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At least 883 records · Page 49

Accelerating multiscale electronic stopping power predictions with time-dependent density functional theory and machine learning

Knowing the rate at which particle radiation releases energy in a material, the “stopping power,” is key to designing nuclear reactors, medical treatments, semiconductor and quantum materials, and many other technologies. While the nuclear contribution to stopping power, i.e., elastic scattering between atoms, is well understood in the literature, the route for gathering data on the electronic contribution has for decades remained costly and reliant on many simplifying assumptions, including that materials are isotropic. We establish a method that combines time-dependent density functional theory (TDDFT) and machine learning to reduce the time to assess new materials to hours on a supercomputer and provide valuable data on how atomic details influence electronic stopping. Our approach uses TDDFT to compute the electronic stopping from first principles in several directions and then machine learning to interpolate to other directions at a cost of 10 million times fewer core-hours. We demonstrate the combined approach in a study of proton irradiation in aluminum and employ it to predict how the depth of maximum energy deposition, the “Bragg Peak,” varies depending on the incident angle—a quantity otherwise inaccessible to modelers and far outside the scales of quantum mechanical simulations. The lack of any experimental information requirement makes our method applicable to most materials, and its speed makes it a prime candidate for enabling quantum-to-continuum models of radiation damage. The prospect of reusing valuable TDDFT data for training the model makes our approach appealing for applications in the age of materials data science.

36 MATERIALS SCIENCE↗

Developing reliable machine learning interatomic potential for Fe–Cr–Ni austenitic alloys

Gaining atomistic understanding of mechanical behavior of heat-resistant structural materials such as Fe–Cr–Ni-based alloys requires an approach with an accuracy close to density functional theory (DFT) that considers the intrinsic properties of the bulk lattice and important defects such as stacking faults, grain boundaries, and surfaces. This work aims to develop reliable machine learning interatomic potential (MLIAP) at cross-scale for Fe–Cr–Ni ternary alloys with a focus on the face-centered-cubic (fcc) solid solution structure. Leveraging the advantages of moment tensor potentials, which typically necessitate a relatively small training dataset and enable rapid calculations using the large-scale atomic/molecular massively parallel simulator package, we ensure the stability and accuracy of the trained potentials. Important defects such as stacking faults, grain boundaries, and surfaces for wide-range compositions are investigated. Structural, thermal, elastic, and defect properties are determined from molecular dynamics simulations comprising several thousand atoms, generated via canonical Monte Carlo simulations guided by the trained potential. The trained potential allows efficient atomic simulations of structural, thermal, and mechanical properties of fcc Fe–Cr–Ni solid solution alloys as a function of composition and temperature. Therefore, the MLIAP approach represents a major advancement from DFT calculations that are limited to small simulation sizes and traditional molecular dynamics simulations using relatively low accuracy potentials. Furthermore, this work outlines a practical foundation for further investigating the structural evolution and mechanical behavior of austenitic stainless steel and nickel-based alloys in a wide array of applications in extreme environments.

Crystal structure↗

A transferable classical force field to describe glyme based lithium solvate ionic liquids

A non-polarizable force field for lithium (Li + ) and bis(trifluoromethanesulfonyl)imide (TFSI – ) ions solvated in diglyme at around 0.2 mol fraction salt concentration was developed based on ab initio molecular dynamics (AIMD) simulations and a modified polymer consistent force field model. A force–torque matching based scheme, in conjunction with a genetic algorithm, was used to determine the Lennard-Jones (LJ) parameters of the ion–ion and ion–solvent interactions. This force field includes a partial charge scaling factor and a scaling factor for the 1–4 interactions. The resulting force field successfully reproduces the radial distribution function of the AIMD simulations and shows better agreement compared to the unmodified force field. The new force field was then used to simulate salt solutions with glymes of increasing chain lengths and different salt concentrations. The comparison of the MD simulations, using the new force field, with experimental data at different salt concentrations and AIMD simulations on equimolar concentrations of the triglyme system demonstrates the transferability of the force field parameters to longer glymes and higher salt concentrations. Furthermore, the force field appears to reproduce the features of the experimental x-ray structure factors, suggesting accuracy beyond the first solvation shell, for equimolar salt solutions using both triglyme and tetraglyme as the solvent. Altogether, the new force field was found to accurately reproduce the molecular descriptions of LiTFSI-glyme systems not only at various salt concentrations but also with glymes of different chain lengths. Thus, the new force field provides a useful and accurate tool to perform in silico studies of this family of systems at the atomistic level.

25 ENERGY STORAGE↗

Initial decomposition mechanisms of 2,4,6-triamino-1,3,5-trinitrobenzene (TATB) and their kinetic isotope effect

2,4,6-triamino-1,3,5-trinitrobenzene (TATB) is an insensitive High Explosive (HE) that is widely studied to better understand the physical properties of safety and sensitivity of HE. A dominant initial decomposition mechanism of TATB is believed to be a dehydration reaction that forms mono- and di-furazans, although other mechanisms have been reported. In this work, seven initial decomposition mechanisms were modeled with ab initio simulations to calculate its free energy barriers, decomposition rates, and kinetic isotope effects. The energy barrier for mono-benzofurazan mechanisms was found to be high, >61 kcal/mol in the gas phase; however, the reaction energy can decrease significantly in a disordered condensed state. The predicted kinetic isotope effect ratio of the furazan mechanism was found to be k h /k d ≈ 1.41 at 60K, in agreement with the experiment. The NO 2 scission mechanism was found to be an entropy-driven mechanism because the free energy barrier decreased significantly with temperature, making it the most energetically favorable mechanism at high temperatures in the gas phase. So the results provide a better understanding of the atomistic decomposition mechanisms of TATB and may be useful for improving models of safety and sensitivity.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Discovery of multimechanisms of screw dislocation interaction in bcc iron from open-ended saddle point searches

Dislocation motion and interactions determine mechanical properties in body-centered cubic (bcc) metallic materials. However, studying mechanisms for the screw dislocation interaction is fundamentally challenging since many underlying processes involve mesotimescales and atomistic resolution, currently inaccessible by either experimental techniques or continuum theoretical methods. Here, in this paper, we develop a computational capability based on self-evolving atomistic kinetic Monte Carlo (SEAKMC) to sample the critical events and saddle point energies related to screw dislocations and their junctions. The method is first validated by calculating the stress dependence of Peierls barriers and formation energies of kink pairs and cross-slip kink pairs on a single screw dislocation in bcc iron. Then the method is applied to a binary junction of a pair of intersecting screw dislocations, the structure of which is crucial for low-temperature plastic deformation. We identify three important mechanisms: coplanar cross-slipping, jog-pinning, and a previously unknown unzipping mechanism during the evolution of the binary junction. The mechanisms are then further validated using classical molecular dynamics simulations. The computational capability developed in this paper provides an effective tool to evaluate screw dislocation related thermally activated events in complex stress conditions. The mechanisms discovered in this paper provide critical insights into temperature dependence of the anomalous slip, a breakdown of the Schmidt law, during the plastic deformation in bcc iron and can be generalized to other bcc metals.

36 MATERIALS SCIENCE↗

Artificial neural network potentials for mechanics and fracture dynamics of two-dimensional crystals **

Understanding the mechanics and failure of materials at the nanoscale is critical for their engineering and applications. The accurate atomistic modeling of brittle failure with crack propagation in covalent crystals requires a quantum mechanics-based description of individual bond-breaking events. Artificial neural network potentials (NNPs) have emerged to overcome the traditional, physics-based modeling tradeoff between accuracy and accessible time and length scales. Previous studies have shown successful applications of NNPs for describing the structure and dynamics of molecular systems and amorphous or liquid phases of materials. However, their application to deformation and failure processes in materials is still uncommon. In this study, we discuss the apparent limitations of NNPs for the description of deformation and fracture under loadings and propose a way to generate and select training data for their employment in simulations of deformation and fracture simulations of crystals. We applied the proposed approach to 2D crystalline graphene, utilizing the density-functional tight-binding method for more efficient and extensive data generation in place of density functional theory. Then, we explored how the data selection affects the accuracy of the developed artificial NNPs. It revealed that NNP’s reliability should not only be measured based on the total energy and atomic force comparisons for reference structures but also utilize comparisons for physical properties, e.g. stress–strain curves and geometric deformation. In sharp contrast to popular reactive bond order potentials, our optimized NNP predicts straight crack propagation in graphene along both armchair and zigzag (ZZ) lattice directions, as well as higher fracture toughness of ZZ edge direction. Our study provides significant insight into crack propagation mechanisms on atomic scales and highlights strategies for NNP developments of broader materials.

2D materials↗

Energy localization efficiency in 1,3,5-trinitro-2,4,6-triaminobenzene pore collapse mechanisms

Atomistic and continuum scale modeling efforts have shown that the shock-induced collapse of porosity can occur via a wide range of mechanisms dependent on pore morphology, the shockwave pressure, and material properties. The mechanisms that occur under weaker shocks tend to be more efficient at localizing thermal energy but do not result in high, absolute temperatures or spatially large localizations compared to mechanisms found under strong shock conditions. However, the energetic material 1,3,5-trinitro-2,4,6-triaminobenzene (TATB) undergoes a wide range of collapse mechanisms that are not typical of similar materials, leaving the collapse mechanisms and the resultant energy localization from the collapse, i.e., hotspots, relatively uncharacterized. Therefore, we present the pore collapse simulations of cylindrical pores in TATB for a wide range of pore sizes and shock strengths that trigger viscoplastic collapses that occur almost entirely perpendicular to the shock direction for weak shocks and hydrodynamic-like collapses for strong shocks that do not break the strong hydrogen bonds of the TATB basal planes. The resulting hotspot temperature fields from these mechanisms follow trends that differ considerably from other energetic materials; hence, we compare them under normalized temperature values to assess the relative efficiency of each mechanism to localize energy. The local intra-molecular strain energy of the hotspots is also assessed to better understand the physical mechanisms behind the phenomena that lead to a latent potential energy.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Machine learning interatomic potential for silicon-nitride (Si 3 N 4 ) by active learning

Silicon nitride (Si 3 N 4 ) is an extensively used material in the automotive, aerospace, and semiconductor industries. However, its widespread use is in contrast to the scarce availability of reliable interatomic potentials that can be employed to study various aspects of this material on an atomistic scale, particularly its amorphous phase. In this work, we developed a machine learning interatomic potential, using an efficient active learning technique, combined with the Gaussian approximation potential (GAP) method. Our strategy is based on using an inexpensive empirical potential to generate an initial dataset of atomic configurations, for which energies and forces were recalculated with density functional theory (DFT); thereafter, a GAP was trained on these data and an iterative re-training algorithm was used to improve it by learning on-the-fly. When compared to DFT, our potential yielded a mean absolute error of 8 meV/atom in energy calculations for a variety of liquid and amorphous structures and a speed-up of molecular dynamics simulations by 3–4 orders of magnitude, while achieving a first-rate agreement with experimental results. Our potential is publicly available in an open-access repository.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Charge Transport in Solvated Donor–Acceptor Functionalized Peptoids: Molecular Dynamics and Rate Theory

Scalable solar-energy conversion requires photoactive materials that combine the efficiency of natural photosynthetic systems with the stability and processability needed for practical applications. Achieving reliable charge transport in soft, self-assembled organic materials remains challenging, as structural fluctuations and environmental effects strongly influence charge-transfer (CT) rates. Here, we present a broadly applicable computational framework for evaluating CT rates in the condensed phase, combining Fermi’s golden rule rate theory with inputs from all-atom molecular dynamics (MD) simulations and first-principles electronic-structure calculations. The approach does not rely on system-specific parametrization and is applicable to a wide range of soft and disordered materials. We demonstrate the applicability and usefulness of the framework on redox-active peptoids functionalized with iron–porphyrin (Fe–P) complexes, a bioinspired platform with programmable donor–acceptor units and tunable three-dimensional organization. The calculated CT rates exhibit strong sensitivity to molecular conformation, with variations spanning several orders of magnitude. This dependence is shown to arise from the pronounced variation in diabatic electronic coupling with the relative orientations and separations of the Fe–P complexes across the conformational ensemble. The framework provides a consistent route for connecting atomistic structure to CT kinetics in the condensed phase and enables analysis of structure–rate relations in organic semiconducting systems.

Charge transfer↗

Ultrafast visualization of incipient plasticity in dynamically compressed matter

Plasticity is ubiquitous and plays a critical role in material deformation and damage; it inherently involves the atomistic length scale and picosecond time scale. A fundamental understanding of the elastic-plastic deformation transition, in particular, incipient plasticity, has been a grand challenge in high-pressure and high-strain-rate environments, impeded largely by experimental limitations on spatial and temporal resolution. Here, we report femtosecond MeV electron diffraction measurements visualizing the three-dimensional (3D) response of single-crystal aluminum to the ultrafast laser-induced compression. We capture lattice transitioning from a purely elastic to a plastically relaxed state within 5 ps, after reaching an elastic limit of ~25 GPa. Our results allow the direct determination of dislocation nucleation and transport that constitute the underlying defect kinetics of incipient plasticity. Large-scale molecular dynamics simulations show good agreement with the experiment and provide an atomic-level description of the dislocation-mediated plasticity.

36 MATERIALS SCIENCE↗

Localized High-Concentration Electrolytes Get More Localized

Liquid electrolytes in batteries are typically treated as macroscopically homogeneous ionic transport media, despite having complex chemical composition and atomistic solvation structures, thus leaving a knowledge gap of microstructural characteristics. A promising electrolyte system design has recently been developed with the title of a localized high-concentration electrolyte (LHCE). These electrolytes are a summation of three components – a charge-carrying salt, a solvent that solvates the salt, and a diluent that is sparingly interactive with the salt in terms of ion solvation. This creates the perception of a high-concentration electrolyte (HCE) with high anion-cation interactions that supports a salt-derived, stable solid-electrolyte interphase, while an LHCE improves bulk electrolyte properties, such as ionic conductivity and viscosity, when compared to an HCE. Much trial by error design of this LHCE concept has been supported by simulations to confirm ionic interactions, cycling data to confirm cell stability, and post-mortem analysis to provide evidence of mechanisms. However, a systematic design to extend the capabilities of LHCEs is still to be desired. Here, we analyzed a specific LHCE mixture to dictate the best viable mixture that extends the localization of solvation structures while maintaining viable cell-level capabilities. We seek to observe and understand solvent-to-salt interactions that impact electrolyte performance. These interactions range from single-ion solvation, multidentate interactions (i.e., solvation-driven clustering), to more widespread network-level interactions. With the support of both experimental and computational analysis of different electrolyte features, we have begun a methodology of formulating the most ideal LHCE mixtures for improving the cyclability of high-capacity battery chemistries.

25 ENERGY STORAGE↗

Molecular Origins of the Barriers to Proton Transport in Acidic Aqueous Solutions

The self-consistent iterative multistate empirical valence bond (SCI-MS-EVB) method is used to analyze the structure, thermodynamics, and dynamics of hydrochloric acid solutions. The reorientation timescales of irreversible proton transport are elucidated by simulating 0.43 M, 0.85 M, 1.68 M, and 3.26 M HCl solutions at 270 K, 285 K, 300 K, 315 K, and 330 K. The results indicate increased counter-ion pairing with increasing concentration, which manifests itself via a reduced hydronium oxygen–chloride (O*-Cl) structuring in the radial distribution functions. Increasing ionic concentration also reduces the diffusion of the hydrated excess protons, principally by reducing the contribution of the Grotthuss proton hopping (shuttling) mechanism to the overall diffusion process. In agreement with prior experimental findings, a decrease in the activation energy of reorientation timescales was also observed, which is explicitly explained using activated rate theory and an energy-entropy decomposition of the state-averaged radial distribution functions. Furthermore, these results provide atomistic verification of suggestions from recent two-dimensional infrared spectroscopy experiments that chloride anions (as opposed to hydrated excess protons) create entropic barriers to proton transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ethanol-Induced Condensation and Decondensation in DNA-Linked Nanoparticles: A Nucleosome-like Model for the Condensed State

Inspired by the conventional use of ethanol to induce DNA precipitation, ethanol condensation has been applied as a routine method to dynamically tune “bond” lengths (i.e., the surface-to-surface distances between adjacent nanoparticles that are linked by DNA) and thermal stabilities of colloidal crystals involving DNA-linked nanoparticles. However, the underlying mechanism of how the DNA bond that links gold nanoparticles changes in this class of colloidal crystals in response to ethanol remains unclear. Here, we conducted a series of all-atom molecular dynamic (MD) simulations to explore the free energy landscape for DNA condensation and decondensation. Our simulations confirm that DNA condensation is energetically much more favorable under 80% ethanol conditions than in pure water, as a result of ethanol’s role in enhancing electrostatic interactions between oppositely charged species. Moreover, the condensed DNA adopts B-form in pure water and A-form in 80% ethanol, which indicates that the higher-order transition does not affect DNA’s conformational preferences. We further propose a nucleosome-like supercoiled model for the DNA condensed state, and we show that the DNA end-to-end distance derived from this model matches the experimentally measured DNA bond length of about 3 nm in the fully condensed state for DNA where the measured length is 16 nm in water. Altogether, this study provides an atomistic understanding of the mechanism underlying ethanol-induced condensation and water-induced decondensation, while our proposed nucleosome-like model allows the design of new strategies for interpreting experimental studies of DNA condensation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Predicting Thermochemical Equilibria with Interacting Defects: Sr 1 − x Ce x Mn O 3 − δ Alloys for Water Splitting

Solar thermochemical hydrogen is one of the few potential routes towards direct fuel production from renewable energy sources, but the thermodynamic boundary conditions for efficient and economic energy conversion are challenging. Success or failure of a given oxide working material depends on the subtle balance between enthalpy and entropy contributions in the redox processes. Developing a mechanistic understanding of the behavior of materials on the basis of atomistic models and first-principles calculations is an important part of advancing the technology. One challenge is to quantitatively predict thermochemical equilibria at high concentrations when the redox-active defects start to interact with each other, thereby impeding the formation of additional defects. This problem is of more general importance to applications that rely on high levels of off-stoichiometry or doping, including, for example, batteries, thermoelectrics, and ceramic fuel cells. To account for such repulsive defect interactions, we introduce a statistical mechanics approach, defining an expression for the free energy of defect interaction based on limited sampling of defect configurations in density functional theory supercell calculations. The parameterization of this energy contribution as a function of defect concentration and temperature allows on-the-fly simulation of thermochemical equilibria. The approach consistently incorporates finite temperature effects by including the leading contributions to the temperature-dependent free energy for the case at hand, i.e., the ideal gas and configurational enthalpies and entropies. We demonstrate the capability and utility of the approach by simulating the water splitting redox processes for Sr 1 − x Ce x Mn O 3 − δ alloys. Published by the American Physical Society 2024

08 HYDROGEN↗

Observations of grain-boundary phase transformations in an elemental metal

The theory of grain boundary (the interface between crystallites, GB) structure has a long history 1 and the concept of GBs undergoing phase transformations was proposed 50 years ago 2,3 . The underlying assumption was that multiple stable and metastable states exist for different GB orientations 4,5,6 . The terminology ‘complexion’ was recently proposed to distinguish between interfacial states that differ in any equilibrium thermodynamic property 7 . Different types of complexion and transitions between complexions have been characterized, mostly in binary or multicomponent systems 8,9,10,11,12,13,14,15,16,17,18,19 . Simulations have provided insight into the phase behaviour of interfaces and shown that GB transitions can occur in many material systems 20,21,22,23,24 . However, the direct experimental observation and transformation kinetics of GBs in an elemental metal have remained elusive. In this work we demonstrate atomic-scale GB phase coexistence and transformations at symmetric and asymmetric $[11\bar{1}]$ tilt GBs in elemental copper. Atomic-resolution imaging reveals the coexistence of two different structures at Σ19b GBs (where Σ19 is the density of coincident sites and b is a GB variant), in agreement with evolutionary GB structure search and clustering analysis 21,25,26 . We also use finite-temperature molecular dynamics simulations to explore the coexistence and transformation kinetics of these GB phases. Our results demonstrate how GB phases can be kinetically trapped, enabling atomic-scale room-temperature observations. Our work paves the way for atomic-scale in situ studies of metallic GB phase transformations, which were previously detected only indirectly 9,15,27,28,29 , through their influence on abnormal grain growth, non-Arrhenius-type diffusion or liquid metal embrittlement.

36 MATERIALS SCIENCE↗

Data Generation for Machine Learning Interatomic Potentials and Beyond

The field of data-driven chemistry is undergoing an evolution, driven by innovations in machine learning models for predicting molecular properties and behavior. Recent strides in ML-based interatomic potentials have paved the way for accurate modeling of diverse chemical and structural properties at the atomic level. The key determinant defining MLIP reliability remains the quality of the training data. A paramount challenge lies in constructing training sets that capture specific domains in the vast chemical and structural space. This Review navigates the intricate landscape of essential components and integrity of training data that ensure the extensibility and transferability of the resulting models. We delve into the details of active learning, discussing its various facets and implementations. We outline different types of uncertainty quantification applied to atomistic data acquisition and the correlations between estimated uncertainty and true error. The role of atomistic data samplers in generating diverse and informative structures is highlighted. Furthermore, we discuss data acquisition via modified and surrogate potential energy surfaces as an innovative approach to diversify training data. The Review also provides a list of publicly available data sets that cover essential domains of chemical space.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ion correlations drive charge overscreening and heterogeneous nucleation at solid–aqueous electrolyte interfaces

Significance Ion distributions at charged solid–water interfaces, referred to as the electrical double layer (EDL), are poorly understood at high ion concentrations, in part due to the lack of molecular-scale descriptions of the interactions between adsorbed hydrated ions. Here, direct visualization of the salinity-dependent evolution of EDL structure reveals molecular origins of nonclassical transformation of the EDL, in which charge overscreening and heterogeneous nucleation are driven by ion–ion correlations at the interfaces. This manifestation of the atomistic basis of nonclassical behaviors provides a much-needed understanding of the impact of ion cooperativity at charged interfaces for the development of predictive models for element transport in natural environments and advanced technologies for material growth and synthesis in saline environments.

36 MATERIALS SCIENCE↗

Complete inhibition of a polyol nucleation by a micromolar biopolymer additive

Preventing spontaneous crystallization of supersaturated solutions by additives is of critical interest to successful process design and implementation, with numerous applications in chemical, pharmaceutical, medical, pigment, and food industries, but challenges remain in laboratory and industry settings and fundamental understanding is lacking. When copresented with antifreeze proteins (AFPs), otherwise spontaneously crystallizing osmolytes are maintained at high supersaturations for months in over-wintering organisms. Thus, we here explore the inhibition phenomenon by AFPs, using persistent crystallization of a common sugar alcohol, D-mannitol, as a case study. We report experimentally that DAFP1, an insect AFP, completely inhibits D-mannitol nucleation. Computer simulations reveal a new mechanism for crystallization inhibition where the population of the crystal-forming conformers are selectively bound and randomized in solution by hydrogen bonding to the protein surface. These results highlight the advantages of using natural polymers to address crystallization inhibition challenges and suggest new strategies in controlling the nucleation processes.

59 BASIC BIOLOGICAL SCIENCES↗