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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Materials Data on ScH16I3O8 by Materials Project

ScH10O7IH2OHI1IH3 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of four hydriodic acid molecules, four molecular hydrogen;hydroiodide molecules, four water molecules, and four ScH10O7I clusters. In each ScH10O7I cluster, Sc3+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of Sc–O bond distances ranging from 1.97–2.35 Å. There are ten inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. In the second H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. In the third H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. In the fourth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. In the fifth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. In the sixth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. In the seventh H1+ site, H1+ is bonded in a single-bond geometry to one O2- and one I1- atom. The H–O bond length is 1.00 Å. The H–I bond length is 2.42 Å. In the eighth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. In the ninth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.97 Å. In the tenth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. There are seven inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted water-like geometry to one Sc3+ and two H1+ atoms. In the second O2- site, O2- is bonded in a single-bond geometry to one Sc3+, one H1+, and one O2- atom. The O–O bond length is 1.48 Å. In the third O2- site, O2- is bonded in a distorted water-like geometry to one Sc3+ and two H1+ atoms. In the fourth O2- site, O2- is bonded in a distorted water-like geometry to one Sc3+ and two H1+ atoms. In the fifth O2- site, O2- is bonded in a 1-coordinate geometry to one Sc3+ and one O2- atom. In the sixth O2- site, O2- is bonded in a distorted water-like geometry to one Sc3+ and one H1+ atom. In the seventh O2- site, O2- is bonded in a distorted water-like geometry to one Sc3+ and two H1+ atoms. I1- is bonded in a 1-coordinate geometry to one H1+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Mixed ortho- H 2 and para- H 2 clusters studied by vibrational coherent anti-Stokes Raman spectroscopy

The search for macroscopic quantum effects, including superfluidity, in molecular hydrogen is mostly focused on its parahydrogen (p-H 2 ) nuclear spin modification because of weaker intermolecular interaction compared to orthohydrogen (o-H 2 ), both modifications being bosonic. In this work, mixed clusters of o-H 2 and p-H 2 containing similar to 10(4) molecules are prepared by supersonic expansion with helium and studied by vibrational coherent anti-Stokes Raman scattering (CARS) spectroscopy. At similar experimental conditions the neat p-H 2 clusters avoid freezing and remain fluid at 1-2 K, which is predicted to be the realm of their superfluid behavior [Phys. Rev. Lett. 101, 205301 (2008)]. Dependence of the vibrational frequencies and intensities of the main CARS peaks due to o-H 2 and p-H 2 versus the ratio of the o-H 2 and p-H 2 concentrations in the expanding gas suggests that o-H 2 and p-H 2 molecules are uniformly mixed in the interior of the clusters. A weak spectral feature at 4157 cm -1 that appears independent of the concentration ratio is assigned to the outer shell of the clusters enriched with p-H 2 molecules. Although the phase of the mixed clusters could not be unambiguously identified, the shift of the vibrational frequencies with respect to the bulk solid is consistent with the liquid state of the clusters.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Development of molecular cluster models to probe pyrite surface reactivity

Abstract The recent discovery that anaerobic methanogens can reductively dissolve pyrite and utilize dissolution products as a source of iron and sulfur to meet their biosynthetic demands for these elements prompted the development of atomic‐scale nanoparticle models, as maquettes of reactive surface sites, for describing the fundamental redox steps that take place at the mineral surface during reduction. The given report describes our computational approach for modeling n (FeS 2 ) nanoparticles originated from mineral bulk structure. These maquettes contain a comprehensive set of coordinatively unsaturated Fe (II) sites that are connected via a range of persulfide (S 2 2− ) ligation. In addition to the specific maquettes with n = 8, 18, and 32 FeS 2 units, we established guidelines for obtaining low‐energy structures by considering the pattern of ionic, covalent, and magnetic interactions among the metal and ligand sites. The developed models serve as computational nano‐reactors that can be used to describe the reductive dissolution mechanism of pyrite to better understand the reactive sites on the mineral, where microbial extracellular electron‐transfer reactions can occur.

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

The Stellar Content of H72.97-69.39, a Potential Super Star Cluster in the Making

Young massive clusters and super star clusters (SSCs) represent an extreme mode of star formation. Far-infrared imaging of the Magellanic Clouds has identified one potential embedded SSC, HSO BMHERICC J72.971176-69.391112 (H72.97-69.39 in short), in the southwest outskirts of the Large Magellanic Cloud. We present Gemini Flamingos 2 and GSAOI near-infrared imaging of a 3′ × 3′ region around H72.97-69.39 in order to characterize the stellar content of the cluster. The stellar content is probed down to 1.5 M {sub ⊙}. We find substantial dust extinction across the cluster region, extending up to A {sub K} of 3. Deeply embedded stars are associated with ALMA-detected molecular gas suggesting that star formation is ongoing. The high spatial resolution of the GSAOI data allows identification of the central massive object associated with the {sup 13}CO ALMA observations and detection of fainter low-mass stars around the H30α ALMA source. The morphology of the molecular gas and the nebulosity from adjacent star formation suggest they have interacted covering a region of several parsecs. The total stellar content in the cluster is estimated from the intermediate- and high-mass stellar content to be at least 10,000 M {sub ⊙}, less than R136 with up to 100,000 M {sub ⊙} within 4.7 pc radius, but places it in the regime of an SSC. Based on the extinction determination of individual stars we estimate a molecular gas mass in the vicinity of H72.97-69.39 of 6600 M {sub ⊙}, suggesting more star formation can be expected.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Self-interacting dark matter and small-scale gravitational lenses in galaxy clusters

Recently, Meneghetti et al. reported an excess of small-scale gravitational lenses in galaxy clusters. We study its implications for self-interacting dark matter (SIDM) compared with standard cold dark matter (CDM). We design controlled N-body simulations that incorporate observational constraints. The presence of early-type galaxies in cluster substructures can deepen gravitational potential and reduce tidal mass loss. Both scenarios require a relatively high baryon concentration in the substructure to accommodate the lensing measurements, and their tangential caustics are similar. The SIDM substructure can experience gravothermal collapse and produce a steeper density profile than its CDM counterpart, leading to a larger radial galaxy-galaxy strong-lensing cross section, although this effect is hard to observe. Our results indicate that SIDM can provide a unified explanation to small-scale lenses in galaxy clusters and stellar motion in dwarf galaxies.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Capturing Surface Coverage Effects in Heterogeneous Catalysis

Adsorbate–adsorbate lateral interactions at relevant surface coverages have a significant effect on chemical kinetics, thereby influencing the activity of a heterogeneous catalyst. Coverage-dependent kinetic and thermodynamic parameters therefore must be included in studies of such complex systems to properly predict the turnover frequencies and kinetic trends. Thus, it becomes extremely important to accurately capture the strength of lateral interactions between neighboring species under realistic reaction conditions. In this Perspective, we discuss the various existing computational and experimental methods for determining adspecies coverage and configurational effects. The choice of the tools and methods employed in such studies depends on factors such as time, length scales, computational cost, the presence of solvents, and reaction conditions. The applications of each method and the respective challenges are also discussed here. As a result, we discuss the recent developments and future of the state-of-the-art for inclusion of surface coverage and configuration into a holistic picture for accurate predictions of catalytic behavior.

09 BIOMASS FUELS↗
DOE OSTI2021

Thermal gradient effect on helium and self-interstitial transport in tungsten

First-wall materials in a fusion reactor are expected to withstand harsh conditions, with high heat and particle fluxes that modify the materials microstructure. These fluxes will create strong gradients of temperature and concentration of diverse species. Besides the He ash and the hydrogenic species, neutron particles generated in the fusion reaction will collide with the material creating intrinsic defects, such as vacancies, self-interstitials atoms (SIAs), and clusters of such point defects. These defects and the He atoms will then migrate in the presence of the aforementioned gradients. In this study, we use nonequilibrium molecular dynamics to analyze the transport of He and SIAs in the presence of a thermal gradient in tungsten. We observe that, in all cases, the defects and impurity atoms tend to migrate toward the hot regions of the tungsten sample. The resulting species concentration profiles are exponential distributions, rising toward the hot regions of the sample, in agreement with irreversible thermodynamics analysis. For both He atoms and SIAs, we find that the resulting species flux is directed opposite to the heat flux, indicating that species transport is governed by a Soret effect (thermal-gradient-driven diffusion) characterized by a negative heat of transport that drives species diffusion uphill (from the cooler to the hot regions of the sample). Here, we demonstrate that the steady-state species profiles obtained accounting for the Soret effect vary significantly from those where temperature-gradient-driven transport is not considered and discuss the implications of such a Soret effect on the response to plasma exposure of plasma-facing tungsten.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Fe2S3O23 by Materials Project

FeSO7Fe(SO6)2(O2)2 crystallizes in the triclinic P-1 space group. The structure is zero-dimensional and consists of four molecular oxygen molecules, two Fe(SO6)2 clusters, and two FeSO7 clusters. In each Fe(SO6)2 cluster, Fe is bonded in a 5-coordinate geometry to five O atoms. There are a spread of Fe–O bond distances ranging from 1.86–2.41 Å. There are two inequivalent S sites. In the first S site, S is bonded in a tetrahedral geometry to four O atoms. There is three shorter (1.47 Å) and one longer (1.54 Å) S–O bond length. In the second S site, S is bonded in a tetrahedral geometry to four O atoms. There are a spread of S–O bond distances ranging from 1.46–1.54 Å. There are twelve inequivalent O sites. In the first O site, O is bonded in a single-bond geometry to one S atom. In the second O site, O is bonded in a 2-coordinate geometry to one Fe and one O atom. The O–O bond length is 1.30 Å. In the third O site, O is bonded in a single-bond geometry to one S atom. In the fourth O site, O is bonded in a single-bond geometry to one O atom. The O–O bond length is 1.24 Å. In the fifth O site, O is bonded in a single-bond geometry to one S atom. In the sixth O site, O is bonded in a bent 120 degrees geometry to one Fe and one S atom. In the seventh O site, O is bonded in a water-like geometry to one Fe and one O atom. In the eighth O site, O is bonded in a 2-coordinate geometry to one Fe and one O atom. In the ninth O site, O is bonded in a single-bond geometry to one S atom. In the tenth O site, O is bonded in a single-bond geometry to one S atom. In the eleventh O site, O is bonded in a single-bond geometry to one S atom. In the twelfth O site, O is bonded in a bent 150 degrees geometry to one Fe and one S atom. In each FeSO7 cluster, Fe is bonded in a see-saw-like geometry to four O atoms. There are a spread of Fe–O bond distances ranging from 1.66–1.84 Å. S is bonded in a tetrahedral geometry to four O atoms. There are a spread of S–O bond distances ranging from 1.46–1.56 Å. There are seven inequivalent O sites. In the first O site, O is bonded in a bent 150 degrees geometry to one Fe and one S atom. In the second O site, O is bonded in a single-bond geometry to one Fe atom. In the third O site, O is bonded in a single-bond geometry to one Fe atom. In the fourth O site, O is bonded in a single-bond geometry to one Fe atom. In the fifth O site, O is bonded in a single-bond geometry to one S atom. In the sixth O site, O is bonded in a single-bond geometry to one S atom. In the seventh O site, O is bonded in a single-bond geometry to one S atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on H9Au(ClO)4 by Materials Project

AuCl4(H2O)2H5O2 crystallizes in the triclinic P1 space group. The structure is zero-dimensional and consists of one molecular hydrogen;dihydrate molecule, two water molecules, and one AuCl4 cluster. In the AuCl4 cluster, Au3+ is bonded in a rectangular see-saw-like geometry to four Cl1- atoms. There are one shorter (2.31 Å) and three longer (2.32 Å) Au–Cl bond lengths. There are four inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to one Au3+ atom. In the second Cl1- site, Cl1- is bonded in a single-bond geometry to one Au3+ atom. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one Au3+ atom. In the fourth Cl1- site, Cl1- is bonded in a single-bond geometry to one Au3+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on ZnH12(NO3)2 by Materials Project

ZnNHO3(H2)5HNO3 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of sixteen hydrogen molecules, four molecular hydrogen molecules, four nitric acid molecules, and four ZnNHO3 clusters. In each ZnNHO3 cluster, Zn2+ is bonded in a distorted linear geometry to one H1+ and one O2- atom. The Zn–H bond length is 1.51 Å. The Zn–O bond length is 1.89 Å. N1- is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of N–O bond distances ranging from 1.23–1.37 Å. H1+ is bonded in a single-bond geometry to one Zn2+ atom. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 120 degrees geometry to one Zn2+ and one N1- atom. In the second O2- site, O2- is bonded in a single-bond geometry to one N1- atom. In the third O2- site, O2- is bonded in a single-bond geometry to one N1- atom.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Computational study of the electrostatic potential and charges of multivalent ionic liquid molecules

The electrostatic interactions in ionic liquids (ILs) can be difficult to quantify, but this information is very valuable for improving intermolecular potentials for performing molecular-level simulations. Although polarizable forcefields can provide improved accuracy, the computational efficiency of fixed charge molecular models is often preferred for larger systems. Here, we propose a multi-scale screening approach for analyzing the charge scaling behavior and other electrostatic properties of ILs, which is more attainable than previous analysis methods that rely on the IL crystalline structures. Based on isolated molecules and small clusters, we study the electrostatic potential properties and charges of multivalent IL molecules using density-functional theory calculations and ab initio molecular dynamics simulations. The charges of the IL molecules are calculated and compared using several different charge estimation techniques. Although there are some differences among the estimated partial charges on the atoms, the total anion and cation charges are very similar. In conclusion, the charge scaling factors are substantial, and they are only slightly affected by the IL cluster size model.

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

Combined Machine Learning and Molecular Dynamics Reveal Two States of Hydration of a Single Functional Group of Cationic Polymeric Brushes

The state of hydration of a macromolecular system regulates a plethora of different properties of such a system. In this article, we develop a novel machine learning (ML) approach, based on the unsupervised clustering algorithm, for probing the hydration behavior of the {N(CH 3 ) 3 } + functional group of the PMETAC [Poly(2-(methacryloyloxy)ethyl trimethylammonium chloride] polyelectrolyte (PE) brush system. The PE brushes and the brush-supported water molecules and counterions (chloride ions) are first described using all-atom molecular dynamics (MD) simulations. The simulation data is subsequently used in our ML framework to identify that (1) the {N(CH 3 ) 3 } + functional groups of the PMETAC brushes have two distinct hydration states with one state (state 1) being characterized by less structured water molecules and the other state (state 2) being characterized by more structured water molecules and (2) an enhancement in the brush grafting density leads to the progressive dissapparenace of state 2. An increase in the grafting density increases the number of chloride counterions in a given volume around the {N(CH 3 ) 3 } + functional group and increases the number of shared water molecules between the {N(CH 3 ) 3 } + and Cl - . The chloride counterions are associated with a hydration layer with much less structured water molecules. Therefore, with an increase in the grafting density, an increase in the percentage of shared water molecules leads to the prevalence of the hydration state [of the {N(CH 3 ) 3 } + moiety] with less structured water molecules. Finally, we explain how the present findings are commensurate with two key previous related results, namely a significantly large chloride ion mobility inside the PMETAC brush layer and the {N(CH 3 ) 3 } + -Cl - average distance remaining independent of the PMETAC brush grafting density. Furthermore, we anticipate that the combined ML-MD-simulation approach proposed in this study can be adapted to probe other soft matter systems to reveal new insights of the underlying mechanisms of emergent phenomenon.

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

Unconventional low temperature decomposition of a saturated hydrocarbon over atomically-dispersed titanium-aluminum-boron catalyst

Sonochemically-synthesized atomically-dispersed titanium-aluminum-boron nanopowder (TiAlB NP) exhibits a remarkable low-temperature catalytic activation of aliphatic C-H bonds at 750 K followed by C-C bond activation thus emerging as a potent low-cost alternative to expensive platinum group metals. Here, the model saturated hydrocarbon, exo-tetrahydrodicyclopentadiene (C10H16), undergoes catalytic decomposition on TiAlB NPs in a chemical microreactor to produce 1,3-cyclopentadiene (c-C5H6), cyclopentene (c-C5H8), and molecular hydrogen (H2) as detected in situ via isomer-selective, single-photon ionization time-of-flight mass spectrometry. Extensive electronic structure theory calculations on model clusters of the catalyst decode a unique synergy among the atomic constituents of the catalyst and chemical bonding in this stepwise, retro Diels Alder reaction: Ti, although insensitive to C-H activation in its metallic state, initiates the catalysis via chemisorption of the hydrocarbon, adjacent B centers readily abstract hydrogen atoms and store them during the catalytic cycle, while Al stabilizes the catalyst structure yet providing space for critical docking sites for the departing hydrocarbons.

Biswas, Souvick↗
DOE OSTI2023

The Debye-Waller factor of disordered solids: The case for amorphous silicon

This paper presents a first-principles study of the Debye-Waller factor and the Debye temperature for amorphous silicon (α-Si) from lattice-dynamical calculations and direct molecular-dynamics simulations using density-functional theory (DFT). The effects of temperature and structural disorder on the intensity of the diffraction maxima and the vibrational mean-square displacement (MSD) of Si atoms are studied in the harmonic approximation, with particular emphasis on the bond-length disorder, the presence of coordination defects, and microvoids in α-Si networks. It has been observed that the MSDs associated with tetrahedrally bonded Si atoms are considerably lower than their dangling-bond counterparts—originating from isolated and vacancy-induced clustered defects—and those on the surface of microvoids, leading to an asymmetric non-Gaussian tail in the distribution of atomic displacements. An examination of the effect of anharmonicity on the MSD at high temperatures using direct ab initio molecular-dynamics simulations (without the harmonic approximation) suggests that the vibrational motion in α-Si is practically unaffected by anharmonic effects at temperatures below 400 K, as far as the present DFT calculations are concerned. The Debye temperature of α-Si is found to be in the range of 488–541 K from specific-heat and MSD calculations using first-principles lattice-dynamical calculations in the harmonic approximation, which matches closely with the experimental value of 487–528 K obtained from specific-heat measurements of α-Si at low temperatures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Ab initio studies of the impact of the Debye-Waller factor on the structural and dynamical properties of amorphous semiconductors: The case of a-Si

This paper presents a first-principles study of the Debye-Waller factor and the Debye temperature for amorphous silicon (a-Si) from lattice-dynamical calculations and direct molecular-dynamics simulations using density-functional theory (DFT). The effects of temperature and structural disorder on the intensity of the diffraction maxima and the vibrational mean-square displacement (MSD) of Si atoms are studied in the harmonic approximation, with particular emphasis on the bond-length disorder, the presence of coordination defects, and microvoids in a-Si networks. It has been observed that the MSDs associated with tetrahedrally-bonded Si atoms are considerably lower than their dangling-bond counterparts – originating from isolated and vacancy-induced clustered defects – and those on the surface of microvoids, leading to an asymmetric non-gaussian tail in the distribution of atomic displacements. An examination of the effect of anharmonicity on the MSD at high temperatures using direct ab initio molecular-dynamics simulations (without the harmonic approximation) suggests that the vibrational motion in a-Si is practically unaffected by anharmonic effects at temperatures below 400 K, as far as the present DFT calculations are concerned. The Debye temperature of a-Si is found to be in the range of 488–541 K from specific-heat and MSD calculations using first-principles lattice-dynamical calculations in the harmonic approximation, which matches closely with the experimental value of 487–528 K obtained from specific-heat measurements of a-Si at low temperatures.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Simplified tuning of long-range corrected density functionals for use in symmetry-adapted perturbation theory

Long considered a failure, second-order symmetry-adapted perturbation theory (SAPT) based on Kohn–Sham orbitals, or SAPT0(KS), can be resurrected for semiquantitative purposes using long-range corrected density functionals whose asymptotic behavior is adjusted separately for each monomer. Here, as in other contexts, correct asymptotic behavior can be enforced via “optimal tuning” based on the ionization energy theorem of density functional theory, but the tuning procedure is tedious, expensive for large systems, and comes with a troubling dependence on system size. Here, we show that essentially identical results are obtained using a fast, convenient, and automated tuning procedure based on the size of the exchange hole. In conjunction with “extended” (X)SAPT methods that improve the description of dispersion, this procedure achieves benchmark-quality interaction energies, along with the usual SAPT energy decomposition, without the hassle of system-specific tuning.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Fast calculation of diffraction patterns from an ensemble of aligned molecules

We report an algorithm to calculate electron diffraction patterns for molecules with anisotropic angular distribution, which is significantly faster than existing methods. The algorithm uses a transform to convert the molecular orientation distribution, which is a function of three Euler angles, to the atom-pair distribution functions which depend on the polar and azimuthal angles. The diffraction signal can then be calculated from the atom-pair distributions. We demonstrate the computation method numerically by calculating electron diffraction patterns for a symmetric top molecule (trifluoroiodomethane) and an asymmetric top molecule (formaldehyde) and show that it reduces the calculation time by approximately two orders of magnitude compared to the standard brute-force method. Here, the method can also be applied to the calculation of x-ray diffraction patterns.

74 ATOMIC AND MOLECULAR PHYSICS↗