resulted in the development of a novel manufacturing process to integrate metal inserts with tailored polymer composite preforms through overmolding. Leveraging this proven manufacturing process, a lightweight seat back was designed through topology optimization and numerical simulations. The designed seat back uses AM metal inserts and compression overmolding of tailored polymer composite preforms obtained via large scale additive manufacturing. The metal polymer composite structures fabricated through this process exhibited enhancement in stiffness and improved ductility upon testing. Overall, the project provided an alternative design and manufacturing technique for automotive seat back that enables weight saving while meeting the safety and performance requirements.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Photoluminescence of Cis-Polyacetylene Semiconductor Material

Photoluminescence (PL) is one of the key experimental characterizations of optoelectronic materials, including conjugated polymers (CPs). In this study, a simplified model of an undoped cis-polyacetylene (cis-PA) oligomer was selected and used to explain the mechanism of photoluminescence (PL) of the CPs. Using a combination of the ab initio electronic structure and a time-dependent density matrix methodology, the photo-induced time-dependent excited state dynamics were computed. We explored the phonon-induced relaxation of the photoexcited state for a single oligomer of cis-PA. Here, the dissipative Redfield equation of the motion was used to compute the dissipative excited state dynamics of electronic degrees of freedom. This equation used the nonadiabatic couplings as parameters. The computed excited state dynamics showed that the relaxation rate of the electron is faster than the relaxation rate of the hole. The dissipative excited-state dynamics were combined with radiative recombination channels to predict the PL spectrum. The simulated results showed that the absorption and emission spectra both have a similar transition. The main result is that the computed PL spectrum demonstrates two mechanisms of light emission originating from (i) the inter-band transitions, corresponding to the same range of transition energies as the absorption spectrum and (ii) intra-band transitions not available in the absorption spectra. However, the dissipative Redfield equation of the motion was used to compute the electronic degrees of freedom of the nonadiabatic couplings, which helped to process the time propagation of the excited dynamic state. This excited dynamic state shows that the relaxation rate of the electron is faster than the relaxation rate of the hole, which can be used for improving organic semiconductor materials for photovoltaic and LED applications.

36 MATERIALS SCIENCE↗

A Perspective on Multiscale Modeling of Explicit Solvation-Enabled Simulations of Catalysis at Liquid–Solid Interfaces

Catalysis at liquid-solid interfaces is profoundly influenced by the interfacial solvent structure, which affects catalytic activity, selectivity, and reaction pathways. This perspective discusses state-of-the-art multiscale modeling methods that integrate quantum mechanics and molecular mechanics approaches to apply explicit solvent molecules to capture these interfacial phenomena. Specifically, the construction of multiscale models, the importance of capturing the interfacial solvent structure, and the computational strategies used to achieve this are explored, and the challenges in balancing chemical accuracy with computational expense are highlighted. Additionally, this perspective addresses the limitations of current methods. Opportunities for integrating machine learning are proposed. Here, by advancing the efficiency and user friendliness of multiscale modeling, it is argued that deeper insights into heterogeneous catalysis in liquid phases can be provided, which will ultimately contribute to the development of more efficient catalytic processes.

Ab initio molecular dynamics↗

Mechanistic insights into metal, nitrogen doped carbon catalysts for oxygen reduction: progress in computational modeling

We report metal and nitrogen doped carbon materials (denoted as M–N–C) synthesized through high-temperature pyrolysis have been found to exhibit activity for oxygen reduction reaction (ORR) approaching that of Pt and electrochemical stability higher than previous MN 4 -containing macrocyclic molecular catalysts. Tremendous efforts have thus been devoted to the advancement of M–N–C catalysts as an economical alternative to Pt-based catalysts for proton exchange membrane fuel cell cathodes with a focus on simultaneously improving activity and stability. To this end, novel computational modeling techniques have been developed and applied to acquire knowledge crucial for accelerating the pace of M–N–C catalyst development. In this review, recent progress in computational method development, as well as the predictions of chemical structure of active sites, reaction pathways, ORR kinetics, and catalyst stability in electrochemical environments, are critically surveyed. Moreover, the crucial role of computational modeling to elucidate the functional mechanism of M–N–C catalysts for ORR in acid media and enable rational design of M–N–C catalysts is discussed with a visionary outlook for the field.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Tardigrade: Summary (LL20-AM-sensor)

Tardigrade is an effort to create small, passive remote sensor for material detection and identification. The microbolometer based sensor design uses custom bandpass filter bands combined with tuned thermal expansion materials in a ruggedized lens housing to provide passive mechanical correction for optical changes across a wide temperature range. This requires developing computational tools to model and predict thermal performance of meta-materials composed of multiple structured base materials and void-space, along with matching and developing 3D print technology to demonstrate the housing. Current efforts in the project are in 3 areas: material design algorithm development (transitioning into full 3D material design space), multi-material additive manufacturing process exploration, and sensor/optics design and engineering.

42 ENGINEERING↗

Fabrication and Preliminary Demonstration of Microwave Resonant Cavity Transducer Performance

We are investigating a microwave cavity-based transducer for in-core high-temperature fluid flow sensing in molten salt cooled reactors (MSCR) and sodium fast reactors (SFR). This sensor is a hollow metallic cylindrical cavity, which can be fabricated from stainless steel, and as such is expected to be resilient to radiation, high temperature and corrosive environment of MSCR and SFR. The principle of sensing consists of making one wall of the cylindrical cavity flexible enough so that dynamic pressure, which is proportional to fluid velocity, will cause membrane deflection. Membrane deflection causes cavity volume change, which leads to a shift in the resonant frequency. We have developed an initial design for proof-of-principle testing of the flow sensor performance in microwave K-band. A cylindrical resonator prototype was fabricated from brass for initial tests in water. The cavity size is matched to the flange of a standard WR-42 waveguide. Microwave field is coupled into the resonant cavity through a subwavelength-size aperture. A test article was developed, consisting of a piping Tee with bulkhead WR-42 microwave waveguide installed in leak-proof design. In the test article, the cylindrical cavity is positioned in the center of the pipe. A microwave waveguide circulator was installed in the setup to suppress microwave reflections at the cavity entrance. Preliminary spectral characterization of cavity spectral response was performed with microwave VNA. Applying mechanical pressure to cavity membrane showed a measurable shift in the microwave resonant frequency. We also investigate mechanical integrity of the flowmeter’s membrane through computer simulations. By calculating the stress on the plate due to deflection and, comparing the stress to the material ultimate tensile strength and yield strength, it can be estimated if the plate will fail. The stress on the plate was calculated with an analytic closed form solution model, and with COMSOL Structural Mechanics Module which does not involve any approximations. Both the analytic model and COMSOL model showed that maximum stresses on the plate, which are at the radial boundary of the plate, are three orders of magnitude smaller than the yield strength and ultimate tensile strength. This indicates that the sensor is at a low risk of mechanical failure.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Advances in relaxation and memory effects of magnetic nanoparticles for biomedical applications

Functionalized magnetic nanoparticles are pivotal in magnetic resonance imaging, computed tomography, controlled drug delivery, and hyperthermia treatments due to their exceptional magnetic relaxation and functional properties. The magnetic core composition and structure significantly affects the complex magnetic properties of these nanoparticles necessitating a thorough examination of magnetism fundamentals related to these systems. One important aspect is the ability of magnetic nanoparticles to retain previous magnetic state configurations known as memory effect, primarily governed by domain structure and magnetic anisotropy. Despite its relevance to advanced applications, comprehensive studies on magnetic relaxation and memory effects remain limited. Here, the present review aims to bridge this gap by investigating relaxation mechanisms, synthesis strategies, and applications, fostering further innovation. It investigates the memory effects and their dependence on particle composition and morphology along with key synthesis techniques for large-scale production in industrial adoption. Structured into focused sections on magnetic properties and their influence on biomedical and technological applications, this review provides essential insights into memory effects, magneto-relaxation mechanisms, influencing factors, and both experimental and theoretical methodologies. It also delves into computational modelling and AI-driven design, which are revolutionizing the prediction, discovery, and optimization of materials with tailored properties.

36 MATERIALS SCIENCE↗

Computational and Experimental Study of Film-Cooling Effectiveness With and Without Downstream Vortex Generators

Downstream vortex generators that involve a pair of rectangular plates arranged in an open V-shape placed just downstream of each film-cooling hole were shown to create flow and vortical structures that entrain lifted film-cooling flow back to the surface and increase its lateral spreading on the surface (GT2020–14317). In this study, computations and measurements were performed to examine the flow mechanisms this vortex generator induces to improve film-cooling effectiveness of a flat plate with the cooling flow emanating from one row of inclined holes. Parameters studied include blowing ratio (BR = 0.75 and 1.0) and temperature ratio (TR = 1.07 and 1.9). Here, the computational study is based on steady Reynolds-averaged Navier–Stokes (RANS) closed by the shear-stress transport (SST) turbulence model with and without conjugate analysis. The experimental study was conducted by using a conjugate heat transfer test rig with a plenum, where cooling flow is introduced. Measurements made include velocity and temperature profiles upstream and downstream of the film-cooling holes as well as the temperature at several locations on the hot and cold sides of the film-cooled flat plate. The computational study was validated by comparing computed results with those from measurements at BR = 0.75 and 1.0 and TR = 1.9. Computational and experimental results are presented to show the effects of BR and TR on the flow structures and how those structures improve the effectiveness of film cooling with and without the downstream vortex generators and with and without conjugate heat transfer.

42 ENGINEERING↗

On the Rapid Calculation of Binding Affinities for Antigen and Antibody Design and Affinity Maturation Simulations

The accurate and efficient calculation of protein-protein binding affinities is an essential component in antibody and antigen design and optimization, and in computer modeling of antibody affinity maturation. Such calculations remain challenging despite advances in computer hardware and algorithms, primarily because proteins are flexible molecules, and thus, require explicit or implicit incorporation of multiple conformational states into the computational procedure. The astronomical size of the amino acid sequence space further compounds the challenge by requiring predictions to be computed within a short time so that many sequence variants can be tested. In this study, we compare three classes of methods for antibody/antigen (Ab/Ag) binding affinity calculations: (i) a method that relies on the physical separation of the Ab/Ag complex in equilibrium molecular dynamics (MD) simulations, (ii) a collection of 18 scoring functions that act on an ensemble of structures created using homology modeling software, and (iii) methods based on the molecular mechanics-generalized Born surface area (MM-GBSA) energy decomposition, in which the individual contributions of the energy terms are scaled to optimize agreement with the experiment. When applied to a set of 49 antibody mutations in two Ab/HIV gp120 complexes, all of the methods are found to have modest accuracy, with the highest Pearson correlations reaching about 0.6. In particular, the most computationally intensive method, i.e., MD simulation, did not outperform several scoring functions. The optimized energy decomposition methods provided marginally higher accuracy, but at the expense of requiring experimental data for parametrization. Within each method class, we examined the effect of the number of independent computational replicates, i.e., modeled structures or reinitialized MD simulations, on the prediction accuracy. We suggest using about ten modeled structures for scoring methods, and about five simulation replicates for MD simulations as a rule of thumb for obtaining reasonable convergence. We anticipate that our study will be a useful resource for practitioners working to incorporate binding affinity calculations within their protein design and optimization process.

59 BASIC BIOLOGICAL SCIENCES↗

A sharp interface Lagrangian-Eulerian method for flexible-body fluid-structure interaction

This paper introduces a sharp-interface approach to simulating fluid-structure interaction (FSI) involving flexible bodies described by general nonlinear material models and across a broad range of mass density ratios. This new flexible-body immersed Lagrangian-Eulerian (ILE) scheme extends our prior work on integrating partitioned and immersed approaches to rigid-body FSI. Our numerical approach incorporates the geometrical and domain solution flexibility of the immersed boundary (IB) method with an accuracy comparable to body-fitted approaches that sharply resolve flows and stresses up to the fluid-structure interface. Unlike many IB methods, our ILE formulation uses distinct momentum equations for the fluid and solid subregions with a Dirichlet-Neumann coupling strategy that connects fluid and solid subproblems through simple interface conditions. As in earlier work, we use approximate Lagrange multiplier forces to treat the kinematic interface conditions along the fluid-structure interface. This penalty approach simplifies the linear solvers needed by our formulation by introducing two representations of the fluid-structure interface, one that moves with the fluid and another that moves with the structure, that are connected by stiff springs. This approach also enables the use of multi-rate time stepping, which allows us to use different time step sizes for the fluid and structure subproblems. Our fluid solver relies on an immersed interface method (IIM) for discrete surfaces to impose stress jump conditions along complex interfaces while enabling the use of fast structured-grid solvers for the incompressible Navier-Stokes equations. The dynamics of the volumetric structural mesh are determined using a standard finite element approach to large-deformation nonlinear elasticity via a nearly incompressible solid mechanics formulation. This formulation also readily accommodates compressible structures with a constant total volume, and it can handle fully compressible solid structures for cases in which at least part of the solid boundary does not contact the incompressible fluid. Selected grid convergence studies demonstrate second-order convergence in volume conservation and in the pointwise discrepancies between corresponding positions of the two interface representations as well as between first and second-order convergence in the structural displacements. The time stepping scheme is also demonstrated to yield second-order convergence. To assess and validate the robustness and accuracy of the new algorithm, comparisons are made with computational and experimental FSI benchmarks. Test cases include both smooth and sharp geometries in various flow conditions. Furthermore, we also demonstrate the capabilities of this methodology by applying it to model the transport and capture of a geometrically realistic, deformable blood clot in an inferior vena cava filter.

97 MATHEMATICS AND COMPUTING↗

A crossed molecular beams and computational study on the unusual reactivity of banana bonds of cyclopropane (c-C 3 H 6 ; X 1 A$^{'}_{1}$ ) through insertion by ground state carbon atoms (C( 3 P j ))

The mechanism and chemical dynamics of the reaction of ground electronic state atomic carbon C( 3 P j ) with cyclopropane c-C 3 H 6 (X 1 A$^{'}_{1}$) have been explored by combining crossed molecular beams experiments with electronic structure calculations of the pertinent triplet C 4 H 6 potential energy surface and statistical computations of product branching ratios under single-collision conditions. The experimental findings suggest that the reaction proceeds via indirect scattering dynamics through triplet C 4 H 6 reaction intermediate(s) leading to C 4 H 5 product(s) plus atomic hydrogen via a tight exit transition state, with the overall reaction exoergicity evaluated as 231 ± 52 kJ mol –1 . The calculations indicate that C( 3 P j ) can easily insert into one of the three equivalent C–C ‘banana’ bonds of cyclopropane overcoming a low barrier of only 2 kJ mol –1 following the formation of a van der Waals reactant complex stabilized by 15 kJ mol –1 . The carbon atom insertion into one of the six C–H bonds is also feasible via a slightly higher barrier of 5 kJ mol –1 . Here, these results highlight an unusual reactivity of cyclopropane's banana C–C bonds, which behave more like unsaturated C–C bonds with a π-character than saturated σ C–C bonds, which are known to be generally unreactive toward the ground electronic state atomic carbon such as in ethane (C 2 H 6 ). The statistical theory predicts the overall product branching ratios at the experimental collision energy as 50% for 1-butyn-4-yl, 33% for 1,3-butadien-2-yl, i-C 4 H 5 , and 11% for 1,3-butadien-1-yl, n-C 4 H 5 , with i-C 4 H 5 (230 kJ mol –1 below the reactants) favored by the C–C insertion providing the best match with the experimentally observed reaction exoergicity. The C( 3 P j ) + c-C 3 H 6 reaction is predicted to be a source of C 4 H 5 radicals under the conditions where its low entrance barriers can be overcome, such as in planetary atmospheres or in circumstellar envelopes but not in cold molecular clouds. Both i- and n-C 4 H 5 can further react with acetylene eventually producing the first aromatic ring and hence, the reaction of the atomic carbon with c-C 3 H 6 can be considered as an initial step toward the formation of benzene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigating the Electronic Structure of Prospective Water-Splitting Oxide BaCe 0.25 Mn 0.75 O 3-δ before and after Thermal Reduction

BaCe 0.25 Mn 0.75 O 3-δ (BCM), a non-stoichiometric oxide with a layered perovskite-like crystal structure, has recently emerged as a prospective contender for application in renewable energy harvesting by solar thermochemical hydrogen generation. Using solar-thermal energy and a reducing environment, oxygen vacancies can be created in high-temperature BCM, and the reduced crystal so obtained can, in turn, produce H 2 by stripping oxygen from H 2 O. Therefore, a first step toward understanding the working mechanism and optimizing the performance of BCM is a thorough and comparative analysis of the electronic structure of the pristine and the reduced material. In this paper, we probe the electronic structure of BCM using the combined effort of first-principles calculations and experimental O K-edge X-ray absorption spectroscopy (XAS). The computed projected density of states (PDOS) and orbital plots are used to propose a simplified model for orbital mixing between the oxygen and metal atoms. With the help of state-of-the-art simulations, we are able to find the origins of the XAS peaks and categorize them on the basis of contribution from Ce and Mn. For the reduced crystal, the calculations show that the change in electron density resulting from the reduction is strongly localized around the oxygen vacancy. Experimental measurements reveal a marked lowering of the first O K-edge peak in the reduced crystal. Using theoretical analysis, this is shown to result from lifting of spin degeneracy in the absorption peaks as well as from a diminished O 2p contribution to the frontier unoccupied orbitals, in accordance with the tight binding scheme. The simulated results serve as a reference for the extent of spectral change as a function of the percentage of oxygen vacancies in the reduced crystal. Here, our study paves the way for the investigation of the working mechanism of BCM and for computational and experimental efforts aimed at design and discovery of efficient water-splitting oxides.

08 HYDROGEN↗

Unlocking multiphysics design guidelines on Si/C composite nanostructures for high-energy-density and robust lithium-ion battery anode

In general, current material fabrication guidance for novel designs of Si/C composite particle materials focuses on electrochemical behavior and redox reactions at the nano/micro level. However, such guidance cannot provide detailed information for predicting mechanical deformations of the composite particles, especially when the mechanical field coupled with electrochemical and thermal fields. Here, we establish an electro-chemo-mechanical model and implement it to quantitatively analyze the multiphysics behavior of five representative Si/C composite nanostructures. Modeling and computation discover that yolk-shell and dual-shell structures are more robust in terms of particle fractures. When considering electrochemical performance, the yolk-shell structure is the best among the compared five Si/C composites. Finally, we map design guidance to further illustrate quantitative structure-property relationships. This study provides novel insights on Si/C composite nanostructure anode material design and additional powerful design tools for next-generation high-energy-density lithium-ion batteries.

25 ENERGY STORAGE↗

Direct functionalization of C-H bonds by electrophilic anions

Bond formation between two of the most inert molecules, alkanes and [B12X12]2- (X = Cl, Br), is performed in a two step process. Fragmentation of [B12X12]2- in the gas phase generates highly reactive [B12X11]- ions which spontaneously react with alkanes. The reaction mechanism was investigated using tandem mass spectrometry and gas-phase vibrational spectroscopy combined with electronic structure calculations. This effort revealed the unprecedented and counterintuitive electrophilic substitution of a proton in an alkane by a negatively charged ion resulting in a B-C bond formation. The product is a dianionic [B12X11CnH2n+1]2- species, in which H+ is electrostatically bound to the dianion. High flux ion soft-landing was performed to co-deposit [B12X11]- and complex organic molecules (phthalates) in thin layers on surfaces. Molecular structure analysis of the product films revealed that C-H functionalization by [B12X11]- occured in the presence of other more reactive functional groups. This observation demonstrates the utility of highly reactive fragment ions for defined bond formation processes and may pave the way to the use of gas phase ion chemistry for chemical synthesis in the condensed phase.

Warneke, Jonas↗

Hidden Rotation Symmetry of the Jordan–Wigner Transformation and Its Application to Measurement in Quantum Computation

Using a global rotation by 𝜃 about the z-axis in the spin sector of the Jordan–Wigner transformation rotates Pauli matrices 𝑋̂ and 𝑌̂ in the 𝑥−𝑦 -plane, while it adds a global complex phase to fermionic quantum states that have a fixed number of particles. With the right choice of angles, this relates expectation values of Pauli strings containing products of 𝑋̂ and 𝑌̂ to different products, which can be employed to reduce the number of measurements needed when simulating fermionic systems on a quantum computer. Here, we derive this symmetry and show how it can be applied to systems in Physics and Chemistry that involve Hamiltonians with only single-particle (hopping) and two-particle (interaction) terms. We also discuss the consequences of this for finding efficient measurement circuits in variational ground state preparation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗