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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 487 records · Page 27
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Data-Driven Discovery of Linear Molecular Probes with Optimal Selective Affinity for PFAS in Water

Approaches to tackle the wide and growing variety of highly persistent per- and polyfluoroalkyl substances (PFAS) are of pressing global need because of their detrimental human health effects, such as cancer, birth defects, and hormone imbalance. Sensitive, selective, and easy-to-use real-time sensors to monitor and detect PFAS and sorbents to extract them are critical to meeting government-mandated environmental concentrations. In this work, we combine all-atom molecular dynamics simulations, enhanced sampling, deep representational learning, and Bayesian optimization to perform high-throughput virtual screening for highly sensitive and selective molecular probes. Our molecular design space consists of 3850 linear hydrocarbon chains with varying degrees of halogenation with and without amine- and phosphine-based headgroups. By employing a data-driven search process, we efficiently explore the molecular design space to optimize the sensitivity to perfluorooctanesulfonic acid (PFOS) as a prototypical PFAS analyte and selectivity relative to a sodium dodecyl sulfate (SDS) interferent. We calculate 504 Gibbs free energies of probe-analyte and probe-interferent interactions and identify probes with PFOS association free energies of up to (-ΔG PFOS ) = 9.8 ± 0.2 kJ/mol and selectivities relative to SDS of (-ΔΔG PFOS–SDS ) = 3.1 ± 1.5 kJ/mol. A C 11 Br 23 P(CH 3 ) 2 probe containing 11 backbone brominated carbons and a tertiary phosphine headgroup possesses the most sensitive binding constant to PFOS within the defined search space of K b PFOS = 177.4 ± 12.7, and a semibrominated probe C 5 H 11 C 7 Br 14 N(CH 3 ) 2 containing 12 backbone carbons and a tertiary amine headgroup possesses the highest selectivity relative to SDS of K b PFOS /K b SDS = 4.6 ± 1.7. A retrospective analysis of our data to extract interpretable design rules reveals that the sensitivity of linear hydrogenated probes increases by approximately 1 kJ/mol per C–C bond. The addition or removal of halogen atoms and amine or phosphine headgroups produces nonmonotonic changes in both sensitivity and selectivity with changes to the sensitivity of up to 2.5 kJ/mol. Finally, this work places empirical limitations on the performance of a wide range of linear probes for PFOS detection and offers a generic strategy for high-throughput computational screening to promote selective and sensitive binding.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Linear Discriminant Analysis-Based Machine Learning and All-Atom Molecular Dynamics Simulations for Probing Electro-Osmotic Transport in Cationic-Polyelectrolyte-Brush-Grafted Nanochannels

Deciphering the correct mechanisms governing certain phenomena in polyelectrolyte (PE) brush grafted systems, revealed through atomistic simulations, is an extremely challenging problem. In a recent study, our all-atom molecular dynamics (MD) simulations revealed a non-linearly large electroosmotic (EOS) flow (in the presence of an applied electric field) in nanochannels grafted with PMETAC [Poly(2-(methacryloyloxy)ethyl trimethylammonium chloride] brushes. Given the lack of any formal procedure that would have directed us to identify the correct factors responsible for such an occurrence, we needed to spend several months and devote significant analyses to unravel the involved mechanisms. In this paper, we propose a Linear Discriminant Analysis (LDA) based Machine Learning (ML) approach to address this gap. At first, we obtain data on certain basic features from the all-atom MD data. These basic features represent the number of atoms of certain species around one atom of another (or same) species. Here, we obtain such data on basic features for a reference case (case of an EOS flow in PMETAC-brush-grafted nanochannels with a smaller electric field) and a perturbed case (case of an EOS flow in PMETAC-brush-grafted nanochannels with a larger electric field) in bins in which the nanochannel half height has been divided into. These datasets are high-dimensional dataset, to which the LDA is applied. This leads to the projection of the data (between the reference and the perturbed states) in a highly separated form on a 1D line. From such LDA calculations, we are able to identify the relative importance of the different basic features in ensuring this separation of the data (between the reference and the perturbed states) on the 1D line. This relative importance of the different basic features is quantified as “importance scores” for the different features, which in turn tell us what to study and where to study. Such knowledge enables us to rapidly identify the key factors responsible for the non-linearly large EOS transport in PMETAC-brush-grafted nanochannels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Optimal Linear Water Density for Proton Transport in Tunnel Oxides

Proton intercalation and transport is key to pseudocapacitive energy storage of oxide electrodes in acidic electrolytes. Although proton transport in water confined in layered or 2D materials is attracting great interest, much less is known about how the proton is transported in the 1D channels of tunnel oxides such as hexagonal WO 3 (h-WO 3 ). Here, we use first-principles molecular dynamics to reveal an optimal linear density of four water molecules per nanometer that yields the highest proton diffusivity. The volcano shape of proton diffusivity versus linear water density is a result of balancing the linear hydrogen-bond chain and the rotation of the water molecules to enable the Grotthuss mechanism. Furthermore, this insight provides a unifying view of proton transport along a single file of water molecules confined in hydrophilic 1D channels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Altering Linear Scaling Relationships on Metal Catalysts via Ligand–Adsorbate Hydrogen Bonding

Linear scaling relationships for adsorption energies of related molecules provide a simple tool for the prediction of catalytic properties and also reveal inherent constraints in heterogeneous catalyst design. In an effort to predict materials that preferentially stabilize intermediates capable of forming hydrogen bonds (H-bonds) and thus reduce these constraints, scaling relations for thiolate-coated fcc (111) surfaces were developed. Here, we demonstrate how ligand–adsorbate H-bonds lead to the stabilization of certain adsorbates and how this affects the linear scaling of adsorption energies for similarly bound intermediates. For H-bonds that occur remote from the surface, ligand–adsorbate H-bond strength is independent of metal composition and instead depends only on the acidities of the H-bond-forming functional groups. As the distance of H-bond-accepting groups from the surface decreases and interactions with the metal strengthen, the effect of surface composition on H-bond strength increases while additional factors, such as conformational changes and steric hinderance, can offset the stabilizing effect of the ligands. In this work, these competing factors may influence both the slope and y-intercept of adsorption strength scaling. These findings aid the rational design of enhanced catalytic materials by enabling the screening of ligand- or spectator-modified materials that do not conform to the linear scaling relations of bare metal surfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Mapping the Interfacial Chemistry and Structure of Partially Fluorinated Bottlebrush Polymers and Their Linear Analogues

Polymer interfaces are key to a range of applications including membranes for chemical separations, hydrophobic coatings, and passivating layers for antifouling. While important, challenges remain in probing the interfacial monolayer where the molecular ordering and orientation can change depending on the chemical makeup or processing conditions. In this work, we leverage surface specific vibrational sum frequency generation (SFG) and the associated dependence on molecular symmetry to elucidate the ordering and orientations of key functional groups for poly(2,2,2-trifluoroethyl methacrylate) bottlebrush polymers and their linear polymer analogues. These measurements were framed by atomistic molecular dynamic simulations to provide a complementary physical picture of the gas–polymer interface. Simulations and SFG measurements show that methacrylate backbones are buried beneath a layer of trifluoroethyl containing side groups that result in structurally similar interfaces regardless of the polymer molecular weight or architecture. The average orientational angles of the trifluoroethyl containing side groups differ depending on polymer linear and bottlebrush architectures, suggesting that the surface groups can reorient via available rotational degrees of freedom. Results show that the surfaces of the bottlebrush and linear polymer samples do not strongly depend on molecular weight or architecture. As such, one cannot rely on increasing the molecular weight or altering the architecture to tune surface properties. This insight into the polymer interfacial structure is expected to advance the design of new material interfaces with tailored chemical/functional properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Topological Frustration as a New Parameter to Tune Morphology Revealed through Exploring the Continuum between A-B-C 3-Arm Star and Linear Triblock Polymers

Block polymers assemble into a variety of phase-separated morphologies based on volume fraction (φ) and interactions (χ) of the respective blocks. The arrangement of three different polymer blocks could either be a 3-arm star, with each block having one terminus attached to a common junction point or a linear A-B-C architecture. A versatile strategy is reported to synthesize a series of well-defined graft polymers that lie along the unexplored continuum between a 3-arm star and an A-B-C linear triblock polymer architecture. Using the technique of single-molecule insertion, precise control over the position of graft arm C along the B chain was achieved. A series of discrete graft polymers (PMMA-b-PS-g-PEO) with fixed φ and prescribed ω values that lie on the continuum between a 3-arm star (ω = 0) and linear triblock polymer (ω = 1) were synthesized. Morphological studies using small-angle X-ray scattering and conventional and energy-filtered transmission electron microscopy reveal the transition between lamellae, perforated lamellae, and cylindrical morphologies with systematic variation in the ω values, a trend attributed to the topological frustration and the associated χ values between the three blocks. Molecular dynamic simulations of coarse-grained models were found to predict phase diagrams that are consistent with the experimentally observed morphologies. Furthermore, our results suggest that changes in ω lead to topological frustration which is an important additional new design parameter that can be used to tune the morphology of multiblock polymers in addition to φ and χ.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Hydroesterification of Polycyclooctene to Access Linear Ethylene Ethyl Acrylate Copolymers as a Step Toward Polyolefin Functionalization

To advance a strategy of polymer-to-polymer upcycling of waste polyolefin by dehydrogenation then functionalization, we report successful hydroesterification of polycyclooctene (PCOE), an analogue for partially unsaturated polyethylene. Here, we convert PCOE to a linear analog for poly(ethylene-co-ethyl acrylate) (EEA) across a range of ethyl acrylate incorporations (0 to 18 mol % of ethylene units). The ester incorporation was well controlled by reaction time, and the remaining C=C bonds were subsequently hydrogenated. Here, the bulky ethyl acrylate groups did not incorporate into orthorhombic PE crystals, decreasing the crystallinity, crystallite size, and melting temperature with increasing functionalization. Additionally, hydroesterification tuned the dynamic mechanical properties, decreasing both the glass transition temperature and the storage modulus in the rubbery regime with greater functionalization. The linear EEA analogs reported here achieve remarkable extensibility (strain > 4000%) and high toughness, comparable to commercial random and branched EEA. Ultimately, we demonstrate successful conversion of an analogue to dehydrogenated PE to a linear EEA with favorable mechanical properties.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Confined dynamics of grafted polymer chains in solutions of linear polymer

Here, we measure the dynamics of high molecular weight polystyrene grafted to silica nanoparticles dispersed in semidilute solutions of linear polymer. Structurally, the linear free chains do not penetrate the grafted corona but increase the osmotic pressure of the solution, collapsing the grafted polymer and leading to eventual aggregation of the grafted particles at high matrix concentrations. Dynamically, the relaxations of the grafted polymer are controlled by the solvent viscosity according to the Zimm model on short time scales. On longer time scales, the grafted chains are confined by neighboring grafted chains, preventing full relaxation over the experimental time scale. Adding free linear polymer to the solution does not affect the initial Zimm relaxations of the grafted polymer but does increase the confinement of the grafted chains. Finally, our results elucidate the physics underlying the slow relaxations of grafted polymer.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Brush-Like Polymers and Entanglements: From Linear Chains to Filaments

Dynamics of melts and solutions of high molecular weight polymers and biopolymers is controlled by topological constraints (entanglements) imposing a sliding chain motion along an effective confining tube. For linear chains, the tube size is determined by universal packing number P e , the number of polymer strands within a confining tube that is required for chains to entangle. In this work, we show that in melts of brush-like (graft) polymers, consisting of linear chain backbones with grafted side chains, P e is not a universal number and depends on the molecular architecture. Specifically, we use coarse-grained molecular dynamics simulations to demonstrate that the packing number is a nonmonotonic function of the ratio R nsc /R ng of the size of the side chains R nsc to that of the backbone spacer between neighboring grafting points R ng . This parameter characterizes the degree of mutual interpenetration between side chains of the same macromolecule. We demonstrate that P e of brush-like polymers first decreases with increasing side chain grafting density in the dilute side chain regime (R nsc < R ng ), then begins to increase in the regime of overlapping side chains (R nsc > R ng ), approaching the value for linear chains in the limit of densely grafted side chains. This dependence of the packing number reflects a crossover from chain-like entanglements in systems with loosely grafted side chains (comb-like polymers) to entanglements between flexible filaments (bottlebrush-like polymers). Our simulation results are in agreement with the experimental data for the dependence of a plateau modulus on the molecular architecture of graft poly(n-butyl acrylates) and poly(norbornene)-graft-poly(lactide) melts.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Electron Inertial Effects on Linearly Polarized Electromagnetic Ion Cyclotron Waves at Earth's Magnetosphere

We propose a role of the electron inertial effect on linearly polarized electromagnetic ion cyclotron (EMIC) waves at Earth. The linearly polarized EMIC waves have been previously suggested to be generated via mode conversion from the fast compressional wave at the ion-ion hybrid (IIH) resonance. When the electron inertial effects are neglected, the wave normal angle of the mode-converted IIH waves is 90° because the wave vector perpendicular to the magnetic field becomes infinite at the IIH resonance. When the electron inertial effect is considered, the mode-converted IIH waves can propagate across the magnetic field lines, and the wavelength perpendicular to the magnetic field approaches the electron inertial length scale near the Buchsbaum resonance. These waves are referred to as electron inertial waves. Due to the electron inertial effect, the perpendicular wave number to the ambient magnetic field near the IIH resonance remains finite, and the wave normal angle is less than 90°. The wave normal angle where the maximum absorption occurs in a dipole magnetic field is 30–80°, which is consistent with the observed values near the magnetic equator. Thus, the numerical results imply that the linearly polarized EMIC wave generated via mode conversion near the IIH resonance can be detected in between the Buchsbaum and the IIH resonance frequencies, and these waves can have normal angle less than 90°.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Improving the MJO Forecast of S2S Operation Models by Correcting Their Biases in Linear Dynamics

The operational dynamic subseasonal to seasonal (S2S) models for Madden-Julian oscillation (MJO) forecasting mostly still suffer from systematic errors in capturing the MJO's key dynamic features, such as its growth rate and propagation speed. By deriving the linear dynamic operators using the linear inverse modeling (LIM) approach, we propose a method to partly correct the errors in MJO linear dynamic operators to improve the MJO predictions of three operational dynamic S2S models. Correcting the deficiencies of the too-fast decay rates and the unrealistic propagating phase speeds lead to MJO prediction skills being extended by approximately 2–4 days. The improvements are more significant for the models with larger biases in MJO amplitude and propagation. This approach in principle may be extendable to predictions of other types of climate variability such as ENSO on one hand, and possible inclusions of nonlinear dynamics effects on the other hand.

58 GEOSCIENCES↗
DOE OSTI2022

Electrical Conductivity of Clayey Rocks and Soils: A Non-Linear Model

It is well-accepted that Archie's law is only applicable to “clean” rocks and soils but fails in “dirty” ones where clay minerals possess an additional component of surface conductivity. Although several models, for example, Waxman-Smits model, were presented to account for this phenomenon, surface conductivity is always inappropriately treated as constant, which actually only holds at high salinities. The essential non-linear characteristic differing over fluid salinities has not been physically or mathematically explained well in those models. Here, we scrutinize the conduction mechanism of clayey rocks and soils and ascribe this non-linear feature to (a) variation of the electrical double layer and (b) the intrinsic clay-and-water conduction pattern. With effective medium theory, we develop an easy-to-use non-linear model that both reflects electrochemical theories and explains the measurement data well. Our model can be used to produce more accurate results for laboratory- and field-scale petrophysical parameter evaluations than the previous models.

58 GEOSCIENCES↗
DOE OSTI2023

Potential Non-Linearities in the High Latitude Circulation and Ozone Response to Stratospheric Aerosol Injection

The impacts of Stratospheric Aerosol Injection (SAI) on the atmosphere and surface climate depend on when and where the sulfate aerosol precursors are injected, as well as on how much surface cooling is to be achieved. We use a set of CESM2(WACCM6) SAI simulations achieving three different levels of global mean surface cooling and demonstrate that unlike some direct surface climate impacts driven by the reflection of solar radiation by sulfate aerosols, the SAI-induced changes in the high latitude circulation and ozone are more complex and could be non-linear. This manifests in our simulations by disproportionally larger Antarctic springtime ozone loss, significantly larger intra-ensemble spread of the Arctic stratospheric jet and ozone responses, and non-linear impacts on the extratropical modes of surface climate variability under the strongest-cooling SAI scenario compared to the weakest one. These potential non-linearities may add to uncertainties in projections of regional surface impacts under SAI.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Nonlinear encoding in diffractive information processing using linear optical materials

Nonlinear encoding of optical information can be achieved using various forms of data representation. Here, we analyze the performances of different nonlinear information encoding strategies that can be employed in diffractive optical processors based on linear materials and shed light on their utility and performance gaps compared to the state-of-the-art digital deep neural networks. For a comprehensive evaluation, we used different datasets to compare the statistical inference performance of simpler-to-implement nonlinear encoding strategies that involve, e.g., phase encoding, against data repetition-based nonlinear encoding strategies. We show that data repetition within a diffractive volume (e.g., through an optical cavity or cascaded introduction of the input data) causes the loss of the universal linear transformation capability of a diffractive optical processor. Therefore, data repetition-based diffractive blocks cannot provide optical analogs to fully connected or convolutional layers commonly employed in digital neural networks. However, they can still be effectively trained for specific inference tasks and achieve enhanced accuracy, benefiting from the nonlinear encoding of the input information. Our results also reveal that phase encoding of input information without data repetition provides a simpler nonlinear encoding strategy with comparable statistical inference accuracy to data repetition-based diffractive processors. Our analyses and conclusions would be of broad interest to explore the push-pull relationship between linear material-based diffractive optical systems and nonlinear encoding strategies in visual information processors.

42 ENGINEERING↗
DOE OSTI2024

A linear response framework for quantum simulation of bosonic and fermionic correlation functions

Response functions are a fundamental aspect of physics; they represent the link between experimental observations and the underlying quantum many-body state. However, this link is often under-appreciated, as the Lehmann formalism for obtaining response functions in linear response has no direct link to experiment. Within the context of quantum computing, and via a linear response framework, we restore this link by making the experiment an inextricable part of the quantum simulation. This method can be frequency- and momentum-selective, avoids limitations on operators that can be directly measured, and can be more efficient than competing methods. As prototypical examples of response functions, we demonstrate that both bosonic and fermionic Green’s functions can be obtained, and apply these ideas to the study of a charge-density-wave material on the ibm_auckland superconducting quantum computer. The linear response method provides a robust framework for using quantum computers to study systems in physics and chemistry.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2017

Laser-Induced Linear-Field Particle Acceleration in Free Space

Linear-field particle acceleration in free space (which is distinct from geometries like the linac that requires components in the vicinity of the particle) has been studied for over 20 years, and its ability to eventually produce high-quality, high energy multi-particle bunches has remained a subject of great interest. Arguments can certainly be made that linear-field particle acceleration in free space is very doubtful given that first-order electron-photon interactions are forbidden in free space. Nevertheless, we chose to develop an accurate and truly predictive theoretical formalism to explore this remote possibility when intense, few-cycle electromagnetic pulses are used in a computational experiment. The formalism includes exact treatment of Maxwell’s equations and exact treatment of the interaction among the multiple individual particles at near and far field. Several surprising results emerge. We find that electrons interacting with intense laser pulses in free space are capable of gaining substantial amounts of energy that scale linearly with the feld amplitude. For example, 30keV electrons (2.5% energy spread) are accelerated to 61MeV (0.5% spread) and to 205MeV (0.25% spread) using 250 mJ and 2.5J lasers respectively. Furthermore, these findings carry important implications for our understanding of ultrafast electron-photon interactions in strong fields.

43 PARTICLE ACCELERATORS↗
DOE OSTI2022

Quantum computing and preconditioners for hydrological linear systems

Modeling hydrological fracture networks is a hallmark challenge in computational earth sciences. Accurately predicting critical features of fracture systems, e.g. percolation, can require solving large linear systems far beyond current or future high performance capabilities. Quantum computers can theoretically bypass the memory and speed constraints faced by classical approaches, however several technical issues must first be addressed. Chief amongst these difficulties is that such systems are often ill-conditioned, i.e. small changes in the system can produce large changes in the solution, which can slow down the performance of linear solving algorithms. We test several existing quantum techniques to improve the condition number, but find they are insufficient. We then introduce the inverse Laplacian preconditioner, which improves the scaling of the condition number of the system from O(N) to O($\sqrt{N}$) and admits a quantum implementation. These results are a critical first step in developing a quantum solver for fracture systems, both advancing the state of hydrological modeling and providing a novel real-world application for quantum linear systems algorithms.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2016

Linear dependence of surface expansion speed on initial plasma temperature in warm dense matter

Recent progress in laser-driven quasi-monoenergetic ion beams enabled the production of uniformly heated warm dense matter. Matter heated rapidly with this technique is under extreme temperatures and pressures, and promptly expands outward. While the expansion speed of an ideal plasma is known to have a square-root dependence on temperature, computer simulations presented here show a linear dependence of expansion speed on initial plasma temperature in the warm dense matter regime. The expansion of uniformly heated 1–100 eV solid density gold foils was modeled with the RAGE radiation-hydrodynamics code, and the average surface expansion speed was found to increase linearly with temperature. The origin of this linear dependence is explained by comparing predictions from the SESAME equation-of-state tables with those from the ideal gas equation-of-state. In conclusion, these simulations offer useful insight into the expansion of warm dense matter and motivate the application of optical shadowgraphy for temperature measurement.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗