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At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Reversible motions and disordered structure of soft particles in amorphous solids

In amorphous solids, soft vibrational modes derived from normal mode analysis can be utilized to identify the soft particles that are prone to irreversible rearrangements. However, the normal mode analysis approach cannot explain why the spatial distributions of clustered soft particles do not change over time. We define a softness parameter based on the vibrational density of states calculated directly from molecular dynamics simulations with both the harmonic vibrations and anharmonic relaxations being properly captured at finite temperatures. This parameter spontaneously correlates with the real space atomic motions and the dynamics heterogeneity. Using the softness parameter, we show that the softest particles are confined within rigid cages. These particles keep rearranging reversibly without long-range diffusion. The moderately soft particles rearrange irreversibly, and the hard particles mainly participate in vibrations without rearrangement. Here, we also show that the soft particles form locally disordered structures, while the hard particles present strong ordering. These findings confirm the defective nature of soft particles, and provide insights on the nature of softness as the ability to rearrange, but not necessarily irreversibly.

36 MATERIALS SCIENCE↗
NASA NTRS1996

Computational Nanotechnology at NASA Ames Research Center, 1996

Some forms of nanotechnology appear to have enormous potential to improve aerospace and computer systems; computational nanotechnology, the design and simulation of programmable molecular machines, is crucial to progress. NASA Ames Research Center has begun a computational nanotechnology program including in-house work, external research grants, and grants of supercomputer time. Four goals have been established: (1) Simulate a hypothetical programmable molecular machine replicating itself and building other products. (2) Develop molecular manufacturing CAD (computer aided design) software and use it to design molecular manufacturing systems and products of aerospace interest, including computer components. (3) Characterize nanotechnologically accessible materials of aerospace interest. Such materials may have excellent strength and thermal properties. (4) Collaborate with experimentalists. Current in-house activities include: (1) Development of NanoDesign, software to design and simulate a nanotechnology based on functionalized fullerenes. Early work focuses on gears. (2) A design for high density atomically precise memory. (3) Design of nanotechnology systems based on biology. (4) Characterization of diamonoid mechanosynthetic pathways. (5) Studies of the laplacian of the electronic charge density to understand molecular structure and reactivity. (6) Studies of entropic effects during self-assembly. Characterization of properties of matter for clusters up to sizes exhibiting bulk properties. In addition, the NAS (NASA Advanced Supercomputing) supercomputer division sponsored a workshop on computational molecular nanotechnology on March 4-5, 1996 held at NASA Ames Research Center. Finally, collaborations with Bill Goddard at CalTech, Ralph Merkle at Xerox Parc, Don Brenner at NCSU (North Carolina State University), Tom McKendree at Hughes, and Todd Wipke at UCSC are underway.

Globus, Al↗
DOE OSTI2022

Atomic isotropic hyperfine properties for first row elements (B–F) revisited

Benchmark quality isotropic hyperfine properties have been obtained for first row elements (B–F) using a systematic composite approach consisting of a sequence of core/valence correlation consistent basis sets, up through aug-cc-pCV8Z, along with configuration interaction and coupled cluster theory methods. The best nonrelativistic final values (in MHz) are 10.64 (B), 20.22 (C), 10.59 (N), –31.74 (O), and 318.30 (F) and are in very good agreement with available experimental values for these difficult-to-describe properties. Agreement is especially close in the case of N, which has the most accurate experimental value. The spin densities derived from the best composite level of theory were found to closely follow a simple quadratic scaling with the atomic number, Z. Finally, observed convergence rates in the 1-particle and n-particle expansions obtained here may be useful in judging likely accuracy that can be expected in studies of molecular systems.

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

Evolution of dislocation loops in irradiated α-Uranium: An atomistically-informed cluster dynamics investigation

An atomistically-informed mean field cluster dynamics model has been developed to investigate the nucleation and growth of prismatic loops in irradiated a-Uranium. TEM analysis of neutron irradiated a-Uranium shows the evolution of self-interstitial atom and vacancy loops on (010) and (100) crystallographic planes, respectively, resulting in an anisotropic lattice swelling of its face-centered orthorhombic crystal. To provide model parameters, the crystallography of loops and the binding energy of point defects to these loops were studied using an angular dependent EAM potential and classical molecular dynamics (MD) simulations. Furthermore, using the bond-boost hyperdynamics method, the anisotropic diffusion of interstitials and vacancies in a-Uranium was investigated. Here, the mechanisms of point defect diffusion and the associated migration energies were reported and compared with previous DFT studies. The energetics and kinetic quantities mentioned above were used in the cluster dynamics model to predict the cluster density as a function of dose rate, dose and temperature and the results were compared to the reported neutron irradiation experiments. The model predictions reveal an accumulation of small sized vacancy loops along with a population of large and growing self-interstitial loops, which closely corresponds to the TEM observations.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Iodine recombination in xenon solvent: Clusters in the gas to liquid-like state transition

Supercritical fluids (SCFs) have attracted significant attention as solvents for chemical reactions due to their unique properties, such as high diffusivity, low viscosity, and tunable solvation properties. These properties profoundly influence reaction kinetics and are often attributed to the formation of molecular clusters within SCFs. To study the effect of supercritical solvent on chemical reactivity and dynamics of reactions, one needs to understand the dynamics of clusters in supercritical fluid. Extensive experiments on the photodissociation and recombination of iodine in supercritical fluids served as a model system for understanding these effects. Experimental studies have been complemented by theoretical and computational investigations, which mostly employ Monte Carlo or empirical molecular dynamics simulations. However, computational studies using non-reactive force fields and ab initio approaches present challenges in capturing reactive processes at larger scales within supercritical fluids. Here, in this work, we developed the ReaxFF parameters by training against quantum mechanics data. ReaxFF reactive force field based molecular dynamics simulations were performed, studying the dynamics of a xenon solvent and cage effect at different thermodynamic conditions for the iodine recombination reaction. We show that the conditions near the critical point are the optimal conditions to study the cage effect. We show that the average lifetime of xenon clusters ranging between 5 and 11 ps is comparable to iodine geminate recombination. Our simulation results of iodine recombination in xenon solvent demonstrate the higher probability of iodine molecule formation in the presence of xenon clusters. Finally, we show that the supercritical condition exhibits the highest recombination rate for iodine atoms.

Cage effect↗
DOE OSTI2026

Vapor-Phase Heteroatom Incorporation into Semiconductive Molecular-Scale Magic-Size Clusters

Magic-size metal chalcogenide clusters of molecular size exhibit well-defined structure and unique properties that might be further expanded with the incorporation or substitution of a second metal. Here, we report the postmodification of magic-size clusters synthesized in polymer thin films via exposure to volatile metal organic precursors commonly utilized for atomic layer deposition. Exposure of In 6 S 6 (CH 3 ) 6 clusters to dimethylcadmium results in exposure-dependent incorporation of Cd 2+ , which extends the optical absorbance of the clusters into the visible spectrum. The mechanism for Cd 2+ incorporation is consistent with Cd 2+ replacement of In 3+ that includes methyl ligand removal to maintain charge neutrality. Even for clusters embedded in a polymer matrix, ligand loss leads to sintering and transformation into larger nanoscale aggregates with zinc blende-type structure. The extent of Cd incorporation can be modulated by varying the process temperature and volatile metal organic exposure as well as the choice of volatile metal organic precursor. A computational thermodynamic analysis of heteroatom incorporation for several metals and chemistries reveals that both the stability of the substituted cluster and the favorability of reaction byproducts jointly determine the favorability of cation incorporation.

atomic layer deposition↗
DOE OSTI2020

In search of molecular ions for optical cycling: a difficult road

Optical cycling, a continuous photon scattering off atoms or molecules, plays a central role in the quantum information science. While optical cycling has been experimentally achieved for many neutral species, few molecular ions have been investigated. We present a systematic theoretical search for diatomic molecular ions suitable for optical cycling using equation-of-motion coupled-cluster methods. Inspired by the electronic structure patterns of laser-cooled neutral molecules, we establish the design principles for molecular ions and explore various possible cationic molecular frameworks. The results show that finding a perfect molecular ion for optical cycling is challenging, yet possible. Among various possible diatomic molecules we suggest several candidates, which require further attention from both theory and experiment: YF + , SiO + , PN + , SiBr + , and BO + .

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

From synchrotrons for XFELs: the soft x-ray near-edge spectrum of the ESCA molecule

A predictive understanding of soft x-ray near-edge absorption spectra of small molecules is an enduring theoretical challenge and of current interest for x-ray probes of molecular dynamics. We report the experimental absorption spectrum for the electron spectroscopy for chemical analysis (ESCA) molecule (ethyl trifluoroacetate) near the carbon 1s absorption edge between 285-300 eV. Furthermore, the ESCA molecule with four chemically distinct carbon sites has previously served as a theoretical benchmark for photoelectron spectra and now for photoabsorption spectra. We report a simple edge-specific approach for systematically expanding standard basis sets to properly describe diffuse Rydberg orbitals and the importance of triple excitations in equation-of-motion coupled-cluster calculations of the energy interval between valence and Rydberg excitations.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1985

Optical radiation from the interaction of energetic atoms, ions, electrons, and photons with surfaces

Heavy particle, electron, and UV photon bombardment of solid surfaces has been recently observed to result in the emission of infrared, visible, and ultraviolet radiation. This effect occurs over a wide range of incident projectile energies. Line radiation arising from transitions between discrete atomic or molecular levels may be attributed to the decay of excited particles which have been sputtered or electronically/chemically desorbed from the surface. Broadband continuum radiation, which is also observed, is believed to arise either from fluorescence of the near surface bulk or from the radiative decay of desorbed excited clusters. Spacecraft, in the ambient near Earth environment, are subject to such bombardment. The dynamics of energetic particle and photon beam interactions with surfaces which lead to surface erosion and glow phenomena will be treated. In addition, projected experimental and theoretical studies of oxygen and nitrogen beam surface interactions on materials characteristic of spacecraft surfaces will be discussed.

Tolk, N. H.↗
NASA NTRS2003

Studies of Atomic Free Radicals Stored in a Cryogenic Environment

Impurity-Helium Solids are porous gel-like solids consisting of impurity atoms and molecules surrounded by thin layers of solid helium. They provide an ideal medium for matrix isolation of free radicals to prevent recombination and store chemical energy. In this work electron spin resonance, nuclear magnetic resonance, X-ray diffraction, and ultrasound techniques have all been employed to study the properties of these substances. Detailed studies via electron spin resonance of exchange tunneling chemical reactions involving hydrogen and deuterium molecular and atomic impurities in these solids have been performed and compared with theory. Concentrations of hydrogen approaching the quantum solid criterion have been produced. Structured studies involving X ray diffraction, ultrasound, and electron spin resonance have shown that the impurities in impurity helium solids are predominantly contained in impurity clusters, with each cluster being surrounded by thin layers of solid helium.

Lee, David M.↗
DOE OSTI2020

Superatomic molecules with internal electric fields for light harvesting

Traditional p–n junctions used for photovoltaics require an interface where a light induced electron–hole pair is separated by an electric field. Developing alternative strategies for forming strong internal electric fields for electron–hole pair separation offers the possibility for better performance. We demonstrate that fusing two superatomic clusters with donor/acceptor ligands on opposite sides of the cluster leads to such a strong internal electric field. In two fused metal–chalcogenide Re6S8Cl2(L)4 clusters with donor PMe3 ligands and acceptor CO ligands on the opposite sides of the fused clusters, the electronic levels undergo shifts analogous to band bending in traditional p–n junctions. The fused cluster has a large dipole moment, and an optical spectrum that strongly absorbs excitation above the HOMO–LUMO gap of the fused clusters, but is optically very weak for the lowest energy excitation that can lead to electron–hole pair recombination. This is because the electron is localized on the CO portion of the fused cluster, while the electron–hole pair is localized on the PMe3 side of the cluster. It is shown that the electronic states localized on each side of the cluster can be aligned/misaligned by applying a voltage in different directions, offering diode like characteristics.

14 SOLAR ENERGY↗
DOE OSTI2022

On the prospects of optical cycling in diatomic cations: effects of transition metals, spin–orbit couplings, and multiple bonds

Molecules with optical cycling centers (OCCs) are highly desirable in the context of fundamental studies as well as applications (e.g., quantum computing) because they can be effectively cooled to very low temperatures by repeated absorption and emission (hence, cycling). Charged species offer additional advantages for experimental control and manipulation. Here, we present a systematic computational study of a series of diatomic radical-cations made of a d-block metal and a p-block ligand, that are isoelectronic (in their valence shell) to the successfully laser-cooled neutral molecules. Using high-level electronic structure methods, we characterize state and transition properties of low-lying electronic states and compute Franck-Condon factors. The computed branching ratios and radiative lifetimes reveal that the electronic transitions analogous to those successfully used in the laser cooling of neutral molecules are less than optimal in the cations. We propose alternative transitions suitable for optical cycling and highlight trends that could assist future designs of OCCs in charged or neutral molecules.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Electronic Structure and Anion Photoelectron Spectroscopy of Uranium–Gold Clusters UAu n – , n = 3–7

A collaborative effort between experiment and theory towards elucidating the electronic and molecular structures of uranium-gold clusters is presented. Anion photoelectron spectra of UAu n – (n=3-7) were taken at third (355 nm) and fourth (266 nm) harmonics of a Nd:YAG laser, as well as excimer (ArF 193nm) photon energies, where the experimental adiabatic electron affinities (AEA) and vertical detachment energies (VDE) values were measured. Complementary first principles calculations were subsequently carried out to corroborate experimentally determined electron detachment energies and to determine the geometry and electronic structure for each cluster. Except for the ring-like neutral isomer of UAu 6 where one unpaired electron is spread over the Au atoms, all other neutral and anionic UAu n clusters (n = 3 - 7) were calculated to possess open-shell electrons with the unpaired electrons localized on the central U atom. The smaller clusters closely resemble the analogous UF n species, but significant deviations are seen starting with UAu 5 where a competition between U-Au and Au-Au bonding begins to become apparent. The UAu 6 system appears to mark a transition where Au-Au interactions begin to dominate, where both a ring-like and two heavily distorted octahedral structures around the central U atom are to be nearly isoenergetic. With UAu 7 , only ring-like structures are calculated. Altogether, the calculated electron detachment energies are in good agreement with the experimental values

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

The design space of E(3)-equivariant atom-centred interatomic potentials

Abstract Molecular dynamics simulation is an important tool in computational materials science and chemistry, and in the past decade it has been revolutionized by machine learning. This rapid progress in machine learning interatomic potentials has produced a number of new architectures in just the past few years. Particularly notable among these are the atomic cluster expansion, which unified many of the earlier ideas around atom-density-based descriptors, and Neural Equivariant Interatomic Potentials (NequIP), a message-passing neural network with equivariant features that exhibited state-of-the-art accuracy at the time. Here we construct a mathematical framework that unifies these models: atomic cluster expansion is extended and recast as one layer of a multi-layer architecture, while the linearized version of NequIP is understood as a particular sparsification of a much larger polynomial model. Our framework also provides a practical tool for systematically probing different choices in this unified design space. An ablation study of NequIP, via a set of experiments looking at in- and out-of-domain accuracy and smooth extrapolation very far from the training data, sheds some light on which design choices are critical to achieving high accuracy. A much-simplified version of NequIP, which we call BOTnet (for body-ordered tensor network), has an interpretable architecture and maintains its accuracy on benchmark datasets.

Computer Science↗
DOE OSTI2023

Metallization and spin fluctuations in Cu-doped lead apatite

An electronic structure and magnetic properties analysis of the recently proposed Cu-doped lead apatite is performed. Here, we show that electronic structures of differently Cu-substituted structures are characterized by localized molecular Cu-O bands at or near the Fermi level. The Cu substitutions can happen at both Pb1 and Pb2 sites, leading to metallic and semiconducting systems differently. The electronic systems in these bands are highly unstable magnetically and form clusters of rigidly ferromagnetically coupled magnetic moments on Cu and neighboring oxygen atoms with a total moment of about 1µ B . The ground state of uniformly Cu-doped lead apatite appears to be magnetic and semiconducting. The nonuniform distribution of two Cu atoms at the nearest Pb2 sites leads to an antiferromagnetic semiconducting state with formation energy close to uniformly distributed Cu configurations. The inclusion of quantum spin fluctuations confirms the stability of magnetic Cu-O clusters. Our calculations revealed the absence of the long-range magnetic order between uniformly distributed Cu-O clusters, creating the spin glass type of system.

36 MATERIALS SCIENCE↗
NASA NTRS1984

Detection of shocked atomic gas in the Kleinmann-Low nebula

The 63 micrometer (3)p(1)-(3)P(2) fine structure line emission of neutral atomic oxygen at the center of the Orion nebula with a resolution of 30" is presented. There are three main emission peaks. One is associated with the region of strongest thermal radio continuum radiation close to the Trapezium cluster, and probably arises at the interface between the HII region and the dense Orion molecular cloud. The other two line emission peaks, associated with the Kleinmann Low nebula, are similar in both distribution and velocity to those of the 2 micrometer S(1) line of molecular hydrogen and of the high velocity wings of rotational CO emission. The OI emission from the KL nebula can be produced in the shocked gas associated with the mass outflows in this region and is an important coolant of the shocked gas.

Werner, M.↗
DOE OSTI2021

Short- and medium-range orders in Al90Tb10 glass and their relation to the structures of competing crystalline phases

Molecular dynamics simulations using an interatomic potential developed by artificial neural network deep machine learning are performed to study the local structural order in Al90Tb10 metallic glass. We show that more than 80% of the Tb-centered clusters in Al90Tb10 glass have short-range order (SRO) with their 17 first coordination shell atoms stacked in a ‘3661’ or ‘15551’ sequence. Medium-range order (MRO) in Bergman-type packing extended out to the second and third coordination shells is also clearly observed. Analysis of the network formed by the ‘3661’ and ‘15551’ clusters show that ~82% of such SRO units share their faces or vertexes, while only ~6% of neighboring SRO pairs are interpenetrating. Such a network topology is consistent with the Bergman-type MRO around the Tb-centers. Moreover, crystal structure searches using genetic algorithm and the neural network interatomic potential reveal several low-energy metastable crystalline structures in the composition range close to Al 90 Tb 10 . Some of these crystalline structures have the ‘3661’ SRO while others have the ‘15551’ SRO. While the crystalline structures with the ‘3661’ SRO also exhibit the MRO very similar to that observed in the glass, the ones with the ‘15551’ SRO have very different atomic packing in the second and third shells around the Tb centers from that of the Bergman-type MRO observed in the glassy phase.

36 MATERIALS SCIENCE↗