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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 505 records · Page 28
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Coupled-cluster techniques for computational chemistry: The CFOUR program package

An up-to-date overview of the CFOUR program system is given. After providing a brief outline of the evolution of the program since its inception in 1989, a comprehensive presentation is given of its well-known capabilities for high-level coupled-cluster theory and its application to molecular properties. Subsequent to this generally well-known background information, much of the remaining content focuses on lesser-known capabilities of CFOUR, most of which have become available to the public only recently or will become available in the near future. Each of these new features is illustrated by a representative example, with additional discussion targeted to educating users as to classes of applications that are now enabled by these capabilities. Lastly, some speculation about future directions is given, and the mode of distribution and support for CFOUR are outlined in the appendix.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

The Dependence of Iron-rich Metal-poor Star Occurrence on Galactic Environment Supports an Origin in Thermonuclear Supernova Nucleosynthesis

It has been suggested that a class of chemically peculiar metal-poor stars called iron-rich metal-poor (IRMP) stars formed from molecular cores with metal contents dominated by thermonuclear supernova nucleosynthesis. If this interpretation is accurate, then IRMP stars should be more common in environments where thermonuclear supernovae were important contributors to chemical evolution. Conversely, IRMP stars should be less common in environments where thermonuclear supernovae were not important contributors to chemical evolution. At constant [Fe/H] ≲ -1, the Milky Way's satellite classical dwarf spheroidal (dSph) galaxies and the Magellanic Clouds have lower [α/Fe] than the Milky Way field and globular cluster populations. This difference is thought to demonstrate the importance of thermonuclear supernova nucleosynthesis for the chemical evolution of the Milky Way's satellite classical dSph galaxies and the Magellanic Clouds. We use data from the Sloan Digital Sky Survey Apache Point Observatory Galactic Evolution Experiment and Gaia to infer the occurrence of IRMP stars in the Milky Way's satellite classical dSph galaxies η dSph and the Magellanic Clouds η Mag , as well as in the Milky Way field η MWF and globular cluster populations η MWGC . In order of decreasing occurrence, we find η dSph = $0.07$$^{+0.02}_{-0.02}$, η Mag = $0.037$$^{+0.007}_{-0.006}$, η MWF = $0.0013$$^{+0.0006}_{-0.0005}$, and a 1σ upper limit η MWGC < 0.00057. These occurrences support the inference that IRMP stars formed in environments dominated by thermonuclear supernova nucleosynthesis and that the time lag between the formation of the first and second stellar generations in globular clusters was longer than the thermonuclear supernova delay time.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Graphic contrastive learning analyses of discontinuous molecular dynamics simulations: Study of protein folding upon adsorption

A comprehensive understanding of the interfacial behaviors of biomolecules holds great significance in the development of biomaterials and biosensing technologies. In this work, we used discontinuous molecular dynamics (DMD) simulations and graphic contrastive learning analysis to study the adsorption of ubiquitin protein on a graphene surface. Our high-throughput DMD simulations can explore the whole protein adsorption process including the protein structural evolution with sufficient accuracy. Contrastive learning was employed to train a protein contact map feature extractor aiming at generating contact map feature vectors. Subsequently, these features were grouped using the k-means clustering algorithm to identify the protein structural transition stages throughout the adsorption process. The machine learning analysis can illustrate the dynamics of protein structural changes, including the pathway and the rate-limiting step. Our study indicated that the protein–graphene surface hydrophobic interactions and the π–π stacking were crucial to the seven-stage adsorption process. Upon adsorption, the secondary structure and tertiary structure of ubiquitin disintegrated. The unfolding stages obtained by contrastive learning-based algorithm were not only consistent with the detailed analyses of protein structures but also provided more hidden information about the transition states and pathway of protein adsorption process and structural dynamics. Our combination of efficient DMD simulations and machine learning analysis could be a valuable approach to studying the interfacial behaviors of biomolecules.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Bacterial Efflux Pumps and Their Inhibitors

Bacterial multidrug efflux transporters have distinct molecular features and mechanisms that enable their impressive substrate polyspecificity. These transporters are involved in all physiological processes where nonspecific but active transport across membranes is critical for survival and proliferation. Importantly, efflux pumps contribute to bacterial virulence and pathogenesis, as well as the spread of antibiotic resistance in clinics. Transporters belonging to several protein superfamilies have been selected for polyspecificity by evolution and augmented with accessory proteins that extend and couple transport reactions across the inner and outer membranes of the bacterium. As a result, bacteria are equipped with diverse efflux machines that protect cells from a broad variety of toxic compounds including antibiotics and other small molecule therapeutics. The inhibition of such polyspecific biomolecular machines is a challenging task, which still awaits an efficient solution. Here, we review the molecular mechanisms of efflux pumps from Gram-negative bacteria and recent advances and challenges associated with the discovery of effective inhibitors of these pumps.

Zgurskaya, Helen↗
DOE OSTI2023

Spatio-temporal patterning of extensile active stresses in microtubule-based active fluids

Abstract Microtubule-based active fluids exhibit turbulent-like autonomous flows, which are driven by the molecular motor powered motion of filamentous constituents. Controlling active stresses in space and time is an essential prerequisite for controlling the intrinsically chaotic dynamics of extensile active fluids. We design single-headed kinesin molecular motors that exhibit optically enhanced clustering and thus enable precise and repeatable spatial and temporal control of extensile active stresses. Such motors enable rapid, reversible switching between flowing and quiescent states. In turn, spatio-temporal patterning of the active stress controls the evolution of the ubiquitous bend instability of extensile active fluids and determines its critical length dependence. Combining optically controlled clusters with conventional kinesin motors enables one-time switching from contractile to extensile active stresses. These results open a path towards real-time control of the autonomous flows generated by active fluids.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Role of Postdeposition Thermal Annealing on Intracrystallite and Intercrystallite Structuring and Charge Transport in Poly(3-hexylthiophene)

The performance of electronic devices comprising conjugated polymers as the active layer depends not only on the intrinsic characteristics of the materials but also on the details of the extrinsic processing conditions. Here, we examine the effect of postdeposition thermal treatments on the microstructure of poly(3-hexylthiophene) (P3HT) thin films and its impact on their electrical properties. Unsurprisingly, we find thermal annealing of P3HT thin films to generally increase their crystallinity and crystallite coherence length while retaining the same crystal structure. Despite such favorable structural improvements of the polymer active layers, however, thermal annealing at high temperatures can lead to a net reduction in the mobility of transistors, implicating structural changes in the intercrystallite amorphous regions of these semicrystalline active layers take place on annealing, and the simplistic picture that crystallinity governs charge transport is not always valid. Our results instead suggest tie-chain pullout, which occurs during crystal growth and perfection upon thermal annealing to govern charge transport, particularly in low-molecular-weight systems in which the tie-chain fraction is low. By demonstrating the interplay between intracrystallite and intercrystallite structuring in determining the macroscopic charge transport, we shed light on how structural evolution and charge-transport properties of nominally the same polymer can vary depending on the details of processing.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Mechanistic Insights into Defect-Mediated Crystallization Revealed by Lattice Strain Evolution

Structural defects and lattice strain are intrinsic to many crystalline materials, yet their roles in controlling chemical reaction mechanisms and directing crystallization pathways remain poorly understood. Here, in this study, we revealed the three-dimensional evolution of strain and dislocation defects at the nanoscale during the growth of heterogeneously nucleated barite (BaSO 4 ) and calcite (CaCO 3 ) crystals by using coherent X-ray scattering, electron microscopy, and molecular simulations. Unlike barite, which formed with minimal internal strain, calcite developed dislocation defects and exhibited spatially varying strain that increased during growth. During growth in Sr-rich solutions, calcite likely incorporates Sr 2+ into the defects, which further modulates the local lattice structure and increases both the compressive and tensile strain. These findings suggest that calcite crystallization was likely dominated by attachment of precursor phases, which gave rise to defect-enriched domain structures not predicted by classical growth models. By linking defect formation to ion incorporation and growth dynamics, this work provides fundamental insight into how lattice-level strain heterogeneity governs the chemical reactivity of ionic crystals.

Bragg coherent diffractive imaging↗
DOE OSTI2023

Unsupervised machine learning discovery of structural units and transformation pathways from imaging data

We show that unsupervised machine learning can be used to learn chemical transformation pathways from observational Scanning Transmission Electron Microscopy (STEM) data. To enable this analysis, we assumed the existence of atoms, a discreteness of atomic classes, and the presence of an explicit relationship between the observed STEM contrast and the presence of atomic units. With only these postulates, we developed a machine learning method leveraging a rotationally invariant variational autoencoder (VAE) that can identify the existing molecular fragments observed within a material. The approach encodes the information contained in STEM image sequences using a small number of latent variables, allowing the exploration of chemical transformation pathways by tracing the evolution of atoms in the latent space of the system. The results suggest that atomically resolved STEM data can be used to derive fundamental physical and chemical mechanisms involved, by providing encodings of the observed structures that act as bottom-up equivalents of structural order parameters. The approach also demonstrates the potential of variational (i.e., Bayesian) methods in the physical sciences and will stimulate the development of more sophisticated ways to encode physical constraints in the encoder–decoder architectures and generative physical laws and causal relationships in the latent space of VAEs.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2020

Temperature-induced structural evolution in liquid Ag-Ga alloys

Temperature-dependent atomic structural evolutions of liquid Ag 60 Ga 40 and Ag 70 Ga 30 alloys have been studied by in situ high-energy x-ray-diffraction (HEXRD) experiments combined with ab initio molecular-dynamics simulations. The experimental data show a reversible structural crossover at about 1050 ~ 1100 (± 50) K in both liquid Ag 60 Ga 40 and Ag 70 Ga 30 alloys. Obvious changes of the electrical resistivity, absolute thermoelectric power, and atomic diffusivity around the similar temperature range for both Ag-Ga liquids strongly support the HEXRD results. The origin of the liquid-to-liquid crossover in both Ag-Ga liquids was suggested to link with the rearrangements of Ag and Ga atoms, i.e., Ag and Ga atoms prefer to associate with themselves in the higher temperature range above 1100 K, consistent with the accelerated increase of the strong covalently bonded Ga–Ga dimers in both Ag-Ga liquids. In addition, more studies from the energy aspect are still desirable to understand the rearrangements of Ag and Ga atoms in the higher temperature range in both Ag-Ga liquids.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Structural inversion asymmetry in epitaxial ultrathin films of Bi(111)/InSb(111)B

Bismuth (Bi) films hold potential for spintronic devices due to strong spin-orbit coupling. Understanding the growth, surface states, and interactions with the substrate is key to their functionalization. Large-area high-quality (111) Bi ultrathin films were grown on InSb (111)B substrates by molecular beam epitaxy (MBE). Strong film-substrate interactions epitaxially stabilize the (111) orientation and lead to nonequivalent interface potentials. Analysis of angle-resolved photoemission spectroscopy (ARPES) measurements, employed to characterize the evolution of the surface states with film thickness, indicate a crossing at the $\overline{M}$ point, suggesting a topologically trivial phase in the thin film. In conclusion, the results show the presence of interfacial bonds to the substrate breaks inversion symmetry, preventing the semimetal-to-semiconductor transition predicted for freestanding bismuth layers, highlighting the importance of controlled functionalization and surface passivation of two-dimensional materials.

Inbar, Hadass S. [Univ. of California, Santa Barba↗
DOE OSTI2025

Accelerating charge estimation in molecular dynamics simulations using physics-informed neural networks: corrosion applications

Molecular Dynamics (MD) simulations are used to understand the effects of corrosion on metallic materials in salt brine. Reactive force fields in classical MD enable accurate modeling of bond formation and breakage in the aqueous medium and at the metal-electrolyte interface, while also facilitating dynamic partial charge equilibration. However, MD simulations are computationally intensive and unsuitable for modeling the long time scales characteristic of corrosive phenomena. To address this, we develop reduced-order machine learning models that provide accurate and efficient predictions of charge density in corrosive environments. Specifically, we use Long Short-Term Memory (LSTM) networks to forecast charge density evolution based on atomic environments represented by Smooth Overlap of Atomic Positions (SOAP) descriptors. A physics-informed loss function enforces charge neutrality and electronegativity equivalence. The atomic charges predicted by the deep learning model trained on this work were obtained two orders of magnitude faster than those from molecular dynamics (MD) simulations, with an error of less than 3% compared to the MD-obtained charges, even in extrapolative scenarios, while adhering to physical constraints. This demonstrates the excellent accuracy, computational efficiency, and validity of the developed model. Lastly, even though developed for corrosion, these protocols are formulated in a phenomenon-agnostic manner, allowing application to various variable-charge interatomic potentials and related fields.

Atomistic models↗
DOE OSTI2023

Atomically Local Electric Field Induced Interface Water Reorientation for Alkaline Hydrogen Evolution Reaction

The slow water dissociation process in alkaline electrolyte severely limits the kinetics of HER. The orientation of H 2 O is well known to affect the dissociation process, but H 2 O orientation is hard to control because of its random distribution. Herein, an atomically asymmetric local electric field was designed by IrRu dizygotic single-atom sites (IrRu DSACs) to tune the H 2 O adsorption configuration and orientation, thus optimizing its dissociation process. The electric field intensity of IrRu DSACs is over 4.00×10 10 N/C. The ab initio molecular dynamics simulations combined with in situ Raman spectroscopy analysis on the adsorption behavior of H 2 O show that the M–H bond length (M=active site) is shortened at the interface due to the strong local electric field gradient and the optimized water orientation promotes the dissociation process of interfacial water. This work provides a new way to explore the role of single atomic sites in alkaline hydrogen evolution reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Shape-preserving amorphous-to-crystalline transformation of CaCO3 revealed by in situ TEM

Organisms use inorganic ions and macromolecules to regulate crystallization from amorphous- precursors, endowing natural biominerals with complex morphologies and enhanced properties. The mechanisms by which modifiers enable these shape preserving transformations are poorly understood. We used in situ liquid-phase transmission electron microscopy to follow the evolution from amorphous calcium carbonate to calcite in the presence of additives. A combination of contrast analysis and infrared spectroscopy shows that Mg ions, which are widely present in seawater and biological fluids, alter the transformation pathway in a concentration-dependent manner. The ions bring excess (structural) water into the amorphous bulk so that a direct transformation is triggered by dehydration in the absence of morphological changes. Molecular dynamics simulations suggest Mg-incorporated water induces structural fluctuations, allowing transformation without the need to nucleate a separate crystal. Thus, the obtained calcite retains the original morphology of the amorphous state, biomimetically achieving the morphological control of crystals seen in biominerals

crystallization, biomineralization, calcium carbon↗
DOE OSTI2026

Achieving 20.1% Efficiency in Organic Solar Cells Through Interconnected Fibrillar Networks via Local Molecular Stacking

ABSTRACT The performance of organic solar cells (OSCs) is governed by how molecular packing evolves into interconnected networks that facilitate exciton dissociation and charge transport. Using an all‐small‐molecule blend DR3TSBDT:Y6 as a model system, we study how local molecular stacking evolves into performance‐relevant morphology during solvent vapor annealing (SVA) and subsequent thermal annealing (TA). SVA promotes end‐to‐end stacking of amorphous acceptors to form interconnected fibrils, while TA compacts inter‐fibril spacing without disrupting favorable local order. Such molecular‐to‐morphological refinements broaden light absorption, enhance charge transport, and markedly improve device efficiency. Extending this approach to additional blend systems (D18:Y6, D18:L8‐BO, and DR3TSBDT:L8‐BO) yields similar structural evolution and performance gains, with the D18:L8‐BO system achieving up to 20.10% PCE. Our study establishes control over local stacking in amorphous acceptors into fibrillar networks as a general and effective route to realize high‐performance OSCs.

Wu, Junying↗
DOE OSTI2020

Electrokinetic Analysis of Poorly Conductive Electrocatalytic Materials

While many factors can influence the activity of the electrochemical interface at atomic and molecular levels, the electron and ion transport have a big impact on the overall electrochemical performance. Here, we investigate how electrical resistance (conductivity) of the electrode affects the measured electrocatalytic activity using the hydrogen evolution reaction as a model reaction. We clearly demonstrate the effect of the poor electronic conductivity of MoS 2 on the electrochemical performance, as both values of the exchange current density as well as the Tafel slope depend on the level of utilization of the active material and the ohmic losses. A quantitative analysis using the composite electrode model is provided, showing the importance of the experimental conditions and good control of electrode/electrolyte system for the proper evaluation and comparison of electrocatalysts’ kinetic parameters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗