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At least 1,189 records · Page 66

Scale-free, programmable design of morphable chain loops of kilobots and colloidal motors

Micron-scale robots require systems that can morph into arbitrary target configurations controlled by external agents such as heat, light, electricity, and chemical environment. Achieving this behavior using conventional approaches is challenging because the available materials at these scales are not programmable like their macroscopic counterparts. To overcome this challenge, we propose a design strategy to make a robotic machine that is both programmable and compatible with colloidal-scale physics. Our strategy uses motors in the form of active colloidal particles that constantly propel forward. We sequence these motors end-to-end in a closed chain forming a two-dimensional loop that folds under its mechanical constraints. We encode the target loop shape and its motion by regulating six design parameters, each scale-invariant and achievable at the colloidal scale. We demonstrate the plausibility of our design strategy using centimeter-scale robots called kilobots . We use Brownian dynamics simulation to explore the large design space beyond that possible with kilobots, and present an analytical theory to aid the design process. Multiple loops can also be fused together to achieve several complex shapes and robotic behaviors, demonstrated by folding a letter shape “M,” a dynamic gripper , and a dynamic pacman . The material-agnostic, scale-free, and programmable nature of our design enables building a variety of reconfigurable and autonomous robots at both colloidal scales and macroscales.

36 MATERIALS SCIENCE↗

Unraveling disadhesion mechanism of epoxy/CSH interface under aggressive conditions

Almost all FRP-reinforced concrete exposed to the marine environment are susceptible to durability deficiencies due to failure of the FRP/epoxy/concrete interface, especially the vulnerable epoxy/concrete interface, which is frequently attacked by water and ions. Herein, molecular dynamics simulations of epoxy/CSH interface under different environmental exposures are utilized to specifically elucidate the degradation principles of water and ions on the bonding properties and mechanical responses of the epoxy/concrete interface. The environmental sequences associated with the interfacial bonding degradation are arranged as Na{sub 2}SO{sub 4} + NaCl>NaCl>Na{sub 2}SO{sub 4} > Water>Dry. Remarkably, water molecules weaken the interaction between the epoxy and CSH by robbing interfacial H- and Ca-O bonds, thereby reducing the energy barrier to interfacial peel and shear failure. The weakening effects are exacerbated by the presence of aggressive ions, as Na{sup +} ions attracted to the CSH surface accumulate more water molecules in the interfacial region by forming hydrated ions clusters, which ultimately accelerates the epoxy/CSH interfacial degradation.

36 MATERIALS SCIENCE↗

Response of Sulfonated Polystyrene Melts to Nonlinear Elongation Flows

Ionizable polymers form dynamic networks with domains controlled by two distinct energy scales, ionic interactions and van der Waals forces; both evolve under elongational flows during their processing into viable materials. A molecular level insight of their nonlinear response, paramount to controlling their structure, is attained by fully atomistic molecular dynamics simulations of a model ionizable polymer, polystyrene sulfonate. As a function of increasing elongational flow rate, the systems display an initial elastic response, followed by an ionic fraction-dependent strain hardening, stress overshoot, and eventually strain-thinning. As the sulfonation fraction increases, the chain elongation becomes more heterogeneous. Finally, flow-driven ionic assembly dynamics that continuously break and reform control the response of the system.

36 MATERIALS SCIENCE↗

Neural network representation of electronic structure from ab initio molecular dynamics

Despite their rich information content, electronic structure data amassed at high volumes in ab initio molecular dynamics simulations are generally under-utilized. Here we introduce a transferable high-fidelity neural network representation of such data in the form of tight-binding Hamiltonians for crystalline materials. This predictive representation of ab initio electronic structure, combined with machine-learning boosted molecular dynamics, enables efficient and accurate electronic evolution and sampling. When it is applied to a one-dimension charge-density wave material, carbyne, we are able to compute the spectral function and optical conductivity in the canonical ensemble. The spectral functions evaluated during soliton-antisoliton pair annihilation process reveal significant renormalization of low-energy edge modes due to retarded electron-lattice coupling beyond the Born–Oppenheimer limit. The availability of an efficient and reusable surrogate model for the electronic structure dynamical system will enable calculating many interesting physical properties, paving the way to previously inaccessible or challenging avenues in materials modeling.

74 ATOMIC AND MOLECULAR PHYSICS↗

Addition of Chloroform in a Solvent-in-Salt Electrolyte: Outcomes in the Microscopic Dynamics in Bulk and Confinement

Solvent-in-salt electrolytes (SISEs) are a promising alternative to the electrolytes currently used in commercial devices. Despite the SISEs’ advantages, their utilization is not yet realized due to the poor mobility of their chemical species. Here, we explore this problem by adding chloroform to a SISE formed by acetonitrile and a Li-salt. First, we performed illustrative cycling experiments to highlight the potential of this approach. Then, we focused on the description of the microscopic dynamics of the electrolytes and exposed the relevant aspects to be considered for their optimal performance. While the conductivity at low temperatures may be enhanced by the addition of chloroform, only subtle changes occur at room temperature. As revealed by molecular dynamics simulations and quasielastic neutron scattering (QENS) experiments, this effect is related to the preservation of the structure expected for a highly concentrated solution and promotion of the formation of ionic aggregates. These outcomes occur despite the increase in the overall mobility of the chemical species. The dynamics of the electrolytes in porous carbon was also investigated using QENS. In these circumstances, low concentrations of chloroform lead to diffusivities of the molecular species higher than those observed for the bulk electrolytes. As chloroform’s concentration increases, no further changes in the diffusivities are observed. Nonetheless, chloroform is mostly immobilized on the carbon surfaces and this behavior may be intensified at compositions closer to the eutectic mixture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Charge Dependence of Local Hydration Dynamics in Poly(Acrylic Acid) Solutions

Localized measurements of hydration dynamics surrounding poly(acrylic acid) (pAA) chains are executed using Overhauser dynamic nuclear polarization relaxometry to determine the role of polymer protonation state on the polymer solvation environment. Alterations in polymer concentration and solution pH uncovered three different regimes of local water dynamics ranging from bulk-water-like to subdued water diffusivity. These experiments, combined with molecular dynamics simulations, reveal that the presence of deprotonated carboxylic acid groups promotes a hydrophilic local environment and extended polymer chain configurations that together incentivize the incorporation of bulk-like water near the polymer. This results in a stretched polymer conformation that leads to faster observed hydration dynamics in the local hydration environment. Meanwhile, protonated carboxylic acid groups are expected to engage in intrapolymer hydrogen bonding between monomer groups, resulting in a more collapsed conformation and slower observed hydration dynamics. The importance of the carboxylic acid groups on mediating hydration behavior is further illustrated by their role in dictating the solvation environment around poly(acrylic acid-stat-(poly(ethylene glycol) methyl ether acrylate) (p(AA-stat-PEGMEA)) copolymers with varying monomer ratios. Furthermore, these local hydration measurements establish a connection between local water dynamics and polymer chain conformation and may provide additional molecular perspective into poly(acrylic acid)’s classification as a superabsorbent polymer.

Conformation↗

Dynamics of Radiation Damage Buildup in Ultrathin Hexagonal Boron Nitride Films under Ion Bombardment

Two-dimensional hexagonal boron nitride (hBN) is attractive for several emerging applications. Ion bombardment can be used to modify the hBN properties. However, the understanding of radiation damage buildup in hBN remains limited. Here, we investigate the effects of the dose rate and ion mass on radiation damage buildup by studying 40 nm-thick hBN films bombarded at room temperature with 500 keV 4 He, 15 N, 40 Ar, and 129 Xe ions and comparing with results for ion bombardment of polycrystalline hBN ceramics. Raman spectroscopy is used to quantify damage buildup, and transmission electron microscopy is used for microstructural analysis. Experiments are complemented by molecular dynamics simulations of the formation and evolution of point defects. Lighter ions are found to be more efficient at disordering hBN than heavier ions. This observation points to a critical role of intracascade defect processes. In contrast, a negligible dose rate effect observed suggests limited intercascade defect dynamic annealing processes for these irradiation conditions. These findings provide a fundamental basis for hBN defect engineering.

2D materials↗

Effects of surface vacancy-adatom pair formation on PFC tungsten surface morphological response

Abstract We report a simulation study of the effect of He-irradiation-induced surface vacancy-adatom pair formation on the surface morphological evolution of plasma-facing component (PFC) tungsten and examine a number of factors that impact such evolution. Our analysis is based on self-consistent dynamical simulations according to an atomistically-informed, continuum-scale surface evolution model that has been developed following a hierarchical multiscale modeling strategy and can access the spatiotemporal scales of relevance to fuzz formation. The model accounts for the flux of surface adatoms generated as a result of the surface vacancy-adatom pair formation effect upon He implantation, which contributes to the anisotropic growth of surface nanostructural features due to the different rates of adatom diffusion along and across step edges of islands on the tungsten surface. We have carried out atomic-scale computations of optimal diffusion pathways along and across island step edges on the W(110) surface and calculated Ehrlich–Schwoebel (ES) barriers in adatom diffusion along and across such step edges. This aspect of surface adatom diffusion contributes to anisotropic surface atomic fluxes, terrace and step diffusive currents, and has been incorporated into our PFC surface evolution model, which predicts the formation of preferentially aligned nanoridge stripe patterns on the PFC surface. We establish that these anisotropic diffusive currents accelerate nanotendril growth on the PFC surface and the onset of surface nanostructure pattern formation. We also explore systematically the dependence of the PFC surface morphological response on the surface temperature and He ion incident flux, characterize in detail the resulting surface topographies and growth kinetics, and compare the predicted surface morphologies with experimental observations. Our simulation predictions for the emerging surface nanostructure patterns under certain plasma exposure conditions are consistent with experimental findings in the literature.

36 MATERIALS SCIENCE↗

Helium bubble size effects on the surface morphological response of plasma-facing tungsten

Abstract We report a simulation study on the effects of helium (He) bubble size on the morphological evolution and pattern formation on the surface of tungsten used as a plasma-facing component (PFC) in nuclear fusion devices. We have carried out a systematic investigation based on self-consistent dynamical simulations of surface morphological evolution according to an atomistically-informed, 3D continuum-scale model that captures well the relevant length and time scales of surface nanostructure formation in PFC tungsten. The model accounts for PFC surface diffusion, driven by the biaxial compressive stress originating from the over-pressurized He bubbles in the near-surface region of PFC tungsten as a result of He plasma exposure, combined with the formation of self-interstitial atoms in tungsten that diffuse toward the PFC surface and the flux of surface adatoms generated as a result of surface vacancy-adatom pair formation upon He implantation; this transport of surface adatoms contributes to the anisotropic growth of surface nanostructural features due to the different rates of adatom diffusion along and across step edges of islands on the tungsten surface. Our detailed analysis reveals that varying the average He bubble size plays an important role in the PFC surface growth kinetics as well as the resulting surface topography. Specifically, we find that an increase in the He bubble size leads to a deceleration in the growth rate of the tungsten nanotendrils that emanate from the PFC surface. We also find that the separation distance between the resulting surface features increases with increasing He bubble size, as well as over time. This coarsening effect is a thermally activated process resulting in an accurate description of the temperature dependence of the average surface feature separation by an Arrhenius relation.

36 MATERIALS SCIENCE↗

Uncertainty Error Modeling for Non-Linear State Estimation With Unsynchronized SCADA and µPMU Measurements

Distribution systems of the future smart grid require enhancements to the reliability of distribution system state estimation (DSSE) in the face of low measurement redundancy, unsynchronized measurements, and dynamic load profiles. Micro phasor measurement units (µPMUs) facilitate co-synchronized measurements with high granularity, albeit at an often prohibitively expensive installation cost. Supervisory control and data acquisition (SCADA) measurements can supplement µPMU data, although they are received at a slower sampling rate. Further complicating matters is the uncertainty associated with load dynamics and unsynchronized measurements–not only are the SCADA and µPMU measurements not synchronized with each other, but the SCADA measurements themselves are received at different time intervals with respect to one another. This paper proposes a non-linear state estimation framework which models dynamic load uncertainty error by updating the variances of the unsynchronized measurements, leading to a time-varying system of weights in the weighted least squares state estimator. Case studies are performed on the 33-Bus Distribution System in MATPOWER, using Ornstein–Uhlenbeck stochastic processes to simulate dynamic load conditions.

Cooper, Austin↗

Extending JuTrack’s capabilities to the FRIB accelerator to enhance online modeling

JuTrack is a Julia-based accelerator modeling and tracking package that utilizes compiler-level automatic differentiation (AD) to enable fast and accurate derivative calculations. While JuTrack provides a solid foundation for beam dynamics simulations, its capabilities must be extended to support the Facility for Rare Isotopes (FRIB) linac. This includes modeling heavy-ion linac accelerator components such as the liquid-lithium charge stripper, which facilitates efficient acceleration by remove electrons from heavy isotopes, and incorporating multi-charge state acceleration tracking, which allows for charge-dependent beam dynamics. These extensions address challenges such as the beam matching and optimization of multi charge state through various accelerating structures and beam-material interaction modeling while maintaining the auto differentiation capability. This work focuses on adapting JuTrack to incorporate these elements, enhancing its online modeling abilities. We present modifications to JuTrack’s framework and demonstrate their performance in FRIB simulations.

Accelerator Physics↗

Minimization of Disorder as a Key Design Principle for Natural Sizes of Light Harvesting 2 Complexes

The light harvesting 2 (LH2) complex of purple bacteria has excellent energy conversion efficiency. Clarifying the design principle behind such efficiency at the atomistic level is crucial for understanding its structure–function relationship and can be utilized for the design of artificial light harvesting systems. To this end, we conducted comprehensive computational investigation of the dynamical and statistical nature of electronic excited states of pigment molecules in a natural LH2 complex with 9-fold symmetry and its two non-natural in silico analogues with 6- and 12-fold symmetries. To ensure reliable and efficient all-atomistic molecular dynamics simulations, we combined a well established interpolation approach for the construction of the potential energy surface with a neural network machine learning approach. Outcomes of these calculations clarify that non-natural forms of LH2-type complexes have significantly larger quasistatic disorder than those for the natural one. In addition, non-natural systems have more disruptions of the hydrogen bonding, underscoring its crucial role for reducing the disorder. On the other hand, local environmental dynamics are relatively insensitive to the structural changes although there is moderate enhancement in the anharmonic or interatomic components for the synthetic ones. These findings based on all-atomistic simulations provide direct computational evidence that the structure and sizes of natural LH2 complexes are designed to minimize the energetic disorder. We analyze quantitative implications of these for the energy transferring capability of the LH2 complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly tail-asymmetric lipids interdigitate and cause bidirectional ordering

Phospholipids form structurally and compositionally diverse membranes. A less studied type of compositional diversity involves phospholipid tail variety. Some phospholipids contain two acyl tails which differ in length. These tail-asymmetric lipids are shown to contribute to temperature sensitivity, oxygen adaptability, and membrane fluidity. Membranes of a highly virulent intracellular bacterium, Francisella tularensis, contain highly tail-asymmetric 1-lignoceroyl-2-decanoyl-sn-glycero-3-phosphatidylethanolamine (XJPE) lipids which were previously shown to inhibit inflammatory responses in host cells. XJPE tails have unusually high asymmetry, and how they contribute to membrane properties on a molecular level is unknown. Here, we use small angle X-ray scattering and molecular dynamics simulations to investigate how varying XJPE ratios alters properties of simple membranes. Our results demonstrate that at high concentration they promote liquid-to-gel transition in otherwise liquid membranes, while at low concentration they are tolerated well, minimally altering membrane properties. In liquid membranes, XJPE lipids dynamically adopt two main conformations; with the long tail extended into the opposing leaflet or bent-back residing in its own leaflet. When added to both leaflets XJPE primarily adopts an extended confirmation, while asymmetric addition results in more bent-back orientations. The former increases tail ordering and the latter decreases it. XJPE tails adopt different conformations that induce composition- and leaflet-dependent bidirectional effect on membrane fluidity and this suggests that Francisella tularensis could use tail asymmetry to facilitate vesicle fusion and destabilize host cells. The effect of tail-asymmetric lipids on complex membranes should be further investigated to reveal the regulatory roles of high tail asymmetry.

59 BASIC BIOLOGICAL SCIENCES↗

Ab Initio Bulk Free Energy Surface of Proper Ferroelectrics

We report a systematic and accurate approach for deriving the bulk free energy surface (FES), a function of temperature, polarization, and strain, from the first-principles density functional theory (DFT) of proper ferroelectrics. The core of our approach is the metadynamics algorithm that extracts the polarization dependence of the FES from all-atom molecular dynamics simulations without an a priori ansatz. The rest of the FES is derived from the metadynamics trajectories that span the relevant phase space. We demonstrate our approach in the case of lead titanate. The errors across the phase transition, due to DFT numerics, all-atom molecular dynamics, and free energy evaluation by enhanced sampling, can be systematically controlled and are of the order of 1 meV/atom. The accuracy of the resulting ab initio FES is only limited by the adopted functional approximation of DFT.

Xie, Pinchen [Lawrence Berkeley National Laborator↗

Temperature-induced gradual polymorphic structural crossover in liquid indium, tin, and antimony

Temperature-induced polymorphic structural crossover in metallic liquid indium (In), tin (Sn), and antimony (Sb) is investigated by in situ high-energy x-ray diffraction and ab initio molecular dynamics simulations. The results demonstrate the existence of a temperature-induced reversible and gradual structural crossover in these three liquids, reflecting from both “static” structures, e.g., peak positions of the structure factor and pair distribution function, bond angle distribution, number of tetrahedra, cluster connection, free volume, and dynamical behaviors, including the relaxation time, diffusion coefficient, and non-Gaussian parameter. Further, the main difference from liquid In, Sn, to Sb is that not only the large-sized free volume but also the anharmonicity and the dynamical heterogeneity increase significantly with the appearance of strong covalent bonds. These findings will deepen the understanding of liquid structure and the liquid-liquid transition in metallic liquids.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Spectra of magnetic fields from electroweak symmetry breaking

We characterize magnetic fields produced during electroweak symmetry breaking by nondynamical numerical simulations based on the Kibble mechanism. The generated magnetic fields were thought to have an energy spectrum ∝ k3 for small wave numbers k, but here we show that it is actually a spectrum ∝ k4 along with characteristic fluctuations in the magnetic helicity. Using scaling results from magnetohydro- dynamics simulations for the evolution and assuming that the initial magnetic field is coherent on the electroweak Hubble scale, we estimate the magnetic field strength to be ∼10−13 G on kpc scales at the present epoch for nonhelical fields. For maximally helical fields we obtain ∼10−10 G on Mpc scales. We also give scalings of these estimates for partially helical fields.

Vachaspati, Tanmay [Arizona State University]↗

Spin Dynamics of Triple-𝐐 Magnetic Orderings in a Triangular Lattice: Implications for Multi-𝐐 Orderings in General Two-Dimensional Lattices

Multi-𝐐 magnetic structures on two-dimensional (2D) lattices provide a key route to realizing topological physics in 2D magnetism. A major experimental challenge is to unambiguously confirm their formation by excluding the possibility of topologically trivial multidomain single- or double-𝐐 magnetic orders, which cannot be distinguished using conventional diffraction techniques. Here, we propose that long-wavelength spin dynamics offers a universal diagnostic for triangular lattices: Triple-𝐐 orders that preserve rotational symmetry and single- or double-𝐐 orders that break it exhibit qualitatively distinct anisotropies in their Goldstone-mode velocities, stemming from fundamental differences in their underlying spin configurations. We validate this concept using the metallic triangular-lattice antiferromagnet Co 0.325 ⁢TaS 2 , which hosts both a stripe-type single-𝐐 state and a triple-𝐐 tetrahedral ordering at different temperatures. Using inelastic neutron-scattering and spin dynamics simulations, we first refine the spin Hamiltonian by fitting the paramagnetic excitation spectra, allowing us to develop an unbiased model independent of magnetic ordering. We then show that the observed velocity profiles of the Goldstone modes agree with the high-temperature model’s predictions: markedly anisotropic for the single-𝐐 phase and near isotropic for the triple-𝐐 phase. Importantly, this contrast persists across various exchange parameters, highlighting its model-independent nature and suggesting potential applicability to other 2D lattice systems. Beyond the long-wavelength regime, we present a substantial discrepancy between the measured and simulated magnon spectra exclusively in the triple-𝐐 phase. We attribute this discrepancy to magnon energy renormalization arising from order-of-magnitude-enhanced magnon-magnon interactions in the triple-𝐐 phase, due to its noncollinear configuration. This work provides universal insight into the dynamical properties of topological multi-𝐐 magnetic orderings in 2D lattice structures, offering a broadly applicable diagnostic to distinguishing them from topologically trivial single- or double-𝐐 counterparts. The unequivocal confirmation of the triple-𝐐 structure in Co 0.325 ⁢TaS 2 further establishes it as a prominent material platform for exploring topological spin textures in the genuine 2D limit.

Park, Pyeongjae [Oak Ridge National Laboratory (OR↗

Relationship between microporous structure and light gas transport through glassy polymeric membranes revealed by molecular simulations

Microporous glassy polymers are attractive materials for gas separation membranes, due to their high permeability and tailorable selectivity, provided physical aging can be delayed. The archetypal microporous glassy polymer, PTMSP, can be blended with a hyper-crosslinked isatin–triptycene porous polymer network (PPN) to delay physical aging. However, while PPN is effective at reducing physical aging, it also affects the permeability of light gases through PTMSP. Molecular dynamics simulations were used here to shed fundamental light on the mechanisms responsible for these effects. Atomistic models are developed that satisfactorily reproduce experimental observations such as matrix density and cavity size distributions for neat PTMSP as well as for PTMSP–PPN blends. Analysis of the simulation results suggests that physical aging is delayed because the PPN inclusions slow down PTMSP relaxation while reducing the connectivity between free volume pockets. To understand how PPN inclusions affect light gas permeability, the atomistic models developed are used to probe CO 2 and CH 4 diffusion and sorption. These simulations are conducted for PTMSP matrices exhibiting varying density, towards reproducing experimental permeability data. Interrogating the simulation trajectories, it is discovered that while CH 4 travels preferentially through the free volume cavities, CO 2 preferentially interacts with the available surfaces, especially in the presence of PPN. These differences help interpret experimental observations. The transport of C 2 H 6 and H 2 S through PTMSP matrices was also investigated. These gases, and in particular H 2 S, were found to absorb within PTMSP, yielding very low diffusion coefficients. The ability to predict differences in diffusion pathways for various natural gas components unveils the possibility of engineering membranes to control permeability and selectivity towards large-scale applications.

Bao Le, Tran Thi [Univ. of Oklahoma, Norman, OK (U↗