How do energetic ions damage metallic surfaces?

DOE PAGES

Osetskiy, Yury N.; Calder, Andrew F.; Stoller, Roger E.

2015-02-20

Surface modification under bombardment by energetic ions observed under different conditions in structural and functional materials and can be either unavoidable effect of the conditions or targeted modification to enhance materials properties. Understanding basic mechanisms is necessary for predicting properties changes. The mechanisms activated during ion irradiation are of atomic scale and atomic scale modeling is the most suitable tool to study these processes. In this paper we present results of an extensive simulation program aimed at developing an understanding of primary surface damage in iron by energetic particles. We simulated 25 keV self-ion bombardment of Fe thin films withmore » (100) and (110) surfaces at room temperature. A large number of simulations, ~400, were carried out allow a statistically significant treatment of the results. The particular mechanism of surface damage depends on how the destructive supersonic shock wave generated by the displacement cascade interacts with the free surface. Three basic scenarios were observed, with the limiting cases being damage created far below the surface with little or no impact on the surface itself, and extensive direct surface damage on the timescale of a few picoseconds. In some instances, formation of large <100> vacancy loops beneath the free surface was observed, which may explain some earlier experimental observations.« less

Influence of an external electric field on the potential-energy surface of alkali-metal-decorated C60

NASA Astrophysics Data System (ADS)

De, Deb Sankar; Saha, Santanu; Genovese, Luigi; Goedecker, Stefan

2018-06-01

We present a fully ab initio, unbiased structure search of the configurational space of decorated C60 fullerenes in the presence of an electric field. We observed that the potential-energy surface is significantly perturbed by an external electric field and that the energetic ordering of low-energy isomers differs with and without electric field. We identify the energetically lowest configuration for a varying number of decorating atoms (1 ≤n ≤12 ) for Li and (1 ≤n ≤6 ) for K on the C60 surface at different electric-field strengths. Using the correct geometric ground state in the electric field for the calculation of the dipole we obtain better agreement with the experimentally measured values than previous calculations based on the ground state in absence of an electric field. Since the lowest-energy structures are typically nearly degenerate in energy, a combination of different structures is expected to be found at room temperature. The experimentally measured dipole is therefore also expected to contain significant contributions from several low-energy structures.

Nonlinear simulation of the fishbone instability

NASA Astrophysics Data System (ADS)

Idouakass, Malik; Faganello, Matteo; Berk, Herbert; Garbet, Xavier; Benkadda, Sadruddin; PIIM Team; IFS Team; IRFM Team

2014-10-01

We propose to extend the Odblom-Breizman precessional fishbone model to account for both the MagnetoHydroDynamic (MHD) nonlinearity at the q = 1 surface and the nonlinear response of the energetic particles contained within the q = 1 surface. This electromagnetic mode, whose excitation, damping and frequency chirping are determined by the self-consistent interaction between an energetic trapped particle population and the bulk plasma evolution, can induce effective transport and losses for the energetic particles, being them alpha-particles in next-future fusion devices or heated particles in present Tokamaks. The model is reduced to its simplest form, assuming a reduced MHD description for the bulk plasma and a two-dimensional phase-space evolution (gyro and bounce averaged) for deeply trapped energetic particles. Numerical simulations have been performed in order to characterize the mode chirping and saturation, in particular looking at the interplay between the development of phase-space structures and the system dissipation associated to the MHD non-linearities at the resonance locations.

The effect of the averaged structural and energetic features on the cohesive energy of nanocrystals

NASA Astrophysics Data System (ADS)

Ali Safaei

2010-03-01

The size dependency of the cohesive energy of nanocrystals is obtained in terms of their averaged structural and energetic properties, which are in direct proportion with their cohesive energies. The significance of the effect of the geometrical shape of nanoparticles on their thermal stability has been discussed. The model has been found to have good prediction for the case of Cu and Al nanoparticles, with sizes in the ranges of 1-22 nm and 2-22 nm, respectively. Defining a new parameter, named as the surface-to-volume energy-contribution ratio, the relative thermal stabilities of different nanoclusters and their different surface-crystalline faces are discussed and compared to the molecular dynamic (MD) simulation results of copper nanoclusters. Finally, based on the size dependency of the cohesive energy, a formula for the size-dependent diffusion coefficient has been presented which includes the structural and energetic effects. Using this formula, the faster-than-expected interdiffusion/alloying of Au(core)-Ag(shell) nanoparticles with the core-shell structure, the Au-core diameter of 20 nm and the Ag-shell thickness of 2.91 nm, has been discussed and the calculated diffusion coefficient has been found to be consistent with its corresponding experimental value.

Complementarity of stability patches at the interfaces of protein complexes: Implication for the structural organization of energetic hot spots.

PubMed

Kuttner, Yosef Y; Engel, Stanislav

2018-02-01

A rational design of protein complexes with defined functionalities and of drugs aimed at disrupting protein-protein interactions requires fundamental understanding of the mechanisms underlying the formation of specific protein complexes. Efforts to develop efficient small-molecule or protein-based binders often exploit energetic hot spots on protein surfaces, namely, the interfacial residues that provide most of the binding free energy in the complex. The molecular basis underlying the unusually high energy contribution of the hot spots remains obscure, and its elucidation would facilitate the design of interface-targeted drugs. To study the nature of the energetic hot spots, we analyzed the backbone dynamic properties of contact surfaces in several protein complexes. We demonstrate that, in most complexes, the backbone dynamic landscapes of interacting surfaces form complementary "stability patches," in which static areas from the opposing surfaces superimpose, and that these areas are predominantly located near the geometric center of the interface. We propose that a diminished enthalpy-entropy compensation effect augments the degree to which residues positioned within the complementary stability patches contribute to complex affinity, thereby giving rise to the energetic hot spots. These findings offer new insights into the nature of energetic hot spots and the role that backbone dynamics play in facilitating intermolecular recognition. Mapping the interfacial stability patches may provide guidance for protein engineering approaches aimed at improving the stability of protein complexes and could facilitate the design of ligands that target complex interfaces. © 2017 Wiley Periodicals, Inc.

A periodic mixed gaussians-plane waves DFT study on simple thiols on Au(111): adsorbate species, surface reconstruction, and thiols functionalization.

PubMed

Rajaraman, Gopalan; Caneschi, Andrea; Gatteschi, Dante; Totti, Federico

2011-03-07

Here we present DFT calculations based on a periodic mixed gaussians/plane waves approach to study the energetics, structure, bonding of SAMs of simple thiols on Au(111). Several open issues such as structure, bonding and the nature of adsorbate are taken into account. We started with methyl thiols (MeSH) on Au(111) to establish the nature of the adsorbate. We have considered several structural models embracing the reconstructed surface scenario along with the MeS˙-Au(ad)-MeS˙ type motif put forward in recent years. Our calculations suggest a clear preference for the homolytic cleavage of the S-H bond leading to a stable MeS˙ on a gold surface. In agreement with the recent literature studies, the reconstructed models of the MeS˙ species are found to be energetically preferred over unreconstructed models. Besides, our calculations reveal that the model with 1:2 Au(ad)/thiols ratio, i.e. MeS˙-Au(ad)-MeS˙, is energetically preferred compared to the clean and 1:1 ratio models, in agreement with the experimental and theoretical evidences. We have also performed Molecular Orbital/Natural Bond Orbital, MO/NBO, analysis to understand the electronic structure and bonding in different structural motifs and many useful insights have been gained. Finally, the studies have then been extended to alkyl thiols of the RSR' (R, R' = Me, Et and Ph) type and here our calculations again reveal a preference for the RS˙ type species adsorption for clean as well as for reconstructed 1:2 Au(ad)/thiols ratio models.

First-principles study of water desorption from montmorillonite surface.

PubMed

Zhang, Yao; Meng, Yingfeng; Liu, Houbin; Yang, Mingli

2016-05-01

Knowledge about water desorption is important to give a full picture of water diffusion in montmorillonites (MMT), which is a driving factor in MMT swelling. The desorption paths and energetics of water molecules from the surface of MMT with trapped Li(+), Na(+) or K(+) counterions were studied using periodic density functional theory calculations. Two paths--surface and vacuum desorption--were designed for water desorption starting from a stationary structure in which water bonds with both the counterion and the MMT surface. Surface desorption is energetically more favorable than vacuum desorption due to water-surface hydrogen bonds that help stabilize the intermediate structure of water released from the counterion. The energy barriers of water desorption are in the order of Li(+) > Na(+) > K(+), which can be attributed to the short ionic radius of Li(+), which favors strong binding with the water molecule. The temperature dependence of water adsorption and desorption rates were compared based on the computed activation energies. Our calculations reveal that the water desorption on the MMT surface has a different mechanism from water adsorption, which results from surface effects favoring stabilization of water conformers during the desorption process.

The role of titanium nitride supports for single-atom platinum-based catalysts in fuel cell technology.

PubMed

Zhang, Ren-Qin; Lee, Tae-Hun; Yu, Byung-Deok; Stampfl, Catherine; Soon, Aloysius

2012-12-28

As a first step towards a microscopic understanding of single-Pt atom-dispersed catalysts on non-conventional TiN supports, we present density-functional theory (DFT) calculations to investigate the adsorption properties of Pt atoms on the pristine TiN(100) surface, as well as the dominant influence of surface defects on the thermodynamic stability of platinized TiN. Optimized atomic geometries, energetics, and analysis of the electronic structure of the Pt/TiN system are reported for various surface coverages of Pt. We find that atomic Pt does not bind preferably to the clean TiN surface, but under typical PEM fuel cell operating conditions, i.e. strongly oxidizing conditions, TiN surface vacancies play a crucial role in anchoring the Pt atom for its catalytic function. Whilst considering the energetic stability of the Pt/TiN structures under varying N conditions, embedding Pt at the surface N-vacancy site is found to be the most favorable under N-lean conditions. Thus, the system of embedding Pt at the surface N-vacancy sites on TiN(100) surfaces could be promising catalysts for PEM fuel cells.

Density functional theory study of defect energies and space charge distribution at a solid-oxide electrolyte surface

NASA Astrophysics Data System (ADS)

Han, Chu; Bongiorno, Angelo

2014-03-01

Yttrium-doped barium zirconate (BZY) is a proton conducting electrolyte forming a class of novel materials for new generation of solid oxide fuel cells, for hydrogen separation and purification, and for electrolysis of water. Here we use density functional theory calculations to compute the energy of protons and oxygen vacancies at the surface and in the bulk of lightly Y-doped BZY materials. We found that protons are energetically more stable at the surface termination than in the bulk of BZY by about 1 eV. In contrast, doubly-positively charged oxygen vacancies are found to form iso-energetic defects at both the terminal surface layer and in the bulk of BZY, while in the sub-surface region the defect energy raises by about 1 eV with respect to the value in the bulk. The energetic behavior of protons and oxygen vacancies in the near surface region of BZY is attributed to the competition of strain and electrostatic effects. Lattice model representations of BZY surfaces are then used in combination with Monte Carlo simulations to solve the Poisson-Boltzmann equation and investigate the implication of the results above on the structure of the space charge region at the surface of BZY materials.

Energetic and entropic components of the Tolman length for mW and TIP4P/2005 water nanodroplets

NASA Astrophysics Data System (ADS)

Joswiak, Mark N.; Do, Ryan; Doherty, Michael F.; Peters, Baron

2016-11-01

The surface free energy of a droplet is approximately γ ( R ) = γ ( ∞ ) ( 1 - 2 δ / R ) , with R being the droplet radius and δ being the Tolman length. Here we use the mitosis method to compute δ = - 0.56 ± 0.1 Å at 300 K for mW water, indicating that γ ( R ) increases as the droplet size decreases. The computed Tolman length agrees quite well with a previous study of TIP4P/2005 water. We also decompose the size-dependent surface free energy into energetic and entropic contributions for the mW and TIP4P/2005 force fields. Despite having similar Tolman lengths, the energy-entropy decompositions are very different for the two force fields. We discuss critical assumptions which lead to these findings and their relation to experiments on the nucleation of water droplets. We also discuss surface broken bonds and structural correlations as possible explanations for the energetic and entropic contributions.

H2O incorporation in the phosphorene/a-SiO2 interface: a first-principles study

NASA Astrophysics Data System (ADS)

Scopel, Wanderlã L.; Souza, Everson S.; Miwa, R. H.

2017-02-01

Based on first-principles calculations, we investigate (i) the energetic stability and electronic properties of single-layer phosphorene (SLP) adsorbed on an amorphous SiO2 surface (SLP/a-SiO2), and (ii) the further incorporation of water molecules at the phosphorene/a-SiO2 interface. In (i), we find that the phosphorene sheet binds to a-SiO2 through van der Waals interactions, even in the presence of oxygen vacancies on the surface. The SLP/a-SiO2 system presents a type-I band alignment, with the valence (conduction) band maximum (minimum) of the phosphorene lying within the energy gap of the a-SiO2 substrate. The structure and the surface-potential corrugations promote the formation of electron-rich and electron-poor regions on the phosphorene sheet and at the SLP/a-SiO2 interface. Such charge density puddles are strengthened by the presence of oxygen vacancies in a-SiO2. In (ii), because of the amorphous structure of the surface, we consider a number of plausible geometries for H2O embedded in the SLP/a-SiO2 interface. There is an energetic preference for the formation of hydroxyl (OH) groups on the a-SiO2 surface. Meanwhile, in the presence of oxygenated water or interstitial oxygen in the phosphorene sheet, we observe the formation of metastable OH bonded to the phosphorene, and the formation of energetically stable P-O-Si chemical bonds at the SLP/a-SiO2 interface. Further x-ray absorption spectra simulations are performed, which aim to provide additional structural/electronic information on the oxygen atoms forming hydroxyl groups or P-O-Si chemical bonds at the interface region.

H2O incorporation in the phosphorene/a-SiO2 interface: a first-principles study.

PubMed

Scopel, Wanderlã L; Souza, Everson S; Miwa, R H

2017-02-22

Based on first-principles calculations, we investigate (i) the energetic stability and electronic properties of single-layer phosphorene (SLP) adsorbed on an amorphous SiO 2 surface (SLP/a-SiO 2 ), and (ii) the further incorporation of water molecules at the phosphorene/a-SiO 2 interface. In (i), we find that the phosphorene sheet binds to a-SiO 2 through van der Waals interactions, even in the presence of oxygen vacancies on the surface. The SLP/a-SiO 2 system presents a type-I band alignment, with the valence (conduction) band maximum (minimum) of the phosphorene lying within the energy gap of the a-SiO 2 substrate. The structure and the surface-potential corrugations promote the formation of electron-rich and electron-poor regions on the phosphorene sheet and at the SLP/a-SiO 2 interface. Such charge density puddles are strengthened by the presence of oxygen vacancies in a-SiO 2 . In (ii), because of the amorphous structure of the surface, we consider a number of plausible geometries for H 2 O embedded in the SLP/a-SiO 2 interface. There is an energetic preference for the formation of hydroxyl (OH) groups on the a-SiO 2 surface. Meanwhile, in the presence of oxygenated water or interstitial oxygen in the phosphorene sheet, we observe the formation of metastable OH bonded to the phosphorene, and the formation of energetically stable P-O-Si chemical bonds at the SLP/a-SiO 2 interface. Further x-ray absorption spectra simulations are performed, which aim to provide additional structural/electronic information on the oxygen atoms forming hydroxyl groups or P-O-Si chemical bonds at the interface region.

Manganese molybdate nanoflakes on silicon microchannel plates as novel nano energetic material

PubMed Central

Zhang, Chi; Wu, Dajun; Shi, Liming; Zhu, Yiping; Xiong, Dayuan; Xu, Shaohui; Huang, Rong; Qi, Ruijuan; Zhang, Wenchao; Chu, Paul K.

2017-01-01

Nano energetic materials have attracted great attention recently owing to their potential applications for both civilian and military purposes. By introducing silicon microchannel plates (Si-MCPs) three-dimensional (3D)-ordered structures, monocrystalline MnMoO4 with a size of tens of micrometres and polycrystalline MnMoO4 nanoflakes are produced on the surface and sidewall of nickel-coated Si-MCP, respectively. The MnMoO4 crystals ripen controllably forming polycrystalline nanoflakes with lattice fringes of 0.542 nm corresponding to the (1¯11) plane on the sidewall. And these MnMoO4 nanoflakes show apparent thermite performance which is rarely reported and represents MnMoO4 becoming a new category of energetic materials after nanocrystallization. Additionally, the nanocrystallization mechanism is interpreted by ionic diffusion caused by 3D structure. The results indicate that the Si-MCP is a promising substrate for nanocrystallization of energetic materials such as MnMoO4. PMID:29308255

Manganese molybdate nanoflakes on silicon microchannel plates as novel nano energetic material.

PubMed

Zhang, Chi; Wu, Dajun; Shi, Liming; Zhu, Yiping; Xiong, Dayuan; Xu, Shaohui; Huang, Rong; Qi, Ruijuan; Zhang, Wenchao; Wang, Lianwei; Chu, Paul K

2017-12-01

Nano energetic materials have attracted great attention recently owing to their potential applications for both civilian and military purposes. By introducing silicon microchannel plates (Si-MCPs) three-dimensional (3D)-ordered structures, monocrystalline MnMoO 4 with a size of tens of micrometres and polycrystalline MnMoO 4 nanoflakes are produced on the surface and sidewall of nickel-coated Si-MCP, respectively. The MnMoO 4 crystals ripen controllably forming polycrystalline nanoflakes with lattice fringes of 0.542 nm corresponding to the [Formula: see text] plane on the sidewall. And these MnMoO 4 nanoflakes show apparent thermite performance which is rarely reported and represents MnMoO 4 becoming a new category of energetic materials after nanocrystallization. Additionally, the nanocrystallization mechanism is interpreted by ionic diffusion caused by 3D structure. The results indicate that the Si-MCP is a promising substrate for nanocrystallization of energetic materials such as MnMoO 4 .

Exploring the Structure of Nitrogen-Rich Ionic Liquids and Their Binding to the Surface of Oxide-Free Boron Nanoparticles

DTIC Science & Technology

2013-01-29

Shreeve et al . synthesized a number of highly energetic ionic liquids with multiple nitrogen atoms in their structures,18−23 in the hope of increasing...results have to be interpreted with caution. Lovelock et al .61 have shown that clean surfaces can be obtained by sputtering for the [CnC1Im][Tf2N] IL...flat on the gold surface while a long chain ether functional group is directed away from the surface, providing steric stabilization.74 Zhang et al

Self-organized microstructures induced by MeV ion beam on silicon surface

NASA Astrophysics Data System (ADS)

Ahmad, Muthanna

2017-02-01

Micro patterning of self organized structure on silicon surface is induced by ion implantation of energetic (MeV) copper ions. This work reports for the first time the ability of using energetic ions for producing highly ordered ripples and dots of micro sizes. The experiments are realized at the Tandem ion beam accelerator (3 MV) at the IBA laboratory of the Atomic Energy Commission of Syria. Similarly to nano patterning formed by slow ions, the formation of micro patterned structures dots and ripples is observed to be depending on the angle of ion beam incidence, energy and ion fluence. The observation of such microstructures formation is limited to a range of ion energies (few MeV) at fluence higher than 1.75 × 1017 ion cm-2. The patterned surface layer is completely amorphousized by the ion implantation. Shadowing effect is observed in the formation of microripples and superstructures in the top of ripples. The superstructure develops new morphology that is not observed before. This morphology has butterfly shape with symmetry in its structure.

The variability, structure and energy conversion of the northern hemisphere traveling waves simulated in a Mars general circulation model

NASA Astrophysics Data System (ADS)

Wang, Huiqun; Toigo, Anthony D.

2016-06-01

Investigations of the variability, structure and energetics of the m = 1-3 traveling waves in the northern hemisphere of Mars are conducted with the MarsWRF general circulation model. Using a simple, annually repeatable dust scenario, the model reproduces many general characteristics of the observed traveling waves. The simulated m = 1 and m = 3 traveling waves show large differences in terms of their structures and energetics. For each representative wave mode, the geopotential signature maximizes at a higher altitude than the temperature signature, and the wave energetics suggests a mixed baroclinic-barotropic nature. There is a large contrast in wave energetics between the near-surface and higher altitudes, as well as between the lower latitudes and higher latitudes at high altitudes. Both barotropic and baroclinic conversions can act as either sources or sinks of eddy kinetic energy. Band-pass filtered transient eddies exhibit strong zonal variations in eddy kinetic energy and various energy transfer terms. Transient eddies are mainly interacting with the time mean flow. However, there appear to be non-negligible wave-wave interactions associated with wave mode transitions. These interactions include those between traveling waves and thermal tides and those among traveling waves.

Adsorption of benzene on low index surfaces of platinum in the presence of van der Waals interactions

NASA Astrophysics Data System (ADS)

K, Ayishabi P.; Chatanathodi, Raghu

2017-10-01

We have studied the adsorption of benzene on three low index surfaces of platinum using plane-wave Density Functional Theory (DFT) calculations, taking into consideration van der Waals (vdW) interaction. Experimentally, it is known that benzene adsorbs at the bridge site on the (111) surface, but in case of (110) and (100), this is not known yet. Our calculations show that benzene preferably adsorbs on bridge position on Pt(111) surface, whereas on Pt(110) and Pt(100) surfaces, the hollow position is energetically more favoured. The structural and electronic modifications of molecule and the surfaces are also examined. In all cases, adsorption-induced distortions of adsorbate-substrate complex are found to be modest in character, but relatively maximum in case of the (110) facet. The molecule is bound most strongly to the (110) surface. Importantly, we find that adsorption at bridge and atop positions are energetically feasible on the (110) surface, with the canting of benzene ring at a small angle from the metal plane. We study changes in electronic structure and the net charge transfer upon adsorption of benzene on all three low index planes. Inclusion of vdW interactions is important for obtaining realistic adsorption strengths for benzene on various Pt facets.

Simulation of Nanowires on Metal Vicinal Surfaces: Effect of Growth Parameters and Energetic Barriers

NASA Astrophysics Data System (ADS)

Hamouda, Ajmi B. H.; Blel, Sonia; Einstein, T. L.

2012-02-01

Growing one-dimensional metal structures is an important task in the investigation of the electronic and magnetic properties of new devices. We used kinetic Monte-Carlo (kMC) method to simulate the formation of nanowires of several metallic and non-metallic adatoms on Cu and Pt vicinal surfaces. We found that mono-atomic chains form on step-edges due to energetic barriers (the so-called Ehrlich-shwoebel and exchange barriers) on step-edge. Creation of perfect wires is found to depend on growth parameters and binding energies. We measure the filling ratio of nanowires for different chemical species in a wide range of temperature and flux. Perfect wires were obtained at lower deposition rate for all tested adatoms, however we notice different temperature ranges. Our results were compared with experimental ones [Gambardella et al., Surf. Sci.449, 93-103 (2000), PRB 61, 2254-2262, (2000)]. We review the role of impurities in nanostructuring of surfaces [Hamouda et al., Phys. Rev. B 83, 035423, (2011)] and discuss the effect of their energetic barriers on the obtained quality of nanowires. Our work provides experimentalists with optimum growth parameters for the creation of a uniform distribution of wires on surfaces.

Surface energetics and protein-protein interactions: analysis and mechanistic implications

PubMed Central

Peri, Claudio; Morra, Giulia; Colombo, Giorgio

2016-01-01

Understanding protein-protein interactions (PPI) at the molecular level is a fundamental task in the design of new drugs, the prediction of protein function and the clarification of the mechanisms of (dis)regulation of biochemical pathways. In this study, we use a novel computational approach to investigate the energetics of aminoacid networks located on the surface of proteins, isolated and in complex with their respective partners. Interestingly, the analysis of individual proteins identifies patches of surface residues that, when mapped on the structure of their respective complexes, reveal regions of residue-pair couplings that extend across the binding interfaces, forming continuous motifs. An enhanced effect is visible across the proteins of the dataset forming larger quaternary assemblies. The method indicates the presence of energetic signatures in the isolated proteins that are retained in the bound form, which we hypothesize to determine binding orientation upon complex formation. We propose our method, BLUEPRINT, as a complement to different approaches ranging from the ab-initio characterization of PPIs, to protein-protein docking algorithms, for the physico-chemical and functional investigation of protein-protein interactions. PMID:27050828

Method and Apparatus for Creating a Topography at a Surface

DOEpatents

Adams, David P.; Sinclair, Michael B.; Mayer, Thomas M.; Vasile, Michael J.; Sweatt, William C.

2008-11-11

Methods and apparatus whereby an optical interferometer is utilized to monitor and provide feedback control to an integrated energetic particle column, to create desired topographies, including the depth, shape and/or roughness of features, at a surface of a specimen. Energetic particle columns can direct energetic species including, ions, photons and/or neutral particles to a surface to create features having in-plane dimensions on the order of 1 micron, and a height or depth on the order of 1 nanometer. Energetic processes can include subtractive processes such as sputtering, ablation, focused ion beam milling and, additive processes, such as energetic beam induced chemical vapor deposition. The integration of interferometric methods with processing by energetic species offers the ability to create desired topographies at surfaces, including planar and curved shapes.

Self-assembled ultrathin nanotubes on diamond (100) surface

NASA Astrophysics Data System (ADS)

Lu, Shaohua; Wang, Yanchao; Liu, Hanyu; Miao, Mao-Sheng; Ma, Yanming

2014-04-01

Surfaces of semiconductors are crucially important for electronics, especially when the devices are reduced to the nanoscale. However, surface structures are often elusive, impeding greatly the engineering of devices. Here we develop an efficient method that can automatically explore the surface structures using structure swarm intelligence. Its application to a simple diamond (100) surface reveals an unexpected surface reconstruction featuring self-assembled carbon nanotubes arrays. Such a surface is energetically competitive with the known dimer structure under normal conditions, but it becomes more favourable under a small compressive strain or at high temperatures. The intriguing covalent bonding between neighbouring tubes creates a unique feature of carrier kinetics (that is, one dimensionality of hole states, while two dimensionality of electron states) that could lead to novel design of superior electronics. Our findings highlight that the surface plays vital roles in the fabrication of nanodevices by being a functional part of them.

Bulk and surface properties of liquid Al-Cr and Cr-Ni alloys.

PubMed

Novakovic, R

2011-06-15

The energetics of mixing and structural arrangement in liquid Al-Cr and Cr-Ni alloys has been analysed through the study of surface properties (surface tension and surface segregation), dynamic properties (chemical diffusion) and microscopic functions (concentration fluctuations in the long-wavelength limit and chemical short-range order parameter) in the framework of statistical mechanical theory in conjunction with quasi-lattice theory. The Al-Cr phase diagram exhibits the existence of different intermetallic compounds in the solid state, while that of Cr-Ni is a simple eutectic-type phase diagram at high temperatures and includes the low-temperature peritectoid reaction in the range near a CrNi(2) composition. Accordingly, the mixing behaviour in Al-Cr and Cr-Ni alloy melts was studied using the complex formation model in the weak interaction approximation and by postulating Al(8)Cr(5) and CrNi(2) chemical complexes, respectively, as energetically favoured.

Controlled nanopatterning & modifications of materials by energetic ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sinha, O. P.

Compound semiconductors (InP, InAs and GaSb) has been exposed to energetic 3 keV Ar{sup +} ions for a varying fluence range of 10{sup 13} ions/cm{sup 2} to 10{sup 18} ions/cm{sup 2} at room temperature. Morphological modifications of the irradiated surfaces have been investigated by Scanning Tunneling Microscopy (STM) in UHV conditions. It is observed that InP and GaSb have fluence dependent nanopattering e.g. nanoneedle, aligned nanodots, superimposed nanodots ripple like structures while InAs has little fluence dependent behaviour indicating materials dependent growth of features on irradiated surfaces. Moreover, surface roughness and wavelength of the features are also depending on themore » materials and fluences. The RMS surface roughness has been found to be increased rapidly in the early stage of irradiation followed by slower escalate rate and later tends to saturate indicating influence of the nonlinear processes.« less

Probing the energetics of organic–nanoparticle interactions of ethanol on calcite

PubMed Central

Wu, Di; Navrotsky, Alexandra

2015-01-01

Knowing the nature of interactions between small organic molecules and surfaces of nanoparticles (NP) is crucial for fundamental understanding of natural phenomena and engineering processes. Herein, we report direct adsorption enthalpy measurement of ethanol on a series of calcite nanocrystals, with the aim of mimicking organic–NP interactions in various environments. The energetics suggests a spectrum of adsorption events as a function of coverage: strongest initial chemisorption on active sites on fresh calcite surfaces, followed by major chemical binding to form an ethanol monolayer and, subsequently, very weak, near-zero energy, physisorption. These thermochemical observations directly support a structure where the ethanol monolayer is bonded to the calcite surface through its polar hydroxyl group, leaving the hydrophobic ends of the ethanol molecules to interact only weakly with the next layer of adsorbing ethanol and resulting in a spatial gap with low ethanol density between the monolayer and subsequent added ethanol molecules, as predicted by molecular dynamics and density functional calculations. Such an ordered assembly of ethanol on calcite NP is analogous to, although less strongly bonded than, a capping layer of organics intentionally introduced during NP synthesis, and suggests a continuous variation of surface structure depending on molecular chemistry, ranging from largely disordered surface layers to ordered layers that nevertheless are mobile and can rearrange or be displaced by other molecules to strongly bonded immobile organic capping layers. These differences in surface structure will affect chemical reactions, including the further nucleation and growth of nanocrystals on organic ligand-capped surfaces. PMID:25870281

Multiscale study of metal nanoparticles

NASA Astrophysics Data System (ADS)

Lee, Byeongchan

Extremely small structures with reduced dimensionality have emerged as a scientific motif for their interesting properties. In particular, metal nanoparticles have been identified as a fundamental material in many catalytic activities; as a consequence, a better understanding of structure-function relationship of nanoparticles has become crucial. The functional analysis of nanoparticles, reactivity for example, requires an accurate method at the electronic structure level, whereas the structural analysis to find energetically stable local minima is beyond the scope of quantum mechanical methods as the computational cost becomes prohibitingly high. The challenge is that the inherent length scale and accuracy associated with any single method hardly covers the broad scale range spanned by both structural and functional analyses. In order to address this, and effectively explore the energetics and reactivity of metal nanoparticles, a hierarchical multiscale modeling is developed, where methodologies of different length scales, i.e. first principles density functional theory, atomistic calculations, and continuum modeling, are utilized in a sequential fashion. This work has focused on identifying the essential information that bridges two different methods so that a successive use of different methods is seamless. The bond characteristics of low coordination systems have been obtained with first principles calculations, and incorporated into the atomistic simulation. This also rectifies the deficiency of conventional interatomic potentials fitted to bulk properties, and improves the accuracy of atomistic calculations for nanoparticles. For the systematic shape selection of nanoparticles, we have improved the Wulff-type construction using a semi-continuum approach, in which atomistic surface energetics and crystallinity of materials are added on to the continuum framework. The developed multiscale modeling scheme is applied to the rational design of platinum nanoparticles in the range of 2.4 nm to 3.1 nm: energetically favorable structures have been determined in terms of semi-continuum binding energy, and the reactivity of the selected nanoparticle has been investigated based on local density of states from first principles calculations. The calculation suggests that the reactivity landscape of particles is more complex than the simple reactivity of clean surfaces, and the reactivity towards a particular reactant can be predicted for a given structure.

Space Weathering Investigations Enabled by NASA's Virtual Heliophysical Observatories

NASA Technical Reports Server (NTRS)

Cooper, John F.; King, Joseph H.; Papitashvili, Natalia E.; Lal, Nand; Sittler, Edward C.; Sturner, Steven J.; Hills, Howard K.; Lipatov, Alexander S.; Kovalick, Tamara J.; Johnson, Rita C.;

Photonic guiding structures in lithium niobate crystals produced by energetic ion beams

NASA Astrophysics Data System (ADS)

Chen, Feng

2009-10-01

A range of ion beam techniques have been used to fabricate a variety of photonic guiding structures in the well-known lithium niobate (LiNbO3 or LN) crystals that are of great importance in integrated photonics/optics. This paper reviews the up-to-date research progress of ion-beam-processed LiNbO3 photonic structures and reports on their fabrication, characterization, and applications. Ion beams are being used with this material in a wide range of techniques, as exemplified by the following examples. Ion beam milling/etching can remove the selected surface regions of LiNbO3 crystals via the sputtering effects. Ion implantation and swift ion irradiation can form optical waveguide structures by modifying the surface refractive indices of the LiNbO3 wafers. Crystal ion slicing has been used to obtain bulk-quality LiNbO3 single-crystalline thin films or membranes by exfoliating the implanted layer from the original substrate. Focused ion beams can either generate small structures of micron or submicron dimensions, to realize photonic bandgap crystals in LiNbO3, or directly write surface waveguides or other guiding devices in the crystal. Ion beam-enhanced etching has been extensively applied for micro- or nanostructuring of LiNbO3 surfaces. Methods developed to fabricate a range of photonic guiding structures in LiNbO3 are introduced. Modifications of LiNbO3 through the use of various energetic ion beams, including changes in refractive index and properties related to the photonic guiding structures as well as to the materials (i.e., electro-optic, nonlinear optic, luminescent, and photorefractive features), are overviewed in detail. The application of these LiNbO3 photonic guiding structures in both micro- and nanophotonics are briefly summarized.

Adsorption of metal-phthalocyanine molecules onto the Si(111) surface passivated by δ doping: Ab initio calculations

NASA Astrophysics Data System (ADS)

Veiga, R. G. A.; Miwa, R. H.; McLean, A. B.

2016-03-01

We report first-principles calculations of the energetic stability and electronic properties of metal-phthalocyanine (MPc) molecules (M = Cr, Mn, Fe, Co, Ni, Cu, and Zn) adsorbed on the δ -doped Si(111)-B (√{3 }×√{3 }) reconstructed surface. (i) It can be seen that CrPc, MnPc, FePc, and CoPc are chemically anchored to the topmost Si atom. (ii) Contrastingly, the binding of the NiPc, CuPc, and ZnPc molecules to the Si (111 ) -B (√{3 }×√{3 }) surface is exclusively ruled by van der Waals interactions, the main implication being that these molecules may diffuse and rearrange to form clusters and/or self-organized structures on this surface. The electronic structure calculations reveal that in point (i), owing to the formation of the metal-Si covalent bond, the net magnetic moment of the molecule is quenched by 1 μB , remaining unchanged in point (ii). In particular, the magnetic moment of CuPc (1 μB ) is preserved after adsorption. Finally, we verify that the formation of ZnPc, CuPc, and NiPc molecular (self-assembled) arrangements on the Si(111)-B (√{3 }×√{3 } ) surface is energetically favorable, in good agreement with recent experimental findings.

Structure and energetics of high index Fe, Al, Cu and Ni surfaces using equivalent crystal theory

NASA Technical Reports Server (NTRS)

Rodriguez, Agustin M.; Bozzolo, Guillermo; Ferrante, John

1993-01-01

Equivalent crystal theory (ECT) is applied to the study of multilayer relaxations and surface energies of high-index faces of Fe, Al, Ni, and Cu. Changes in interplanar spacing as well as registry of planes close to the surface and the ensuing surface energies changes are discussed in reference to available experimental data and other theoretical calculations. Since ECT is a semiempirical method, the dependence of the results on the variation of the input used was investigated.

Spin-polarized surface resonances accompanying topological surface state formation

PubMed Central

Jozwiak, Chris; Sobota, Jonathan A.; Gotlieb, Kenneth; Kemper, Alexander F.; Rotundu, Costel R.; Birgeneau, Robert J.; Hussain, Zahid; Lee, Dung-Hai; Shen, Zhi-Xun; Lanzara, Alessandra

2016-01-01

Topological insulators host spin-polarized surface states born out of the energetic inversion of bulk bands driven by the spin-orbit interaction. Here we discover previously unidentified consequences of band-inversion on the surface electronic structure of the topological insulator Bi2Se3. By performing simultaneous spin, time, and angle-resolved photoemission spectroscopy, we map the spin-polarized unoccupied electronic structure and identify a surface resonance which is distinct from the topological surface state, yet shares a similar spin-orbital texture with opposite orientation. Its momentum dependence and spin texture imply an intimate connection with the topological surface state. Calculations show these two distinct states can emerge from trivial Rashba-like states that change topology through the spin-orbit-induced band inversion. This work thus provides a compelling view of the coevolution of surface states through a topological phase transition, enabled by the unique capability of directly measuring the spin-polarized unoccupied band structure. PMID:27739428

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruzic, David

The Thermoelectric-Driven Liquid-Metal Plasma-Facing Structures (TELS) project was able to establish the experimental conditions necessary for flowing liquid metal surfaces in order to be utilized as surfaces facing fusion relevant energetic plasma flux. The work has also addressed additional developments along with progressing along the timeline detailed in the proposal. A no-cost extension was requested to conduct other relevant experiment- specifically regarding the characterization droplet ejection during energetic plasma flux impact. A specially designed trench module, which could accommodate trenches with different aspect ratios was fabricated and installed in the TELS setup and plasma gun experiments were performed. Droplet ejectionmore » was characterized using high speed image acquisition and also surface mounted probes were used to characterize the plasma. The Gantt chart below had been provided with the original proposal, indicating the tasks to be performed in the third year of funding. These tasks are listed above in the progress report outline, and their progress status is detailed below.« less

Monthly mean forecast experiments with the GISS model

NASA Technical Reports Server (NTRS)

Spar, J.; Atlas, R. M.; Kuo, E.

1976-01-01

The GISS general circulation model was used to compute global monthly mean forecasts for January 1973, 1974, and 1975 from initial conditions on the first day of each month and constant sea surface temperatures. Forecasts were evaluated in terms of global and hemispheric energetics, zonally averaged meridional and vertical profiles, forecast error statistics, and monthly mean synoptic fields. Although it generated a realistic mean meridional structure, the model did not adequately reproduce the observed interannual variations in the large scale monthly mean energetics and zonally averaged circulation. The monthly mean sea level pressure field was not predicted satisfactorily, but annual changes in the Icelandic low were simulated. The impact of temporal sea surface temperature variations on the forecasts was investigated by comparing two parallel forecasts for January 1974, one using climatological ocean temperatures and the other observed daily ocean temperatures. The use of daily updated sea surface temperatures produced no discernible beneficial effect.

Theoretical Study of Tautomerization Reactions for the Ground and First Excited Electronic States of Adenine

NASA Technical Reports Server (NTRS)

Salter, Latasha M.; Chaban, Galina M.; Kwak, Dochan (Technical Monitor)

2002-01-01

Geometrical structures and energetic properties for different tautomers of adenine are calculated in this study, using multi-configurational wave functions. Both the ground and the lowest singlet excited state potential energy surfaces are studied. Four tautomeric forms are considered, and their energetic order is found to be different on the ground and the excited state potential energy surfaces. Minimum energy reaction paths are obtained for hydrogen atom transfer (tautomerization) reactions in the ground and the lowest excited electronic states. It is found that the barrier heights and the shapes of the reaction paths are different for the ground and the excited electronic states, suggesting that the probability of such tautomerization reaction is higher on the excited state potential energy surface. This tautomerization process should become possible in the presence of water or other polar solvent molecules and should play an important role in the photochemistry of adenine.

CO adsorption on small Au{sub n} (n = 1–4) structures supported on hematite. I. Adsorption on iron terminated α-Fe{sub 2}O{sub 3} (0001) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pabisiak, Tomasz; Kiejna, Adam, E-mail: kiejna@ifd.uni.wroc.pl; Winiarski, Maciej J.

2016-01-28

This is the first of two papers dealing with the adsorption of Au and formation of Au{sub n} nanostructures (n = 1–4) on hematite (0001) surface and adsorption of CO thereon. The stoichiometric Fe-terminated (0001) surface of hematite was investigated using density functional theory in the generalized gradient approximation of Perdew-Burke-Ernzerhof (PBE) form with Hubbard correction U, accounting for strong electron correlations (PBE+U). The structural, energetic, and electronic properties of the systems studied were examined for vertical and flattened configurations of Au{sub n} nanostructures adsorbed on the hematite surfaces. The flattened ones, which can be viewed as bilayer-like structures, weremore » found energetically more favored than vertical ones. For both classes of structures the adsorption binding energy increases with the number of Au atoms in a structure. The adsorption of Au{sub n} induces charge rearrangement at the Au{sub n}/oxide contact which is reflected in work function changes. In most considered cases Au{sub n} adsorption increases the work function. A detailed analysis of the bonding electron charge is presented and the corresponding electron charge rearrangements at the contacts were quantified by a Bader charge analyses. The interaction of a CO molecule with the Au{sub n} nanostructures supported on α-Fe{sub 2}O{sub 3} (0001) and the oxide support was studied. It is found that the CO adsorption binding to the hematite supported Au{sub n} structures is more than twice as strong as to the bare hematite surface. Analysis of the Bader charges on the atoms showed that in each case CO binds to the most positively charged (cationic) atom of the Au{sub n} structure. Changes in the electronic structure of the Au{sub n} species and of the oxide support, and their consequences for the interactions with CO, are discussed.« less

Packing interface energetics in different crystal forms of the λ Cro dimer.

PubMed

Ahlstrom, Logan S; Miyashita, Osamu

2014-07-01

Variation among crystal structures of the λ Cro dimer highlights conformational flexibility. The structures range from a wild type closed to a mutant fully open conformation, but it is unclear if each represents a stable solution state or if one may be the result of crystal packing. Here we use molecular dynamics (MD) simulation to investigate the energetics of crystal packing interfaces and the influence of site-directed mutagenesis on them in order to examine the effect of crystal packing on wild type and mutant Cro dimer conformation. Replica exchange MD of mutant Cro in solution shows that the observed conformational differences between the wild type and mutant protein are not the direct consequence of mutation. Instead, simulation of Cro in different crystal environments reveals that mutation affects the stability of crystal forms. Molecular Mechanics Poisson-Boltzmann Surface Area binding energy calculations reveal the detailed energetics of packing interfaces. Packing interfaces can have diverse properties in strength, energetic components, and some are stronger than the biological dimer interface. Further analysis shows that mutation can strengthen packing interfaces by as much as ∼5 kcal/mol in either crystal environment. Thus, in the case of Cro, mutation provides an additional energetic contribution during crystal formation that may stabilize a fully open higher energy state. Moreover, the effect of mutation in the lattice can extend to packing interfaces not involving mutation sites. Our results provide insight into possible models for the effect of crystallization on Cro conformational dynamics and emphasize careful consideration of protein crystal structures. © 2013 Wiley Periodicals, Inc.

Packing Interface Energetics in Different Crystal Forms of the λ Cro Dimer

PubMed Central

Ahlstrom, Logan S.; Miyashita, Osamu

2014-01-01

Variation among crystal structures of the λ Cro dimer highlights conformational flexibility. The structures range from a wild type closed to a mutant fully open conformation, but it is unclear if each represents a stable solution state or if one may be the result of crystal packing. Here we use molecular dynamics (MD) simulation to investigate the energetics of crystal packing interfaces and the influence of site-directed mutagenesis on them, in order to examine the effect of crystal packing on wild type and mutant Cro dimer conformation. Replica exchange MD of mutant Cro in solution shows that the observed conformational differences between the wild type and mutant protein are not the direct consequence of mutation. Instead, simulation of Cro in different crystal environments reveals that mutation affects the stability of crystal forms. Molecular Mechanics Poisson-Boltzmann Surface Area binding energy calculations reveal the detailed energetics of packing interfaces. Packing interfaces can have diverse properties in strength, energetic components, and some are stronger than the biological dimer interface. Further analysis shows that mutation can strengthen packing interfaces by as much as ~5 kcal/mol in either crystal environment. Thus, in the case of Cro, mutation provides an additional energetic contribution during crystal formation that may stabilize a fully open higher energy state. Moreover, the effect of mutation in the lattice can extend to packing interfaces not involving mutation sites. Our results provide insight into possible models for the effect of crystallization on Cro conformational dynamics and emphasize careful consideration of protein crystal structures. PMID:24218107

Formic Acid Dissociative Adsorption on NiO(111): Energetics and Structure of Adsorbed Formate

DOE PAGES

Zhao, Wei; Doyle, Andrew D.; Morgan, Sawyer E.; ...

2017-11-21

Here, the dissociative adsorption of carboxylic acids on oxide surfaces is important for understanding adsorbed carboxylates, which are important as intermediates in catalytic reactions, for the organo-functionalization of oxide surfaces, and in many other aspects of oxide surface chemistry. We present here the first direct experimental measurement of the heat of dissociative adsorption of any carboxylic acid on any single-crystal oxide surface. The enthalpy of the dissociative adsorption of formic acid, the simplest carboxylic acid, to produce adsorbed formate and hydrogen (as a surface hydroxyl) on a (2 × 2)-NiO(111) surface is measured by single crystal adsorption calorimetry. The differentialmore » heat of adsorption decreases with formic acid coverage from 202 to 99 kJ/mol at saturation (0.25 ML). The structure of the adsorbed products is clarified by density functional theory (DFT) calculations, which provide energies in reasonable agreement with the calorimetry. These calculations show that formic acid readily dissociates on both the oxygen and Ni terminations of the octapolar NiO(111) surfaces, donating its acid H to a surface lattice oxygen, while HCOO adsorbs preferentially with bridging-type geometry near the M-O 3/O-M 3 sites. The calculated energetics at low coverages agrees well with experimental data, while larger differences are observed at high coverage (0.25 ML). The large decrease in experimental heat of adsorption with coverage can be brought into agreement with the DFT energies if we assume that both types of octapolar surface terminations (O- and Ni-) are present on the starting surface.« less

Formic Acid Dissociative Adsorption on NiO(111): Energetics and Structure of Adsorbed Formate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Wei; Doyle, Andrew D.; Morgan, Sawyer E.

Here, the dissociative adsorption of carboxylic acids on oxide surfaces is important for understanding adsorbed carboxylates, which are important as intermediates in catalytic reactions, for the organo-functionalization of oxide surfaces, and in many other aspects of oxide surface chemistry. We present here the first direct experimental measurement of the heat of dissociative adsorption of any carboxylic acid on any single-crystal oxide surface. The enthalpy of the dissociative adsorption of formic acid, the simplest carboxylic acid, to produce adsorbed formate and hydrogen (as a surface hydroxyl) on a (2 × 2)-NiO(111) surface is measured by single crystal adsorption calorimetry. The differentialmore » heat of adsorption decreases with formic acid coverage from 202 to 99 kJ/mol at saturation (0.25 ML). The structure of the adsorbed products is clarified by density functional theory (DFT) calculations, which provide energies in reasonable agreement with the calorimetry. These calculations show that formic acid readily dissociates on both the oxygen and Ni terminations of the octapolar NiO(111) surfaces, donating its acid H to a surface lattice oxygen, while HCOO adsorbs preferentially with bridging-type geometry near the M-O 3/O-M 3 sites. The calculated energetics at low coverages agrees well with experimental data, while larger differences are observed at high coverage (0.25 ML). The large decrease in experimental heat of adsorption with coverage can be brought into agreement with the DFT energies if we assume that both types of octapolar surface terminations (O- and Ni-) are present on the starting surface.« less

Water dissociative adsorption on NiO(111): Energetics and structure of the hydroxylated surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Wei; Bajdich, Michal; Carey, Spencer

The energetics of the reactions of water with metal oxide surfaces are of tremendous interest for catalysis, electrocatalysis, and geochemistry, yet the energy for the dissociative adsorption of water was only previously measured on one well-defined oxide surface, iron oxide. In the present paper, the enthalpy of the dissociative adsorption of water is measured on NiO(111)-2 × 2 at 300 K using single-crystal adsorption calorimetry. The differential heat of dissociative adsorption decreases with coverage from 170 to 117 kJ/mol in the first 0.25 ML of coverage. Water adsorbs molecularly on top of that, with a heat of ~92 kJ/mol. Densitymore » functional theory (DFT) calculations reproduce the measured energies well (all within 17 kJ/mol) and provide insight into the atomic-level structure of the surfaces studied experimentally. They show that the oxygen-terminated O-octo(2 × 2) structure is the most stable NiO(111)-2 × 2 termination and gives reaction energies with water that are more consistent with the calorimetry results than the metal-terminated surface. They show that water adsorbs dissociatively on this (2 × 2)-O-octo surface to produce a hydroxyl-covered surface with a heat of adsorption of 171 ± 5 kJ/mol in the low-coverage limit (very close to 170 kJ/mol experimentally) and an integral heat that decreases by 14 kJ/mol up to saturation (compared to ~30 kJ/mol experimentally). As a result, sensitivity of this reaction’s energy to choice of DFT method is tested using a variety of different exchange correlation functionals, including HSE06, and found to be quite weak.« less

Water dissociative adsorption on NiO(111): Energetics and structure of the hydroxylated surface

DOE PAGES

Zhao, Wei; Bajdich, Michal; Carey, Spencer; ...

2016-09-19

The energetics of the reactions of water with metal oxide surfaces are of tremendous interest for catalysis, electrocatalysis, and geochemistry, yet the energy for the dissociative adsorption of water was only previously measured on one well-defined oxide surface, iron oxide. In the present paper, the enthalpy of the dissociative adsorption of water is measured on NiO(111)-2 × 2 at 300 K using single-crystal adsorption calorimetry. The differential heat of dissociative adsorption decreases with coverage from 170 to 117 kJ/mol in the first 0.25 ML of coverage. Water adsorbs molecularly on top of that, with a heat of ~92 kJ/mol. Densitymore » functional theory (DFT) calculations reproduce the measured energies well (all within 17 kJ/mol) and provide insight into the atomic-level structure of the surfaces studied experimentally. They show that the oxygen-terminated O-octo(2 × 2) structure is the most stable NiO(111)-2 × 2 termination and gives reaction energies with water that are more consistent with the calorimetry results than the metal-terminated surface. They show that water adsorbs dissociatively on this (2 × 2)-O-octo surface to produce a hydroxyl-covered surface with a heat of adsorption of 171 ± 5 kJ/mol in the low-coverage limit (very close to 170 kJ/mol experimentally) and an integral heat that decreases by 14 kJ/mol up to saturation (compared to ~30 kJ/mol experimentally). As a result, sensitivity of this reaction’s energy to choice of DFT method is tested using a variety of different exchange correlation functionals, including HSE06, and found to be quite weak.« less

An improved quasi-diabatic representation of the 1, 2, 3{sup 1}A coupled adiabatic potential energy surfaces of phenol in the full 33 internal coordinates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Xiaolei, E-mail: virtualzx@gmail.com; Malbon, Christopher L., E-mail: clmalbon@gmail.com; Yarkony, David R., E-mail: yarkony@jhu.edu

2016-03-28

In a recent work we constructed a quasi-diabatic representation, H{sup d}, of the 1, 2, 3{sup 1}A adiabatic states of phenol from high level multireference single and double excitation configuration interaction electronic structure data, energies, energy gradients, and derivative couplings. That H{sup d} accurately describes surface minima, saddle points, and also regions of strong nonadiabatic interactions, reproducing the locus of conical intersection seams and the coordinate dependence of the derivative couplings. The present work determines the accuracy of H{sup d} for describing phenol photodissociation. Additionally, we demonstrate that a modest energetic shift of two diabats yields a quantifiably more accuratemore » H{sup d} compared with experimental energetics. The analysis shows that in favorable circumstances it is possible to use single point energies obtained from the most reliable electronic structure methods available, including methods for which the energy gradients and derivative couplings are not available, to improve the quality of a global representation of several coupled potential energy surfaces. Our data suggest an alternative interpretation of kinetic energy release measurements near λ{sub phot} ∼ 248 nm.« less

Ignition sensitivity study of an energetic train configuration using experiments and simulation

NASA Astrophysics Data System (ADS)

Kim, Bohoon; Yu, Hyeonju; Yoh, Jack J.

2018-06-01

A full scale hydrodynamic simulation intended for the accurate description of shock-induced detonation transition was conducted as a part of an ignition sensitivity analysis of an energetic component system. The system is composed of an exploding foil initiator (EFI), a donor explosive unit, a stainless steel gap, and an acceptor explosive. A series of velocity interferometer system for any reflector measurements were used to validate the hydrodynamic simulations based on the reactive flow model that describes the initiation of energetic materials arranged in a train configuration. A numerical methodology with ignition and growth mechanisms for tracking multi-material boundary interactions as well as severely transient fluid-structure coupling between high explosive charges and metal gap is described. The free surface velocity measurement is used to evaluate the sensitivity of energetic components that are subjected to strong pressure waves. Then, the full scale hydrodynamic simulation is performed on the flyer impacted initiation of an EFI driven pyrotechnical system.

Structural, electronic and vibrational properties of few-layer 2H-and 1T-TaSe 2

DOE PAGES

Yan, Jia -An; Dela Cruz, Mack A.; Cook, Brandon G.; ...

2015-11-16

Two-dimensional metallic transition metal dichalcogenides (TMDs) are of interest for studying phenomena such as charge-density wave (CDW) and superconductivity. Few-layer tantalum diselenides (TaSe 2) are typical metallic TMDs exhibiting rich CDW phase transitions. However, a description of the structural, electronic and vibrational properties for different crystal phases and stacking configurations, essential for interpretation of experiments, is lacking. We present first principles calculations of structural phase energetics, band dispersion near the Fermi level, phonon properties and vibrational modes at the Brillouin zone center for different layer numbers, crystal phases and stacking geometries. Evolution of the Fermi surfaces as well as themore » phonon dispersions as a function of layer number reveals dramatic dimensionality effects in this CDW material. Lastly, our results indicate strong electronic interlayer coupling, detail energetically possible stacking geometries, and provide a basis for interpretation of Raman spectra.« less

Spin-polarized surface resonances accompanying topological surface state formation

DOE PAGES

Jozwiak, Chris; Sobota, Jonathan A.; Gotlieb, Kenneth; ...

2016-10-14

Topological insulators host spin-polarized surface states born out of the energetic inversion of bulk bands driven by the spin-orbit interaction. Here we discover previously unidentified consequences of band-inversion on the surface electronic structure of the topological insulator Bi 2Se 3. By performing simultaneous spin, time, and angle-resolved photoemission spectroscopy, we map the spin-polarized unoccupied electronic structure and identify a surface resonance which is distinct from the topological surface state, yet shares a similar spin-orbital texture with opposite orientation. Its momentum dependence and spin texture imply an intimate connection with the topological surface state. Calculations show these two distinct states canmore » emerge from trivial Rashba-like states that change topology through the spin-orbit-induced band inversion. As a result, this work thus provides a compelling view of the coevolution of surface states through a topological phase transition, enabled by the unique capability of directly measuring the spin-polarized unoccupied band structure.« less

The role of electro-explosion alloying with titanium diboride and treatment with pulsed electron beam in the surface modification of VT6 alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Konovalov, Sergey, E-mail: konovserg@gmail.com; Gromov, Victor, E-mail: gromov@physics.sibsiu.ru; Kobzareva, Tatyana

The paper presents the results of the investigation of VT6 titanium alloy subjected to electro-explosion alloying with TiB{sub 2} and irradiation with pulsed electron beam. It was established that electro-explosion alloying resulted in a high level of roughness of the surface layer with high adhesion of the modified layer and matrix. Further irradiation of the material with electron beam resulted in the smoothing of the surface of alloying and formation of a porous structure with various scale levels in the surface layer. It was also established that the energetic exposure causes the formation of a gradient structure with a changingmore » elemental composition along the direction from the surface of alloying.« less

First principles study of the atomic layer deposition of alumina by TMA-H2O-process.

PubMed

Weckman, Timo; Laasonen, Kari

2015-07-14

Atomic layer deposition (ALD) is a coating technology used to produce highly uniform thin films. Aluminiumoxide, Al2O3, is mainly deposited using trimethylaluminium (TMA) and water as precursors and is the most studied ALD-process to date. However, only few theoretical studies have been reported in the literature. The surface reaction mechanisms and energetics previously reported focus on a gibbsite-like surface model but a more realistic description of the surface can be achieved when the hydroxylation of the surface is taken into account using dissociatively adsorbed water molecules. The adsorbed water changes the structure of the surface and reaction energetics change considerably when compared to previously studied surface model. Here we have studied the TMA-H2O process using density functional theory on a hydroxylated alumina surface and reproduced the previous results for comparison. Mechanisms and energetics during both the TMA and the subsequent water pulse are presented. TMA is found to adsorb exothermically onto the surface. The reaction barriers for the ligand-exchange reactions between the TMA and the surface hydroxyl groups were found to be much lower compared to previously presented results. TMA dissociation on the surface is predicted to saturate at monomethylaluminium. Barriers for proton diffusion between surface sites are observed to be low. TMA adsorption was also found to be cooperative with the formation of methyl bridges between the adsorbants. The water pulse was studied using single water molecules reacting with the DMA and MMA surface species. Barriers for these reactions were found to reasonable in the process conditions. However, stabilizing interactions amongst water molecules were found to lower the reaction barriers and the dynamical nature of water is predicted to be of importance. It is expected that these calculations can only set an upper limit for the barriers during the water pulse.

Theoretical studies of growth processes and electronic properties of nanostructures on surfaces

NASA Astrophysics Data System (ADS)

Mo, Yina

Low dimensional nanostructures have been of particular interest because of their potential applications in both theoretical studies and industrial use. Although great efforts have been put into obtaining better understanding of the formation and properties of these materials, many questions still remain unanswered. This thesis work has focused on theoretical studies of (1) the growth processes of magnetic nanowires on transition-metal surfaces, (2) the dynamics of pentacene thin-film growth and island structures on inert surfaces, and (3) our proposal of a new type of semiconducting nanotube. In the first study, we elucidated a novel and intriguing kinetic pathway for the formation of Fe nanowires on the upper edge of a monatomic-layer-high step on Cu(111) using first-principles calculations. The identification of a hidden fundamental Fe basal line within the Cu steps prior to the formation of the apparent upper step edge Fe wire produces a totally different view of step-decorating wire structures and offers new possibilities for the study of the properties of these wires. Subsequent experiments with scanning tunneling microscopy unambiguously established the essential role of embedded Fe atoms as precursors to monatomic wire growth. A more general study of adatom behavior near transition-metal step edges illustrated a systematic trend in the adatom energetics and kinetics, resulted from the electronic interactions between the adatom and the surfaces. This work opens the possibility of controlled manufacturing of one-dimensional nanowires. In the second study, we investigated pentacene thin-films on H-diamond, H-silica and OH-silica surfaces via force field molecular dynamics simulations. Pentacene island structures on these surfaces were identified and found to have a 90-degree rotation relative to the structure proposed by some experimental groups. Our work may facilitate the design and control of experimental pentacene thin-film growth, and thus the development of organic thin-film transistors. Finally, in our third study, we proposed a new type of structurally simple and energetically stable cyanide transition metal nanotube, based on the planar structure of M(CN)2, (M = Ni, Pd, Pt). These nanotubes have semiconducting character with large band gaps (2--3 eV), which are insensitive to the chirality and diameter. We have investigated the energetic, electronic, and mechanical properties of these materials in both planar and tubular forms through first-principles density functional calculations. These calculations reveal interesting multi-center bonding features that should lead to preferential growth of tubes of a particular chirality. The unique features of these nanotubes should make them capable of being mass-produced, which is one of the most significant shortcomings of semiconducting carbon nanotubes.

Structure of a Water Monolayer on the Anatase TiO2(101) Surface

NASA Astrophysics Data System (ADS)

Patrick, Christopher E.; Giustino, Feliciano

2014-07-01

Titanium dioxide (TiO2) plays a central role in the study of artificial photosynthesis, owing to its ability to perform photocatalytic water splitting. Despite over four decades of intense research efforts in this area, there is still some debate over the nature of the first water monolayer on the technologically relevant anatase TiO2(101) surface. In this work, we use first-principles calculations to reverse engineer the experimental high-resolution x-ray photoelectron spectra measured for this surface by Walle et al. [J. Phys. Chem. C 115, 9545 (2011)] and find evidence supporting the existence of a mix of dissociated and molecular water in the first monolayer. Using both semilocal and hybrid functional calculations, we revise the current understanding of the adsorption energetics by showing that the energetic cost of water dissociation is reduced via the formation of a hydrogen-bonded hydroxyl-water complex. We also show that such a complex can provide an explanation of an unusual superstructure observed in high-resolution scanning tunneling microscopy experiments.

Basic Research Plan.

DTIC Science & Technology

1996-05-01

detection, catalysts for enhancing and controlling energetic reactions, synthesis of new compounds (e.g., narrow band-gap materials and non-linear...design for synthesis of advanced materials Fabricate porous lightweight and resilient structural materials with novel properties and uses Demonstrate...elements for 10 nm computer memory elements Demonstrate enhanced propellants and explosives with nanoparticle surface chemistry Demonstrate sensing of

Charge-free low-temperature method of forming thin film-based nanoscale materials and structures on a substrate

DOEpatents

Hoffbauer, Mark [Los Alamos, NM; Mueller, Alex [Santa Fe, NM

2008-07-01

A method of forming a nanostructure at low temperatures. A substrate that is reactive with one of atomic oxygen and nitrogen is provided. A flux of neutral atoms of at least one of nitrogen and oxygen is generated within a laser-sustained-discharge plasma source and a collimated beam of energetic neutral atoms and molecules is directed from the plasma source onto a surface of the substrate to form the nanostructure. The energetic neutral atoms and molecules in the plasma have an average kinetic energy in a range from about 1 eV to about 5 eV.

Flow turbulence topology in regular porous media: From macroscopic to microscopic scale with direct numerical simulation

NASA Astrophysics Data System (ADS)

Chu, Xu; Weigand, Bernhard; Vaikuntanathan, Visakh

2018-06-01

Microscopic analysis of turbulence topology in a regular porous medium is presented with a series of direct numerical simulation. The regular porous media are comprised of square cylinders in a staggered array. Triply periodic boundary conditions enable efficient investigations in a representative elementary volume. Three flow patterns—channel with sudden contraction, impinging surface, and wake—are observed and studied quantitatively in contrast to the qualitative experimental studies reported in the literature. Among these, shear layers in the channel show the highest turbulence intensity due to a favorable pressure gradient and shed due to an adverse pressure gradient downstream. The turbulent energy budget indicates a strong production rate after the flow contraction and a strong dissipation on both shear and impinging walls. Energy spectra and pre-multiplied spectra detect large scale energetic structures in the shear layer and a breakup of scales in the impinging layer. However, these large scale structures break into less energetic small structures at high Reynolds number conditions. This suggests an absence of coherent structures in densely packed porous media at high Reynolds numbers. Anisotropy analysis with a barycentric map shows that the turbulence in porous media is highly isotropic in the macro-scale, which is not the case in the micro-scale. In the end, proper orthogonal decomposition is employed to distinguish the energy-conserving structures. The results support the pore scale prevalence hypothesis. However, energetic coherent structures are observed in the case with sparsely packed porous media.

Ab initio density functional theory study on the atomic and electronic structure of GaP/Si(001) heterointerfaces

NASA Astrophysics Data System (ADS)

Romanyuk, O.; Supplie, O.; Susi, T.; May, M. M.; Hannappel, T.

2016-10-01

The atomic and electronic band structures of GaP/Si(001) heterointerfaces were investigated by ab initio density functional theory calculations. Relative total energies of abrupt interfaces and mixed interfaces with Si substitutional sites within a few GaP layers were derived. It was found that Si diffusion into GaP layers above the first interface layer is energetically unfavorable. An interface with Si/Ga substitution sites in the first layer above the Si substrate is energetically the most stable one in thermodynamic equilibrium. The electronic band structure of the epitaxial GaP/Si(001) heterostructure terminated by the (2 ×2 ) surface reconstruction consists of surface and interface electronic states in the common band gap of two semiconductors. The dispersion of the states is anisotropic and differs for the abrupt Si-Ga, Si-P, and mixed interfaces. Ga 2 p , P 2 p , and Si 2 p core-level binding-energy shifts were computed for the abrupt and the lowest-energy heterointerface structures. Negative and positive core-level shifts due to heterovalent bonds at the interface are predicted for the abrupt Si-Ga and Si-P interfaces, respectively. The distinct features in the heterointerface electronic structure and in the core-level shifts open new perspectives in the experimental characterization of buried polar-on-nonpolar semiconductor heterointerfaces.

Probing the energetics of organic–nanoparticle interactions of ethanol on calcite

DOE PAGES

Wu, Di; Navrotsky, Alexandra

2015-04-13

Knowing the nature of interactions between small organic molecules and surfaces of nanoparticles (NP) is crucial for fundamental understanding of natural phenomena and engineering processes. In this paper, we report direct adsorption enthalpy measurement of ethanol on a series of calcite nanocrystals, with the aim of mimicking organic–NP interactions in various environments. The energetics suggests a spectrum of adsorption events as a function of coverage: strongest initial chemisorption on active sites on fresh calcite surfaces, followed by major chemical binding to form an ethanol monolayer and, subsequently, very weak, near-zero energy, physisorption. Furthermore, these thermochemical observations directly support a structuremore » where the ethanol monolayer is bonded to the calcite surface through its polar hydroxyl group, leaving the hydrophobic ends of the ethanol molecules to interact only weakly with the next layer of adsorbing ethanol and resulting in a spatial gap with low ethanol density between the monolayer and subsequent added ethanol molecules, as predicted by molecular dynamics and density functional calculations. Such an ordered assembly of ethanol on calcite NP is analogous to, although less strongly bonded than, a capping layer of organics intentionally introduced during NP synthesis, and suggests a continuous variation of surface structure depending on molecular chemistry, ranging from largely disordered surface layers to ordered layers that nevertheless are mobile and can rearrange or be displaced by other molecules to strongly bonded immobile organic capping layers. Finally, these differences in surface structure will affect chemical reactions, including the further nucleation and growth of nanocrystals on organic ligand-capped surfaces.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Bing; Bernstein, Elliot R., E-mail: erb@Colostate.edu

Unimolecular decomposition of nitrogen-rich energetic salt molecules bis(ammonium)5,5′-bistetrazolate (NH{sub 4}){sub 2}BT and bis(triaminoguanidinium) 5,5′-azotetrazolate TAGzT, has been explored via 283 nm laser excitation. The N{sub 2} molecule, with a cold rotational temperature (<30 K), is observed as an initial decomposition product, subsequent to UV excitation. Initial decomposition mechanisms for the two electronically excited salt molecules are explored at the complete active space self-consistent field (CASSCF) level. Potential energy surface calculations at the CASSCF(12,8)/6-31G(d) ((NH{sub 4}){sub 2}BT) and ONIOM (CASSCF/6-31G(d):UFF) (TAGzT) levels illustrate that conical intersections play an essential role in the decomposition mechanism as they provide non-adiabatic, ultrafast radiationless internalmore » conversion between upper and lower electronic states. The tetrazole ring opens on the S{sub 1} excited state surface and, through conical intersections (S{sub 1}/S{sub 0}){sub CI}, N{sub 2} product is formed on the ground state potential energy surface without rotational excitation. The tetrazole rings open at the N2—N3 ring bond with the lowest energy barrier: the C—N ring bond opening has a higher energy barrier than that for any of the N—N ring bonds: this is consistent with findings for other nitrogen-rich neutral organic energetic materials. TAGzT can produce N{sub 2} either by the opening of tetrazole ring or from the N=N group linking its two tetrazole rings. Nonetheless, opening of a tetrazole ring has a much lower energy barrier. Vibrational temperatures of N{sub 2} products are hot based on theoretical predictions. Energy barriers for opening of the tetrazole ring for all the nitrogen-rich energetic materials studied thus far, including both neutral organic molecules and salts, are in the range from 0.31 to 2.71 eV. Energy of the final molecular structure of these systems with dissociated N{sub 2} product is in the range from −1.86 to 3.11 eV. The main difference between energetic salts and neutral nitrogen-rich energetic material is that energetic salts usually have lower excitation energy.« less

Mechanisms of the Wurtzite to Rocksalt Transformation in CdSe Nanocrystals

NASA Astrophysics Data System (ADS)

Grünwald, Michael; Rabani, Eran; Dellago, Christoph

2006-06-01

We study the pressure-driven phase transition from the four-coordinate wurtzite to the six-coordinate rocksalt structure in CdSe nanocrystals with molecular dynamics computer simulations. With an ideal gas as the pressure medium, we apply hydrostatic pressure to spherical and faceted nanocrystals ranging in diameter from 25 to 62 Å. In spherical crystals, the main mechanism of the transformation involves the sliding of (100) planes, but depending on the specific surface structure we also observe a second mechanism proceeding through the flattening of (100) planes. In faceted crystals, the transition proceeds via a five-coordinated hexagonal structure, which is stabilized at intermediate pressures due to dominant surface energetics.

Effects of sugar functional groups, hydrophobicity, and fluorination on carbohydrate-DNA stacking interactions in water.

PubMed

Lucas, Ricardo; Peñalver, Pablo; Gómez-Pinto, Irene; Vengut-Climent, Empar; Mtashobya, Lewis; Cousin, Jonathan; Maldonado, Olivia S; Perez, Violaine; Reynes, Virginie; Aviñó, Anna; Eritja, Ramón; González, Carlos; Linclau, Bruno; Morales, Juan C

2014-03-21

Carbohydrate-aromatic interactions are highly relevant for many biological processes. Nevertheless, experimental data in aqueous solution relating structure and energetics for sugar-arene stacking interactions are very scarce. Here, we evaluate how structural variations in a monosaccharide including carboxyl, N-acetyl, fluorine, and methyl groups affect stacking interactions with aromatic DNA bases. We find small differences on stacking interaction among the natural carbohydrates examined. The presence of fluorine atoms within the pyranose ring slightly increases the interaction with the C-G DNA base pair. Carbohydrate hydrophobicity is the most determinant factor. However, gradual increase in hydrophobicity of the carbohydrate does not translate directly into a steady growth in stacking interaction. The energetics correlates better with the amount of apolar surface buried upon sugar stacking on top of the aromatic DNA base pair.

Enhancing Reactivity in Structural Energetic Materials

NASA Astrophysics Data System (ADS)

Glumac, Nick

2017-06-01

In many structural energetic materials, only a small fraction of the metal oxidizes, and yet this provides a significant boost in the overall energy release of the system. Different methodologies to enhance this reactivity include alloying and geometric modifications of microstructure of the reactive material (RM). In this presentation, we present the results of several years of systematic study of both chemical (alloy) and mechanical (geometry) effects on reactivity for systems with typical charge to case mass ratios. Alloys of aluminum with magnesium and lithium are considered, as these are common alloys in aerospace applications. In terms of geometric modifications, we consider surface texturing, inclusion of dense additives, and inclusion of voids. In all modifications, a measurable influence on output is observed, and this influence is related to the fragment size distribution measured from the observed residue. Support from DTRA is gratefully acknowledged.

Bis(4-nitraminofurazanyl-3-azoxy)azofurazan and Derivatives: 1,2,5-Oxadiazole Structures and High-Performance Energetic Materials.

PubMed

Liu, Yuji; Zhang, Jiaheng; Wang, Kangcai; Li, Jinshan; Zhang, Qinghua; Shreeve, Jean'ne M

2016-09-12

Bis(4-nitraminofurazanyl-3-azoxy)azofurazan (1) and ten of its energetic salts were prepared and fully characterized. Computational analysis based on isochemical shielding surface and trigger bond dissociation enthalpy provide a better understanding of the thermal stabilities for nitramine-furazans. These energetic compounds exhibit good densities, high heats of formation, and excellent detonation velocity and pressure. Some representative compounds, for example, 1 (vD : 9541 m s(-1) ; P: 40.5 GPa), and 4 (vD : 9256 m s(-1) ; P: 38.0 GPa) exhibit excellent detonation performances, which are comparable with current high explosives such as RDX (vD : 8724 m s(-1) ; P: 35.2 GPa) and HMX (vD : 9059 m s(-1) ; P: 39.2 GPa). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Density functional theory study of phase stability and defect thermodynamics in iron-oxyhydroxide mineral materials

NASA Astrophysics Data System (ADS)

Pinney, Nathan Douglas

Due to their high surface area and reactivity toward a variety of heavy metal and oxyanion species of environmental concern, Fe-(oxyhydr)oxide materials play an important role in the geochemical fate of natural and anthropogenic contaminants in soils, aquifers and surface water environments worldwide. In this research, ab initio simulations describe the bulk structure, magnetic properties, and relative phase stability of major Fe-(oxyhydr)oxide materials, including hematite, goethite, lepidocrocite, and ferrihydrite.These bulk models are employed in further studies of point defect and alloy/dopant thermodynamics in these materials, allowing construction of a phase stability model that better replicates the structure and composition of real materials. Li + adsorption at the predominant goethite (101) surface is simulated using ab initio methods, offering energetic and structural insight into the binding mechanisms of metal cations over a range of surface protonation conditions.

Density Functional Theory Simulations of Water Adsorption and Activation on the (-201) β-Ga2 O3 Surface.

PubMed

Anvari, Roozbeh; Spagnoli, Dino; Parish, Giacinta; Nener, Brett

2018-03-09

Density functional theory calculations are used to study the molecular and dissociative adsorption of water on the (-201) β-Ga 2 O 3 surface. The effect of adsorption of different water-like species on the geometry, binding energies, vibrational spectra and the electronic structure of the surface are discussed. The study shows that although the hydrogen evolution reaction requires a small amount of energy to become energetically favourable, the over potential for activating the oxygen evolution reaction is quite high. The results of our calculations provide insight as to why a high voltage is required in experiments to activate the water-splitting reaction, whereas previous studies of gallium oxide predicted very low activation energies for other energetically more favourable facets. Application of this work to studies of GaN-based chemical sensors with gallium oxide surfaces shows that it is possible to select the gate bias so that the sensors are not influenced by water-splitting reactions. It was also found that in the region where water splitting does not occur, the surface can exist in two states, that is, water or hydroxyl terminated. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lateral Interactions in Monolayer Thick Mercury Films

NASA Astrophysics Data System (ADS)

Kime, Yolanda Jan

An understanding of lateral adatom-adatom interactions is often an important part of understanding electronic structure and adsorption energetics in monolayer thick films. In this dissertation I use angle-resolved photoemission and thermal desorption spectroscopies to explore the relationship between the adatom-adatom interaction and other characteristics of the adlayer, such as electronic structure, defects, or coexistent structural phases in the adlayer. Since Hg binds weakly to many substrates, the lateral interactions are often a major contribution to the dynamics of the overlayer. Hg adlayer systems are thus ideal for probing lateral interactions. The electronic structures of Hg adlayers on Ag(100), Cu(100), and Cu_3Au(100) are studied with angle-resolved ultraviolet photoemission. The Hg atomic 5d_{5/2} electronic band is observed to split into two levels following adsorption onto some surfaces. The energetic splitting of the Hg 5d_{5/2} level is found to be directly correlated to the adlayer homogeneous strain energy. The existence of the split off level also depends on the order or disorder of the Hg adlayer. The energetics of Hg adsorption on Cu(100) are probed using thermal desorption spectroscopy. Two different ordered adlayer structures are observed for Hg adsorption on Cu(100) at 200 K. Under some adsorption conditions and over a range of exposures, the two phases are seen to coexist on the surface prior to the thermal desorption process. A phase transition from the more dense to the less dense phase is observed to occur during the thermal desorption process. Inherent differences in defect densities are responsible for the observed differences between lateral interactions measured previously with equilibrium (atom beam scattering) and as measured by the non-equilibrium (thermal desorption) technique reported here. Theoretical and experimental evidence for an indirect through-metal interaction between adatoms is also discussed. Although through-metal interactions may play a role in some adsorption systems, there is little compelling evidence that this effect is significant in many experimental reports where the through metal bond is invoked.

Conformational elasticity can facilitate TALE-DNA recognition

PubMed Central

Lei, Hongxing; Sun, Jiya; Baldwin, Enoch P.; Segal, David J.; Duan, Yong

2015-01-01

Sequence-programmable transcription activator-like effector (TALE) proteins have emerged as a highly efficient tool for genome engineering. Recent crystal structures depict a transition between an open unbound solenoid and more compact DNA-bound solenoid formed by the 34 amino acid repeats. How TALEs switch conformation between these two forms without substantial energetic compensation, and how the repeat-variable di-residues (RVDs) discriminate between the cognate base and other bases still remain unclear. Computational analysis on these two aspects of TALE-DNA interaction mechanism has been conducted in order to achieve a better understanding of the energetics. High elasticity was observed in the molecular dynamics simulations of DNA-free TALE structure that started from the bound conformation where it sampled a wide range of conformations including the experimentally determined apo- and bound- conformations. This elastic feature was also observed in the simulations starting from the apo form which suggests low free energy barrier between the two conformations and small compensation required upon binding. To analyze binding specificity, we performed free energy calculations of various combinations of RVDs and bases using Poisson-Boltzmann/surface area (PBSA) and other approaches. The PBSA calculations indicated that the native RVD-base structures had lower binding free energy than mismatched structures for most of the RVDs examined. Our theoretical analyses provided new insight on the dynamics and energetics of TALE-DNA binding mechanism. PMID:24629191

Conformational elasticity can facilitate TALE-DNA recognition.

PubMed

Lei, Hongxing; Sun, Jiya; Baldwin, Enoch P; Segal, David J; Duan, Yong

2014-01-01

Sequence-programmable transcription activator-like effector (TALE) proteins have emerged as a highly efficient tool for genome engineering. Recent crystal structures depict a transition between an open unbound solenoid and more compact DNA-bound solenoid formed by the 34 amino acid repeats. How TALEs switch conformation between these two forms without substantial energetic compensation, and how the repeat-variable di-residues (RVDs) discriminate between the cognate base and other bases still remain unclear. Computational analysis on these two aspects of TALE-DNA interaction mechanism has been conducted in order to achieve a better understanding of the energetics. High elasticity was observed in the molecular dynamics simulations of DNA-free TALE structure that started from the bound conformation where it sampled a wide range of conformations including the experimentally determined apo and bound conformations. This elastic feature was also observed in the simulations starting from the apo form which suggests low free energy barrier between the two conformations and small compensation required upon binding. To analyze binding specificity, we performed free energy calculations of various combinations of RVDs and bases using Poisson-Boltzmann surface area (PBSA) and other approaches. The PBSA calculations indicated that the native RVD-base structures had lower binding free energy than mismatched structures for most of the RVDs examined. Our theoretical analyses provided new insight on the dynamics and energetics of TALE-DNA binding mechanism. © 2014 Elsevier Inc. All rights reserved.

Gulf of Aden eddies and their impact on Red Sea Water

NASA Astrophysics Data System (ADS)

Bower, Amy S.; Fratantoni, David M.; Johns, William E.; Peters, Hartmut

2002-11-01

New oceanographic observations in the Gulf of Aden in the northwestern Indian Ocean have revealed large, energetic, deep-reaching mesoscale eddies that fundamentally influence the spreading rates and pathways of intermediate-depth Red Sea Water (RSW). Three eddies were sampled in February 2001, two cyclonic and one anticyclonic, with diameters 150-250 km. Both cyclones had surface-intensified velocity structure with maxima ~0.5 m s-1, while the equally-energetic anticyclone appeared to be decoupled from the surface circulation. All three eddies reached nearly to the 1000-2000 m deep sea floor, with speeds as high as 0.2-0.3 m s-1 extending through the depth range of RSW. Comparison of salinity and direct velocity measurements indicates that the eddies advect and stir RSW through the Gulf of Aden. Anomalous water properties in the center of the anticyclonic eddy point to a possible formation site in the Somali Current System.

In situ plasma fabrication of ceramic-like structure on polymeric implant with enhanced surface hardness, cytocompatibility and antibacterial capability.

PubMed

Liu, Jun; Zhang, Wei; Shi, Haigang; Yang, Kun; Wang, Gexia; Wang, Pingli; Ji, Junhui; Chu, Paul K

2016-05-01

Polymeric materials are commonly found in orthopedic implants due to their unique mechanical properties and biocompatibility but the poor surface hardness and bacterial infection hamper many biomedical applications. In this study, a ceramic-like surface structure doped with silver is produced by successive plasma implantation of silicon (Si) and silver (Ag) into the polyamine 66 (PA66) substrate. Not only the surface hardness and elastic modulus are greatly enhanced due to the partial surface carbonization and the ceramic-like structure produced by the reaction between energetic Si and the carbon chain of PA66, but also the antibacterial activity is improved because of the combined effects rendered by Ag and SiC structure. Furthermore, the modified materials which exhibit good cytocompatibility upregulate bone-related genes and proteins expressions of the contacted bone mesenchymal stem cells (BMSCs). For the first time, it explores out that BMSCs osteogenesis on the antibacterial ceramic-like structure is mediated via the iNOS and nNOS signal pathways. The results reveal that in situ plasma fabrication of an antibacterial ceramic-like structure can endow PA66 with excellent surface hardness, cytocompatibility, as well as antibacterial capability. © 2016 Wiley Periodicals, Inc.

Molecular dynamics simulation of water at mineral surfaces: Structure, dynamics, energetics and hydrogen bonding

NASA Astrophysics Data System (ADS)

Kalinichev, A. G.; Wang, J.; Kirkpatrick, R.

2006-05-01

Fundamental molecular-level understanding of the properties of aqueous mineral interfaces is of great importance for many geochemical and environmental systems. Interaction between water and mineral surfaces substantially affects the properties of both phases, including the reactivity and functionality of the substrate surface, and the structure, dynamics, and energetics of the near surface aqueous phase. Experimental studies of interfacial water structure and dynamics using surface-sensitive techniques such as sum-frequency vibrational spectroscopy or X-ray and neutron reflectivity are not always possible for many practically important substrates, and their results often require interpretation concerning the atomistic mechanisms responsible for the observed behavior. Molecular computer simulations can provide new insight into the underlying molecular- level relationships between the inorganic substrate structure and composition and the structure, ordering, and dynamics of interfacial water. We have performed a series of molecular dynamics (MD) computer simulations of aqueous interfaces with several silicates (quartz, muscovite, and talc) and hydroxides (brucite, portlandite, gibbsite, Ca/Al and Mg/Al double hydroxides) to quantify the effects of the substrate mineral structure and composition on the structural, transport, and thermodynamic properties of water on these mineral surfaces. Due to the prevalent effects of the development of well-interconnected H-bonding networks across the mineral- water interfaces, all the hydroxide surfaces (including a fully hydroxylated quartz surface) show very similar H2O density profiles perpendicular to the interface. However, the predominant orientations of the interfacial H2O molecules and their detailed 2-dimensional near-surface structure and dynamics parallel to the interface are quite different reflecting the differences in the substrate structural charge distribution and the density and orientations of the surface OH groups. The H2O density profiles and other structural and dynamic characteristics of water at the two siloxane surfaces are very different from each other and from the hydroxide surfaces, since the muscovite surface is negatively charged and hydrophilic, while the talc surface is electrostatically neutral and hydrophobic. In general, at hydrophilic neutral surfaces both donating and accepting H-bonds from the H2O molecules are contributing to the development of the interfacial H-bond network, whereas at hydrophilic but charged surfaces only accepting or donating H-bonds with H2O molecules are possible. At the hydrophobic talc surface H-bonds among H2O molecules dominate the interfacial H-bond network and the water-surface interactions are very weak. The first water layer at all substrates is well ordered parallel to the surface, reflecting substrate crystal structures and indicating the reduced translational and orientational mobility of interfacial H2O molecules. At longer time scale (~100ps) their dynamics can be decomposed into a slow, virtually frozen, regime due to the substrate- bound H2O and a faster regime of almost free water reflecting the dynamics far from the surface. At shorter times (>10ps) the two dynamical regimes are superimposed. The much higher ordering of interfacial water (compared to bulk liquid) can not be adequately described as simply "ice-like". To some extent, it rather resembles the behavior of supercooled water.

Magnetospheric considerations for solar system ice state

NASA Astrophysics Data System (ADS)

Paranicas, C.; Hibbitts, C. A.; Kollmann, P.; Ligier, N.; Hendrix, A. R.; Nordheim, T. A.; Roussos, E.; Krupp, N.; Blaney, D.; Cassidy, T. A.; Clark, G.

2018-03-01

The current lattice configuration of the water ice on the surfaces of the inner satellites of Jupiter and Saturn is likely shaped by many factors. But laboratory experiments have found that energetic proton irradiation can cause a transition in the structure of pure water ice from crystalline to amorphous. It is not known to what extent this process is competitive with other processes in solar system contexts. For example, surface regions that are rich in water ice may be too warm for this effect to be important, even if the energetic proton bombardment rate is very high. In this paper, we make predictions, based on particle flux levels and other considerations, about where in the magnetospheres of Jupiter and Saturn the ∼MeV proton irradiation mechanism should be most relevant. Our results support the conclusions of Hansen and McCord (2004), who related relative level of radiation on the three outer Galilean satellites to the amorphous ice content within the top 1 mm of surface. We argue here that if magnetospheric effects are considered more carefully, the correlation is even more compelling. Crystalline ice is by far the dominant ice state detected on the inner Saturnian satellites and, as we show here, the flux of bombarding energetic protons onto these bodies is much smaller than at the inner Jovian satellites. Therefore, the ice on the Saturnian satellites also corroborates the correlation.

First-principles study of native defects in bulk Sm2CuO4 and its (001) surface structure

NASA Astrophysics Data System (ADS)

Zheng, Fubao; Zhang, Qinfang; Meng, Qiangqiang; Wang, Baolin; Song, Fengqi; Yunoki, Seiji; Wang, Guanghou

2018-04-01

Using the first-principles calculations based on the density functional theory, we have studied the bulk defect formation and surface structures of Sm2CuO4. To ensure the accuracy of calculations, the spin order of Cu atoms is rechecked and it is the well-known nearest-neighbor antiferromagnetic ground state, which can be attributed to the hole-mediated superexchange through the strong pdσ hybridization interaction between Cu dx2-y2 electron and the neighboring oxygen px (or py) electron. Under each present experimental condition, the Sm vacancy has a very high formation energy and is unlikely to be stable. The Cu vacancy is a shallow acceptor, which is preferred under O-rich conditions, whereas the O vacancy is a donor and energetically favorable under O-poor conditions. To construct its (001) surface structure, CuOO, CuO, and Cu terminated surfaces are found to be most favorable under different experimental conditions. The stable surface structures are always accompanied by significant surface atomic reconstructions and electron charge redistribution, which are intimately correlated to each other.

Synthesis and energetics of gold nanoclusters tailored by interfacial bonding structure

NASA Astrophysics Data System (ADS)

Tang, Zhenghua

In addition to the well known quantum confinement effects resulted from size and shape, interfacial bond structure is another factor, affecting the properties of the nanomaterial that is rarely studied. Inspired by the "Au-S-Au" staple motif discovered from the crystal structure of monothiol protected Au102 nanocluster (Science, 2007, 318, 430), dithiol molecules (e.g. 1, 2-dithiol, 1, 4-dithiol, etc.) with molecular structural constraint have been employed to create dithiolate protected clusters or mixed monothiolate and dithiolate protected clusters. The structure and properties of the Au clusters are expected to change due to two effects: The entropy gain of dithiol over monothiol protection and the constraint to the formation of the thiol bridging motif. DMPS (1, 2-dithiol molecule) stabilized clusters with characteristic absorption bands have been obtained, and characterized by multiple techniques. Monolayer reaction on gold core surface between the monothiol tiopronin and dithiol DMPS has been performed, and the mechanism has been probed. Mixed phenylethanethiolate and durene-dithiolate (1, 4-dithiol molecule) protected Au130 clusters with rich electrochemical features have been created, and the optical and electrochemical energetics have been successfully correlated based on core and core-ligand energy states. Furthermore, the impact of 1, 4-dithiolate-Au bonding on the near infrared luminescence has been studied. INDEX WORDS: Au MPCs, Staple motif, DMPS, Au DTCs, Au4, Tiopronin, Monolayer reaction, Durene-DT, Au MTCs, Au130, Optical energetic, Electrochemistry, Near infrared luminescence, 1, 4-Dithiolate-Au bonding.

Software Package Completed for Alloy Design at the Atomic Level

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo H.; Noebe, Ronald D.; Abel, Phillip B.; Good, Brian S.

2001-01-01

As a result of a multidisciplinary effort involving solid-state physics, quantum mechanics, and materials and surface science, the first version of a software package dedicated to the atomistic analysis of multicomponent systems was recently completed. Based on the BFS (Bozzolo, Ferrante, and Smith) method for the calculation of alloy and surface energetics, this package includes modules devoted to the analysis of many essential features that characterize any given alloy or surface system, including (1) surface structure analysis, (2) surface segregation, (3) surface alloying, (4) bulk crystalline material properties and atomic defect structures, and (5) thermal processes that allow us to perform phase diagram calculations. All the modules of this Alloy Design Workbench 1.0 (ADW 1.0) are designed to run in PC and workstation environments, and their operation and performance are substantially linked to the needs of the user and the specific application.

Mode structure symmetry breaking of energetic particle driven beta-induced Alfvén eigenmode

NASA Astrophysics Data System (ADS)

Lu, Z. X.; Wang, X.; Lauber, Ph.; Zonca, F.

2018-01-01

The mode structure symmetry breaking of energetic particle driven Beta-induced Alfvén Eigenmode (BAE) is studied based on global theory and simulation. The weak coupling formula gives a reasonable estimate of the local eigenvalue compared with global hybrid simulation using XHMGC. The non-perturbative effect of energetic particles on global mode structure symmetry breaking in radial and parallel (along B) directions is demonstrated. With the contribution from energetic particles, two dimensional (radial and poloidal) BAE mode structures with symmetric/asymmetric tails are produced using an analytical model. It is demonstrated that the symmetry breaking in radial and parallel directions is intimately connected. The effects of mode structure symmetry breaking on nonlinear physics, energetic particle transport, and the possible insight for experimental studies are discussed.

Kaolinite-catalyzed air oxidation of hydrazine: Consideration of several compositional, structural and energetic factors in surface activation

NASA Technical Reports Server (NTRS)

Coyne, L. M.; Mariner, R.; Rice, A.

1991-01-01

Clay minerals have been shown to have numerous, curious, energetic properties by virtue of ultra-violet light release which can be triggered by gentle environmental changes such as wetting and dewetting by a variety of liquids, unique among them water and hydrazine. Since both water and hydrazine play multiple key roles in the air-oxidation of hydrazine on kaolinite surfaces, this reaction would seem to have prime potential for studying interrelationships of energy storage, release and chemical reactivity of clay surfaces, capacities basic to either the Bernal or Cairns-Smith roles of minerals in the origin of life. Establishment of the capacity for stored electronic energy to significantly alter surface chemistry is important, regardless of the reaction chosen to demonstrate it. Hydrazine air oxidation is overawingly complex, given the possibilities for step-wise control and monitoring of parameters. In the light of recently extended characterization of the kaolinite and model sheet catalysts we used to study hydrazine oxidation and gamma-irradiated silica, previous studies of hydrazine air-oxidation on aluminosilicate surfaces have been reevaluated. Our former conclusion remains intact that, whereas trace structural and surface contaminants do play some role in the catalysis of oxidation, they are not the only, nor even the dominant, catalytic centers. Initial intermediates in the oxidation can now be proposed which are consistent with production via O(-)-centers as well as ferric iron centers. The greater than square dependence of the initial reaction rate on the weight of the clay is discussed in the light of these various mechanistic possibilities.

The role of energetic ions from plasma in the creation of nanostructured materials and stable polymer surface treatments

NASA Astrophysics Data System (ADS)

Bilek, M. M. M.; Newton-McGee, K.; McKenzie, D. R.; McCulloch, D. G.

2006-01-01

Plasma processes for the synthesis of new materials as thin films have enabled the production of a wide variety of new materials. These include meta-stable phases, which are not readily found in nature, and more recently, materials with structure on the nanoscale. Study of plasma synthesis processes at the fundamental level has revealed that ion energy, depositing flux and growth surface temperature are the critical parameters affecting the microstructure and the properties of the thin film materials formed. In this paper, we focus on the role of ion flux and impact energy in the creation of thin films with nanoscale structure in the form of multilayers. We describe three synthesis strategies, based on the extraction of ions from plasma sources and involving modulation of ion flux and ion energy. The microstructure, intrinsic stress and physical properties of the multilayered samples synthesized are studied and related back to the conditions at the growth surface during deposition. When energetic ions of a non-condensing species are used, it is possible to place active groups on the surfaces of materials such as polymers. These active groups can then be used as bonding sites in subsequent chemical attachment of proteins or other macromolecules. If the energy of the non-condensing ions is increased to a few keV then modified layers buried under the surface can be produced. Here we describe a method by which the aging effect, which is often observed in plasma surface modifications on polymers, can be reduced and even eliminated using high energy ion bombardment.

Energetic charged particle interactions at icy satellites

NASA Astrophysics Data System (ADS)

Nordheim, T.; Hand, K. P.; Paranicas, C.; Howett, C.; Hendrix, A. R.

2016-12-01

Satellites embedded within planetary magnetospheres are typically exposed to bombardment by charged particles, from thermal plasma to more energetic particles at radiation belt energies. At many planetary satellites, energetic charged particles are typically unimpeded by patchy atmospheres or induced satellite magnetic fields and instead are stopped in the surface itself. Most of these primaries have ranges in porous water ice that are at most centimeters, but some of their secondary photons, emitted during the deceleration process, can reach meter depths [Paranicas et al., 2002, 2004; Johnson et al., 2004]. Examples of radiation-induced surface alteration includes sputtering, radiolysis and grain sintering, processes that are capable of significantly altering the physical properties of surface material. Thus, accurate characterization of energetic charged particle weathering at icy satellites is crucial to a more comprehensive understanding of these bodies. At Saturn's inner mid-size moons remote sensing observations by several instruments onboard the Cassini spacecraft have revealed distinct weathering patterns which have been attributed to energetic electron bombardment of the surface [Howett et al., 2011, 2012, 2014; Schenk et al., 2011; Paranicas et al., 2014]. In the Jovian system, radiolytic production of oxidants has been invoked as a potential source of energy for life which may reside in the sub-surface ocean of its satellite Europa [Johnson et al., 2003; Hand et al., 2007; Vance et al., 2016]. Here we will discuss the near-surface energetic charged particle environment of icy satellites, with particular emphasis on comparative studies between the Saturnian and Jovian systems and interpretation of remote sensing observations by instruments onboard missions such as Cassini and Galileo. In addition, we will discuss implications for surface sampling by future lander missions (e.g. the proposed Europa lander now under study).

A structural study of the K adsorption site on a Si(001)2 × 1 surface: Dimer, caves or both

NASA Astrophysics Data System (ADS)

Asensio, M. C.; Michel, E. G.; Alvarez, J.; Ocal, C.; Miranda, R.; Ferrer, S.

1989-04-01

The atomic structure of the clean Si(100) and K covered surfaces has been investigated by Auger electron diffraction (AED) monitoring the intensities along polar scans. This technique is sensitive to the asymmetric-dimer nature of the 2 × 1 reconstruction of the Si(001) surface. Data taken at room temperature for submonolayer coverages are consistent with adsorption of K on the troughs (cave position) existing between two consecutive dimer chains along the [110] direction. At 110 K both dimer and cave sites are occupied. A mild annealing to 300 K produces an overlayer redistribution in favor of the "cave" site further indicating that this site is energetically favoured as found in some recent calculations.

First-principles calculations of the thermal stability of Ti 3SiC 2(0001) surfaces

NASA Astrophysics Data System (ADS)

Orellana, Walter; Gutiérrez, Gonzalo

2011-12-01

The energetic, thermal stability and dynamical properties of the ternary layered ceramic Ti3SiC2(0001) surface are addressed by density-functional theory calculations and molecular dynamic (MD) simulations. The equilibrium surface energy at 0 K of all terminations is contrasted with thermal stability at high temperatures, which are investigated by ab initio MD simulations in the range of 800 to 1400 °C. We find that the toplayer (sublayer) surface configurations: Si(Ti2) and Ti2(Si) show the lowest surface energies with reconstruction features for Si(Ti2). However, at high temperatures they are unstable, forming disordered structures. On the contrary, Ti1(C) and Ti2(C) despite their higher surface energies, show a remarkable thermal stability at high temperatures preserving the crystalline structures up to 1400 °C. The less stable surfaces are those terminated in C atoms, C(Ti1) and C(Ti2), which at high temperatures show surface dissociation forming amorphous TiCx structures. Two possible atomic scale mechanisms involved in the thermal stability of Ti3SiC2(0001) are discussed.

Understanding structure, metal distribution, and water adsorption in mixed-metal MOF-74

DOE PAGES

Howe, Joshua D.; Morelock, Cody R.; Jiao, Yang; ...

2016-11-30

We present a joint computational and experimental study of Mg–Ni-MOF-74 and Mg–Cd-MOF-74 to gain insight into the mixing of metals and understand how metal mixing affects the structure of the undercoordinated open-metal sites. Our calculations predict that metal mixing is energetically preferred in these materials. Recent experimental work has demonstrated that Mg–Ni-MOF-74 shows a much greater surface area retention in the presence of water than Mg-MOF-74. To probe this effect, we study H 2O adsorption in Mg–Ni-MOF-74, finding that the adsorption energetics and electronic structure do not change significantly at the metal sites when compared to Mg-MOF-74 and Ni-MOF-74, respectively.more » Lastly, we conclude that the increased stability of Mg–Ni-MOF-74 is a result of a M–O bond length distortion in mixed-metal MOF-74, consistent with recent work on the stability of MOF-74 under water exposure.« less

Three-dimensional simulations of void collapse in energetic materials

NASA Astrophysics Data System (ADS)

Rai, Nirmal Kumar; Udaykumar, H. S.

2018-03-01

The collapse of voids in porous energetic materials leads to hot-spot formation and reaction initiation. This work advances the current knowledge of the dynamics of void collapse and hot-spot formation using 3D reactive void collapse simulations in HMX. Four different void shapes, i.e., sphere, cylinder, plate, and ellipsoid, are studied. For all four shapes, collapse generates complex three-dimensional (3D) baroclinic vortical structures. The hot spots are collocated with regions of intense vorticity. The differences in the vortical structures for the different void shapes are shown to significantly impact the relative sensitivity of the voids. Voids of high surface area generate hot spots of greater intensity; intricate, highly contorted vortical structures lead to hot spots of corresponding tortuosity and therefore enhanced growth rates of reaction fronts. In addition, all 3D voids are shown to be more sensitive than their two-dimensional (2D) counterparts. The results provide physical insights into hot-spot formation and growth and point to the limitations of 2D analyses of hot-spot formation.

Cysteine and cystine adsorption on FeS2(100)

NASA Astrophysics Data System (ADS)

Suzuki, Teppei; Yano, Taka-aki; Hara, Masahiko; Ebisuzaki, Toshikazu

2018-08-01

Iron pyrite (FeS2) is the most abundant metal sulfide on Earth. Owing to its reactivity and catalytic activity, pyrite has been studied in various research fields such as surface science, geochemistry, and prebiotic chemistry. Importantly, native iron-sulfur clusters are typically coordinated by cysteinyl ligands of iron-sulfur proteins. In the present paper, we study the adsorption of L-cysteine and its oxidized dimer, L-cystine, on the FeS2 surface, using electronic structure calculations based density functional theory and Raman spectroscopy measurements. Our calculations suggest that sulfur-deficient surfaces play an important role in the adsorption of cysteine and cystine. In the thiol headgroup adsorption on the sulfur-vacancy site, dissociative adsorption is found to be energetically favorable compared with molecular adsorption. In addition, the calculations indicate that, in the cystine adsorption on the defective surface under vacuum conditions, the formation of the S-Fe bond is energetically favorable compared with molecular adsorption. Raman spectroscopic measurements suggest the formation of cystine molecules through the S-S bond on the pyrite surface in aqueous solution. Our results might have implications for chemical evolution at mineral surfaces on the early Earth and the origin of iron-sulfur proteins, which are believed to be one of the most ancient families of proteins.

Organized energetic composites based on micro and nanostructures and methods thereof

DOEpatents

Gash, Alexander E.; Han, Thomas Yong-Jin; Sirbuly, Donald J.

2012-09-04

An ordered energetic composite structure according to one embodiment includes an ordered array of metal fuel portions; and an oxidizer in gaps located between the metal fuel portions. An ordered energetic composite structure according to another embodiment includes at least one metal fuel portion having an ordered array of nanopores; and an oxidizer in the nanopores. A method for forming an ordered energetic composite structure according to one embodiment includes forming an ordered array of metal fuel portions; and depositing an oxidizer in gaps located between the metal fuel portions. A method for forming an ordered energetic composite structure according to another embodiment includes forming an ordered array of nanopores in at least one metal fuel portion; and depositing an oxidizer in the nanopores.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Howe, Joshua D.; Morelock, Cody R.; Jiao, Yang

We present a joint computational and experimental study of Mg–Ni-MOF-74 and Mg–Cd-MOF-74 to gain insight into the mixing of metals and understand how metal mixing affects the structure of the undercoordinated open-metal sites. Our calculations predict that metal mixing is energetically preferred in these materials. Recent experimental work has demonstrated that Mg–Ni-MOF-74 shows a much greater surface area retention in the presence of water than Mg-MOF-74. To probe this effect, we study H 2O adsorption in Mg–Ni-MOF-74, finding that the adsorption energetics and electronic structure do not change significantly at the metal sites when compared to Mg-MOF-74 and Ni-MOF-74, respectively.more » Lastly, we conclude that the increased stability of Mg–Ni-MOF-74 is a result of a M–O bond length distortion in mixed-metal MOF-74, consistent with recent work on the stability of MOF-74 under water exposure.« less

Effect of Electronic Excitation on Hydrogen Atom Transfer (Tautomerization) Reactions for the DNA Base Adenine

NASA Technical Reports Server (NTRS)

Chaban, Galina M.; Salter, Latasha M.; Kwak, Dochan (Technical Monitor)

2002-01-01

Geometrical structures and energetic properties for four different tautomers of adenine are calculated in this study, using multi-configurational wave functions. Both the ground and the lowest single excited state potential energy surface are studied. The energetic order of the tautomers on the ground state potential surface is 9H less than 7H less than 3H less than 1H, while on the excited state surface this order is found to be different: 3H less than 1H less than 9H less than 7H. Minimum energy reaction paths are obtained for hydrogen atom transfer (9 yields 3 tautomerization) reactions in the ground and the lowest excited electronic state. It is found that the barrier heights and the shapes of the reaction paths are different for the ground and the excited electronic state, suggesting that the probability of such tautomerization reaction is higher on the excited state potential energy surface. The barrier for this reaction in the excited state may become very low in the presence of water or other polar solvent molecules, and therefore such tautomerization reaction may play an important role in the solution phase photochemistry of adenine.

First-principles studies of the v7×v7R19.1° structure of sulfur on the Pd(1 1 1) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alfonso, D.R.

2007-11-01

Density functional theory is used to investigate the v7×v7R19.1° structure of sulfur on the Pd(111) surface. Among the different models that were considered, the densely packed mixed sulfur-metal overlayer structure proposed by Liu et al. [W. Liu, K.A.R. Mitchell, W. Berndt, Surf. Sci. 393 (1997) L119] was found to be the most energetically favorable. This model consists of arrangement of Pd triangles and pentagons on top of Pd(111) with the sulfur atoms at 3/7 monolayer coverage. The dominant mechanism for sulfur interaction with Pd in the overlayer region is the rehybridization of sulfur 3p and metal 4d bands. Simulated scanningmore » tunneling microscopy image for this structure shows some similarity with that obtained from experiment. Our study confirms that surface sulfide with no structural resemblance to its bulk counterparts can form on Pd(111).« less

Structure and energetics of model amphiphilic molecules at the water liquid-vapor interface - A molecular dynamics study

NASA Technical Reports Server (NTRS)

Pohorille, Andrew; Benjamin, Ilan

1993-01-01

A molecular dynamics study of adsorption of p-n-pentylphenol at infinite dilution at the water liquid-vapor interface is reported. The calculated free energy of adsorption is -8.8 +/- 0.7 kcal/mol, in good agreement with the experimental value of -7.3 kcal/mol. The transition between the interfacial region and the bulk solution is sharp and well-defined by energetic, conformational, and orientational criteria. At the water surface, the phenol head group is mostly immersed in aqueous solvent. The most frequent orientation of the hydrocarbon tail is parallel to the interface, due to dispersion interactions with the water surface. This arrangement of the phenol ring and the alkyl chain requires that the chain exhibits a kink. As the polar head group is being moved into the solvent, the chain length increases and the tail becomes increasingly aligned toward the surface normal, such that the nonpolar part of the molecule exposed to water is minimized. The same effect was achieved when phenol was replaced by a more polar head group, phenolate.

Electronic, magnetic and structural properties of Co3O4 (100) surface: a DFT+U study

NASA Astrophysics Data System (ADS)

Hashim, Ameerul Hazeeq; Zayed, Ala'Omar Hasan; Zain, Sharifuddin Md; Lee, Vannajan Sanghiran; Said, Suhana Mohd

2018-01-01

The three most stable (100), (110), and (111) surfaces exposed by Co3O4 are effective catalysts for various oxidation reactions. Among these surfaces, (100) has not yet received ample attention. In this study, we investigated the structural, electronic and magnetic properties of Co3O4 (100) surface using density functional theory calculations. By considering both stoichiometric and nonstoichiometric surface structures of the two possible terminations, A and B. Besides the greater stability of the newly proposed stoichiometric models compared to nonstoichiometric models reported in previous studies, the results show that the B termination is energetically preferred over the entire range of oxygen chemical potentials. Unlike the bulk, Co3+ octahedral ions become magnetic at the surface, which leads to interesting surface magnetic properties. Density of states (DOS) indicate a small band gap of 1.15 eV for the B-stoichiometric model, due to the presence of surface states in the bulk band gap. More polar surface with a very narrow band gap is found in the A-nonstoichiometric model. These surface states may play an important role in the magnetism and metallicity observed experimentally in several Co3O4 systems.

Hybrid quantum and molecular mechanics embedded cluster models for chemistry on silicon and silicon carbide surfaces

NASA Astrophysics Data System (ADS)

Shoemaker, James Richard

Fabrication of silicon carbide (SiC) semiconductor devices are of interest for aerospace applications because of their high-temperature tolerance. Growth of an insulating SiO2 layer on SiC by oxidation is a poorly understood process, and sometimes produces interface defects that degrade device performance. Accurate theoretical models of surface chemistry, using quantum mechanics (QM), do not exist because of the huge computational cost of solving Schrodinger's equation for a molecular cluster large enough to represent a surface. Molecular mechanics (MM), which describes a molecule as a collection of atoms interacting through classical potentials, is a fast computational method, good at predicting molecular structure, but cannot accurately model chemical reactions. A new hybrid QM/MM computational method for surface chemistry was developed and applied to silicon and SiC surfaces. The addition of MM steric constraints was shown to have a large effect on the energetics of O atom adsorption on SiC. Adsorption of O atoms on Si-terminated SiC(111) favors above surface sites, in contrast to Si(111), but favors subsurface adsorption sites on C- terminated SiC(111). This difference, and the energetics of C atom etching via CO2 desorption, can explain the observed poor performance of SiC devices in which insulating layers were grown on C-terminated surfaces.

Modeling of surface effects in crystalline materials within the framework of gradient crystal plasticity

NASA Astrophysics Data System (ADS)

Peng, Xiang-Long; Husser, Edgar; Huang, Gan-Yun; Bargmann, Swantje

2018-03-01

A finite-deformation gradient crystal plasticity theory is developed, which takes into account the interaction between dislocations and surfaces. The model captures both energetic and dissipative effects for surfaces penetrable by dislocations. By taking advantage of the principle of virtual power, the surface microscopic boundary equations are obtained naturally. Surface equations govern surface yielding and hardening. A thin film under shear deformation serves as a benchmark problem for validation of the proposed model. It is found that both energetic and dissipative surface effects significantly affect the plastic behavior.

Cancer: a profit-driven biosystem?

PubMed

Deisboeck, Thomas S

2008-08-01

The argument is made that solid malignant tumors behave as profit-driven biological systems in that they expand their nutrient-uptaking surface to increase energetic revenue, at a comparably low metabolic cost. Within this conceptual framework, cancer cell migration is a critical mechanism as it maximizes systemic surface expansion while minimizing diffusion distance. Treating these tumor systems with adjuvant anti-proliferative regimen only should increase the energetic net gain of the viable cancer cells left behind, hence would facilitate tumor recurrence. Therapeutic attempts to better control tumor (re)growth should therefore aim primarily at containing its surface expansion, thus reducing its energetic revenue, or increasing its metabolic costs or better yet, both.

Cancer: A profit-driven biosystem ?

PubMed Central

Deisboeck, Thomas S.

2008-01-01

The argument is made that solid malignant tumors behave as profit-driven biological systems in that they expand their nutrient-uptaking surface to increase energetic revenue, at a comparably low metabolic cost. Within this conceptual framework, cancer cell migration is a critical mechanism as it maximizes systemic surface expansion while minimizing diffusion distance. Treating these tumor systems with adjuvant anti-proliferative regimen only should increase the energetic net gain of the viable cancer cells left behind, hence would facilitate tumor recurrence. Therapeutic attempts to better control tumor (re)growth should therefore aim primarily at containing its surface expansion, thus reducing its energetic revenue, or increasing its metabolic costs or better yet, both. PMID:18420354

Substrate effect on the growth of Sn thin films

NASA Astrophysics Data System (ADS)

Chakraborty, Suvankar; Menon, Krishnakumar S. R.

2018-05-01

Growth of tin (Sn) on Ag(001), Ag(111) and W(110) substrate has been studied at elevated temperatures (473 K) using x-ray photoemission spectroscopy (XPS) and low energy electron diffraction (LEED). For Sn growth on silver substrates, it is noticed that both Sn 3d and Ag 3d core-level spectra shift in the higher binding energy direction due to the formation of surface alloy with the substrate. In both cases, surface alloy finally transforms into bulk alloy finally reaching bulk Sn value. For Sn growth on W(110) only Sn 3d core-level spectra shift in the higher binding energy direction due to surface core-level effect whereas no shift for tungsten core-level was noticed confirming no alloy formation. Sn is incorporated into the surface of substrate silver layer by removing every alternate or every third silver atoms to relieve the surface tensile stress as confirmed by LEED. On the other hand, tungsten being hard, Sn forms an overlayer structure by sitting in different energetically available positions rather than forming an alloy as energetically also it is not possible. Sn forms alloy with soft substrate silver and form overlayer films with tungsten. These studies are important in understanding the growth mechanism of Sn films on metal substrates.

Boosting protein stability with the computational design of β-sheet surfaces.

PubMed

Kim, Doo Nam; Jacobs, Timothy M; Kuhlman, Brian

2016-03-01

β-sheets often have one face packed against the core of the protein and the other facing solvent. Mutational studies have indicated that the solvent-facing residues can contribute significantly to protein stability, and that the preferred amino acid at each sequence position is dependent on the precise structure of the protein backbone and the identity of the neighboring amino acids. This suggests that the most advantageous methods for designing β-sheet surfaces will be approaches that take into account the multiple energetic factors at play including side chain rotamer preferences, van der Waals forces, electrostatics, and desolvation effects. Here, we show that the protein design software Rosetta, which models these energetic factors, can be used to dramatically increase protein stability by optimizing interactions on the surfaces of small β-sheet proteins. Two design variants of the β-sandwich protein from tenascin were made with 7 and 14 mutations respectively on its β-sheet surfaces. These changes raised the thermal midpoint for unfolding from 45°C to 64°C and 74°C. Additionally, we tested an empirical approach based on increasing the number of potential salt bridges on the surfaces of the β-sheets. This was not a robust strategy for increasing stability, as three of the four variants tested were unfolded. © 2016 The Protein Society.

Stability of M 3S 3 complexes on fcc M(111) surfaces: M = Au, Ag, Cu, and Ni

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Da-Jiang; Lee, Jiyoung; Windus, Theresa L.

Density Functional Theory is utilized to assess the stability of metal (M)-sulfur (S) complexes adsorbed on fcc M(111) surfaces, specifically considering S-decorated planar M trimers, M 3S 3. Scanning Tunneling Microscopy studies have identified structures proposed to be Ni 3S 3 on Ni(111), and Au 3S 3 on Au(111). In addition, Cu 3S 3 on Cu(111) has been suggested to facilitate enhanced Cu surface mass transport. Our analysis considers M 3S 3 complexes for M = Au, Ag, Cu, and Ni, assessing key measures of stability on surfaces, and also comparing behavior with trends in gas-phase stability. These surface andmore » gas-phase analyses are systematically related within the framework of Hess’s law, which allows elucidation of various contributions to the overall energetics. In all cases, the adsorbed complex is stable relative to its separated constituents adsorbed on the terrace. However, only for Ag does one find a negative energy of formation from excess S on terraces and M extracted from kink sites along step edges, implying spontaneous complex formation for this pathway. We interpret various experimental observations in the context of our results for energetics.« less

Stability of M 3S 3 complexes on fcc M(111) surfaces: M = Au, Ag, Cu, and Ni

DOE PAGES

Liu, Da-Jiang; Lee, Jiyoung; Windus, Theresa L.; ...

2018-02-08

Density Functional Theory is utilized to assess the stability of metal (M)-sulfur (S) complexes adsorbed on fcc M(111) surfaces, specifically considering S-decorated planar M trimers, M 3S 3. Scanning Tunneling Microscopy studies have identified structures proposed to be Ni 3S 3 on Ni(111), and Au 3S 3 on Au(111). In addition, Cu 3S 3 on Cu(111) has been suggested to facilitate enhanced Cu surface mass transport. Our analysis considers M 3S 3 complexes for M = Au, Ag, Cu, and Ni, assessing key measures of stability on surfaces, and also comparing behavior with trends in gas-phase stability. These surface andmore » gas-phase analyses are systematically related within the framework of Hess’s law, which allows elucidation of various contributions to the overall energetics. In all cases, the adsorbed complex is stable relative to its separated constituents adsorbed on the terrace. However, only for Ag does one find a negative energy of formation from excess S on terraces and M extracted from kink sites along step edges, implying spontaneous complex formation for this pathway. We interpret various experimental observations in the context of our results for energetics.« less

Energetically Unfavorable Amide Conformations for N6-Acetyllysine Side Chains in Refined Protein Structures

PubMed Central

Genshaft, Alexander; Moser, Joe-Ann S.; D'Antonio, Edward L.; Bowman, Christine M.; Christianson, David W.

2013-01-01

The reversible acetylation of lysine to form N6-acetyllysine in the regulation of protein function is a hallmark of epigenetics. Acetylation of the positively charged amino group of the lysine side chain generates a neutral N-alkylacetamide moiety that serves as a molecular “switch” for the modulation of protein function and protein-protein interactions. We now report the analysis of 381 N6-acetyllysine side chain amide conformations as found in 79 protein crystal structures and 11 protein NMR structures deposited in the Protein Data Bank (PDB) of the Research Collaboratory for Structural Bioinformatics. We find that only 74.3% of N6-acetyllysine residues in protein crystal structures and 46.5% in protein NMR structures contain amide groups with energetically preferred trans or generously trans conformations. Surprisingly, 17.6% of N6-acetyllysine residues in protein crystal structures and 5.3% in protein NMR structures contain amide groups with energetically unfavorable cis or generously cis conformations. Even more surprisingly, 8.1% of N6-acetyllysine residues in protein crystal structures and 48.2% in NMR structures contain amide groups with energetically prohibitive twisted conformations that approach the transition state structure for cis-trans isomerization. In contrast, 109 unique N-alkylacetamide groups contained in 84 highly-accurate small molecule crystal structures retrieved from the Cambridge Structural Database exclusively adopt energetically preferred trans conformations. Therefore, we conclude that cis and twisted N6-acetyllysine amides in protein structures deposited in the PDB are erroneously modeled due to their energetically unfavorable or prohibitive conformations. PMID:23401043

Effects of a transient sea surface temperature anomaly on the energetics of the Mintz-Arakawa model atmosphere

NASA Technical Reports Server (NTRS)

Chow, S. H.

1974-01-01

The possible response of the atmosphere, as simulated by the two level Mintz-Arakawa global general circulation model, to a transient North Pacific sea surface temperature anomaly is investigated in terms of the energetics both in the spatial and wave number domains. Results indicate that the transient SST variations of reasonable magnitude in the North Pacific Ocean can induce a disturbing effect on the global energetics both in the spatial and wave number domains. The ability of the two level Mintz-Arakawa model to simulate the atmospheric energetics is also examined. Except in the tropics, the model exhibits a reasonable and realistic energy budget.

Decomposition of energetic molecules by interfacing with a catalytic oxide: opportunities and challenges

NASA Astrophysics Data System (ADS)

Wang, Fenggong; Tsyshevsky, Roman; Zverev, Anton; Mitrofanov, Anatoly; Kuklja, Maija

Organic-inorganic interfaces provide both intrigues and opportunities for designing systems that possess properties and functionalities inaccessible by each individual component. In particular, mixing with a photocatalyst may significantly affect the adsorption, decomposition, and photoresponse of organic molecules. Here, we choose the formulation of TiO2 and trinitrotoluene (TNT), a highly catalytic oxide and a prominent explosive, as a prototypical example to explore the interaction at the interface on the photosensitivity of energetic materials. We show that, whether or not a catalytic oxide additive can help molecular decompositions under light illumination depends largely on the band alignment between the oxide surface and the energetic molecule. Furthermore, an oxygen vacancy can lead to the electron density transfer from the surface to the energetic molecules, causing an enhancement of the bonding between molecules and surface and a reduction of the molecular decomposition activation barriers.

The influence of anthropometric, kinematic and energetic variables and gender on swimming performance in youth athletes.

PubMed

Morais, Jorge E; Garrido, Nuno D; Marques, Mário C; Silva, António J; Marinho, Daniel A; Barbosa, Tiago M

2013-12-18

(i) gender; (ii) performance and; (iii) gender versus performance interactions in young swimmers' anthropometric, kinematic and energetic variables. One hundred and thirty six young swimmers (62 boys: 12.76 ± 0.72 years old at Tanner stages 1-2 by self-evaluation; and 64 girls: 11.89 ± 0.93 years old at Tanner stages 1-2 by self-evaluation) were evaluated. Performance, anthropometrics, kinematics and energetic variables were selected. There was a non-significant gender effect on performance, body mass, height, arm span, trunk transverse surface area, stroke length, speed fluctuation, swimming velocity, propulsive efficiency, stroke index and critical velocity. A significant gender effect was found for foot surface area, hand surface area and stroke frequency. A significant sports level effect was verified for all variables, except for stroke frequency, speed fluctuation and propulsive efficiency. Overall, swimmers in quartile 1 (the ones with highest sports level) had higher anthropometric dimensions, better stroke mechanics and energetics. These traits decrease consistently throughout following quartiles up to the fourth one (i.e. swimmers with the lowest sports level). There was a non-significant interaction between gender and sports level for all variables. Our main conclusions were as follows: (i) there are non-significant differences in performance, anthropometrics, kinematics and energetics between boys and girls; (ii) swimmers with best performance are taller, have higher surface areas and better stroke mechanics; (iii) there are non-significant interactions between sports level and gender for anthropometrics, kinematics and energetics.

Thermodynamics of manganese oxides: Sodium, potassium, and calcium birnessite and cryptomelane

PubMed Central

Birkner, Nancy; Navrotsky, Alexandra

2017-01-01

Manganese oxides with layer and tunnel structures occur widely in nature and inspire technological applications. Having variable compositions, these structures often are found as small particles (nanophases). This study explores, using experimental thermochemistry, the role of composition, oxidation state, structure, and surface energy in the their thermodynamic stability. The measured surface energies of cryptomelane, sodium birnessite, potassium birnessite and calcium birnessite are all significantly lower than those of binary manganese oxides (Mn3O4, Mn2O3, and MnO2), consistent with added stabilization of the layer and tunnel structures at the nanoscale. Surface energies generally decrease with decreasing average manganese oxidation state. A stabilizing enthalpy contribution arises from increasing counter-cation content. The formation of cryptomelane from birnessite in contact with aqueous solution is favored by the removal of ions from the layered phase. At large surface area, surface-energy differences make cryptomelane formation thermodynamically less favorable than birnessite formation. In contrast, at small to moderate surface areas, bulk thermodynamics and the energetics of the aqueous phase drive cryptomelane formation from birnessite, perhaps aided by oxidation-state differences. Transformation among birnessite phases of increasing surface area favors compositions with lower surface energy. These quantitative thermodynamic findings explain and support qualitative observations of phase-transformation patterns gathered from natural and synthetic manganese oxides. PMID:28130549

A kinetic model for stress generation in thin films grown from energetic vapor fluxes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chason, E.; Karlson, M.; Colin, J. J.

We have developed a kinetic model for residual stress generation in thin films grown from energetic vapor fluxes, encountered, e.g., during sputter deposition. The new analytical model considers sub-surface point defects created by atomic peening, along with processes treated in already existing stress models for non-energetic deposition, i.e., thermally activated diffusion processes at the surface and the grain boundary. According to the new model, ballistically induced sub-surface defects can get incorporated as excess atoms at the grain boundary, remain trapped in the bulk, or annihilate at the free surface, resulting in a complex dependence of the steady-state stress on themore » grain size, the growth rate, as well as the energetics of the incoming particle flux. We compare calculations from the model with in situ stress measurements performed on a series of Mo films sputter-deposited at different conditions and having different grain sizes. The model is able to reproduce the observed increase of compressive stress with increasing growth rate, behavior that is the opposite of what is typically seen under non-energetic growth conditions. On a grander scale, this study is a step towards obtaining a comprehensive understanding of stress generation and evolution in vapor deposited polycrystalline thin films.« less

Toward rational nanoparticle synthesis: predicting surface intermixing in bimetallic alloy nanocatalysts

DOE PAGES

Roling, Luke T.; Mavrikakis, Manos

2017-09-19

In this paper, we present a database of first-principles calculated activation energy barriers for two competitive processes involving bimetallic adatom-surface permutations of ten transition metals: (i) adatom “hopping” diffusion and (ii) adatom substitution into the surface. We consider the surface structure sensitivity of these events as well as coverage effects. We find that surface hopping mechanisms are facile and always preferred to substitution events on close-packed fcc(111) and hcp(0001) surfaces. However, surface atom substitution is more facile on the more open fcc(100) surfaces and is competitive with adatom surface hopping, which is more difficult than on the close-packed surfaces. Finally,more » by comparing the absolute and relative magnitudes of the energetics of hopping and substitution, our calculations can offer qualitative predictions of intermixing and other phenomena relevant to nanocrystal growth, such as the tendency to form intermixed alloys or core–shell structures during layer-by-layer nanoparticle synthesis involving a given bimetallic pair, and thereby inform the rational design and synthesis of novel bimetallic nanomaterials.« less

2009 Insensitive Munitions and Energetic Materials Technology Symposium

DTIC Science & Technology

2009-05-14

Multilayer Structure 1D STIMULI Flat end rod Round end rod Flat cookie -cutter Spherical fragment Simple shaped charge jet Real shaped charge jet Thin plate... cookie -cutter Spherical fragment Simple shaped charge jet Real shaped charge jet Thin plate Constant Temperature Rising Temperature Multilayer...Propellants  Plasticizer mixed into the Propellant - Dough NO SURFACE COATING Formulation Impetus (J/g) Flame Temp (K) Mw (g/mole) A

Hemispheric and Topographic Asymmetry of Magnetospheric Particle Irradiation for Icy Moon Surfaces

NASA Technical Reports Server (NTRS)

Cooper, John F.; Sturner, S. J.

2007-01-01

All surfaces of icy moons without significant atmospheres, i.e. all except Titan in the giant planet systems, are irradiated by hot plasma and more energetic charged particles from the local magnetospheric environments. This irradiation can significantly impact the chemical composition, albedo, and detectable presence of signs of life on the sensible surfaces, while also limiting lifetimes and science operations of orbital spacecraft for extreme radiation environments as at Europa. Planning of surface remote sensing and lander operations, and interpretation of remote sensing and in-situ measurements, should include consideration of natural shielding afforded by the body of the moon, by any intrinsic or induced magnetic fields as at Ganyrnede, and by topographic structures.

Final Report: Mechanisms of sputter ripple formation: coupling among energetic ions, surface kinetics, stress and composition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chason, Eric; Shenoy, Vivek

Self-organized pattern formation enables the creation of nanoscale surface structures over large areas based on fundamental physical processes rather than an applied template. Low energy ion bombardment is one such method that induces the spontaneous formation of a wide variety of interesting morphological features (e.g., sputter ripples and/or quantum dots). This program focused on the processes controlling sputter ripple formation and the kinetics controlling the evolution of surfaces and nanostructures in high flux environments. This was done by using systematic, quantitative experiments to measure ripple formation under a variety of processing conditions coupled with modeling to interpret the results.

A high-resolution simulation of Supertyphoon Rammasun (2014)—Part I: Model verification and surface energetics analysis

NASA Astrophysics Data System (ADS)

Zhang, Xinghai; Duan, Yihong; Wang, Yuqing; Wei, Na; Hu, Hao

2017-06-01

A 72-h high-resolution simulation of Supertyphoon Rammasun (2014) is performed using the Advanced Research Weather Research and Forecasting model. The model covers an initial 18-h spin-up, the 36-h rapid intensification (RI) period in the northern South China Sea, and the 18-h period of weakening after landfall. The results show that the model reproduces the track, intensity, structure of the storm, and environmental circulations reasonably well. Analysis of the surface energetics under the storm indicates that the storm's intensification is closely related to the net energy gain rate ( ɛ g), defined as the difference between the energy production ( P D) due to surface entropy flux and the energy dissipation ( D S) due to surface friction near the radius of maximum wind (RMW). Before and during the RI stage, the ɛ g is high, indicating sufficient energy supply for the storm to intensify. However, the ɛ g decreases rapidly as the storm quickly intensifies, because the DS increases more rapidly than the P D near the RMW. By the time the storm reaches its peak intensity, the D S is about 20% larger than the P D near the RMW, leading to a local energetics deficit under the eyewall. During the mature stage, the P D and D S can reach a balance within a radius of 86 km from the storm center (about 2.3 times the RMW). This implies that the local P D under the eyewall is not large enough to balance the D S, and the radially inward energy transport from outside the eyewall must play an important role in maintaining the storm's intensity, as well as its intensification.

Structure and stability of CaH 2 surfaces: on the possibility of electron-rich surfaces in metal hydrides for catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ong, Phuong-Vu; Johnson, Lewis E.; Hosono, Hideo

Structure, thermodynamic stability, and electronic properties of CaH 2 surfaces in (001),(110), and (111) crystallographic orientations are investigated using ab initio modeling. We show that stoichiometric surfaces terminated with a hydrogen atomic plane are the most energetically favorable and discuss properties of hydrogen vacancies (VH) at these surfaces. The average calculated work function of the most stable pristine surfaces (~5.2 eV) is in agree-ment with experimental data for powder samples. Neutral hydrogen vacancies host localized electrons and induce defect states in the band gap, thereby shifting the effective work function to much lower values of ~2.7 eV. Surface VH aremore » predicted to aggregate into dimers and form electron-rich centers (e -)Ca 2+(e -) stable to over 800 K. These results suggest that hydrogen-deficient surfaces of CaH 2 can host a large concentration of localized electrons and, thus, give rise to new catalytic functionalities involving electron transfer between the surface, catalysts supported on it, and reacting species.« less

The Role of Structural Enthalpy in Spherical Nucleic Acid Hybridization.

PubMed

Fong, Lam-Kiu; Wang, Ziwei; Schatz, George C; Luijten, Erik; Mirkin, Chad A

2018-05-23

DNA hybridization onto DNA-functionalized nanoparticle surfaces (e.g., in the form of a spherical nucleic acid (SNA)) is known to be enhanced relative to hybridization free in solution. Surprisingly, via isothermal titration calorimetry, we reveal that this enhancement is enthalpically, as opposed to entropically, dominated by ∼20 kcal/mol. Coarse-grained molecular dynamics simulations suggest that the observed enthalpic enhancement results from structurally confining the DNA on the nanoparticle surface and preventing it from adopting enthalpically unfavorable conformations like those observed in the solution case. The idea that structural confinement leads to the formation of energetically more stable duplexes is evaluated by decreasing the degree of confinement a duplex experiences on the nanoparticle surface. Both experiment and simulation confirm that when the surface-bound duplex is less confined, i.e., at lower DNA surface density or at greater distance from the nanoparticle surface, its enthalpy of formation approaches the less favorable enthalpy of duplex formation for the linear strand in solution. This work provides insight into one of the most important and enabling properties of SNAs and will inform the design of materials that rely on the thermodynamics of hybridization onto DNA-functionalized surfaces, including diagnostic probes and therapeutic agents.

Surface states and annihilation characteristics of positrons trapped at the oxidized Cu(100) surface

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Weiss, A. H.

2013-06-01

In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. Oxidation of the Cu(100) surface has been studied by performing an ab-initio investigation of the stability and electronic structure of the Cu(100) missing row reconstructed surface at various on-surface and subsurface oxygen coverages ranging from 0.5 to 1.5 monolayers using density functional theory (DFT). All studied structures have been found to be energetically more favorable as compared to structures formed by purely on-surface oxygen adsorption. The observed decrease in the positron work function when oxygen atoms occupy on-surface and subsurface sites has been attributed to a significant charge redistribution within the first two layers, buckling effects within each layer and an interlayer expansion. The computed positron binding energy, positron surface state wave function, and annihilation probabilities of the surface trapped positrons with relevant core electrons demonstrate their sensitivity to oxygen coverage, atomic structure of the topmost layers of surfaces, and charge transfer effects. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES). The results presented provide an explanation for the changes observed in the probability of annihilation of surface trapped positrons with Cu 3p core-level electrons as a function of annealing temperature.

Interfacial Interaction of Titania Nanoparticles and Ligated Uranyl Species: A Relativistic DFT Investigation.

PubMed

Zhao, Hong-Bo; Zheng, Ming; Schreckenbach, Georg; Pan, Qing-Jiang

2017-03-06

To understand interfacial behavior of actinides adsorbed onto mineral surfaces and unravel their structure-property relationship, the structures, electronic properties, and energetics of various ligated uranyl species adsorbed onto TiO 2 surface nanoparticle clusters (SNCs) were examined using relativistic density functional theory. Rutile (110) and anatase (101) titania surfaces, experimentally known to be stable, were fully optimized. For the former, models studied include clean and water-free Ti 27 O 64 H 20 (dry), partially hydrated (Ti 27 O 64 H 20 )(H 2 O) 8 (sol) and proton-saturated [(Ti 27 O 64 H 20 )(H 2 O) 8 (H) 2 ] 2+ (sat), while defect-free and defected anatase SNCs involving more than 38 TiO 2 units were considered. The aquouranyl sorption onto rutile SNCs is energetically preferred, with interaction energies of -8.54, -10.36, and -2.39 eV, respectively. Energy decomposition demonstrates that the sorption is dominated by orbital attractive interactions and modified by steric effects. Greater hydrogen-bonding involvement leads to increased orbital interactions (i.e., more negative energy) from dry to sol/sat complexes, while much larger steric interaction in the sat complex significantly reduces the sorption interaction (i.e., more positive energy). For dry SNC, adsorbates were varied from aquo to aquo-carbonato, to carbonato, to hydroxo uranyl species. Longer U-O surf /U-Ti distances and more positive sorption energies were calculated upon introducing carbonato and hydroxo ligands, indicative of weaker uranyl sorption onto the substrate. This is consistent with experimental observations that the uranyl sorption rate decreases upon raising solution pH value or adding carbon dioxide. Anatase SNCs adsorbing aquouranyl are even more exothermic, because more bonds are formed than in the case of rutile. Moreover, the anatase sorption can be tuned by surface defects as well as its Ti and O stoichiometry. All the aquouranyl-SNC complexes show similar character of molecular orbitals and energetic order although differing in highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps and orbital energy levels, but changes can be accomplished by adding carbonato and hydroxo ligands.

Off-axis fishbone-like instability and excitation of resistive wall modes in JT-60U and DIII-D

DOE Office of Scientific and Technical Information (OSTI.GOV)

Okabayashi, M.; Solomon, W. M.; Budny, R. V.

2011-05-15

An energetic-particle (EP)-driven ''off-axis-fishbone-like mode (OFM)'' often triggers a resistive wall mode (RWM) in JT-60U and DIII-D devices, preventing long-duration high-{beta}{sub N} discharges. In these experiments, the EPs are energetic ions (70-85 keV) injected by neutral beams to produce high-pressure plasmas. EP-driven bursting events reduce the EP density and the plasma rotation simultaneously. These changes are significant in high-{beta}{sub N} low-rotation plasmas, where the RWM stability is predicted to be strongly influenced by the EP precession drift resonance and by the plasma rotation near the q=2 surface (kinetic effects). Analysis of these effects on stability with a self-consistent perturbation tomore » the mode structure using the MARS-K code showed that the impact of EP losses and rotation drop is sufficient to destabilize the RWM in low-rotation plasmas, when the plasma rotation normalized by Alfven frequency is only a few tenths of a percent near the q=2 surface. The OFM characteristics are very similar in JT-60U and DIII-D, including nonlinear mode evolution. The modes grow initially like a classical fishbone, and then the mode structure becomes strongly distorted. The dynamic response of the OFM to an applied n=1 external field indicates that the mode retains its external kink character. These comparative studies suggest that an energetic particle-driven 'off-axis-fishbone-like mode' is a new EP-driven branch of the external kink mode in wall-stabilized plasmas, analogous to the relationship of the classical fishbone branch to the internal kink mode.« less

Vibrational spectroscopy and molecular dynamics of water monomers and dimers adsorbed on polycyclic aromatic hydrocarbons.

PubMed

Simon, Aude; Rapacioli, Mathias; Mascetti, Joëlle; Spiegelman, Fernand

2012-05-21

This paper reports structures, energetics, dynamics and spectroscopy of H2O and (H2O)2 systems adsorbed on coronene (C24H12), a compact polycyclic aromatic hydrocarbon (PAH). On-the-fly Born-Oppenheimer molecular dynamics simulations are performed for temperatures T varying from 10 to 300 K, on a potential energy surface obtained within the self-consistent-charge density-functional based tight-binding (SCC-DFTB) approach. Anharmonic infrared (IR) spectra are extracted from these simulations. We first benchmark the SCC-DFTB semi-empirical hamiltonian vs. DFT (Density Functional Theory) calculations that include dispersion, on (C6H6)(H2O)1,2 small complexes. We find that charge corrections and inclusion of dispersion contributions in DFTB are necessary to obtain consistent structures, energetics and IR spectra. Using this Hamiltonian, the structures, energetics and IR features of the low-energy isomers of (C24H12)(H2O)1,2 are found to be similar to the DFT ones, with evidence for a stabilizing edge-coordination. The temperature dependence of the motions of H2O and (H2O)2 on the surface of C24H12 is analysed, revealing ultra-fast periodic motion. The water dimer starts diffusing at a higher temperature than the water monomer (150 K vs. 10 K respectively), which appears to be consistent with the binding energies. Qualitative and quantitative analyses of the effects of T on the IR spectra are performed. Anharmonic factors in particular are derived and it is shown that they can be used as signatures for the presence of PAH-water complexes. Finally, this paper lays the foundations for the studies of larger (PAH)m(H2O)n clusters, that can be treated with the efficient computational approach benchmarked in this paper.

Atomistic Method Applied to Computational Modeling of Surface Alloys

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo H.; Abel, Phillip B.

2000-01-01

The formation of surface alloys is a growing research field that, in terms of the surface structure of multicomponent systems, defines the frontier both for experimental and theoretical techniques. Because of the impact that the formation of surface alloys has on surface properties, researchers need reliable methods to predict new surface alloys and to help interpret unknown structures. The structure of surface alloys and when, and even if, they form are largely unpredictable from the known properties of the participating elements. No unified theory or model to date can infer surface alloy structures from the constituents properties or their bulk alloy characteristics. In spite of these severe limitations, a growing catalogue of such systems has been developed during the last decade, and only recently are global theories being advanced to fully understand the phenomenon. None of the methods used in other areas of surface science can properly model even the already known cases. Aware of these limitations, the Computational Materials Group at the NASA Glenn Research Center at Lewis Field has developed a useful, computationally economical, and physically sound methodology to enable the systematic study of surface alloy formation in metals. This tool has been tested successfully on several known systems for which hard experimental evidence exists and has been used to predict ternary surface alloy formation (results to be published: Garces, J.E.; Bozzolo, G.; and Mosca, H.: Atomistic Modeling of Pd/Cu(100) Surface Alloy Formation. Surf. Sci., 2000 (in press); Mosca, H.; Garces J.E.; and Bozzolo, G.: Surface Ternary Alloys of (Cu,Au)/Ni(110). (Accepted for publication in Surf. Sci., 2000.); and Garces, J.E.; Bozzolo, G.; Mosca, H.; and Abel, P.: A New Approach for Atomistic Modeling of Pd/Cu(110) Surface Alloy Formation. (Submitted to Appl. Surf. Sci.)). Ternary alloy formation is a field yet to be fully explored experimentally. The computational tool, which is based on the BFS (Bozzolo, Ferrante, and Smith) method for the calculation of the energetics, consists of a small number of simple PCbased computer codes that deal with the different aspects of surface alloy formation. Two analysis modes are available within this package. The first mode provides an atom-by-atom description of real and virtual stages 1. during the process of surface alloying, based on the construction of catalogues of configurations where each configuration describes one possible atomic distribution. BFS analysis of this catalogue provides information on accessible states, possible ordering patterns, and details of island formation or film growth. More importantly, it provides insight into the evolution of the system. Software developed by the Computational Materials Group allows for the study of an arbitrary number of elements forming surface alloys, including an arbitrary number of surface atomic layers. The second mode involves large-scale temperature-dependent computer 2. simulations that use the BFS method for the energetics and provide information on the dynamic processes during surface alloying. These simulations require the implementation of Monte-Carlo-based codes with high efficiency within current workstation environments. This methodology capitalizes on the advantages of the BFS method: there are no restrictions on the number or type of elements or on the type of crystallographic structure considered. This removes any restrictions in the definition of the configuration catalogues used in the analytical calculations, thus allowing for the study of arbitrary ordering patterns, ultimately leading to the actual surface alloy structure. Moreover, the Monte Carlo numerical technique used for the large-scale simulations allows for a detailed visualization of the simulated process, the main advantage of this type of analysis being the ability to understand the underlying features that drive these processes. Because of the simplicity of the BFS method for e energetics used in these calculations, a detailed atom-by-atom analysis can be performed at any point in the simulation, providing necessary insight on the details of the process. The main objective of this research program is to develop a tool to guide experimenters in understanding and interpreting often unexpected results in alloy formation experiments. By reducing the computational effort without losing physical accuracy, we expect that powerful simulation tools will be developed in the immediate future, which will allow material scientists to easily visualize and analyze processes at a level not achievable experimentally.

Zinc-blende MnN bilayer formation on the GaN(111) surface

NASA Astrophysics Data System (ADS)

Gutierrez-Ojeda, S. J.; Guerrero-Sánchez, J.; Garcia-Diaz, R.; Ramirez-Torres, A.; Takeuchi, Noboru; H. Cocoletzi, Gregorio

2017-07-01

Atomic layers of manganese nitride, deposited on the cubic gallium nitride (111) surface, are investigated using spin polarized periodic density functional theory calculations. The adsorption of a manganese atom has been evaluated at different high symmetry sites. Incorporation into the GaN substrate by replacing gallium atoms drives the formation of a site in which the displaced Ga atom forms bonds with Ga atoms at the surface. This energetically favorable configuration shows a ferromagnetic alignment. Surface formation energy calculations demonstrate that when a full Mn ML is incorporated into the GaN structure, a Ga ML on top of a MnN bilayer may be formed for very Ga-rich conditions. On the other hand, when a full Mn ML is deposited on top of the nitrogen terminated surface, an epitaxial MnN bilayer is formed with antiferromagnetic characteristics. Density of states and partial density of states are reported to show the antiferromagnetic alignment in both structures. This behavior is mainly induced by the Mn-d orbitals.

Effects of Coronal Magnetic Field Structures on the Transport of Solar Energetic Particles

NASA Astrophysics Data System (ADS)

Zhao, Lulu; Zhang, Ming

2018-06-01

This Letter presents a model calculation of solar energetic particle (SEP) transport to test the sensitivity of the distribution of escaped SEPs in interplanetary space and dependence upon the details of the magnetic field structure in the corona. It is applied to a circumsolar event on 2011 November 3, in which SEPs are observed promptly after the solar event eruption by three spacecraft (the twin Solar TErrestrial RElations Observatories (STEREO-A and STEREO-B) and ACE) separated by more than 100° in longitude from each other. The corona magnetic field reconstructed from photosphseric field measurements using the PFSS method changes substantially before and after the solar eruption, especially around the active region. The locations of open field regions, separatrix surfaces including the heliospheric current sheet, and footpoints of magnetic field lines connected to the spacecraft location have shifted substantially. We inject 100 keV energetic electrons on the open field lines at 1.5 R s within the size of observed coronal mass ejections (CMEs) and follow their propagation in the corona and the interplanetary space. We find that with a perpendicular diffusion due to field line random walk equal to 10% of the supergranular diffusion rate, the overall distribution of escaped SEPs does not change much even though the region of open field lines from SEPs has changed. The result suggests that detailed small-scale coronal magnetic field structures and the exact magnetic field connection are not crucially important for observing SEPs in the interplanetary space.

Trigger mechanism for the abrupt loss of energetic ions in magnetically confined plasmas.

PubMed

Ida, K; Kobayashi, T; Yoshinuma, M; Akiyama, T; Tokuzawa, T; Tsuchiya, H; Itoh, K; Itoh, S-I

2018-02-12

Interaction between a quasi-stable stationary MHD mode and a tongue-shaped deformation is observed in the toroidal plasma with energetic particle driven MHD bursts. The quasi-stable stationary 1/1 MHD mode with interchange parity appears near the resonant rational surface of q = 1 between MHD bursts. The tongue-shaped deformation rapidly appears at the non-resonant non-rational surface as a localized large plasma displacement and then collapses (tongue event). It curbs the stationary 1/1 MHD mode and then triggers the collapse of energetic particle and magnetic field reconnection. The rotating 1/1 MHD mode with tearing parity at the q = 1 resonant surface, namely, the MHD burst, is excited after the tongue event.

Energetic Particles Dynamics in Mercury's Magnetosphere

NASA Technical Reports Server (NTRS)

Walsh, Brian M.; Ryou, A.S.; Sibeck, D. G.; Alexeev, I. I.

2013-01-01

We investigate the drift paths of energetic particles in Mercury's magnetosphere by tracing their motion through a model magnetic field. Test particle simulations solving the full Lorentz force show a quasi-trapped energetic particle population that gradient and curvature drift around the planet via "Shabansky" orbits, passing though high latitudes in the compressed dayside by equatorial latitudes on the nightside. Due to their large gyroradii, energetic H+ and Na+ ions will typically collide with the planet or the magnetopause and will not be able to complete a full drift orbit. These simulations provide direct comparison for recent spacecraft measurements from MESSENGER. Mercury's offset dipole results in an asymmetric loss cone and therefore an asymmetry in particle precipitation with more particles precipitating in the southern hemisphere. Since the planet lacks an atmosphere, precipitating particles will collide directly with the surface of the planet. The incident charged particles can kick up neutrals from the surface and have implications for the formation of the exosphere and weathering of the surface

Chlorine adsorption on the InAs (001) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bakulin, A. V.; Eremeev, S. V.; Tereshchenko, O. E.

2011-01-15

Chlorine adsorption on the In-stabilized InAs(001) surface with {zeta}-(4 Multiplication-Sign 2) and {beta}3 Prime -(4 Multiplication-Sign 2) reconstructions and on the Ga-stabilized GaAs (001)-{zeta}-(4 Multiplication-Sign 2) surface has been studied within the electron density functional theory. The equilibrium structural parameters of these reconstructions, surface atom positions, bond lengths in dimers, and their changes upon chlorine adsorption are determined. The electronic characteristics of the clean surface and the surface with adsorbed chlorine are calculated. It is shown that the most energetically favorable positions for chlorine adsorption are top positions over dimerized indium or gallium atoms. The mechanism of chlorine binding withmore » In(Ga)-stabilized surface is explained. The interaction of chlorine atoms with dimerized surface atoms weakens surface atom bonds and controls the initial stage of surface etching.« less

Structure of Energetic Particle Mediated Shocks Revisited

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mostafavi, P.; Zank, G. P.; Webb, G. M.

2017-05-20

The structure of collisionless shock waves is often modified by the presence of energetic particles that are not equilibrated with the thermal plasma (such as pickup ions [PUIs] and solar energetic particles [SEPs]). This is relevant to the inner and outer heliosphere and the Very Local Interstellar Medium (VLISM), where observations of shock waves (e.g., in the inner heliosphere) show that both the magnetic field and thermal gas pressure are less than the energetic particle component pressures. Voyager 2 observations revealed that the heliospheric termination shock (HTS) is very broad and mediated by energetic particles. PUIs and SEPs contribute bothmore » a collisionless heat flux and a higher-order viscosity. We show that the incorporation of both effects can completely determine the structure of collisionless shocks mediated by energetic ions. Since the reduced form of the PUI-mediated plasma model is structurally identical to the classical cosmic ray two-fluid model, we note that the presence of viscosity, at least formally, eliminates the need for a gas sub-shock in the classical two-fluid model, including in that regime where three are possible. By considering parameters upstream of the HTS, we show that the thermal gas remains relatively cold and the shock is mediated by PUIs. We determine the structure of the weak interstellar shock observed by Voyager 1 . We consider the inclusion of the thermal heat flux and viscosity to address the most general form of an energetic particle-thermal plasma two-fluid model.« less

"Soft docking": matching of molecular surface cubes.

PubMed

Jiang, F; Kim, S H

1991-05-05

Molecular recognition is achieved through the complementarity of molecular surface structures and energetics with, most commonly, associated minor conformational changes. This complementarity can take many forms: charge-charge interaction, hydrogen bonding, van der Waals' interaction, and the size and shape of surfaces. We describe a method that exploits these features to predict the sites of interactions between two cognate molecules given their three-dimensional structures. We have developed a "cube representation" of molecular surface and volume which enables us not only to design a simple algorithm for a six-dimensional search but also to allow implicitly the effects of the conformational changes caused by complex formation. The present molecular docking procedure may be divided into two stages. The first is the selection of a population of complexes by geometric "soft docking", in which surface structures of two interacting molecules are matched with each other, allowing minor conformational changes implicitly, on the basis of complementarity in size and shape, close packing, and the absence of steric hindrance. The second is a screening process to identify a subpopulation with many favorable energetic interactions between the buried surface areas. Once the size of the subpopulation is small, one may further screen to find the correct complex based on other criteria or constraints obtained from biochemical, genetic, and theoretical studies, including visual inspection. We have tested the present method in two ways. First is a control test in which we docked the components of a molecular complex of known crystal structure available in the Protein Data Bank (PDB). Two molecular complexes were used: (1) a ternary complex of dihydrofolate reductase, NADPH and methotrexate (3DFR in PDB) and (2) a binary complex of trypsin and trypsin inhibitor (2PTC in PDB). The components of each complex were taken apart at an arbitrary relative orientation and then docked together again. The results show that the geometric docking alone is sufficient to determine the correct docking solutions in these ideal cases, and that the cube representation of the molecules does not degrade the docking process in the search for the correct solution. The second is the more realistic experiment in which we docked the crystal structures of uncomplexed molecules and then compared the structures of docked complexes with the crystal structures of the corresponding complexes. This is to test the capability of our method in accommodating the effects of the conformational changes in the binding sites of the molecules in docking.(ABSTRACT TRUNCATED AT 400 WORDS)

Azole energetic materials: Initial mechanisms for the energy release from electronical excited nitropyrazoles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Bing; Yu, Zijun; Bernstein, Elliot R., E-mail: erb@lamar.Colostate.edu

2014-01-21

Decomposition of energetic material 3,4-dinitropyrazole (DNP) and two model molecules 4-nitropyrazole and 1-nitropyrazole is investigated both theoretically and experimentally. The initial decomposition mechanisms for these three nitropyrazoles are explored with complete active space self-consistent field (CASSCF) level. The NO molecule is observed as an initial decomposition product from all three materials subsequent to UV excitation. Observed NO products are rotationally cold (<50 K) for all three systems. The vibrational temperature of the NO product from DNP is (3850 ± 50) K, 1350 K hotter than that of the two model species. Potential energy surface calculations at the CASSCF(12,8)/6-31+G(d) level illustratemore » that conical intersections plays an essential role in the decomposition mechanism. Electronically excited S{sub 2} nitropyraozles can nonradiatively relax to lower electronic states through (S{sub 2}/S{sub 1}){sub CI} and (S{sub 1}/S{sub 0}){sub CI} conical intersection and undergo a nitro-nitrite isomerization to generate NO product either in the S{sub 1} state or S{sub 0} state. In model systems, NO is generated in the S{sub 1} state, while in the energetic material DNP, NO is produced on the ground state surface, as the S{sub 1} decomposition pathway is energetically unavailable. The theoretically predicted mechanism is consistent with the experimental results, as DNP decomposes in a lower electronic state than do the model systems and thus the vibrational energy in the NO product from DNP should be hotter than from the model systems. The observed rotational energy distributions for NO are consistent with the final structures of the respective transition states for each molecule.« less

Lunar Surface Charging during Solar Energetic Particle Events

NASA Astrophysics Data System (ADS)

Halekas, Jasper S.; Delory, G. T.; Mewaldt, R. A.; Lin, R. P.; Fillingim, M. O.; Brain, D. A.; Lee, C. O.; Stubbs, T. J.; Farrell, W. M.; Hudson, M. K.

2006-09-01

The surface of the Moon, not protected by any substantial atmosphere, is directly exposed to the impact of both solar UV and solar wind plasma and energetic particles. This creates a complex lunar electrostatic environment, with the surface typically charging slightly positive in sunlight, and negative in shadow. Observations from the Apollo era and theoretical considerations strongly suggest that surface charging leads to dust electrification and transport, posing a potentially significant hazard for exploration. The most significant charging effects should occur when the Moon is exposed to high-temperature plasmas like those encountered in the terrestrial plasmasheet or in solar storms. We now present evidence for kilovolt-scale negative charging of the shadowed lunar surface during solar energetic particle (SEP) events, utilizing data from the Lunar Prospector Electron Reflectometer (LP ER). We find that SEP events are associated with the most extreme lunar surface charging observed during the LP mission - rivaled only by previously reported charging during traversals of the terrestrial plasmasheet. The largest charging event observed by LP is a 4 kV negative surface potential (as compared to typical values of V) during a SEP event in May 1998. We characterize lunar surface charging during several SEP events, and compare to energetic particle measurements from ACE, Wind, and SOHO in order to determine the relationship between SEP events and extreme lunar surface charging. Space weather events are already considered by NASA to be a significant hazard to lunar exploration, due to high-energy ionizing radiation. Our observations demonstrate that plasma interactions with the lunar surface during SEP events, causing extreme surface charging and potentially significant dust electrification and transport, represent an additional hazard associated with space weather.

Sputtering of rough surfaces: a 3D simulation study

NASA Astrophysics Data System (ADS)

von Toussaint, U.; Mutzke, A.; Manhard, A.

2017-12-01

The lifetime of plasma-facing components is critical for future magnetic confinement fusion power plants. A key process limiting the lifetime of the first-wall is sputtering by energetic ions. To provide a consistent modeling of the sputtering process of realistic geometries, the SDTrimSP-code has been extended to enable the processing of analytic as well as measured arbitrary 3D surface morphologies. The code has been applied to study the effect of varying the impact angle of ions on rough surfaces on the sputter yield as well as the influence of the aspect ratio of surface structures on the 2D distribution of the local sputtering yields. Depending on the surface morphologies reductions of the effective sputter yields to less than 25% have been observed in the simulation results.

Shock Wave Structure Mediated by Energetic Particles

NASA Astrophysics Data System (ADS)

Mostafavi, P.; Zank, G. P.; Webb, G. M.

2016-12-01

Energetic particles such as cosmic rays, Pick Up Ions (PUIs), and solar energetic particles can affect all facets of plasma physics and astrophysical plasma. Energetic particles play an especially significant role in the dissipative process at shocks and in determining their structure. The very interesting recent observations of shocks in the inner heliosphere found that many shocks appear to be significantly mediated by solar energetic particles which have a pressure that exceeds considerably both the thermal gas pressure and the magnetic field pressure. Energetic particles contribute an isotropic scalar pressure to the plasma system at the leading order, as well as introducing dissipation via a collisionless heat flux (diffusion) at the next order and a collisionless stress tensor (viscosity) at the second order. Cosmic-ray modified shocks were discussed by Axford et al. (1982), Drury (1983), and Webb (1983). Zank et al. (2014) investigated the incorporation of PUIs in the supersonic solar wind beyond 10AU, in the inner Heliosheath and in the Very Local Interstellar Medium. PUIs do not equilibrate collisionally with the background plasma in these regimes. In the absence of equilibration between plasma components, a separate coupled plasma description for the energetic particles is necessary. This model is used to investigate the structure of shock waves assuming that we can neglect the magnetic field. Specifically, we consider the dissipative role that both the energetic particle collisionless heat flux and viscosity play in determining the structure of collisionless shock waves. We show that the incorporation of both energetic particle collisionless heat flux and viscosity is sufficient to completely determine the structure of a shock. Moreover, shocks with three sub-shocks converge to the weak sub-shocks. This work differs from the investigation of Jokipii and Williams (1992) who restricted their attention to a cold thermal gas. For a cold thermal non-magnetized gas, all shocks are smoothed by cosmic ray diffusion and therefore viscosity is not an important process.

Analysis of Mass Profiles and Cooling Flows of Bright, Early-Type Galaxies AO2, AO3 and Surface Brightness Profiles and Energetics of Intracluster Gas in Cool Galaxy Clusters AO3

NASA Technical Reports Server (NTRS)

White, Raymond E., III

1998-01-01

This final report uses ROSAT observations to analyze two different studies. These studies are: Analysis of Mass Profiles and Cooling Flows of Bright, Early-Type Galaxies; and Surface Brightness Profiles and Energetics of Intracluster Gas in Cool Galaxy Clusters.

EFFECT OF COHERENT STRUCTURES ON ENERGETIC PARTICLE INTENSITY IN THE SOLAR WIND AT 1 AU

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tessein, Jeffrey A.; Matthaeus, William H.; Wan, Minping

2015-10-10

We present results from an analysis of Advanced Composition Explorer (ACE) observations of energetic particles in the 0.047–4.78 MeV range associated with shocks and discontinuities in the solar wind. Previous work found a strong correlation between coherent structures and energetic particles measured by ACE/EPAM. Coherent structures are identified using the Partial Variance of Increments (PVI) method, which is essentially a normalized vector increment. The correlation was based on a superposed epoch analysis using over 12 years of data. Here, we examine many individual high-PVI events to better understand this association emphasizing intervals selected from data with shock neighborhoods removed. Wemore » find that in many cases the local maximum in PVI is in a region of rising or falling energetic particle intensity, which suggests that magnetic discontinuities may act as barriers inhibiting the motion of energetic particles across them.« less

Energetics of Mg incorporation at GaN(0001) and GaN(0001¯) surfaces

NASA Astrophysics Data System (ADS)

Sun, Qiang; Selloni, Annabella; Myers, T. H.; Doolittle, W. Alan

2006-04-01

By using density functional calculations in the generalized gradient approximation, we investigate the energetics of Mg adsorption and incorporation at GaN(0001) and GaN(0001¯) surfaces under various Ga and Mg coverage conditions as well as in presence of light or electron beam-induced electronic excitation. We find significant differences in Mg incorporation between Ga- and N-polar surfaces. Mg incorporation is easier at the Ga-polar surface, but high Mg coverages are found to cause important distortions which locally change the polarity from Ga to N polar. At the N-rich and moderately Ga-rich GaN(0001) surface, 0.25 ML of Mg substituting Ga in the top bilayer strongly reduce the surface diffusion barriers of Ga and N adatoms, in agreement with the surfactant effect observed in experiments. As the Mg coverage exceeds 0.5 ML, partial incorporation in the subsurface region (second bilayer) becomes favorable. A surface structure with 0.5 ML of incorporated Mg in the top bilayer and 0.25 ML in the second bilayer is found to be stable over a wide range of Ga chemical potential. At the Ga bilayer-terminated GaN(0001) surface, corresponding to Ga-rich conditions, configurations where Mg is incorporated in the interface region between the metallic Ga bilayer and the underlying GaN bilayer appear to be favored. At the N-polar surface, Mg is not incorporated under N-rich or moderately Ga-rich conditions, whereas incorporation in the adlayer may take place under Ga-rich conditions. In the presence of light or electron beam induced excitation, energy differences between Mg incorporated at the surface and in deeper layers are reduced so that the tendency toward surface segregation is also reduced.

Simulation studies for surfaces and materials strength

NASA Technical Reports Server (NTRS)

Halicioglu, T.

1986-01-01

During this reporting period three investigations were carried out. The first area of research concerned the analysis of the structure-energy relationship in small clusters. This study is very closely related to the improvement of the potential energy functions which are suitable and simple enough to be used in atomistic simulation studies. Parameters obtained from ab initio calculations for dimers and trimers of Al were used to estimate energetics and global minimum energy structures of clusters continuing up to 15 Al atoms. The second research topic addressed modeling of the collision process for atoms impinging on surfaces. In this simulation study qualitative aspects of the O atom collision with a graphite surface were analyzed. Four different O/graphite systems were considered and the aftermath of the impact was analyzed. The final area of investigation was related to the simulation of thin amorphous Si films on crystalline Si substrates. Parameters obtained in an earlier study were used to model an exposed amorphous Si surface and an a-Si/c-Si interface. Structural details for various film thicknesses were investigated at an atomistic level.

First-Principles Study of the Self-Assembled Pentacene Molecules on Metal Surfaces

NASA Astrophysics Data System (ADS)

Lee, Kyuho; Han, Myung-Joon; Yu, Jaejun

2003-03-01

Oriented thin films of organic semiconducting small molecules have received considerable attention as active semiconductors for device applications such as Schottky diodes and thin-film transistors (TFTs). Among these organic materials, pentacene has been found to have the highest mobilities for hole transport. Understanding the formation of self-organized ad-layers of pentacene would contribute to the fabrication of nanostructures and possibly highly oriented pentacene layers by epitaxy for use in electronic devices. To understand the ordering patterns of pentacene ad-layers on metal surfaces, we investigated the energetics between pentacene molecules with and without metal substrates and analyzed its electronic structure. We used a self-consistent first-principles calculation method based on the density functional theory (DFT) within local density approximation (LDA). The localized pseudo-atomic orbitals (PAO) are employed for a real-space numerical basis set, which was suggested by Sankey and Niklewski, and the Troullier-Martins-type pseudo-potential is used. As results, we found that the ordering patterns can be explained by the energetics between pentacene molecules, and the metal substrates appears not to influence too much on the interaction between pentacenes. To investigate the nature of the self-assembled structure, we calculated the total energies of various configurations for the molecule pattern, e.g., side-by-side and head-to-head ordering or on-top stacking. Depending on its direction, extremely different interaction character between two pentacenes is found and explained by its electronic structure analysis.

First-principles calculations of different (001) surface terminations of three cubic perovskites CsCaBr3, CsGeBr3, and CsSnBr3

NASA Astrophysics Data System (ADS)

Ma, C.-G.; Krasnenko, V.; Brik, M. G.

2018-04-01

Three cubic bromide perovskites CsMBr3 (M = Ca, Ge, Sn) with two different surface terminations (CsBr and MBr2) were studied in this work using the first principles method. A wide range of physical properties, including electronic band structures, atom-projected density of states for each layer, surface relaxation effects, and surface energy, were evaluated for each considered surface termination. Differences between the properties of the bulk and slab models were highlighted. It was shown that surfaces with the CsBr termination have a lower energy and a more pronounced surface rumpling than those with the MBr2 termination. As a main result of this study, it was demonstrated that the CsBr-terminated surfaces appear to be energetically more stable in each of these three considered perovskites.

Molecular dynamics simulations of hydrogen bombardment of tungsten carbide surfaces

NASA Astrophysics Data System (ADS)

Träskelin, P.; Juslin, N.; Erhart, P.; Nordlund, K.

2007-05-01

The interaction between energetic hydrogen and tungsten carbide (WC) is of interest both due to the use of hydrogen-containing plasmas in thin-film manufacturing and due to the presence of WC in the divertor of fusion reactors. In order to study this interaction, we have carried out molecular dynamics simulations of the low-energy bombardment of deuterium impinging onto crystalline as well as amorphous WC surfaces. We find that prolonged bombardment leads to the formation of an amorphous WC surface layer, regardless of the initial structure of the WC sample. Loosely bound hydrocarbons, which can erode by swift chemical sputtering, are formed at the surface. Carbon-terminated surfaces show larger sputtering yields than tungsten-terminated surfaces. In both cumulative and noncumulative simulations, C is seen to sputter preferentially. Implications for mixed material erosion in ITER are discussed.

Self-organization of S adatoms on Au(111): √3R30° rows at low coverage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Walen, Holly, E-mail: hwalen@iastate.edu; Liu, Da-Jiang; Oh, Junepyo

Using scanning tunneling microscopy, we observe an adlayer structure that is dominated by short rows of S atoms, on unreconstructed regions of a Au(111) surface. This structure forms upon adsorption of low S coverage (less than 0.1 monolayer) on a fully reconstructed clean surface at 300 K, then cooling to 5 K for observation. The rows adopt one of three orientations that are rotated by 30° from the close-packed directions of the Au(111) substrate, and adjacent S atoms in the rows are separated by √3 times the surface lattice constant, a. Monte Carlo simulations are performed on lattice-gas models, derivedmore » using a limited cluster expansion based on density functional theory energetics. Models which include long-range pairwise interactions (extending to 5a), plus selected trio interactions, successfully reproduce the linear rows of S atoms at reasonable temperatures.« less

Self-organization of S adatoms on Au(111): √3R30° rows at low coverage.

PubMed

Walen, Holly; Liu, Da-Jiang; Oh, Junepyo; Lim, Hyunseob; Evans, J W; Kim, Yousoo; Thiel, P A

2015-07-07

Using scanning tunneling microscopy, we observe an adlayer structure that is dominated by short rows of S atoms, on unreconstructed regions of a Au(111) surface. This structure forms upon adsorption of low S coverage (less than 0.1 monolayer) on a fully reconstructed clean surface at 300 K, then cooling to 5 K for observation. The rows adopt one of three orientations that are rotated by 30° from the close-packed directions of the Au(111) substrate, and adjacent S atoms in the rows are separated by √3 times the surface lattice constant, a. Monte Carlo simulations are performed on lattice-gas models, derived using a limited cluster expansion based on density functional theory energetics. Models which include long-range pairwise interactions (extending to 5a), plus selected trio interactions, successfully reproduce the linear rows of S atoms at reasonable temperatures.

Nanofractography of Composition B Fracture Surfaces With AFM

DTIC Science & Technology

2004-12-01

structures (Miller and Garroway , 2001). Also, the monoclinic form(s), mostly assumed to be the ones present at low temperature, are known to exhibit...parameters of ~ 0.6, ~ 1.5, and ~ 2.0 - 2.1 nm lengths. No identification of potential cleavage planes are given in Miller and Garroway (Miller...and Garroway , 2001). TNT is known to be relatively ductile compared to the other listed energetic materials and shear deformation before fracture is

Polynitrogen/Nanoaluminum Surface Interactions

DTIC Science & Technology

2009-05-12

atomic and molecular oxygen and of other energetic species like nitromethane (CH3NO2) with AlN(0001) and AlN )1(000 surfaces have been analyzed. 15...molecular oxygen and of other energetic species like nitromethane (CH3NO2) with AlN(0001) and AlN )1(000 surfaces have been analyzed. For these...materials. For this set of compounds we have analyzed several high explosive salts containing the CN7 - anion, namely the hydrazinium ([N2H5][CN7

Structure and energetics of hydrogen-bonded networks of methanol on close packed transition metal surfaces

NASA Astrophysics Data System (ADS)

Murphy, Colin J.; Carrasco, Javier; Lawton, Timothy J.; Liriano, Melissa L.; Baber, Ashleigh E.; Lewis, Emily A.; Michaelides, Angelos; Sykes, E. Charles H.

2014-07-01

Methanol is a versatile chemical feedstock, fuel source, and energy storage material. Many reactions involving methanol are catalyzed by transition metal surfaces, on which hydrogen-bonded methanol overlayers form. As with water, the structure of these overlayers is expected to depend on a delicate balance of hydrogen bonding and adsorbate-substrate bonding. In contrast to water, however, relatively little is known about the structures methanol overlayers form and how these vary from one substrate to another. To address this issue, herein we analyze the hydrogen bonded networks that methanol forms as a function of coverage on three catalytically important surfaces, Au(111), Cu(111), and Pt(111), using a combination of scanning tunneling microscopy and density functional theory. We investigate the effect of intermolecular interactions, surface coverage, and adsorption energies on molecular assembly and compare the results to more widely studied water networks on the same surfaces. Two main factors are shown to direct the structure of methanol on the surfaces studied: the surface coverage and the competition between the methanol-methanol and methanol-surface interactions. Additionally, we report a new chiral form of buckled hexamer formed by surface bound methanol that maximizes the interactions between methanol monomers by sacrificing interactions with the surface. These results serve as a direct comparison of interaction strength, assembly, and chirality of methanol networks on Au(111), Cu(111), and Pt(111) which are catalytically relevant for methanol oxidation, steam reforming, and direct methanol fuel cells.

Exploration Consequences of Particle Radiation Environments at Airless Planetary Surfaces: Lessons Learned at the Moon by LRO/CRaTER and Scaling to Other Solar System Objects

NASA Astrophysics Data System (ADS)

Spence, H. E.

2017-12-01

We examine and compare the energetic particle ionizing radiation environments at airless planetary surfaces throughout the solar system. Energetic charged particles fill interplanetary space and bathe the environments of planetary objects with a ceaseless source of sometimes powerful yet ever-present ionizing radiation. In turn, these charged particles interact with planetary bodies in various ways, depending upon the properties of the body as well as upon the nature of the charged particles themselves. The Cosmic Ray Telescope for the Effects of Radiation (CRaTER) on the Lunar Reconnaisance Orbiter (LRO), launched in 2009, continues to provide new insights into the ways by which the lunar surface is influenced by these energetic particles. In this presentation, we briefly review some of these mechanisms and how they operate at the Moon, and then compare and contrast the radiation environments at other atmospherereless planetary objects within our solar system that are potential future human exploration targets. In particular, we explore two primary sources of ionizing radiation, galactic cosmic rays (GCR) and solar energetic particles (SEP), in the environments of planetary objects that have weak or absent atmospheres and intrinsic magnetic fields. We motivate the use of simplified scaling relationships with heliocentric distance to estimate their intensity, which then serves as a basis for estimating the relative importance of various energetic particle and planetary surface physical interactions, in the context of humankind's expanding explorations beyond low-Earth orbit.

Interactions of small platinum clusters with the TiC(001) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mao, Jianjun; Li, Shasha; Chu, Xingli

2015-11-14

Density functional theory calculations are used to elucidate the interactions of small platinum clusters (Pt{sub n}, n = 1–5) with the TiC(001) surface. The results are analyzed in terms of geometric, energetic, and electronic properties. It is found that a single Pt atom prefers to be adsorbed at the C-top site, while a Pt{sub 2} cluster prefers dimerization and a Pt{sub 3} cluster forms a linear structure on the TiC(001). As for the Pt{sub 4} cluster, the three-dimensional distorted tetrahedral structure and the two-dimensional square structure almost have equal stability. In contrast with the two-dimensional isolated Pt{sub 5} cluster, the adsorbed Pt{submore » 5} cluster prefers a three-dimensional structure on TiC(001). Substantial charge transfer takes place from TiC(001) surface to the adsorbed Pt{sub n} clusters, resulting in the negatively charged Pt{sub n} clusters. At last, the d-band centers of the absorbed Pt atoms and their implications in the catalytic activity are discussed.« less

Electronic Structure of Energetic Molecules and Crystals Under Compression

NASA Astrophysics Data System (ADS)

Kay, Jeffrey

Understanding how the electronic structure of energetic materials change under compression is important to elucidating mechanisms of shock-induced reactions and detonation. In this presentation, the electronic structure of prototypical energetic crystals are examined under high degrees of compression using ab initio quantum chemical calculations. The effects of compression on and interactions between the constituent molecules are examined in particular. The insights these results provide into previous experimental observations and theoretical predictions of energetic materials under high pressure are discussed. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. DOE's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Improved Energetic-Behaviors of Spontaneously Surface-Mediated Al Particles.

PubMed

Kim, Dong Won; Kim, Kyung Tae; Min, Tae Sik; Kim, Kyung Ju; Kim, Soo Hyung

2017-07-05

Surface-mediated Al particles are synthesized by incorporating the stable fluoride reaction of Al-F on a pure Al surface in place of natural oxides. Al particles with fluoro-polymer directly adsorbed on the surface show a considerable capability to overcome limitations caused by the surface oxide. Here, we report that Al fluoride when spontaneously formed at the poly(vinylidene fluoride)/Al interface serves as an oxidation-protecting layer while also providing an efficient combustion path along which the internal Al rapidly reacts with external oxygen atoms. Both thermal oxidation and explosion tests of the poly(vinylidene fluoride)/Al particles show superior exothermic enthalpy energy and simultaneously rapid oxidation reactivity compared to those of Al 2 O 3 passivated Al particles. It is clearly elucidated that the enhanced energetic properties of Al particles mediated by poly(vinylidene fluoride) originate from the extraordinary pyrolytic process of Al fluoride occurring at a low temperature compared to Al 2 O 3 passivated Al. Hence, these results clarify that the surface mediation of Al particles can be significantly considered as advanced technology for many energetic applications.

Molecular dynamics simulation study of the structure of poly(ethylene oxide) brushes on nonpolar surfaces in aqueous solution.

PubMed

Bedrov, Dmitry; Smith, Grant D

2006-07-04

The structure of poly(ethylene oxide) (PEO, M(w) = 526) brushes of various grafting density (sigma) on nonpolar graphite and hydrophobic (oily) surfaces in aqueous solution has been studied using atomistic molecular dynamics simulations. Additionally, the influence of PEO-surface interactions on the brush structure was investigated by systematically reducing the strength of the (dispersion) attraction between PEO and the surfaces. PEO chains were found to adsorb strongly to the graphite surface due primarily to the relative strength of dispersion interactions between PEO and the atomically dense graphite compared to those between water and graphite. For the oily surface, PEO-surface and water-surface dispersion interactions are much weaker, greatly reducing the energetic driving force for PEO adsorption. This reduction is mediated to some extent by a hydrophobic driving force for PEO adsorption on the oily surface. Reduction in the strength of PEO-surface attraction results in reduced adsorption of PEO for both surfaces, with the effect being much greater for the graphite surface where the strong PEO-surface dispersion interactions dominate. At high grafting density (sigma approximately 1/R(g)(2)), the PEO density profiles exhibited classical brush behavior and were largely independent of the strength of the PEO-surface interaction. With decreasing grafting density (sigma < 1/R(g)(2)), coverage of the surface by PEO requires an increasingly large fraction of PEO segments resulting in a strong dependence of the PEO density profile on the nature of the PEO-surface interaction.

Towards identifying the active sites on RuO 2 (110) in catalyzing oxygen evolution

DOE PAGES

Rao, Reshma R.; Kolb, Manuel J.; Halck, Niels Bendtsen; ...

2017-11-17

While the surface atomic structure of RuO 2 has been well studied in ultra high vacuum, much less is known about the interaction between water and RuO 2 in aqueous solution. In this work, in situ surface X-ray scattering measurements combined with density functional theory (DFT) were used to determine the surface structural changes on single-crystal RuO2(110) as a function of potential in acidic electrolyte. The redox peaks at 0.7, 1.1 and 1.4 V vs. reversible hydrogen electrode (RHE) could be attributed to surface transitions associated with the successive deprotonation of –H 2O on the coordinatively unsaturated Ru sites (CUS)more » and hydrogen adsorbed to the bridging oxygen sites. At potentials relevant to the oxygen evolution reaction (OER), an –OO species on the Ru CUS sites was detected, which was stabilized by a neighboring –OH group on the Ru CUS or bridge site. Combining potential-dependent surface structures with their energetics from DFT led to a new OER pathway, where the deprotonation of the –OH group used to stabilize –OO was found to be rate-limiting.« less

Effects of surface stability on the morphological transformation of metals and metal oxides as investigated by first-principles calculations.

PubMed

Andrés, Juan; Gracia, Lourdes; Gouveia, Amanda Fernandes; Ferrer, Mateus Meneghetti; Longo, Elson

2015-10-09

Morphology is a key property of materials. Owing to their precise structure and morphology, crystals and nanocrystals provide excellent model systems for joint experimental and theoretical investigations into surface-related properties. Faceted polyhedral crystals and nanocrystals expose well-defined crystallographic planes depending on the synthesis method, which allow for thoughtful investigations into structure-reactivity relationships under practical conditions. This feature article introduces recent work, based on the combined use of experimental findings and first-principles calculations, to provide deeper knowledge of the electronic, structural, and energetic properties controlling the morphology and the transformation mechanisms of different metals and metal oxides: Ag, anatase TiO2, BaZrO3, and α-Ag2WO4. According to the Wulff theorem, the equilibrium shapes of these systems are obtained from the values of their respective surface energies. These investigations are useful to gain further understanding of how to achieve morphological control of complex three-dimensional crystals by tuning the ratio of the surface energy values of the different facets. This strategy allows the prediction of possible morphologies for a crystal and/or nanocrystal by controlling the relative values of surface energies.

Towards identifying the active sites on RuO 2 (110) in catalyzing oxygen evolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rao, Reshma R.; Kolb, Manuel J.; Halck, Niels Bendtsen

While the surface atomic structure of RuO 2 has been well studied in ultra high vacuum, much less is known about the interaction between water and RuO 2 in aqueous solution. In this work, in situ surface X-ray scattering measurements combined with density functional theory (DFT) were used to determine the surface structural changes on single-crystal RuO2(110) as a function of potential in acidic electrolyte. The redox peaks at 0.7, 1.1 and 1.4 V vs. reversible hydrogen electrode (RHE) could be attributed to surface transitions associated with the successive deprotonation of –H 2O on the coordinatively unsaturated Ru sites (CUS)more » and hydrogen adsorbed to the bridging oxygen sites. At potentials relevant to the oxygen evolution reaction (OER), an –OO species on the Ru CUS sites was detected, which was stabilized by a neighboring –OH group on the Ru CUS or bridge site. Combining potential-dependent surface structures with their energetics from DFT led to a new OER pathway, where the deprotonation of the –OH group used to stabilize –OO was found to be rate-limiting.« less

Floating stacking faults on the (111) surface of FCC metals: a finite-temperature first-principles study

NASA Astrophysics Data System (ADS)

Rechtsman, Mikael; de Gironcoli, Stefano; Ceder, Gerbrand; Marzari, Nicola

2003-03-01

The (111) surfaces of FCC metals can develop anomalous thermal expansion properties at high temperatures (e.g. for the case of Ag(111)), and display floating stacking faults during homoepitaxial growth in the presence of surfactants. Inspired by the results of high-temperature ensemble-DFT molecular dynamics simulations, we investigate here the relative stability of FCC and HCP stacking in simple and transition metals (Al, Ag, Zn), searching for a structural phase transition taking place at the surface layer in the high-temperature regime. We use a combination of total-energy structural relaxations and linear-response perturbation theory to determine the surface phonon dispersions, and then the relative free energies in the quasi-harmonic approximation. Our results in Al show that the vibrational entropy strongly favors HCP stacking, substantially offsetting the energetic cost of the stacking fault that becomes favored close to the melting temperature. Besides its fundamental interest, HCP phonon softening is relevant in determining the relative stability of small islands during homoeptiaxial growth.

Influence of exothermic chemical reactions on laser-induced shock waves.

PubMed

Gottfried, Jennifer L

2014-10-21

Differences in the excitation of non-energetic and energetic residues with a 900 mJ, 6 ns laser pulse (1064 nm) have been investigated. Emission from the laser-induced plasma of energetic materials (e.g. triaminotrinitrobenzene [TATB], cyclotrimethylene trinitramine [RDX], and hexanitrohexaazaisowurtzitane [CL-20]) is significantly reduced compared to non-energetic materials (e.g. sugar, melamine, and l-glutamine). Expansion of the resulting laser-induced shock wave into the air above the sample surface was imaged on a microsecond timescale with a high-speed camera recording multiple frames from each laser shot; the excitation of energetic materials produces larger heat-affected zones in the surrounding atmosphere (facilitating deflagration of particles ejected from the sample surface), results in the formation of additional shock fronts, and generates faster external shock front velocities (>750 m s(-1)) compared to non-energetic materials (550-600 m s(-1)). Non-explosive materials that undergo exothermic chemical reactions in air at high temperatures such as ammonium nitrate and magnesium sulfate produce shock velocities which exceed those of the inert materials but are less than those generated by the exothermic reactions of explosive materials (650-700 m s(-1)). The most powerful explosives produced the highest shock velocities. A comparison to several existing shock models demonstrated that no single model describes the shock propagation for both non-energetic and energetic materials. The influence of the exothermic chemical reactions initiated by the pulsed laser on the velocity of the laser-induced shock waves has thus been demonstrated for the first time.

Quantum beating patterns observed in the energetics of Pb film nanostructures.

PubMed

Czoschke, P; Hong, Hawoong; Basile, L; Chiang, T-C

2004-07-16

We have studied the nanoscale structural evolution of Pb films grown at 110 K on a Si(111) substrate as they are annealed to increasingly higher temperatures. Surface x-ray diffraction from a synchrotron source is used to observe the morphology evolve from an initial smooth film through various metastable states before reaching a state of local equilibrium, at which point the coverage of different height Pb structures is analyzed and related to the thickness-dependent surface energy. Rich patterns are seen in the resulting energy landscape similar to the beating patterns heard from the interference of two musical notes of similar pitch. The explanation is, however, very simple, as demonstrated by a model calculation based on the confinement of free electrons to a quantum well.

Quantum Beating Patterns Observed in the Energetics of Pb Film Nanostructures

NASA Astrophysics Data System (ADS)

Czoschke, P.; Hong, Hawoong; Basile, L.; Chiang, T.-C.

2004-07-01

We have studied the nanoscale structural evolution of Pb films grown at 110K on a Si(111) substrate as they are annealed to increasingly higher temperatures. Surface x-ray diffraction from a synchrotron source is used to observe the morphology evolve from an initial smooth film through various metastable states before reaching a state of local equilibrium, at which point the coverage of different height Pb structures is analyzed and related to the thickness-dependent surface energy. Rich patterns are seen in the resulting energy landscape similar to the beating patterns heard from the interference of two musical notes of similar pitch. The explanation is, however, very simple, as demonstrated by a model calculation based on the confinement of free electrons to a quantum well.

Surface Roughness of Various Diamond-Like Carbon Films

NASA Astrophysics Data System (ADS)

Liu, Dongping; Liu, Yanhong; Chen, Baoxiang

2006-11-01

Atomic force microscopy is used to estimate and compare the surface morphology of hydrogenated and hydrogen-free diamond-like carbon (DLC) films. The films were prepared by using DC magnetron sputtering of a graphite target, pulsed cathodic carbon arcs, electron cyclotron resonance (ECR), plasma source ion implantation and dielectric barrier discharge (DBD). The difference in the surface structure is presented for each method of deposition. The influences of various discharge parameters on the film surface properties are discussed based upon the experimental results. The coalescence process via the diffusion of adsorbed carbon species is responsible for the formation of hydrogen-free DLC films with rough surfaces. The films with surface roughness at an atomic level can be deposited by energetic ion impacts in a highly ionized carbon plasma. The dangling bonds created by atomic hydrogen lead to the uniform growth of hydrocarbon species at the a-C:H film surfaces of the ECR or DBD plasmas.

[Incursion into bioelectromagnetism].

PubMed

Goldura, Neguţa; Goţia, Stela

2010-01-01

The term of bioelectromagnetism include electromagnetosenzitive processes at the fundamental interaction of energetical fields with the matter. The alive matter has a dynamical, chemical and energetics structure, but above all, an intense informational activity. The bioelectromagnetism was gradually discovered and understood throughout history of humanity. J. Bernstein defined the cell's bioelectricity, Wagner calculated electrical conductivity and permeability of cells, starting from the Maxwell's field equations, others discovered "mitogenetic radiation" or "dark luminescence" or "ultraweak bioluminescence" and F. A. Popp founded the biophotons theory. On the other hand, Hirata and Nakatani finded points with different electrical conductivity on the surface of the skin and Voll invented the system of electro dermal testing. The practical applications of the bioelectromagnetism are the medical devices based on bioresonance, useful in diagnosis and treatment, as shown in the 17 studies (902 patients) published in 1999-2006.

Transition in discharge plasma of Hall thruster type in presence of secondary electron emissive surface

NASA Astrophysics Data System (ADS)

Schweigert, I. V.; Yadrenkin, M. A.; Fomichev, V. P.

2017-11-01

Modification of the sheath structure near the emissive plate placed in magnetized DC discharge plasma of Hall thruster type was studied in the experiment and in kinetic simulations. The plate is made from Al2O3 which has enhanced secondary electron emission yield. The energetic electrons emitted by heated cathode provide the volume ionization and the secondary electron emission from the plate. An increase of the electron beam energy leads to an increase of the secondary electron generation, which initiates the transition in sheath structure over the emissive plate.

First-Principles Study of the Electric Field Effect on the Water-Adsorbed Rutile Titanium Dioxide Surface

NASA Astrophysics Data System (ADS)

Hmiel, Abraham L.

TiO2 is a semiconducting material that has been used extensively in many industrial applications, and recently has become a candidate for photocatalytic water splitting, fuel cell anode support materials, sensors, and other novel nanodevices. The interface of TiO2 with water, historically well-studied but still poorly understood, presents a ubiquitous environmental challenge towards the ultimate practical usefulness of these technologies. Ground-state density functional theory (DFT) calculations studying the characteristics of molecular adsorption on model surfaces have been studied for decades, showing constant improvement in the description of the energetics and electronic structure at interfaces. These simulations are invaluable in the materials science innovation pipeline because they can interpret the results of experiments and investigate properties at the nanoscale that traditional methods cannot reach. In this work, spin-polarized DFT calculations within the generalized gradient approximation and with the recent self-consistent opt-B88 van der Waals functional have been applied to investigate the problem of molecularly adsorbed water on the rutile (110) TiO2 surface under the influence of an applied electric field. The effective screening medium theory is used to break the symmetry of the simulation in the slab normal direction and implement a metal-like boundary condition at the edges of the simulation cell to model the charged capacitor in a real electrochemical device. This study begins with an investigation of bulk and surface properties of TiO2 to obtain a sound theoretical baseline. Following that, an attempt to obtain simple and meaningful structure-property relationships of rectangular TiO 2 nanowires with (110) facets resulting from quantum confinement. Finally, a systematic study of energetics, geometrical configuration, charge partitioning, and electronic structure of water in monomer coverage up to monolayer coverage provides insight into the usefulness of the inclusion of self-consistent van der Waals correlation effects and the effect of an external electric field in this model of adsorption on a prototypical metal oxide surface. Nontrivial differences between the two functionals' description of adsorption of water, electrostatic characteristics, and electronic structure of the model surface are reported in the zero-field limit as well as with an applied field.

On the molecular origins of biomass recalcitrance: the interaction network and solvation structures of cellulose microfibrils.

PubMed

Gross, Adam S; Chu, Jhih-Wei

2010-10-28

Biomass recalcitrance is a fundamental bottleneck to producing fuels from renewable sources. To understand its molecular origin, we characterize the interaction network and solvation structures of cellulose microfibrils via all-atom molecular dynamics simulations. The network is divided into three components: intrachain, interchain, and intersheet interactions. Analysis of their spatial dependence and interaction energetics indicate that intersheet interactions are the most robust and strongest component and do not display a noticeable dependence on solvent exposure. Conversely, the strength of surface-exposed intrachain and interchain hydrogen bonds is significantly reduced. Comparing the interaction networks of I(β) and I(α) cellulose also shows that the number of intersheet interactions is a clear descriptor that distinguishes the two allomorphs and is consistent with the observation that I(β) is the more stable form. These results highlight the dominant role of the often-overlooked intersheet interactions in giving rise to biomass recalcitrance. We also analyze the solvation structures around the surfaces of microfibrils and show that the structural and chemical features at cellulose surfaces constrict water molecules into specific density profiles and pair correlation functions. Calculations of water density and compressibility in the hydration shell show noticeable but not drastic differences. Therefore, specific solvation structures are more prominent signatures of different surfaces.

DFT study of adsorption and dissociation of thiophene molecules on Ni(1 1 0)

NASA Astrophysics Data System (ADS)

Morin, C.; Eichler, A.; Hirschl, R.; Sautet, P.; Hafner, J.

2003-08-01

The different adsorption possibilities of thiophene (C 4H 4S) on the Ni(1 1 0) surface have been studied using first principle local-density-functional calculations, with the Vienna ab initio simulation package, which is based on a plane wave basis set and projector augmented wave potentials. For each configuration, a geometric optimisation has been performed. A detailed analysis of the structural and electronic properties of the molecule and the surface in the most stable conformations is presented, showing the combined roles of the molecular distortion and the interactions between the molecule and the surface. Three structures with comparatively large adsorption energies are identified, all with the molecule plane parallel to the surface. Starting from these stabilised structures, various scenarios for the desulfurisation process have been envisaged. While, for the most stable structure, the formation of an adsorbed thiol is an activated process, with an energetic barrier of 0.70 eV, the two structures which are just a bit less stable can dissociate to a C 4H 4 species and a sulfur atom with barriers as low as 0.07 eV. A description of the different transition states and a kinetic analysis of the desulfurisation reaction is also presented.

Detection of lower tropospheric responses to solar energetic particles at midlatitudes.

PubMed

Nicoll, K A; Harrison, R G

2014-06-06

Solar energetic particles (SEPs) occasionally contribute additional atmospheric ionization beyond that arising from the usual galactic cosmic ray background. During an SEP event associated with a solar flare on April 11, 2013, the vertical ionization rate profile obtained using a balloon-borne detector showed enhanced ionization with a 26% increase at 20 km, over Reading, United Kingdom. Fluctuations in atmospheric electrical parameters were also detected at the surface, beneath the balloon's trajectory. As no coincident changes in geomagnetism occurred, the electrical fluctuations are very likely to be associated with increased ionization, as observed by the balloon measurements. The lack of response of surface neutron monitors during this event indicates that energetic particles that are not detected at the surface by neutron monitors can nevertheless enter and influence the atmosphere's weather-generating regions.

Energetic frustrations in protein folding at residue resolution: a homologous simulation study of Im9 proteins.

PubMed

Sun, Yunxiang; Ming, Dengming

2014-01-01

Energetic frustration is becoming an important topic for understanding the mechanisms of protein folding, which is a long-standing big biological problem usually investigated by the free energy landscape theory. Despite the significant advances in probing the effects of folding frustrations on the overall features of protein folding pathways and folding intermediates, detailed characterizations of folding frustrations at an atomic or residue level are still lacking. In addition, how and to what extent folding frustrations interact with protein topology in determining folding mechanisms remains unclear. In this paper, we tried to understand energetic frustrations in the context of protein topology structures or native-contact networks by comparing the energetic frustrations of five homologous Im9 alpha-helix proteins that share very similar topology structures but have a single hydrophilic-to-hydrophobic mutual mutation. The folding simulations were performed using a coarse-grained Gō-like model, while non-native hydrophobic interactions were introduced as energetic frustrations using a Lennard-Jones potential function. Energetic frustrations were then examined at residue level based on φ-value analyses of the transition state ensemble structures and mapped back to native-contact networks. Our calculations show that energetic frustrations have highly heterogeneous influences on the folding of the four helices of the examined structures depending on the local environment of the frustration centers. Also, the closer the introduced frustration is to the center of the native-contact network, the larger the changes in the protein folding. Our findings add a new dimension to the understanding of protein folding the topology determination in that energetic frustrations works closely with native-contact networks to affect the protein folding.

Electron-emission-induced cooling of boundary region in fusion devices

NASA Astrophysics Data System (ADS)

Mishra, Sanjay K.; Avinash, K.; Kaw, Predhiman; Kaw

2014-12-01

In this brief communication we have explored whether the electron emission from the boundary region surfaces (or from additional fine structured dust particles/droplets of some benign material put purposely in the area surrounding the surfaces) can act as an efficient cooling mechanism for boundary region surfaces/dust electrons and hence the lattice. In order to estimate the contribution of this cooling process a simple kinetic model based on charge flux balance and associated energetics has been established. Along with some additional sophistication like suitable choice of material and modification in the work function via surface coating, the estimates show that it is possible to keep the temperature of the plate/particles well within the critical limit, i.e. melting/sublimation point for the desired regime of incident heat flux.

Communication: transition state theory for dissipative systems without a dividing surface.

PubMed

Revuelta, F; Bartsch, Thomas; Benito, R M; Borondo, F

2012-03-07

Transition state theory is a central cornerstone in reaction dynamics. Its key step is the identification of a dividing surface that is crossed only once by all reactive trajectories. This assumption is often badly violated, especially when the reactive system is coupled to an environment. The calculations made in this way then overestimate the reaction rate and the results depend critically on the choice of the dividing surface. In this Communication, we study the phase space of a stochastically driven system close to an energetic barrier in order to identify the geometric structure unambiguously determining the reactive trajectories, which is then incorporated in a simple rate formula for reactions in condensed phase that is both independent of the dividing surface and exact. © 2012 American Institute of Physics

Energetics and magnetic properties of V-doped MgO bulk and (001) surface: A GGA, GGA+U , and hybrid density functional study

NASA Astrophysics Data System (ADS)

Århammar, C.; Moyses Araujo, C.; Rao, K. V.; Norgren, Susanne; Johansson, Börje; Ahuja, Rajeev

2010-10-01

In this work, a first-principles study of the energetic and magnetic properties of V-doped MgO is presented, where both the bulk and (001) surface were investigated. It is found that V assumes a high-spin state with a local moment of about 3μB . In the bulk, the interaction between these local moments is very short ranged and the antiferromagnetic (AFM) ordering is energetically more favorable. The formation of V-VMg-V defect clusters is found to weaken the antiferromagnetic coupling in bulk MgO, degenerating the AFM and ferromagnetic state. However, these clusters are high in energy and will not form at equilibrium conditions. By employing the GGA+U approach, with U=5eV , the V3d states on the (001) surface are shifted below the Fermi level, and a reasonable surface geometry was achieved. A calculation with the hybrid HSE03 functional, contradicts the GGA+U results, indicating that the V-MgO surface should be metallic at this concentration. From the energetics it is concluded that, at the modeled concentration, VxOy phases will limit the solubility of V in MgO at equilibrium conditions, which is in agreement with previous experimental findings. In order to achieve higher concentrations of V, an off-equilibrium synthesis method is needed. Finally, we find that the formation energy of V at the surface is considerably higher than in the bulk and V is thus expected to diffuse from the surface into the bulk of MgO.

Investigating the Impact of Current Sheet Crossings on the Propagation of Solar Energetic Particles in the Inner Heliosphere

NASA Astrophysics Data System (ADS)

Schooley, A. K.; Kahler, S.; Lepri, S. T.; Liemohn, M. W.

2017-12-01

Gradual solar energetic particle events (SEPs) are produced in the solar corona and as these particle events propagate through the inner heliosphere and interplanetary space they might encounter intervening magnetic obstacles such as the heliospheric current sheet. These encounters may impact SEP acceleration or production. We investigate the extent to which propagation through these intervening structures might be affecting later in-situ SEP measurements at 1 AU. By analyzing large gradual SEP rise phases in a multi-year survey, we investigate the impact crossing a current sheet or other interplanetary magnetic structure has on in-situ SEP time-intensity profiles. Simultaneous Advanced Composition Explorer (ACE) magnetometer observations and measurements of suprathermal electron pitch angle distributions from ACE's Solar Wind Electron, Proton & Alpha Monitor (SWEPAM) are considered to indicate changes in magnetic polarity and magnetic topology. Potential field source surface models of the heliospheric current sheet are used to validate potential current sheet crossing times. We discuss those magnetic obstacles identified that SEPs likely encountered. We discuss the frequency of such encounters, their possible structure and their impact on the SEP time-intensity profiles. Preliminary results indicate that possible intervening interplanetary magnetic structures should be considered when analyzing in-situ SEP observations.

Energetic Neutral Atom (ENA) Imaging of Mercury's Magnetosphere Onboard BepiColombo

NASA Astrophysics Data System (ADS)

Barabash, S.; Wieser, M.; Futaana, Y.; Holmström, M.; Asamura, K.; Saito, Y.; Wurz, P.

2018-05-01

We describe how energetic neutral atoms (ENA) are produced in Mercury’s magnetosphere, how they can be used to image the magnetosphere and surface, and how they are measured onboard the BepiColombo mission.

Very High Performance High Nitrogen Energetic Ingredients and Energetic Polymers for Structural Components

DTIC Science & Technology

2011-12-31

have developed a vastly improved procedure for synthesis of the n- propyl ester that gives essentially quantitative yield and uses concentrated... Synthesis of n- propyl 4-aminofurazan-3-carboxylate. We next turned our attention to the synthesis of the amide. Again, the literature procedure is... synthesis and chemistry of 3-hydroxymethyl-4-amino[1,2,5]oxadiazole and 5) work on energetic polymers for structural components. 15. SUBJECT TERMS

Hydration structure of the α-chymotrypsin substrate binding pocket: the impact of constrained geometry

NASA Astrophysics Data System (ADS)

Carey, Christina; Cheng, Yuen-Kit; Rossky, Peter J.

2000-08-01

The concave substrate binding pocket of α-chymotrypsin binds specifically hydrophobic side chains. In order to understand the hydration structure present in the absence of substrate, and elucidate the character of the solvent displaced on binding, molecular dynamics computer simulation of the solvent in a fully hydrated protein has been carried out and analyzed. The pocket is found to be characterized in terms of a mixed polar and apolar macromolecular surface. It is shown that the simulated solvent structure within it is spatially consistent with that seen via crystallography. The solvent structure is energetically characterized by large losses in hydrogen bonding among solvent molecules except at the mouth of the pocket where exposure to bulk-like solvent is possible. The loss in hydrogen bonding is attributed to the highly constrained geometry available to the solvent, preventing formation of a hydrogen bonding network, with only partial compensation by interactions with the macromolecular surface. The solvent displacement concomitant with substrate binding will therefore be associated with a large enthalpic driving force. This result is at the extreme of a continuum of variable cases of "hydrophobic" hydration, which differ most basically in surface curvature. These range from convex solute surfaces, inducing clathrate-like structures, with negligible hydrogen bond loss, to flat surfaces with significant interfacial loss, to the present concave case with hydrogen bonding losses exceeding 50%.

Water decontamination via the removal of Pb (II) using a new generation of highly energetic surface nano-material: Co(+2)Mo(+6) LDH.

PubMed

Mostafa, Mohsen S; Bakr, Al-Sayed A; El Naggar, Ahmed M A; Sultan, El-Sayed A

2016-01-01

CoMo(CO3(2-)) layered double hydroxide of a highly energetic surface, as a new LDH consisting of divalent and hexavalent cations (M(+2)/M(+6)-LDH), was prepared by a homogeneous co-precipitation method. The structure and morphology of the prepared material was confirmed by several analytical techniques namely; X-ray diffraction analysis (XRD), X-ray fluorescence (XRF), Fourier transform infra-red (FT-IR) spectroscopy, differential scanning calorimetry and thermal gravimetric analysis (DSC-TGA), N2 adsorption-desorption isotherm and scanning electron microscope (SEM). The highly energetic surface of the prepared LDH was demonstrated via the X-ray photoelectron spectroscopy (XPS). The surface energy is due to the formation of +4 surface charges in the brucite layer between Co(+2) and Mo(+6). The prepared LDH was applied as a novel adsorbent for the removal of Pb (II) from its aqueous solution at different experimental conditions of time, temperature and initial Pb (II) concentrations. The change of the Pb (II) concentrations; due to adsorption, was monitored by atomic absorption spectrophotometer (AAS). The maximum uptake of Pb (II) by the Co Mo LDH was (73.4 mg/g) at 298 K. The Pb (II) adsorption was found to follow Langmuir isotherm and pseudo second order model. The adsorption process was spontaneous and endothermic. The interference of other cations on the removal of the Pb (II) was studied. Na(+) and K(+) were found to increase the adsorption capacity of the Co Mo LDH toward Pb (II) while it was slightly decreased by the presence of Mn(+2) and Cu(+2). The synthesized LDH showed a great degree of recoverability (7 times) while completely conserving its parental morphology and adsorption capacity. The mechanism of the lead ions removal had exhibited more reliability through a surface adsorption by the coordination between the Mo(+6) of the brucite layers and the oxygen atoms of the nitrates counter ions. Copyright © 2015 Elsevier Inc. All rights reserved.

Self-similarity in nature

NASA Astrophysics Data System (ADS)

Timashev, S. F.

2000-02-01

A general phenomenological approach to the analysis of experimental temporal, spatial and energetic series for extracting truly physical non-model parameters ("passport data") is presented, which may be used to characterize and distinguish the evolution as well as the spatial and energetic structure of any open nonlinear dissipative system. This methodology is based on a postulate concerning the crucial information contained in the sequences of non-regularities of the measured dynamic variable (temporal, spatial, energetic). In accordance with this approach, multi-parametric formulas for dynamic variable power spectra as well as for structural functions of different orders are identical for every spatial-temporal-energetic level of the system under consideration. In effect, this entails the introduction of a new kind of self-similarity in Nature. An algorithm has been developed for obtaining as many "passport data" as are necessary for the characterization of a dynamic system. Applications of this approach in the analysis of various experimental series (temporal, spatial, energetic) demonstrate its potential for defining adequate phenomenological parameters of different dynamic processes and structures.

Theoretical characterization of the potential energy surface for NH + NO

NASA Technical Reports Server (NTRS)

Walch, Stephen P.

1993-01-01

The potential energy surface for NH + NO was characterized using complete active space self-consistent field (CASSCF) gradient calculation to determine the stationary point geometries and frequencies followed by CASSCF/internally contracted configuration interaction calculations to refine the energetics. The present results are in qualitative accord with the BAC-MP4 calculations, but there are differences as large as 8 kcal/mol in the detailed energetics.

Energetic additive manufacturing process with feed wire

DOEpatents

Harwell, Lane D.; Griffith, Michelle L.; Greene, Donald L.; Pressly, Gary A.

2000-11-07

A process for additive manufacture by energetic wire deposition is described. A source wire is fed into a energy beam generated melt-pool on a growth surface as the melt-pool moves over the growth surface. This process enables the rapid prototyping and manufacture of fully dense, near-net shape components, as well as cladding and welding processes. Alloys, graded materials, and other inhomogeneous materials can be grown using this process.

Multi-walled carbon nanotube structural instability with/without metal nanoparticles under electron beam irradiation

NASA Astrophysics Data System (ADS)

Khan, Imran; Huang, Shengli; Wu, Chenxu

2017-12-01

The structural transformation of multi-walled carbon nanotubes (MWCNT) under electron beam (e-beam) irradiation at room temperature is studied, with respect to a novel passivation effect due to gold nanoparticles (Au NPs). MWCNT structural evolution induced by energetic e-beam irradiation leads to faster shrinkage, as revealed via in situ transmission electron microscopy, while MWCNT surface modification with Au NPs (Au-MWCNT) slows down the shrinkage by impeding the structural evolution process for a prolonged time under the same irradiation conditions. The new relationship between MWCNT and Au-MWCNT shrinking radii and irradiation time illustrates that the MWCNT shrinkage rate is faster than either theoretical predictions or the same process in Au-MWCNTs. As compared with the outer surface energy (positive curvature), the inner surface energy (negative curvature) of the MWCNT contributes more to the athermal evaporation of tube wall atoms, leading to structural instability and shrinkage under e-beam irradiation. Conversely, Au NPs possess only outer surface energy (positive curvature) compared with the MWCNT. Their presence on MWCNT surfaces retards the dynamics of MWCNT structural evolution by slowing down the evaporation process of carbon atoms, thus restricting Au-MWCNT shrinkage. Au NP interaction and growth evolves athermally on MWCNT surfaces, exhibits increase in their size, and indicates the association of this mechanism with the coalescence induced by e-beam activated electronic excitations. Despite their growth, Au NPs show extreme structural stability, and remain crystalline under prolonged irradiation. It is proposed that the surface energy of MWCNTs and Au NPs, together with e-beam activated soft modes or lattice instability effects, predominantly govern all the above varieties of structural evolution.

Density Functional Studies of Stoichiometric Surfaces of Orthorhombic Hybrid Perovskite CH3NH3PbI3

DOE PAGES

Wang, Yun; Huang, Jingsong; Sumpter, Bobby G.; ...

2014-12-19

Organic/inorganic hybrid perovskite materials are highly attractive for dye-sensitized solar cells as demonstrated by their rapid advances in energy conversion efficiency. In this work, the structures, energetics, and electronic properties for a range of stoichiometric surfaces of the orthorhombic perovskite CH3NH3PbI3 are theoretically studied using density functional theory. Various possible spatially and constitutionally isomeric surfaces are considered by diversifying the spatial orientations and connectivities of surface Pb-I bonds. The comparison of the surface energies for the most stable configurations identified for various surfaces shows that the stabilities of stoichiometric surfaces are mainly dictated by the coordination numbers of surface atoms,more » which are directly correlated with the numbers of broken bonds. Additionally, Coulombic interactions between I anions and organic countercations on the surface also contribute to the stabilization. Electronic properties are compared between the most stable (100) surface and the bulk phase, showing generally similar features except for the lifted band degeneracy and the enhanced bandgap energy for the surface. These studies on the stoichiometric surfaces serve as the first step toward gaining a fundamental understanding of the interfacial properties in the current structural design of perovskite based solar cells, in order to achieve further breakthroughs in solar conversion efficiencies.« less

Nanoscale analysis of the morphology and surface stability of calcium carbonate polymorphs

PubMed Central

Sekkal, W.; Zaoui, A.

2013-01-01

Under earth surface conditions, in ocean and natural water, calcium carbonate is ubiquitous, forming anhydrous and hydrous minerals. These hydrous phases are of considerable interest for their role as precursors to stable carbonate minerals. Atomistic simulation techniques have been employed here to perform a comprehensive and quantitative study of the structural and energetic stability of dry and hydrous surfaces of calcium carbonate polymorphs using two recently developed forcefields. Results show that the dry forms are prone to ductility; while hydrous phases are found to be brittle. The (001) surface of monohydrocalcite appears to be the most stable (0.99 J/m2) whereas for the ikaite phase, the (001) surface is the most stable. The corresponding value is 0.2 J/m2, i.e. even lower than the surface energy of the Beautiful computed morphology pictures are obtained with Xiao's model and are very similar to the observed SEM images. PMID:23545842

Nanoscale analysis of the morphology and surface stability of calcium carbonate polymorphs.

PubMed

Sekkal, W; Zaoui, A

2013-01-01

Under earth surface conditions, in ocean and natural water, calcium carbonate is ubiquitous, forming anhydrous and hydrous minerals. These hydrous phases are of considerable interest for their role as precursors to stable carbonate minerals. Atomistic simulation techniques have been employed here to perform a comprehensive and quantitative study of the structural and energetic stability of dry and hydrous surfaces of calcium carbonate polymorphs using two recently developed forcefields. Results show that the dry forms are prone to ductility; while hydrous phases are found to be brittle. The (001) surface of monohydrocalcite appears to be the most stable (0.99 J/m(2)) whereas for the ikaite phase, the (001) surface is the most stable. The corresponding value is 0.2 J/m(2), i.e. even lower than the surface energy of the Beautiful computed morphology pictures are obtained with Xiao's model and are very similar to the observed SEM images.

Nanoscale analysis of the morphology and surface stability of calcium carbonate polymorphs

NASA Astrophysics Data System (ADS)

Sekkal, W.; Zaoui, A.

2013-04-01

Under earth surface conditions, in ocean and natural water, calcium carbonate is ubiquitous, forming anhydrous and hydrous minerals. These hydrous phases are of considerable interest for their role as precursors to stable carbonate minerals. Atomistic simulation techniques have been employed here to perform a comprehensive and quantitative study of the structural and energetic stability of dry and hydrous surfaces of calcium carbonate polymorphs using two recently developed forcefields. Results show that the dry forms are prone to ductility; while hydrous phases are found to be brittle. The (001) surface of monohydrocalcite appears to be the most stable (0.99 J/m2) whereas for the ikaite phase, the (001) surface is the most stable. The corresponding value is 0.2 J/m2, i.e. even lower than the surface energy of the Beautiful computed morphology pictures are obtained with Xiao's model and are very similar to the observed SEM images.

Preparation and Reactivity of Gasless Nanostructured Energetic Materials

PubMed Central

Manukyan, Khachatur V.; Shuck, Christopher E.; Rogachev, Alexander S.; Mukasyan, Alexander S.

2015-01-01

High-Energy Ball Milling (HEBM) is a ball milling process where a powder mixture placed in the ball mill is subjected to high-energy collisions from the balls. Among other applications, it is a versatile technique that allows for effective preparation of gasless reactive nanostructured materials with high energy density per volume (Ni+Al, Ta+C, Ti+C). The structural transformations of reactive media, which take place during HEBM, define the reaction mechanism in the produced energetic composites. Varying the processing conditions permits fine tuning of the milling-induced microstructures of the fabricated composite particles. In turn, the reactivity, i.e., self-ignition temperature, ignition delay time, as well as reaction kinetics, of high energy density materials depends on its microstructure. Analysis of the milling-induced microstructures suggests that the formation of fresh oxygen-free intimate high surface area contacts between the reagents is responsible for the enhancement of their reactivity. This manifests itself in a reduction of ignition temperature and delay time, an increased rate of chemical reaction, and an overall decrease of the effective activation energy of the reaction. The protocol provides a detailed description for the preparation of reactive nanocomposites with tailored microstructure using short-term HEBM method. It also describes a high-speed thermal imaging technique to determine the ignition/combustion characteristics of the energetic materials. The protocol can be adapted to preparation and characterization of a variety of nanostructured energetic composites. PMID:25868065

Diffusion of small Cu islands on the Ni(111) surface: A self-learning kinetic Monte Carlo study

NASA Astrophysics Data System (ADS)

Acharya, Shree Ram; Shah, Syed Islamuddin; Rahman, Talat S.

2017-08-01

We elucidate the diffusion kinetics of a heteroepitaxial system consisting of two-dimensional small (1-8 atoms) Cu islands on the Ni(111) surface at (100-600) K using the Self-Learning Kinetic Monte Carlo (SLKMC-II) method. Study of the statics of the system shows that compact CuN (3≤N≤8) clusters made up of triangular units on fcc occupancy sites are the energetically most stable structures of those clusters. Interestingly, we find a correlation between the height of the activation energy barrier (Ea) and the location of the transition state (TS). The Ea of processes for Cu islands on the Ni(111) surface are in general smaller than those of their counterpart Ni islands on the same surface. We find this difference to correlate with the relative strength of the lateral interaction of the island atoms in the two systems. While our database consists of hundreds of possible processes, we identify and discuss the energetics of those that are the most dominant, or are rate-limiting, or most contributory to the diffusion of the islands. Since the Ea of single- and multi-atom processes that convert compact island shapes into non-compact ones are larger (with a significantly smaller Ea for their reverse processes) than that for the collective (concerted) motion of the island, the later dominate in the system kinetics - except for the cases of the dimer, pentamer and octamer. Short-jump involving one atom, long jump dimer-shearing, and long-jump corner shearing (via a single-atom) are, respectively, the dominating processes in the diffusion of the dimer, pentamer and octamer. Furthermore single-atom corner-rounding are the rate-limiting processes for the pentamer and octamer islands. Comparison of the energetics of selected processes and lateral interactions obtained from semi-empirical interatomic potentials with those from density functional theory show minor quantitative differences and overall qualitative agreement.

Field-induced structural control of COx molecules adsorbed on graphene

NASA Astrophysics Data System (ADS)

Matsubara, Manaho; Okada, Susumu

2018-05-01

Using the density functional theory combined with both the van der Waals correction and the effective screening medium method, we investigate the energetics and electronic structures of CO and CO2 molecules adsorbed on graphene surfaces in the field-effect-transistor structure with respect to the external electric field by the excess electrons/holes. The binding energies of CO and CO2 molecules to graphene monotonically increase with increasing hole and electron concentrations. The increase occurs regardless of the molecular conformations to graphene and the counter electrode, indicating that the carrier injection substantially enhances the molecular adsorption on graphene. Injected carriers also modulate the stable molecular conformation, which is metastable in the absence of an electric field.

Electrostatic origin of the mechanochemical rotary mechanism and the catalytic dwell of F1-ATPase

PubMed Central

Mukherjee, Shayantani; Warshel, Arieh

2011-01-01

Understanding the nature of energy transduction in life processes requires a quantitative description of the energetics of the conversion of ATP to ADP by ATPases. Previous attempts to do so have provided an interesting insight but could not account for the rotary mechanism by a nonphenomenological structure/energy description. In particular it has been very challenging to account for the observations of the 80° and 40° rotational substates, without any prior information about such states in the simulation procedure. Here we use a coarse-grained model of F1-ATPase and generate, without the adjustment of phenomenological parameters, a structure-based free energy landscape that reproduces the energetics of the mechanochemical process. It is found that the landscape along the relevant rotary path is determined by the electrostatic free energy and not by steric effects. Furthermore, the generated surface and the corresponding Langevin dynamics simulations identify a hidden conformational barrier that provides a new fundamental interpretation of the catalytic dwell and illuminate the nature of the energy conversion process. PMID:22143769

Structure and energetics of InN and GaN dimers

NASA Astrophysics Data System (ADS)

Šimová, Lucia; Tzeli, Demeter; Urban, Miroslav; Černušák, Ivan; Theodorakopoulos, Giannoula; Petsalakis, Ioannis D.

2008-06-01

Large-scale mapping of various dimers of indium nitride and gallium nitride in singlet and triplet electronic states is reported. Second-order perturbation theory with Møller-Plesset partitioning of the Hamiltonian (MP2) and coupled-cluster with single and double excitations corrected for the triple excitations (CCSD(T)) are used for the geometry determinations and evaluation of excitation and dissociation energies. For gallium and nitrogen we have used the singly augmented correlation-consistent triple-zeta basis set (aug-cc-pVTZ), for indium we have used the aug-cc-pVTZ-pseudopotential basis set. The dissociation energies are corrected for basis set superposition error (BBSE) including geometrical relaxation of the monomers. We compare and discuss the similarities and dissimilarities in the structural patterns and energetics of both groups of isomers, including the effect of the BSSE. Our computations show that there are not only different ground states for In 2N 2 and Ga 2N 2 but also different numbers of stable stationary points on their potential energy surface. We compare our results with the molecular data published so far for these systems.

Extended-area nanostructuring of TiO2 with femtosecond laser pulses at 400 nm using a line focus.

PubMed

Das, Susanta Kumar; Dasari, Kiran; Rosenfeld, Arkadi; Grunwald, Ruediger

2010-04-16

An efficient way to generate nanoscale laser-induced periodic surface structures (LIPSS) in rutile-type TiO(2) with frequency-converted femtosecond laser pulses at wavelengths around 400 nm is reported. Extended-area structuring on fixed and moving substrates was obtained by exploiting the line focus of a cylindrical lens. Under defined conditions with respect to pulse number, pulse energy and scanning velocity, two types of ripple-like LIPSS with high and low spatial frequencies (HSFL, LSFL) with periods in the range of 90 nm and 340 nm, respectively, were formed. In particular, lower numbers of high energetic pulses favour the generation of LSFL whereas higher numbers of lower energetic pulses enable the preferential creation of HSFL. Theoretical calculations on the basis of the Drude model support the assumption that refractive index changes by photo-excited carriers are a major mechanism responsible for LSFL. Furthermore, the appearance of random substructures as small as 30 nm superimposing low spatial frequency ripples is demonstrated and their possible origin is discussed.

Peierls instability as the insulating origin of the Na/Si(111)-(3 × 1) surface with a Na coverage of 2/3 monolayers

NASA Astrophysics Data System (ADS)

Kang, Myung Ho; Kwon, Se Gab; Jung, Sung Chul

2018-03-01

Density functional theory (DFT) calculations are used to investigate the insulating origin of the Na/Si(111)-(3 × 1) surface with a Na coverage of 2/3 monolayers. In the coverage definition, one monolayer refers to one Na atom per surface Si atom, so this surface contains an odd number of electrons (i.e., three Si dangling-bond electrons plus two Na electrons) per 3 × 1 unit cell. Interestingly, this odd-electron surface has been ascribed to a Mott-Hubbard insulator to account for the measured insulating band structure with a gap of about 0.8 eV. Here, we instead propose a Peierls instability as the origin of the experimental band gap. The concept of Peierls instability is fundamental in one-dimensional metal systems but has not been taken into account in previous studies of this surface. Our DFT calculations demonstrate that the linear chain structure of Si dangling bonds in this surface is energetically unstable with respect to a × 2 buckling modulation, and the buckling-induced band gap of 0.79 eV explains well the measured insulating nature.

Increased Biocompatibility and Bioactivity after Energetic PVD Surface Treatments

PubMed Central

Mändl, Stephan

2009-01-01

Ion implantation, a common technology in semiconductor processing, has been applied to biomaterials since the 1960s. Using energetic ion bombardment, a general term which includes conventional ion implantation plasma immersion ion implantation (PIII) and ion beam assisted thin film deposition, functionalization of surfaces is possible. By varying and adjusting the process parameters, several surface properties can be attuned simultaneously. Extensive research details improvements in the biocompatibility, mainly by reducing corrosion rates and increasing wear resistance after surface modification. Recently, enhanced bioactivity strongly correlated with the surface topography and less with the surface chemistry has been reported, with an increased roughness on the nanometer scale induced by self-organisation processes during ion bombardment leading to faster cellular adhesion processes.

Energetic-particle-induced geodesic acoustic mode.

PubMed

Fu, G Y

2008-10-31

A new energetic particle-induced geodesic acoustic mode (EGAM) is shown to exist. The mode frequency and mode structure are determined nonperturbatively by energetic particle kinetic effects. In particular the EGAM frequency is found to be substantially lower than the standard GAM frequency. The radial mode width is determined by the energetic particle drift orbit width and can be fairly large for high energetic particle pressure and large safety factor. These results are consistent with the recent experimental observation of the beam-driven n=0 mode in DIII-D.

The ion environment near Europa and its role in surface energetics

NASA Astrophysics Data System (ADS)

Paranicas, C.; Ratliff, J. M.; Mauk, B. H.; Cohen, C.; Johnson, R. E.

2002-03-01

This paper gives the composition, energy spectra, and time variability of energetic ions measured just upstream of Europa. From 100 keV to 100 MeV, ion intensities vary by less than a factor of ~5 among Europa passes considered between 1997 and 2000. We use the data to estimate the radiation dose rate into Europa's surface for depths 0.01 mm - 1 m. We find that in a critical fraction of the upper layer on Europa's trailing hemisphere, energetic electrons are the principal agent for radiolysis, and their bremsstrahlung photon products, not included in previous studies, dominate the dose below about 1 m. Because ion bombardment is more uniform across Europa's surface, the radiation dose on the leading hemisphere is dominated by the proton flux. Differences exist between this calculation and published doses based on the E4 wake pass. For instance, proton doses presented here are much greater below 1 mm.

Electrostatic origin of the unidirectionality of walking myosin V motors.

PubMed

Mukherjee, Shayantani; Warshel, Arieh

2013-10-22

Understanding the basis for the action of myosin motors and related molecular machines requires a quantitative energy-based description of the overall functional cycle. Previous theoretical attempts to do so have provided interesting insights on parts of the cycle but could not generate a structure-based free energy landscape for the complete cycle of myosin. In particular, a nonphenomenological structure/energy-based understanding of the unidirectional motion is still missing. Here we use a coarse-grained model of myosin V and generate a structure-based free energy surface of the largest conformational change, namely the transition from the post- to prepowerstroke movement. We also couple the observed energetics of ligand binding/hydrolysis and product release to that of the conformational surface and reproduce the energetics of the complete mechanochemical cycle. It is found that the release in electrostatic free energy upon changing the conformation of the lever arm and the convertor domain from its post- to prepowerstroke state provides the necessary energy to bias the system towards the unidirectional movement of myosin V on the actin filament. The free energy change of 11 kcal is also in the range of ∼2-3 pN, which is consistent with the experimentally observed stalling force required to stop the motor completely on its track. The conformational-chemical coupling generating a successful powerstroke cycle is believed to be conserved among most members of the myosin family, thus highlighting the importance of the previously unknown role of electrostatics free energy in guiding the functional cycle in other actin-based myosin motors.

Depletion zones and crystallography on pinched spheres

NASA Astrophysics Data System (ADS)

Chen, Jingyuan; Xing, Xiangjun; Yao, Zhenwei

2018-03-01

Understanding the interplay between ordered structures and substrate curvature is an interesting problem with versatile applications, including functionalization of charged supramolecular surfaces and modern microfluidic technologies. In this work, we investigate the two-dimensional packing structures of charged particles confined on a pinched sphere. By continuously pinching the sphere, we observe cleavage of elongated scars into pleats, proliferation of disclinations, and subsequently, emergence of a depletion zone at the negatively curved waist that is completely void of particles. We systematically study the geometrics and energetics of the depletion zone, and reveal its physical origin as a finite size effect, due to the interplay between Coulomb repulsion and concave geometry of the pinched sphere. These results further our understanding of crystallography on curved surfaces, and have implications in design and manipulation of charged, deformable interfaces in various applications.

Energy level alignment of self-assembled linear chains of benzenediamine on Au(111) from first principles

DOE PAGES

Li, Guo; Rangel, Tonatiuh; Liu, Zhen -Fei; ...

2016-03-24

Using density functional theory (DFT) with van der Waals functionals, we calculate the adsorption energetics and geometry of benzenediamine (BDA) molecules on Au(111) surfaces. Our results demonstrate that the reported self-assembled linear chain structure of BDA, stabilized via hydrogen bonds between amine groups, is energetically favored over previously-studied monomeric phases. Moreover, using a model based on many-body perturbation theory within the GW approximation, we obtain approximate self-energy corrections to the DFT highest occupied molecular orbital (HOMO) energy associated with BDA adsorbate phases. As a result, we find that, independent of coverage, the HOMO energy of the linear chain phase ismore » lower relative to the Fermi energy than that of the monomer phase, and in good agreement with values measured with ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy.« less

Energy level alignment of self-assembled linear chains of benzenediamine on Au(111) from first principles

NASA Astrophysics Data System (ADS)

Li, Guo; Rangel, Tonatiuh; Liu, Zhen-Fei; Cooper, Valentino R.; Neaton, Jeffrey B.

2016-03-01

Using density functional theory (DFT) with a van der Waals density functional, we calculate the adsorption energetics and geometry of benzenediamine (BDA) molecules on Au(111) surfaces. Our results demonstrate that the reported self-assembled linear chain structure of BDA, stabilized via hydrogen bonds between amine groups, is energetically favored over previously studied monomeric phases. Moreover, using a model, which includes nonlocal polarization effects from the substrate and the neighboring molecules and incorporates many-body perturbation theory calculations within the GW approximation, we obtain approximate self-energy corrections to the DFT highest occupied molecular orbital (HOMO) energy associated with BDA adsorbate phases. We find that, independent of coverage, the HOMO energy of the linear chain phase is lower relative to the Fermi energy than that of the monomer phase, and in good agreement with values measured with ultraviolet photoelectron spectroscopy and x-ray photoelectron spectroscopy.

Do Ag{sub n} (up to n = 8) clusters retain their identity on graphite? Insights from first-principles calculations including dispersion interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, Akansha; Sen, Prasenjit, E-mail: prasen@hri.res.in; Majumder, Chiranjib

Adsorption of pre-formed Ag{sub n} clusters for n = 1 − 8 on a graphite substrate is studied within the density functional theory employing the vdW-DF2 functional to treat dispersion interactions. Top sites above surface layer carbon atoms turn out to be most favorable for a Ag adatom, in agreement with experimental observations. The same feature is observed for clusters of almost all sizes which have the lowest energies when the Ag atoms are positioned over top sites. Most gas phase isomers retain their structures over the substrate, though a couple of them undergo significant distortions. Energetics of the adsorptionmore » can be understood in terms of a competition between energy cost of disturbing Ag–Ag bonds in the cluster and energy gain from Ag–C interactions at the surface. Ag{sub 3} turns out to be an exceptional candidate in this regard that undergoes significant structural distortion and has only two of the Ag atoms close to surface C atoms in its lowest energy structure.« less

High pressure structural, elastic and vibrational properties of green energetic oxidizer ammonium dinitramide

NASA Astrophysics Data System (ADS)

Yedukondalu, N.; Ghule, Vikas D.; Vaitheeswaran, G.

2016-08-01

Ammonium DiNitramide (ADN) is one of the most promising green energetic oxidizers for future rocket propellant formulations. In the present work, we report a detailed theoretical study on structural, elastic, and vibrational properties of the emerging oxidizer under hydrostatic compression using various dispersion correction methods to capture weak intermolecular (van der Waals and hydrogen bonding) interactions. The calculated ground state lattice parameters, axial compressibilities, and equation of state are in good accord with the available experimental results. Strength of intermolecular interactions has been correlated using the calculated compressibility curves and elastic moduli. Apart from this, we also observe discontinuities in the structural parameters and elastic constants as a function of pressure. Pictorial representation and quantification of intermolecular interactions are described by the 3D Hirshfeld surfaces and 2D finger print maps. In addition, the computed infra-red (IR) spectra at ambient pressure reveal that ADN is found to have more hygroscopic nature over Ammonium Perchlorate (AP) due to the presence of strong hydrogen bonding. Pressure dependent IR spectra show blue- and red-shift of bending and stretching frequencies which leads to weakening and strengthening of the hydrogen bonding below and above 5 GPa, respectively. The abrupt changes in the calculated structural, mechanical, and IR spectra suggest that ADN might undergo a first order structural transformation to a high pressure phase around 5-6 GPa. From the predicted detonation properties, ADN is found to have high and low performance characteristics (DCJ = 8.09 km/s and PCJ = 25.54 GPa) when compared with ammonium based energetic oxidizers (DCJ = 6.50 km/s and PCJ = 17.64 GPa for AP, DCJ = 7.28 km/s and PCJ = 18.71 GPa for ammonium nitrate) and well-known secondary explosives for which DCJ = ˜8-10 km/s and PCJ = ˜30-50 GPa, respectively.

Modeling the Role of Bulk and Surface Characteristics of Carbon Fiber on Thermal Conductance across the Carbon Fiber/Matrix Interface (Postprint)

DTIC Science & Technology

2015-11-09

Osguthorpe, D. J.; Wolff, J.; Genest, M.; Hagler, A. T. Structure and Energetics of Ligand Binding to Proteins: Escherichia Coli Dihydrofolate...available at DOI: 10.1021/acsami.5b08591 14. ABSTRACT (Maximum 200 words) The rapid heating of carbon-fiber-reinforced polymer matrix composites leads ...polymer matrix composites leads to complex thermophysical interactions which not only are dependent on the thermal properties of the constituents and

Understanding oxygen adsorption on 9.375 at. % Ga-stabilized δ-Pu (111) surface: A DFT study

DOE PAGES

Hernandez, Sarah C.; Wilkerson, Marianne P.; Huda, Muhammad N.

2015-08-30

Plutonium (Pu) metal reacts rapidly in the presence of oxygen (O), resulting in an oxide layer that will eventually have an olive green rust appearance over time. Recent experimental work suggested that the incorporation of gallium (Ga) as an alloying impurity to stabilize the highly symmetric high temperature δ-phase lattice may also provide resistance against corrosion/oxidation of plutonium. In this paper, we modeled a 9.375 at. % Ga stabilized δ-Pu (111) surface and investigated adsorption of atomic O using all-electron density functional theory. Key findings revealed that the O bonded strongly to a Pu-rich threefold hollow fcc site with amore » chemisorption energy of –5.06 eV. Migration of the O atom to a Pu-rich environment was also highly sensitive to the surface chemistry of the Pu–Ga surface; when the initial on-surface O adsorption site included a bond to a nearest neighboring Ga atom, the O atom relaxed to a Ga deficient environment, thus affirming the O preference for Pu. Only one calculated final on-surface O adsorption site included a Ga-O bond, but this chemisorption energy was energetically unfavorable. Chemisorption energies for interstitial adsorption sites that included a Pu or Pu-Ga environment suggested that over-coordination of the O atom was energetically unfavorable as well. Electronic structure properties of the on-surface sites, illustrated by the partial density of states, implied that the Ga 4p states indirectly but strongly influenced the Pu 6d states strongly to hybridize with the O 2p states, while also weakly influenced the Pu 5f states to hybridize with the O 2p states, even though Ga was not participating in bonding with O.« less

Understanding oxygen adsorption on 9.375 at. % Ga-stabilized δ-Pu (111) surface: A DFT study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hernandez, Sarah C.; Wilkerson, Marianne P.; Huda, Muhammad N.

Plutonium (Pu) metal reacts rapidly in the presence of oxygen (O), resulting in an oxide layer that will eventually have an olive green rust appearance over time. Recent experimental work suggested that the incorporation of gallium (Ga) as an alloying impurity to stabilize the highly symmetric high temperature δ-phase lattice may also provide resistance against corrosion/oxidation of plutonium. In this paper, we modeled a 9.375 at. % Ga stabilized δ-Pu (111) surface and investigated adsorption of atomic O using all-electron density functional theory. Key findings revealed that the O bonded strongly to a Pu-rich threefold hollow fcc site with amore » chemisorption energy of –5.06 eV. Migration of the O atom to a Pu-rich environment was also highly sensitive to the surface chemistry of the Pu–Ga surface; when the initial on-surface O adsorption site included a bond to a nearest neighboring Ga atom, the O atom relaxed to a Ga deficient environment, thus affirming the O preference for Pu. Only one calculated final on-surface O adsorption site included a Ga-O bond, but this chemisorption energy was energetically unfavorable. Chemisorption energies for interstitial adsorption sites that included a Pu or Pu-Ga environment suggested that over-coordination of the O atom was energetically unfavorable as well. Electronic structure properties of the on-surface sites, illustrated by the partial density of states, implied that the Ga 4p states indirectly but strongly influenced the Pu 6d states strongly to hybridize with the O 2p states, while also weakly influenced the Pu 5f states to hybridize with the O 2p states, even though Ga was not participating in bonding with O.« less

Strong non-radial propagation of energetic electrons in solar corona

NASA Astrophysics Data System (ADS)

Klassen, A.; Dresing, N.; Gómez-Herrero, R.; Heber, B.; Veronig, A.

2018-06-01

Analyzing the sequence of solar energetic electron events measured at both STEREO-A (STA) and STEREO-B (STB) spacecraft during 17-21 July 2014, when their orbital separation was 34°, we found evidence of a strong non-radial electron propagation in the solar corona below the solar wind source surface. The impulsive electron events were associated with recurrent flare and jet (hereafter flare/jet) activity at the border of an isolated coronal hole situated close to the solar equator. We have focused our study on the solar energetic particle (SEP) event on 17 July 2014, during which both spacecraft detected a similar impulsive and anisotropic energetic electron event suggesting optimal connection of both spacecraft to the parent particle source, despite the large angular separation between the parent flare and the nominal magnetic footpoints on the source surface of STA and STB of 68° and 90°, respectively. Combining the remote-sensing extreme ultraviolet (EUV) observations, in-situ plasma, magnetic field, and energetic particle data we investigated and discuss here the origin and the propagation trajectory of energetic electrons in the solar corona. We find that the energetic electrons in the energy range of 55-195 keV together with the associated EUV jet were injected from the flare site toward the spacecraft's magnetic footpoints and propagate along a strongly non-radial and inclined magnetic field below the source surface. From stereoscopic (EUV) observations we estimated the inclination angle of the jet trajectory and the respective magnetic field of 63° ± 11° relative to the radial direction. We show how the flare accelerated electrons reach very distant longitudes in the heliosphere, when the spacecraft are nominally not connected to the particle source. This example illustrates how ballistic backmapping can occasionally fail to characterize the magnetic connectivity during SEP events. This finding also provides an additional mechanism (one among others), which may explain the origin of widespread SEP events.

Variation in lipid and free fatty acid content during spawning in two temperate octocorals with different reproductive strategies: surface versus internal brooder

NASA Astrophysics Data System (ADS)

Viladrich, Núria; Bramanti, Lorenzo; Tsounis, Georgios; Chocarro, Blanca; Martínez-Quitana, Angela; Ambroso, Stefano; Madurell, Teresa; Rossi, Sergio

2016-09-01

This study investigates the energetic investment during spawning of two Mediterranean gorgonians characterized by different reproductive strategies: Corallium rubrum (internal brooder) and Paramuricea clavata (surface brooder). Sexual products (number of oocytes and spermatic sacs) were quantified, and biochemical characteristics (lipid content and free fatty acid content and composition) were determined to investigate the parental energetic investment and demand in reproduction. Results suggested that the majority of the energetic cost was due to reproductive activity (i.e., gametogenesis and spawning). The two species exhibited different life history strategies, with P. clavata investing more energy in reproduction than C. rubrum. However, P. clavata is reproductively more sensitive to inter-annual changes in environmental conditions.

Surface Thermometry of Energetic Materials by Laser-Induced Fluorescence

DTIC Science & Technology

1989-09-01

at 34 yttrium- aluminum -garnet (Dy:YAG). The simplified energy diagram of Dy:YAG is shown in Fig. 1. Absorbed laser light (at 355 nrm) can 5 excite the...the thermometric technique on a surface similar to that of an energetic material, a thermal-setting plastic supplied by Buehler, Ltd., was employed...temperature over the temperature range of interest. The rare-earth ion dysprosium (Dy) doped into a yttrium- aluminum -garnet (YAG) crystal was I determined

Structure, reactivity, and electronic properties of V-doped Co clusters

NASA Astrophysics Data System (ADS)

Datta, Soumendu; Kabir, Mukul; Saha-Dasgupta, Tanusri; Mookerjee, Abhijit

2009-08-01

Structures and physicochemical properties of V-doped Co13 clusters have been studied in detail using density-functional-theory-based first-principles method. We have found anomalous variation in stability of the doped clusters with increasing V concentration, which has been nicely demonstrated in terms of energetics and electronic properties of the clusters. Our study explains the nonmonotonic variation in reactivity of Co13-mVm clusters toward H2 molecules as reported experimentally [Nonose , J. Phys. Chem. 94, 2744 (1990)]. Moreover, it provides useful insight into the cluster geometry and chemically active sites on the cluster surface, which can help to design better catalytic processes.

Neutral vs zwitterionic glycine forms at the water/silica interface: structure, energies, and vibrational features from B3LYP periodic simulations.

PubMed

Rimola, Albert; Civalleri, Bartolomeo; Ugliengo, Piero

2008-12-16

B3LYP periodic calculations with a triple-xi-polarized Gaussian basis set have been used to study adsorption of glycine on a hydroxylated silica surface (2.2 OH/nm2) model derived from the (001) surface of edingtonite. The simulation envisages glycine adsorbed either as a gas-phase molecule or when microsolvated by up to five H20 molecules. Both neutral and zwitterionic forms of glycine have been considered and their structural, energetic, and spectroscopic vibrational features compared internally and with experiments. As a gas phase glycine sticks in its neutral form at the silica surface, the zwitterion being highly unstable and with transition-state character. When glycine is microsolvated at the silica interface, two H20 molecules render the zwitterion population comparable to that of the neutral form whereas with four H2O molecules the neutral glycine population is wiped out in favor of the zwitterion. With four H20 molecules the most stable structure shows no direct contact between glycine and the silica surface, H20 acting as a mediator via H-bond interactions. The B3LYP energies and structural data were also supported by comparing the scaled harmonic vibrational features with literature FTIR data of glycine adsorbed on an amorphous silica surface either from the gas phase or in water solution.

Fragmentation of structural energetic materials: implications for performance

NASA Astrophysics Data System (ADS)

Aydelotte, B.; Braithwaite, C. H.; Thadhani, N. N.

2014-05-01

Fragmentation results for structural energetic materials based on intermetallic forming mixtures are reviewed and the implications of the fragment populations are discussed. Cold sprayed Ni+Al and explosively compacted mixtures of Ni+Al+W and Ni+Al+W+Zr powders were fabricated into ring shaped samples and explosively fragmented. Ring velocity was monitored and fragments were soft captured in order to study the fragmentation process. It was determined that the fragments produced by these structural energetic materials are much smaller than those typically produced by ductile metals such as steel or aluminum. This has implications for combustion processes that may occur subsequent to the fragmentation process.

SASS: A symmetry adapted stochastic search algorithm exploiting site symmetry

NASA Astrophysics Data System (ADS)

Wheeler, Steven E.; Schleyer, Paul v. R.; Schaefer, Henry F.

2007-03-01

A simple symmetry adapted search algorithm (SASS) exploiting point group symmetry increases the efficiency of systematic explorations of complex quantum mechanical potential energy surfaces. In contrast to previously described stochastic approaches, which do not employ symmetry, candidate structures are generated within simple point groups, such as C2, Cs, and C2v. This facilitates efficient sampling of the 3N-6 Pople's dimensional configuration space and increases the speed and effectiveness of quantum chemical geometry optimizations. Pople's concept of framework groups [J. Am. Chem. Soc. 102, 4615 (1980)] is used to partition the configuration space into structures spanning all possible distributions of sets of symmetry equivalent atoms. This provides an efficient means of computing all structures of a given symmetry with minimum redundancy. This approach also is advantageous for generating initial structures for global optimizations via genetic algorithm and other stochastic global search techniques. Application of the SASS method is illustrated by locating 14 low-lying stationary points on the cc-pwCVDZ ROCCSD(T) potential energy surface of Li5H2. The global minimum structure is identified, along with many unique, nonintuitive, energetically favorable isomers.

Friction of water on graphene and hexagonal boron nitride from ab initio methods: very different slippage despite very similar interface structures.

PubMed

Tocci, Gabriele; Joly, Laurent; Michaelides, Angelos

2014-12-10

Friction is one of the main sources of dissipation at liquid water/solid interfaces. Despite recent progress, a detailed understanding of water/solid friction in connection with the structure and energetics of the solid surface is lacking. Here, we show for the first time that ab initio molecular dynamics can be used to unravel the connection between the structure of nanoscale water and friction for liquid water in contact with graphene and with hexagonal boron nitride. We find that although the interface presents a very similar structure between the two sheets, the friction coefficient on boron nitride is ≈ 3 times larger than that on graphene. This comes about because of the greater corrugation of the energy landscape on boron nitride arising from specific electronic structure effects. We discuss how a subtle dependence of the friction on the atomistic details of a surface, which is not related to its wetting properties, may have a significant impact on the transport of water at the nanoscale, with implications for the development of membranes for desalination and for osmotic power harvesting.

Crystalline oxides on semiconductors: A structural transition of the interface phase

NASA Astrophysics Data System (ADS)

Walker, F. J.; Buongiorno-Nardelli, Marco; Billman, C. A.; McKee, R. A.

2004-03-01

The growth of crystalline oxides on silicon is facilitated by the preparation of a surface phase of alkaline earth silicide. We describe how the surface phase serves as a precursor of the final interface phase using reflection high energy electron diffraction (RHEED) and density functional theory (DFT). RHEED intensity oscillations of the growth of BaSrO show layer-by-layer build up of the oxide on the interface. The 2x1 symmetry of the surface precursor persists up to 3 ML BaSrO coverage at which point a 1x1 pattern characteristic of the rock-salt structure of BaSrO is observed. Prior to 3 ML growth of alkaline earth oxide, DFT calculations and RHEED show that the surface precursor persists as the interface phase and induces large displacements in the growing oxide layer away from the rock-salt structure and having a 2x1 symmetry. These distortions of the rock-salt structure are energetically unfavorable and become more unfavorable as the oxide thickness increases. At 3 ML, the stability of the rock-salt structure drives a structural transformation of the film and the interface phase to a structure that is distinct from the surface precursor. Research sponsored jointly by the Division of Materials Sciences and Engineering, Office of Basic Energy Sciences, U.S. Department of Energy at Oak Ridge National Laboratory under contract DE-AC05-00OR22725 with UT-Battelle, LLC and at the University of Tennessee under contract DE-FG02-01ER45937. Calculations have been performed on CCS supercomputers at Oak Ridge National Laboratory.

Comparative surface energetic study of Matrigel® and collagen I interactions with endothelial cells.

PubMed

Hill, Michael J; Sarkar, Debanjan

2017-07-01

Understanding of the surface energetic aspects of the spontaneously deposited proteins on biomaterial surfaces and how this influences cell adhesion and differentiation is an area of regenerative medicine that has not received adequate attention. Current controversies surround the role of the biomaterial substratum surface chemistry, the range of influence of said substratum, and the effects of different surface energy components of the protein interface. Endothelial cells (ECs) are a highly important cell type for regenerative medicine applications, such as tissue engineering, and In-vivo they interact with collagen I based stromal tissue and basement membranes producing different behavioral outcomes. The surface energetic properties of these tissue types and how they control EC behavior is not well known. In this work we studied the surface energetic properties of collagen I and Matrigel ® on various previously characterized substratum polyurethanes (PU) via contact angle analysis and examined the subsequent EC network forming characteristics. A combinatorial surface energy approach was utilized that compared Zisman's critical surface tension, Kaelble's numerical method, and van Oss-Good-Chaudhury theory (vOGCT). We found that the unique, rapid network forming characteristics of ECs on Matrigel ® could be attributed to the apolar or monopolar basic interfacial characteristics according to Zisman/Kaelble or vOGCT, respectively. We also found a lack of significant substratum influence on EC network forming characteristics for Matrigel ® but collagen I showed a distinct influence where more apolar PU substrata tended to produce higher Lewis acid character collagen I interfaces which led to a greater interaction with ECs. Collagen I interfaces on more polar PU substrata lacked Lewis acid character and led to similar EC network characteristics as Matrigel ® . We hypothesized that bipolar character of the protein film favored cell-substratum over cell-cell adhesive interactions which resulted in less rapidly forming but more stable networks. Copyright © 2017 Elsevier B.V. All rights reserved.

A case study of cumulus formation beneath a stratocumulus sheet: Its structure and effect on boundary layer budgets

NASA Technical Reports Server (NTRS)

Barlow, Roy W.; Nicholls, S.

1990-01-01

On several occasions during the FIRE Marine Stratocumulus IFO off the California coast, small cumulus were observed to form during the morning beneath the main stratocumulus (Sc) deck. This occurs in the type of situation described by Turton and Nicholls (1987) in which there is insufficient generation of turbulent kinetic energy (TKE) from the cloudtop or the surface to sustain mixing throughout the layer, and a separation of the surface and cloud layers occurs. The build up of humidity in the surface layer allows cumuli to form, and the more energetic of these may penetrate back into the Sc deck, reconnecting the layers. The results presented were collected by the UKMO C-130 aircraft flying in a region where these small cumulus had grown to the extent that they had penetrated into the main Sc deck above. The structure of these penetrative cumulus are examined and their implications on the layer flux and radiation budget discussed.

Reaction of hydrogen with Ag(111): binding states, minimum energy paths, and kinetics.

PubMed

Montoya, Alejandro; Schlunke, Anna; Haynes, Brian S

2006-08-31

The interaction of atomic and molecular hydrogen with the Ag(111) surface is studied using periodic density functional total-energy calculations. This paper focuses on the site preference for adsorption, ordered structures, and energy barriers for H diffusion and H recombination. Chemisorbed H atoms are unstable with respect to the H(2) molecule in all adsorption sites below monolayer coverage. The three-hollow sites are energetically the most favorable for H chemisorption. The binding energy of H to the surface decreases slightly up to one monolayer, suggesting a small repulsive H-H interaction on nonadjacent sites. Subsurface and vacancy sites are energetically less favorable for H adsorption than on-top sites. Recombination of chemisorbed H atoms leads to the formation of gas-phase H(2) with no molecular chemisorbed state. Recombination is an exothermic process and occurs on the bridge site with a pronounced energy barrier. This energy barrier is significantly higher than that inferred from experimental temperature-programmed desorption (TPD) studies. However, there is significant permeability of H atoms through the recombination energy barrier at low temperatures, thus increasing the rate constant for H(2) desorption due to quantum tunneling effects, and improving the agreement between experiment and theory.

Space Weathering Radiation Environment of the Inner Solar System from the Virtual Energetic Particle Observatory

NASA Astrophysics Data System (ADS)

Cooper, J. F.; Papitashvili, N. E.

2016-12-01

The surfaces of Mercury, the Moon, the moons of Mars, the asteroids, and other small bodies of the inner solar system have been directly weathered for millions to billions of years by solar wind, energetic particle, and solar ultraviolet irradiation. Surface regolith layers to meters in depth are formed by impacts of smaller bodies and micrometeoroids. Sample return missions to small bodies, such as Osiris-REx to the asteroid Bennu, are intended to recover information on the early history of solar system formation, but must contend with the long-term space weathering effects that perturb the original structure and composition of the affected bodies. Solar wind plasma ions at keV energies penetrate only to sub-micron depths, while more energetic solar & heliospheric particles up to MeV energies reach centimeter depths, and higher-energy galactic cosmic rays to GeV energies fully penetrate through the impact regolith. The weathering effects vary with energy and penetration depth from ion implantation and erosive sputtering at solar wind energies to chemical and structural evolution driven by MeV - GeV particles. The energy versus depth dependence of such effects is weighted by the differential flux distributions of the incident particles as measured near the orbits of the affected bodies over long periods of time. Our Virtual Energetic Particle Observatory (http://vepo.gsfc.nasa.gov/) enables simultaneous access to multiple data sets from 1973 through the present in the form of differential flux spectral plots and downloadable data tables. The most continuous VEPO coverage exists for geospace data sources at 1 AU from the Interplanetary Monitoring Platform 8 (IMP-8), launched in 1973, through the present 1-AU constellation including the ACE, WIND, SOHO, and Stereo-A/B spacecraft. Other mission data, e.g. more occasionally from Pioneer-10/11, Helios-1/2, Voyager-1/2, and Ulysses, extend heliospheric coverage from the orbit of Mercury to that of Mars, the asteroid belt, and beyond. Using data from the VEPO services, we show the time-averaged spectra of protons and helium during 1973 - 2016 from Mercury to Mars. The main contributors on solar cycle time scales at keV to MeV energies are large solar flare and ICME events. These time-averaged spectra can then be used for space weathering models of the inner solar system.

Temperature Dependence and Energetics of Single Ions at the Aqueous Liquid-Vapor Interface

PubMed Central

Ou, Shuching; Patel, Sandeep

2014-01-01

We investigate temperature-dependence of free energetics with two single halide anions, I− and Cl−, crossing the aqueous liquid-vapor interface through molecular dynamics simulations. The result shows that I− has a modest surface stability of 0.5 kcal/mol at 300 K and the stability decreases as the temperature increases, indicating the surface adsorption process for the anion is entropically disfavored. In contrast, Cl− shows no such surface state at all temperatures. Decomposition of free energetics reveals that water-water interactions provide a favorable enthalpic contribution, while the desolvation of ion induces an increase in free energy. Calculations of surface fluctuations demonstrate that I− generates significantly greater interfacial fluctuations compared to Cl−. The fluctuation is attributed to the malleability of the solvation shells, which allows for more long-ranged perturbations and solvent density redistribution induced by I− as the anion approaches the liquid-vapor interface. The increase in temperature of the solvent enhances the inherent thermally-excited fluctuations and consequently reduces the relative contribution from anion to surface fluctuations, which is consistent with the decrease in surface-stability of I−. Our results indicate a strong correlation with induced interfacial fluctuations and anion surface stability; moreover, resulting temperature dependent behavior of induced fluctuations suggests the possibility of a critical level of induced fluctuations associated with surface stability. PMID:23537166

Mechanics and energetics of human locomotion on sand.

PubMed

Lejeune, T M; Willems, P A; Heglund, N C

1998-07-01

Moving about in nature often involves walking or running on a soft yielding substratum such as sand, which has a profound effect on the mechanics and energetics of locomotion. Force platform and cinematographic analyses were used to determine the mechanical work performed by human subjects during walking and running on sand and on a hard surface. Oxygen consumption was used to determine the energetic cost of walking and running under the same conditions. Walking on sand requires 1.6-2.5 times more mechanical work than does walking on a hard surface at the same speed. In contrast, running on sand requires only 1.15 times more mechanical work than does running on a hard surface at the same speed. Walking on sand requires 2.1-2.7 times more energy expenditure than does walking on a hard surface at the same speed; while running on sand requires 1.6 times more energy expenditure than does running on a hard surface. The increase in energy cost is due primarily to two effects: the mechanical work done on the sand, and a decrease in the efficiency of positive work done by the muscles and tendons.

An equilibrium ab initio atomistic thermodynamics study of chlorine adsorption on the Cu(001) surface.

PubMed

Suleiman, Ibrahim A; Radny, Marian W; Gladys, Michael J; Smith, Phillip V; Mackie, John C; Kennedy, Eric M; Dlugogorski, Bogdan Z

2011-06-07

The effect of chlorine (Cl) chemisorption on the energetics and atomic structure of the Cu(001) surface over a wide range of chlorine pressures and temperatures has been studied using equilibrium ab initio atomistic thermodynamics to elucidate the formation of cuprous chloride (CuCl) as part of the Deacon reaction on copper metal. The calculated surface free energies show that the 1/2 monolayer (ML) c(2 × 2)-Cl phase with chlorine atoms adsorbed at the hollow sites is the most stable structure for a wide range of Cl chemical potential, in agreement with experimental observations. It is also found that at very low pressure and exposure, but elevated temperature, the 1/9 ML and 1/4 ML phases become the most stable. By contrast, a high coverage of Cl does not lead to thermodynamically stable geometries. The subsurface adsorption of Cl atoms, however, dramatically increases the stability of the 1 ML and 2 ML adsorption configurations providing a possible pathway for the formation of the bulk-chloride surface phases in the kinetic regime.

Apparatus for improving performance of electrical insulating structures

DOEpatents

Wilson, Michael J.; Goerz, David A.

2004-08-31

Removing the electrical field from the internal volume of high-voltage structures; e.g., bushings, connectors, capacitors, and cables. The electrical field is removed from inherently weak regions of the interconnect, such as between the center conductor and the solid dielectric, and places it in the primary insulation. This is accomplished by providing a conductive surface on the inside surface of the principal solid dielectric insulator surrounding the center conductor and connects the center conductor to this conductive surface. The advantage of removing the electric fields from the weaker dielectric region to a stronger area improves reliability, increases component life and operating levels, reduces noise and losses, and allows for a smaller compact design. This electric field control approach is currently possible on many existing products at a modest cost. Several techniques are available to provide the level of electric field control needed. Choosing the optimum technique depends on material, size, and surface accessibility. The simplest deposition method uses a standard electroless plating technique, but other metalization techniques include vapor and energetic deposition, plasma spraying, conductive painting, and other controlled coating methods.

Apparatus for improving performance of electrical insulating structures

DOEpatents

Wilson, Michael J.; Goerz, David A.

2002-01-01

Removing the electrical field from the internal volume of high-voltage structures; e.g., bushings, connectors, capacitors, and cables. The electrical field is removed from inherently weak regions of the interconnect, such as between the center conductor and the solid dielectric, and places it in the primary insulation. This is accomplished by providing a conductive surface on the inside surface of the principal solid dielectric insulator surrounding the center conductor and connects the center conductor to this conductive surface. The advantage of removing the electric fields from the weaker dielectric region to a stronger area improves reliability, increases component life and operating levels, reduces noise and losses, and allows for a smaller compact design. This electric field control approach is currently possible on many existing products at a modest cost. Several techniques are available to provide the level of electric field control needed. Choosing the optimum technique depends on material, size, and surface accessibility. The simplest deposition method uses a standard electroless plating technique, but other metalization techniques include vapor and energetic deposition, plasma spraying, conductive painting, and other controlled coating methods.

Method for improving performance of highly stressed electrical insulating structures

DOEpatents

Wilson, Michael J.; Goerz, David A.

2002-01-01

Removing the electrical field from the internal volume of high-voltage structures; e.g., bushings, connectors, capacitors, and cables. The electrical field is removed from inherently weak regions of the interconnect, such as between the center conductor and the solid dielectric, and places it in the primary insulation. This is accomplished by providing a conductive surface on the inside surface of the principal solid dielectric insulator surrounding the center conductor and connects the center conductor to this conductive surface. The advantage of removing the electric fields from the weaker dielectric region to a stronger area improves reliability, increases component life and operating levels, reduces noise and losses, and allows for a smaller compact design. This electric field control approach is currently possible on many existing products at a modest cost. Several techniques are available to provide the level of electric field control needed. Choosing the optimum technique depends on material, size, and surface accessibility. The simplest deposition method uses a standard electroless plating technique, but other metalization techniques include vapor and energetic deposition, plasma spraying, conductive painting, and other controlled coating methods.

Incipient motion in gravel bed rivers due to energetic turbulent flow events

NASA Astrophysics Data System (ADS)

Valyrakis, Manousos

2013-04-01

This contribution reviews recent developments and contributions in the field of incipient motion and entrainment of coarse sediment grains due to the action of near bed turbulent flows. Specifically, traditional shear based spatio-temporally averaged concepts and instantaneous stress tensor criteria are contrasted to the newly proposed flow event based impulse and energy criteria. The energy criterion, suggests that only sufficiently energetic turbulent events can remove a particle from its resting position on the bed surface and result on its entrainment downstream. While the impulse and energy criteria are interconnected through the energy-impulse equation, the later appears to be more versatile and appropriate for generalising to sediment transport. These flow event based criteria have a sound physical basis for describing the intermittent character of particle entrainment as inherited by near boundary turbulence at near threshold conditions. These criteria can be derived from fundamental laws of physics such as Newtonian classical mechanics and the Lagrange equations respectively. The energetic events that are capable of performing geomorphic work at the scale of individual particles are shown to follow a power law, meaning that more energetic events (capable of removing larger stones) are expected to occur less frequently. In addition, this paper discusses the role of the coefficient of energy transfer efficiency introduced in the energy equation for particle entrainment. A preliminary investigation from analysis of a series of mobile grain flume experiments illustrates that different signatures of turbulence or sequence of flow structures may have different effectiveness towards particle transport. Characteristic cases of specific energetic flow events and the associated particle response are shown and classified with regard to the time required for complete entrainment. Finally these findings are commented with respect to the implications for sediment transport.

Surface Characterization of Mechanochemically Modified Exfoliated Halloysite Nanoscrolls.

PubMed

Zsirka, Balázs; Táborosi, Attila; Szabó, Péter; Szilágyi, Róbert K; Horváth, Erzsébet; Juzsakova, Tatjána; Fertig, Dávid; Kristóf, János

2017-04-11

Surface modifications fundamentally influence the morphology of kaolinite nanostructures as a function of crystallinity and the presence of contaminants. Besides morphology, the catalytic properties of 1:1-type exfoliated aluminosilicates are also influenced by the presence of defect sites that can be generated in a controlled manner by mechanochemical activation. In this work, we investigated exfoliated halloysite nanoparticles with a quasi-homogeneous, scroll-type secondary structure toward developing structural/functional relationships for composition, atomic structure, and morphology. The surface properties of thin-walled nanoscrolls were studied as a function of mechanochemical activation expressed by the duration of dry-grinding. The surface characterizations were carried out using N 2 , NH 3 , and CO 2 adsorption measurements. The effects of grinding on the nanohalloysite structure were followed using thermoanalytical thermogravimetric/derivative thermogravimetric (TG/DTG) and infrared spectroscopic [Fourier transform infrared/attenuated total reflection (FTIR/ATR)] techniques. Grinding results in partial dehydroxylation with similar changes as those observed for heat treatment above 300 °C. Mechanochemical activation shows a decrease in the dehydroxylation mass loss and the DTG peak temperature, a decrease in the specific surface area and the number of mesopores, an increase in the surface acidity, blue shift of surface hydroxide bands, and a decrease in the intensity of FTIR/ATR bands as a function of the grinding time. The experimental observations were used to guide atomic-scale structural and energetic simulations using realistic molecular cluster models for a nanohalloysite particle. A full potential energy surface description was developed for the mechanochemical activation and/or heating toward nanometahalloysite formation that aids the interpretation of experimental results. The calculated differences upon dehydroxylation show a remarkable agreement with the mass loss values from DTG measurements.

Atomistic simulations of bulk, surface and interfacial polymer properties

NASA Astrophysics Data System (ADS)

Natarajan, Upendra

In chapter I, quasi-static molecular mechanics based simulations are used to estimate the activation energy of phenoxy rings flips in the amorphous region of a semicrystalline polyimide. Intra and intermolecular contributions to the flip activation energy, the torsional cooperativity accompanying the flip, and the effect of the flip on the motion in the glassy bulk state, are looked at. Also, comparison of the weighted mean activation energy is made with experimental data from solid state NMR measurements; the simulated value being 17.5 kcal/mol., while the experimental value was observed to be 10.5 kcal/mol. Chapter II deals with construction of random copolymer thin films of styrene-butadiene (SB) and styrene-butadiene-acrylonitrile (SBA). The structure and properties of the free surfaces presented by these thin films are analysed by, the atom mass density profiles, backbone bond orientation function, and the spatial distribution of acrylonitrile groups and styrene rings. The surface energies of SB and SBA are calculated using an atomistic equation and are compared with experimental data in the literature. In chapter III, simulations of polymer-polymer interfaces between like and unlike polymers, specifically cis-polybutadiene (PBD) and atatic polypropylene (PP), are presented. The structure of an incompatible polymer-polymer interface, and the estimation of the thermodynamic work of adhesion and interfacial energy between different incompatible polymers, form the focus here. The work of adhesion is calculated using an atomistic equation and is further used in a macroscopic equation to estimate the interfacial energy. The interfacial energy is compared with typical values for other immiscible systems in the literature. The interfacial energy compared very well with interfacial energy values for a few other immiscible hydrocarbon pairs. In chapter IV, the study proceeds to look at the interactions between nonpolar and polar small molecules with SB and SBA thin film surfaces. Toluene, hexadecane and water molecules are separately simulated to interact with SB and SBA surfaces in vacuum. The energetics of interaction are calculated atomistically and used in the atomistic equation to calculate the interfacial energy or the interaction energy. Comparisons with experimental data are not made due to the small concentrations of the molecules on the polymer surface. However, fundamental understanding of the structure of the system and the breakup of the energetics are provided by such a study.

Clustering on Magnesium Surfaces - Formation and Diffusion Energies.

PubMed

Chu, Haijian; Huang, Hanchen; Wang, Jian

2017-07-12

The formation and diffusion energies of atomic clusters on Mg surfaces determine the surface roughness and formation of faulted structure, which in turn affect the mechanical deformation of Mg. This paper reports first principles density function theory (DFT) based quantum mechanics calculation results of atomic clustering on the low energy surfaces {0001} and [Formula: see text]. In parallel, molecular statics calculations serve to test the validity of two interatomic potentials and to extend the scope of the DFT studies. On a {0001} surface, a compact cluster consisting of few than three atoms energetically prefers a face-centered-cubic stacking, to serve as a nucleus of stacking fault. On a [Formula: see text], clusters of any size always prefer hexagonal-close-packed stacking. Adatom diffusion on surface [Formula: see text] is high anisotropic while isotropic on surface (0001). Three-dimensional Ehrlich-Schwoebel barriers converge as the step height is three atomic layers or thicker. Adatom diffusion along steps is via hopping mechanism, and that down steps is via exchange mechanism.

First-principles study of Au–Cu alloy surface changes induced by gas adsorption of CO, NO, or O{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dhifallah, Marwa; Université de Gabes, Unité de recherche environnement, Catalyse et Analyse des Procédés, 6072 Gabes; Dhouib, Adnene

2016-07-14

The surface composition of bimetallics can be strongly altered by adsorbing molecules where the metal with the strongest interaction with the adsorbate segregates into the surface. To investigate the effect of reactive gas on the surface composition of Au–Cu alloy, we examined by means of density functional theory to study the segregation behavior of copper in gold matrices. The adsorption mechanisms of CO, NO, and O{sub 2} gas molecules on gold, copper, and gold-copper low index (111), (100), and (110) surfaces were analyzed from energetic and electronic points of view. Our results show a strong segregation of Cu toward themore » (110) surface in the presence of all adsorbed molecules. Interestingly, the Cu segregation toward the (111) and (100) surface could occur only in the presence of CO and at a lower extent in the presence of NO. The analysis of the electronic structure highlights the different binding characters of adsorbates inducing the Cu segregation.« less

Diamond nanowires: fabrication, structure, properties, and applications.

PubMed

Yu, Yuan; Wu, Liangzhuan; Zhi, Jinfang

2014-12-22

C(sp(3) )C-bonded diamond nanowires are wide band gap semiconductors that exhibit a combination of superior properties such as negative electron affinity, chemical inertness, high Young's modulus, the highest hardness, and room-temperature thermal conductivity. The creation of 1D diamond nanowires with their giant surface-to-volume ratio enhancements makes it possible to control and enhance the fundamental properties of diamond. Although theoretical comparisons with carbon nanotubes have shown that diamond nanowires are energetically and mechanically viable structures, reproducibly synthesizing the crystalline diamond nanowires has remained challenging. We present a comprehensive, up-to-date review of diamond nanowires, including a discussion of their synthesis along with their structures, properties, and applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Technical Reports Server (NTRS)

Tolk, N. H.; Albridge, R. G.; Haglund, R. F., Jr.; Mendenhall, M. H.

1985-01-01

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.

A spectroscopic experimental and computer-assisted empirical model for the production and energetics of excited oxygen molecules formed by atom recombination on shuttle tile surfaces

NASA Technical Reports Server (NTRS)

Owan, D. A.

1981-01-01

A visible emission spectroscopic method was developed. The amounts of excited singlet and triplet oxygen molecules produced by recombination on the Space Shuttle Orbiter thermal protective tiles at elevated temperatures are determined. Rate constants and energetics of the extremely exothermic reaction are evaluated in terms of a chemical and mathematical model. Implications for potential contribution to Shuttle surface reentry heating fluxes are outlined.

Ab initio quantum mechanical calculation of the reaction probability for the Cl-+PH2Cl→ClPH2+Cl- reaction

NASA Astrophysics Data System (ADS)

Farahani, Pooria; Lundberg, Marcus; Karlsson, Hans O.

2013-11-01

The SN2 substitution reactions at phosphorus play a key role in organic and biological processes. Quantum molecular dynamics simulations have been performed to study the prototype reaction Cl-+PH2Cl→ClPH2+Cl-, using one and two-dimensional models. A potential energy surface, showing an energy well for a transition complex, was generated using ab initio electronic structure calculations. The one-dimensional model is essentially reflection free, whereas the more realistic two-dimensional model displays involved resonance structures in the reaction probability. The reaction rate is almost two orders of magnitude smaller for the two-dimensional compared to the one-dimensional model. Energetic errors in the potential energy surface is estimated to affect the rate by only a factor of two. This shows that for these types of reactions it is more important to increase the dimensionality of the modeling than to increase the accuracy of the electronic structure calculation.

Oxygen and sulfur adsorption on vicinal surfaces of copper and silver: Preferred adsorption sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Da-Jiang; Thiel, Patricia A.

We present an extensive density functional theory (DFT) study of adsorption site energetics for oxygen and sulfur adsorbed on two vicinal surfaces of Cu and Ag, with the goal of identifying the most stable adsorption site(s), identifying trends and common themes, and comparing with experimental work in the literature where possible. We also present benchmark calculations for adsorption on the flat (111) and (100) surfaces. The first vicinal surface is the (211), and results are similar for both metals. Here, we find that the step-doubling reconstruction is favored with both adsorbates and is driven by the creation of a specialmore » stable fourfold hollow (4fh) site at the reconstructed step. Zig-zag chain structures consisting of X–M–X units (X = chalcogen, M = metal) at the step edge are considered, in which the special 4fh site is partially occupied. The zig-zag configuration is energetically competitive for oxygen but not sulfur. DFT results for oxygen agree with experiment in terms of the stability of the reconstruction, but contradict the original site assignment. The second vicinal surface is the (410), where again results are similar for both metals. For oxygen, DFT predicts that step sites are filled preferentially even at lowest coverage, followed by terrace sites, consistent with the experiment. For sulfur, in contrast, DFT predicts that terrace sites fill first. Oxygen forms O–M–O rows on the top edge of the step, where it occupies incomplete 4fh sites. This resolves an experimental ambiguity in the site assignment. Finally, for both the (211) and (410) surfaces, the interaction energy that stabilizes the X–M–X chain or row correlates with the linearity of the X–M–X unit, which may explain key differences between oxygen and sulfur.« less

Oxygen and sulfur adsorption on vicinal surfaces of copper and silver: Preferred adsorption sites

DOE PAGES

Liu, Da-Jiang; Thiel, Patricia A.

2018-03-28

We present an extensive density functional theory (DFT) study of adsorption site energetics for oxygen and sulfur adsorbed on two vicinal surfaces of Cu and Ag, with the goal of identifying the most stable adsorption site(s), identifying trends and common themes, and comparing with experimental work in the literature where possible. We also present benchmark calculations for adsorption on the flat (111) and (100) surfaces. The first vicinal surface is the (211), and results are similar for both metals. Here, we find that the step-doubling reconstruction is favored with both adsorbates and is driven by the creation of a specialmore » stable fourfold hollow (4fh) site at the reconstructed step. Zig-zag chain structures consisting of X–M–X units (X = chalcogen, M = metal) at the step edge are considered, in which the special 4fh site is partially occupied. The zig-zag configuration is energetically competitive for oxygen but not sulfur. DFT results for oxygen agree with experiment in terms of the stability of the reconstruction, but contradict the original site assignment. The second vicinal surface is the (410), where again results are similar for both metals. For oxygen, DFT predicts that step sites are filled preferentially even at lowest coverage, followed by terrace sites, consistent with the experiment. For sulfur, in contrast, DFT predicts that terrace sites fill first. Oxygen forms O–M–O rows on the top edge of the step, where it occupies incomplete 4fh sites. This resolves an experimental ambiguity in the site assignment. Finally, for both the (211) and (410) surfaces, the interaction energy that stabilizes the X–M–X chain or row correlates with the linearity of the X–M–X unit, which may explain key differences between oxygen and sulfur.« less

On the relationship between collisionless shock structure and energetic particle acceleration

NASA Technical Reports Server (NTRS)

Kennel, C. F.

1983-01-01

Recent experimental research on bow shock structure and theoretical studies of quasi-parallel shock structure and shock acceleration of energetic particles were reviewed, to point out the relationship between structure and particle acceleration. The phenomenological distinction between quasi-parallel and quasi-perpendicular shocks that has emerged from bow shock research; present efforts to extend this work to interplanetary shocks; theories of particle acceleration by shocks; and particle acceleration to shock structures using multiple fluid models were discussed.

Impacts of Fire Ecology Range Management (FERM) on the Fate and Transport of Energetic Materials on Testing and Training Ranges

DTIC Science & Technology

2006-04-01

be significantly reduced or eliminated. Phytoremediation . Plants can have important effects on the fate and distribution of energetic compounds...place, and they can act as a surface for adherence of energetic compounds. Phytoremediation is frequently applied as a plant based remedial...intermediate log Kow (0.5 to 4) tend to be good targets 2 for phytoremediation because they are taken up by the roots and considered xylem mobile and

Europa Surface Radiation Environment for Lander Assessment

NASA Technical Reports Server (NTRS)

Cooper, John F.; Sturner, Steven J.

2006-01-01

The Jovian magnetospheric particle environment at Europa's surface is critical to assessment of landed astrobiological experiments in three respects: (1) the landing site must be chosen for the best prospects for detectable organic or inorganic signs of Life, e.g. regions of freshly emergent flows from the subsurface; (2) lander systems must reach the surface through the Jovian magnetospheric environment and operate long enough on the surface to return useful data; (3) lander instrumentation must be capable of detecting signs of life in the context of the local environmental radiation and associated chemistry. The Galileo, Voyager, and Pioneer missions have provided a wealth of data on energetic particle intensities throughout the Jovian magnetosphere including from many flybys of Europa. cumulative radiation dosages for spacecraft enroute to Europa can be well characterized, but knowledge of the surface radiation environment is very limited. Energetic electrons should primarily impact the trailing hemisphere with decreasing intensity towards the center of the leading hemisphere and are the most significant radiation component down to meter depths in the surface regolith due to secondary interactions. Observed surface distribution for sulfates is suggestive of electron irradiation but may have alternative interpretations. Having much-larger magnetic gyroradii than electrons, energetic protons and heavier ions irradiate more of the global surface. The particular orientations of electron, proton, and ion gyromotion would project into corresponding directional (e.g., east-west) anisotropies of particle flu into the surface. Particular topographic features at the landing site may therefore offer shielding from part of the incident radiation.

Self-organization of S adatoms on Au(111): √3R30° rows at low coverage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Walen, Holly; Liu, Da -Jiang; Oh, Junepyo

Using scanning tunneling microscopy, we observe an adlayer structure that is dominated by short rows of S atoms, on unreconstructed regions of a Au(111) surface. This structure forms upon adsorption of low S coverage (less than 0.1 monolayer) on a fully reconstructed cleansurface at 300 K, then cooling to 5 K for observation. The rows adopt one of three orientations that are rotated by 30° from the close-packed directions of the Au(111) substrate, and adjacent S atoms in the rows are separated by √3 times the surface lattice constant, a. Monte Carlo simulations are performed on lattice-gas models, we derivedmore » using a limited cluster expansion based on density functional theory energetics. Furthermore, models which include long-range pairwise interactions (extending to 5a), plus selected trio interactions, successfully reproduce the linear rows of S atoms at reasonable temperatures.« less

Self-organization of S adatoms on Au(111): √3R30° rows at low coverage

DOE PAGES

Walen, Holly; Liu, Da -Jiang; Oh, Junepyo; ...

2015-07-06

Using scanning tunneling microscopy, we observe an adlayer structure that is dominated by short rows of S atoms, on unreconstructed regions of a Au(111) surface. This structure forms upon adsorption of low S coverage (less than 0.1 monolayer) on a fully reconstructed cleansurface at 300 K, then cooling to 5 K for observation. The rows adopt one of three orientations that are rotated by 30° from the close-packed directions of the Au(111) substrate, and adjacent S atoms in the rows are separated by √3 times the surface lattice constant, a. Monte Carlo simulations are performed on lattice-gas models, we derivedmore » using a limited cluster expansion based on density functional theory energetics. Furthermore, models which include long-range pairwise interactions (extending to 5a), plus selected trio interactions, successfully reproduce the linear rows of S atoms at reasonable temperatures.« less

Mechanical Properties of a vdW molecular monolayer at a metal surface: Structural Polymorphism leading to facile compression

NASA Astrophysics Data System (ADS)

Sun, Dezheng; Kim, Daeho; Le, Duy; Borck, Øyvind; Berland, Kristian; Kim, Kwangmoo; Lu, Wenhao; Zhu, Yeming; Luo, Miaomiao; Wyrick, Jon; Cheng, Zhihai; Einstein, T. L.; Rahman, Talat; Hyldgaard, Per; Bartels, Ludwig

2011-03-01

Intermolecular force plays an important role in self-assembly and surface pattern formation. Anthracene and similar unsubstituted arenes attach to a metallic substrate predominantly through van der Waals interaction leading. In this contribution we present images how anthracene on Cu(111) forms a large number of highly ordered patterns that feature a broad array of structural motifs. Density functional theory modeling including vdW interactions allows us to model the energetic of the pattern formation at high fidelity. Moreover, it allows us to deduce the strain energy associated with films of varying coverage. From this work, we obtain the Young's modulus and Poisson Ratio of a molecular monolayer, which resemble properties conventionally found for porous materials. These patterns are in marked contrast to those found after introduction of functional groups in the molecules, such as carbonyls or thiols.

Energetics of Nanomaterials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hellman, Frances

2004-12-13

This project, ''Energetics of Nanomaterials'', represents a three-year collaboration among Alexandra Navrotsky (University of California at Davis), Brian Woodfield and Juliana Boerio-Goates (Brigham Young University) and Frances Hellman (University of California at San Diego). Its purpose has been to explore the differences between bulk materials, nanoparticles, and thin films in terms of their thermodynamic properties, with an emphasis on heat capacities and entropies, as well as enthalpies. We used our combined experimental techniques to address the following questions: How does energy and entropy depend on particle size and crystal structure? Do entropic differences have their origins in changes in vibrationalmore » densities of states or configurational (including surface configuration) effects? Do material preparation and sample geometry, i.e., nanoparticles versus thin films, change these quantities? How do the thermodynamics of magnetic and structural transitions change in nanoparticles and thin films? Are different crystal structures stabilized for a given composition at the nanoscale, and are the responsible factors energetic, entropic, or both? How do adsorption energies (for water and other gases) depend on particle size and crystal structure in the nanoregime? What are the energetics of formation and strain energies in artificially layered thin films? Do the differing structures of grain boundaries in films and nanocomposites alter the energetics of nanoscale materials? Of the several directions we first proposed, we initially concentrated on a few systems: TiO(sub 2), CoO, and CoO-MgO. In these systems, we were able to clearly identify particle size-dependent effects on energy and vibrational entropy, and to separate out the effect of particle size and water content on the enthalpy of formation of the various TiO(sub 2) polymorphs. With CoO, we were able to directly compare nanoparticle films and bulk materials; this comparison is important because films can be either 2 dimensional structures, limited by thickness, or can be dominated by nanoparticle granular behavior. These materials represent good model systems which are relevant to technological and geochemical applications as well as to the fundamental underlying science. The collaboration was both congenial and fruitful. We exchanged both samples and scholars among the laboratories. We met several times a year, rotating these meetings among the three institutions. We had frequent conference calls and were in constant email contact. We learned an immense amount from each other because we brought not just different methodologies but different disciplines to the project. In particular, the interplay of physics (Hellman), chemistry (Woodfield, Boerio-Goates, Navrotsky) and geochemistry (Navrotsky) viewpoints has been very enriching. The result has been a number of publications already in print, and several more in preparation, graduate student PhD and MS degrees, and undergraduate research students supported, as well as a well-developed collaboration that will lead to even more fruitful and important science in the coming years.« less

Synthesis and Thermal Analysis of Nano-Aluminum/Fluorinated Polyurethane Elastomeric Composites for Structural Energetics.

PubMed

Zhang, Xianyu; Kim, Jin Seuk; Kwon, Younghwan

2017-04-01

Here we describe the synthesis of polyurethane (PU)-based energetic nanocomposites loaded with nano-aluminum (n-Al) particles. The energetic nanocomposite was prepared by polyurethane reaction of poly(glycidyl azide-co-tetramethylene glycol) (PGT) prepolymers and IPDI/N-100 isocyanates with simultaneous catalyst-free azide-alkyne Click reaction in the presence of n-Al. Initial study carried out with various n-Al/fluorinated PGT blends and demonstrated the potential of fluorinated PGT prepolymer for an energetic PU matrix. Thermal analysis of n-Al/fluorinated PGT-based PU energetic nanocomposite was performed using DSC and TGA.

Europa's surface radiation environment and considerations for in-situ sampling and biosignature detection

NASA Astrophysics Data System (ADS)

Nordheim, T.; Paranicas, C.; Hand, K. P.

2017-12-01

Jupiter's moon Europa is embedded deep within the Jovian magnetosphere and is thus exposed to bombardment by charged particles, from thermal plasma to more energetic particles at radiation belt energies. In particular, energetic charged particles are capable of affecting the uppermost layer of surface material on Europa, in some cases down to depths of several meters (Johnson et al., 2004; Paranicas et al., 2009, 2002). Examples of radiation-induced surface alteration include sputtering, radiolysis and grain sintering; processes that are capable of significantly altering the physical properties of surface material. Radiolysis of surface ices containing sulfur-bearing contaminants from Io has been invoked as a possible explanation for hydrated sulfuric acid detected on Europa's surface (Carlson et al., 2002, 1999) and radiolytic production of oxidants represents a potential source of energy for life that could reside within Europa's sub-surface ocean (Chyba, 2000; Hand et al., 2007; Johnson et al., 2003; Vance et al., 2016). Accurate knowledge of Europa's surface radiation environment is essential to the interpretation of space and Earth-based observations of Europa's surface and exosphere. Furthermore, future landed missions may seek to sample endogenic material emplaced on Europa's surface to investigate its chemical composition and to search for biosignatures contained within. Such material would likely be sampled from the shallow sub-surface, and thus, it becomes crucial to know to which degree this material is expected to have been radiation processed.Here we will present modeling results of energetic electron and proton bombardment of Europa's surface, including interactions between these particles and surface material. In addition, we will present predictions for biosignature destruction at different geographical locations and burial depths and discuss the implications of these results for surface sampling by future missions to Europa's surface.

Refined energetic ordering for sulphate-water (n = 3-6) clusters using high-level electronic structure calculations

NASA Astrophysics Data System (ADS)

Lambrecht, Daniel S.; McCaslin, Laura; Xantheas, Sotiris S.; Epifanovsky, Evgeny; Head-Gordon, Martin

2012-10-01

This work reports refinements of the energetic ordering of the known low-energy structures of sulphate-water clusters ? (n = 3-6) using high-level electronic structure methods. Coupled cluster singles and doubles with perturbative triples (CCSD(T)) is used in combination with an estimate of basis set effects up to the complete basis set limit using second-order Møller-Plesset theory. Harmonic zero-point energy (ZPE), included at the B3LYP/6-311 + + G(3df,3pd) level, was found to have a significant effect on the energetic ordering. In fact, we show that the energetic ordering is a result of a delicate balance between the electronic and vibrational energies. Limitations of the ZPE calculations, both due to electronic structure errors, and use of the harmonic approximation, probably constitute the largest remaining errors. Due to the often small energy differences between cluster isomers, and the significant role of ZPE, deuteration can alter the relative energies of low-lying structures, and, when it is applied in conjunction with calculated harmonic ZPEs, even alters the global minimum for n = 5. Experiments on deuterated clusters, as well as more sophisticated vibrational calculations, may therefore be quite interesting.

Identification of Complex Carbon Nanotube Structures

NASA Technical Reports Server (NTRS)

Han, Jie; Saini, Subhash (Technical Monitor)

1998-01-01

A variety of complex carbon nanotube (CNT) structures have been observed experimentally. These include sharp bends, branches, tori, and helices. They are believed to be formed by using topological defects such as pentagons and heptagons to connect different CNT. The effects of type, number, and arrangement (separation and orientation) of defects on atomic structures and energetics of complex CNT are investigated using topology, quantum mechanics and molecular mechanics calculations. Energetically stable models are derived for identification of observed complex CNT structures.

Effects of nonadditive interactions on ion solvation at the water/vapor interface: a molecular dynamics study.

PubMed

Yagasaki, Takuma; Saito, Shinji; Ohmine, Iwao

2010-12-09

The solvation of halide ions at the water/vapor interface is investigated by using molecular dynamics simulations with nonpolarizable molecular mechanical (MM), polarizable MM, and quantum mechanical (QM)/MM methods. The free energy profile of the ion solvation is decomposed into the energy and the entropic contributions along the ion displacement from inside to the surface of water. It is found that the surface affinity of the ion, relative to the bulk value, is determined by a subtle balance between the energetic destabilization and the entropic stabilization with the ion displacement. The amount of energetic destabilization is found to be reduced when nonadditive interactions are included, as in the polarizable MM and QM/MM models. The structure of water around the ion at the interface is also largely modified when the higher order effects are considered. For example, the induced dipole effect enhances the solvation structure around the ion at the interface significantly and thus reduces the amount of entropic stabilization at the interface, relative to in the bulk. It is found that this induced dipole effect causes the slowing in the ion-water hydrogen bond dynamics at the interface. On the other hand, the higher order induced multipole effects in the QM/MM method suppress both the excessive enhancement of the solvation structure and the slowing of the ion-water hydrogen bond dynamics at the interface. The present study demonstrates that not only the induced dipole moment but also the higher order induced multipole moments, which are neglected in standard empirical models, are essential for the correct description of the ion solvation at the water/vapor interface.

Interplay between structure, stoichiometry, and electron transfer dynamics in SILAR-based quantum dot-sensitized oxides.

PubMed

Wang, Hai; Barceló, Irene; Lana-Villarreal, Teresa; Gómez, Roberto; Bonn, Mischa; Cánovas, Enrique

2014-10-08

We quantify the rate and efficiency of picosecond electron transfer (ET) from PbS nanocrystals, grown by successive ionic layer adsorption and reaction (SILAR), into a mesoporous SnO2 support. Successive SILAR deposition steps allow for stoichiometry- and size-variation of the QDs, characterized using transmission electron microscopy. Whereas for sulfur-rich (p-type) QD surfaces substantial electron trapping at the QD surface occurs, for lead-rich (n-type) QD surfaces, the QD trapping channel is suppressed and the ET efficiency is boosted. The ET efficiency increase achieved by lead-rich QD surfaces is found to be QD-size dependent, increasing linearly with QD surface area. On the other hand, ET rates are found to be independent of both QD size and surface stoichiometry, suggesting that the donor-acceptor energetics (constituting the driving force for ET) are fixed due to Fermi level pinning at the QD/oxide interface. Implications of our results for QD-sensitized solar cell design are discussed.

Construct 3D porous hollow Co3O4 micro-sphere: A potential oxidizer of nano-energetic materials with superior reactivity

NASA Astrophysics Data System (ADS)

Wang, Jun; Zheng, Bo; Qiao, Zhiqiang; Chen, Jin; Zhang, Liyuan; Zhang, Long; Li, Zhaoqian; Zhang, Xingquan; Yang, Guangcheng

2018-06-01

High energy density and rapid reactivity are the future trend for nano-energetic materials. Energetic performance of nano-energetic materials depends on the interfacial diffusion and mass transfer during the reacted process. However, the development of desired structure to significantly enhance reactivity still remains challenging. Here we focused on the design and preparation of 3D porous hollow Co3O4 micro-spheres, in which gas-blowing agents (air) and maximize interfacial interactions were introduced to enhance mass transport and reduce the diffusion distance between the oxidizer and fuel (Aluminum). The 3D hierarchical Co3O4/Al based nano-energetic materials show a low-onset decomposition temperature (423 °C), and high heat output (3118 J g-1) resulting from porous and hollow nano-structure of Co3O4 micro-spheres. Furthermore, 3D hierarchical Co3O4/Al arrays were directly fabricated on the silicon substrate, which was fully compatible with silicon-based microelectromechanical systems to achieve functional nanoenergetics-on-a-chip. This approach provides a simple and efficient way to fabricate 3D ordered nano-energetic arrays with superior reactivity and the potential on the application in micro-energetic devices.

Structure, energetics and vibrational spectra of dimers, trimers, and tetramers of HX (X = Cl, Br, I)

NASA Astrophysics Data System (ADS)

Latajka, Zdzislaw; Scheiner, Steve

1997-03-01

The title complexes are studied by correlated ab initio methods using a pseudopotential double-ζ basis set, augmented by diffuse sp and two sets of polarization functions. The binding energies of the complexes decrease in the order HCl > HBr > HI. In the mixed HX…HX' dimers, the nature of the proton-donor molecule is more important than is the proton-acceptor with respect to the strength of the interaction. Only one minimum is found on the potential energy surface of the trimers and tetramers, which corresponds to the C nh cyclic structure. Enlargement of the complex leads to progressively greater individual H-bond energy and HX bond stretch, coupled with reduced intermolecular separation and smaller nonlinearity of each H-bond. Electron correlation makes a larger contribution as the atomic number of X increases. The highest degree of cooperativity is noted for oligomers of HCl and HBr, as compared to HI. The nonadditivity is dominated by terms present at the SCF level. The vibrational frequencies exhibit trends that generally parallel the energetics and geometry patterns, particularly the red shifts of the HX stretches and the intermolecular modes.

Estimating Eulerian spectra from pairs of drifters

NASA Astrophysics Data System (ADS)

LaCasce, Joe

2017-04-01

GPS-tracked surface drifters offer the possibility of sampling energetic variations at the ocean surface on scales of only 10s of meters, much less than that resolved by satellite. Here we investigate whether velocity differences between pairs of drifters can be used to estimate kinetic energy spectra. Theoretical relations between the spectrum and the second-order longitudinal structure function for 2D non-divergent flow are derived. The structure function is a natural statistic for particle pairs and is easily calculated. However it integrates contributions across wavenumber, and this tends to obscure the spectral dependencies when turbulent inertial ranges are of finite extent. Nevertheless, the transform from spectrum to structure function is robust, as illustrated with Eulerian data collected from aircraft. The inverse transform, from structure function to spectrum, is much less robust, yielding poor results in particular at large wavenumbers. This occurs because the transform involves a filter function which magnifies contributions from large pair separations, which tend to be noisy. Fitting the structure function to a polynomial improves the spectral estimate, but not sufficiently to distinguish correct inertial range dependencies. Thus with Lagrangian data, it is appears preferable to focus on structure functions, despite their shortcomings.

An evaluation of complementary approaches to elucidate fundamental interfacial phenomena driving adhesion of energetic materials

DOE PAGES

Hoss, Darby J.; Knepper, Robert; Hotchkiss, Peter J.; ...

2016-03-23

In this study, cohesive Hamaker constants of solid materials are measured via optical and dielectric properties (i.e., Lifshitz theory), inverse gas chromatography (IGC), and contact angle measurements. To date, however, a comparison across these measurement techniques for common energetic materials has not been reported. This has been due to the inability of the community to produce samples of energetic materials that are readily compatible with contact angle measurements. Here we overcome this limitation by using physical vapor deposition to produce thin films of five common energetic materials, and the contact angle measurement approach is applied to estimate the cohesive Hamakermore » constants and surface energy components of the materials. The cohesive Hamaker constants range from 85 zJ to 135 zJ across the different films. When these Hamaker constants are compared to prior work using Lifshitz theory and nonpolar probe IGC, the relative magnitudes can be ordered as follows: contact angle > Lifshitz > IGC. Furthermore, the dispersive surface energy components estimated here are in good agreement with those estimated by IGC. Due to these results, researchers and technologists will now have access to a comprehensive database of adhesion constants which describe the behavior of these energetic materials over a range of settings.« less

Molecular simulations and experimental studies of zeolites

NASA Astrophysics Data System (ADS)

Moloy, Eric C.

Zeolites are microporous aluminosilicate tetrahedral framework materials that have symmetric cages and channels with open-diameters between 0.2 and 2.0 nm. Zeolites are used extensively in the petrochemical industries for both their microporosity and their catalytic properties. The role of water is paramount to the formation, structure, and stability of these materials. Zeolites frequently have extra-framework cations, and as a result, are important ion-exchange materials. Zeolites also play important roles as molecular sieves and catalysts. For all that is known about zeolites, much remains a mystery. How, for example, can the well established metastability of these structures be explained? What is the role of water with respect to the formation, stabilization, and dynamical properties? This dissertation addresses these questions mainly from a modeling perspective, but also with some experimental work as well. The first discussion addresses a special class of zeolites: pure-silica zeolites. Experimental enthalpy of formation data are combined with molecular modeling to address zeolitic metastability. Molecular modeling is used to calculate internal surface areas, and a linear relationship between formation enthalpy and internal surface areas is clearly established, producing an internal surface energy of approximately 93 mJ/m2. Nitrate bearing sodalite and cancrinite have formed under the caustic chemical conditions of some nuclear waste processing centers in the United States. These phases have fouled expensive process equipment, and are the primary constituents of the resilient heels in the bottom of storage tanks. Molecular modeling, including molecular mechanics, molecular dynamics, and density functional theory, is used to simulate these materials with respect to structure and dynamical properties. Some new, very interesting results are extracted from the simulation of anhydrous Na6[Si6Al 6O24] sodalite---most importantly, the identification of two distinct oxygen sites (rather than one), and formation of a new supercell. New calorimetric measurements of enthalpy are used to examine the energetics of the hydrosodalite family of zeolites---specifically, formation enthalpies and hydration energies. Finally, force-field computational methods begin the examination of water in terms of energetics, structure, and radionuclide containment and diffusion.

Effects of fusion relevant transient energetic radiation, plasma and thermal load on PLANSEE double forged tungsten samples in a low-energy plasma focus device

NASA Astrophysics Data System (ADS)

Javadi, S.; Ouyang, B.; Zhang, Z.; Ghoranneviss, M.; Salar Elahi, A.; Rawat, R. S.

2018-06-01

Tungsten is the leading candidate for plasma facing component (PFC) material for thermonuclear fusion reactors and various efforts are ongoing to evaluate its performance or response to intense fusion relevant radiation, plasma and thermal loads. This paper investigates the effects of hot dense decaying pinch plasma, highly energetic deuterium ions and fusion neutrons generated in a low-energy (3.0 kJ) plasma focus device on the structure, morphology and hardness of the PLANSEE double forged tungsten (W) samples surfaces. The tungsten samples were provided by Forschungszentrum Juelich (FZJ), Germany via International Atomic Energy Agency, Vienna, Austria. Tungsten samples were irradiated using different number of plasma focus (PF) shots (1, 5 and 10) at a fixed axial distance of 5 cm from the anode top and also at various distances from the top of the anode (5, 7, 9 and 11 cm) using fixed number (5) of plasma focus shots. The virgin tungsten sample had bcc structure (α-W phase). After PF irradiation, the XRD analysis showed (i) the presence of low intensity new diffraction peak corresponding to β-W phase at (211) crystalline plane indicating the partial structural phase transition in some of the samples, (ii) partial amorphization, and (iii) vacancy defects formation and compressive stress in irradiated tungsten samples. Field emission scanning electron microscopy showed the distinctive changes to non-uniform surface with nanometer sized particles and particle agglomerates along with large surface cracks at higher number of irradiation shots. X-ray photoelectron spectroscopy analysis demonstrated the reduction in relative tungsten oxide content and the increase in metallic tungsten after irradiation. Hardness of irradiated samples initially increased for one shot exposure due to reduction in tungsten oxide phase, but then decreased with increasing number of shots due to increasing concentration of defects. It is demonstrated that the plasma focus device provides appropriate intense fusion relevant pulses for testing the structural, morphological and mechanical changes on irradiated tungsten samples.

The Dominant Folding Route Minimizes Backbone Distortion in SH3

PubMed Central

Lammert, Heiko; Noel, Jeffrey K.; Onuchic, José N.

2012-01-01

Energetic frustration in protein folding is minimized by evolution to create a smooth and robust energy landscape. As a result the geometry of the native structure provides key constraints that shape protein folding mechanisms. Chain connectivity in particular has been identified as an essential component for realistic behavior of protein folding models. We study the quantitative balance of energetic and geometrical influences on the folding of SH3 in a structure-based model with minimal energetic frustration. A decomposition of the two-dimensional free energy landscape for the folding reaction into relevant energy and entropy contributions reveals that the entropy of the chain is not responsible for the folding mechanism. Instead the preferred folding route through the transition state arises from a cooperative energetic effect. Off-pathway structures are penalized by excess distortion in local backbone configurations and contact pair distances. This energy cost is a new ingredient in the malleable balance of interactions that controls the choice of routes during protein folding. PMID:23166485

Defect states and their energetic position and distribution in organic molecular semiconductors

NASA Astrophysics Data System (ADS)

Sharma, Akanksha; Yadav, Sarita; Kumar, Pramod; Ray Chaudhuri, Sumita; Ghosh, Subhasis

2013-04-01

Energetic position and distribution of defect states due to structural disorder in pentacene and copper phthalocyanine have been obtained by capacitance based spectroscopic techniques. It has been shown that capacitance-frequency and capacitance-voltage characteristics exhibit Gaussian distribution of traps with an energetic position at around 0.5 eV above the highest occupied molecular orbital level of the pentacene and CuPc. These traps have been created by varying growth conditions and almost identical trap parameters in pentacene and copper phthalocyanine indicate that similar structural disorder is responsible for these traps.

Dangling bond energetics in carbon nitride and phosphorus carbide thin films with fullerene-like and amorphous structure

NASA Astrophysics Data System (ADS)

Gueorguiev, G. K.; Broitman, E.; Furlan, A.; Stafström, S.; Hultman, L.

2009-11-01

The energy cost for dangling bond formation in Fullerene-like Carbon Nitride (FL-CN x) and Phosphorus carbide (FL-CP x) as well as their amorphous counterparts: a-CN x, a-CP x, and a-C has been calculated within the framework of Density Functional Theory and compared with surface water adsorption measurements. The highest energy cost is found in the FL-CN x (about 1.37 eV) followed by FL-CP x compounds (0.62-1.04 eV).

Surface regulated arsenenes as Dirac materials: From density functional calculations

NASA Astrophysics Data System (ADS)

Yuan, Junhui; Xie, Qingxing; Yu, Niannian; Wang, Jiafu

2017-02-01

Using first principle calculations based on density functional theory (DFT), we have systematically investigated the structure stability and electronic properties of chemically decorated arsenenes, AsX (X = CN, NC, NCO, NCS and NCSe). Phonon dispersion and formation energy analysis reveal that all the five chemically decorated buckled arsenenes are energetically favorable and could be synthesized. Our study shows that wide-bandgap arsenene would turn into Dirac materials when functionalized by -X (X = CN, NC, NCO, NCS and NCSe) groups, rendering new promises in next generation high-performance electronic devices.

Fragmentation of Structural Energetic Materials: Implications for Performance

NASA Astrophysics Data System (ADS)

Aydelotte, Brady; Braithwaite, Christopher; Thadhani, Naresh

2013-06-01

Fragmentation results for structural energetic materials based on intermetallic forming mixtures are reviewed and the implications of the fragment populations are discussed. Cold Sprayed Ni+Al and explosively compacted mixtures of Ni+Al+W and Ni+Al+W+Zr powders were fabricated into ring shaped samples and subjected to fragmentation tests. Ring velocity was monitored and fragments were soft captured in order to study the fragmentation process. It was determined that the fragments produced by these structural energetic materials are much smaller than those typically produced by ductile metals such as steel or aluminum. This has implications for combustion processes that may occur subsequent to the fragmentation process. ONR/MURI grant No. N00014-07-1-0740 Dr. Cliff Bedford PM.

Theory and observation of the onset of nonlinear structures due to eigenmode destabilization by fast ions in tokamaks

DOE PAGES

Duarte, V. N.; Berk, H. L.; Gorelenkov, N. N.; ...

2017-12-12

Alfvén waves can induce the ejection of fast ions in different forms in tokamaks. In order to develop predictive capabilities to anticipate the nature of fast ion transport, a methodology is proposed to differentiate the likelihood of energetic-particle-driven instabilities to produce frequency chirping or fixed-frequency oscillations. Furthermore, the proposed method employs numerically calculated eigenstructures and multiple resonance surfaces of a given mode in the presence of energetic ion drag and stochasticity (due to collisions and micro-turbulence). Toroidicity-induced, reversed-shear and beta-induced Alfvén-acoustic eigenmodes are used as examples. Waves measured in experiments are characterized, and compatibility is found between the proposed criterionmore » predictions and the experimental observation or lack of observation of chirping behavior of Alfvénic modes in different tokamaks. It is found that the stochastic diffusion due to micro-turbulence can be the dominant energetic particle detuning mechanism near the resonances in many plasma experiments, and its strength is the key as to whether chirping solutions are likely to arise. We proposed a criterion that constitutes a useful predictive tool in assessing whether the nature of the transport for fast ion losses in fusion devices will be dominated by convective or diffusive processes.« less

Theory and observation of the onset of nonlinear structures due to eigenmode destabilization by fast ions in tokamaks

NASA Astrophysics Data System (ADS)

Duarte, V. N.; Berk, H. L.; Gorelenkov, N. N.; Heidbrink, W. W.; Kramer, G. J.; Nazikian, R.; Pace, D. C.; Podestà, M.; Van Zeeland, M. A.

2017-12-01

Alfvén waves can induce the ejection of fast ions in different forms in tokamaks. In order to develop predictive capabilities to anticipate the nature of fast ion transport, a methodology is proposed to differentiate the likelihood of energetic-particle-driven instabilities to produce frequency chirping or fixed-frequency oscillations. The proposed method employs numerically calculated eigenstructures and multiple resonance surfaces of a given mode in the presence of energetic ion drag and stochasticity (due to collisions and micro-turbulence). Toroidicity-induced, reversed-shear and beta-induced Alfvén-acoustic eigenmodes are used as examples. Waves measured in experiments are characterized, and compatibility is found between the proposed criterion predictions and the experimental observation or lack of observation of chirping behavior of Alfvénic modes in different tokamaks. It is found that the stochastic diffusion due to micro-turbulence can be the dominant energetic particle detuning mechanism near the resonances in many plasma experiments, and its strength is the key as to whether chirping solutions are likely to arise. The proposed criterion constitutes a useful predictive tool in assessing whether the nature of the transport for fast ion losses in fusion devices will be dominated by convective or diffusive processes.

Theory and observation of the onset of nonlinear structures due to eigenmode destabilization by fast ions in tokamaks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Duarte, V. N.; Berk, H. L.; Gorelenkov, N. N.

Alfvén waves can induce the ejection of fast ions in different forms in tokamaks. In order to develop predictive capabilities to anticipate the nature of fast ion transport, a methodology is proposed to differentiate the likelihood of energetic-particle-driven instabilities to produce frequency chirping or fixed-frequency oscillations. Furthermore, the proposed method employs numerically calculated eigenstructures and multiple resonance surfaces of a given mode in the presence of energetic ion drag and stochasticity (due to collisions and micro-turbulence). Toroidicity-induced, reversed-shear and beta-induced Alfvén-acoustic eigenmodes are used as examples. Waves measured in experiments are characterized, and compatibility is found between the proposed criterionmore » predictions and the experimental observation or lack of observation of chirping behavior of Alfvénic modes in different tokamaks. It is found that the stochastic diffusion due to micro-turbulence can be the dominant energetic particle detuning mechanism near the resonances in many plasma experiments, and its strength is the key as to whether chirping solutions are likely to arise. We proposed a criterion that constitutes a useful predictive tool in assessing whether the nature of the transport for fast ion losses in fusion devices will be dominated by convective or diffusive processes.« less

Fast moving plasma structures in the distant magnetotail

NASA Technical Reports Server (NTRS)

Scholer, M.; Klecker, B.; Hovestadt, D.; Gloeckler, G.; Ipavich, F. M.; Smith, E. J.

1984-01-01

The paper reports for the first time the detailed time behavior of the intensities and the angular distributions of energetic protons and electrons in the distant magnetotail of the earth at 220 earth radii and 110 earth radii. The data have been obtained by the Max-Planck-Institut/University of Maryland sensor system on ISEE 3 during the spacecraft's first deep tail passage. Three energetic particle bursts are studied in detail. It is suggested that the satellite encounters detached plasma structures evidenced by the isotropic electrons. These structures, probably plasmoids, move with high velocities (about 800 km/s) down the tail. The energetic electrons and protons stream ahead of these fast tailward moving plasma structures, which leads to the various time dispersion effects. This allows, in principle, a determination of the source distance from the satellite.

The eXtra Small Analyzer for Neutrals (XSAN) instrument on-board of the Lunar-Glob lander

NASA Astrophysics Data System (ADS)

Wieser, Martin; Barabash, Stas

A large fraction of up to 20 precent of the solar wind impinging onto the lunar surface is reflected back to space as energetic neutral atoms. The SARA instrument on the Chandrayaan-1 mission provided a comprehensive coverage of the lunar surface of this interaction by mapping it from a 100 - 200 km orbit. The micro-physics of this reflection process is unexplored however. With the eXtra Small Analyzer for Neutrals instrument (XSAN) placed on the Lunar-Glob lander, we will directly investigate the production process of energetic neutral atoms from a vantage point of only meters from the surface for the first time. The XSAN design is based on the Solar Wind Monitor (SWIM) family of instruments originally flown on the Indian Chandrayaan-1 mission and with derivatives built e.g. for ESA's BepiColombo Mission to Mercury or for Phobos-Grunt. XSAN extends the functionality of this instrument family by adding a neutral atom to ion conversion surface in its entrance system. This will make it possible to measure detailed energy spectra and mass composition of the energetic neutral atoms originating from the lunar surface. We present an overview of the XSAN instrument and its science and report on latest developments.

Final Report: “Energetics of Nanomaterials”

DOE Office of Scientific and Technical Information (OSTI.GOV)

Woodfield, Brian F.; navrotsky, alexandra; Ross, Nancy

2016-08-30

Nanomaterials, solids with very small particle size, form the basis of new technologies that are revolutionizing fields such as energy, lighting, electronics, medical diagnostics, and drug delivery. These nanoparticles are different from conventional bulk materials in many ways we do not yet fully understand. This project focused on their structure and thermodynamics and emphasized the role of water in nanoparticle surfaces. Using a unique and synergistic combination of high-tech techniques—namely oxide melt solution calorimetry, cryogenic heat capacity measurements, and inelastic neutron scattering—this work has identified differences in structure, thermodynamic stability, and water behavior on nanoparticles as a function of compositionmore » and particle size. The systematics obtained increase the fundamental understanding needed to synthesize, retain, and apply these technologically important nanomaterials and to predict and tailor new materials for enhanced functionality, eventually leading to a more sustainable way of life. Highlights are reported on the following topics: surface energies, thermochemistry of nanoparticles, and changes in stability at the nanoscale; heat capacity models and the gapped phonon spectrum; control of pore structure, acid sites, and thermal stability in synthetic γ-aluminas; the lattice contribution is the same for bulk and nanomaterials; and inelastic neutron scattering studies of water on nanoparticle surfaces.« less

Final Report: "Energetics of Nanomaterials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Navrotsky, Alexandra; Ross, Nancy; Woodfield, Brian

2015-02-14

Nanomaterials, solids with very small particle size, form the basis of new technologies that are revolutionizing fields such as energy, lighting, electronics, medical diagnostics, and drug delivery. These nanoparticles are different from conventional bulk materials in many ways we do not yet fully understand. This project focused on their structure and thermodynamics and emphasized the role of water in nanoparticle surfaces. Using a unique and synergistic combination of high-tech techniques—namely oxide melt solution calorimetry, cryogenic heat capacity measurements, and inelastic neutron scattering—this work has identified differences in structure, thermodynamic stability, and water behavior on nanoparticles as a function of compositionmore » and particle size. The systematics obtained increase the fundamental understanding needed to synthesize, retain, and apply these technologically important nanomaterials and to predict and tailor new materials for enhanced functionality, eventually leading to a more sustainable way of life. Highlights are reported on the following topics: surface energies, thermochemistry of nanoparticles, and changes in stability at the nanoscale; heat capacity models and the gapped phonon spectrum; control of pore structure, acid sites, and thermal stability in synthetic γ-aluminas; the lattice contribution is the same for bulk and nanomaterials; and inelastic neutron scattering studies of water on nanoparticle surfaces.« less

CURVATURE-DRIVEN MOLECULAR FLOW ON MEMBRANE SURFACE*

PubMed Central

MIKUCKI, MICHAEL; ZHOU, Y. C.

2017-01-01

This work presents a mathematical model for the localization of multiple species of diffusion molecules on membrane surfaces. Morphological change of bilayer membrane in vivo is generally modulated by proteins. Most of these modulations are associated with the localization of related proteins in the crowded lipid environments. We start with the energetic description of the distributions of molecules on curved membrane surface, and define the spontaneous curvature of bilayer membrane as a function of the molecule concentrations on membrane surfaces. A drift-diffusion equation governs the gradient flow of the surface molecule concentrations. We recast the energetic formulation and the related governing equations by using an Eulerian phase field description to define membrane morphology. Computational simulations with the proposed mathematical model and related numerical techniques predict (i) the molecular localization on static membrane surfaces at locations with preferred mean curvatures, and (ii) the generation of preferred mean curvature which in turn drives the molecular localization. PMID:29056778

Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation

PubMed Central

Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H.; Navrotsky, Alexandra

2013-01-01

Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn3+/Mn4+ ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states. PMID:23667149

Ni2C surface carbide to catalyze low-temperature graphene growth

NASA Astrophysics Data System (ADS)

Martinez-Gordillo, Rafael; Varvenne, Céline; Amara, Hakim; Bichara, Christophe

2018-05-01

The possibility to grow a graphene layer using the chemical-vapor-deposition technique over a Ni2C /Ni (111 ) substrate has been identified experimentally, with the advantage of having a lower processing temperature (T <500 ∘C ), compared to standard growth over a Ni (111 ) surface. To understand the role of the metal carbide/metal catalyst, we first perform a static study of the Ni2C /Ni (111 ) structure and of the binding and removal of a carbon atom at the surface, using both a tight-binding (TB) energetic model and ab initio calculations. Grand-canonical Monte Carlo TB simulations then allow us (i) to determine the thermodynamic conditions to grow graphene and (ii) to separate key reaction steps in the growth mechanism explaining how the Ni2C /Ni (111 ) substrate catalyzes graphene formation at low temperature.

Transfer doping of single isolated nanodiamonds, studied by scanning probe microscopy techniques.

PubMed

Bolker, Asaf; Saguy, Cecile; Kalish, Rafi

2014-09-26

The transfer doping of diamond surfaces has been applied in various novel two-dimensional electronic devices. Its extension to nanodiamonds (ND) is essential for ND-based applications in many fields. In particular, understanding the influence of the crystallite size on transfer doping is desirable. Here, we report the results of a detailed study of the electronic energetic band structure of single, isolated transfer-doped nanodiamonds with nanometric resolution using a combination of scanning tunneling spectroscopy and Kelvin force microscopy measurements. The results show how the band gap, the valence band maximum, the electron affinity and the work function all depend on the ND's size and nanoparticle surface properties. The present analysis, which combines information from both scanning tunneling spectroscopy and Kelvin force microscopy, should be applicable to any nanoparticle or surface that can be measured with scanning probe techniques.

Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation.

PubMed

Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H; Navrotsky, Alexandra

2013-05-28

Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn(3+)/Mn(4+) ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states.

Energetics of oscillating lifting surfaces using integral conservation laws

NASA Technical Reports Server (NTRS)

Ahmadi, Ali R.; Widnall, Sheila E.

1987-01-01

The energetics of oscillating flexible lifting surfaces in two and three dimensions is calculated by the use of integral conservation laws in inviscid incompressible flow for general and harmonic transverse oscillations. Total thrust is calculated from the momentum theorem and energy loss rate due to vortex shedding in the wake from the principle of conservation of mechanical energy. Total power required to maintain the oscillations and hydrodynamic efficiency are also determined. In two dimensions, the results are obtained in closed form. In three dimensions, the distribution of vorticity on the lifting surface is also required as input to the calculations. Thus, unsteady lifting-surface theory must be used as well. The analysis is applicable to oscillating lifting surfaces of arbitrary planform, aspect ratio, and reduced frequency and does not require calculation of the leading-edge thrust.

Molecular dynamics simulations to calculate glass transition temperature and elastic constants of novel polyethers.

PubMed

Sarangapani, Radhakrishnan; Reddy, Sreekantha T; Sikder, Arun K

2015-04-01

Molecular dynamics simulations studies are carried out on hydroxyl terminated polyethers that are useful in energetic polymeric binder applications. Energetic polymers derived from oxetanes with heterocyclic side chains with different energetic substituents are designed and simulated under the ensembles of constant particle number, pressure, temperature (NPT) and constant particle number, volume, temperature (NVT). Specific volume of different amorphous polymeric models is predicted using NPT-MD simulations as a function of temperature. Plots of specific volume versus temperature exhibited a characteristic change in slope when amorphous systems change from glassy to rubbery state. Several material properties such as Young's, shear, and bulk modulus, Poisson's ratio, etc. are predicted from equilibrated structures and established the structure-property relations among designed polymers. Energetic performance parameters of these polymers are calculated and results reveal that the performance of the designed polymers is comparable to the benchmark energetic polymers like polyNIMMO, polyAMMO and polyBAMO. Overall, it is worthy remark that this molecular simulations study on novel energetic polyethers provides a good guidance on mastering the design principles and allows us to design novel polymers of tailored properties. Copyright © 2015 Elsevier Inc. All rights reserved.

Energetic ion losses caused by magnetohydrodynamic activity resonant and non-resonant with energetic ions in Large Helical Device

NASA Astrophysics Data System (ADS)

Ogawa, Kunihiro; Isobe, Mitsutaka; Toi, Kazuo; Shimizu, Akihiro; Spong, Donald A.; Osakabe, Masaki; Yamamoto, Satoshi; the LHD Experiment Group

2014-09-01

Experiments to reveal energetic ion dynamics associated with magnetohydrodynamic activity are ongoing in the Large Helical Device (LHD). Interactions between beam-driven toroidal Alfvén eigenmodes (TAEs) and energetic ions have been investigated. Energetic ion losses induced by beam-driven burst TAEs have been observed using a scintillator-based lost fast-ion probe (SLIP) in neutral beam-heated high β plasmas. The loss flux of co-going beam ions increases as the TAE amplitude increases. In addition to this, the expulsion of beam ions associated with edge-localized modes (ELMs) has been also recognized in LHD. The SLIP has indicated that beam ions having co-going and barely co-going orbits are affected by ELMs. The relation between ELM amplitude and ELM-induced loss has a dispersed structure. To understand the energetic ion loss process, a numerical simulation based on an orbit-following model, DELTA5D, that incorporates magnetic fluctuations is performed. The calculation result shows that energetic ions confined in the interior region are lost due to TAE instability, with a diffusive process characterizing their loss. For the ELM, energetic ions existing near the confinement/loss boundary are lost through a convective process. We found that the ELM-induced loss flux measured by SLIP changes with the ELM phase. This relation between the ELM amplitude and measured ELM-induced loss results in a more dispersed loss structure.

Morphological effects on sensitivity of heterogeneous energetic materials

NASA Astrophysics Data System (ADS)

Roy, Sidhartha; Rai, Nirmal; Sen, Oishik; Udaykumar, H. S.

2017-06-01

The mesoscale physical response under shock loading in heterogeneous energetics is inherently linked to the microstructural characteristics. The current work demonstrates the connection between the microstructural features of porous energetic material and its sensitivity. A unified levelset based framework is developed to characterize the microstructures of a given sample. Several morphological metrics describing the mesoscale geometry of the materials are extracted using the current tool including anisotropy, tortuosity, surface to volume, nearest neighbors, size and curvature distributions. The relevant metrics among the ones extracted are identified and correlated to the mesoscale response of the energetic materials under shock loading. Two classes of problems are considered here: (a) field of idealized voids embedded in the HMX material and (b) real samples of pressed HMX. The effects of stochasticity associated with void arrangements on the sensitivity of the energetic material samples are shown. In summary, this work demonstrates the relationship between the mesoscale morphology and shock response of heterogeneous energetic materials using a levelset based framework.

Vertical structure of the near-surface expanding ionosphere of comet 67P probed by Rosetta

NASA Astrophysics Data System (ADS)

Heritier, K. L.; Henri, P.; Vallières, X.; Galand, M.; Odelstad, E.; Eriksson, A. I.; Johansson, F. L.; Altwegg, K.; Behar, E.; Beth, A.; Broiles, T. W.; Burch, J. L.; Carr, C. M.; Cupido, E.; Nilsson, H.; Rubin, M.; Vigren, E.

2017-07-01

The plasma environment has been measured for the first time near the surface of a comet. This unique data set has been acquired at 67P/Churyumov-Gerasimenko during ESA/Rosetta spacecraft's final descent on 2016 September 30. The heliocentric distance was 3.8 au and the comet was weakly outgassing. Electron density was continuously measured with Rosetta Plasma Consortium (RPC)-Mutual Impedance Probe (MIP) and RPC-LAngmuir Probe (LAP) during the descent from a cometocentric distance of 20 km down to the surface. Data set from both instruments have been cross-calibrated for redundancy and accuracy. To analyse this data set, we have developed a model driven by Rosetta Orbiter Spectrometer for Ion and Neutral Analysis-COmetary Pressure Sensor total neutral density. The two ionization sources considered are solar extreme ultraviolet radiation and energetic electrons. The latter are estimated from the RPC-Ion and Electron Sensor (IES) and corrected for the spacecraft potential probed by RPC-LAP. We have compared the results of the model to the electron densities measured by RPC-MIP and RPC-LAP at the location of the spacecraft. We find good agreement between observed and modelled electron densities. The energetic electrons have access to the surface of the nucleus and contribute as the main ionization source. As predicted, the measurements exhibit a peak in the ionospheric density close to the surface. The location and magnitude of the peak are estimated analytically. The measured ionospheric densities cannot be explained with a constant outflow velocity model. The use of a neutral model with an expanding outflow is critical to explain the plasma observations.

Tuning the acid/base properties of nanocarbons by functionalization via amination.

PubMed

Arrigo, Rosa; Hävecker, Michael; Wrabetz, Sabine; Blume, Raoul; Lerch, Martin; McGregor, James; Parrott, Edward P J; Zeitler, J Axel; Gladden, Lynn F; Knop-Gericke, Axel; Schlögl, Robert; Su, Dang Sheng

2010-07-21

The surface chemical properties and the electronic properties of vapor grown carbon nanofibers (VGCNFs) have been modified by treatment of the oxidized CNFs with NH(3). The effect of treatment temperature on the types of nitrogen functionalities introduced was evaluated by synchrotron based X-ray photoelectron spectroscopy (XPS), while the impact of the preparation methods on the surface acid-base properties was investigated by potentiometric titration, microcalorimetry, and zeta potential measurements. The impact of the N-functionalization on the electronic properties was measured by THz-Time Domain spectroscopy. The samples functionalized via amination are characterized by the coexistence of acidic and basic O and N sites. The population of O and N species is temperature dependent. In particular, at 873 K nitrogen is stabilized in substitutional positions within the graphitic structure, as heterocyclic-like moieties. The surface presents heterogeneously distributed and energetically different basic sites. A small amount of strong basic sites gives rise to a differential heat of CO(2) adsorption of 150 kJ mol(-1). However, when functionalization is carried out at 473 K, nitrogen moieties with basic character are introduced and the maximum heat of adsorption is significantly lower, at approximately 90 kJ mol(-1). In the latter sample, energetically different basic sites coexist with acidic oxygen groups introduced during the oxidative step. Under these conditions, a bifunctional acidic and basic surface is obtained with high hydrophilic character. N-functionalization carried out at higher temperature changes the electronic properties of the CNFs as evaluated by THz-TDS. The functionalization procedure presented in this work allows high versatility and flexibility in tailoring the surface chemistry of nanocarbon material to specific needs. This work shows the potential of the N-containing nanocarbon materials obtained via amination in catalysis as well as electronic device materials.

Convective dynamics - Panel report

NASA Technical Reports Server (NTRS)

Carbone, Richard; Foote, G. Brant; Moncrieff, Mitch; Gal-Chen, Tzvi; Cotton, William; Heymsfield, Gerald

1990-01-01

Aspects of highly organized forms of deep convection at midlatitudes are reviewed. Past emphasis in field work and cloud modeling has been directed toward severe weather as evidenced by research on tornadoes, hail, and strong surface winds. A number of specific issues concerning future thrusts, tactics, and techniques in convective dynamics are presented. These subjects include; convective modes and parameterization, global structure and scale interaction, convective energetics, transport studies, anvils and scale interaction, and scale selection. Also discussed are analysis workshops, four-dimensional data assimilation, matching models with observations, network Doppler analyses, mesoscale variability, and high-resolution/high-performance Doppler. It is also noted, that, classical surface measurements and soundings, flight-level research aircraft data, passive satellite data, and traditional photogrammetric studies are examples of datasets that require assimilation and integration.

Potential approaches to the spectroscopic characterization of high performance polymers exposed to energetic protons and heavy ions

NASA Technical Reports Server (NTRS)

Suleman, Naushadalli K.

1991-01-01

A potential limitation to human activity on the lunar surface or in deep space is the exposure of the crew to unacceptably high levels of penetrating space radiations. The radiations of most concerns for such missions are high-energy protons emitted during solar flares, and galactic cosmic rays which are high-energy ions ranging from protons to iron. The development of materials for effective shielding from energetic space radiations will clearly require a greater understanding of the underlying mechanisms of radiation-induced damage in bulk materials. This can be accomplished in part by the detailed spectroscopic characterization of bulk materials that were exposed to simulated space radiations. An experimental data base thus created can then be used in conjunction with existing radiation transport codes in the design and fabrication of effective radiation shielding materials. Electron Paramagnetic Resonance Spectroscopy was proven very useful in elucidating radiation effects in polymers (high performance polymers are often an important components of structural composites).

Initial mechanisms for the decomposition of electronically excited energetic materials: 1,5′-BT, 5,5′-BT, and AzTT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Bing; Yu, Zijun; Bernstein, Elliot R., E-mail: erb@lamar.Colostate.edu

2015-03-28

Decomposition of nitrogen-rich energetic materials 1,5′-BT, 5,5′-BT, and AzTT (1,5′-Bistetrazole, 5,5′-Bistetrazole, and 5-(5-azido-(1 or 4)H-1,2,4-triazol-3-yl)tetrazole, respectively), following electronic state excitation, is investigated both experimentally and theoretically. The N{sub 2} molecule is observed as an initial decomposition product from the three materials, subsequent to UV excitation, with a cold rotational temperature (<30 K). Initial decomposition mechanisms for these three electronically excited materials are explored at the complete active space self-consistent field (CASSCF) level. Potential energy surface calculations at the CASSCF(12,8)/6-31G(d) level illustrate that conical intersections play an essential role in the decomposition mechanism. Electronically excited S{sub 1} molecules can non-adiabatically relaxmore » to their ground electronic states through (S{sub 1}/S{sub 0}){sub CI} conical intersections. 1,5′-BT and 5,5′-BT materials have several (S{sub 1}/S{sub 0}){sub CI} conical intersections between S{sub 1} and S{sub 0} states, related to different tetrazole ring opening positions, all of which lead to N{sub 2} product formation. The N{sub 2} product for AzTT is formed primarily by N–N bond rupture of the –N{sub 3} group. The observed rotational energy distributions for the N{sub 2} products are consistent with the final structures of the respective transition states for each molecule on its S{sub 0} potential energy surface. The theoretically derived vibrational temperature of the N{sub 2} product is high, which is similar to that found for energetic salts and molecules studied previously.« less

Mars' surface radiation environment measured with the Mars Science Laboratory's Curiosity rover.

PubMed

Hassler, Donald M; Zeitlin, Cary; Wimmer-Schweingruber, Robert F; Ehresmann, Bent; Rafkin, Scot; Eigenbrode, Jennifer L; Brinza, David E; Weigle, Gerald; Böttcher, Stephan; Böhm, Eckart; Burmeister, Soenke; Guo, Jingnan; Köhler, Jan; Martin, Cesar; Reitz, Guenther; Cucinotta, Francis A; Kim, Myung-Hee; Grinspoon, David; Bullock, Mark A; Posner, Arik; Gómez-Elvira, Javier; Vasavada, Ashwin; Grotzinger, John P

2014-01-24

The Radiation Assessment Detector (RAD) on the Mars Science Laboratory's Curiosity rover began making detailed measurements of the cosmic ray and energetic particle radiation environment on the surface of Mars on 7 August 2012. We report and discuss measurements of the absorbed dose and dose equivalent from galactic cosmic rays and solar energetic particles on the martian surface for ~300 days of observations during the current solar maximum. These measurements provide insight into the radiation hazards associated with a human mission to the surface of Mars and provide an anchor point with which to model the subsurface radiation environment, with implications for microbial survival times of any possible extant or past life, as well as for the preservation of potential organic biosignatures of the ancient martian environment.

High-Pressure Structural Response of an Insensitive Energetic Crystal: Dihydroxylammonium 5,5'-Bistetrazole-1,1'-diolate (TKX-50)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dreger, Zbigniew A.; Stash, Adam I.; Yu, Zhi-Gang

2017-03-06

The structural response of a novel, insensitive energetic crystal—dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50)—was examined under high pressure. Using synchrotron single-crystal X-ray diffraction measurements, details of molecular, intermolecular, and crystal changes were determined to ~10 GPa to understand its structural stability. The experimental results showed that TKX-50 exhibits highly anisotropic compression and significantly lower volume compressibility than currently known energetic crystals. These results are found to be in general agreement with our previous predictions from the DFT calculations. Additionally, the experimental data revealed anomalous compression—an expansion of the unit cell along the a axis (negative linear compressibility, NLC) upon compression to ~3 GPa.more » The structural analyses demonstrated that this unusual effect, the first such observation in an energetic crystal, is a consequence of the highly anisotropic response of 3D motifs, comprised of two parallel anions [(C 2N 8O 2) 2–] linked with two cations [(NH 3OH) +] through four strong hydrogen bonds. The present results demonstrate that the structural stability of TKX-50 is controlled by the strong and highly anisotropic intermolecular interactions, and these may contribute to its shock insensitivity.« less

High-pressure structural response of an insensitive energetic crystal: Dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dreger, Zbigniew A.; Stash, Adam I.; Yu, Zhi -Gang

The structural response of a novel, insensitive energetic crystal—dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50)—was examined under high pressure. Using synchrotron single-crystal X-ray diffraction measurements, details of molecular, intermolecular, and crystal changes were determined to ~10 GPa to understand its structural stability. The experimental results showed that TKX-50 exhibits highly anisotropic compression and significantly lower volume compressibility than currently known energetic crystals. These results are found to be in general agreement with our previous predictions from the DFT calculations. Additionally, the experimental data revealed anomalous compression—an expansion of the unit cell along the a axis (negative linear compressibility, NLC) upon compression to ~3 GPa.more » The structural analyses demonstrated that this unusual effect, the first such observation in an energetic crystal, is a consequence of the highly anisotropic response of 3D motifs, comprised of two parallel anions [(C 2N 8O 2) 2–] linked with two cations [(NH 3OH) +] through four strong hydrogen bonds. Finally, the present results demonstrate that the structural stability of TKX-50 is controlled by the strong and highly anisotropic intermolecular interactions, and these may contribute to its shock insensitivity.« less

High-pressure structural response of an insensitive energetic crystal: Dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50)

DOE PAGES

Dreger, Zbigniew A.; Stash, Adam I.; Yu, Zhi -Gang; ...

2017-02-28

The structural response of a novel, insensitive energetic crystal—dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50)—was examined under high pressure. Using synchrotron single-crystal X-ray diffraction measurements, details of molecular, intermolecular, and crystal changes were determined to ~10 GPa to understand its structural stability. The experimental results showed that TKX-50 exhibits highly anisotropic compression and significantly lower volume compressibility than currently known energetic crystals. These results are found to be in general agreement with our previous predictions from the DFT calculations. Additionally, the experimental data revealed anomalous compression—an expansion of the unit cell along the a axis (negative linear compressibility, NLC) upon compression to ~3 GPa.more » The structural analyses demonstrated that this unusual effect, the first such observation in an energetic crystal, is a consequence of the highly anisotropic response of 3D motifs, comprised of two parallel anions [(C 2N 8O 2) 2–] linked with two cations [(NH 3OH) +] through four strong hydrogen bonds. Finally, the present results demonstrate that the structural stability of TKX-50 is controlled by the strong and highly anisotropic intermolecular interactions, and these may contribute to its shock insensitivity.« less

Mechanism Responsible for Intercalation of Dimethyl Sulfoxide in Kaolinite: Molecular Dynamics Simulations.

PubMed

Zhang, Shuai; Liu, Qinfu; Cheng, Hongfei; Gao, Feng; Liu, Cun; Teppen, Brian J

2018-01-01

Intercalation is the promising strategy to expand the interlayer region of kaolinite for their further applications. Herein, the adaptive biasing force (ABF) accelerated molecular dynamics simulations were performed to calculate the free energies involved in the kaolinite intercalation by dimethyl sulfoxide (DMSO). Additionally, the classical all atom molecular dynamics simulations were carried out to calculate the interfacial interactions between kaolinite interlayer surfaces and DMSO with the aim at exploring the underlying force that drives the DMSO to enter the interlayer space. The results showed that the favorable interaction of DMSO with both kaolinite interlayer octahedral surface and tetrahedral surface can help in introducing DMSO enter kaolinite interlayer. The hydroxyl groups on octahedral surface functioned as H-donors attracting the S=O groups of DMSO through hydrogen bonding interaction. The tetrahedral surface featuring hydrophobic property attracted the methyl groups of DMSO through hydrophobic interaction. The results provided a detailed picture of the energetics and interlayer structure of kaolinite-DMSO intercalate.

Synthesis, crystal structure and catalytic effect on thermal decomposition of RDX and AP: An energetic coordination polymer [Pb{sub 2}(C{sub 5}H{sub 3}N{sub 5}O{sub 5}){sub 2}(NMP)·NMP]{sub n}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Jin-jian; Yancheng Teachers College, Yancheng 224002; Liu, Zu-Liang, E-mail: liuzl@mail.njust.edu.cn

2013-04-15

An energetic lead(II) coordination polymer based on the ligand ANPyO has been synthesized and its crystal structure has been got. The polymer was characterized by FT-IR spectroscopy, elemental analysis, DSC and TG-DTG technologies. Thermal analysis shows that there are one endothermic process and two exothermic decomposition stages in the temperature range of 50–600 °C with final residues 57.09%. The non-isothermal kinetic has also been studied on the main exothermic decomposition using the Kissinger's and Ozawa–Doyle's methods, the apparent activation energy is calculated as 195.2 KJ/mol. Furthermore, DSC measurements show that the polymer has significant catalytic effect on the thermal decompositionmore » of ammonium perchlorate. - Graphical abstract: An energetic lead(II) coordination polymer of ANPyO has been synthesized, structurally characterized and properties tested. Highlights: ► We have synthesized and characterized an energetic lead(II) coordination polymer. ► We have measured its molecular structure and thermal decomposition. ► It has significant catalytic effect on thermal decomposition of AP.« less

Energetic Neutral Atom Imaging of the Lunar Poles and Night-Side

NASA Astrophysics Data System (ADS)

Vorburger, Audrey; Wurz, Peter; Barabash, Stas; Wieser, Martin; Futaana, Yoshifumi; Bhardwaj, Anil; Dhanya, Mb; Asamura, Kazushi

2016-04-01

So far all reported scientific results derived from measurements of the Chandrayaan-1 Energetic Neutral Analyzer (CENA) on board the Indian lunar mission Chandrayaan-1 focused on the sun-lit part of the Moon. Here, for the first time, we present the analysis of the Moon - solar wind interaction in Energetic Neutral Atoms (ENAs) from measurements over the poles and the night-side of the Moon. The Moon, not being protected by a global magnetic field or an atmosphere, is constantly bombarded by solar wind ions. Until recently, it was tacitly assumed that the solar wind ions that impinge onto the lunar surface are almost completely absorbed ( < 1% reflection) by the lunar surface (e.g. Crider and Vondrak [Adv. Space Res., 2002]; Feldman et al. [J. Geophys. Res., 2000]). However, recent observations conducted by the two ENA sensors of NASA's Interstellar Boundary Explorer and by Chandrayaan-1/CENA showed an average global energetic neutral atom (ENA) albedo of 10% - 20% (e.g. McComas et al. [Geophys. Res. Lett., 2009], Wieser et al. [Planet. Space Sci., 2009], Vorburger et al. [J. Geophys. Res., 2013]). In the past 6 years, several studies have closely investigated this solar wind - lunar surface interaction from various viewpoints. The main findings of these studies include (1) the dependency of the hydrogen reflection ratio on the local crustal magnetic fields (e.g., Wieser et al. [Geophys. Res. Lett. ,2010] and Vorburger et al. [J. Geophys. Res., 2012]), (2) the determination of the energy spectra of backscattered neutralized solar wind protons (Futaana et al. [J. Geophys. Res., 2012]) (3) the use of the spectra shape to remotely define an electric potential above a lunar magnetic anomaly (Futaana et al. [Geophys. Res. Lett., 2012]), (4) the favouring of backscattering over forward-scattering of impinging solar wind hydrogen particles (Vorburger et al. [Geophys. Res. Lett., 2011]), (5) the first-ever measurements of sputtered lunar oxygen (Vorburger et al. [J. Geophys. Res., 2012]), (6) the first-ever observation of backscattered solar wind helium (Vorburger et al. [J. Geophys. Res., 2012]), and (7) the determination of the scattering properties of backscattered solar wind hydrogen measured when the Moon transversed Earth's magneto-sheath (Lue et al. [J. Geophys. Res., 2016]). All findings above are based on measurements from the sun-lit side of the Moon's surface, where solar wind particles can impinge freely onto the lunar surface. On the night-side, in contrast, a large scale wake structure is formed as a result of the high absorption of solar wind plasma on the lunar day-side. Very recent ion measurements of Chandrayaan-1's Solar Wind Monitor (SWIM) have revealed the presence of protons in the near-lunar wake, though (Dhanya et al., [Icarus 2016 (submitted)]). The presence of protons in the near lunar wake implies that there is also some sort of solar wind - lunar surface interaction on the lunar night-side. A complete analysis of this interaction will be presented herein.

DMSO Induces Dehydration near Lipid Membrane Surfaces

PubMed Central

Cheng, Chi-Yuan; Song, Jinsuk; Pas, Jolien; Meijer, Lenny H.H.; Han, Songi

2015-01-01

Dimethyl sulfoxide (DMSO) has been broadly used in biology as a cosolvent, a cryoprotectant, and an enhancer of membrane permeability, leading to the general assumption that DMSO-induced structural changes in cell membranes and their hydration water play important functional roles. Although the effects of DMSO on the membrane structure and the headgroup dehydration have been extensively studied, the mechanism by which DMSO invokes its effect on lipid membranes and the direct role of water in this process are unresolved. By directly probing the translational water diffusivity near unconfined lipid vesicle surfaces, the lipid headgroup mobility, and the repeat distances in multilamellar vesicles, we found that DMSO exclusively weakens the surface water network near the lipid membrane at a bulk DMSO mole fraction (XDMSO) of <0.1, regardless of the lipid composition and the lipid phase. Specifically, DMSO was found to effectively destabilize the hydration water structure at the lipid membrane surface at XDMSO <0.1, lower the energetic barrier to dehydrate this surface water, whose displacement otherwise requires a higher activation energy, consequently yielding compressed interbilayer distances in multilamellar vesicles at equilibrium with unaltered bilayer thicknesses. At XDMSO >0.1, DMSO enters the lipid interface and restricts the lipid headgroup motion. We postulate that DMSO acts as an efficient cryoprotectant even at low concentrations by exclusively disrupting the water network near the lipid membrane surface, weakening the cohesion between water and adhesion of water to the lipid headgroups, and so mitigating the stress induced by the volume change of water during freeze-thaw. PMID:26200868

Probing the (110)-Oriented plane of rutile ZnF2: A DFT investigation

NASA Astrophysics Data System (ADS)

Tamijani, Ali Abbaspour; Ebrahimiaqda, Elham

2017-12-01

For many years, rutile-like crystals have given rise to pronounced enthusiasm amongst mineralogists. In this context, rutile-type ZnF2 has found numerous applications across a variety of disciplines, ranging from material sciences to optoelectronics. Surprisingly, very limited literature is concerned with the molecular adsorption on ZnF2 surfaces and related energetics. Additionally, surface probing with small particles is a well-entrenched technique to analyze the interfacial properties. In this regard, small organic species are valuable picks. In the present work, we have employed electronic structure calculations to simulate the adsorption of methane, chloroform, pyrrole, benzene, naphthalene, anthracene, tetracene and pentacene at the (110) plane of rutile ZnF2. Dispersion-corrected DFT method was chosen to predict the binding energies and structures of molecule-adsorbed surfaces. Interestingly, a linear proportionality relationship was found between the binding energies of aromatic adsorbates and their respective molecular lengths. By applying this relationship, we were able to predict the adsorption energy of pentacene on ZnF2 to within 2% of our DFT-based result.

First principles study of biomineral hydroxyapatite

NASA Astrophysics Data System (ADS)

Slepko, Alexander

2010-03-01

Hydroxyapatite (HA) [Ca10(PO4)6(OH)2] is one of the most abundant materials in mammal bone. It crystallizes within the spaces between the tropocollagen chains and strengthens the bone tissue. The mineral content of human bone increases with age reaching a maximum value from which it starts to decrease leading to diseases such as osteomalacia. Therefore, an emergent application of this study is bone repair and the production of synthetic bone. Despite its importance, little is known about the growth of HA crystallites in bones. Nor is it well understood how the HA attaches to protein chains and interacts with the surrounding aqueous solution. Using density functional theory (DFT) we calculate the theoretical ground state structure, electronic and vibration properties of hexagonal HA. We find several low energy structures and analyze the energy barriers for spontaneous phase transitions. We calculate the phonon density of states and study the surface energetics for different orientations. We identify the surfaces with highest reactivity using the frontier orbital approach and analyze interactions between these surfaces and water molecules/amino acids.

Adsorbed Polymer Nanolayers on Solids: Mechanism, Structure and Applications

NASA Astrophysics Data System (ADS)

Sen, Mani Kuntal

In this thesis, by combining various advanced x-ray scattering, spectroscopic and other surface sensitive characterization techniques, I report the equilibrium polymer chain conformations, structures, dynamics and properties of polymeric materials at the solid-polymer melt interfaces. Following the introduction, in chapter 2, I highlight that the backbone chains (constituted of CH and CH2 groups) of the flattened polystyrene (PS) chains preferentially orient normal to the weakly interactive substrate surface via thermal annealing regardless of the initial chain conformations, while the orientation of the phenyl rings becomes randomized, thereby increasing the number of surface-segmental contacts (i.e., enthalpic gain) which is the driving force for the flattening process of the polymer chains even onto a weakly interactive solid. In chapter 3, I elucidate the flattened structures in block copolymer (BCP) thin films where both blocks lie flat on the substrate, forming a 2D randomly phase-separated structure irrespective of their microdomain structures and interfacial energetics. In chapter 4, I reveal the presence of an irreversibly adsorbed BCP layer which showed suppressed dynamics even at temperatures far above the individual glass transition temperatures of the blocks. Furthermore, this adsorbed BCP layer plays a crucial role in controlling the microdomain orientation in the entire film. In chapter 5, I report a radically new paradigm of designing a polymeric coating layer of a few nanometers thick ("polymer nanolayer") with anti-biofouling properties.

The structure of PbCl2 on the {100} surface of NaCl and its consequences for crystal growth

NASA Astrophysics Data System (ADS)

Townsend, Eleanor R.; Brugman, Sander J. T.; Blijlevens, Melian A. R.; Smets, Mireille M. H.; de Poel, Wester; van Enckevort, Willem J. P.; Meijer, Jan A. M.; Vlieg, Elias

2018-04-01

The role that additives play in the growth of sodium chloride is a topic which has been widely researched but not always fully understood at an atomic level. Lead chloride (PbCl2) is one such additive which has been reported to have growth inhibition effects on NaCl {100} and {111}; however, no definitive evidence has been reported which details the mechanism of this interaction. In this investigation, we used the technique of surface x-ray diffraction to determine the interaction between PbCl2 and NaCl {100} and the structure at the surface. We find that Pb2+ replaces a surface Na+ ion, while a Cl- ion is located on top of the Pb2+. This leads to a charge mismatch in the bulk crystal, which, as energetically unfavourable, leads to a growth blocking effect. While this is a similar mechanism as in the anticaking agent ferrocyanide, the effect of PbCl2 is much weaker, most likely due to the fact that the Pb2+ ion can more easily desorb. Moreover, PbCl2 has an even stronger effect on NaCl {111}.

Intrinsic Thermodynamics and Structure Correlation of Benzenesulfonamides with a Pyrimidine Moiety Binding to Carbonic Anhydrases I, II, VII, XII, and XIII

PubMed Central

Kišonaitė, Miglė; Zubrienė, Asta; Čapkauskaitė, Edita; Smirnov, Alexey; Smirnovienė, Joana; Kairys, Visvaldas; Michailovienė, Vilma; Manakova, Elena; Gražulis, Saulius; Matulis, Daumantas

2014-01-01

The early stage of drug discovery is often based on selecting the highest affinity lead compound. To this end the structural and energetic characterization of the binding reaction is important. The binding energetics can be resolved into enthalpic and entropic contributions to the binding Gibbs free energy. Most compound binding reactions are coupled to the absorption or release of protons by the protein or the compound. A distinction between the observed and intrinsic parameters of the binding energetics requires the dissection of the protonation/deprotonation processes. Since only the intrinsic parameters can be correlated with molecular structural perturbations associated with complex formation, it is these parameters that are required for rational drug design. Carbonic anhydrase (CA) isoforms are important therapeutic targets to treat a range of disorders including glaucoma, obesity, epilepsy, and cancer. For effective treatment isoform-specific inhibitors are needed. In this work we investigated the binding and protonation energetics of sixteen [(2-pyrimidinylthio)acetyl]benzenesulfonamide CA inhibitors using isothermal titration calorimetry and fluorescent thermal shift assay. The compounds were built by combining four sulfonamide headgroups with four tailgroups yielding 16 compounds. Their intrinsic binding thermodynamics showed the limitations of the functional group energetic additivity approach used in fragment-based drug design, especially at the level of enthalpies and entropies of binding. Combined with high resolution crystal structural data correlations were drawn between the chemical functional groups on selected inhibitors and intrinsic thermodynamic parameters of CA-inhibitor complex formation. PMID:25493428

Response of Simple, Model Systems to Extreme Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ewing, Rodney C.; Lang, Maik

2015-07-30

The focus of the research was on the application of high-pressure/high-temperature techniques, together with intense energetic ion beams, to the study of the behavior of simple oxide systems (e.g., SiO 2, GeO 2, CeO 2, TiO 2, HfO 2, SnO 2, ZnO and ZrO 2) under extreme conditions. These simple stoichiometries provide unique model systems for the analysis of structural responses to pressure up to and above 1 Mbar, temperatures of up to several thousands of kelvin, and the extreme energy density generated by energetic heavy ions (tens of keV/atom). The investigations included systematic studies of radiation- and pressure-induced amorphizationmore » of high P-T polymorphs. By studying the response of simple stoichiometries that have multiple structural “outcomes”, we have established the basic knowledge required for the prediction of the response of more complex structures to extreme conditions. We especially focused on the amorphous state and characterized the different non-crystalline structure-types that result from the interplay of radiation and pressure. For such experiments, we made use of recent technological developments, such as the perforated diamond-anvil cell and in situ investigation using synchrotron x-ray sources. We have been particularly interested in using extreme pressures to alter the electronic structure of a solid prior to irradiation. We expected that the effects of modified band structure would be evident in the track structure and morphology, information which is much needed to describe theoretically the fundamental physics of track-formation. Finally, we investigated the behavior of different simple-oxide, composite nanomaterials (e.g., uncoated nanoparticles vs. core/shell systems) under coupled, extreme conditions. This provided insight into surface and boundary effects on phase stability under extreme conditions.« less

Energetics of protein homodimerization: effects of water sequestering on the formation of beta-lactoglobulin dimer.

PubMed

Bello, Martiniano; Pérez-Hernández, Gerardo; Fernández-Velasco, D Alejandro; Arreguín-Espinosa, Roberto; García-Hernández, Enrique

2008-03-01

Transient protein-protein interactions are functionally relevant as a control mechanism in a variety of biological processes. Analysis of the 3D structure of protein-protein complexes indicates that water molecules trapped at the interface are very common; however, their role in the stability and specificity of protein homodimer interactions has been not addressed yet. To provide new insights into the energetic bases that govern the formation of highly hydrated interfaces, the dissociation process of bovine beta lg variant A at a neutral pH was characterized here thermodynamically by conducting dilution experiments with an isothermal titration calorimeter. Association was enthalpically driven throughout the temperature range spanned. DeltaH and deltaC(p) were significantly more negative than estimates based on surface area changes, suggesting the occurrence of effects additional to the dehydration of the contact surfaces between subunits. Near-UV CD spectra proved to be independent of protein concentration, indicating a rigid body-like association. Furthermore, the process proved not to be coupled to significant changes in the protonation state of ionizable groups or counterion exchange. In contrast, both osmotic stress experiments and a computational analysis of the dimer's 3D structure indicated that a large number of water molecules are incorporated into the interface upon association. Numerical estimates considering the contributions of interface area desolvation and water immobilization accounted satisfactorily for the experimental deltaC(p). Thus, our study highlights the importance of explicitly considering the effects of water sequestering to perform a proper quantitative analysis of the formation of homodimers with highly hydrated interfaces. 2007 Wiley-Liss, Inc.

Computational investigation of CO adsorbed on Aux, Agx and (AuAg)x nanoclusters (x = 1 - 5, 147) and monometallic Au and Ag low-energy surfaces*

NASA Astrophysics Data System (ADS)

Gould, Anna L.; Catlow, C. Richard A.; Logsdail, Andrew J.

2018-02-01

Density functional theory calculations have been performed to investigate the use of CO as a probe molecule for the determination of the structure and composition of Au, Ag and AuAg nanoparticles. For very small nanoclusters (x = 1 - 5), the CO vibrational frequencies can be directly correlated to CO adsorption strength, whereas larger 147-atom nanoparticles show a strong energetic preference for CO adsorption at a vertex position but the highest wavenumbers are for the bridge positions. We also studied CO adsorption on Au and Ag (100) and (111) surfaces, for a 1 monolayer coverage, which proves to be energetically favourable on atop only and bridge positions for Au (100) and atop for Ag (100); vibrational frequencies of the CO molecules red-shift to lower wavenumbers as a result of increased metal coordination. We conclude that CO vibrational frequencies cannot be solely relied upon in order to obtain accurate compositional analysis, but we do propose that elemental rearrangement in the core@shell nanoclusters, from Ag@Au (or Au@Ag) to an alloy, would result in a shift in the CO vibrational frequencies that indicate changes in the surface composition. Contribution to the Topical Issue "Shaping Nanocatalysts", edited by Francesca Baletto, Roy L. Johnston, Jochen Blumberger and Alex Shluger.Supplementary material in the form of one pdf file available from the Journal web page at http://https://doi.org/10.1140/epjb/e2017-80280-7

Computational investigation of structural and electronic properties of aqueous interfaces of GaN, ZnO, and a GaN/ZnO alloy.

PubMed

Kharche, Neerav; Hybertsen, Mark S; Muckerman, James T

2014-06-28

The GaN/ZnO alloy functions as a visible-light photocatalyst for splitting water into hydrogen and oxygen. As a first step toward understanding the mechanism and energetics of water-splitting reactions, we investigate the microscopic structure of the aqueous interfaces of the GaN/ZnO alloy and compare them with the aqueous interfaces of pure GaN and ZnO. Specifically, we have studied the (101̄0) surface of GaN and ZnO and the (101̄0) and (12̄10) surfaces of the 1 : 1 GaN/ZnO alloy. The calculations are carried out using first-principles density functional theory based molecular dynamics (DFT-MD). The structure of water within a 3 Å distance from the semiconductor surface is significantly altered by the acid/base chemistry of the aqueous interface. Water adsorption on all surfaces is substantially dissociative such that the surface anions (N or O) act as bases accepting protons from dissociated water molecules while the corresponding hydroxide ions bond with surface cations (Ga or Zn). Additionally, the hard-wall interface presented by the semiconductor imparts ripples in the density of water. Beyond a 3 Å distance from the semiconductor surface, water exhibits a bulk-like hydrogen bond network and oxygen-oxygen radial distribution function. Taken together, these characteristics represent the resting (or "dark") state of the catalytic interface. The electronic structure analysis of the aqueous GaN/ZnO interface suggests that the photogenerated holes may get trapped on interface species other than the adsorbed OH(-) ions. This suggests additional dynamical steps in the water oxidation process.

Saturn Magnetospheric Impact on Surface Molecular Chemistry and Astrobiological Potential of Enceladus

NASA Technical Reports Server (NTRS)

Cooper, Paul D.; Cooper, John F.; Sittler, Edward C.; Burger, Matthew H.; Sturner, Steven J.; Rymer, Abigail M.

2008-01-01

The active south polar surface of Enceladus is exposed to strong chemical processing by direct interaction with charged plasma and energetic particles in the local magnetospheric environment of this icy moon. Chemical oxidation activity is suggested by detection of H202 at the surface in this region and less directly by substantial presence of C02, CO, and N2 in the plume gases. Molecular composition of the uppermost surface, including ejecta from plume activity, is radiolytically transformed mostly by penetrating energetic electrons with lesser effects from more depleted populations of energetic protons. The main sources of molecular plasma ions and E-ring dust grains in the magnetospheric environment are the cryovolcanic plume emissions from Enceladus. These molecular ions and the dust grains are chemically processed by magnetospheric interactions that further impact surface chemistry on return to Enceladus. For example, H20 neutrals dominating the emitted plume gas return to the surface mostly as H30+ ions after magnetospheric processing. Surface oxidant loading is further increased by return of radiolytically processed ice grains from the E-ring. Plume frost deposition and micrometeoroid gardening protect some fraction of newly produced molecular species from destruction by further irradiation. The evident horizontal and vertical mobility of surface ices in the south polar region drive mixing of these processed materials into the moon interior with potential impacts on deep ice molecular chemistry and plume gas production. Similarly as suggested previously for Europa, the externally driven source of radiolytic oxidants could affect evolution of life in any subsurface liquid water environments of Enceladus.

Clustering on Magnesium Surfaces – Formation and Diffusion Energies

DOE PAGES

Chu, Haijian; Huang, Hanchen; Wang, Jian

2017-07-12

The formation and diffusion energies of atomic clusters on Mg surfaces determine the surface roughness and formation of faulted structure, which in turn affect the mechanical deformation of Mg. This paper reports first principles density function theory (DFT) based quantum mechanics calculation results of atomic clustering on the low energy surfaces {0001} and {more » $$\\bar{1}$$011} . In parallel, molecular statics calculations serve to test the validity of two interatomic potentials and to extend the scope of the DFT studies. On a {0001} surface, a compact cluster consisting of few than three atoms energetically prefers a face-centered-cubic stacking, to serve as a nucleus of stacking fault. On a {$$\\bar{1}$$011} , clusters of any size always prefer hexagonal-close-packed stacking. Adatom diffusion on surface {$$\\bar{1}$$011} is high anisotropic while isotropic on surface (0001). Three-dimensional Ehrlich–Schwoebel barriers converge as the step height is three atomic layers or thicker. FInally, adatom diffusion along steps is via hopping mechanism, and that down steps is via exchange mechanism.« less

Clustering on Magnesium Surfaces – Formation and Diffusion Energies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chu, Haijian; Huang, Hanchen; Wang, Jian

The formation and diffusion energies of atomic clusters on Mg surfaces determine the surface roughness and formation of faulted structure, which in turn affect the mechanical deformation of Mg. This paper reports first principles density function theory (DFT) based quantum mechanics calculation results of atomic clustering on the low energy surfaces {0001} and {more » $$\\bar{1}$$011} . In parallel, molecular statics calculations serve to test the validity of two interatomic potentials and to extend the scope of the DFT studies. On a {0001} surface, a compact cluster consisting of few than three atoms energetically prefers a face-centered-cubic stacking, to serve as a nucleus of stacking fault. On a {$$\\bar{1}$$011} , clusters of any size always prefer hexagonal-close-packed stacking. Adatom diffusion on surface {$$\\bar{1}$$011} is high anisotropic while isotropic on surface (0001). Three-dimensional Ehrlich–Schwoebel barriers converge as the step height is three atomic layers or thicker. FInally, adatom diffusion along steps is via hopping mechanism, and that down steps is via exchange mechanism.« less

Theoretical study of the noble metals on semiconductor surfaces and Ti-base shape memory alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ding, Yungui

1994-07-27

The electronic and structural properties of the (√3 x√3) R30° Ag/Si(111) and (√3 x √3) R30° Au/Si(111) surfaces are investigated using first principles total energy calculations. We have tested almost all experimentally proposed structural models for both surfaces and found the energetically most favorable model for each of them. The lowest energy model structure of the (√3 x √3) R30° Ag/Si(111) surface consists of a top layer of Ag atoms arranged as ``honeycomb-chained-trimers`` lying above a distorted ``missing top layer`` Si(111) substrate. The coverage of Ag is 1 monolayer (ML). We find that the honeycomb structure observed in STM imagesmore » arise from the electronic charge densities of an empty surface band near the Fermi level. The electronic density of states of this model gives a ``pseudo-gap`` around the Fermi level, which is consistent with experimental results. The lowest energy model for the (√3 x √3) R30° Au/Si(111) surface is a conjugate honeycomb-chained-trimer (CHCT-1) configuration which consists of a top layer of trimers formed by 1 ML Au atoms lying above a ``missing top layer`` Si(111) substrate with a honeycomb-chained-trimer structure for its first layer. The structures of Au and Ag are in fact quite similar and belong to the same class of structural models. However, small variation in the structural details gives rise to quite different observed STM images, as revealed in the theoretical calculations. The electronic charge density from bands around the Fermi level for the (√3 x √3) R30°, Au/Si(111) surface also gives a good description of the images observed in STM experiments. First principles calculations are performed to study the electronic and structural properties of a series of Ti-base binary alloys TiFe, TiNi, TiPd, TiMo, and TiAu in the B2 structure.« less

Origin of two time-scale regimes in potentiometric titration of metal oxides. A replica kinetic Monte Carlo study.

PubMed

Zarzycki, Piotr; Rosso, Kevin M

2009-06-16

Replica kinetic Monte Carlo simulations were used to study the characteristic time scales of potentiometric titration of the metal oxides and (oxy)hydroxides. The effect of surface heterogeneity and surface transformation on the titration kinetics were also examined. Two characteristic relaxation times are often observed experimentally, with the trailing slower part attributed to surface nonuniformity, porosity, polymerization, amorphization, and other dynamic surface processes induced by unbalanced surface charge. However, our simulations show that these two characteristic relaxation times are intrinsic to the proton-binding reaction for energetically homogeneous surfaces, and therefore surface heterogeneity or transformation does not necessarily need to be invoked. However, all such second-order surface processes are found to intensify the separation and distinction of the two kinetic regimes. The effect of surface energetic-topographic nonuniformity, as well dynamic surface transformation, interface roughening/smoothing were described in a statistical fashion. Furthermore, our simulations show that a shift in the point-of-zero charge is expected from increased titration speed, and the pH-dependence of the titration measurement error is in excellent agreement with experimental studies.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zarzycki, Piotr P.; Rosso, Kevin M.

Replica Kinetic Monte Carlo simulations were used to study the characteristic time scales of potentiometric titration of the metal oxides and (oxy)hydroxides. The effect of surface heterogeneity and surface transformation on the titration kinetics were also examined. Two characteristic relaxation times are often observed experimentally, with the trailing slower part attributed to surface non-uniformity, porosity, polymerization, amorphization, and other dynamic surface processes induced by unbalanced surface charge. However, our simulations show that these two characteristic relaxation times are intrinsic to the proton binding reaction for energetically homogeneous surfaces, and therefore surface heterogeneity or transformation do not necessarily need to bemore » invoked. However, all such second-order surface processes are found to intensify the separation and distinction of the two kinetic regimes. The effect of surface energetic-topographic non-uniformity, as well dynamic surface transformation, interface roughening/smoothing were described in a statistical fashion. Furthermore, our simulations show that a shift in the point-of-zero charge is expected from increased titration speed and the pH-dependence of the titration measurement error is in excellent agreement with experimental studies.« less

X-ray Probes of Magnetospheric Interactions with Jupiter's Auroral zones, the Galilean Satellites, and the Io Plasma Torus

NASA Technical Reports Server (NTRS)

Elsner, R. F.; Ramsey, B. D.; Waite, J. H., Jr.; Rehak, P.; Johnson, R. E.; Cooper, J. F.; Swartz, D. A.

2004-01-01

Remote observations with the Chandra X-ray Observatory and the XMM-Newton Observatory have shown that the Jovian system is a source of x-rays with a rich and complicated structure. The planet's polar auroral zones and its disk are powerful sources of x-ray emission. Chandra observations revealed x-ray emission from the Io Plasma Torus and from the Galilean moons Io, Europa, and possibly Ganymede. The emission from these moons is certainly due to bombardment of their surfaces of highly energetic protons, oxygen and sulfur ions from the region near the Torus exciting atoms in their surfaces and leading to fluorescent x-ray emission lines. Although the x-ray emission from the Galilean moons is faint when observed fiom Earth orbit, an imaging x-ray spectrometer in orbit around these moons, operating at 200 eV and above with 150 eV energy resolution, would provide a detailed mapping (down to 40 m spatial resolution) of the elemental composition in their surfaces. Here we describe the physical processes leading to x-ray emission fiom the surfaces of Jupiter's moons and the instrumental properties, as well as energetic ion flux models or measurements, required to map the elemental composition of their surfaces. We discuss the proposed scenarios leading to possible surface compositions. For Europa, the two most extreme are (1) a patina produced by exogenic processes such as meteoroid bombardment and ion implantation, and (2) upwelling of material fiom the subsurface ocean. We also describe the characteristics of X - m , an imaging x-ray spectrometer under going a feasibility study for the JIM0 mission, with the ultimate goal of providing unprecedented x-ray studies of the elemental composition of the surfaces of Jupiter's icy moons and Io, as well as of Jupiter's auroral x-ray emission.

Computational simulation of the effects of oxygen on the electronic states of hydrogenated 3C-porous SiC

PubMed Central

2012-01-01

A computational study of the dependence of the electronic band structure and density of states on the chemical surface passivation of cubic porous silicon carbide (pSiC) was performed using ab initio density functional theory and the supercell method. The effects of the porosity and the surface chemistry composition on the energetic stability of pSiC were also investigated. The porous structures were modeled by removing atoms in the [001] direction to produce two different surface chemistries: one fully composed of silicon atoms and one composed of only carbon atoms. The changes in the electronic states of the porous structures as a function of the oxygen (O) content at the surface were studied. Specifically, the oxygen content was increased by replacing pairs of hydrogen (H) atoms on the pore surface with O atoms attached to the surface via either a double bond (X = O) or a bridge bond (X-O-X, X = Si or C). The calculations show that for the fully H-passivated surfaces, the forbidden energy band is larger for the C-rich phase than for the Si-rich phase. For the partially oxygenated Si-rich surfaces, the band gap behavior depends on the O bond type. The energy gap increases as the number of O atoms increases in the supercell if the O atoms are bridge-bonded, whereas the band gap energy does not exhibit a clear trend if O is double-bonded to the surface. In all cases, the gradual oxygenation decreases the band gap of the C-rich surface due to the presence of trap-like states. PMID:22913486

First-principles study of the solid solution of hydrogen in lanthanum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schoellhammer, Gunther; Herzig, Peter; Wolf, Walter

2011-09-01

Results from first-principles investigations of the energetical, structural, electronic, and vibrational properties of model structures probing the metal-rich region of the lanthanum-hydrogen system, i.e., the region of the solid solution of hydrogen in lanthanum, are presented. We have studied the site preference and the ordering tendency of hydrogen atoms interstitially bonded in close-packed lanthanum. Spatially separated hydrogen atoms have turned out to exhibit an energetical preference for the occupation of octahedral interstitial sites at low temperature. Indications for a reversal of the site preference in favor of the occupation of tetrahedral interstitial sites at elevated temperature have been found. Linearmore » arrangements consisting of pairs of octahedrally and/or tetrahedrally coordinated hydrogen atoms collinearly bonded to a central lanthanum atom have turned out to be energetically favorable structure elements. Further stabilization is achieved if such hydrogen pairs are in turn linked together so that extended chains of La-H bonds are formed. Pair formation and chain linking counteract the energetical preference for octahedral coordination observed for separated hydrogen atoms.« less

Plasma and energetic particle structure upstream of a quasi-parallel interplanetary shock

NASA Technical Reports Server (NTRS)

Kennel, C. F.; Scarf, F. L.; Coroniti, F. V.; Russell, C. T.; Wenzel, K.-P.; Sanderson, T. R.; Van Nes, P.; Smith, E. J.; Tsurutani, B. T.; Scudder, J. D.

1984-01-01

ISEE 1, 2 and 3 data from 1978 on interplanetary magnetic fields, shock waves and particle energetics are examined to characterize a quasi-parallel shock. The intense shock studied exhibited a 640 km/sec velocity. The data covered 1-147 keV protons and electrons and ions with energies exceeding 30 keV in regions both upstream and downstream of the shock, and also the magnitudes of ion-acoustic and MHD waves. The energetic particles and MHD waves began being detected 5 hr before the shock. Intense halo electron fluxes appeared ahead of the shock. A closed magnetic field structure was produced with a front end 700 earth radii from the shock. The energetic protons were cut off from the interior of the magnetic bubble, which contained a markedly increased density of 2-6 keV protons as well as the shock itself.

Exploring the work function variability and structural stability of VO2(1 1 0) surface upon noble metal (Ag, Au, Pt) adsorption and incorporation

NASA Astrophysics Data System (ADS)

Chen, Lanli; Cui, Yuanyuan; Shi, Siqi; Luo, Hongjie; Gao, Yanfeng

2018-08-01

Vanadium dioxide (VO2) has attracted great attention, with scientific and technological advances over the past few decades due to its reversible metal-insulator transition at 340 K. However, the high phase transition temperature (Tc) of VO2 limits its practical applications. Our first-principles calculations show that VO2(1 1 0) surfaces with adsorbed noble metals (Ag, Au, Pt) exhibit a lower work function compared with the clean surface and further induces a lower Tc due to charge transfer from the noble metals to the VO2(1 1 0) surface. However, the work functions of the VO2(1 1 0) surfaces after the incorporation of noble metals are higher than that of the clean surface. In addition, the results of formation energies of various configurations show that the VO2(1 1 0) surface with the adsorption and incorporation of Ag is energetically more favorable than those with Au and Pt. Therefore, it may be concluded that the adsorption and incorporation of noble metals can not only tailor the work function of VO2, in turn realizing the rational tuning of Tc of VO2, but also stabilize the structures of VO2 thin films. These results provide guidance for further exploration of VO2-based optical switching devices and smart windows.

Polymorphism in Energetic Materials

DTIC Science & Technology

2008-01-01

2Department of Chemistry, Howard University Polymorphism often occurs in energetic materials. Differences in the forms range from conformational changes in...these two areas. rayMond J. ButchEr is a professor of inorganic and structural chemistry at Howard University , Washington, DC. He has worked at Howard ... University since 1977 and has been associated with the NRL Laboratory for Structure of Matter since 1989 (primarily during the summer months as an

Environmental Assessment, Establishing a Drop Zone at the Energetic Materials Research and Testing Center in Socorro, New Mexico and Finding of No Significant Impact (FONSI)

DTIC Science & Technology

2007-11-07

action is open space, and free of any residential or other structures . Biological Resources Minor impacts to vegetation and wildlife may occur from...mountains, rills, gullies, or other notable geologic features. There are no residences or other structures within the proposed drop zone. 3.2 Airspace...research, testing and training related to energetic materials. The land has also been used for livestock grazing. There are no structures on the

Investigating the Energetic Ordering of Stable and Metastable TiO 2 Polymorphs Using DFT+ U and Hybrid Functionals

DOE PAGES

Curnan, Matthew T.; Kitchin, John R.

2015-08-12

Prediction of transition metal oxide BO 2 (B = Ti, V, etc.) polymorph energetic properties is critical to tunable material design and identifying thermodynamically accessible structures. Determining procedures capable of synthesizing particular polymorphs minimally requires prior knowledge of their relative energetic favorability. Information concerning TiO 2 polymorph relative energetic favorability has been ascertained from experimental research. In this study, the consistency of first-principles predictions and experimental results involving the relative energetic ordering of stable (rutile), metastable (anatase and brookite), and unstable (columbite) TiO 2 polymorphs is assessed via density functional theory (DFT). Considering the issues involving electron–electron interaction and chargemore » delocalization in TiO 2 calculations, relative energetic ordering predictions are evaluated over trends varying Ti Hubbard U 3d or exact exchange fraction parameter values. Energetic trends formed from varying U 3d predict experimentally consistent energetic ordering over U 3d intervals when using GGA-based functionals, regardless of pseudopotential selection. Given pertinent linear response calculated Hubbard U values, these results enable TiO 2 polymorph energetic ordering prediction. Here, the hybrid functional calculations involving rutile–anatase relative energetics, though demonstrating experimentally consistent energetic ordering over exact exchange fraction ranges, are not accompanied by predicted fractions, for a first-principles methodology capable of calculating exact exchange fractions precisely predicting TiO 2 polymorph energetic ordering is not available.« less

Initial mechanisms for the unimolecular decomposition of electronically excited bisfuroxan based energetic materials.

PubMed

Yuan, Bing; Bernstein, Elliot R

2017-01-07

Unimolecular decomposition of energetic molecules, 3,3'-diamino-4,4'-bisfuroxan (labeled as A) and 4,4'-diamino-3,3'-bisfuroxan (labeled as B), has been explored via 226/236 nm single photon laser excitation/decomposition. These two energetic molecules, subsequent to UV excitation, create NO as an initial decomposition product at the nanosecond excitation energies (5.0-5.5 eV) with warm vibrational temperature (1170 ± 50 K for A, 1400 ± 50 K for B) and cold rotational temperature (<55 K). Initial decomposition mechanisms for these two electronically excited, isolated molecules are explored at the complete active space self-consistent field (CASSCF(12,12)/6-31G(d)) level with and without MP2 correction. Potential energy surface calculations illustrate that conical intersections play an essential role in the calculated decomposition mechanisms. Based on experimental observations and theoretical calculations, NO product is released through opening of the furoxan ring: ring opening can occur either on the S 1 excited or S 0 ground electronic state. The reaction path with the lowest energetic barrier is that for which the furoxan ring opens on the S 1 state via the breaking of the N1-O1 bond. Subsequently, the molecule moves to the ground S 0 state through related ring-opening conical intersections, and an NO product is formed on the ground state surface with little rotational excitation at the last NO dissociation step. For the ground state ring opening decomposition mechanism, the N-O bond and C-N bond break together in order to generate dissociated NO. With the MP2 correction for the CASSCF(12,12) surface, the potential energies of molecules with dissociated NO product are in the range from 2.04 to 3.14 eV, close to the theoretical result for the density functional theory (B3LYP) and MP2 methods. The CASMP2(12,12) corrected approach is essential in order to obtain a reasonable potential energy surface that corresponds to the observed decomposition behavior of these molecules. Apparently, highly excited states are essential for an accurate representation of the kinetics and dynamics of excited state decomposition of both of these bisfuroxan energetic molecules. The experimental vibrational temperatures of NO products of A and B are about 800-1000 K lower than previously studied energetic molecules with NO as a decomposition product.

Molecular Dynamics of "Fuzzy" Transcriptional Activator-Coactivator Interactions

PubMed Central

Scholes, Natalie S.; Weinzierl, Robert O. J.

2016-01-01

Transcriptional activation domains (ADs) are generally thought to be intrinsically unstructured, but capable of adopting limited secondary structure upon interaction with a coactivator surface. The indeterminate nature of this interface made it hitherto difficult to study structure/function relationships of such contacts. Here we used atomistic accelerated molecular dynamics (aMD) simulations to study the conformational changes of the GCN4 AD and variants thereof, either free in solution, or bound to the GAL11 coactivator surface. We show that the AD-coactivator interactions are highly dynamic while obeying distinct rules. The data provide insights into the constant and variable aspects of orientation of ADs relative to the coactivator, changes in secondary structure and energetic contributions stabilizing the various conformers at different time points. We also demonstrate that a prediction of α-helical propensity correlates directly with the experimentally measured transactivation potential of a large set of mutagenized ADs. The link between α-helical propensity and the stimulatory activity of ADs has fundamental practical and theoretical implications concerning the recruitment of ADs to coactivators. PMID:27175900

Role of distortion in the hcp vs fcc competition in rare-gas solids

NASA Astrophysics Data System (ADS)

Krainyukova, N. V.

2011-05-01

As a prototype of an initial or intermediate structure between hcp and fcc lattices we consider a distorted bcc crystal. We calculate the temperature and pressure dependences of the lattice parameters for the heavier rare gas solids Ar, Kr, Xe in a quasiharmonic approximation with Aziz potentials, and confirm earlier predictions that the hcp structure predominates over fcc in the bulk within wide ranges of P and T. The situation is different for confined clusters with up to 105 atoms, where, owing to the specific surface energetics and terminations, structures with five-fold symmetry made up of fcc fragments are dominant. As a next step we consider the free relaxation of differently distorted bcc clusters, and show that two types (monoclinic and orthorhombic) of initial distortion are a driving force for the final hcp vs fcc configurations. Possible energy relationships between the initial and final structures are obtained and analyzed.

Models of S/π interactions in protein structures: Comparison of the H2S–benzene complex with PDB data

PubMed Central

Ringer, Ashley L.; Senenko, Anastasia; Sherrill, C. David

2007-01-01

S/π interactions are prevalent in biochemistry and play an important role in protein folding and stabilization. Geometries of cysteine/aromatic interactions found in crystal structures from the Brookhaven Protein Data Bank (PDB) are analyzed and compared with the equilibrium configurations predicted by high-level quantum mechanical results for the H2S–benzene complex. A correlation is observed between the energetically favorable configurations on the quantum mechanical potential energy surface of the H2S–benzene model and the cysteine/aromatic configurations most frequently found in crystal structures of the PDB. In contrast to some previous PDB analyses, configurations with the sulfur over the aromatic ring are found to be the most important. Our results suggest that accurate quantum computations on models of noncovalent interactions may be helpful in understanding the structures of proteins and other complex systems. PMID:17766371

INTENSE ENERGETIC GAS DISCHARGE

DOEpatents

Luce, J.S.

1960-03-01

A method and apparatus for initiating and sustaining an energetic gas arc discharge are described. A hollow cathode and a hollow anode are provided. By regulating the rate of gas flow into the interior of the cathode, the arc discharge is caused to run from the inner surface of the cathode with the result that adequate space-charge neutralization is provided inside the cathode but not in the main arc volume. Thus, the gas fed to the cathode is substantially completely ionized before it leaves the cathode, with the result that an energetic arc discharge can be maintained at lower operating pressures.

Tuning electronic and magnetic properties of GaN nanosheets by surface modifications and nanosheet thickness.

PubMed

Xiao, Meixia; Yao, Tingzhen; Ao, Zhimin; Wei, Peng; Wang, Danghui; Song, Haiyang

2015-04-14

Density-functional theory calculations are performed to investigate the effects of surface modifications and nanosheet thickness on the electronic and magnetic properties of gallium nitride (GaN) nanosheets (NSs). Unlike the bare GaN NSs terminating with polar surfaces, the systems with hydrogenated Ga (H-GaN), fluorinated Ga (F-GaN), and chlorinated Ga (Cl-GaN) preserve their initial wurtzite structures and exhibit ferromagnetic states. The abovementioned three different decorations on Ga atoms are energetically more favorable for thicker GaN NSs. Moreover, as the thickness increases, H-GaN and F-GaN NSs undergo semiconductor to metal and half-metal to metal transition, respectively, while Cl-GaN NSs remain completely metallic. The predicted diverse and tunable electronic and magnetic properties highlight the potential of GaN NSs for novel electronic and spintronic nanodevices.

Transfer doping of single isolated nanodiamonds, studied by scanning probe microscopy techniques

NASA Astrophysics Data System (ADS)

Bolker, Asaf; Saguy, Cecile; Kalish, Rafi

2014-09-01

The transfer doping of diamond surfaces has been applied in various novel two-dimensional electronic devices. Its extension to nanodiamonds (ND) is essential for ND-based applications in many fields. In particular, understanding the influence of the crystallite size on transfer doping is desirable. Here, we report the results of a detailed study of the electronic energetic band structure of single, isolated transfer-doped nanodiamonds with nanometric resolution using a combination of scanning tunneling spectroscopy and Kelvin force microscopy measurements. The results show how the band gap, the valence band maximum, the electron affinity and the work function all depend on the ND’s size and nanoparticle surface properties. The present analysis, which combines information from both scanning tunneling spectroscopy and Kelvin force microscopy, should be applicable to any nanoparticle or surface that can be measured with scanning probe techniques.

Surface modification of montmorillonite on surface Acid-base characteristics of clay and thermal stability of epoxy/clay nanocomposites.

PubMed

Park, Soo-Jin; Seo, Dong-Il; Lee, Jae-Rock

2002-07-01

In this work, the effect of surface treatments on smectitic clay was investigated in surface energetics and thermal behaviors of epoxy/clay nanocomposites. The pH values, X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR) were used to analyze the effect of cation exchange on clay surface and the exfoliation phenomenon of clay interlayer. The surface energetics of clay and thermal properties of epoxy/clay nanocomposites were investigated in contact angles and thermogravimetric analysis (TGA), respectively. From the experimental results, the surface modification of clay by dodecylammonium chloride led to the increases in both distance between silicate layers of about 8 A and surface acid values, as well as in the electron acceptor component (gamma(+)(s)) of surface free energy, resulting in improved interfacial adhesion between basic (or electron donor) epoxy resins and acidic (electron acceptor) clay interlayers. Also, the thermal stability of nanocomposites was highly superior to pure epoxy resin due to the presence of the well-dispersed clay nanolayer, which has a barrier property in a composite system.

The HZE radiation problem. [highly-charged energetic galactic cosmic rays

NASA Technical Reports Server (NTRS)

Schimmerling, Walter

1990-01-01

Radiation-exposure limits have yet to be established for missions envisioned in the framework of the Space Exploration Initiative. The radiation threat outside the earth's magnetosphere encompasses protons from solar particle events and the highly charged energetic particles constituting galactic cosmic rays; radiation biology entails careful consideration of the extremely nonuniform patterns of such particles' energy deposition. The ability to project such biological consequences of exposure to energetic particles as carcinogenicity currently involves great uncertainties from: (1) different regions of space; (2) the effects of spacecraft structures; and (3) the dose-effect relationships of single traversals of energetic particles.

Fe embedded in ice: The impacts of sublimation and energetic particle bombardment

NASA Astrophysics Data System (ADS)

Frankland, Victoria L.; Plane, John M. C.

2015-05-01

Icy particles containing a variety of Fe compounds are present in the upper atmospheres of planets such as the Earth and Saturn. In order to explore the role of ice sublimation and energetic ion bombardment in releasing Fe species into the gas phase, Fe-dosed ice films were prepared under UHV conditions in the laboratory. Temperature-programmed desorption studies of Fe/H2O films revealed that no Fe atoms or Fe-containing species co-desorbed along with the H2O molecules. This implies that when noctilucent ice cloud particles sublimate in the terrestrial mesosphere, the metallic species embedded in them will coalesce to form residual particles. Sputtering of the Fe-ice films by energetic Ar+ ions was shown to be an efficient mechanism for releasing Fe into the gas phase, with a yield of 0.08 (Ar+ energy=600 eV). Extrapolating with a semi-empirical sputtering model to the conditions of a proton aurora indicates that sputtering by energetic protons (>100 keV) should also be efficient. However, the proton flux in even an intense aurora will be too low for the resulting injection of Fe species into the gas phase to compete with that from meteoric ablation. In contrast, sputtering of the icy particles in the main rings of Saturn by energetic O+ ions may be the source of recently observed Fe+ in the Saturnian magnetosphere. Electron sputtering (9.5 keV) produced no detectable Fe atoms or Fe-containing species. Finally, it was observed that Fe(OH)2 was produced when Fe was dosed onto an ice film at 140 K (but not at 95 K). Electronic structure theory shows that the reaction which forms this hydroxide from adsorbed Fe has a large barrier of about 0.7 eV, from which we conclude that the reaction requires both translationally hot Fe atoms and mobile H2O molecules on the ice surface.

Graphene as a Coating for Plasma Facing Components

NASA Astrophysics Data System (ADS)

Navarro, Marcos; Zamiri, Marziyeh; Kulcinski, Gerald; Lagally, Max; Santarius, John

2017-10-01

This research explores the protection by graphene of plasma facing materials bombarded with energetic ions of helium. Few studies have shown that graphene can act as a protective layer against sputtering due to energetic ions. In the presence of such irradiation, plasma facing components (PFC's) tend to develop surface morphologies that lead to the sputtering of wall material, potentially diminishing the lifetime of the PFC's and plasma performance. Since plasmas have broad applications and the quality of transferred and grown graphene is different, we have used a chemical vapor deposition method to grow on other substrates. We have also shown that graphene can reduce changes on surface morphology due to energetic helium. After irradiation, in the case of graphene-covered tungsten, our results show that, compared to the uncovered W, graphene suppresses these morphologies that form on the surface of hot W. Using Raman spectroscopy as a diagnostic, the graphene coating shows little sign of damage after being irradiated, indicating that there is little to no sputtering of carbon impurities from the surface. We have determined that the mass losses in W have been reduced significantly, which may lead to an improved plasma performance and longer PFC lifetimes. Supported by DHS Project 2015-DN-077-ARI095 and the Grainger Foundation.

Viewing Mercury's Surface-bound Exosphere from Orbit: Eighteen Months of Observations by the Mercury Atmospheric and Surface Composition Spectrometer aboard the MESSENGER Spacecraft

NASA Astrophysics Data System (ADS)

McClintock, W. E.; Benna, M.; Burger, M. H.; Cassidy, T.; Killen, R. M.; Merkel, A. W.; Sarantos, M.; Solomon, S. C.; Sprague, A. L.; Vervack, R. J.

2012-12-01

Prior to the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) mission, Mercury's surface-bounded exosphere was known to contain H and He, observed by Mariner 10, as well as Na, K, and Ca, observed from the ground. The exosphere is the interface between the planet's surface and the surrounding space environment. Its composition and structure are controlled by interactions among the surface, magnetosphere, solar wind, sunlight, and impacting meteoroids. When species are liberated from the surface with sufficient energy, they can be accelerated by solar radiation pressure to form an anti-sunward tail. During three flybys en route to orbit, the Ultraviolet and Visible Spectrometer (UVVS) channel of the Mercury Atmospheric and Surface Composition Spectrometer (MASCS) aboard MESSENGER discovered Mg in the tail and detected Ca+ in a narrow region centered ~ 2.5 Mercury radii anti-sunward of the planet's terminator. UVVS began routine orbital observations of both the dayside and nightside exosphere on March 29, 2011. It regularly measures altitude profiles for all previously detected neutral species with the exception of He and K. The former has no emission features within the UVVS wavelength range (115-600 nm), and the latter has only one relatively weak feature there. A single component of Ca is usually observed at lower altitudes (~2000 km) and exhibits the strong equatorial, dawn enhancement observed during the flybys. Mg distributions exhibit two components. The more energetic component has been detected at high altitudes, up to 4000 km above the surface on both the dayside and nightside, and shows a dawn enhancement similar to Ca. Dayside distributions of Na exhibit two components with e-folding heights comparable to profiles above the poles obtained during the third flyby. Concentrations of all three species exhibit seasonal variability. The best studied of these is Na, for which maximum dayside density occurs at a Mercury true anomaly angle of 180°. UVVS also observes H. It is less well studied than Ca, Mg, and Na because signal from the exospheric H is often contaminated by emission from interplanetary hydrogen and sunlight reflected from the surface. O has also been detected near the subsolar point, but its emission is too weak for routine study. UVVS observations also include wavelength scans for neutral species that are known or are predicted to be present in the surface materials (e.g., Si, Al, S, Mn, Fe, and OH), but emissions from these species are not sufficiently bright for detection with current operational scenarios. The UVVS team uses a variety of techniques to relate exosphere composition and structure to source processes, including tomographic inversion and Monte Carlo modeling. Correlations of Mercury's neutral exosphere composition and structure with direct measurements of the space environment from MESSENGER's Magnetometer (MAG) and Energetic Particle and Plasma Spectrometer (EPPS) provide further insight into source processes.

Thermodynamic analysis of water molecules at the surface of proteins and applications to binding site prediction and characterization.

PubMed

Beuming, Thijs; Che, Ye; Abel, Robert; Kim, Byungchan; Shanmugasundaram, Veerabahu; Sherman, Woody

2012-03-01

Water plays an essential role in determining the structure and function of all biological systems. Recent methodological advances allow for an accurate and efficient estimation of the thermodynamic properties of water molecules at the surface of proteins. In this work, we characterize these thermodynamic properties and relate them to various structural and functional characteristics of the protein. We find that high-energy hydration sites often exist near protein motifs typically characterized as hydrophilic, such as backbone amide groups. We also find that waters around alpha helices and beta sheets tend to be less stable than waters around loops. Furthermore, we find no significant correlation between the hydration site-free energy and the solvent accessible surface area of the site. In addition, we find that the distribution of high-energy hydration sites on the protein surface can be used to identify the location of binding sites and that binding sites of druggable targets tend to have a greater density of thermodynamically unstable hydration sites. Using this information, we characterize the FKBP12 protein and show good agreement between fragment screening hit rates from NMR spectroscopy and hydration site energetics. Finally, we show that water molecules observed in crystal structures are less stable on average than bulk water as a consequence of the high degree of spatial localization, thereby resulting in a significant loss in entropy. These findings should help to better understand the characteristics of waters at the surface of proteins and are expected to lead to insights that can guide structure-based drug design efforts. Copyright © 2011 Wiley Periodicals, Inc.

The Radiation Environment on the Martian Surface and during MSL's Cruise to Mars

NASA Astrophysics Data System (ADS)

Hassler, Donald M.; Zeitlin, Cary; Wimmer-Schweingruber, Robert F.; Ehresmann, Bent; Rafkin, Scot; Martin, Cesar; Boettcher, Stephan; Koehler, Jan; Guo, Jingnan; Brinza, David E.; Reitz, Guenther; Posner, Arik; the MSL Science Team

2013-04-01

An important part of assessing present and past habitability of Mars is to understand and characterize "life limiting factors" on the surface, such as the radiation environment. Radiation exposure is also a major concern for future human missions and characterizing the radiation environment, both on the surface of Mars and inside the spacecraft during the cruise to Mars, provides critical information to aid in the planning for future human exploration of Mars. RAD was the first MSL instrument to start collecting data, beginning its science investigation during cruise (10 days after launch) and making the first ever measurements of the radiation environment on another planet. RAD is an energetic particle analyzer designed to characterize a broad spectrum of energetic particle radiation including galactic cosmic rays, solar energetic particles, and secondary neutrons created both in the Mars atmosphere and regolith. RAD observations consist of a time series of periodic (typically hourly) measurements of charged particles from protons (Z=1) up to iron (Z=26) for energies above >10 MeV/nucleon, as well as neutrons from 10 to ~ 100 MeV. These synoptic observations are designed to characterize both the short term variability associated with the onset of solar energetic particle events as well as the long term variability of galactic cosmic rays over the solar cycle. RAD measurements will also be used to quantify the flux of biologically hazardous radiation at the surface of Mars today, and determine how these fluxes vary on diurnal, seasonal, solar cycle and episodic (flare, storm) timescales. These measurements will allow calculations of the depth in rock or soil to which this flux, when integrated over long timescales, provides a lethal dose for known terrestrial organisms. Through such measurements, we can learn how deep below the surface life would have to be, or have been in the past, to be protected. This talk will discuss the results obtained during the ~7 months of cruise observations, which included good characterization of the radiation dose inside MSL. The radiation environment inside the MSL spacecraft is not unlike that expected inside a future manned spacecraft in deep space. Modeling of the effective shielding inside the MSL spacecraft (backshell, heat shield, descent stage, etc.) shows that the average shielding provided by MSL is similar to that of the International Space Station, as well as that being assumed for future manned vehicles. During the 221 days of cruise observations, RAD measured the charged particle flux and dose from galactic cosmic rays as well as significant dose enhancements from 5 solar energetic particle events observed during this period. Even with the level of shielding inside MSL, these solar energetic particle events contributed significantly to the cumulative dose and dose equivalent. Finally, we will present the first-ever measurements of the radiation environment on the surface of Mars. With increased solar activity as we approach the next solar maximum (expected in 2013), direct measurements of the contribution from solar energetic particle events to the total effective dose on the surface of Mars, as well as the contribution from atmospheric and albedo neutrons, will be increasingly important. RAD is supported by NASA (HEOMD) under JPL subcontract #1273039 to SwRI, and by DLR in Germany under contract with Christian-Albrechts-Universitat (CAU).

The Radiation Environment on the Martian Surface and during MSL's Cruise to Mars

NASA Astrophysics Data System (ADS)

Hassler, D. M.; Zeitlin, C.; Wimmer-Schweingruber, R. F.

2012-12-01

An important part of assessing present and past habitability of Mars is to understand and characterize "life limiting factors" on the surface, such as the radiation environment. Radiation exposure is also a major concern for future human missions and characterizing the radiation environment, both on the surface of Mars and inside the spacecraft during the cruise to Mars, provides critical information to aid in the planning for future human exploration of Mars. RAD was the first MSL instrument to start collecting data, beginning its science investigation during cruise (10 days after launch) and making the first ever measurements of the radiation environment on another planet. RAD is an energetic particle analyzer designed to characterize a broad spectrum of energetic particle radiation including galactic cosmic rays, solar energetic particles, and secondary neutrons created both in the Mars atmosphere and regolith. RAD observations consist of a time series of periodic (typically hourly) measurements of charged particles from protons (Z=1) up to iron (Z=26) for energies above >10 MeV/nucleon, as well as neutrons from 10 to ~ 100 MeV. These synoptic observations are designed to characterize both the short term variability associated with the onset of solar energetic particle events as well as the long term variability of galactic cosmic rays over the solar cycle. RAD measurements will also be used to quantify the flux of biologically hazardous radiation at the surface of Mars today, and determine how these fluxes vary on diurnal, seasonal, solar cycle and episodic (flare, storm) timescales. These measurements will allow calculations of the depth in rock or soil to which this flux, when integrated over long timescales, provides a lethal dose for known terrestrial organisms. Through such measurements, we can learn how deep below the surface life would have to be, or have been in the past, to be protected. This talk will discuss the results obtained during the ~7 months of cruise observations, which included good characterization of the radiation dose inside MSL. The radiation environment inside the MSL spacecraft is not unlike that expected inside a future manned spacecraft in deep space. Modeling of the effective shielding inside the MSL spacecraft (backshell, heat shield, descent stage, etc.) shows that the average shielding provided by MSL is similar to that of the International Space Station, as well as that being assumed for future manned vehicles. During the 221 days of cruise observations, RAD measured the charged particle flux and dose from galactic cosmic rays as well as significant dose enhancements from 5 solar energetic particle events observed during this period. Even with the level of shielding inside MSL, these solar energetic particle events contributed significantly to the cumulative dose and dose equivalent. Finally, we will present the first-ever measurements of the radiation environment on the surface of Mars. With increased solar activity as we approach the next solar maximum (expected in 2013), direct measurements of the contribution from solar energetic particle events to the total effective dose on the surface of Mars, as well as the contribution from atmospheric and albedo neutrons, will be increasingly important. RAD is supported by NASA (HEOMD) under JPL subcontract #1273039 to SwRI, and by DLR in Germany under contract with Christian-Albrechts-Universitat (CAU).

Critical Role of Water and Oxygen Defects in C-O Scission during CO2 Reduction on Zn2GeO4(010).

PubMed

Yang, Jing; Li, Yanlu; Zhao, Xian; Fan, Weiliu

2018-03-27

Exploration of catalyst structure and environmental sensitivity for C-O bond scission is essential for improving the conversion efficiency because of the inertness of CO 2 . We performed density functional theory calculations to understand the influence of the properties of adsorbed water and the reciprocal action with oxygen vacancy on the CO 2 dissociation mechanism on Zn 2 GeO 4 (010). When a perfect surface was hydrated, the introduction of H 2 O was predicted to promote the scission step by two modes based on its appearance, with the greatest enhancement from dissociative adsorbed H 2 O. The dissociative H 2 O lowers the barrier and reaction energy of CO 2 dissociation through hydrogen bonding to preactivate the C-O bond and assisted scission via a COOH intermediate. The perfect surface with bidentate-binding H 2 O was energetically more favorable for CO 2 dissociation than the surface with monodentate-binding H 2 O. Direct dissociation was energetically favored by the former, whereas monodentate H 2 O facilitated the H-assisted pathway. The defective surface exhibited a higher reactivity for CO 2 decomposition than the perfect surface because the generation of oxygen vacancies could disperse the product location. When the defective surface was hydrated, the reciprocal action for vacancy and surface H 2 O on CO 2 dissociation was related to the vacancy type. The presence of H 2 O substantially decreased the reaction energy for the direct dissociation of CO 2 on O 2c1 - and O 3c2 -defect surfaces, which converts the endoergic reaction to an exoergic reaction. However, the increased decomposition barrier made the step kinetically unfavorable and reduced the reaction rate. When H 2 O was present on the O 2c2 -defect surface, both the barrier and reaction energy for direct dissociation were invariable. This result indicated that the introduction of H 2 O had little effect on the kinetics and thermodynamics. Moreover, the H-assisted pathway was suppressed on all hydrated defect surfaces. These results provide a theoretical perspective for the design of highly efficient catalysts.

Quantized vortices and superflow in arbitrary dimensions: structure, energetics and dynamics

NASA Astrophysics Data System (ADS)

Goldbart, Paul M.; Bora, Florin

2009-05-01

The structure and energetics of superflow around quantized vortices, and the motion inherited by these vortices from this superflow, are explored in the general setting of a superfluid in arbitrary dimensions. The vortices may be idealized as objects of codimension 2, such as one-dimensional loops and two-dimensional closed surfaces, respectively, in the cases of three- and four-dimensional superfluidity. By using the analogy between the vortical superflow and Ampère-Maxwell magnetostatics, the equilibrium superflow containing any specified collection of vortices is constructed. The energy of the superflow is found to take on a simple form for vortices that are smooth and asymptotically large, compared with the vortex core size. The motion of vortices is analyzed in general, as well as for the special cases of hyper-spherical and weakly distorted hyper-planar vortices. In all dimensions, vortex motion reflects vortex geometry. In dimension 4 and higher, this includes not only extrinsic but also intrinsic aspects of the vortex shape, which enter via the first and second fundamental forms of classical geometry. For hyper-spherical vortices, which generalize the vortex rings of three-dimensional superfluidity, the energy-momentum relation is determined. Simple scaling arguments recover the essential features of these results, up to numerical and logarithmic factors.

3D Realistic Modeling of the Interaction of Quiet-Sun Magnetic Fields with the Chromosphere

NASA Technical Reports Server (NTRS)

Kitiashvili, I. N.; Kosovichev, A. G.; Mansour, N. N.; Wray, A. A.

2017-01-01

High-resolution observations and 3D simulations suggest that a local dynamo operates near the surface and produces ubiquitous small-scale magnetic elements, thus contributing to the magnetic carpet in the photosphere and to the magnetic structure and dynamics of the solar atmosphere. It appears that the traditional mechanisms of chromospheric energy and mass transport by acoustic waves and shocks are likely to play a secondary role; instead, the primary drivers in the energetics and dynamics of the chromosphere and transition region are small-scale, previously unresolved, quiet-Sun magnetic fields. These fields appear as ubiquitous, rapidly changing (on the scale of a few seconds), tiny magnetic loops and magnetized vortex tubes. Questions then arise about their origin and dynamics in the chromosphere, their links to magnetic fields in the photosphere, and their role in the energy storage and exchange between subsurface layers and the chromosphere. In the talk we will present results of 3D radiative MHD simulations obtained with the StellarBox code and discuss the energetics and dynamical interlinks between the subphotospheric layers and low chromosphere, their effects on the structure of the chromosphere, and signatures of the fine-scale magnetic features in high-resolution spectro-polarimetric observations.

Probing semiconductor gap states with resonant tunneling.

PubMed

Loth, S; Wenderoth, M; Winking, L; Ulbrich, R G; Malzer, S; Döhler, G H

2006-02-17

Tunneling transport through the depletion layer under a GaAs {110} surface is studied with a low temperature scanning tunneling microscope (STM). The observed negative differential conductivity is due to a resonant enhancement of the tunneling probability through the depletion layer mediated by individual shallow acceptors. The STM experiment probes, for appropriate bias voltages, evanescent states in the GaAs band gap. Energetically and spatially resolved spectra show that the pronounced anisotropic contrast pattern of shallow acceptors occurs exclusively for this specific transport channel. Our findings suggest that the complex band structure causes the observed anisotropies connected with the zinc blende symmetry.

Metal Interactions at the Biochar-Water Interface: Energetics and Structure-Sorption Relationships Elucidated by Flow Adsorption Microcalorimetry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harvey, Omar R.; Herbert, Bruce; Rhue, Roy D.

2011-06-01

Interest in biochars and their role in the biogeochemical cycling of metals have increased in recent years. However, a systematic understanding of the mechanisms involved in biochar-metal interactions and conditions under which a given mechanism is predominant is still needed. We used flow adsorption micro-calorimetry to study structure-sorption relationships between twelve plant-derived biochars and two metals of different ionization potential (Ip). Biochar structure influenced the amount of K+ (Ip = 419 kJ mol-1) or Cd(II) (Ip = 868 kJ mol-17 ) sorption but had no effect on the mechanism of sorption. Irrespective of the biochar, K+ sorption was exothermic, surface-controlledmore » and occurred via an ion-exchange mechanism on negatively- charged sites with molar heats of adsorption (_Hads) of -4 kJ mol-1 on wood versus -8 kJ mol-1 on grass biochars. In contrast, Cd(II) sorption was endothermic and favored surface complexation on uncharged biochar surfaces with _Hads of around +17 kJ mol-1. Cadmium sorption transitioned from surface- to diffusion-controlled on biochars formed at ≥ 350 oC and _Hads for Cd(II) sorption was the same on grass and wood biochars. We concluded that, in general, metals with lower Ip favor electrostatic interactions with biochars, while metals of higher Ip favor more covalent-like interactions.« less

Direct vs. indirect pathway for nitrobenzene reduction reaction on a Ni catalyst surface: a density functional study.

PubMed

Mahata, Arup; Rai, Rohit K; Choudhuri, Indrani; Singh, Sanjay K; Pathak, Biswarup

2014-12-21

Density functional theory (DFT) calculations are performed to understand and address the previous experimental results that showed the reduction of nitrobenzene to aniline prefers direct over indirect reaction pathways irrespective of the catalyst surface. Nitrobenzene to aniline conversion occurs via the hydroxyl amine intermediate (direct pathway) or via the azoxybenzene intermediate (indirect pathway). Through our computational study we calculated the spin polarized and dispersion corrected reaction energies and activation barriers corresponding to various reaction pathways for the reduction of nitrobenzene to aniline over a Ni catalyst surface. The adsorption behaviour of the substrate, nitrobenzene, on the catalyst surface was also considered and the energetically most preferable structural orientation was elucidated. Our study indicates that the parallel adsorption behaviour of the molecules over a catalyst surface is preferable over vertical adsorption behaviour. Based on the reaction energies and activation barrier of the various elementary steps involved in direct or indirect reaction pathways, we find that the direct reduction pathway of nitrobenzene over the Ni(111) catalyst surface is more favourable than the indirect reaction pathway.

High-Energy-Density LCA-Coupled Structural Energetic Materials for Counter WMD Applications

DTIC Science & Technology

2014-04-01

reactive ( thermite ) fillers as high-energy-density structural energetic materials. The specific objectives include performing fundamental studies to...a) investigate mechanics of dynamic densification and reaction initiation in Ta+Fe2O3 and Ta+Bi2O3 thermite powder mixtures and to (b) design and...initiation in the thermite filler and allow controlled fragmentation. Linear Cellular A; counter WMDs; shock-compression and impact-initiated reactions

Self-assembly of triangular particles via capillary interactions

NASA Astrophysics Data System (ADS)

Bedi, Deshpreet; Zhou, Shangnan; Ferrar, Joseph; Solomon, Michael; Mao, Xiaoming

Colloidal particles adsorbed to a fluid interface deform the interface around them, resulting in either attractive or repulsive forces mediated by the interface. In particular, particle shape and surface roughness can produce an undulating contact line, such that the particles will assume energetically-favorable relative orientations and inter-particle distances to minimize the excess interfacial surface area. By expediently selecting specific particle shapes and associated design parameters, capillary interactions can be utilized to promote self-assembly of these particles into extended regular open structures, such as the kagome lattice, which have novel mechanical properties. We present the results of numerical simulations of equilateral triangle microprisms at an interface, including individually and in pairs. We show how particle bowing can yield two distinct binding events and connect it to theory in terms of a capillary multipole expansion and also to experiment, as presented in an accompanying talk. We also discuss and suggest design principles that can be used to create desirable open structures.

Efficient energy absorption of intense ps-laser pulse into nanowire target

NASA Astrophysics Data System (ADS)

Habara, H.; Honda, S.; Katayama, M.; Sakagami, H.; Nagai, K.; Tanaka, K. A.

2016-06-01

The interaction between ultra-intense laser light and vertically aligned carbon nanotubes is investigated to demonstrate efficient laser-energy absorption in the ps laser-pulse regime. Results indicate a clear enhancement of the energy conversion from laser to energetic electrons and a simultaneously small plasma expansion on the surface of the target. A two-dimensional plasma particle calculation exhibits a high absorption through laser propagation deep into the nanotube array, even for a dense array whose structure is much smaller than the laser wavelength. The propagation leads to the radial expansion of plasma perpendicular to the nanotubes rather than to the front side. These features may contribute to fast ignition in inertial confinement fusion and laser particle acceleration, both of which require high current and small surface plasma simultaneously.

A theoretical study of the reaction of Ti+ with ethane

NASA Astrophysics Data System (ADS)

Moc, Jerzy; Fedorov, Dmitri G.; Gordon, Mark S.

2000-06-01

The doublet and quartet potential energy surfaces for the Ti++C2H6→TiC2H4++H2 and Ti++C2H6→TiCH2++CH4 reactions are studied using density functional theory (DFT) with the B3LYP functional and ab initio coupled cluster CCSD(T) methods with high quality basis sets. Structures have been optimized at the DFT level and the minima connected to each transition state (TS) by following the intrinsic reaction coordinate (IRC). Relative energies are calculated both at the DFT and coupled-cluster levels of theory. The relevant parts of the potential energy surface, especially key transition states, are also studied using multireference wave functions with the final energetics obtained with multireference second-order perturbation theory.

Monomolecular Siloxane Film as a Model of Single Site Catalysts

DOE PAGES

Martynowycz, Michael W.; Hu, Bo; Kuzmenko, Ivan; ...

2016-09-06

Achieving structurally well-defined catalytic species requires a fundamental understanding of surface chemistry. Detailed structural characterization of the catalyst binding sites in situ, such as single site catalysts on silica supports, is technically challenging or even unattainable. Octadecyltrioxysilane (OTOS) monolayers formed from octadecyltrimethoxysilane (OTMS) at the air-liquid interface after hydrolysis and condensation at low pH were chosen as a model system of surface binding sites in silica-supported Zn 2+ catalysts. We characterize the system by grazing incidence X-ray diffraction, X-ray reflectivity (XR), and X-ray fluorescence spectroscopy (XFS). Previous X-ray and infrared surface studies of OTMS/OTOS films at the airliquid interface proposedmore » the formation of polymer OTOS structures. According to our analysis, polymer formation is inconsistent with the X-ray observations and structural properties of siloxanes; it is energetically unfavorable and thus highly unlikely. We suggest an alternative mechanism of hydrolysis/condensation in OTMS leading to the formation of structurally allowed cyclic trimers with the six-membered siloxane rings, which explain well both the X-ray and infrared results. XR and XFS consistently demonstrate that tetrahedral [Zn(NH 3) 4] 2+ ions bind to hydroxyl groups of the film at a stoichiometric ratio of OTOS:Zn ~ 2:1. The high binding affinity of zinc ions to OTOS trimers suggests that the six-membered siloxane rings are binding locations for single site Zn/SiO 2 catalysts. Finally, our results show that OTOS monolayers may serve as a platform for studying silica surface chemistry or hydroxyl-mediated reactions.« less

Design of New Bridge-Ring Energetic Compounds Obtained by Diels-Alder Reactions of Tetranitroethylene Dienophile.

PubMed

He, Piao; Mei, Hao-Zheng; Wu, Le; Yang, Jun-Qing; Zhang, Jian-Guo; Cohen, Adva; Gozin, Michael

2018-03-29

The density functional theory method was employed to calculate three-dimensional structures for a series of novel explosophores. The design of new molecules (DA1-DA12) was based on the bridge-ring structures that could be formed via Diels-Alder (DA) reaction of selected nitrogen-rich dienes and tetranitroethylene dienophile. The feasibility of the proposed DA reactions was predicted on the basis of the molecular orbital theory. The strong interactions between the HOMO of dienes, with electron-donating groups (Diene2, Diene6, and Diene8), and the LUMO of tetranitroethylene dienophile suggested thermodynamically favorable formation of the desired DA reaction products. In addition to molecular structures of the explored DA compounds, their physicochemical and energetic properties were also calculated in detail. Due to compact bridge-ring structures, new energetic molecules have highly positive heats of formation (up to 1124.90 kJ·mol -1 ) and high densities (up to 2.04 g·cm -3 ). Also, as a result of all-right ratios of nitrogen and oxygen, most of the new compounds possess high detonation velocities (8.28-10.02 km·s -1 ) and high detonation pressures (30.87-47.83 GPa). Energetic compounds DA1, DA4, and DA12 exhibit a superior detonation performance over widely used HMX explosive, and DA5, DA7, and DA10 could be comparable to the state-of-the-art CL-20 and ONC explosives. Our proposed designs and synthetic methodology should provide a platform for the development of novel energetic materials with superior performance.

ProtPOS: a python package for the prediction of protein preferred orientation on a surface.

PubMed

Ngai, Jimmy C F; Mak, Pui-In; Siu, Shirley W I

2016-08-15

Atomistic molecular dynamics simulation is a promising technique to investigate the energetics and dynamics in the protein-surface adsorption process which is of high relevance to modern biotechnological applications. To increase the chance of success in simulating the adsorption process, favorable orientations of the protein at the surface must be determined. Here, we present ProtPOS which is a lightweight and easy-to-use python package that can predict low-energy protein orientations on a surface of interest. It combines a fast conformational sampling algorithm with the energy calculation of GROMACS. The advantage of ProtPOS is it allows users to select any force fields suitable for the system at hand and provide structural output readily available for further simulation studies. ProtPOS is freely available for academic and non-profit uses at http://cbbio.cis.umac.mo/software/protpos Supplementary data are available at Bioinformatics online. shirleysiu@umac.mo. © The Author 2016. Published by Oxford University Press.

Regulation of oxygen vacancy types on SnO{sub 2} (110) surface by external strain

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Z. H.; Min, Y. M.; Liu, X. X.

2016-05-15

In tin dioxide nanostructures, oxygen vacancies (OVs) play an important role in their optical properties and thus regulation of both OV concentration and type via external strain is crucial to exploration of more applications. First-principle calculations of SnO{sub 2} (110) surface disclose that asymmetric deformations induced by external strain not only lead to its intrinsic surface elastic changes, but also result in different OV formation energy. In the absence of external strain, the energetically favorable oxygen vacancies(EFOV) appear in the bridging site of second layer. When -3.5% external strain is applied along y direction, the EFOV moves into plane site.more » This can be ascribed that the compressed deformation gives rise to redistribution of electronic wave function near OVs, therefore, formation of newly bond structures. Our results suggest that different type OVs in SnO{sub 2} surface can be controlled by strain engineering.« less

ProtPOS: a python package for the prediction of protein preferred orientation on a surface

PubMed Central

Ngai, Jimmy C. F.; Mak, Pui-In; Siu, Shirley W. I.

2016-01-01

Summary: Atomistic molecular dynamics simulation is a promising technique to investigate the energetics and dynamics in the protein–surface adsorption process which is of high relevance to modern biotechnological applications. To increase the chance of success in simulating the adsorption process, favorable orientations of the protein at the surface must be determined. Here, we present ProtPOS which is a lightweight and easy-to-use python package that can predict low-energy protein orientations on a surface of interest. It combines a fast conformational sampling algorithm with the energy calculation of GROMACS. The advantage of ProtPOS is it allows users to select any force fields suitable for the system at hand and provide structural output readily available for further simulation studies. Availability and Implementation: ProtPOS is freely available for academic and non-profit uses at http://cbbio.cis.umac.mo/software/protpos Supplementary information: Supplementary data are available at Bioinformatics online. Contact: shirleysiu@umac.mo PMID:27153619

Predicting Catalytic Activity of Nanoparticles by a DFT-Aided Machine-Learning Algorithm.

PubMed

Jinnouchi, Ryosuke; Asahi, Ryoji

2017-09-07

Catalytic activities are often dominated by a few specific surface sites, and designing active sites is the key to realize high-performance heterogeneous catalysts. The great triumphs of modern surface science lead to reproduce catalytic reaction rates by modeling the arrangement of surface atoms with well-defined single-crystal surfaces. However, this method has limitations in the case for highly inhomogeneous atomic configurations such as on alloy nanoparticles with atomic-scale defects, where the arrangement cannot be decomposed into single crystals. Here, we propose a universal machine-learning scheme using a local similarity kernel, which allows interrogation of catalytic activities based on local atomic configurations. We then apply it to direct NO decomposition on RhAu alloy nanoparticles. The proposed method can efficiently predict energetics of catalytic reactions on nanoparticles using DFT data on single crystals, and its combination with kinetic analysis can provide detailed information on structures of active sites and size- and composition-dependent catalytic activities.

Theoretical aspects of graphene-like group IV semiconductors

NASA Astrophysics Data System (ADS)

Houssa, M.; van den Broek, B.; Scalise, E.; Ealet, B.; Pourtois, G.; Chiappe, D.; Cinquanta, E.; Grazianetti, C.; Fanciulli, M.; Molle, A.; Afanas'ev, V. V.; Stesmans, A.

2014-02-01

Silicene and germanene are the silicon and germanium counterparts of graphene, respectively. Recent experimental works have reported the growth of silicene on (1 1 1)Ag surfaces with different atomic configurations, depending on the growth temperature and surface coverage. We first theoretically study the structural and electronic properties of silicene on (1 1 1)Ag surfaces, focusing on the (4 × 4)silicene/Ag structure. Due to symmetry breaking in the silicene layer (nonequivalent number of top and bottom Si atoms), the corrugated silicene layer, with the Ag substrate removed, is predicted to be semiconducting, with a computed energy bandgap of about 0.3 eV. However, the hybridization between the Si 3p orbitals and the Ag 5s orbital in the silicene/(1 1 1)Ag slab model leads to an overall metallic system, with a distribution of local electronic density of states, which is related to the slightly disordered structure of the silicene layer on the (1 1 1)Ag surface. We next study the interaction of silicene and germanene with different hexagonal non-metallic substrates, namely ZnS and ZnSe. On reconstructed (0 0 0 1)ZnS or ZnSe surfaces, which should be more energetically stable for very thin layers, silicene and germanene are found to be semiconducting. Remarkably, the nature and magnitude of their energy bandgap can be controlled by an out-of-plane electric field, an important finding for the potential use of these materials in nanoelectronic devices.

Physics of Alfvén waves and energetic particles in burning plasmas

NASA Astrophysics Data System (ADS)

Chen, Liu; Zonca, Fulvio

2016-01-01

Dynamics of shear Alfvén waves and energetic particles are crucial to the performance of burning fusion plasmas. This article reviews linear as well as nonlinear physics of shear Alfvén waves and their self-consistent interaction with energetic particles in tokamak fusion devices. More specifically, the review on the linear physics deals with wave spectral properties and collective excitations by energetic particles via wave-particle resonances. The nonlinear physics deals with nonlinear wave-wave interactions as well as nonlinear wave-energetic particle interactions. Both linear as well as nonlinear physics demonstrate the qualitatively important roles played by realistic equilibrium nonuniformities, magnetic field geometries, and the specific radial mode structures in determining the instability evolution, saturation, and, ultimately, energetic-particle transport. These topics are presented within a single unified theoretical framework, where experimental observations and numerical simulation results are referred to elucidate concepts and physics processes.

Molecular origins of fluorocarbon hydrophobicity

PubMed Central

Dalvi, Vishwanath H.; Rossky, Peter J.

2010-01-01

We have undertaken atomistic molecular simulations to systematically determine the structural contributions to the hydrophobicity of fluorinated solutes and surfaces compared to the corresponding hydrocarbon, yielding a unified explanation for these phenomena. We have transformed a short chain alkane, n-octane, to n-perfluorooctane in stages. The free-energy changes and the entropic components calculated for each transformation stage yield considerable insight into the relevant physics. To evaluate the effect of a surface, we have also conducted contact-angle simulations of water on self-assembled monolayers of hydrocarbon and fluorocarbon thiols. Our results, which are consistent with experimental observations, indicate that the hydrophobicity of the fluorocarbon, whether the interaction with water is as solute or as surface, is due to its “fatness.” In solution, the extra work of cavity formation to accommodate a fluorocarbon, compared to a hydrocarbon, is not offset by enhanced energetic interactions with water. The enhanced hydrophobicity of fluorinated surfaces arises because fluorocarbons pack less densely on surfaces leading to poorer van der Waals interactions with water. We find that interaction of water with a hydrophobic solute/surface is primarily a function of van der Waals interactions and is substantially independent of electrostatic interactions. This independence is primarily due to the strong tendency of water at room temperature to maintain its hydrogen bonding network structure at an interface lacking hydrophilic sites. PMID:20643968

The Modeling of Coupled Electromagnetic-Thermo-Mechanical Laser Interactions and Microstructural Behavior of Energetic Aggregates

DTIC Science & Technology

2015-01-01

analytical Beer - Lambert absorption profile to model laser heating of pure energetic crystals without considering any EM wave propagation effects...temperature. These aggregates were studied using both an analytical distribution for laser heating following Beer - Lambert absorption and the full EM finite...surface (ysurface - y) and material absorption coefficient, α, following a Beer - Lambert absorption relation given by , = !()

Growth energetics of germanium quantum dots by atomistic simulation

NASA Astrophysics Data System (ADS)

Wagner, Richard Joseph

Strained epitaxial growth of Ge on Si(001) produces self-assembled, nanometer scale islands, or quantum dots. We study this growth by atomistic simulation, computing the energy of island structures to determine when and how islanding occurs. We also describe experimental methods of island growth and characterization in order to understand the relevant physical processes and to interpret experimental observations for comparison with simulation. We show that pyramidal Ge islands with rebonded step {105} facets are energetically favorable compared to growth of planar Ge (2 x 8) on Si(001). We determine how the chemical potential of these islands varies with size, lateral spacing, and wetting layer thickness. We also illustrate the atomic-level structure of these islands with favorable formation energy. Intermixing can occur between the growing Ge film and the Si substrate. We show that although Ge prefers to wet the surface, entropy drives some fraction into the underlying layers. We present a simple model of intermixing by equilibration of the top crystal layers. The equilibration is performed with a flexible lattice Monte Carlo simulation. Ultimately, intermixing produces a temperature-dependent graded Ge concentration. The resulting chemical potential leads to the onset of islanding after 3-4 monolayers of deposition, consistent with experimental observations. The distribution of island sizes on a surface is determined by the relation of island energy to size. We find that there exists a minimum-energy island size due to the interaction of surface energy and bulk relaxation. Applying the calculated chemical potential to the Boltzmann-Gibbs distribution, we predict size distributions as functions of coverage and temperature. The distributions, with peak populations around 86 000 atoms, compare favorably with experiment. This work explores the driving force in growth of Ge on Si(001). The knowledge derived here explains why islanding occurs and provides guidance for the control of island self-assembly to construct useful microelectronic devices from quantum dots.

Self-assembled monolayer structures of hexadecylamine on Cu surfaces: density-functional theory.

PubMed

Liu, Shih-Hsien; Balankura, Tonnam; Fichthorn, Kristen A

2016-12-07

We used dispersion-corrected density-functional theory to probe possible structures for adsorbed layers of hexadecylamine (HDA) on Cu(100) and Cu(111). HDA forms self-assembled layers on these surfaces, analogous to alkanethiols on various metal surfaces, and it binds by donating electrons in the amine group to the Cu surface atoms, consistent with experiment. van der Waals interactions between the alkyl tails of HDA molecules are stronger than the interaction between the amine group and the Cu surfaces. Strong HDA-tail interactions lead to coverage-dependent tilting of the HDA layers, such that the tilt angle is larger for lower coverages. At full monolayer coverage, the energetically preferred binding configuration for HDA on Cu(100) is a (5 × 3) pattern - although we cannot rule out incommensurate structures - while the pattern is preferred on Cu(111). A major motivation for this study is to understand the experimentally observed capability of HDA as a capping agent for producing {100}-faceted Cu nanocrystals. Consistent with experiment, we find that HDA binds more strongly to Cu(100) than to Cu(111). This strong binding stems from the capability of HDA to form more densely packed layers on Cu(100), which leads to stronger HDA-tail interactions, as well as the stronger binding of the amine group to Cu(100). We estimate the surface energies of HDA-covered Cu(100) and Cu(111) surfaces and find that these surfaces are nearly isoenergetic. By drawing analogies to previous theoretical work, it seems likely that HDA-covered Cu nanocrystals could have kinetic shapes that primarily express {100} facets, as is seen experimentally.

A first principles study of the oxidation energetics and kinetics of realgar

NASA Astrophysics Data System (ADS)

Renock, Devon; Becker, Udo

2010-08-01

Quantum-mechanical calculations allow resolving and quantifying in detail important aspects of reaction mechanisms such as spin transitions and oxygen dissociation that can be the major rate-limiting steps in redox processes on sulfide and oxide surfaces. In addition, this knowledge can help experimentalists in setting up the framework of rate equations that can be used to describe the kinetics of, e.g., oxidation processes. The unique molecular crystal structure of realgar, As 4S 4 clusters held together by van der Waals bonds, allows for a convenient quantum-mechanical (q.m.) cluster approach to investigate the thermodynamics and kinetic pathways of oxidation. The interaction of As 4S 4 clusters with oxygen and co-adsorbed ions provides a model system for understanding the molecular-scale processes that underpin empirically-derived rate expressions, and provides clues to the oxidation mechanisms of other sulfides and oxides. Two activated processes are shown to dominate the kinetics of oxidation by molecular oxygen: (i) a paramagnetic 3O to diamagnetic 1O spin transition and (ii) oxygen dissociation on the surface, in that order. The activation energies for the spin transition and O 2 dissociation step were determined to be 1.1 eV (106 kJ/mol) and 0.9 eV (87 kJ/mol), respectively, if molecular oxygen is the only reactant on the surface. In the case of As 4S 4, q.m. calculations reveal that 3O transfers its spin to the cluster and forms a low-spin, peroxo intermediate on the surface before dissociating. The adsorption of a hydroxide ion on the surface proximate to the 3O adsorption site changes the adsorption mechanism by lowering the activation energy barriers for both the spin transition (0.30 eV/29 kJ/mol) and the O 2 dissociation step (0.72 eV/69 kJ/mol). Thus, while spin transition is rate limiting for oxidation with O 2 alone, dissociation becomes the rate-limiting step for oxidation with co-adsorption of OH -. First-principles, periodic calculations of the realgar (1¯20) surface show that the energetics and structural changes that accompany oxidation of As 4S 4 clusters on the surface are similar to those involving individual As 4S 4 clusters. Thus, assuming that an As 4S 4 cluster with an adsorbed hydroxyl group is a reasonable approximation of the surface of As 4S 4 at high pH, the theoretically calculated oxidation rate (˜1 × 10 -10 mol m -2 s -1) is of the same order as empirically-derived rates from experiments at T = 298 K, pH = 8, and similar dissolved oxygen concentrations. In addition, the co-adsorption of other anions found in alkaline waters (i.e. carbonate, bicarbonate, sulfate, and sulfite) were shown to energetically promote the oxidation of As 4S 4 (on the order of 5-40 kJ/mol depending on the co-adsorbed anion, OH -, CO32-, HCO3-, SO42-, or SO32-, and accounting for changes in the hydration of products and reactants). The effect of the co-adsorbate on the kinetics and thermodynamics of oxidation is due to each adsorbate modifying the electronic and structural environment of the other adsorption site. Activation-energy barriers due to spin transitions are rarely discussed in the literature as key factors for controlling oxidation rates of mineral surfaces, even though the magnitude of these barriers is enough to alter the kinetics significantly. The attenuation of the activation energy by co-adsorbed anions suggests the possibility of pH- or p(co-adsorbate)-dependent activation energies that can be used to refine oxidation rate laws for sulfide minerals and other, especially semiconducting minerals, such as oxides.

New findings on the influence of carbon surface curvature on energetics of benzene adsorption from aqueous solutions

NASA Astrophysics Data System (ADS)

Wiśniewski, Marek; Werengowska-Ciećwierz, Karolina; Terzyk, Artur P.

2015-01-01

Immersional measurements of benzene adsorption form dilute aqueous solutions are reported for the first time together with the measurements of the enthalpy of benzene adsorption. Benzene adsorption from aqueous solution is an exothermic process. Our results show that with the decrease in carbon nanotube diameter the process becomes more exothermic, and the enthalpy of benzene adsorption correlates with the BET surface area and the electrostatic field strength of the tubes. Possible explanations of the results are proposed, and the most probable is that the change in carbon hybridisation with curvature leads to creation of stronger energetically adsorption sites than observed for graphite.

Chlorination of zirconium (0001) surface: A first-principles study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, E.; Weck, Philippe F; Poineau, F.

The mechanisms and energetics of Zr(0001) surface chlorination by dissociative adsorption of gaseous Cl 2, and associated speciation and surface degradation processes, have been investigated within the framework of density functional theory. Chlorination of Zr(0001) is predicted to be exothermic by 3 eV/Cl for dissociative adsorption of a single Cl 2 molecule, followed by exothermic chlorination to 1ML and 2 ML under Cl-rich conditions, with respective energy gains of 1.93 and 2.79 eV/Cl. Calculations also show that exfoliation of the top Cl-Zr-Cl sandwich layers is exothermic and most energetically favorable, and can thus be considered as a leading mechanism formore » Zr(0001) surface dissolution. Finally, consistent with experimental findings, formation of ZrCl 4 molecular products is also found to be dominant during Zr(0001) chlorination.« less

Chlorination of zirconium (0001) surface: A first-principles study.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Eunja; Weck, Philippe F; Borjas, Rosendo

Here, the mechanisms and energetics of Zr(0001) surface chlorination by dissociative adsorption of gaseous Cl 2, and associated speciation and surface degradation processes, have been investigated within the framework of density functional theory. Chlorination of Zr(0001) is predicted to be exothermic by ~3 eV/Cl for dissociative adsorption of a single Cl 2 molecule, followed by exothermic chlorination to 1ML and 2 ML under Cl-rich conditions, with respective energy gains of 1.93 and 2.79 eV/Cl. Calculations also show that exfoliation of the top Cl-Zr-Cl sandwich layers is exothermic and most energetically favorable, and can thus be considered as a leading mechanismmore » for Zr(0001) surface dissolution. Consistent with experimental findings, formation of ZrCl 4 molecular products is also found to be dominant during Zr(0001) chlorination.« less

Energetic lanthanide complexes: coordination chemistry and explosives applications

NASA Astrophysics Data System (ADS)

Manner, V. W.; Barker, B. J.; Sanders, V. E.; Laintz, K. E.; Scott, B. L.; Preston, D. N.; Sandstrom, M.; Reardon, B. L.

2014-05-01

Metals are generally added to organic molecular explosives in a heterogeneous composite to improve overall heat and energy release. In order to avoid creating a mixture that can vary in homogeneity, energetic organic molecules can be directly bonded to high molecular weight metals, forming a single metal complex with Angstrom-scale separation between the metal and the explosive. To probe the relationship between the structural properties of metal complexes and explosive performance, a new series of energetic lanthanide complexes has been prepared using energetic ligands such as NTO (5-nitro-2,4-dihydro-1,2,4-triazole-3-one). These are the first examples of lanthanide NTO complexes where no water is coordinated to the metal, demonstrating novel control of the coordination environment. The complexes have been characterized by X-ray crystallography, NMR and IR spectroscopies, photoluminescence, and sensitivity testing. The structural and energetic properties are discussed in the context of enhanced blast effects and detection. Cheetah calculations have been performed to fine-tune physical properties, creating a systematic method for producing explosives with 'tailor made' characteristics. These new complexes will be benchmarks for further study in the field of metalized high explosives.

Energetic Lanthanide Complexes: Coordination Chemistry and Explosives Applications

NASA Astrophysics Data System (ADS)

Manner, Virginia; Barker, Beau; Sanders, Eric; Laintz, Kenneth; Scott, Brian; Preston, Daniel; Sandstrom, Mary; Reardon, Bettina

2013-06-01

Metals are generally added to organic molecular explosives in a heterogeneous composite to improve overall heat and energy release. In order to avoid creating a mixture that can vary in homogeneity, energetic organic molecules can be directly bonded to high molecular weight metals, forming a single metal complex with Angstrom-scale separation between the metal and the explosive. To probe the relationship between the structural properties of metal complexes and explosive performance, a new series of energetic lanthanide complexes has been prepared using energetic ligands such as NTO (5-nitro-2,4-dihydro-1,2,4-triazole-3-one). These are the first examples of lanthanide NTO complexes where no water is coordinated to the metal, demonstrating novel control of the coordination environment. The complexes have been characterized by X-ray crystallography, NMR and IR spectroscopies, photoluminescence, and sensitivity testing. The structural and energetic properties are discussed in the context of enhanced blast effects and detection. Cheetah calculations have been performed to fine-tune physical properties, creating a systematic method for producing explosives with ``tailor made'' characteristics. These new complexes will be benchmarks for further study in the field of metalized high explosives.

Investigation of energetic particle induced geodesic acoustic mode

NASA Astrophysics Data System (ADS)

Schneller, Mirjam; Fu, Guoyong; Chavdarovski, Ilija; Wang, Weixing; Lauber, Philipp; Lu, Zhixin

2017-10-01

Energetic particles are ubiquitous in present and future tokamaks due to heating systems and fusion reactions. Anisotropy in the distribution function of the energetic particle population is able to excite oscillations from the continuous spectrum of geodesic acoustic modes (GAMs), which cannot be driven by plasma pressure gradients due to their toroidally and nearly poloidally symmetric structures. These oscillations are known as energetic particle-induced geodesic acoustic modes (EGAMs) [G.Y. Fu'08] and have been observed in recent experiments [R. Nazikian'08]. EGAMs are particularly attractive in the framework of turbulence regulation, since they lead to an oscillatory radial electric shear which can potentially saturate the turbulence. For the presented work, the nonlinear gyrokinetic, electrostatic, particle-in-cell code GTS [W.X. Wang'06] has been extended to include an energetic particle population following either bump-on-tail Maxwellian or slowing-down [Stix'76] distribution function. With this new tool, we study growth rate, frequency and mode structure of the EGAM in an ASDEX Upgrade-like scenario. A detailed understanding of EGAM excitation reveals essential for future studies of EGAM interaction with micro-turbulence. Funded by the Max Planck Princeton Research Center. Computational resources of MPCDF and NERSC are greatefully acknowledged.

Intense energetic electron flux enhancements in Mercury's magnetosphere: An integrated view with high-resolution observations from MESSENGER.

PubMed

Baker, Daniel N; Dewey, Ryan M; Lawrence, David J; Goldsten, John O; Peplowski, Patrick N; Korth, Haje; Slavin, James A; Krimigis, Stamatios M; Anderson, Brian J; Ho, George C; McNutt, Ralph L; Raines, Jim M; Schriver, David; Solomon, Sean C

2016-03-01

The MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) mission to Mercury has provided a wealth of new data about energetic particle phenomena. With observations from MESSENGER's Energetic Particle Spectrometer, as well as data arising from energetic electrons recorded by the X-Ray Spectrometer and Gamma-Ray and Neutron Spectrometer (GRNS) instruments, recent work greatly extends our record of the acceleration, transport, and loss of energetic electrons at Mercury. The combined data sets include measurements from a few keV up to several hundred keV in electron kinetic energy and have permitted relatively good spatial and temporal resolution for many events. We focus here on the detailed nature of energetic electron bursts measured by the GRNS system, and we place these events in the context of solar wind and magnetospheric forcing at Mercury. Our examination of data at high temporal resolution (10 ms) during the period March 2013 through October 2014 supports strongly the view that energetic electrons are accelerated in the near-tail region of Mercury's magnetosphere and are subsequently "injected" onto closed magnetic field lines on the planetary nightside. The electrons populate the plasma sheet and drift rapidly eastward toward the dawn and prenoon sectors, at times executing multiple complete drifts around the planet to form "quasi-trapped" populations.

Spiroiminodihydantoin lesions derived from guanine oxidation: structures, energetics, and functional implications.

PubMed

Jia, Lei; Shafirovich, Vladimir; Shapiro, Robert; Geacintov, Nicholas E; Broyde, Suse

2005-04-26

Reactive oxygen species present in the cell generate DNA damage. One of the major oxidation products of guanine in DNA, 8-oxo-7,8-dihydroguanine, formed by loss of two electrons, is among the most extensively studied base lesions. The further removal of two electrons from this product can yield spiroiminodihydantoin (Sp) R and S stereoisomers. Both in vitro and in vivo experiments have shown that the Sp stereoisomers are highly mutagenic, causing G --> T and G --> C transversions. Hence, they are of interest as examples of endogenous DNA damage that may initiate cancer. To interpret the mutagenic properties of the Sp lesions, an understanding of their structural properties is needed. To elucidate these structural effects, we have carried out computational investigations at the level of the Sp-modified base and nucleoside. At the base level, quantum mechanical geometry optimization studies have revealed exact mirror image symmetry of the R and S stereoisomers, with a near-perpendicular geometry of the two rings. At the nucleoside level, an extensive survey of the potential energy surface by molecular mechanics calculations using AMBER has provided three-dimensional potential energy maps. These maps reveal that the range and flexibility of the glycosidic torsion angles are significantly more restricted in both stereoisomeric adducts than in unmodified 2'-deoxyguanosine. The structural and energetic results suggest that the unusual geometric, steric, and hydrogen bonding properties of these lesions underlie their mutagenicity. In addition, stereoisomer-specific differences indicate the possibility that their processing by cellular replication and repair enzymes may be differentially affected by their absolute configuration.

Density functional studies of the defect-induced electronic structure modifications in bilayer boronitrene

NASA Astrophysics Data System (ADS)

Ukpong, A. M.; Chetty, N.

2012-05-01

The van der Waals interaction-corrected density functional theory is used in this study to investigate the formation, energetic stability, and inter-layer cohesion in bilayer hexagonal boronitrene. The effect of inter-layer separation on the electronic structure is systematically investigated. The formation and energetic stability of intrinsic defects are also investigated at the equilibrium inter-layer separation. It is found that nonstoichiometric defects, and their complexes, that induce excess nitrogen or excess boron, in each case, are relatively more stable in the atmosphere that corresponds to the excess atomic species. The modifications of the electronic structure due to formation of complexes are also investigated. It is shown that van der Waals density functional theory gives an improved description of the cohesive properties but not the electronic structure in bilayer boronitrene compared to other functionals. We identify energetically favourable topological defects that retain the energy gap in the electronic structure, and discuss their implications for band gap engineering in low-n layer boronitrene insulators. The relative strengths and weaknesses of the functionals in predicting the properties of bilayer boronitrene are also discussed.

Kinetic theory of passing energetic ion transport in presence of the resonant interactions with a rotating magnetic island

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cao, Jinjia; Gong, Xueyu; Xiang, Dong

The enhanced transport of passing energetic ions (PEIs) in presence of the resonant interactions with a rotating magnetic island is investigated within the drift kinetic framework. When the island rotation plays a role in the resonant interaction, we find that the velocities of PEIs satisfy a constraint relation of resonant flux surface in phase space. The resonant flux surfaces overlap with the magnetic flux surfaces in real space. A new transport channel responsible for the PEIs moving across the magnetic flux surfaces, i.e., continuously overlapping, is found. Two kinds of radial motions can be induced by the surface overlapping: onemore » arises from the coupling between the resonance and the collision with the background plasma and the other from not completely overlapping of the two surfaces. The two radial motions and the symmetry-breaking induced radial motion constitute the total radial motion. When the pitch-angle scattering rate is very weak, the surface-shear induced transport is dominant. Only a small increase in the collision rate can significantly influence the total transport.« less

Energetics of surface confined ferritin during iron loading.

PubMed

Federici, Stefania; Padovani, Francesco; Poli, Maura; Rodriguez, Fernando Carmona; Arosio, Paolo; Depero, Laura E; Bergese, Paolo

2016-09-01

We report on the first quantitative picture on how iron loading inside ferritin molecules occurs when they are self-assembled onto solid surfaces. Recombinant human ferritin H-chain with ferroxidase activity was adsorbed onto microcantilever beams to form a stable close-packed thin film. The obtained nanomechanical system was used to track in real time the energetics of inter-ferritin surface interactions during incubation with Fe(II) for iron loading. We observed that iron loading is accompanied by increasing attractive in-plane inter-ferritin interactions able to perform a maximum surface work of 6.0±1.5mJ/m(2), corresponding to a surface energy variation per ferritin of about 40kbT. Unique to this protein surface transformation, part of the surface work is exerted by the attractive electrostatic forces arising among the new born nanosized iron cores inside the ferritin shells. The remaining work comes from subtle action of steric, bridging and depletion forces. These findings are of fundamental interest and add important information for the rational development of ferritin nanotechnology. Copyright © 2016 Elsevier B.V. All rights reserved.

Molecular statics simulation of CdTe grain boundary structures and energetics using a bond-order potential

NASA Astrophysics Data System (ADS)

Stechmann, Guillaume; Zaefferer, Stefan; Raabe, Dierk

2018-06-01

The structure and energetics of coincidence site lattice grain boundaries (GB) in CdTe are investigated by mean of molecular statics simulations, using the Cd–Zn–Te bond-order potential (second iteration) developed by Ward et al (2012 Phys. Rev. B 86 245203; 2013 J. Mol. Modelling 19 5469–77). The effects of misorientation (Σ value) and interface plane are treated separately, complying with the critical need for full five-parameter characterization of GB. In addition, stoichiometric shifts, occurring between the inner interfaces and their adjacent atomic layers, are also predicted, revealing the energetic preference of Te-rich boundaries, opening opportunities for crystallography-based intrinsic interface doping. Our results also suggest that the intuitive assumption that Σ3 boundaries with low-indexed planes are more energetically favorable is often unfounded, except for coherent twins developing on {111} boundary planes. Therefore, Σ5, 7 or 9 boundaries, with lower interface energy than that of twin boundaries lying on different facets, are frequently encountered.

Energetic neutral atoms from a trans-Europa gas torus at Jupiter.

PubMed

Mauk, B H; Mitchell, D G; Krimigis, S M; Roelof, E C; Paranicas, C P

2003-02-27

The space environments--or magnetospheres--of magnetized planets emit copious quantities of energetic neutral atoms (ENAs) at energies between tens of electron volts to hundreds of kiloelectron volts (keV). These energetic atoms result from charge exchange between magnetically trapped energetic ions and cold neutral atoms, and they carry significant amounts of energy and mass from the magnetospheres. Imaging their distribution allows us to investigate the structure of planetary magnetospheres. Here we report the analysis of 50-80 keV ENA images of Jupiter's magnetosphere, where two distinct emission regions dominate: the upper atmosphere of Jupiter itself, and a torus of emission residing just outside the orbit of Jupiter's satellite Europa. The trans-Europa component shows that, unexpectedly, Europa generates a gas cloud comparable in gas content to that associated with the volcanic moon Io. The quantity of gas found indicates that Europa has a much greater impact than hitherto believed on the structure of, and the energy flow within, Jupiter's magnetosphere.

An insight into the origin of room-temperature ferromagnetism in SnO2 and Mn-doped SnO2 quantum dots: an experimental and DFT approach.

PubMed

Manikandan, Dhamodaran; Boukhvalov, D W; Amirthapandian, S; Zhidkov, I S; Kukharenko, A I; Cholakh, S O; Kurmaev, E Z; Murugan, Ramaswamy

2018-02-28

SnO 2 and Mn-doped SnO 2 single-phase tetragonal crystal structure quantum dots (QDs) of uniform size with control over dopant composition and microstructure were synthesized using the high pressure microwave synthesis technique. On a broader vision, we systematically investigated the influence of dilute Mn ions in SnO 2 under the strong quantum confinement regime through various experimental techniques and density functional theoretical (DFT) calculations to disclose the physical mechanism governing the observed ferromagnetism. DFT calculations revealed that the formation of the stable (001) surface was much more energetically favorable than that of the (100) surface, and the formation energy of the oxygen vacancies in the stable (001) surface was comparatively higher in the undoped SnO 2 QDs. X-ray photoelectron spectroscopy (XPS) and first-principles modeling of doped QDs revealed that the lower doping concentration of Mn favored the formation of MnO-like (Mn 2+ ) structures in defect-rich areas and the higher doping concentration of Mn led to the formation of multiple configurations of Mn (Mn 2+ and Mn 3+ ) in the stable surfaces of SnO 2 QDs. Electronic absorption spectra indicated the characteristic spin allowed ligand field transitions of Mn 2+ and Mn 3+ and the red shift in the band gap. DFT calculations clearly indicated that only the substitutional dopant antiferromagnetic configurations were more energetically favorable. The gradual increase of magnetization at a low level of Mn-doping could be explained by the prevalence of antiferromagnetic manganese-vacancy pairs. Higher concentrations of Mn led to the appearance of ferromagnetic interactions between manganese and oxygen vacancies. The increase in the concentration of metallic dopants caused not just an increase in the total magnetic moment of the system but also changed the magnetic interactions between the magnetic moments on the metal ions and oxygen. The present study provides new insight into the fundamental understanding of the origin of ferromagnetism in transition metal-doped QDs.

Hydration water and bulk water in proteins have distinct properties in radial distributions calculated from 105 atomic resolution crystal structures.

PubMed

Chen, Xianfeng; Weber, Irene; Harrison, Robert W

2008-09-25

Water plays a critical role in the structure and function of proteins, although the experimental properties of water around protein structures are not well understood. The water can be classified by the separation from the protein surface into bulk water and hydration water. Hydration water interacts closely with the protein and contributes to protein folding, stability, and dynamics, as well as interacting with the bulk water. Water potential functions are often parametrized to fit bulk water properties because of the limited experimental data for hydration water. Therefore, the structural and energetic properties of the hydration water were assessed for 105 atomic resolution (

Infragravity waves on fringing reefs in the tropical Pacific: Dynamic setup

NASA Astrophysics Data System (ADS)

Becker, J. M.; Merrifield, M. A.; Yoon, H.

2016-05-01

Cross-shore pressure and current observations from four fringing reefs of lengths ranging from 135 to 420 m reveal energetic low-frequency (˜0.001-0.05 Hz) motions. The spatial structure and temporal amplitudes of an empirical orthogonal function analysis of the pressure measurements suggest the dominant low-frequency variability is modal. Incoming and outgoing linear flux estimates also support partially standing modes on the reef flat during energetic events. A cross-covariance analysis suggests that breakpoint forcing excites these partially standing modes, similar to previous findings at other steep reefs. The dynamics of Symonds et al. (1982) with damping are applied to a step reef, with forcing obtained by extending a point break model of Vetter et al. (2010) for breaking wave setup to the low-frequency band using the shoaled envelope of the incident free surface elevation. A one parameter, linear analytical model for the reef flat free surface elevation is presented, which describes between 75% and 97% of the variance of the observed low-frequency shoreline significant wave height for all reefs considered over a range of conditions. The linear model contains a single dimensionless parameter that is the ratio of the inertial to dissipative time scales, and the observations from this study exhibit more low-frequency variability when the dissipative time scale is greater than the inertial time scale for the steep reefs considered.

Molecular dynamics simulations of void defects in the energetic material HMX.

PubMed

Duan, Xiao Hui; Li, Wen Peng; Pei, Chong Hua; Zhou, Xiao Qing

2013-09-01

A molecular dynamics (MD) simulation was carried out to characterize the dynamic evolution of void defects in crystalline octahydro-1, 3, 5, 7-tetranitro-1, 3, 5, 7-tetrazocine (HMX). Different models were constructed with the same concentration of vacancies (10 %) to discuss the size effects of void. Energetic ground state properties were determined by annealing simulations. The void formation energy per molecule removed was found to be 55-63 kcal/mol(-1), and the average binding energy per molecule was between 32 and 34 kcal/mol(-1) according to the change in void size. Voids with larger size had lower formation energy. Local binding energies for molecules directly on the void surface decreased greatly compared to those in defect-free lattice, and then gradually increased until the distance away from the void surface was around 10 Å. Analysis of 1 ns MD simulations revealed that the larger the void size, the easier is void collapse. Mean square displacements (MSDs) showed that HMX molecules that had collapsed into void present liquid structure characteristics. Four unique low-energy conformers were found for HMX molecules in void: two whose conformational geometries corresponded closely to those found in HMX polymorphs and two, additional, lower energy conformers that were not seen in the crystalline phases. The ratio of different conformers changed with the simulated temperature, in that the ratio of α conformer increased with the increase in temperature.

The fate of meteoric metals in ice particles: Effects of sublimation and energetic particle bombardment

NASA Astrophysics Data System (ADS)

Mangan, T. P.; Frankland, V. L.; Murray, B. J.; Plane, J. M. C.

2017-08-01

The uptake and potential reactivity of metal atoms on water ice can be an important process in planetary atmospheres and on icy bodies in the interplanetary and interstellar medium. For instance, metal atom uptake affects the gas-phase chemistry of the Earth's mesosphere, and has been proposed to influence the agglomeration of matter into planets in protoplanetary disks. In this study the fate of Mg and K atoms incorporated into water-ice films, prepared under ultra-high vacuum conditions at temperatures of 110-140 K, was investigated. Temperature-programmed desorption experiments reveal that Mg- and K-containing species do not co-desorb when the ice sublimates, demonstrating that uptake on ice particles causes irreversible removal of the metals from the gas phase. This implies that uptake on ice particles in terrestrial polar mesospheric clouds accelerates the formation of large meteoric smoke particles (≥1 nm radius above 80 km) following sublimation of the ice. Energetic sputtering of metal-dosed ice layers by 500 eV Ar+ and Kr+ ions shows that whereas K reacts on (or within) the ice surface to form KOH, adsorbed Mg atoms are chemically inert. These experimental results are consistent with electronic structure calculations of the metals bound to an ice surface, where theoretical adsorption energies on ice are calculated to be -68 kJ mol-1 for K, -91 kJ mol-1 for Mg, and -306 kJ mol-1 for Fe. K can also insert into a surface H2O to produce KOH and a dangling H atom, in a reaction that is slightly exothermic.

Precipitation and Release of Solar Energetic Particles from the Solar Coronal Magnetic Field

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Ming; Zhao, Lulu, E-mail: mzhang@fit.edu

Most solar energetic particles (SEPs) are produced in the corona. They propagate through complex coronal magnetic fields subject to scattering and diffusion across the averaged field lines by turbulence. We examine the behaviors of particle transport using a stochastic 3D focused transport simulation in a potential field source surface model of coronal magnetic field. The model is applied to an SEP event on 2010 February 7. We study three scenarios of particle injection at (i) the compact solar flare site, (ii) the coronal mass ejection (CME) shock, and (iii) the EUV wave near the surface. The majority of particles injectedmore » on open field lines are able to escape the corona. We found that none of our models can explain the observations of wide longitudinal SEP spread without perpendicular diffusion. If the perpendicular diffusion is about 10% of what is derived from the random walk of field lines at the rate of supergranular diffusion, particles injected at the compact solar flare site can spread to a wide range of longitude and latitude, very similar to the behavior of particles injected at a large CME shock. Stronger pitch-angle scattering results in a little more lateral spread by holding the particles in the corona for longer periods of time. Some injected particles eventually end up precipitating onto the solar surface. Even with a very small perpendicular diffusion, the pattern of the particle precipitation can be quite complicated depending on the detailed small-scale coronal magnetic field structures, which could be seen with future sensitive gamma-ray telescopes.« less

Molecular-dynamics simulations of energetic C{sub 60} impacts on (2x1)-(100) silicon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Xiaoyuan; Albe, Karsten; Averback, Robert S.

2000-07-01

Single impacts of energetic C{sub 60} clusters on (2x1)-(100) silicon substrates are studied by molecular-dynamics simulations. The role of impact energies and internal cluster energy are investigated in detail. Six different energy regimes can be identified at the end of the ballistic phase: At thermal energies below 20 eV the fullerene cages undergo elastic deformation, while impinging on the surface, and are mostly chemisorpted on top of the (2x1)-dimer rows. Between 20 and 100 eV the cage structure is preserved after the collision, but the cluster comes to rest within a few monolayers of the silicon surface. At energies ofmore » 100-500 eV the cluster partially decomposes and small coherent carbon caps are embedded in the surface. At higher energies up to 1.5 keV complete decomposition of the fullerene cluster occurs and an amorphous zone is formed in the subsurface area. At energies greater than approximately 1.5 keV craters form and above 6 keV sputtering becomes significant. In all cases the substrate temperature is of minor influence on the final result, but the projectile temperature is important for impacts at lower energies (<1.5 keV). For high energy impacts the ballistics resemble that of single atom impacts. Nearly 1:1 stoichiometry is obtained for impact energies around 1 keV. These results reveal an interesting possibility for controlled implantation of C in Si at high local concentrations, which might allow the formation of silicon carbide. (c) 2000 American Institute of Physics.« less

Precipitation and Release of Solar Energetic Particles from the Solar Coronal Magnetic Field

NASA Astrophysics Data System (ADS)

Zhang, Ming; Zhao, Lulu

2017-09-01

Most solar energetic particles (SEPs) are produced in the corona. They propagate through complex coronal magnetic fields subject to scattering and diffusion across the averaged field lines by turbulence. We examine the behaviors of particle transport using a stochastic 3D focused transport simulation in a potential field source surface model of coronal magnetic field. The model is applied to an SEP event on 2010 February 7. We study three scenarios of particle injection at (I) the compact solar flare site, (II) the coronal mass ejection (CME) shock, and (III) the EUV wave near the surface. The majority of particles injected on open field lines are able to escape the corona. We found that none of our models can explain the observations of wide longitudinal SEP spread without perpendicular diffusion. If the perpendicular diffusion is about 10% of what is derived from the random walk of field lines at the rate of supergranular diffusion, particles injected at the compact solar flare site can spread to a wide range of longitude and latitude, very similar to the behavior of particles injected at a large CME shock. Stronger pitch-angle scattering results in a little more lateral spread by holding the particles in the corona for longer periods of time. Some injected particles eventually end up precipitating onto the solar surface. Even with a very small perpendicular diffusion, the pattern of the particle precipitation can be quite complicated depending on the detailed small-scale coronal magnetic field structures, which could be seen with future sensitive gamma-ray telescopes.

Theoretical Studies of Alfven Waves and Energetic Particle Physics in Fusion Plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Liu

This report summarizes major theoretical findings in the linear as well as nonlinear physics of Alfvén waves and energetic particles in magnetically confined fusion plasmas. On the linear physics, a variational formulation, based on the separation of singular and regular spatial scales, for drift-Alfvén instabilities excited by energetic particles is established. This variational formulation is then applied to derive the general fishbone-like dispersion relations corresponding to the various Alfvén eigenmodes and energetic-particle modes. It is further employed to explore in depth the low-frequency Alfvén eigenmodes and demonstrate the non-perturbative nature of the energetic particles. On the nonlinear physics, new novelmore » findings are obtained on both the nonlinear wave-wave interactions and nonlinear wave-energetic particle interactions. It is demonstrated that both the energetic particles and the fine radial mode structures could qualitatively affect the nonlinear evolution of Alfvén eigenmodes. Meanwhile, a theoretical approach based on the Dyson equation is developed to treat self-consistently the nonlinear interactions between Alfvén waves and energetic particles, and is then applied to explain simulation results of energetic-particle modes. Relevant list of journal publications on the above findings is also included.« less

Free energetics of carbon nanotube association in aqueous inorganic NaI salt solutions: Temperature effects using all-atom molecular dynamics simulations.

PubMed

Ou, Shu-Ching; Cui, Di; Wezowicz, Matthew; Taufer, Michela; Patel, Sandeep

2015-06-15

In this study, we examine the temperature dependence of free energetics of nanotube association using graphical processing unit-enabled all-atom molecular dynamics simulations (FEN ZI) with two (10,10) single-walled carbon nanotubes in 3 m NaI aqueous salt solution. Results suggest that the free energy, enthalpy and entropy changes for the association process are all reduced at the high temperature, in agreement with previous investigations using other hydrophobes. Via the decomposition of free energy into individual components, we found that solvent contribution (including water, anion, and cation contributions) is correlated with the spatial distribution of the corresponding species and is influenced distinctly by the temperature. We studied the spatial distribution and the structure of the solvent in different regions: intertube, intratube and the bulk solvent. By calculating the fluctuation of coarse-grained tube-solvent surfaces, we found that tube-water interfacial fluctuation exhibits the strongest temperature dependence. By taking ions to be a solvent-like medium in the absence of water, tube-anion interfacial fluctuation shows similar but weaker dependence on temperature, while tube-cation interfacial fluctuation shows no dependence in general. These characteristics are discussed via the malleability of their corresponding solvation shells relative to the nanotube surface. Hydrogen bonding profiles and tetrahedrality of water arrangement are also computed to compare the structure of solvent in the solvent bulk and intertube region. The hydrophobic confinement induces a relatively lower concentration environment in the intertube region, therefore causing different intertube solvent structures which depend on the tube separation. This study is relevant in the continuing discourse on hydrophobic interactions (as they impact generally a broad class of phenomena in biology, biochemistry, and materials science and soft condensed matter research), and interpretations of hydrophobicity in terms of alternative but parallel signatures such as interfacial fluctuations, dewetting transitions, and enhanced fluctuation probabilities at interfaces. © 2015 Wiley Periodicals, Inc.

Mapping the Excited State Potential Energy Surface of a Retinal Chromophore Model with Multireference and Equation-of-Motion Coupled-Cluster Methods.

PubMed

Gozem, Samer; Melaccio, Federico; Lindh, Roland; Krylov, Anna I; Granovsky, Alexander A; Angeli, Celestino; Olivucci, Massimo

2013-10-08

The photoisomerization of the retinal chromophore of visual pigments proceeds along a complex reaction coordinate on a multidimensional surface that comprises a hydrogen-out-of-plane (HOOP) coordinate, a bond length alternation (BLA) coordinate, a single bond torsion and, finally, the reactive double bond torsion. These degrees of freedom are coupled with changes in the electronic structure of the chromophore and, therefore, the computational investigation of the photochemistry of such systems requires the use of a methodology capable of describing electronic structure changes along all those coordinates. Here, we employ the penta-2,4-dieniminium (PSB3) cation as a minimal model of the retinal chromophore of visual pigments and compare its excited state isomerization paths at the CASSCF and CASPT2 levels of theory. These paths connect the cis isomer and the trans isomer of PSB3 with two structurally and energetically distinct conical intersections (CIs) that belong to the same intersection space. MRCISD+Q energy profiles along these paths provide benchmark values against which other ab initio methods are validated. Accordingly, we compare the energy profiles of MRPT2 methods (CASPT2, QD-NEVPT2, and XMCQDPT2) and EOM-SF-CC methods (EOM-SF-CCSD and EOM-SF-CCSD(dT)) to the MRCISD+Q reference profiles. We find that the paths produced with CASSCF and CASPT2 are topologically and energetically different, partially due to the existence of a "locally excited" region on the CASPT2 excited state near the Franck-Condon point that is absent in CASSCF and that involves a single bond, rather than double bond, torsion. We also find that MRPT2 methods as well as EOM-SF-CCSD(dT) are capable of quantitatively describing the processes involved in the photoisomerization of systems like PSB3.

Sulfur Adsorption on the Goethite (110) Surface

NASA Astrophysics Data System (ADS)

Simonetti, S.; Damiani, D.; Brizuela, G.; Juan, A.

The electronic structure of S adsorption on goethite (110) surface has been studied by ASED-MO cluster calculations. For S location, the most exposed surface atoms of goethite surface were selected. The calculations show that the surface offers several places for S adsorption. The most energetically stable system corresponds to S location above H atom. We studied in detail the configurations that correspond to the higher OP values. For these configurations, the H-S and Fe-S computed distances are 2.1 and 3.7 Å, respectively. The H-S and Fe-S are mainly bonding interaction with OP values of 0.156 and 0.034, respectively. The Fe-S interaction mainly involves Fe 3dx2-y2 atomic orbitals with lesser participation of Fe 4py and Fe 3dyz atomic orbitals. The O-S interaction shows the same bonding and antibonding contributions giving a small OP value. The O-S interaction involves O 2p orbitals. There is an electron transfer to the Fe atom from the S atom. On the other hand, there is an electron transfer to S atom from the H and O atoms, respectively.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mourey, Odile; Petit-Etienne, Camille; Cunge, Gilles, E-mail: gilles.cunge@cea.fr

Pulsed plasmas are promising candidates to go beyond limitations of continuous waves' plasma. However, their interaction with surfaces remains poorly understood. The authors investigated the silicon etching mechanism in inductively coupled plasma (ICP) Cl{sub 2} operated either in an ICP-pulsed mode or in a bias-pulsed mode (in which only the bias power is pulsed). The authors observed systematically the development of an important surface roughness at a low duty cycle. By using plasma diagnostics, they show that the roughness is correlated to an anomalously large (Cl atoms flux)/(energetic ion flux) ratio in the pulsed mode. The rational is that themore » Cl atom flux is not modulated on the timescale of the plasma pulses although the ion fluxes and energy are modulated. As a result, a very strong surface chlorination occurs during the OFF period when the surface is not exposed to energetic ions. Therefore, each energetic ion in the ON period will bombard a heavily chlorinated silicon surface, leading to anomalously high etching yield. In the ICP pulsed mode (in which the ion energy is high), the authors report yields as high as 40, which mean that each individual ion impacts will generate a “crater” of about 2 nm depth at the surface. Since the ion flux is very small in the pulsed ICP mode, this process is stochastic and is responsible for the roughness initiation. The roughness expansion can then be attributed partly to the ion channeling effect and is probably enhanced by the formation of a SiClx reactive layer with nonhomogeneous thickness over the topography of the surface. This phenomenon could be a serious limitation of pulsed plasma processes.« less

Submesoscale dispersion in the vicinity of the Deepwater Horizon spill.

PubMed

Poje, Andrew C; Ozgökmen, Tamay M; Lipphardt, Bruce L; Haus, Brian K; Ryan, Edward H; Haza, Angelique C; Jacobs, Gregg A; Reniers, A J H M; Olascoaga, Maria Josefina; Novelli, Guillaume; Griffa, Annalisa; Beron-Vera, Francisco J; Chen, Shuyi S; Coelho, Emanuel; Hogan, Patrick J; Kirwan, Albert D; Huntley, Helga S; Mariano, Arthur J

2014-09-02

Reliable forecasts for the dispersion of oceanic contamination are important for coastal ecosystems, society, and the economy as evidenced by the Deepwater Horizon oil spill in the Gulf of Mexico in 2010 and the Fukushima nuclear plant incident in the Pacific Ocean in 2011. Accurate prediction of pollutant pathways and concentrations at the ocean surface requires understanding ocean dynamics over a broad range of spatial scales. Fundamental questions concerning the structure of the velocity field at the submesoscales (100 m to tens of kilometers, hours to days) remain unresolved due to a lack of synoptic measurements at these scales. Using high-frequency position data provided by the near-simultaneous release of hundreds of accurately tracked surface drifters, we study the structure of submesoscale surface velocity fluctuations in the Northern Gulf of Mexico. Observed two-point statistics confirm the accuracy of classic turbulence scaling laws at 200-m to 50-km scales and clearly indicate that dispersion at the submesoscales is local, driven predominantly by energetic submesoscale fluctuations. The results demonstrate the feasibility and utility of deploying large clusters of drifting instruments to provide synoptic observations of spatial variability of the ocean surface velocity field. Our findings allow quantification of the submesoscale-driven dispersion missing in current operational circulation models and satellite altimeter-derived velocity fields.

Submesoscale dispersion in the vicinity of the Deepwater Horizon spill

PubMed Central

Poje, Andrew C.; Özgökmen, Tamay M.; Lipphardt, Bruce L.; Haus, Brian K.; Ryan, Edward H.; Haza, Angelique C.; Jacobs, Gregg A.; Reniers, A. J. H. M.; Olascoaga, Maria Josefina; Novelli, Guillaume; Griffa, Annalisa; Beron-Vera, Francisco J.; Chen, Shuyi S.; Coelho, Emanuel; Hogan, Patrick J.; Kirwan, Albert D.; Huntley, Helga S.; Mariano, Arthur J.

2014-01-01

Reliable forecasts for the dispersion of oceanic contamination are important for coastal ecosystems, society, and the economy as evidenced by the Deepwater Horizon oil spill in the Gulf of Mexico in 2010 and the Fukushima nuclear plant incident in the Pacific Ocean in 2011. Accurate prediction of pollutant pathways and concentrations at the ocean surface requires understanding ocean dynamics over a broad range of spatial scales. Fundamental questions concerning the structure of the velocity field at the submesoscales (100 m to tens of kilometers, hours to days) remain unresolved due to a lack of synoptic measurements at these scales. Using high-frequency position data provided by the near-simultaneous release of hundreds of accurately tracked surface drifters, we study the structure of submesoscale surface velocity fluctuations in the Northern Gulf of Mexico. Observed two-point statistics confirm the accuracy of classic turbulence scaling laws at 200-m to 50-km scales and clearly indicate that dispersion at the submesoscales is local, driven predominantly by energetic submesoscale fluctuations. The results demonstrate the feasibility and utility of deploying large clusters of drifting instruments to provide synoptic observations of spatial variability of the ocean surface velocity field. Our findings allow quantification of the submesoscale-driven dispersion missing in current operational circulation models and satellite altimeter-derived velocity fields. PMID:25136097

Observing Planets and Small Bodies in Sputtered High Energy Atom (SHEA) Fluxes

NASA Technical Reports Server (NTRS)

Milillo, A.; Orsini, S.; Hsieh, K. C.; Baragiola, R.; Fama, M.; Johnson, R.; Mura, A.; Plainaki, Ch.; Sarantos, M.; Cassidy, T. A.;

Radiation Environment of Phobos

NASA Astrophysics Data System (ADS)

Cooper, John F.; Clark, John H.; Sturner, Steven J.; Stubbs, Timothy; Wang, Yongli; Glenar, David A.; Schwadron, Nathan A.; Joyce, Colin J.; Spence, Harlan E.; Farrell, William M.

2017-10-01

The innermost Martian moon Phobos is a potential way station for the human exploration of Mars and the solar system beyond the orbit of Mars. It has a similar radiation environment to that at 1 AU for hot plasma and more energetic particles from solar, heliospheric and galactic sources. In the past two decades there have been many spacecraft measurements at 1 AU, and occasionally in the Mars orbital region around the Sun, that can be used to define a reference model for the time-averaged and time-variable radiation environments at Mars and Phobos. Yearly to hourly variance comes from the eleven-year solar activity cycle and its impact on solar energetic, heliospheric, and solar-modulated galactic cosmic ray particles. We report progress on compilation of the reference model from U.S. and international spacecraft data sources of the NASA Space Physics Data Facility and the Virtual Energetic Particle Observatory (VEPO), and from tissue-equivalent dosage rate measurements by the CRaTER instrument on the Lunar Reconnaissance Observer spacecraft now in lunar orbit. Similar dosage rate data are also available from the Mars surface via the NASA Planetary Data System archive from the Radiation Assessment Detector (RAD) instrument aboard the Mars Science Laboratory (MSL) Curiosity rover. The sub-Mars surface hemisphere of Phobos is slightly blocked from energetic particle irradiation by the body of Mars but there is a greater global variance of interplanetary radiation exposure as we have calculated from the known topography of this irregularly shaped moon. Phobos receives a relatively small flux of secondary radiation from galactic cosmic ray interactions with the Mars surface and atmosphere, and at plasma energies from pickup ions escaping out of the Mars atmosphere. The greater secondary radiation source is from cosmic ray interactions with the moon surface, which we have simulated with the GEANT radiation transport code for various cases of the surface regolith composition. We evaluate the efficiency of these materials relative to water for radiation shielding of human explorers on Phobos. The low-energy plasma environment is also considered for impact on surface charging.

A Novel Intrinsic Interface State Controlled by Atomic Stacking Sequence at Interfaces of SiC/SiO2.

PubMed

Matsushita, Yu-Ichiro; Oshiyama, Atsushi

2017-10-11

On the basis of ab initio total-energy electronic-structure calculations, we find that electron states localized at the SiC/SiO 2 interface emerge in the energy region between 0.3 eV below and 1.2 eV above the bulk conduction-band minimum (CBM) of SiC, being sensitive to the sequence of atomic bilayers in SiC near the interface. These new interface states unrecognized in the past are due to the peculiar characteristics of the CBM states that are distributed along the crystallographic channels. We also find that the electron doping modifies the energetics among the different stacking structures. Implication for performance of electron devices fabricated on different SiC surfaces is discussed.

Compilation, design tests: Energetic particles Satellite S-3 including design tests for S-3A, S-3B and S-3C

NASA Technical Reports Server (NTRS)

Ledoux, F. N.

1973-01-01

A compilation of engineering design tests which were conducted in support of the Energetic Particle Satellite S-3, S-3A, and S-3b programs. The purpose for conducting the tests was to determine the adequacy and reliability of the Energetic Particles Series of satellites designs. The various tests consisted of: (1) moments of inertia, (2) functional reliability, (3) component and structural integrity, (4) initiators and explosives tests, and (5) acceptance tests.

Nature of adsorption on TiC(111) investigated with density-functional calculations

NASA Astrophysics Data System (ADS)

Ruberto, Carlo; Lundqvist, Bengt I.

2007-06-01

Extensive density-functional calculations are performed for chemisorption of atoms in the three first periods (H, B, C, N, O, F, Al, Si, P, S, and Cl) on the polar TiC(111) surface. Calculations are also performed for O on TiC(001), for full O(1×1) monolayer on TiC(111), as well as for bulk TiC and for the clean TiC(111) and (001) surfaces. Detailed results concerning atomic structures, energetics, and electronic structures are presented. For the bulk and the clean surfaces, previous results are confirmed. In addition, detailed results are given on the presence of C-C bonds in the bulk and at the surface, as well as on the presence of a Ti-based surface resonance (TiSR) at the Fermi level and of C-based surface resonances (CSR’s) in the lower part of the surface upper valence band. For the adsorption, adsorption energies Eads and relaxed geometries are presented, showing great variations characterized by pyramid-shaped Eads trends within each period. An extraordinarily strong chemisorption is found for the O atom, 8.8eV /adatom. On the basis of the calculated electronic structures, a concerted-coupling model for the chemisorption is proposed, in which two different types of adatom-substrate interactions work together to provide the obtained strong chemisorption: (i) adatom-TiSR and (ii) adatom-CSR’s. This model is used to successfully describe the essential features of the calculated Eads trends. The fundamental nature of this model, based on the Newns-Anderson model, should make it apt for general application to transition-metal carbides and nitrides and for predictive purposes in technological applications, such as cutting-tool multilayer coatings and MAX phases.

Energetic Particle Measurements on Mars and in Lunar Orbit

NASA Astrophysics Data System (ADS)

Zeitlin, C. J.; Hassler, D.; Schwadron, N.; Spence, H. E.; Wimmer-Schweingruber, R. F.; Appel, J. K.; Boehm, E.; Boettcher, S. S.; Brinza, D. E.; Burmeister, S.; Ehresmann, B.; Guo, J.; Kohler, J.; Lohf, H.; Martin-Garcia, C.; Posner, A.; Rafkin, S. C.; weigle, G., II; Martín-Torres, J.; Zorzano, M. P.

2014-12-01

The Radiation Assessment Detector (RAD) aboard the Curiosity rover has been making measurements of energetic particles on the surface of Mars since the rover landed in August 2012. RAD also acquired data for most of the cruise to Mars, from Dec. 2011 through July 2012. In both cruise and on the surface, RAD is under considerable shielding, averaging 22 g cm-2 of CO2 during the surface mission, and ~ 16 g cm-2 during cruise. The Cosmic Ray Telescope for the Effects of Radiation (CRaTER) aboard the LRO spacecraft in lunar orbit has been making measurements since mid-2009. CRaTER contains three sets of detectors, of which one is unshielded, one is under 6 g cm-2 of tissue-equivalent plastic (TEP) shielding, and one is under 9 g cm-2 of TEP. Taken together, the two experiments provide a wealth of data concerning the effects of shielding on Galactic Cosmic Rays (GCRs) and Solar Energetic Particles (SEPs). Comparison of data from the two instruments is complicated by their different locations in the heliosphere, which at most times causes them to be magnetically connected to different regions on the Sun. Variability of the atmospheric shielding above RAD, which is both diurnal and seasonal, also influences the comparison. During solar quiet time, when the energetic particle flux is due to GCRs, many similarities - and some small but significant differences - are seen in detailed time series data. In contrast, during SEP events, both the shielding and location disparities cause large differences in the measured particle fluxes.

End-boundary sheath potential, electron and ion energy distribution in the low-pressure non-ambipolar electron plasma

NASA Astrophysics Data System (ADS)

Chen, Lee; Chen, Zhiying; Funk, Merritt

2013-12-01

The end-boundary floating-surface sheath potential, electron and ion energy distribution functions (EEDf, IEDf) in the low-pressure non-ambipolar electron plasma (NEP) are investigated. The NEP is heated by an electron beam extracted from an inductively coupled electron-source plasma (ICP) through a dielectric injector by an accelerator located inside the NEP. This plasma's EEDf has a Maxwellian bulk followed by a broad energy continuum connecting to the most energetic group with energies around the beam energy. The NEP pressure is 1-3 mTorr of N2 and the ICP pressure is 5-15 mTorr of Ar. The accelerator is biased positively from 80 to 600 V and the ICP power range is 200-300 W. The NEP EEDf and IEDf are determined using a retarding field energy analyser. The EEDf and IEDf are measured at various NEP pressures, ICP pressures and powers as a function of accelerator voltage. The accelerator current and sheath potential are also measured. The IEDf reveals mono-energetic ions with adjustable energy and it is proportionally controlled by the sheath potential. The NEP end-boundary floating surface is bombarded by a mono-energetic, space-charge-neutral plasma beam. When the injected energetic electron beam is adequately damped by the NEP, the sheath potential is linearly controlled at almost a 1 : 1 ratio by the accelerator voltage. If the NEP parameters cannot damp the electron beam sufficiently, leaving an excess amount of electron-beam power deposited on the floating surface, the sheath potential will collapse and become unresponsive to the accelerator voltage.

Structure, Energetics, and Dynamics of Screw Dislocations in Even n-Alkane Crystals.

PubMed

Olson, Isabel A; Shtukenberg, Alexander G; Hakobyan, Gagik; Rohl, Andrew L; Raiteri, Paolo; Ward, Michael D; Kahr, Bart

2016-08-18

Spiral hillocks on n-alkane crystal surfaces were observed immediately after Frank recognized the importance of screw dislocations for crystal growth, yet their structures and energies in molecular crystals remain ill-defined. To illustrate the structural chemistry of screw dislocations that are responsible for plasticity in organic crystals and upon which the organic electronics and pharmaceutical industries depend, molecular dynamics was used to examine heterochiral dislocation pairs with Burgers vectors along [001] in n-hexane, n-octane, and n-decane crystals. The cores were anisotropic and elongated in the (110) slip plane, with significant local changes in molecular position, orientation, conformation, and energy. This detailed atomic level picture produced a distribution of strain consistent with linear elastic theory, giving confidence in the simulations. Dislocations with doubled Burgers vectors split into pairs with elementary displacements. These results suggest a pathway to understanding the mechanical properties and failure associated with elastic and plastic deformation in soft crystals.

Structure sensitivity in oxide catalysis: First-principles kinetic Monte Carlo simulations for CO oxidation at RuO 2(111)

DOE PAGES

Wang, Tongyu; Reuter, Karsten

2015-11-24

We present a density-functional theory based kinetic Monte Carlo study of CO oxidation at the (111) facet of RuO 2. We compare the detailed insight into elementary processes, steady-state surface coverages, and catalytic activity to equivalent published simulation data for the frequently studied RuO 2(110) facet. Qualitative differences are identified in virtually every aspect ranging from binding energetics over lateral interactions to the interplay of elementary processes at the different active sites. Nevertheless, particularly at technologically relevant elevated temperatures, near-ambient pressures and near-stoichiometric feeds both facets exhibit almost identical catalytic activity. As a result, these findings challenge the traditional definitionmore » of structure sensitivity based on macroscopically observable turnover frequencies and prompt scrutiny of the applicability of structure sensitivity classifications developed for metals to oxide catalysis.« less

Progress in the Modeling of NiAl-Based Alloys Using the BFS Method

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Noebe, Ronald D.; Ferrante, John; Garg, Anita

1997-01-01

The BFS method has been applied to the study of NiAl-based materials to assess the effect of alloying additions on structure. Ternary, quaternary and even pent-alloys based on Ni-rich NiAl with additions of Ti, Cr and Cu were studied. Two approaches were used, Monte Carlo simulations to determine ground state structures and analytical calculations of high symmetry configurations which give physical insight into preferred bonding. Site occupancy energetics for ternary and the more complicated case of quaternary additions were determined, and solubility limits and precipitate formation with corresponding information concerning structure and lattice parameter were also 'observed' computationally. The method was also applied to determine the composition of alloy surfaces and interfaces. Overall, the results demonstrate that the BFS method for alloys is a powerful tool for alloy design and with its simplicity and obvious advantages can be used to complement any experimental alloy design program.

Structure sensitivity in oxide catalysis: First-principles kinetic Monte Carlo simulations for CO oxidation at RuO{sub 2}(111)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Tongyu; Reuter, Karsten, E-mail: karsten.reuter@ch.tum.de; SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory and Stanford University, 443 Via Ortega, Stanford, California 94035-4300

2015-11-28

We present a density-functional theory based kinetic Monte Carlo study of CO oxidation at the (111) facet of RuO{sub 2}. We compare the detailed insight into elementary processes, steady-state surface coverages, and catalytic activity to equivalent published simulation data for the frequently studied RuO{sub 2}(110) facet. Qualitative differences are identified in virtually every aspect ranging from binding energetics over lateral interactions to the interplay of elementary processes at the different active sites. Nevertheless, particularly at technologically relevant elevated temperatures, near-ambient pressures and near-stoichiometric feeds both facets exhibit almost identical catalytic activity. These findings challenge the traditional definition of structure sensitivitymore » based on macroscopically observable turnover frequencies and prompt scrutiny of the applicability of structure sensitivity classifications developed for metals to oxide catalysis.« less

Study of the structural and thermal properties of plasma treated jute fibre

NASA Astrophysics Data System (ADS)

Sinha, E.; Rout, S. K.; Barhai, P. K.

2008-08-01

Jute fibres ( Corchorus olitorius), were treated with argon cold plasma for 5, 10 and 15 min. Structural macromolecular parameters of untreated and plasma treated fibres were investigated using small angle X-ray scattering (SAXS), and the crystallinity parameters of the same fibres were determined by using X-ray diffraction (XRD). Differential scanning calorimetry (DSC) was used to study the thermal behavior of the untreated and treated fibres. Comparison and analysis of the results confirmed the changes in the macromolecular structure after plasma treatment. This is due to the swelling of cellulosic particles constituting the fibres, caused by the bombardment of high energetic ions onto the fibre surface. Differential scanning calorimetry data demonstrated the thermal instability of the fibre after cold plasma treatment, as the thermal degradation temperature of hemicelluloses and cellulose was found lowered than that of raw fibre after plasma treatment.

Electro-Optic Surface Field Imaging System

DTIC Science & Technology

1989-06-01

ELECTRO - OPTIC SURFACE FIELD IMAGING SYSTEM L. E. Kingsley and W. R. Donaldson LABORATORY FOR LASER ENERGETICS University of Rochester 250 East...surface electric fields present during switch operation. The electro - optic , or Pockel’s effect, provides an extremely useful probe of surface electric...fields. Using the electro - optic effect, surface fields can be measured with an optical probe. This paper describes an electro - optic probe which is

Electron-induced origins of prebiotic building blocks of sugars: mechanism of self-reactions of a methanol anion dimer

NASA Astrophysics Data System (ADS)

Karsili, Tolga N. V.; Fennimore, Mark A.; Matsika, Spiridoula

The elementary synthesis of prebiotic molecules has attracted vast attention in recent years. Due to their rich surface chemistry and lack of suitable atmosphere, comets represent an important host for such synthesis, especially since they are routinely irradiated with short wavelength electromagnetic radiation and energetic cosmological electrons. Using high-level electronic structure theory, we present the details of the reactivity associated with the electron-impact induced prebiotic synthesis of ethylene glycol (a carbohydrate building block) from elementary methanol. The results suggest that the experimentally observed intermediates and fragment products can be viably formed by both neutral excited-state chemistry and by dissociative electron attachment - highlighting the importance of a theoretical mapping of the relevant potential energy surfaces that ultimately act as an important guide to the experimental results.

A charging model for three-axis stabilized spacecraft

NASA Technical Reports Server (NTRS)

Massaro, M. J.; Green, T.; Ling, D.

1977-01-01

A charging model was developed for geosynchronous, three-axis stabilized spacecraft when under the influence of a geomagnetic substorm. The differential charging potentials between the thermally coated or blanketed outer surfaces and metallic structure of a spacecraft were determined when the spacecraft was immersed in a dense plasma cloud of energetic particles. The spacecraft-to-environment interaction was determined by representing the charged particle environment by equivalent current source forcing functions and by representing the spacecraft by its electrically equivalent circuit with respect to the plasma charging phenomenon. The charging model included a sun/earth/spacecraft orbit model that simulated the sum illumination conditions of the spacecraft outer surfaces throughout the orbital flight on a diurnal as well as a seasonal basis. Transient and steady-state numerical results for a three-axis stabilized spacecraft are presented.

Efficient energy absorption of intense ps-laser pulse into nanowire target

DOE Office of Scientific and Technical Information (OSTI.GOV)

Habara, H.; Honda, S.; Katayama, M.

The interaction between ultra-intense laser light and vertically aligned carbon nanotubes is investigated to demonstrate efficient laser-energy absorption in the ps laser-pulse regime. Results indicate a clear enhancement of the energy conversion from laser to energetic electrons and a simultaneously small plasma expansion on the surface of the target. A two-dimensional plasma particle calculation exhibits a high absorption through laser propagation deep into the nanotube array, even for a dense array whose structure is much smaller than the laser wavelength. The propagation leads to the radial expansion of plasma perpendicular to the nanotubes rather than to the front side. Thesemore » features may contribute to fast ignition in inertial confinement fusion and laser particle acceleration, both of which require high current and small surface plasma simultaneously.« less

The application of thermodynamic and spectroscopic techniques to adhesion in the polyimide/Ti 6-4 and polyphenylquinoxaline/Ti 6-4 systems

NASA Technical Reports Server (NTRS)

Dias, S.; Wightman, J. P.

1984-01-01

The results of calorimetric measurements of Ti adherend surfaces are presented. The measurements were carried out after several chemical pretreatments and after fracture of several lap shear samples aged at high temperature. The exact composition of the Ti samples was Ti(6 percent Al-4 percent V). The adhesives used were polyimides and polyphenylquinoxalines (PPQ). Each chemical pretreatment was accompanied by a unique spectroscopic feature which was characterized by XPS, SEM, and specular reflectance infrared spectroscopy. The energetics of the interaction between primer solutions and the Ti adherend were evaluated by microcalorimetry. Changes in the structure of the surface oxide layer upon heating of the adherend were deduced from immersion temperatures of the PI and PPQ solutions. The XPS and SEM data are given is a table.

Inertial sensing microelectromechanical (MEM) safe-arm device

DOEpatents

Roesler, Alexander W [Tijeras, NM; Wooden, Susan M [Sandia Park, NM

2009-05-12

Microelectromechanical (MEM) safe-arm devices comprise a substrate upon which a sense mass, that can contain an energetic material, is constrained to move along a pathway defined by a track disposed on the surface of the substrate. The pathway has a first end comprising a "safe" position and a second end comprising an "armed" position, whereat the second end the sense mass can be aligned proximal to energetic materials comprising the explosive train, within an explosive component. The sense mass can be confined in the safe position by a first latch, operable to release the sense mass by an acceleration acting in a direction substantially normal to the surface of the substrate. A second acceleration, acting in a direction substantially parallel to the surface of the substrate, can cause the sense mass to traverse the pathway from the safe position to the armed position.

Mapping the nanoscale energetic landscape in conductive polymer films with spatially super-resolved exciton dynamics

NASA Astrophysics Data System (ADS)

Ginsberg, Naomi

2015-03-01

The migration of Frenkel excitons, tightly-bound electron-hole pairs, in polymeric organic semiconducting films is critical to the efficiency of bulk heterojunction solar cells. While these materials exhibit a high degree of structural heterogeneity on the nanoscale, traditional measurements of exciton diffusion lengths are performed on bulk samples. Since both the characteristic length scales of structural heterogeneity and the reported bulk diffusion lengths are smaller than the optical diffraction limit, we adapt far-field super-resolution fluorescence imaging to uncover the correlations between the structural and energetic landscapes that the excitons explore.

Modeling and simulation of protein-surface interactions: achievements and challenges.

PubMed

Ozboyaci, Musa; Kokh, Daria B; Corni, Stefano; Wade, Rebecca C

2016-01-01

Understanding protein-inorganic surface interactions is central to the rational design of new tools in biomaterial sciences, nanobiotechnology and nanomedicine. Although a significant amount of experimental research on protein adsorption onto solid substrates has been reported, many aspects of the recognition and interaction mechanisms of biomolecules and inorganic surfaces are still unclear. Theoretical modeling and simulations provide complementary approaches for experimental studies, and they have been applied for exploring protein-surface binding mechanisms, the determinants of binding specificity towards different surfaces, as well as the thermodynamics and kinetics of adsorption. Although the general computational approaches employed to study the dynamics of proteins and materials are similar, the models and force-fields (FFs) used for describing the physical properties and interactions of material surfaces and biological molecules differ. In particular, FF and water models designed for use in biomolecular simulations are often not directly transferable to surface simulations and vice versa. The adsorption events span a wide range of time- and length-scales that vary from nanoseconds to days, and from nanometers to micrometers, respectively, rendering the use of multi-scale approaches unavoidable. Further, changes in the atomic structure of material surfaces that can lead to surface reconstruction, and in the structure of proteins that can result in complete denaturation of the adsorbed molecules, can create many intermediate structural and energetic states that complicate sampling. In this review, we address the challenges posed to theoretical and computational methods in achieving accurate descriptions of the physical, chemical and mechanical properties of protein-surface systems. In this context, we discuss the applicability of different modeling and simulation techniques ranging from quantum mechanics through all-atom molecular mechanics to coarse-grained approaches. We examine uses of different sampling methods, as well as free energy calculations. Furthermore, we review computational studies of protein-surface interactions and discuss the successes and limitations of current approaches.

Growth and dislocation studies of β-HMX.

PubMed

Gallagher, Hugh G; Sherwood, John N; Vrcelj, Ranko M

2014-01-01

The defect structure of organic materials is important as it plays a major role in their crystal growth properties. It also can play a subcritical role in "hot-spot" detonation processes of energetics and one such energetic is cyclotetramethylene-tetranitramine, in the commonly used beta form (β-HMX). The as-grown crystals grown by evaporation from acetone show prismatic, tabular and columnar habits, all with {011}, {110}, (010) and (101) faces. Etching on (010) surfaces revealed three different types of etch pits, two of which could be identified with either pure screw or pure edge dislocations, the third is shown to be an artifact of the twinning process that this material undergoes. Examination of the {011} and {110} surfaces show only one type of etch pit on each surface; however their natural asymmetry precludes the easy identification of their Burgers vector or dislocation type. Etching of cleaved {011} surfaces demonstrates that the etch pits can be associated with line dislocations. All dislocations appear randomly on the crystal surfaces and do not form alignments characteristic of mechanical deformation by dislocation slip. Crystals of β-HMX grown from acetone show good morphological agreement with that predicted by modelling, with three distinct crystal habits observed depending upon the supersaturation of the growth solution. Prismatic habit was favoured at low supersaturation, while tabular and columnar crystals were predominant at higher super saturations. The twin plane in β-HMX was identified as a (101) reflection plane. The low plasticity of β-HMX is shown by the lack of etch pit alignments corresponding to mechanically induced dislocation arrays. On untwinned {010} faces, two types of dislocations exist, pure edge dislocations with b = [010] and pure screw dislocations with b = [010]. On twinned (010) faces, a third dislocation type exists and it is proposed that these pits are associated with pure screw dislocations with b = [010]. Graphical abstractEtch pits on the twinned (010) face of β-HMX.

Biologically tunable reactivity of energetic nanomaterials using protein cages.

PubMed

Slocik, Joseph M; Crouse, Christopher A; Spowart, Jonathan E; Naik, Rajesh R

2013-06-12

The performance of aluminum nanomaterial based energetic formulations is dependent on the mass transport, diffusion distance, and stability of reactive components. Here we use a biologically inspired approach to direct the assembly of oxidizer loaded protein cages onto the surface of aluminum nanoparticles to improve reaction kinetics by reducing the diffusion distance between the reactants. Ferritin protein cages were loaded with ammonium perchlorate (AP) or iron oxide and assembled with nAl to create an oxidation-reduction based energetic reaction and the first demonstration of a nanoscale biobased thermite material. Both materials showed enhanced exothermic behavior in comparison to nanothermite mixtures of bulk free AP or synthesized iron oxide nanopowders prepared without the use of ferritin. In addition, by utilizing a layer-by-layer (LbL) process to build multiple layers of protein cages containing iron oxide and iron oxide/AP on nAl, stoichiometric conditions and energetic performance can be optimized.

Communication: Local energetic analysis of the interfacial and surface energies of graphene from the single layer to graphite

NASA Astrophysics Data System (ADS)

Kocherlakota, Lakshmi S.; Krajina, Brad A.; Overney, René M.

2015-12-01

Recent advances in scanning probe methods that provide direct access to the surface free energy of inorganic layered materials in terms of the Hamaker constant yield energetic values for monolayer graphene that differ substantially, by a factor of around 0.4, from bulk graphite. The onset of bulk deviating energy values was observed at a multilayer slab thickness of ˜3 nm, corresponding to a layer number of 10. The findings, complemented with extractions from water contact angle measurements and calculated interlayer binding energies, find short-range ordinary van der Waals interactions to be most prominently affected by dimensional constraints and many-body interactions.

Communication: Local energetic analysis of the interfacial and surface energies of graphene from the single layer to graphite.

PubMed

Kocherlakota, Lakshmi S; Krajina, Brad A; Overney, René M

2015-12-28

Recent advances in scanning probe methods that provide direct access to the surface free energy of inorganic layered materials in terms of the Hamaker constant yield energetic values for monolayer graphene that differ substantially, by a factor of around 0.4, from bulk graphite. The onset of bulk deviating energy values was observed at a multilayer slab thickness of ∼3 nm, corresponding to a layer number of 10. The findings, complemented with extractions from water contact angle measurements and calculated interlayer binding energies, find short-range ordinary van der Waals interactions to be most prominently affected by dimensional constraints and many-body interactions.

Energetics of amino acid synthesis in hydrothermal ecosystems

NASA Technical Reports Server (NTRS)

Amend, J. P.; Shock, E. L.

1998-01-01

Thermodynamic calculations showed that the autotrophic synthesis of all 20 protein-forming amino acids was energetically favored in hot (100 degrees C), moderately reduced, submarine hydrothermal solutions relative to the synthesis in cold (18 degrees C), oxidized, surface seawater. The net synthesis reactions of 11 amino acids were exergonic in the hydrothermal solution, but all were endergonic in surface seawater. The synthesis of the requisite amino acids of nine thermophilic and hyperthermophilic proteins in a 100 degreesC hydrothermal solution yielded between 600 and 8000 kilojoules per mole of protein, which is energy that is available to drive the intracellular synthesis of enzymes and other biopolymers in hyperthermophiles thriving in these ecosystems.

Li 2S Film Formation on Lithium Anode Surface of Li–S batteries

DOE PAGES

Liu, Zhixiao; Bertolini, Samuel; Balbuena, Perla B.; ...

2016-02-02

The precipitation of lithium sulfide (Li 2S) on the Li metal anode surface adversely impacts the performance of lithium–sulfur (Li–S) batteries. In this work, a first-principles approach including density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations is employed to theoretically elucidate the Li 2S/Li metal surface interactions and the nucleation and growth of a Li 2S film on the anode surface due to long-chain polysulfide decomposition during battery operation. DFT analyses of the energetic properties and electronic structures demonstrate that a single molecule adsorption on Li surface releases energy forming chemical bonds between the S atoms andmore » Li atoms from the anode surface. Reaction pathways of the Li 2S film formation on Li metal surfaces are investigated based on DFT calculations. It is found that a distorted Li 2S (111) plane forms on a Li(110) surface and a perfect Li 2S (111) plane forms on a Li(111) surface. The total energy of the system decreases along the reaction pathway; hence Li 2S film formation on the Li anode surface is thermodynamically favorable. Finally, the calculated difference charge density of the Li 2S film/Li surface suggests that the precipitated film would interact with the Li anode via strong chemical bonds. AIMD simulations reveal the role of the anode surface structure and the origin of the Li 2S formation via decomposition of Li 2S 8 polysulfide species formed at the cathode side and dissolved in the electrolyte medium in which they travel to the anode side during battery cycling.« less

Li 2S Film Formation on Lithium Anode Surface of Li–S batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Zhixiao; Bertolini, Samuel; Balbuena, Perla B.

The precipitation of lithium sulfide (Li 2S) on the Li metal anode surface adversely impacts the performance of lithium–sulfur (Li–S) batteries. In this work, a first-principles approach including density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations is employed to theoretically elucidate the Li 2S/Li metal surface interactions and the nucleation and growth of a Li 2S film on the anode surface due to long-chain polysulfide decomposition during battery operation. DFT analyses of the energetic properties and electronic structures demonstrate that a single molecule adsorption on Li surface releases energy forming chemical bonds between the S atoms andmore » Li atoms from the anode surface. Reaction pathways of the Li 2S film formation on Li metal surfaces are investigated based on DFT calculations. It is found that a distorted Li 2S (111) plane forms on a Li(110) surface and a perfect Li 2S (111) plane forms on a Li(111) surface. The total energy of the system decreases along the reaction pathway; hence Li 2S film formation on the Li anode surface is thermodynamically favorable. Finally, the calculated difference charge density of the Li 2S film/Li surface suggests that the precipitated film would interact with the Li anode via strong chemical bonds. AIMD simulations reveal the role of the anode surface structure and the origin of the Li 2S formation via decomposition of Li 2S 8 polysulfide species formed at the cathode side and dissolved in the electrolyte medium in which they travel to the anode side during battery cycling.« less

Li2S Film Formation on Lithium Anode Surface of Li-S batteries.

PubMed

Liu, Zhixiao; Bertolini, Samuel; Balbuena, Perla B; Mukherjee, Partha P

2016-02-01

The precipitation of lithium sulfide (Li2S) on the Li metal anode surface adversely impacts the performance of lithium-sulfur (Li-S) batteries. In this study, a first-principles approach including density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations is employed to theoretically elucidate the Li2S/Li metal surface interactions and the nucleation and growth of a Li2S film on the anode surface due to long-chain polysulfide decomposition during battery operation. DFT analyses of the energetic properties and electronic structures demonstrate that a single molecule adsorption on Li surface releases energy forming chemical bonds between the S atoms and Li atoms from the anode surface. Reaction pathways of the Li2S film formation on Li metal surfaces are investigated based on DFT calculations. It is found that a distorted Li2S (111) plane forms on a Li(110) surface and a perfect Li2S (111) plane forms on a Li(111) surface. The total energy of the system decreases along the reaction pathway; hence Li2S film formation on the Li anode surface is thermodynamically favorable. The calculated difference charge density of the Li2S film/Li surface suggests that the precipitated film would interact with the Li anode via strong chemical bonds. AIMD simulations reveal the role of the anode surface structure and the origin of the Li2S formation via decomposition of Li2S8 polysulfide species formed at the cathode side and dissolved in the electrolyte medium in which they travel to the anode side during battery cycling.

Anticorrelated Emission of High Harmonics and Fast Electron Beams From Plasma Mirrors.

PubMed

Bocoum, Maïmouna; Thévenet, Maxence; Böhle, Frederik; Beaurepaire, Benoît; Vernier, Aline; Jullien, Aurélie; Faure, Jérôme; Lopez-Martens, Rodrigo

2016-05-06

We report for the first time on the anticorrelated emission of high-order harmonics and energetic electron beams from a solid-density plasma with a sharp vacuum interface-plasma mirror-driven by an intense ultrashort laser pulse. We highlight the key role played by the nanoscale structure of the plasma surface during the interaction by measuring the spatial and spectral properties of harmonics and electron beams emitted by a plasma mirror. We show that the nanoscale behavior of the plasma mirror can be controlled by tuning the scale length of the electron density gradient, which is measured in situ using spatial-domain interferometry.

Hotspot-Centric De Novo Design of Protein Binders

PubMed Central

Fleishman, Sarel J.; Corn, Jacob E.; Strauch, Eva-Maria; Whitehead, Timothy A.; Karanicolas, John; Baker, David

2014-01-01

Protein–protein interactions play critical roles in biology, and computational design of interactions could be useful in a range of applications. We describe in detail a general approach to de novo design of protein interactions based on computed, energetically optimized interaction hotspots, which was recently used to produce high-affinity binders of influenza hemagglutinin. We present several alternative approaches to identify and build the key hotspot interactions within both core secondary structural elements and variable loop regions and evaluate the method's performance in natural-interface recapitulation. We show that the method generates binding surfaces that are more conformationally restricted than previous design methods, reducing opportunities for off-target interactions. PMID:21945116

A close-up of the sun. [solar probe mission planning conference

NASA Technical Reports Server (NTRS)

Neugebauer, M. (Editor); Davies, R. W. (Editor)

1978-01-01

NASA's long-range plan for the study of solar-terrestrial relations includes a Solar Probe Mission in which a spacecraft is put into an eccentric orbit with perihelion near 4 solar radii (0.02 AU). The scientific experiments which might be done with such a mission are discussed. Topics include the distribution of mass within the Sun, solar angular momentum, the fine structure of the solar surface and corona, the acceleration of the solar wind and energetic particles, and the evolution of interplanetary dust. The mission could also contribute to high-accuracy tests of general relativity and the search for cosmic gravitational radiation.

Intense energetic electron flux enhancements in Mercury's magnetosphere: An integrated view with high‐resolution observations from MESSENGER

PubMed Central

Dewey, Ryan M.; Lawrence, David J.; Goldsten, John O.; Peplowski, Patrick N.; Korth, Haje; Slavin, James A.; Krimigis, Stamatios M.; Anderson, Brian J.; Ho, George C.; McNutt, Ralph L.; Raines, Jim M.; Schriver, David; Solomon, Sean C.

2016-01-01

Abstract The MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) mission to Mercury has provided a wealth of new data about energetic particle phenomena. With observations from MESSENGER's Energetic Particle Spectrometer, as well as data arising from energetic electrons recorded by the X‐Ray Spectrometer and Gamma‐Ray and Neutron Spectrometer (GRNS) instruments, recent work greatly extends our record of the acceleration, transport, and loss of energetic electrons at Mercury. The combined data sets include measurements from a few keV up to several hundred keV in electron kinetic energy and have permitted relatively good spatial and temporal resolution for many events. We focus here on the detailed nature of energetic electron bursts measured by the GRNS system, and we place these events in the context of solar wind and magnetospheric forcing at Mercury. Our examination of data at high temporal resolution (10 ms) during the period March 2013 through October 2014 supports strongly the view that energetic electrons are accelerated in the near‐tail region of Mercury's magnetosphere and are subsequently “injected” onto closed magnetic field lines on the planetary nightside. The electrons populate the plasma sheet and drift rapidly eastward toward the dawn and prenoon sectors, at times executing multiple complete drifts around the planet to form “quasi‐trapped” populations. PMID:27830111

Study on the creation and destruction of transport barriers via the effective safety factors for energetic particles

NASA Astrophysics Data System (ADS)

Ogawa, Shun; Leoncini, Xavier; Dif-Pradalier, Guilhem; Garbet, Xavier

2016-12-01

Charged particles with low kinetic energy move along the magnetic field lines, but so do not the energetic particles. We investigate the topological structure changes in the phase space of energetic particles with respect to the magnetic one. For this study, cylindrical magnetic fields with non-monotonic safety factors that induce the magnetic internal transport barrier are considered. We show that the topological structure of the magnetic field line and of the particle trajectories can be quite different. We explain this difference using the concept of an effective particle q-profile. Using this notion, we can investigate the location and existence of resonances for particle orbits that are different from the magnetic ones. These are examined both numerically by integrating an equation of motion and theoretically by the use of Alfvén's guiding center theory and by the use of an effective reduced Hamiltonian for the integrable unperturbed system. It is clarified that, for the energetic particles, the grad B drift effect shifts the resonances and the drift induced by curvature of the magnetic field line leads to the vanishing of the resonances. As a result, we give two different mechanisms that lead to the creation of transport barriers for energetic particles in the region where the magnetic field line is chaotic.

A new fabrication technique for complex refractive micro-optical systems

NASA Astrophysics Data System (ADS)

Tormen, Massimo; Carpentiero, Alessandro; Ferrari, Enrico; Cabrini, Stefano; Cojoc, Dan; Di Fabrizio, Enzo

2006-01-01

We present a new method that allows to fabricate structures with tightly controlled three-dimensional profiles in the 10 nm to 100 μm scale range. This consists of a sequence of lithographic steps such as Electron Beam (EB) or Focused Ion Beam (FIB) lithography, alternated with isotropic wet etching processes performed on a quartz substrate. Morphological characterization by SEM and AFM shows that 3D structures with very accurate shape control and nanometer scale surface roughness can be realized. Quartz templates have been employed as complex system of micromirrors after metal coating of the patterned surface or used as stamps in nanoimprint, hot embossing or casting processes to shape complex plastic elements. Compared to other 3D micro and nanostructuring methods, in which a hard material is directly "sculptured" by energetic beams, our technique requires a much less intensive use of expensive lithographic equipments, for comparable volumes of structured material, resulting in dramatic increase of throughput. Refractive micro-optical elements have been fabricated and characterized in transmission and reflection modes with white and monochromatic light. The elements produce a distribution of sharp focal spots and lines in the three dimensional space, opening the route for applications of image reconstruction based on refractive optics.

Stab Sensitivity of Energetic Nanolaminates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gash, A; Barbee, T; Cervantes, O

2006-05-22

This work details the stab ignition, small-scale safety, and energy release characteristics of bimetallic Al/Ni(V) and Al/Monel energetic nanolaminate freestanding thin films. The influence of the engineered nanostructural features of the energetic multilayers is correlated with both stab initiation and small-scale energetic materials testing results. Structural parameters of the energetic thin films found to be important include the bi-layer period, total thickness of the film, and presence or absence of aluminum coating layers. In general the most sensitive nanolaminates were those that were relatively thick, possessed fine bi-layer periods, and were not coated. Energetic nanolaminates were tested for their stabmore » sensitivity as freestanding continuous parts and as coarse powders. The stab sensitivity of mock M55 detonators loaded with energetic nanolaminate was found to depend strongly upon both the particle size of the material and the configuration of nanolaminate material, in the detonator cup. In these instances stab ignition was observed with input energies as low as 5 mJ for a coarse powder with an average particle dimension of 400 {micro}m. Selected experiments indicate that the reacting nanolaminate can be used to ignite other energetic materials such as sol-gel nanostructured thermite, and conventional thermite that was either coated onto the multilayer substrate or pressed on it. These results demonstrate that energetic nanolaminates can be tuned to have precise and controlled ignition thresholds and can initiate other energetic materials and therefore are viable candidates as lead-free impact initiated igniters or detonators.« less

The characteristics of a new negative metal ion beam source and its applications

NASA Astrophysics Data System (ADS)

Paik, Namwoong

2001-10-01

Numerous efforts at energetic thin film deposition processes using ion beams have been made to meet the demands of today's thin film industry. As one of these efforts, a new Magnetron Sputter Negative Ion Source (MSNIS) was developed. In this study, the development and the characterization of the MSNIS were investigated. Amorphous carbon films were used as a sample coating medium to evaluate the ion beam energy effect. A review of energetic Physical Vapor Deposition (PVD) techniques is presented in Chapter 1. The energetic PVD methods can be classified into two major categories: the indirect ion beam method Ion Beam Assisted Deposition (IBAD), and the direct ion beam method-Direct Ion Beam Deposition (DIBD). In this chapter, currently available DIBD processes such as Cathodic Arc, Laser Ablation, Ionized Physical Vapor Deposition (I-PVD) and Magnetron Sputter Negative Ion Source (MSNIS) are individually reviewed. The design and construction of the MSNIS is presented in chapter 2. The MSNIS is a hybrid of the conventional magnetron sputter configuration and the cesium surface ionizer. The negative sputtered ions are produced directly from the sputter target by surface ionization. In chapter 3, the ion beam and plasma characteristics of an 8″ diameter MSNIS are investigated using a retarding field analyzer and a cylindrical Langmuir Probe. The measured electron temperature is approximately 2-5 eV, while the plasma density and plasma potential were of the order of 10 11-1012 cm3 and 5-20 V, respectively, depending on the pressure and power. In chapter 4, in order to evaluate the effect of the ion beam on the resultant films, amorphous carbon films were deposited under various conditions. The structure of carbon films was investigated using Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The result suggests the fraction of spa bonding is more than 70% in some samples prepared by MSNIS while magnetron sputtered samples showed less than 30%. (Abstract shortened by UMI.)

The Longitudinal Properties of a Solar Energetic Particle Event Investigated Using Modern Solar Imaging

NASA Technical Reports Server (NTRS)

Rouillard, A. P.; Sheeley, N.R. Jr.; Tylka, A.; Vourlidas, A.; Ng, C. K.; Rakowski, C.; Cohen, C. M. S.; Mewaldt, R. A.; Mason, G. M.; Reames, D.;

Climate impact of idealized winter polar mesospheric and stratospheric ozone losses as caused by energetic particle precipitation

NASA Astrophysics Data System (ADS)

Meraner, Katharina; Schmidt, Hauke

2018-01-01

Energetic particles enter the polar atmosphere and enhance the production of nitrogen oxides and hydrogen oxides in the winter stratosphere and mesosphere. Both components are powerful ozone destroyers. Recently, it has been inferred from observations that the direct effect of energetic particle precipitation (EPP) causes significant long-term mesospheric ozone variability. Satellites observe a decrease in mesospheric ozone up to 34 % between EPP maximum and EPP minimum. Stratospheric ozone decreases due to the indirect effect of EPP by about 10-15 % observed by satellite instruments. Here, we analyze the climate impact of winter boreal idealized polar mesospheric and polar stratospheric ozone losses as caused by EPP in the coupled Max Planck Institute Earth System Model (MPI-ESM). Using radiative transfer modeling, we find that the radiative forcing of mesospheric ozone loss during polar night is small. Hence, climate effects of mesospheric ozone loss due to energetic particles seem unlikely. Stratospheric ozone loss due to energetic particles warms the winter polar stratosphere and subsequently weakens the polar vortex. However, those changes are small, and few statistically significant changes in surface climate are found.

The growth and perfection of β-cyclotetramethylene-tetranitramine (HMX) studied by laboratory and synchrotron X-ray topography

NASA Astrophysics Data System (ADS)

Gallagher, H. G.; Sherwood, J. N.; Vrcelj, R. M.

2017-10-01

An examination has been made of the defect structure of crystals of the energetic material β-cyclotetramethylene-tetranitramine (HMX) using both Laboratory (Lang method) and Synchrotron (Bragg Reflection and Laue method) techniques. The results of the three methods are compared with particular attention to the influence of potential radiation damage caused to the samples by the latter, more energetic, technique. The comparison shows that both techniques can be confidently used to evaluate the defect structures yielding closely similar results. The results show that, even under the relatively casual preparative methods used (slow evaporation of unstirred solutions at constant temperature), HMX crystals of high perfection can be produced. The crystals show well defined bulk defect structures characteristic of organic materials in general: growth dislocations, twins, growth sector boundaries, growth banding and solvent inclusions. The distribution of the defects in specific samples is correlated with the morphological variation of the grown crystals. The results show promise for the further evaluation and characterisation of the structure and properties of dislocations and other defects and their involvement in mechanical and energetic processes in this material.

Dispersion Corrected Structural Properties and Quasiparticle Band Gaps of Several Organic Energetic Solids.

PubMed

Appalakondaiah, S; Vaitheeswaran, G; Lebègue, S

2015-06-18

We have performed ab initio calculations for a series of energetic solids to explore their structural and electronic properties. To evaluate the ground state volume of these molecular solids, different dispersion correction methods were accounted in DFT, namely the Tkatchenko-Scheffler method (with and without self-consistent screening), Grimme's methods (D2, D3(BJ)), and the vdW-DF method. Our results reveal that dispersion correction methods are essential in understanding these complex structures with van der Waals interactions and hydrogen bonding. The calculated ground state volumes and bulk moduli show that the performance of each method is not unique, and therefore a careful examination is mandatory for interpreting theoretical predictions. This work also emphasizes the importance of quasiparticle calculations in predicting the band gap, which is obtained here with the GW approximation. We find that the obtained band gaps are ranging from 4 to 7 eV for the different compounds, indicating their insulating nature. In addition, we show the essential role of quasiparticle band structure calculations to correlate the gap with the energetic properties.

Modeling Solar Energetic Particle Transport near a Wavy Heliospheric Current Sheet

NASA Astrophysics Data System (ADS)

Battarbee, Markus; Dalla, Silvia; Marsh, Mike S.

2018-02-01

Understanding the transport of solar energetic particles (SEPs) from acceleration sites at the Sun into interplanetary space and to the Earth is an important question for forecasting space weather. The interplanetary magnetic field (IMF), with two distinct polarities and a complex structure, governs energetic particle transport and drifts. We analyze for the first time the effect of a wavy heliospheric current sheet (HCS) on the propagation of SEPs. We inject protons close to the Sun and propagate them by integrating fully 3D trajectories within the inner heliosphere in the presence of weak scattering. We model the HCS position using fits based on neutral lines of magnetic field source surface maps (SSMs). We map 1 au proton crossings, which show efficient transport in longitude via HCS, depending on the location of the injection region with respect to the HCS. For HCS tilt angles around 30°–40°, we find significant qualitative differences between A+ and A‑ configurations of the IMF, with stronger fluences along the HCS in the former case but with a distribution of particles across a wider range of longitudes and latitudes in the latter. We show how a wavy current sheet leads to longitudinally periodic enhancements in particle fluence. We show that for an A+ IMF configuration, a wavy HCS allows for more proton deceleration than a flat HCS. We find that A‑ IMF configurations result in larger average fluences than A+ IMF configurations, due to a radial drift component at the current sheet.

Molecular determinants of the interactions between proteins and ssDNA.

PubMed

Mishra, Garima; Levy, Yaakov

2015-04-21

ssDNA binding proteins (SSBs) protect ssDNA from chemical and enzymatic assault that can derail DNA processing machinery. Complexes between SSBs and ssDNA are often highly stable, but predicting their structures is challenging, mostly because of the inherent flexibility of ssDNA and the geometric and energetic complexity of the interfaces that it forms. Here, we report a newly developed coarse-grained model to predict the structure of SSB-ssDNA complexes. The model is successfully applied to predict the binding modes of six SSBs with ssDNA strands of lengths of 6-65 nt. In addition to charge-charge interactions (which are often central to governing protein interactions with nucleic acids by means of electrostatic complementarity), an essential energetic term to predict SSB-ssDNA complexes is the interactions between aromatic residues and DNA bases. For some systems, flexibility is required from not only the ssDNA but also, the SSB to allow it to undergo conformational changes and the penetration of the ssDNA into its binding pocket. The association mechanisms can be quite varied, and in several cases, they involve the ssDNA sliding along the protein surface. The binding mechanism suggests that coarse-grained models are appropriate to study the motion of SSBs along ssDNA, which is expected to be central to the function carried out by the SSBs.

Microwave Spectrum of the Ethanol-Methanol Dimer

NASA Astrophysics Data System (ADS)

Finneran, Ian A.; Carroll, Brandon; Mead, Griffin; Blake, Geoffrey

2016-06-01

The hydrogen bond donor/acceptor competition in mixed alcohol clusters remains a fundamental question in physical chemistry. Previous theoretical work on the prototype ethanol-methanol dimer has been inconclusive in predicting the energetically preferred structure. Here, we report the microwave spectrum of the ethanol-methanol dimer between 8-18 GHz, using a chirped pulse Fourier transform microwave spectrometer. With the aid of ab initio calculations, 36 transitions have been fit and assigned to a t-ethanol-acceptor, methanol-donor structure in an argon-backed expansion. In a helium-backed expansion, a second excited conformer has been observed, and tentatively assigned to a g-ethanol-acceptor, methanol-donor structure. No ethanol-donor, methanol-acceptor structures have been found, suggesting such structures are energetically disfavored.

On-the-fly Numerical Surface Integration for Finite-Difference Poisson-Boltzmann Methods.

PubMed

Cai, Qin; Ye, Xiang; Wang, Jun; Luo, Ray

2011-11-01

Most implicit solvation models require the definition of a molecular surface as the interface that separates the solute in atomic detail from the solvent approximated as a continuous medium. Commonly used surface definitions include the solvent accessible surface (SAS), the solvent excluded surface (SES), and the van der Waals surface. In this study, we present an efficient numerical algorithm to compute the SES and SAS areas to facilitate the applications of finite-difference Poisson-Boltzmann methods in biomolecular simulations. Different from previous numerical approaches, our algorithm is physics-inspired and intimately coupled to the finite-difference Poisson-Boltzmann methods to fully take advantage of its existing data structures. Our analysis shows that the algorithm can achieve very good agreement with the analytical method in the calculation of the SES and SAS areas. Specifically, in our comprehensive test of 1,555 molecules, the average unsigned relative error is 0.27% in the SES area calculations and 1.05% in the SAS area calculations at the grid spacing of 1/2Å. In addition, a systematic correction analysis can be used to improve the accuracy for the coarse-grid SES area calculations, with the average unsigned relative error in the SES areas reduced to 0.13%. These validation studies indicate that the proposed algorithm can be applied to biomolecules over a broad range of sizes and structures. Finally, the numerical algorithm can also be adapted to evaluate the surface integral of either a vector field or a scalar field defined on the molecular surface for additional solvation energetics and force calculations.

Adsorption and Desulfurization Mechanism of Thiophene on Layered FeS(001), (011), and (111) Surfaces: A Dispersion-Corrected Density Functional Theory Study

PubMed Central

2017-01-01

Layered transition-metal chalcogenides have emerged as a fascinating new class of materials for catalysis. Here, we present periodic density functional theory (DFT) calculations of the adsorption of thiophene and the direct desulfurization reaction pathways on the (001), (011), and (111) surfaces of layered FeS. The fundamental aspects of the thiophene adsorption, including the initial adsorption geometries, adsorption energies, structural parameters, and electronic properties, are presented. From the calculated adsorption energies, we show that the flat adsorption geometries, wherein the thiophene molecule forms multiple π-bonds with the FeS surfaces, are energetically more favorable than the upright adsorption geometries, with the strength of adsorption decreasing in the order FeS(111) > FeS(011) > FeS(001). The adsorption of the thiophene onto the reactive (011) and (111) surfaces is shown to be characterized by charge transfer from the interacting Fe d-band to the π-system of the thiophene molecule, which causes changes of the intramolecular structure including loss of aromaticity and elongation of the C–S bonds. The thermodynamic and kinetic analysis of the elementary steps involved in the direct desulfurization of thiophene on the reactive FeS surfaces is also presented. Direct desulfurization of thiophene occurs preferentially on the (111) surface, as reflected by the overall exothermic reaction energy calculated for the process (ER = −0.15 eV), with an activation energy of 1.58 eV. PMID:29348782

Energetics and electronic structures of chemically decorated C60 chains

NASA Astrophysics Data System (ADS)

Furutani, Sho; Okada, Susumu

2018-06-01

We studied the energetics and electronic structures of one-dimensional molecular chains of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) using the density functional theory (DFT). Our DFT calculations show that the binding energies of PCBM range from 90 to 300 meV, depending on not only the intermolecular spacing but also the intermolecular arrangements owing to the interaction between functional groups and C60. The electronic structure of PCBM chains are also sensitive to the mutual arrangements of PCBM in their chain structure. The calculated effective masses of the conduction band range from 0.58 to 634.97m e, giving rise to anisotropic transport properties in their condensed phase.

Probing the Energetics of Dynactin Filament Assembly and the Binding of Cargo Adaptor Proteins Using Molecular Dynamics Simulation and Electrostatics-Based Structural Modeling.

PubMed

Zheng, Wenjun

2017-01-10

Dynactin, a large multiprotein complex, binds with the cytoplasmic dynein-1 motor and various adaptor proteins to allow recruitment and transportation of cellular cargoes toward the minus end of microtubules. The structure of the dynactin complex is built around an actin-like minifilament with a defined length, which has been visualized in a high-resolution structure of the dynactin filament determined by cryo-electron microscopy (cryo-EM). To understand the energetic basis of dynactin filament assembly, we used molecular dynamics simulation to probe the intersubunit interactions among the actin-like proteins, various capping proteins, and four extended regions of the dynactin shoulder. Our simulations revealed stronger intersubunit interactions at the barbed and pointed ends of the filament and involving the extended regions (compared with the interactions within the filament), which may energetically drive filament termination by the capping proteins and recruitment of the actin-like proteins by the extended regions, two key features of the dynactin filament assembly process. Next, we modeled the unknown binding configuration among dynactin, dynein tails, and a number of coiled-coil adaptor proteins (including several Bicaudal-D and related proteins and three HOOK proteins), and predicted a key set of charged residues involved in their electrostatic interactions. Our modeling is consistent with previous findings of conserved regions, functional sites, and disease mutations in the adaptor proteins and will provide a structural framework for future functional and mutational studies of these adaptor proteins. In sum, this study yielded rich structural and energetic information about dynactin and associated adaptor proteins that cannot be directly obtained from the cryo-EM structures with limited resolutions.

An all-atom structure-based potential for proteins: bridging minimal models with all-atom empirical forcefields.

PubMed

Whitford, Paul C; Noel, Jeffrey K; Gosavi, Shachi; Schug, Alexander; Sanbonmatsu, Kevin Y; Onuchic, José N

2009-05-01

Protein dynamics take place on many time and length scales. Coarse-grained structure-based (Go) models utilize the funneled energy landscape theory of protein folding to provide an understanding of both long time and long length scale dynamics. All-atom empirical forcefields with explicit solvent can elucidate our understanding of short time dynamics with high energetic and structural resolution. Thus, structure-based models with atomic details included can be used to bridge our understanding between these two approaches. We report on the robustness of folding mechanisms in one such all-atom model. Results for the B domain of Protein A, the SH3 domain of C-Src Kinase, and Chymotrypsin Inhibitor 2 are reported. The interplay between side chain packing and backbone folding is explored. We also compare this model to a C(alpha) structure-based model and an all-atom empirical forcefield. Key findings include: (1) backbone collapse is accompanied by partial side chain packing in a cooperative transition and residual side chain packing occurs gradually with decreasing temperature, (2) folding mechanisms are robust to variations of the energetic parameters, (3) protein folding free-energy barriers can be manipulated through parametric modifications, (4) the global folding mechanisms in a C(alpha) model and the all-atom model agree, although differences can be attributed to energetic heterogeneity in the all-atom model, and (5) proline residues have significant effects on folding mechanisms, independent of isomerization effects. Because this structure-based model has atomic resolution, this work lays the foundation for future studies to probe the contributions of specific energetic factors on protein folding and function.

An All-atom Structure-Based Potential for Proteins: Bridging Minimal Models with All-atom Empirical Forcefields

PubMed Central

Whitford, Paul C.; Noel, Jeffrey K.; Gosavi, Shachi; Schug, Alexander; Sanbonmatsu, Kevin Y.; Onuchic, José N.

2012-01-01

Protein dynamics take place on many time and length scales. Coarse-grained structure-based (Gō) models utilize the funneled energy landscape theory of protein folding to provide an understanding of both long time and long length scale dynamics. All-atom empirical forcefields with explicit solvent can elucidate our understanding of short time dynamics with high energetic and structural resolution. Thus, structure-based models with atomic details included can be used to bridge our understanding between these two approaches. We report on the robustness of folding mechanisms in one such all-atom model. Results for the B domain of Protein A, the SH3 domain of C-Src Kinase and Chymotrypsin Inhibitor 2 are reported. The interplay between side chain packing and backbone folding is explored. We also compare this model to a Cα structure-based model and an all-atom empirical forcefield. Key findings include 1) backbone collapse is accompanied by partial side chain packing in a cooperative transition and residual side chain packing occurs gradually with decreasing temperature 2) folding mechanisms are robust to variations of the energetic parameters 3) protein folding free energy barriers can be manipulated through parametric modifications 4) the global folding mechanisms in a Cα model and the all-atom model agree, although differences can be attributed to energetic heterogeneity in the all-atom model 5) proline residues have significant effects on folding mechanisms, independent of isomerization effects. Since this structure-based model has atomic resolution, this work lays the foundation for future studies to probe the contributions of specific energetic factors on protein folding and function. PMID:18837035

Study of thermal sensitivity and thermal explosion violence of energetic materials in the LLNL ODTX system

NASA Astrophysics Data System (ADS)

Hsu, P. C.; Hust, G.; Zhang, M. X.; Lorenz, T. K.; Reynolds, J. G.; Fried, L.; Springer, H. K.; Maienschein, J. L.

2014-05-01

Incidents caused by fire and combat operations can heat energetic materials that may lead to thermal explosion and result in structural damage and casualty. Some explosives may thermally explode at fairly low temperatures (< 100 °C) and the violence from thermal explosion may cause significant damage. Thus it is important to understand the response of energetic materials to thermal insults. The One Dimensional Time to Explosion (ODTX) system at the Lawrence Livermore National Laboratory has been used for decades to measure times to explosion, threshold thermal explosion temperature, and determine kinetic parameters of energetic materials. Samples of different configurations (pressed part, powder, paste, and liquid) can be tested in the system. The ODTX testing can also provide useful data for assessing the thermal explosion violence of energetic materials. Recent ODTX experimental data are reported in the paper.

Molecular Level Investigation of CH 4 and CO 2 Adsorption in Hydrated Calcium–Montmorillonite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Mal-Soon; McGrail, B. Peter; Rousseau, Roger

2017-11-17

We have studied the mechanism of intercalation and methane adsorption from a H2O/CH4/CO2 mixture on a prototypical shale component, Ca-montmorillonite. We employed ab initio molecular dynamics simulations at 323 K and 90 bar to obtain molecular level information of adsorption energetics, speciation, and structural and thermodynamic properties. Interaction of CH4 with surface Lewis acidic sites (Ca2+, surface OH) results in large induced dipoles (~1 D) that lead to relatively strong adsorption energies that level off once a full CH4 layer is formed. Intercalated CH4, also exhibits induced dipoles at low hydration levels, when the interaction with Ca2+ cations are lessmore » hindered. CO2 displaces CH4 in the coordination sphere of the cations (in the interlayer) or in the surface, thereby driving CH4 extraction. Our simulations indicate that there is a Goldilocks pressure range (~60-100 bar) where scCO2 –facilitated CH4 extraction will be maximized.« less

Nano-laminate-based ignitors

DOEpatents

Barbee, Jr., Troy W.; Simpson, Randall L.; Gash, Alexander E.; Satcher, Jr., Joe H.

2012-12-11

Sol-gel chemistry is used to prepare igniters comprising energetic multilayer structures coated with energetic materials. These igniters can be tailored to be stable to environmental aging, i.e., where the igniters are exposed to extremes of both hot and cold temperatures (-30 C to 150 C) and both low (0%) and high relative humidity (100%).

Nano-laminate-based ignitors

DOEpatents

Barbee, Jr., Troy W.; Simpson, Randall L [Livermore, CA; Gash, Alexander E [Brentwood, CA; Satcher, Jr., Joe H.

2011-05-31

Sol-gel chemistry is used to prepare igniters comprising energetic multilayer structures coated with energetic booster materials. These igniters can be tailored to be stable to environmental aging, i.e., where the igniters are exposed to extremes of both hot and cold temperatures (-30 C to 150 C) and both low (0%) and high relative humidity (100%).

ALMA Observations of a Quiescent Molecular Cloud in the Large Magellanic Cloud

NASA Astrophysics Data System (ADS)

Wong, Tony; Hughes, Annie; Tokuda, Kazuki; Indebetouw, Rémy; Bernard, Jean-Philippe; Onishi, Toshikazu; Wojciechowski, Evan; Bandurski, Jeffrey B.; Kawamura, Akiko; Roman-Duval, Julia; Cao, Yixian; Chen, C.-H. Rosie; Chu, You-hua; Cui, Chaoyue; Fukui, Yasuo; Montier, Ludovic; Muller, Erik; Ott, Juergen; Paradis, Deborah; Pineda, Jorge L.; Rosolowsky, Erik; Sewiło, Marta

2017-12-01

We present high-resolution (subparsec) observations of a giant molecular cloud in the nearest star-forming galaxy, the Large Magellanic Cloud. ALMA Band 6 observations trace the bulk of the molecular gas in 12CO(2-1) and the high column density regions in 13CO(2-1). Our target is a quiescent cloud (PGCC G282.98-32.40, which we refer to as the “Planck cold cloud” or PCC) in the southern outskirts of the galaxy where star formation activity is very low and largely confined to one location. We decompose the cloud into structures using a dendrogram and apply an identical analysis to matched-resolution cubes of the 30 Doradus molecular cloud (located near intense star formation) for comparison. Structures in the PCC exhibit roughly 10 times lower surface density and five times lower velocity dispersion than comparably sized structures in 30 Dor, underscoring the non-universality of molecular cloud properties. In both clouds, structures with relatively higher surface density lie closer to simple virial equilibrium, whereas lower surface-density structures tend to exhibit supervirial line widths. In the PCC, relatively high line widths are found in the vicinity of an infrared source whose properties are consistent with a luminous young stellar object. More generally, we find that the smallest resolved structures (“leaves”) of the dendrogram span close to the full range of line widths observed across all scales. As a result, while the bulk of the kinetic energy is found on the largest scales, the small-scale energetics tend to be dominated by only a few structures, leading to substantial scatter in observed size-line-width relationships.

Tuning Energetic Material Reactivity Using Surface Functionalization of Aluminum Fuels

DTIC Science & Technology

2012-10-30

analysis of three different thermites consisting of aluminum (Al) particles with and without surface functionalization combined with molybdenum...of thermites , aluminum synthesis, aluminum fluoropolymer combustion, acid coatings Keerti S. Kappagantula, Cory Farley, Michelle L. Pantoya, Jillian...Reactivity Using Surface Functionalization of Aluminum Fuels Report Title ABSTRACT Combustion analysis of three different thermites consisting of aluminum (Al

A density functional study on adsorption and dissociation of O 2 on Ir(1 0 0) surface

NASA Astrophysics Data System (ADS)

Erikat, I. A.; Hamad, B. A.; Khalifeh, J. M.

2011-06-01

The adsorption and the reaction barrier for the dissociation of O 2 on Ir(1 0 0) surface are studied using periodic self-consistent density functional theory (DFT) calculations. Dissociative adsorption is found to be energetically more favorable compared to molecular adsorption. Parallel approaches Prl1 and Prl2 on a hollow site with the same adsorption energy of -3.93 eV for both of them are found to have the most energetically preferred sites of adsorptions among all the studied cases. Hybridization between p-O 2 and d-metal orbitals is responsible for the dissociative adsorption. The minimum energy path is determined by using the nudge elastic band method (NEB). We found that the dissociation occurs immediately and very early in the dissociation path with a small activation barrier (0.26 eV), which means that molecular adsorption of O 2 on Ir(1 0 0) surface occurs at very low temperatures; this is consistent with previous experimental and theoretical studies on Ir surfaces.

Identification of best particle radiation shielded region through Energetic Neutral Atoms mapping

NASA Astrophysics Data System (ADS)

Milillo, A.; De Angelis, E.; Mura, A.; Orsini, S.; Mangano, V.; Massetti, S.; Rispoli, R.; Lazzarotto, F.; Vertolli, N.; Lavagna, M.; Ferrari, F.; Lunghi, P.; Attinà, P.; Parissenti, G.

2017-09-01

The lunar surface is directly exposed either to direct solar wind, or to Earth's magnetospheric plasma due to the Moon's lack of a magnetosphere or a dense atmosphere. This exposure could create inhospitable conditions for a possible human presence on the Moon, so it is crucial to investigate the close-to-surface environment for establishing the best reliable locations for future human bases. Although it lacks a global magnetic field, the Moon possesses magnetic anomalies that create mini-magnetospheres, where the solar wind is partly deflected. The local protection of the surface from the solar wind radiation inside the mini-magnetospheres could make these sites preferred for future lunar colonization. It is crucial a detailed characterization of these sites. In this paper, an investigation based on the detection of Energetic Neutral Atoms (ENA) from the surface for identifying the best particle radiation shielded region is proposed. A high spatial resolution mapping via ENA is a feasible and it is powerful way for reaching this goal.

Kinetic Roughening Transition and Energetics of Tetragonal Lysozyme Crystal Growth

NASA Technical Reports Server (NTRS)

Gorti, Sridhar; Forsythe, Elizabeth L.; Pusey, Marc L.

2004-01-01

Interpretation of lysozyme crystal growth rates using well-established physical theories enabled the discovery of a phenomenon possibly indicative of kinetic roughening. For example, lysozyme crystals grown above a critical supersaturation sigma, (where supersaturation sigma = ln c/c(sub eq), c = the protein concentration and c(sub eq) = the solubility concentration) exhibit microscopically rough surfaces due to the continuous addition of growth units anywhere on the surface of a crystal. The rate of crystal growth, V(sub c), for the continuous growth process is determined by the continuous flux of macromolecules onto a unit area of the crystal surface, a, from a distance, xi, per unit time due to diffusion, and a probability of attachment onto the crystal surface, expressed. Based upon models applied, the energetics of lysozyme crystal growth was determined. The magnitudes of the energy barriers of crystal growth for both the (110) and (101) faces of tetragonal lysozyme crystals are compared. Finally, evidence supportive of the kinetic roughening hypothesis is presented.

Solar Storm's Radiation at Martian Orbit and Surface

NASA Image and Video Library

2017-09-29

Energetic particles from a large solar storm in September 2017 were seen both in Mars orbit and on the surface of Mars by NASA missions to the Red Planet. The horizontal axis for both parts of this graphic is the time from Sept. 10 to Sept. 15, 2017. The upper portion of this graphic shows the increase in protons in two ranges of energy levels (15- to-100 million electron volts and 80-to-220 million electron volts), as recorded by the Solar Energetic Particle instrument on NASA's on NASA's Mars Atmosphere and Volatile Evolution orbiter, or MAVEN. The lower portion shows the radiation dose on the Martian surface, in micrograys per day, as measured by the Radiation Assessment Monitor instrument on NASA' Curiosity Mars rover. Micrograys are unit of measurement for absorbed radiation dose. Note that only protons in the higher bracket of energy levels penetrate the atmosphere enough to be detected on the surface. https://photojournal.jpl.nasa.gov/catalog/PIA21856

Structural basis for binding of aurora-AG198N- INCENP complex: MD simulations and free energy calculations.

PubMed

Tanneeru, Karunakar; Guruprasad, Lalitha

2013-11-01

Aurora-A, B and C are non-receptor serine/threonine kinases in Homo sapiens. In spite of high similarity in their sequences, they possess distinct binding partners. These kinases play an important role in cell division and overexpressed in certain cancers. It has been demonstrated that Gly198 in Aurora-A kinase is responsible for its basal kinase activity, the mutation G198N transforms Aurora-A to Aurora-B like function and localization by binding to Inner centromere protein (INCENP). The molecular mechanisms, structural determinants and the binding energetics of the Aurora-A - INCENP complex owing to a single amino acid G198N mutation are not studied. Therefore, we have docked INCENP into human Aurora-A kinase, mutated Gly198 to Asn, Leu and Ala. The wild type and mutant Aurora-A - INCENP complexes were subjected to 40 ns molecular dynamics (MD) simulations. The Asn198 is located in the amphipathic cavity comprising Leu869(IN), Glu868(IN), Thr872(IN), Tyr197(AurA) and Tyr199(AurA) and the interactions mediated via hydrogen bonds are important to stabilize the Aurora-A(G198N) - INCENP complex. The fluctuations in the secondary structural elements and the solvent accessible surface area of all the four complexes during the MD simulations were studied. We calculated the binding free energy upon mutation in the three mutant complexes. The Aurora-A(G198N) - INCENP complex with hydrophilic amino acid mutation has the negative free energy of solvation indicating favorable interactions with INCENP. Our results provide the structural basis and energetics of the human Aurora-A(G198N) - INCENP complex.

Acceleration and Pickup Ring of Energetic Electrons Observed in Relativistic Magnetic Reconnection Simulations

NASA Astrophysics Data System (ADS)

Ping, Y. L.; Zhong, J. Y.; Wang, X. G.; Sheng, Z. M.; Zhao, G.

2017-11-01

Pickup ring of energetic electrons found in relativistic magnetic reconnection (MR) driven by two relativistic intense femtosecond laser pulses is investigated by particle simulation in 3D geometry. Magnetic reconnection processes and configurations are characterized by plasma current density distributions at different axial positions. Two helical structures associated with the circular polarization of laser pulses break down in the reconnection processes to form a current sheet between them, where energetic electrons are found to pile up and the outflow relativistic electron jets are observed. In the field line diffusion region, electrons are accelerated to multi-MeV with a flatter power-law spectrum due to MR. The development of the pickup ring of energetic electrons is strongly dependent upon laser peak intensities.

Quantum-Chemical ab initio Calculations on the Three Isomers of Diborabenzene (C4H4B2)

NASA Astrophysics Data System (ADS)

Singh, Jaswinder; Wang, Yuekui; Raabe, Gerhard

2010-01-01

Quantum-chemical ab initio calculations up to the ZPE+CCSD(T)/aug-cc-pVTZ//MP2/6- 311++G** level were performed on three possible structural isomers of diborabenzene (C4H4B2). All three molecules were found to be local minima on the C4H4B2 energy surface and to have closed shell singlet ground states. While the ground states of the 1,3- and 1,4-isomer are planar and of C2v and D2h symmetry, respectively, 1,2-diborabenzene is non-planar with a C2 axis passing through the center of the BB bond and the middle of the opposite carbon-carbon bond as the only symmetry element. The energetically most favourable 1,3-diborabenzene was found to be about 19 and 36 kcal/mol lower in energy than the 1,2- and the 1,4-isomer. Planar 1,3- and 1,4-diborabenzene have three doubly occupied π orbitals while non-planar 1,2-diborabenzene has also three doubly occupied orbitals which can be derived from the π orbitals of its 3.7 kcal/mol energetically less favourable planar form ("π-like" orbitals). The lowest unoccupied orbitals of all three isomers have σ symmetry with large coefficients at the two boron atoms. These orbitals are lower in energy than the lowest unoccupied molecular orbitals (LUMOs) of e. g. benzene and pyridine and might cause pronounced acceptor properties which could be one of the reasons for the elusiveness of the title compounds. The results of bond separation reactions show that cyclic conjugation stabilizes all three diborabenzenes relative to their isolated fragments. The most effective stabilization energy of about 24 kcal/mol was found for the energetically lowest 1,3-isomer. This value amounts to approximately one third of the experimental value for the bond separation energy of pyridine. In all cases the energetically lowest triplet states are significantly (16 - 24 kcal/mol) higher in energy than the singlet ground states. Also among the triplets the 1,3-isomer is the energetically most fabourable species.

Formation and Migration Energies of Interstitials in Silicon Under Strain Conditions

NASA Technical Reports Server (NTRS)

Halicioglu, Timur; Barnett, David M.

1999-01-01

Simulation calculations are conducted for Si substrates to analyze formation and diffusion energies of interstitials under strain condition using statics methods .based on a Stillinger-Weber type potential function. Defects in the vicinity of the surface region and in the bulk are examined, and the role played by compressive and tensile strains on the energetics of interstitials is investigated. Results indicate that strain alters defect energetics which, in turn, modifies their diffusion characteristics.

Validation of Sampling Protocol and the Promulgation of Method Modifications for the Characterization of Energetic Residues on Military Testing and Training Ranges

DTIC Science & Technology

2009-06-01

Figure 2. Examples of surface vegetation at a firing point (inset) and near the crater of an 81-mm mortar projectile low-order detonation on an artillery... mortar impact range.......................... 7 Figure 3. Fort Richardson and surrounding areas...crater where an 81-mm mortar projectile had low-ordered on an impact range. If vegetation is removed or avoided during sampling, energetic residue

Energetics and Dynamics of Dissociation of Deprotonated Peptides: Fragmentation of Angiotensin Analogs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laskin, Julia; Yang, Zhibo

2011-12-01

We present a first study of the energetics and dynamics of dissociation of deprotonated peptides using time- and collision-energy resolved surface-induced dissociation (SID) experiments. SID of four model peptides: RVYIHPF, HVYIHPF, DRVYIHPF, and DHVYIHPF was studied using a specially designed Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) configured for studying ion-surface collisions. Energy and entropy effects for the overall decomposition of the precursor ion were deduced by modeling the time- and collision energy-resolved survival curves using an RRKM based approach developed in our laboratory. The results were compared to the energetics and dynamics of dissociation of the correspondingmore » protonated species. We demonstrate that acidic peptides are less stable in the negative mode because of the low threshold associated with the kinetically hindered loss of H2O from [M-H]- ions. Comparison between the two basic peptides indicates that the lower stability of the [M-H]- ion of RVYIHPF as compared to HVYIHPF towards fragmentation is attributed to the differences in fragmentation mechanisms. Specifically, threshold energy associated with losses of NH3 and NHCNH from RVYIHPF is lower than the barrier for backbone fragmentation that dominates gas-phase decomposition of HVYIHPF. The results provide a first quantitative comparison between the energetics and dynamics of dissociation of [M+H]+ and [M-H]- ions of acidic and basic peptides.« less

Surface-induced dissociation: a unique tool for studying energetics and kinetics of the gas-phase fragmentation of large ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laskin, Julia

2015-01-01

Surface-induced dissociation (SID) is valuable tool for investigating activation and dissociation of large ions in tandem mass spectrometry. This account summarizes key findings from studies of the energetics and mechanisms of complex ion dissociation, in which SID experiments were combined with Rice-Ramsperger-Kassel-Marcus (RRKM) modeling of the experimental data. These studies used time- and collision-energy-resolved SID experiments and SID combined with resonant ejection of selected fragment ions on a specially designed Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). Fast ion activation by collision with a surface combined with the long and variable timescale of a FT-ICR MS is perfectlymore » suited for studying the energetics and dynamics of complex ion dissociation in the gas phase. Modeling of time- and collision-energy-resolved SID enables accurate determination of energy and entropy effects in the dissociation process. It has been demonstrated that entropy effects play an important role in determining the dissociation rates of both covalent and non-covalent bonds in large gaseous ions. SID studies have provided important insights on the competition between charge-directed and charge-remote fragmentation in even-electron peptide ions and the role of charge and radical site on the energetics of the dissociation of odd-electron peptide ions. Furthermore, this work examined factors that affect the strength of non-covalent binding, as well as the competition between covalent and non-covalent bond cleavages and between proton and electron transfer in model systems. Finally, SID studies have been used to understand the factors affecting nucleation and growth of clusters in solution and the gas phase.« less

Molecular aspects of the Eu3+/Eu2+ redox reaction at the interface between a molten salt and a metallic electrode

NASA Astrophysics Data System (ADS)

Pounds, Michael A.; Salanne, Mathieu; Madden, Paul A.

2015-09-01

We perform molecular dynamics simulations of a system consisting of Eu3+ and Eu2+ species dissolved in a high-temperature KCl electrolyte between two metallic electrodes. The interaction potential includes ion polarisation effects, and a constant electric potential is maintained within the electrodes by allowing the atomic charges to fluctuate in response to the environment. This setup allows us to study the electrochemical Eu3+/Eu2+ reaction in the framework of Marcus theory. Numerous studies have pointed to the highly structured nature of ionic liquids and molten salts close to solid surfaces which is not accounted for in the conventional mean-field description of this interface that underpins the theories of electrochemical reaction rates. Here we examine the influence on the kinetics of the charge-transfer event of the electrical potential across the electrode-electrolyte interface and on the effect of the presence of charged surface on the coordination structure and energetics of the ions in the region important for the charge-transfer event.

Surface acoustic wave nebulization facilitating lipid mass spectrometric analysis.

PubMed

Yoon, Sung Hwan; Huang, Yue; Edgar, J Scott; Ting, Ying S; Heron, Scott R; Kao, Yuchieh; Li, Yanyan; Masselon, Christophe D; Ernst, Robert K; Goodlett, David R

2012-08-07

Surface acoustic wave nebulization (SAWN) is a novel method to transfer nonvolatile analytes directly from the aqueous phase to the gas phase for mass spectrometric analysis. The lower ion energetics of SAWN and its planar nature make it appealing for analytically challenging lipid samples. This challenge is a result of their amphipathic nature, labile nature, and tendency to form aggregates, which readily precipitate clogging capillaries used for electrospray ionization (ESI). Here, we report the use of SAWN to characterize the complex glycolipid, lipid A, which serves as the membrane anchor component of lipopolysaccharide (LPS) and has a pronounced tendency to clog nano-ESI capillaries. We also show that unlike ESI SAWN is capable of ionizing labile phospholipids without fragmentation. Lastly, we compare the ease of use of SAWN to the more conventional infusion-based ESI methods and demonstrate the ability to generate higher order tandem mass spectral data of lipid A for automated structure assignment using our previously reported hierarchical tandem mass spectrometry (HiTMS) algorithm. The ease of generating SAWN-MS(n) data combined with HiTMS interpretation offers the potential for high throughput lipid A structure analysis.

Ab Initio Study of Chemical Reactions of Cold SrF and CaF Molecules with Alkali-Metal and Alkaline-Earth-Metal Atoms: The Implications for Sympathetic Cooling.

PubMed

Kosicki, Maciej Bartosz; Kędziera, Dariusz; Żuchowski, Piotr Szymon

2017-06-01

We investigate the energetics of the atom exchange reaction in the SrF + alkali-metal atom and CaF + alkali-metal atom systems. Such reactions are possible only for collisions of SrF and CaF with the lithium atoms, while they are energetically forbidden for other alkali-metal atoms. Specifically, we focus on SrF interacting with Li, Rb, and Sr atoms and use ab initio methods to demonstrate that the SrF + Li and SrF + Sr reactions are barrierless. We present potential energy surfaces for the interaction of the SrF molecule with the Li, Rb, and Sr atoms in their energetically lowest-lying electronic spin states. The obtained potential energy surfaces are deep and exhibit profound interaction anisotropies. We predict that the collisions of SrF molecules in the rotational or Zeeman excited states most likely have a strong inelastic character. We discuss the prospects for the sympathetic cooling of SrF and CaF molecules using ultracold alkali-metal atoms.

Measuring ionizing radiation in the atmosphere with a new balloon-borne detector

NASA Astrophysics Data System (ADS)

Aplin, K. L.; Briggs, A. A.; Harrison, R. G.; Marlton, G. J.

2017-05-01

Increasing interest in energetic particle effects on weather and climate has motivated development of a miniature scintillator-based detector intended for deployment on meteorological radiosondes or unmanned airborne vehicles. The detector was calibrated with laboratory gamma sources up to 1.3 MeV and known gamma peaks from natural radioactivity of up to 2.6 MeV. The specifications of our device in combination with the performance of similar devices suggest that it will respond to up to 17 MeV gamma rays. Laboratory tests show that the detector can measure muons at the surface, and it is also expected to respond to other ionizing radiation including, for example, protons, electrons (>100 keV), and energetic helium nuclei from cosmic rays or during space weather events. Its estimated counting error is ±10%. Recent tests, when the detector was integrated with a meteorological radiosonde system and carried on a balloon to 25 km altitude, identified the transition region between energetic particles near the surface, which are dominated by terrestrial gamma emissions, to higher-energy particles in the free troposphere.

Formation of curved micrometer-sized single crystals.

PubMed

Koifman Khristosov, Maria; Kabalah-Amitai, Lee; Burghammer, Manfred; Katsman, Alex; Pokroy, Boaz

2014-05-27

Crystals in nature often demonstrate curved morphologies rather than classical faceted surfaces. Inspired by biogenic curved single crystals, we demonstrate that gold single crystals exhibiting curved surfaces can be grown with no need of any fabrication steps. These single crystals grow from the confined volume of a droplet of a eutectic composition melt that forms via the dewetting of nanometric thin films. We can control their curvature by controlling the environment in which the process is carried out, including several parameters, such as the contact angle and the curvature of the drops, by changing the surface tension of the liquid drop during crystal growth. Here we present an energetic model that explains this phenomenon and predicts why and under what conditions crystals will be forced to grow with the curvature of the microdroplet even though the energetic state of a curved single crystal is very high.

Spin-wave resonance frequency in ferromagnetic thin film with interlayer exchange coupling and surface anisotropy

NASA Astrophysics Data System (ADS)

Zhang, Shuhui; Rong, Jianhong; Wang, Huan; Wang, Dong; Zhang, Lei

2018-01-01

We have investigated the dependence of spin-wave resonance(SWR) frequency on the surface anisotropy, the interlayer exchange coupling, the ferromagnetic layer thickness, the mode number and the external magnetic field in a ferromagnetic superlattice film by means of the linear spin-wave approximation and Green's function technique. The SWR frequency of the ferromagnetic thin film is shifted to higher values corresponding to those of above factors, respectively. It is found that the linear behavior of SWR frequency curves of all modes in the system is observed as the external magnetic field is increasing, however, SWR frequency curves are nonlinear with the lower and the higher modes for different surface anisotropy and interlayer exchange coupling in the system. In addition, the SWR frequency of the lowest (highest) mode is shifted to higher (lower) values when the film thickness is thinner. The interlayer exchange coupling is more important for the energetically higher modes than for the energetically lower modes. The surface anisotropy has a little effect on the SWR frequency of the highest mode, when the surface anisotropy field is further increased.

Experimental and Computational Evidence of Highly Active Fe Impurity Sites on the Surface of Oxidized Au for the Electrocatalytic Oxidation of Water in Basic Media

DOE PAGES

Klaus, Shannon; Trotochaud, Lena; Cheng, Mu-Jeng; ...

2015-10-22

Addition of Fe to Ni- and Co-based (oxy)hydroxides has been shown to enhance the activity of these materials for electrochemical oxygen evolution. Here we show that Fe cations bound to the surface of oxidized Au exhibit enhanced oxygen evolution reaction (OER) activity. We find that the OER activity increases with increasing surface concentration of Fe. Density functional theory analysis of the OER energetics reveals that oxygen evolution over Fe cations bound to a hydroxyl-terminated oxidized Au (Fe-Au 2O 3) occurs at an overpotential ~0.3V lower than over hydroxylated Au 2O 3 (0.82V). This finding agrees well with experimental observations andmore » is a consequence of the more optimal binding energetics of OER reaction intermediates at Fe cations bound to the surface of Au 2O 3. These findings suggest that the enhanced OER activity reported recently upon low-potential cycling of Au may be due to surface Fe impurities rather than to "superactive" Au(III) surfaquo species.« less

Excitonic transitions in highly efficient (GaIn)As/Ga(AsSb) type-II quantum-well structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gies, S.; Kruska, C.; Berger, C.

2015-11-02

The excitonic transitions of the type-II (GaIn)As/Ga(AsSb) gain medium of a “W”-laser structure are characterized experimentally by modulation spectroscopy and analyzed using microscopic quantum theory. On the basis of the very good agreement between the measured and calculated photoreflectivity, the type-I or type-II character of the observable excitonic transitions is identified. Whereas the energetically lowest three transitions exhibit type-II character, the subsequent energetically higher transitions possess type-I character with much stronger dipole moments. Despite the type-II character, the quantum-well structure exhibits a bright luminescence.

Surface modification for interaction study with bacteria and preosteoblast cells

NASA Astrophysics Data System (ADS)

Song, Qing

Surface modification plays a pivotal role in bioengineering. Polymer coatings can provide biocompatibility and biofunctionalities to biomaterials through surface modification. In this dissertation, initiated chemical vapor deposition (iCVD) was utilized to coat two-dimensional (2D) and three-dimensional (3D) substrates with differently charged polyelectrolytes in order to generate antimicrobial and osteocompatible biomaterials. ICVD is a modified CVD technique that enables surface modification in an all-dry condition without substrate damage and solvent contamination. The free-radical polymerization allows the vinyl polymers to conformally coat on various micro- and nano-structured substrates and maintains the delicate structure of the functional groups. The vapor deposition of polycations provided antimicrobial activity to planar and porous substrates through destroying the negatively charged bacterial membrane and brought about high contact-killing efficiency (99.99%) against Gram-positive Bacillus subtilis and Gram-negative Escherichia coli. Additionally, the polyampholytes synthesized by iCVD exhibited excellent antifouling performance against the adhesion of Gram-positive Listeria innocua and Gram-negative E. coli in phosphate buffered saline (PBS). Their antifouling activities were attributed to the electrostatic interaction and hydration layers that served as physical and energetic barriers to prevent bacterial adhesion. The contact-killing and antifouling polymers synthesized by iCVD can be applied to surface modification of food processing equipment and medical devices with the aim of reducing foodborne diseases and medical infections. Moreover, the charged polyelectrolyte modified 2D polystyrene surfaces displayed good osteocompatibility and enhanced osteogenesis of preosteoblast cells than the un-modified polystyrene surface. In order to promote osteoinduction of hydroxyapatite (HA) scaffolds, bioinspired polymer-controlled mineralization was conducted on the polyelectrolyte modified HA scaffolds. The mineralized scaffolds stimulated osteogenesis of preosteoblast cells compared with the control HA scaffolds. Therefore, the surface modification through vapor deposition of polyelectrolytes and polymer-controlled mineralization can improve osteoinduction of bone materials. In summary, the iCVD-mediated surface modification is a simple and promising approach to biofunctionalizing various structured substrates and generating antimicrobial and biocompatible biomaterials.

What Does a Multilayer Canopy Model Tell Us About Our Current Understanding of Snow-Canopy Unloading?

NASA Astrophysics Data System (ADS)

McGowan, L. E.; Paw U, K. T.; Dahlke, H. E.

2017-12-01

In the Western U.S., future water resources depend on the forested mountain snowpack. The variations in and estimates of forest mountain snow volume are vital to projecting annual water availability; yet, snow forest processes are not fully known. Most snow models calculate snow-canopy unloading based on time, temperature, Leaf Area Index (LAI), and/or wind speed. While models crudely consider the canopy shape via LAI, current models typically do not consider the vertical canopy structure or varied energetics within multiple canopy layers. Vertical canopy structure influences the spatiotemporal distribution of snow, and therefore ultimately determines the degree and extent by which snow alters both the surface energy balance and water availability. Within the canopy both the snowpack and energetic exposures to the snowpack (wind, shortwave and longwave radiation, turbulent heat fluxes etc.) vary widely in the vertical. The water and energy balance in each layer is dependent on all other layers. For example, increased snow canopy content in the top of the canopy will reduce available shortwave radiation at the bottom and snow unloading in a mid-layer can cascade and remove snow from all the lower layers. We examined vertical interactions and structures of the forest canopy on the impact of unloading utilizing the Advanced Canopy-Atmosphere-Soil-Algorithm (ACASA), a multilayer soil-vegetation-atmosphere numerical model based on higher-order closure of turbulence equations. Our results demonstrate how a multilayer model can be used to elucidate the physical processes of snow unloading, and could help researchers better parameterize unloading in snow-hydrology models.

Dependence of Raman Spectral Intensity on Crystal Size in Organic Nano Energetics.

PubMed

Patel, Rajen B; Stepanov, Victor; Qiu, Hongwei

2016-08-01

Raman spectra for various nitramine energetic compounds were investigated as a function of crystal size at the nanoscale regime. In the case of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20), there was a linear relationship between intensity of Raman spectra and crystal size. Notably, the Raman modes between 120 cm(-1) and 220 cm(-1) were especially affected, and at the smallest crystal size, were completely eliminated. The Raman spectral intensity of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), like that of CL-20's, depended linearly on crystal size. The Raman spectral intensity of 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), however, was not observably changed by crystal size. A non-nitramine explosive compound, 2,4,6-triamino-1,3,5- trinitrobenzene (TATB), was also investigated. Its spectral intensity was also found to correlate linearly with crystal size, although substantially less so than that of HMX and CL-20. To explain the observed trends, it is hypothesized that disordered molecular arrangement, originating from the crystal surface, may be responsible. In particular, it appears that the thickness of the disordered surface layer is dependent on molecular characteristics, including size and conformational flexibility. Furthermore, as the mean crystal size decreases, the volume fraction of disordered molecules within a specimen increases, consequently, weakening the Raman intensity. These results could have practical benefit for allowing the facile monitoring of crystal size during manufacturing. Finally, these findings could lead to deep insights into the general structure of the surface of crystals. © The Author(s) 2016.

Rock Magnetic Fields Shield the Surface of Mars from Harmful Radiation

NASA Astrophysics Data System (ADS)

Alves, E. I.; Baptista, A. R.

2004-03-01

We intend to show that there is a negative correlation between areas of magnetic anomalies and areas of energetic particles bombardment on the surface of Mars, by comparing MGS MAG-ER and Mars Odyssey MARIE maps. Terra Sirenum is the most shielded area.

Energetics and optimum motion of oscillating lifting surfaces of finite span

NASA Technical Reports Server (NTRS)

Ahmadi, A. R.; Widnall, S. E.

1986-01-01

In certain modes of animal propulsion in nature, such as bird flight and fish swimming, the efficiency compared to man-made vehicles is very high. In such cases, wing and tail motions are typically associated with relatively high Reynolds numbers, where viscous effects are confined to a thin boundary layer at the surface and a thin trailing wake. The propulsive forces, which are generated primarily by the inertial forces, can be calculated from potential-flow theory using linearized unsteady-wing theory (for small-amplitude oscillations). In the present study, a recently developed linearized, low-frequency, unsteady lifting-line theory is employed to calculate the (sectional and total) energetic quantities and optimum motion of an oscillating wing of finite span.

Ion spectral structures observed by the Van Allen Probes

NASA Astrophysics Data System (ADS)

Ferradas, C.; Zhang, J.; Spence, H. E.; Kistler, L. M.; Larsen, B.; Reeves, G. D.; Skoug, R. M.; Funsten, H. O.

2015-12-01

During the last decades several missions have recorded the presence of dynamic spectral features of energetic ions in the inner magnetosphere. Previous studies have reported single "nose-like" structures occurring alone and simultaneous nose-like structures (up to three). These ion structures are named after the characteristic shapes of energy bands or gaps in the energy-time spectrograms of in situ measured ion fluxes. They constitute the observational signatures of ion acceleration, transport, and loss in the global magnetosphere. The HOPE mass spectrometer onboard the Van Allen Probes measures energetic hydrogen, helium, and oxygen ions near the inner edge of the plasma sheet, where these ion structures are observed. We present a statistical study of nose-like structures, using 2-years measurements from the HOPE instrument. The results provide important details about the spatial distribution (dependence on geocentric distance), spectral features of the structures (differences among species), and geomagnetic conditions under which these structures occur.

The ODTX System for the Study of Thermal Sensitivity and Thermal Explosion Violence of Energetic Materials

NASA Astrophysics Data System (ADS)

Hsu, Peter; Hust, Gary; Reynolds, John; Springer, Keo; Fried, Larry; Maienschein, Jon

2013-06-01

Incidents caused by fire and combat operations in battlefields can expose energetic materials to unexpected heat that may cause thermal explosion, structural damage and casualty. Some explosives may thermally explode at fairly low temperatures (<100 C) and the violence from thermal explosion may cause a significant damage. Thus it is important to understand the response of energetic materials to thermal insults. The One Dimensional Time to Explosion (ODTX) system at the Lawrence Livermore National Laboratory can measure times to explosion, threshold thermal explosion temperature, and determine kinetic parameters of energetic materials. Samples of different configurations (pressed part, powder, paste, and liquid) can be tested in the system. The ODTX testing can also provide useful data for assessing the thermal explosion violence of energetic materials. In this paper, we will present some recent ODTX experimental data and compare thermal explosion violence of different energetic materials. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Non-interacting surface solvation and dynamics in protein-protein interactions.

PubMed

Visscher, Koen M; Kastritis, Panagiotis L; Bonvin, Alexandre M J J

2015-03-01

Protein-protein interactions control a plethora of cellular processes, including cell proliferation, differentiation, apoptosis, and signal transduction. Understanding how and why proteins interact will inevitably lead to novel structure-based drug design methods, as well as design of de novo binders with preferred interaction properties. At a structural and molecular level, interface and rim regions are not enough to fully account for the energetics of protein-protein binding, even for simple lock-and-key rigid binders. As we have recently shown, properties of the global surface might also play a role in protein-protein interactions. Here, we report on molecular dynamics simulations performed to understand solvent effects on protein-protein surfaces. We compare properties of the interface, rim, and non-interacting surface regions for five different complexes and their free components. Interface and rim residues become, as expected, less mobile upon complexation. However, non-interacting surface appears more flexible in the complex. Fluctuations of polar residues are always lower compared with charged ones, independent of the protein state. Further, stable water molecules are often observed around polar residues, in contrast to charged ones. Our analysis reveals that (a) upon complexation, the non-interacting surface can have a direct entropic compensation for the lower interface and rim entropy and (b) the mobility of the first hydration layer, which is linked to the stability of the protein-protein complex, is influenced by the local chemical properties of the surface. These findings corroborate previous hypotheses on the role of the hydration layer in shielding protein-protein complexes from unintended protein-protein interactions. © 2014 Wiley Periodicals, Inc.

Surface integral analogy approaches for predicting noise from 3D high-lift low-noise wings

NASA Astrophysics Data System (ADS)

Yao, Hua-Dong; Davidson, Lars; Eriksson, Lars-Erik; Peng, Shia-Hui; Grundestam, Olof; Eliasson, Peter E.

2014-06-01

Three surface integral approaches of the acoustic analogies are studied to predict the noise from three conceptual configurations of three-dimensional high-lift low-noise wings. The approaches refer to the Kirchhoff method, the Ffowcs Williams and Hawkings (FW-H) method of the permeable integral surface and the Curle method that is known as a special case of the FW-H method. The first two approaches are used to compute the noise generated by the core flow region where the energetic structures exist. The last approach is adopted to predict the noise specially from the pressure perturbation on the wall. A new way to construct the integral surface that encloses the core region is proposed for the first two methods. Considering the local properties of the flow around the complex object-the actual wing with high-lift devices-the integral surface based on the vorticity is constructed to follow the flow structures. The surface location is discussed for the Kirchhoff method and the FW-H method because a common surface is used for them. The noise from the core flow region is studied on the basis of the dependent integral quantities, which are indicated by the Kirchhoff formulation and by the FW-H formulation. The role of each wall component on noise contribution is analyzed using the Curle formulation. Effects of the volume integral terms of Lighthill's stress tensors on the noise prediction are then evaluated by comparing the results of the Curle method with the other two methods.

An automated parallel crystallisation search for predicted crystal structures and packing motifs of carbamazepine.

PubMed

Florence, Alastair J; Johnston, Andrea; Price, Sarah L; Nowell, Harriott; Kennedy, Alan R; Shankland, Norman

2006-09-01

An automated parallel crystallisation search for physical forms of carbamazepine, covering 66 solvents and five crystallisation protocols, identified three anhydrous polymorphs (forms I-III), one hydrate and eight organic solvates, including the single-crystal structures of three previously unreported solvates (N,N-dimethylformamide (1:1); hemi-furfural; hemi-1,4-dioxane). Correlation of physical form outcome with the crystallisation conditions demonstrated that the solvent adopts a relatively nonspecific role in determining which polymorph is obtained, and that the previously reported effect of a polymer template facilitating the formation of form IV could not be reproduced by solvent crystallisation alone. In the accompanying computational search, approximately half of the energetically feasible predicted crystal structures exhibit the C=O...H--N R2(2)(8)dimer motif that is observed in the known polymorphs, with the most stable correctly corresponding to form III. Most of the other energetically feasible structures, including the global minimum, have a C=O...H--N C(4) chain hydrogen bond motif. No such chain structures were observed in this or any other previously published work, suggesting that kinetic, rather than thermodynamic, factors determine which of the energetically feasible crystal structures are observed experimentally, with the kinetics apparently favouring nucleation of crystal structures based on the CBZ-CBZ R2(2)(8) motif. (c) 2006 Wiley-Liss, Inc. and the American Pharmacists Association.

Benchmarking Inverse Statistical Approaches for Protein Structure and Design with Exactly Solvable Models.

PubMed

Jacquin, Hugo; Gilson, Amy; Shakhnovich, Eugene; Cocco, Simona; Monasson, Rémi

2016-05-01

Inverse statistical approaches to determine protein structure and function from Multiple Sequence Alignments (MSA) are emerging as powerful tools in computational biology. However the underlying assumptions of the relationship between the inferred effective Potts Hamiltonian and real protein structure and energetics remain untested so far. Here we use lattice protein model (LP) to benchmark those inverse statistical approaches. We build MSA of highly stable sequences in target LP structures, and infer the effective pairwise Potts Hamiltonians from those MSA. We find that inferred Potts Hamiltonians reproduce many important aspects of 'true' LP structures and energetics. Careful analysis reveals that effective pairwise couplings in inferred Potts Hamiltonians depend not only on the energetics of the native structure but also on competing folds; in particular, the coupling values reflect both positive design (stabilization of native conformation) and negative design (destabilization of competing folds). In addition to providing detailed structural information, the inferred Potts models used as protein Hamiltonian for design of new sequences are able to generate with high probability completely new sequences with the desired folds, which is not possible using independent-site models. Those are remarkable results as the effective LP Hamiltonians used to generate MSA are not simple pairwise models due to the competition between the folds. Our findings elucidate the reasons for the success of inverse approaches to the modelling of proteins from sequence data, and their limitations.

Direct Quantum Mechanical Simulations of Shocked Energetic Materials

DTIC Science & Technology

2008-12-01

dynamics (QMD) simulations of shocked pentaerythritol tetranitrate (PETN), a conventional high explosive , and the polymeric cubic gauche phase of...nitrogen (cg-N), proposed as an environmentally acceptable energetic alternative to conventional explosive formulations. These simulations, made...stored structural potential energy can be liberated quickly enough, it is possible that explosion can occur with energies several orders of magnitude

Determining the Energetics of the Hydrogen Bond through FTIR: A Hands-On Physical Chemistry Lab Experiment

ERIC Educational Resources Information Center

Guerin, Abby C.; Riley, Kristi; Rupnik, Kresimir; Kuroda, Daniel G.

2016-01-01

Hydrogen bonds are very important chemical structures that are responsible for many unique and important properties of solvents, such as the solvation power of water. These distinctive features are directly related to the stabilization energy conferred by hydrogen bonds to the solvent. Thus, the characterization of hydrogen bond energetics has…

Passivation of surface states of α-Fe2O3(0001) surface by deposition of Ga2O3 overlayers: A density functional theory study.

PubMed

Ulman, Kanchan; Nguyen, Manh-Thuong; Seriani, Nicola; Gebauer, Ralph

2016-03-07

There is a big debate in the community regarding the role of surface states of hematite in the photoelectrochemical water splitting. Experimental studies on non-catalytic overlayers passivating the hematite surface states claim a favorable reduction in the overpotential for the water splitting reaction. As a first step towards understanding the effect of these overlayers, we have studied the system Ga2O3 overlayers on hematite (0001) surfaces using first principles computations in the PBE+U framework. Our computations suggest that stoichiometric terminations of Ga2O3 overlayers are energetically more favored than the bare surface, at ambient oxygen chemical potentials. Energetics suggest that the overlayers prefer to grow via a layer-plus-island (Stranski-Krastanov) growth mode with a critical layer thickness of 1-2 layers. Thus, a complete wetting of the hematite surface by an overlayer of gallium oxide is thermodynamically favored. We establish that the effect of deposition of the Ga2O3 overlayers on the bare hematite surface is to passivate the surface states for the stoichiometric termination. For the oxygen terminated surface which is the most stable termination under photoelectrochemical conditions, the effect of deposition of the Ga2O3 overlayer is to passivate the hole-trapping surface state.

Lattice Transparency of Graphene.

PubMed

Chae, Sieun; Jang, Seunghun; Choi, Won Jin; Kim, Youn Sang; Chang, Hyunju; Lee, Tae Il; Lee, Jeong-O

2017-03-08

Here, we demonstrated the transparency of graphene to the atomic arrangement of a substrate surface, i.e., the "lattice transparency" of graphene, by using hydrothermally grown ZnO nanorods as a model system. The growth behaviors of ZnO nanocrystals on graphene-coated and uncoated substrates with various crystal structures were investigated. The atomic arrangements of the nucleating ZnO nanocrystals exhibited a close match with those of the respective substrates despite the substrates being bound to the other side of the graphene. By using first-principles calculations based on density functional theory, we confirmed the energetic favorability of the nucleating phase following the atomic arrangement of the substrate even with the graphene layer present in between. In addition to transmitting information about the atomic lattice of the substrate, graphene also protected its surface. This dual role enabled the hydrothermal growth of ZnO nanorods on a Cu substrate, which otherwise dissolved in the reaction conditions when graphene was absent.

Thermal anomaly on Mimas surface: Implications on its regolith structure

NASA Astrophysics Data System (ADS)

Ferrari, C.; Lucas, A.

2015-10-01

Thanks to the Cassini CIRS infrared spectrometer,Howett et al. [1] have discovered a large scale thermal anomaly on the surface of Saturn satellite Mimas. This anomaly translates into a dichotomy in thermal inertia between leading and trailing faces of this synchronous icy satellite: the leading face (region R2) exhibits a high thermal inertia,Γ =66 ± 23 J/m 2/K/s 1/2, compared to the trailing one(region R1), where Γ < 16 J/m2/K/s1/2. The pattern appears to be well correlated with a color anomaly (Schenk et al. [2]) in visible light, also observed on other Saturn moons. It maybe due to the alter ation of their leading face by a focused bombardment of highly energetic electrons.This is thought to increase the contact between regolith grains by gluing them, improving thus the thermal conductivity or decrea sing porosity.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Liang; Abild-Pedersen, Frank

On the basis of an extensive set of density functional theory calculations, it is shown that a simple scheme provides a fundamental understanding of variations in the transition state energies and structures of reaction intermediates on transition metal surfaces across the periodic table. The scheme is built on the bond order conservation principle and requires a limited set of input data, still achieving transition state energies as a function of simple descriptors with an error smaller than those of approaches based on linear fits to a set of calculated transition state energies. Here, we have applied this approach together withmore » linear scaling of adsorption energies to obtain the energetics of the NH 3 decomposition reaction on a series of stepped fcc(211) transition metal surfaces. Moreover, this information is used to establish a microkinetic model for the formation of N 2 and H 2, thus providing insight into the components of the reaction that determines the activity.« less

Improving depth resolutions in positron beam spectroscopy by concurrent ion-beam sputtering

NASA Astrophysics Data System (ADS)

John, Marco; Dalla, Ayham; Ibrahim, Alaa M.; Anwand, Wolfgang; Wagner, Andreas; Böttger, Roman; Krause-Rehberg, Reinhard

2018-05-01

The depth resolution of mono-energetic positron annihilation spectroscopy using a positron beam is shown to improve by concurrently removing the sample surface layer during positron beam spectroscopy. During ion-beam sputtering with argon ions, Doppler-broadening spectroscopy is performed with energies ranging from 3 keV to 5 keV allowing for high-resolution defect studies just below the sputtered surface. With this technique, significantly improved depth resolutions could be obtained even at larger depths when compared to standard positron beam experiments which suffer from extended positron implantation profiles at higher positron energies. Our results show that it is possible to investigate layered structures with a thickness of about 4 microns with significantly improved depth resolution. We demonstrated that a purposely generated ion-beam induced defect profile in a silicon sample could be resolved employing the new technique. A depth resolution of less than 100 nm could be reached.

Influence of topographically patterned angled guidelines on directed self-assembly of block copolymers

NASA Astrophysics Data System (ADS)

Rebello, Nathan; Sethuraman, Vaidyanathan; Blachut, Gregory; Ellison, Christopher J.; Willson, C. Grant; Ganesan, Venkat

2017-11-01

Single chain in mean-field Monte Carlo simulations were employed to study the self-assembly of block copolymers (BCP) in thin films that use trapezoidal guidelines to direct the orientation and alignment of lamellar patterns. The present study explored the influence of sidewall interactions and geometry of the trapezoidal guidelines on the self-assembly of perpendicularly oriented lamellar morphologies. When both the sidewall and the top surface exhibit preferential interactions to the same block of the BCP, trapezoidal guidelines with intermediate taper angles were found to result in less defective perpendicularly orientated morphologies. Similarly, when the sidewall and top surface are preferential to distinct blocks of the BCP, intermediate tapering angles were found to be optimal in promoting defect free structures. Such results are rationalized based on the energetics arising in the formation of perpendicularly oriented lamella on patterned substrates.

The vertical growth of MoS2 layers at the initial stage of CVD from first-principles

NASA Astrophysics Data System (ADS)

Xue, Xiong-Xiong; Feng, Yexin; Chen, Keqiu; Zhang, Lixin

2018-04-01

Chemical vapor deposition (CVD) is the highly preferred method for mass production of transition metal dichalcogenide (TMD) layers, yet the atomic-scale knowledge is still lacking about the nucleation and growth. In this study, by using first-principles calculations, we show that, on Au(111) surface, one-dimensional (1D) MoxSy chains are first formed by coalescing of smaller feeding species and are energetically favored at the early stage of nucleation. Two-dimensional (2D) layers can be stabilized only after the number of Mo atoms exceeds ˜12. A vertical growth mode is revealed which accomplishes the structural transformation from the 1D chains to the 2D layers for the clusters while growing. The competition between intralayer and interlayer interactions is the key. These findings serve as new insights for better understanding the atomistic mechanism of the nucleation and growth of TMDs on the surface.

The structure and energetics of midlatitude disturbances accompanying cold-air outbreaks over East Asia

NASA Technical Reports Server (NTRS)

Lau, N.-C.; Lau, K.-M.

1984-01-01

The evolution of extratropical transient waves as they propagate eastward from the Eurasian land mass toward the Pacific during selected cold surge events in the winter Monsoon Experiment (MONEX) is studied. The outstanding cold surge episodes during MONEX are first identified, and the salient synoptic features related to these events are described using composite streamline charts. The structure of rapidly varying disturbances accompanying the cold surges and the associated energetics are examined, and the behavior of those fluctuations over relatively longer time scales is addressed.

Mechanism and energetics of O and O{sub 2} adsorption on polar and non-polar ZnO surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gorai, Prashun; Seebauer, Edmund G.; Ertekin, Elif, E-mail: ertekin@illinois.edu

2016-05-14

Polar surfaces of semiconducting metal oxides can exhibit structures and chemical reactivities that are distinct from their non-polar surfaces. Using first-principles calculations, we examine O adatom and O{sub 2} molecule adsorption on 8 different known ZnO reconstructions including Zn-terminated (Zn–ZnO) and O-terminated (O–ZnO) polar surfaces, and non-polar surfaces. We find that adsorption tendencies are largely governed by the thermodynamic environment, but exhibit variations due to the different surface chemistries of various reconstructions. The Zn–ZnO surface reconstructions which appear under O-rich and H-poor environments are found to be most amenable to O and O{sub 2} adsorption. We attribute this to themore » fact that on Zn–ZnO, the O-rich environments that promote O adsorption also simultaneously favor reconstructions that involve adsorbed O species. On these Zn–ZnO surfaces, O{sub 2} dissociatively adsorbs to form O adatoms. By contrast, on O–ZnO surfaces, the O-rich conditions required for O or O{sub 2} adsorption tend to promote reconstructions involving adsorbed H species, making further O species adsorption more difficult. These insights about O{sub 2} adsorption on ZnO surfaces suggest possible design rules to understand the adsorption properties of semiconductor polar surfaces.« less

Adsorption of Pyridine at the Au(100)-Solution Interface.

DTIC Science & Technology

1987-09-25

quatiatively characterize the energetics of pyridine adsorption onto a gold ( 100) single crystal electrode surface. Over the potential region investigated...0.8 to +0.6 A., three orientationis of the pyridine molecules on the gold surface have been observed. The pyridine orientation Is strongly 1nflue ied by...the electrode potential. At a positively charged surface, the pyridine assumes a verticle orientation with .fie nitrogen atom facing the gold surface

Energetic Salts Based on 3,5-Bis(dinitromethyl)-1,2,4-triazole Monoanion and Dianion: Controllable Preparation, Characterization, and High Performance.

PubMed

Zhang, Jiaheng; Dharavath, Srinivas; Mitchell, Lauren A; Parrish, Damon A; Shreeve, Jean'ne M

2016-06-22

Molecular modification of known explosives is considered to be an efficient route to design new energetic materials. A new family of energetic salts based on the 3,5-bis(dinitromethyl)-1,2,4-triazole monoanion and dianion were controllably synthesized by using 1-diamino-2,2-dinitroethene as a precursor. X-ray structure determination of monohydrazinium 3,5-bis(dinitromethyl)-1,2,4-triazolate (5) and monoammonium (6) and diammonium 3,5-bis(dinitromethyl)-1,2,4-triazolate hydrate (8·H2O) further confirmed the structures of these anions. In addition, as supported by X-ray data, in the monoanion system, the roving proton on the ring nitrogen rather than on the gem-dinitro carbon results in extensive hydrogen-bonding interactions and higher packing coefficients. Interestingly, 5 and 6 possess the highest calculated crystal densities, 1.965 and 1.957 g cm(-3) at 150 K, for hydrazinium and ammonium energetic salts, respectively. Energetic evaluation indicates that 5 (detonation velocity vD = 9086 m s(-1); detonation pressure P = 38.7 GPa) and 6 (vD, 9271 m s(-1); P = 41.0 GPa) exhibit great detonation properties, superior to those of current highly explosive benchmarks, such as 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX).

Theoretical characterization of the potential energy surface for NH + NO

NASA Technical Reports Server (NTRS)

Walch, Stephen P.

1992-01-01

The potential energy surface (PES) for NH + NO was characterized using complete active space self-consistent field (CASSCF) gradient calculations to determine the stationary point geometries and frequencies followed by CASSCF/internally contracted configuration interaction (CCI) calculations to refine the energetics. The present results are in qualitative accord with the BAC-MP4 calculations, but there are differences as large as 8 kcal/mol in the detailed energetics. Addition of NH to NO on a (2)A' surface, which correlated with N2 + OH or H + N2O products, involves barriers of 3.2 kcal/mol (trans) and 6.3 kcal/mol (cis). Experimental evidence for these barriers is found in earlier works. The (2)A' surface has no barrier to addition, but does not correlate with products. Surface crossings between the barrierless (2)A' surface and the (2)A' surface may be important. Production of N2 + OH products is predicted to occur via a planar saddle point of (2)A' symmetry. This is in accord with the preferential formation of II(A') lambda doublet levels of OH in earlier experiments. Addition of NH (1)delta to NO is found to occur on an excited state surface and is predicted to lead to N2O product as observed in earlier works.

Scattering of low-energetic atoms and molecules from a boron-doped CVD diamond surface

NASA Astrophysics Data System (ADS)

Allenbach, M.; Neuland, M. B.; Riedo, A.; Wurz, P.

2018-01-01

For the detection of low energetic neutral atoms for the remote sensing of space plasmas, charge state conversion surfaces are used to ionize the neutrals for their subsequent measurement. We investigated a boron-doped Chemical Vapor Deposition (CVD) diamond sample for its suitability to serve as a conversion surface on future space missions, such as NASA's Interstellar Mapping and Acceleration Probe. For H and O atoms incident on conversion surface with energies ranging from 195 to 1000 eV and impact angles from 6° to 15° we measured the angular scattering distributions and the ionization yields. Atomic force microscope and laser ablation ionization mass spectrometry analyses were applied to further characterize the sample. Based on a figure-of-merit, which included the ionization yield and angular scatter distribution, the B-doped CVD surface was compared to other, previously characterized conversion surfaces, including e.g. an undoped CVD diamond with a metallized backside. For particle energies below 390 eV the performance of the B-doped CVD conversion surfaces is comparable to surfaces studied before. For higher energies the figure-of-merit indicates a superior performance. From our studies we conclude that the B-doped CVD diamond sample is well suited for its application on future space missions.

A quantum mechanical study of water adsorption on the (110) surfaces of rutile SnO₂ and TiO₂: investigating the effects of intermolecular interactions using hybrid-exchange density functional theory.

PubMed

Patel, M; Sanches, F F; Mallia, G; Harrison, N M

2014-10-21

Periodic hybrid-exchange density functional theory calculations are used to explore the first layer of water at model oxide surfaces, which is an important step for understanding the photocatalytic reactions involved in solar water splitting. By comparing the structure and properties of SnO2(110) and TiO2(110) surfaces in contact with water, the effects of structural and electronic differences on the water chemistry are examined. The dissociative adsorption mode at low coverage (1/7 ML) up to monolayer coverage (1 ML) on both SnO2 and TiO2(110) surfaces is analysed. To investigate further the intermolecular interactions between adjacent adsorbates, monolayer adsorption on each surface is explored in terms of binding energies and bond lengths. Analysis of the water adsorption geometry and energetics shows that the relative stability of water adsorption on SnO2(110) is governed largely by the strength of the chemisorption and hydrogen bonds at the surface of the adsorbate-substrate system. However on TiO2(110), a more complicated scenario of the first layer of water on its surface arises in which there is an interplay between chemisorption, hydrogen bonding and adsorbate-induced atomic displacements in the surface. Furthermore the projected density of states of each surface in contact with a mixture of adsorbed water molecules and adsorbed hydroxyls is presented and sheds some light on the nature of the crystalline chemical bonds as well as on why adsorbed water has often been reported to be unstable on rutile SnO2(110).

Flexible energetic materials and related methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heaps, Ronald J.

Energetic compositions and methods of forming components from the compositions are provided. In one embodiment, a composition includes aluminum, molybdenum trioxide, potassium perchlorate, and a binder. In one embodiment, the binder may include a silicone material. The materials may be mixed with a solvent, such as xylene, de-aired, shaped and cured to provide a self-supporting structure. In one embodiment, one or more reinforcement members may be added to provide additional strength to the structure. For example, a weave or mat of carbon fiber material may be added to the mixture prior to curing. In one embodiment, blade casting techniques maymore » be used to form a structure. In another embodiment, a structure may be formed using 3-dimensional printing techniques.« less

Aerial Neutron Detection of Cosmic-Ray Interactions with the Earth's Surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Richard Maurer

2008-09-18

We have demonstrated the ability to measure the neutron flux produced by the cosmic-ray interaction with nuclei in the ground surface using aerial neutron detection. High energy cosmic-rays (primarily muons with GeV energies) interact with the nuclei in the ground surface and produce energetic neutrons via spallation. At the air-surface interface, the neutrons produced by spallation will either scatter within the surface material, become thermalized and reabsorbed, or be emitted into the air. The mean free path of energetic neutrons in air can be hundreds of feet as opposed to a few feet in dense materials. As such, the fluxmore » of neutrons escaping into the air provides a measure of the surface nuclei composition. It has been demonstrated that this effect can be measured at long range using neutron detectors on low flying helicopters. Radiological survey measurements conducted at Government Wash in Las Vegas, Nevada, have shown that the neutron background from the cosmic-soil interactions is repeatable and directly correlated to the geological data. Government Wash has a very unique geology, spanning a wide variety of nuclide mixtures and formations. The results of the preliminary measurements are presented.« less

Structural and energetic processes related to P300: LORETA findings in depression and effects of antidepressant drugs.

PubMed

Anderer, P; Saletu, B; Semlitsch, H V; Pascual-Marqui, R D

2002-01-01

Noninvasive electrophysiological neuroimaging applied to cognitive components of event-related potentials (ERPs) may differentiate between structural and energetic processes related to information processing. The structural level, revealed by the location of the local maxima of the current source density distribution, describes the time-dependent network of activated brain areas. The magnitude of the source strength, a measure of the energetic component, describes the allocation of processing resources. ERPs were recorded in an odd-ball paradigm and low-resolution brain electromagnetic tomography (LORETA) was applied for standard and target ERP components. In a group of 60 menopausal depressed patients of 45-60 years of age, reduced P300 source strength was observed bilaterally, temporally and medially prefrontally reaching to rostal parts of the anterior cingulate, compared with 29 age-matched controls. In a double-blind, placebo-controlled study, 2 mg of the antidepressant citalopram induced a significant increase of P300 source strength in the (left) prefrontal cortex and precuneus compared with placebo, reaching to the posterior cingulate. Similar increases were observed after 800 mg S-adenosyl-L-methionine (SAMe) administered intravenously in ten young healthy subjects aged 22-33, and they were even more pronounced in ten elderly healthy subjects aged 56-71. Thus, ERP-tomography identified changes in energetic sources in brain areas predominantly involved in depression and in antidepressant action.

Effects of energetic coherent motions on the power and wake of an axial-flow turbine

NASA Astrophysics Data System (ADS)

Chamorro, L. P.; Hill, C.; Neary, V. S.; Gunawan, B.; Arndt, R. E. A.; Sotiropoulos, F.

2015-05-01

A laboratory experiment examined the effects of energetic coherent motions on the structure of the wake and power fluctuations generated by a model axial-flow hydrokinetic turbine. The model turbine was placed in an open-channel flow and operated under subcritical conditions. The incoming flow was locally perturbed with vertically oriented cylinders of various diameters. An array of three acoustic Doppler velocimeters aligned in the cross-stream direction and a torque transducer were used to collect high-resolution and synchronous measurements of the three-velocity components of the incoming and wake flow as well as the turbine power. A strong scale-to-scale interaction between the large-scale and broadband turbulence shed by the cylinders and the turbine power revealed how the turbulence structure modulates the turbine behavior. In particular, the response of the turbine to the distinctive von Kármán-type vortices shed from the cylinders highlighted this phenomenon. The mean and fluctuating characteristics of the turbine wake are shown to be very sensitive to the energetic motions present in the flow. Tip vortices were substantially dampened and the near-field mean wake recovery accelerated in the presence of energetic motions in the flow. Strong coherent motions are shown to be more effective than turbulence levels for triggering the break-up of the spiral structure of the tip-vortices.

Surface Segregation in Cu-Ni Alloys

NASA Technical Reports Server (NTRS)

Good, Brian; Bozzolo, Guillermo; Ferrante, John

1993-01-01

Monte Carlo simulation is used to calculate the composition profiles of surface segregation of Cu-Ni alloys. The method of Bozzolo, Ferrante, and Smith is used to compute the energetics of these systems as a function of temperature, crystal face, and bulk concentration. The predictions are compared with other theoretical and experimental results.

Human development I: twenty fundamental problems of biology, medicine, and neuro-psychology related to biological information.

PubMed

Hermansen, Tyge Dahl; Ventegodt, Søren; Rald, Erik; Clausen, Birgitte; Nielsen, Maj Lyck; Merrick, Joav

2006-07-06

In a new series of papers, we address a number of unsolved problems in biology today. First of all, the unsolved enigma concerning how the differentiation from a single zygote to an adult individual happens has been object for severe research for decades. By uncovering a new holistic biological paradigm that introduces an energetic-informational interpretation of reality as a new way to experience biology, these papers will try to solve the problems connected with the events of biological ontogenesis involving a fractal hierarchy, from a single cell to the function of the human brain. The problems discussed are interpreted within the frames of a universe of roomy fractal structures containing energetic patterns that are able to deliver biological information. We think biological organization is guided by energetic changes on the level of quantum mechanics, interacting with the intention that again guides the energetic conformation of the fractal structures to gain disorders or healthiness. Furthermore, we introduce two new concepts: "metamorphous top down" evolution and "adult human metamorphosis". The first is a new evolutionary theory involving metamorphosis as a main concept of evolution. The last is tightly linked to the evolutionary principle and explains how human self-recovery is governed. Other subjects of special interest that we shall look deeper into are the immunological self-nonself discrimination, the structure and function of the human brain, the etiology and salutogenesis of mental and somatic diseases, and the structure of the consciousness of a human being. We shall criticize Szentagothai's model for the modulated structure of the human cerebral cortex and Jerne's theory of the immunological regulatory anti-idiotypic network.

Internal stress induced natural self-chemisorption of ZnO nanostructured films

PubMed Central

Chi, Po-Wei; Su, Chih-Wei; Wei, Da-Hua

2017-01-01

The energetic particles bombardment can produce large internal stress in the zinc oxide (ZnO) thin film, and it can be used to intentionally modify the surface characteristics of ZnO films. In this article, we observed that the internal stress increased from −1.62 GPa to −0.33 GPa, and the naturally wettability of the textured ZnO nanostructured films changed from hydrophobicity to hydrophilicity. According to analysis of surface chemical states, the naturally controllable wetting behavior can be attributed to hydrocarbon adsorbates on the nanostructured film surface, which is caused by tunable internal stress. On the other hand, the interfacial water molecules near the surface of ZnO nanostructured films have been identified as hydrophobic hydrogen structure by Fourier transform infrared/attenuated total reflection. Moreover, a remarkable near-band-edge emission peak shifting also can be observed in PL spectra due to the transition of internal stress state. Furthermore, our present ZnO nanostructured films also exhibited excellent transparency over 80% with a wise surface wetting switched from hydrophobic to hydrophilic states after exposing in ultraviolet (UV) surroundings. Our work demonstrated that the internal stress of the thin film not only induced natural wettability transition of ZnO nanostructured films, but also in turn affected the surface properties such as surface chemisorption. PMID:28233827

Internal stress induced natural self-chemisorption of ZnO nanostructured films

NASA Astrophysics Data System (ADS)

Chi, Po-Wei; Su, Chih-Wei; Wei, Da-Hua

2017-02-01

The energetic particles bombardment can produce large internal stress in the zinc oxide (ZnO) thin film, and it can be used to intentionally modify the surface characteristics of ZnO films. In this article, we observed that the internal stress increased from -1.62 GPa to -0.33 GPa, and the naturally wettability of the textured ZnO nanostructured films changed from hydrophobicity to hydrophilicity. According to analysis of surface chemical states, the naturally controllable wetting behavior can be attributed to hydrocarbon adsorbates on the nanostructured film surface, which is caused by tunable internal stress. On the other hand, the interfacial water molecules near the surface of ZnO nanostructured films have been identified as hydrophobic hydrogen structure by Fourier transform infrared/attenuated total reflection. Moreover, a remarkable near-band-edge emission peak shifting also can be observed in PL spectra due to the transition of internal stress state. Furthermore, our present ZnO nanostructured films also exhibited excellent transparency over 80% with a wise surface wetting switched from hydrophobic to hydrophilic states after exposing in ultraviolet (UV) surroundings. Our work demonstrated that the internal stress of the thin film not only induced natural wettability transition of ZnO nanostructured films, but also in turn affected the surface properties such as surface chemisorption.

Internal stress induced natural self-chemisorption of ZnO nanostructured films.

PubMed

Chi, Po-Wei; Su, Chih-Wei; Wei, Da-Hua

2017-02-24

The energetic particles bombardment can produce large internal stress in the zinc oxide (ZnO) thin film, and it can be used to intentionally modify the surface characteristics of ZnO films. In this article, we observed that the internal stress increased from -1.62 GPa to -0.33 GPa, and the naturally wettability of the textured ZnO nanostructured films changed from hydrophobicity to hydrophilicity. According to analysis of surface chemical states, the naturally controllable wetting behavior can be attributed to hydrocarbon adsorbates on the nanostructured film surface, which is caused by tunable internal stress. On the other hand, the interfacial water molecules near the surface of ZnO nanostructured films have been identified as hydrophobic hydrogen structure by Fourier transform infrared/attenuated total reflection. Moreover, a remarkable near-band-edge emission peak shifting also can be observed in PL spectra due to the transition of internal stress state. Furthermore, our present ZnO nanostructured films also exhibited excellent transparency over 80% with a wise surface wetting switched from hydrophobic to hydrophilic states after exposing in ultraviolet (UV) surroundings. Our work demonstrated that the internal stress of the thin film not only induced natural wettability transition of ZnO nanostructured films, but also in turn affected the surface properties such as surface chemisorption.

Process for preparing energetic materials

DOEpatents

Simpson, Randall L [Livermore, CA; Lee, Ronald S [Livermore, CA; Tillotson, Thomas M [Tracy, CA; Hrubesh, Lawrence W [Pleasanton, CA; Swansiger, Rosalind W [Livermore, CA; Fox, Glenn A [Livermore, CA

2011-12-13

Sol-gel chemistry is used for the preparation of energetic materials (explosives, propellants and pyrotechnics) with improved homogeneity, and/or which can be cast to near-net shape, and/or made into precision molding powders. The sol-gel method is a synthetic chemical process where reactive monomers are mixed into a solution, polymerization occurs leading to a highly cross-linked three dimensional solid network resulting in a gel. The energetic materials can be incorporated during the formation of the solution or during the gel stage of the process. The composition, pore, and primary particle sizes, gel time, surface areas, and density may be tailored and controlled by the solution chemistry. The gel is then dried using supercritical extraction to produce a highly porous low density aerogel or by controlled slow evaporation to produce a xerogel. Applying stress during the extraction phase can result in high density materials. Thus, the sol-gel method can be used for precision detonator explosive manufacturing as well as producing precision explosives, propellants, and pyrotechnics, along with high power composite energetic materials.

Sol-Gel Manufactured Energetic Materials

DOEpatents

Simpson, Randall L.; Lee, Ronald S.; Tillotson, Thomas M.; Hrubesh, Lawrence W.; Swansiger, Rosalind W.; Fox, Glenn A.

2005-05-17

Sol-gel chemistry is used for the preparation of energetic materials (explosives, propellants and pyrotechnics) with improved homogeneity, and/or which can be cast to near-net shape, and/or made into precision molding powders. The sol-gel method is a synthetic chemical process where reactive monomers are mixed into a solution, polymerization occurs leading to a highly cross-linked three dimensional solid network resulting in a gel. The energetic materials can be incorporated during the formation of the solution or during the gel stage of the process. The composition, pore, and primary particle sizes, gel time, surface areas, and density may be tailored and controlled by the solution chemistry. The gel is then dried using supercritical extraction to produce a highly porous low density aerogel or by controlled slow evaporation to produce a xerogel. Applying stress during the extraction phase can result in high density materials. Thus, the sol-gel method can be used for precision detonator explosive manufacturing as well as producing precision explosives, propellants, and pyrotechnics, along with high power composite energetic materials.

Sol-gel manufactured energetic materials

DOEpatents

Simpson, Randall L.; Lee, Ronald S.; Tillotson, Thomas M.; Hrubesh, Lawrence W.; Swansiger, Rosalind W.; Fox, Glenn A.

2003-12-23

Sol-gel chemistry is used for the preparation of energetic materials (explosives, propellants and pyrotechnics) with improved homogeneity, and/or which can be cast to near-net shape, and/or made into precision molding powders. The sol-gel method is a synthetic chemical process where reactive monomers are mixed into a solution, polymerization occurs leading to a highly cross-linked three dimensional solid network resulting in a gel. The energetic materials can be incorporated during the formation of the solution or during the gel stage of the process. The composition, pore, and primary particle sizes, gel time, surface areas, and density may be tailored and controlled by the solution chemistry. The gel is then dried using supercritical extraction to produce a highly porous low density aerogel or by controlled slow evaporation to produce a xerogel. Applying stress during the extraction phase can result in high density materials. Thus, the sol-gel method can be used for precision detonator explosive manufacturing as well as producing precision explosives, propellants, and pyrotechnics, along with high power composite energetic materials.

Molecular modelling study of changes induced by netropsin binding to nucleosome core particles.

PubMed Central

Pérez, J J; Portugal, J

1990-01-01

It is well known that certain sequence-dependent modulators in structure appear to determine the rotational positioning of DNA on the nucleosome core particle. That preference is rather weak and could be modified by some ligands as netropsin, a minor-groove binding antibiotic. We have undertaken a molecular modelling approach to calculate the relative energy of interaction between a DNA molecule and the protein core particle. The histones particle is considered as a distribution of positive charges on the protein surface that interacts with the DNA molecule. The molecular electrostatic potentials for the DNA, simulated as a discontinuous cylinder, were calculated using the values for all the base pairs. Computing these parameters, we calculated the relative energy of interaction and the more stable rotational setting of DNA. The binding of four molecules of netropsin to this model showed that a new minimum of energy is obtained when the DNA turns toward the protein surface by about 180 degrees, so a new energetically favoured structure appears where netropsin binding sites are located facing toward the histones surface. The effect of netropsin could be explained in terms of an induced change in the phasing of DNA on the core particle. The induced rotation is considered to optimize non-bonded contacts between the netropsin molecules and the DNA backbone. PMID:2165249

Interaction of atmospheric pressure plasmas with dry and wet wounded skin

NASA Astrophysics Data System (ADS)

Babaeva, Natalia; Kushner, Mark

2010-11-01

Non-equilibrium plasmas in direct contact with living tissue can produce therapeutic effects. Dielectric barrier discharge (DBD) devices used for this purpose contain the powered electrode while the tissue being treated is usually the floating electrode. The plasma produces beneficial effects through: (i) electric fields, (ii) production of radicals and charged species, (iii) photons and (iv) energetic ions impinging onto wounds and tissue surfaces. Using a 2-d plasma hydrodynamics model, we discuss the interaction of DBD filaments with human skin. We model the propagation of the streamer across the gap, its intersection with skin, the charging of cell surfaces and the generation of conduction and displacement currents, and electric fields in the cells. The cellular structure in the first few mm of human skin is incorporated into the computational mesh with permittivity and conductivity to represent the electrical properties of the intra- and inter-cell structures. In this talk, we concentrate on the effects of plasmas on open wounds which are either dry or filled with blood serum. We will discuss the penetration of electric fields through the blood serum and into the underlying cells, including the possible interactions with blood platelets, and the distribution of ion energies onto the liquid and cellular surfaces.

Structure and energetics of extended defects in ice Ih

NASA Astrophysics Data System (ADS)

Silva Junior, Domingos L.; de Koning, Maurice

2012-01-01

We consider the molecular structure and energetics of extended defects in proton-disordered hexagonal ice Ih. Using plane-wave density functional theory (DFT) calculations, we compute the energetics of stacking faults and determine the structure of the 30∘ and 90∘ partial dislocations on the basal plane. Consistent with experimental data, the formation energies of all fully reconstructed stacking faults are found to be very low. This is consistent with the idea that basal-plane glide dislocations in ice Ih are dissociated into partial dislocations separated by an area of stacking fault. For both types of partial dislocation we find a strong tendency toward core reconstruction through pairwise hydrogen-bond reformation. In the case of the 30∘ dislocation, the pairwise hydrogen-bond formation leads to a period-doubling core structure equivalent to that seen in zinc-blende semiconductor crystals. For the 90∘ partial we consider two possible core reconstructions, one in which the periodicity of the structure along the core remains unaltered and another in which it is doubled. The latter is preferred, although the energy difference between both is rather small, so that a coexistence of both reconstructions appears plausible. Our results imply that a mobility theory for dislocations on the basal plane in ice Ih should be based on the idea of reconstructed partial dislocations.

Energetics and structural properties of twist grain boundaries in Cu

NASA Technical Reports Server (NTRS)

Karimi, Majid

1992-01-01

Structural and energetics properties of atoms near a grain boundary are of great importance from theoretical and experimental standpoints. From various experimental work it is concluded that diffusion at low temperatures at polycrystalline materials take place near grain boundary. Experimental and theoretical results also indicate changes of up to 70 percent in physical properties near a grain boundary. The Embedded Atom Method (EAM) calculations on structural properties of Au twist grain boundaries are in quite good agreement with their experimental counterparts. The EAM is believed to predict reliable values for the single vacancy formation energy as well as migration energy. However, it is not clear whether the EAM functions which are fitted to the bulk properties of a perfect crystalline solid can produce reliable results on grain boundaries. One of the objectives of this work is to construct the EAM functions for Cu and use them in conjunction with the molecular static simulation to study structures and energetics of atoms near twist grain boundaries in Cu. This provides tests of the EAM functions near a grain boundary. In particular, we determine structure, single vacancy formation energy, migration energy, single vacancy activation energy, and interlayer spacing as a function of distance from grain boundary. Our results are compared with the available experimental and theoretical results from grain boundaries and bulk.

Structural characteristics of liquid nitromethane at the nanoscale confinement in carbon nanotubes.

PubMed

Liu, Yingzhe; Lai, Weipeng; Yu, Tao; Ge, Zhongxue; Kang, Ying

2014-10-01

The stability of energetic materials confined in the carbon nanotubes can be improved at ambient pressure and room temperature, leading to potential energy storage and controlled energy release. However, the microscopic structure of confined energetic materials and the role played by the confinement size are still fragmentary. In this study, molecular dynamics simulations have been performed to explore the structural characteristics of liquid nitromethane (NM), one of the simplest energetic materials, confined in a series of armchair single-walled carbon nanotubes (SWNTs) changing from (5,5) to (16,16) at ambient conditions. The simulation results show that the size-dependent ordered structures of NM with preferred orientations are formed inside the tubular cavities driven by the van der Waals attractions between NM and SWNT together with the dipole-dipole interactions of NM, giving rise to a higher local mass density than that of bulk NM. The NM dipoles prefer to align parallel along the SWNT axis in an end-to-end fashion inside all the nanotubes except the (7,7) SWNT where a unique staggered orientation of NM dipoles perpendicular to the SWNT axis is observed. As the SWNT radius increases, the structural arrangements and dipole orientations of NM become disordered as a result of the weakening of van der Waals interactions between NM and SWNT.