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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Analytic gradients for compressed multistate pair-density functional theory

Photochemical reactions often involve states that are closely coupled due to near degeneracies, for example by proximity to conical intersections. Therefore, a multistate method is used to accurately describe these states; for example, ordinary perturbation theory is replaced by quasidegenerate perturbation theory. Multiconfiguration pair-density functional theory (MC-PDFT) provides an efficient way to approximate the full dynamical correlation energy of strongly correlated systems, and we recently proposed compressed multistate pair-density functional theory (CMS-PDFT) to treat closely coupled states. In the present paper, we report the implementation of analytic gradients for CMS-PDFT in both OpenMolcas and PySCF, and here we illustrate the use of these gradients by applying the method to the excited states of formaldehyde and phenol.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Dynamic Observation of Dendritic Quasicrystal Growth upon Laser-Induced Solid-State Transformation

In this paper, we report the laser-induced solid-state transformation between a periodic “approximant” and quasicrystal in the Al-Cr system during rapid quenching. Dynamic transmission electron microscopy allows us to capture in situ the dendritic growth of the metastable quasicrystals. The formation of dendrites during solid-state transformation is a rare phenomenon, which we attribute to the structural similarity between the two intermetallics. Through ab initio molecular dynamics simulations, we identify the dominant structural motif to be a 13-atom icosahedral cluster transcending the phases of matter.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Colossal Density-Driven Resistance Response in the Negative Charge Transfer Insulator MnS 2

A reversible density driven insulator to metal to insulator transition in high-spin MnS 2 is experimentally observed, leading with a colossal electrical resistance drop of $10^8$ Omega by 12 GPa. Density functional theory simulations reveal the metallization to be unexpectedly driven by previously unoccupied $S_{2}^{-2}$ $\sigma^{*}_{3p}$ antibonding states crossing the Fermi level. This is a unique variant of the charge transfer insulator to metal transition for negative charge transfer insulators having anions with an unsaturated valence. By 36 GPa the emergence of the low-spin insulating arsenopyrite ($P2_1/c$) is confirmed, and the bulk metallicity is broken with the system returning to an insulative electronic state.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Supported Metal Pair-Site Catalysts

Complexes with neighboring metal centers in isolated pairs and their analogues on surfaces are drawing increasing attention as catalysts. These include molecular homogeneous catalysts incorporating various ligands, enzymes, and solids that include pairs of metal atoms mounted on supports. Catalysts in this broad class are active for numerous reactions and offer unexplored opportunities to address challenging reactions, such as oxidation of methane and oxidation of water in artificial photosynthesis. The subject of supported metal pair-site catalysts is in its infancy, facing challenges in (a) precise synthesis, (b) structure determination at the atomic scale, and (c) stabilization in reactive atmospheres. In this Perspective, we summarize key characteristics of molecular and enzymatic catalysts that incorporate neighboring metal centers and build on this foundation to assess the emerging literature of metal pair-site catalysts on various supports. The supported catalysts include those synthesized by anchoring molecular dinuclear precursors to support surfaces and those synthesized by selective formation of dinuclear surface species from mononuclear surface species. Examples of metals in this class are rhodium and iridium, and examples of supports are MgO and Fe 2 O 3 . We summarize characterization of these materials by electron microscopy and spectroscopy, emphasizing atomic-resolution aberration-corrected scanning transmission electron microscopy and spectroscopies that provide atomic-scale structural information and allow characterization of functioning catalysts, especially X-ray absorption spectroscopy. Finally, we list some opportunities for research, including suggestions that might lead to structurally well-defined supported metal pair-sites with new catalytic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

Longitudinal structure in atomic oxygen concentrations observed with WINDII on UARS

WINDII, the Wind Imaging Interferometer on the Upper Atmosphere Research Satellite, began atmospheric observations on September 28, 1991 and since then has been collecting data on winds, temperatures and emissions rates from atomic, molecular and ionized oxygen species, as well as hydroxyl. The validation of winds and temperatures is not yet complete, and scientific interpretation has barely begun, but the dominant characteristic of these data so far is the remarkable structure in the emission rate from the excited species produced by the recombination of atomic oxygen. The latitudinal and temporal variability has been noted before by many others. In this preliminary report on WINDII results we draw attention to the dramatic longitudinal variations of planetary wave character in atomic oxygen concentration, as reflected in the OI 557.7 nm emission, and to similar variations seen in the Meine1 hydroxyl band emission.

Shepherd, G. G.↗
DOE OSTI2023

Surface Chemistry and Reactions for Bimetallic Au Catalysis (Final Report)

Gold-based catalysts offer tremendous opportunities for developing new technologies for selective oxidation reactions that directly use gas-phase oxygen as a benign reagent and produce either no byproducts or water as the only byproduct. These processes are urgently needed and critical for achieving the sustainable production of chemicals. While recent studies demonstrate that the catalytic properties of gold can be significantly enhanced by addition of other metals, the development of these catalysts with sufficient performance for commercialization is hindered by a lack of fundamental understanding of how the catalytic properties of gold can be controlled and tailored. This project addressed this need by synergistically combining experimental and computational studies to establish fundamental composition-structure-activity relationships for gold-based catalysts for several industrially important reactions. Results from surface spectroscopy, atomic imaging and thermal desorption experiments were combined with molecular models and reaction mechanisms from quantum chemical calculations to link observable reaction rates to the structure and composition of surfaces at the molecular level. The results were used to develop improved catalyst formulations and identify optimized reaction conditions for gold-based catalysts. For broader impacts, the developed methodology was extended to other metallic catalysts, such as silver, platinum-molybdenum and nickel-tin, for improved catalytic efficiency and sustainable production of specialty and commodity chemicals.

36 MATERIALS SCIENCE↗
DOE OSTI2021

X-ray spectroscopic identification of strain and structure-based resonances in a series of saturated carbon-cage molecules: Adamantane, twistane, octahedrane, and cubane

Novel nanocarbons such as fullerenes, nanotubes, graphene, and nanodiamond reside at the cutting edge of nanoscience and technology. Along with chemical functionalization, geometric constraints (such as extreme curvature in nanotubes or defects within or at the surfaces of diamond nanoparticles) significantly alter the electronic states of the nanocarbon material. Understanding the effects of steric strain on the electronic structure is critical to developing nanoelectronic applications based on these materials. This paper presents a fundamental study of how strain affects the electronic structure in a benchmark series of some fundamental saturated carbon cage compounds. Adamantane, C10H16, the smallest diamondoid and arguably the smallest nanodiamond crystallite, has carbon atoms essentially commensurate with diamond lattice positions and possesses by far the least molecular strain of this series. Twistane also is a C10H16 isomer but the fixed cyclohexane twist conformation of the central ring introduces additional strain into the cage. Octahedrane [(CH)12] and cubane [(CH)8] are considerably more strained, culminating in cubane where carbon–carbon bonds lie either parallel or orthogonal to one another. Using gas-phase near-edge x-ray absorption fine structure spectroscopy to probe the unoccupied electronic states, we observe two major progressions across this series. First, a broad C–C σ* resonance in the absorption splits into two more narrow and intense resonances with increasing strain. Second, the first manifold of states previously associated with tertiary C–H σ* in the diamondoid series appears to broaden and shift to lower energy. This feature is more than twice as intense in cubane than in octahedrane, even though these two molecules have only tertiary carbons, with the chemical formula (CH)x. The spectral differences are entirely due to the shape of the molecules; in particular, in cubane, the features arise from a high degree of p-p interaction between parallel C–C bonds. In contrast to the conventional wisdom that near-edge x-ray absorption is primarily an atomically localized spectroscopy, molecular shape and associated strain lead to the dominant features in spectra acquired from this fundamental series of carbon cage structures.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Molecular-level solvation and selectivity behavior of Na + , K + , and Li + within glycerol-derived solvents

Ether-based acyclic solvents have a tendency to confine positively charged atoms, forming structures called podands. Due to the stability of these structures, podands have been identified as promising candidates for several different electrochemical applications. In this work, we use molecular dynamics simulations to investigate the solvation and selectivity of Na + , K + , and Li + by different glycerol-derived solvents. The structural properties suggest that the solvent-cation association is stable over a very wide temperature range. Further, a strong correlation is observed between the more electronegative oxygen sites and preferential interaction with the cations, which suggests that the electrostatic oxygen-ion interactions dominate the coordination between these species. Significantly more intense interactions are observed between the solvents and Li + , versus Na + or K + . These molecular-level thermodynamic insights provide fundamental support for further exploring the performance of glycerol-derived podand complexes in Li + capture applications and/or electrolyte formulations.

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

TeraChem: A graphical processing unit-accelerated electronic structure package for large-scale ab initio molecular dynamics

TeraChem was born in 2008 with the goal of providing fast on-the-fly electronic structure calculations to facilitate ab initio molecular dynamics studies of large biochemical systems such as photoswitchable proteins and multichromophoric antenna complexes. Originally developed for videogaming applications, graphics processing units (GPUs) offered a low-cost parallel computer architecture that became more accessible for general-purpose GPU computing with the release of CUDA in 2007. The evaluation of the electron repulsion integrals (ERIs) is a major bottleneck in electronic structure codes and provides an attractive target for acceleration on GPUs. Thus, highly efficient routines for evaluation of and contractions between the ERIs and density matrices were implemented in TeraChem. Here, electronic structure methods were developed and implemented to leverage these integral contraction routines, resulting in the first quantum chemistry package designed from the ground up for GPUs. This GPU acceleration makes TeraChem capable of performing large-scale ground and excited state calculations in the gas and condensed phase. Today, TeraChem's speed forms the basis for a suite of quantum chemistry applications, including optimization and dynamics of proteins, automated and interactive chemical discovery tools, and large-scale nonadiabatic dynamics simulations.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRSDate not supplied

Mixed-Domain Charge Transport in S-Se Alloys as a Li-S Battery Cathode Material

Lithium-sulfur batteries are emerging candidate systems for the next-generation long-range electric aircraft application owing to their potential to deliver high energy density per weight. Their cathodes are to be made primarily with sulfur, but sulfur by itself has much too low electron conductivity to serve as a useful cathode. An idea that has been suggested to overcome this bottleneck is to alloy sulfur with selenium in the hope that electron mobility, which is thought to improve charge transport at some expense of increased weight and reduced energy density. However, understanding of these alloy structures and their transport mechanism is insufficient, and electron mobility at varying degrees of selenium content is not well charted, which are critical for determining the optimum selenium content and testing whether this strategy is generally feasible. The difficulty of computationally characterizing these alloy systems is rooted in the structure. The structures of both sulfur and selenium exhibit eight-atom rings that pack together in various orientations to form their respective crystals. For one, because these crystals (and presumably their alloys as well) feature multiple polymorphs such that their structural coherence is rather unclear. Secondly, these are also relatively large systems (32 atoms per cell) with low-symmetry, which complicate computation both in terms of accuracy and efficiency. Thirdly, such semi-molecular, semi-crystalline structures lead to a combination of band-transport characteristics and hopping-transport characteristics, each of which is a domain with its own physics and set of computational, theoretical challenges. In addition, there is a general dearth of experimental transport data for sulfur-selenium alloys. In this study, we make a comprehensive attempt to tackle this problem using a wide array of first-principles methods. We generate special quasirandom structures to simulate alloy structures, and compute their first-principles Raman spectra for comparison with experimental data to ensure their structural soundness. We then proceed to use recently developed, state-of-the-art tool (AMSET) in order to efficiently compute electronic mobilities under band transport of pure sulfur, pure selenium, as well as their alloys of various compositions at a reasonable accuracy. We then sample numerous dimer configurations of nearest-neighbor eight-atom-ring-pairs and compute electronic hopping rates between them, which yields hopping mobility. A combination of these efforts lead to a general mapping of electron transport behaviors throughout the alloy range. Preliminary results show that introduction of selenium into sulfur initially damages electron mobility due to disorder but eventually improves it beyond that of pure sulfur with additional selenium content, ultimately peaking at the pure-selenium limit. Band transport dominates for holes in sulfur and electrons in selenium, but in all other cases, hopping transport is dominant. Ongoing efforts include determination of charge concentration and conductivity, as well as performing multiphysics modeling to determine the optimum selenium content for best tradeoff between conductivity and energy density for aircraft range.

Junsoo Park↗
DOE OSTI2021

In Situ X-ray Diffraction of High Density Polyethylene During Dynamic Compression: Polymer Chain Compression and Phase Transformations

Polymers are widely implemented materials often used for safety and security in our daily lives. However, we do not have a thorough understanding of the phase transformations of these materials when exposed to extreme condition, high strain rate, events. To study polymers in these severe environments, we performed plate impact experiments that impart a one-dimensional shock wave, at high pressures and temperatures, to observe the materials response. Generally, velocimetry is the experimental diagnostic used to capture the movement of high velocity interfaces to then calculate the mechanical variables associated with shock compression. However, when a material undergoes a phase transition, such as between two crystalline phases or melting to decomposition during shock compression, velocimetry does not explicitly indicate what structural change occurred. At the Dynamic Compression Sector at the Advanced Photon Source gas gun driven compression has been paired with x-ray diffraction, providing the ability to study both the shock parameters and structural changes concurrently. We explored high density polyethylene (HDPE) both on its reactants Hugoniot (<10.12 GPa) and within its transition region (24.3 GPa) where HDPE is hypothesized to decompose from reactants to products. With x-ray diffraction we observed both polymer chain compression and crystal structure reorientation from orthorhombic to monoclinic above 6 GPa, as well as either a possible phase change or chemical decomposition at 24.3 GPa. With these experiments we were able to determine the crystalline and amorphous Hugoniot loci at pressures below the polymer transition region.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Impact of structural biology and the protein data bank on us fda new drug approvals of low molecular weight antineoplastic agents 2019–2023

Abstract Open access to three-dimensional atomic-level biostructure information from the Protein Data Bank (PDB) facilitated discovery/development of 100% of the 34 new low molecular weight, protein-targeted, antineoplastic agents approved by the US FDA 2019–2023. Analyses of PDB holdings, the scientific literature, and related documents for each drug-target combination revealed that the impact of structural biologists and public-domain 3D biostructure data was broad and substantial, ranging from understanding target biology (100% of all drug targets), to identifying a given target as likely druggable (100% of all targets), to structure-guided drug discovery (>80% of all new small-molecule drugs, made up of 50% confirmed and >30% probable cases). In addition to aggregate impact assessments, illustrative case studies are presented for six first-in-class small-molecule anti-cancer drugs, including a selective inhibitor of nuclear export targeting Exportin 1 (selinexor, Xpovio), an ATP-competitive CSF-1R receptor tyrosine kinase inhibitor (pexidartinib,Turalia), a non-ATP-competitive inhibitor of the BCR-Abl fusion protein targeting the myristoyl binding pocket within the kinase catalytic domain of Abl (asciminib, Scemblix), a covalently-acting G12C KRAS inhibitor (sotorasib, Lumakras or Lumykras), an EZH2 methyltransferase inhibitor (tazemostat, Tazverik), and an agent targeting the basic-Helix-Loop-Helix transcription factor HIF-2α (belzutifan, Welireg).

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Specific Ion Effects in Lanthanide–Amphiphile Structures at the Air–Water Interface and Their Implications for Selective Separation

The use of surfactants to attract dissolved ions to water surfaces and interfaces is an essential step in both solvent-based and solvent-free separation processes. Here, we have studied the interactions of lanthanide ions in the aqueous subphase with monolayers of dihexadecyl phosphate at air–water interfaces. With heavier lanthanides (atomic number Z ≥ 65) in the subphase, the floating layer can be compressed to an area/molecule of about half the molecular cross section, indicating bilayer formation. X-ray fluorescence and reflectivity data support this conclusion. In the presence of lighter lanthanides (Z < 65), only monolayers are observed. Subphase-concentration-dependent studies using Er 3+ (heavier) and Nd 3+ (lighter) lanthanides show a stepwise progression, with ions attaching to the monolayer only when the solution concentration is >3 × 10 –7 M. Above ~10 –5 M, bilayers form but only in the presence of the heavier lanthanide. Grazing incidence X-ray diffraction shows evidence of lateral ion–ion correlations in the bilayer structure but not in monolayers. Explicit solvent all-atom molecular dynamics simulations confirm the elevated ion–ion correlation in the bilayer system. This bilayer structure isolates heavier lanthanides but not lighter lanthanides from an aqueous solution and is therefore a potential mechanism for the selective separation of heavier lanthanides.

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

The STAG code: A fully relativistic super transition array calculation using Green’s functions

Calculating opacities for a wide range of plasma conditions (i.e. temperature, density, element) requires detailed knowledge of the plasma configuration space and electronic structure. For plasmas composed of heavier elements, relativistic effects are important in both the electronic structure and the details of opacity spectra. We extend our previously described superconfiguration and super transition array capabilities (Gill et al., 2023) to include a fully relativistic formalism. Further, the use of hybrid bound-continuum supershells in our superconfigurations demonstrates the importance of a consistent treatment of bound and continuum electrons in dense plasma opacities, and we expand the discussion of these consequences to include issues associated with equation of state and electron correlations between bound and continuum electrons.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Size-dependent second-order-like phase transitions in Fe nanocluster melting from low-temperature structural isomerization

Here, in this work, the melting phase transitions of Fe n nanoclusters with 10 ≤ n ≤ 100 atoms are investigated using classical many-body molecular dynamics simulations. For many cluster sizes, surface melting occurs at much lower temperatures than core melting. Surface and core melting points and energetic melting points (temperatures of maximum heat capacity, C v ) are calculated for all cluster sizes. Melting properties are found to be strong functions of cluster structure. Cluster sizes with closed-shell structures always have first-order-like phase transitions. Almost one-third of cluster sizes in the analyzed range exhibit second-order-like phase transitions due to the presence of multiple structural configurations close in energy. 1-shell clusters with one to a few more atoms than a neighboring closed-shell structure have very low surface melting points and very high energetic melting points compared to their closed-shell counterparts. In clusters above 50 atoms with certain core structures, melting of the surface before the core was observed.

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

Solvent Effects on Catalytic Reactions and Related Phenomena at Liquid-Solid Interfaces

Catalytic reactions involve the direct interaction of reactants, intermediates and products with the catalyst surface. We not only need to control the atomic structure and electronic properties of the active site, but also explore the multiple molecular interactions that occur beyond the active site; they play an essential role in altering the binding and reactivity of surface species. In liquid-phase catalysis, solvents provide additional degrees of freedom in the design of the catalytic process for desirable activity and selectivity. Here, the multi-faceted effects of solvents have a profound impact on the catalyst performance by restricting the mass transfer to the site, tuning the chemical potential of the surface species, competing for active sites, stabilizing the initial and transition states, and causing mechanistic changes by participating in the kinetically relevant elementary steps. This review addresses the different aspects of solvent effects, using a few prototype solid-liquid interfaces to illustrate these fundamental features. Recent experimental and computational studies that provide new insight at the molecular level are examined. Solvent structures in the proximity of the catalyst surface are discussed along with their influence in molecular binding and reaction at the solid-liquid interfaces. Furthermore, opportunities to alter such a solid-liquid interaction by tuning the wettability of the catalyst surfaces are explored.

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

Molecular interactions in short-chain perfluoroalkyl carboxylic acids and aqueous solutions

The presence of short-chain per- and polyfluoroalkyl substances in water poses a major health and environmental challenge. Here, we have performed high-energy small- and wide-angle X-ray scattering measurements on CF 3 [CF 2 ] n COOH (where n = 1, 2, 3 represents the chain length) and their aqueous solutions at 10% mole concentrations to characterize their molecular interactions at the atomic and nanometer length scales. The experimental wide-angle structure factors have been modelled using Empirical Potential Structural Refinement. The oxygen–oxygen partial X-ray pair distribution functions show that the coordination number between the hydroxyl oxygen on the acid and surrounding oxygen water molecules increases significantly with acid chain length, rising from 3.2 for n = 1 to 4.1 for n = 3. The small-angle scattering is dominated by a sharp, high-intensity peak at Q 1 ~ 0.2 Å -1 and a smaller peak at Q 2 = 1.2 Å -1 for n = 3, both of which decrease with decreasing chain length. The Q 2 peak is attributed to groups of adjacent non-bonded acid molecules, and Q 1 has contributions from both correlations between acid molecules and water–water interactions. In all cases, the models show nanoscale aggregation occurs in the form of denser channels of winding hydrogen-bonded chains, approximately 20 water molecules in length, surrounding clusters of acid molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗