A new near-linear scaling, efficient and accurate, open-shell domain-based local pair natural orbital coupled cluster singles and doubles theory

NASA Astrophysics Data System (ADS)

Saitow, Masaaki; Becker, Ute; Riplinger, Christoph; Valeev, Edward F.; Neese, Frank

2017-04-01

The Coupled-Cluster expansion, truncated after single and double excitations (CCSD), provides accurate and reliable molecular electronic wave functions and energies for many molecular systems around their equilibrium geometries. However, the high computational cost, which is well-known to scale as O(N6) with system size N, has limited its practical application to small systems consisting of not more than approximately 20-30 atoms. To overcome these limitations, low-order scaling approximations to CCSD have been intensively investigated over the past few years. In our previous work, we have shown that by combining the pair natural orbital (PNO) approach and the concept of orbital domains it is possible to achieve fully linear scaling CC implementations (DLPNO-CCSD and DLPNO-CCSD(T)) that recover around 99.9% of the total correlation energy [C. Riplinger et al., J. Chem. Phys. 144, 024109 (2016)]. The production level implementations of the DLPNO-CCSD and DLPNO-CCSD(T) methods were shown to be applicable to realistic systems composed of a few hundred atoms in a routine, black-box fashion on relatively modest hardware. In 2011, a reduced-scaling CCSD approach for high-spin open-shell unrestricted Hartree-Fock reference wave functions was proposed (UHF-LPNO-CCSD) [A. Hansen et al., J. Chem. Phys. 135, 214102 (2011)]. After a few years of experience with this method, a few shortcomings of UHF-LPNO-CCSD were noticed that required a redesign of the method, which is the subject of this paper. To this end, we employ the high-spin open-shell variant of the N-electron valence perturbation theory formalism to define the initial guess wave function, and consequently also the open-shell PNOs. The new PNO ansatz properly converges to the closed-shell limit since all truncations and approximations have been made in strict analogy to the closed-shell case. Furthermore, given the fact that the formalism uses a single set of orbitals, only a single PNO integral transformation is necessary, which offers large computational savings. We show that, with the default PNO truncation parameters, approximately 99.9% of the total CCSD correlation energy is recovered for open-shell species, which is comparable to the performance of the method for closed-shells. UHF-DLPNO-CCSD shows a linear scaling behavior for closed-shell systems, while linear to quadratic scaling is obtained for open-shell systems. The largest systems we have considered contain more than 500 atoms and feature more than 10 000 basis functions with a triple-ζ quality basis set.

IMPACT OF NEW GAMOW–TELLER STRENGTHS ON EXPLOSIVE TYPE IA SUPERNOVA NUCLEOSYNTHESIS

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

Mori, Kanji; Famiano, Michael A.; Kajino, Toshitaka

2016-12-20

Recent experimental results have confirmed a possible reduction in the Gamow–Teller (GT{sub +}) strengths of pf-shell nuclei. These proton-rich nuclei are of relevance in the deflagration and explosive burning phases of SNe Ia. While prior GT strengths result in nucleosynthesis predictions with a lower-than-expected electron fraction, a reduction in the GT{sub +} strength can result in a slightly increased electron fraction compared to previous shell model predictions, though the enhancement is not as large as previous enhancements in going from rates computed by Fuller, Fowler, and Newman based on an independent particle model. A shell model parametrization has been developed thatmore » more closely matches experimental GT strengths. The resultant electron-capture rates are used in nucleosynthesis calculations for carbon deflagration and explosion phases of SNe Ia, and the final mass fractions are compared to those obtained using more commonly used rates.« less

Impact of New Gamow-Teller Strengths on Explosive Type Ia Supernova Nucleosynthesis

NASA Astrophysics Data System (ADS)

Mori, Kanji; Famiano, Michael A.; Kajino, Toshitaka; Suzuki, Toshio; Hidaka, Jun; Honma, Michio; Iwamoto, Koichi; Nomoto, Ken'ichi; Otsuka, Takaharu

2016-12-01

Recent experimental results have confirmed a possible reduction in the Gamow-Teller (GT+) strengths of pf-shell nuclei. These proton-rich nuclei are of relevance in the deflagration and explosive burning phases of SNe Ia. While prior GT strengths result in nucleosynthesis predictions with a lower-than-expected electron fraction, a reduction in the GT+ strength can result in a slightly increased electron fraction compared to previous shell model predictions, though the enhancement is not as large as previous enhancements in going from rates computed by Fuller, Fowler, and Newman based on an independent particle model. A shell model parametrization has been developed that more closely matches experimental GT strengths. The resultant electron-capture rates are used in nucleosynthesis calculations for carbon deflagration and explosion phases of SNe Ia, and the final mass fractions are compared to those obtained using more commonly used rates.

Second-Order Moller-Plesset Perturbation Theory for Molecular Dirac-Hartree-Fock Wave Functions

NASA Technical Reports Server (NTRS)

Dyall, Kenneth G.; Arnold, James O. (Technical Monitor)

1994-01-01

Moller-Plesset perturbation theory is developed to second order for a selection of Kramers restricted Dirac-Hartree-Fock closed and open-shell reference wave functions. The open-shell wave functions considered are limited to those with no more than two electrons in open shells, but include the case of a two-configuration SCF reference. Denominator shifts are included in the style of Davidson's OPT2 method. An implementation which uses unordered integrals with labels is presented, and results are given for a few test cases.

The equation-of-motion coupled cluster method for triple electron attached states

NASA Astrophysics Data System (ADS)

Musiał, Monika; Olszówka, Marta; Lyakh, Dmitry I.; Bartlett, Rodney J.

2012-11-01

The initial implementation of the triple electron attachment (TEA) equation-of-motion (EOM) coupled cluster (CC) method is presented, aiming at the description of electronic states with three open shell electrons outside a suitably chosen closed shell vacuum. In particular, such an approach can be used for describing dissociation of chemical bonds predominantly formed by three valence electrons, for example, in LiC and NaC molecules. Both ground and excited states are considered while rigorously maintaining the correct spin value. The preliminary results show a correct asymptotic behavior of the dissociation curves. At the same time, we emphasize that a chemically accurate description will require an extension of the minimal TEA-EOM-CC model introduced here, analogous to those already used in the double ionization potential and double electron attachment methods.

Experimental analysis and numerical modeling of mollusk shells as a three dimensional integrated volume.

PubMed

Faghih Shojaei, M; Mohammadi, V; Rajabi, H; Darvizeh, A

2012-12-01

In this paper, a new numerical technique is presented to accurately model the geometrical and mechanical features of mollusk shells as a three dimensional (3D) integrated volume. For this purpose, the Newton method is used to solve the nonlinear equations of shell surfaces. The points of intersection on the shell surface are identified and the extra interior parts are removed. Meshing process is accomplished with respect to the coordinate of each point of intersection. The final 3D generated mesh models perfectly describe the spatial configuration of the mollusk shells. Moreover, the computational model perfectly matches with the actual interior geometry of the shells as well as their exterior architecture. The direct generation technique is employed to generate a 3D finite element (FE) model in ANSYS 11. X-ray images are taken to show the close similarity of the interior geometry of the models and the actual samples. A scanning electron microscope (SEM) is used to provide information on the microstructure of the shells. In addition, a set of compression tests were performed on gastropod shell specimens to obtain their ultimate compressive strength. A close agreement between experimental data and the relevant numerical results is demonstrated. Copyright © 2012 Elsevier Ltd. All rights reserved.

The unrestricted local properties: application in nanoelectronics and for predicting radicals reactivity.

PubMed

Dral, Pavlo O

2014-03-01

The local electron affinity (EA(L)) and the local ionization energy (IE(L)) are successfully used for predicting properties of closed-shell species for drug design and for nanoelectronics. Here the respective unrestricted Hartree-Fock variants of EA(L) and IE(L), i.e., the unrestricted local electron affinity (UHF-EA(L)) and ionization energy (UHF-IE(L)), have been shown to be useful for predicting properties of open-shell species. UHF-EA(L) and UHF-IE(L) have been applied for explaining unique electronic properties of an exemplary nanomaterial carbon peapod. It is also demonstrated that UHF-EA(L) is useful for predicting and better understanding reactivity of radicals related to alkanes activation.

Measurements of the K -Shell Opacity of a Solid-Density Magnesium Plasma Heated by an X-Ray Free-Electron Laser

DOE PAGES

Preston, T. R.; Vinko, S. M.; Ciricosta, O.; ...

2017-08-25

We present measurements of the spectrally resolved x rays emitted from solid-density magnesium targets of varying sub-μm thicknesses isochorically heated by an x-ray laser. The data exhibit a largely thickness independent source function, allowing the extraction of a measure of the opacity to K-shell x rays within well-defined regimes of electron density and temperature, extremely close to local thermodynamic equilibrium conditions. The deduced opacities at the peak of the Kα transitions of the ions are consistent with those predicted by detailed atomic-kinetics calculations.

Investigation of magnetic and magneto-transport properties of ferromagnetic-charge ordered core-shell nanostructures

NASA Astrophysics Data System (ADS)

Das, Kalipada

2017-10-01

In our present study, we address in detail the magnetic and magneto-transport properties of ferromagnetic-charge ordered core-shell nanostructures. In these core-shell nanostructures, well-known half metallic La0.67Sr0.33MnO3 nanoparticles (average particle size, ˜20 nm) are wrapped by the charge ordered antiferromagnetic Pr0.67Ca0.33MnO3 (PCMO) matrix. The intrinsic properties of PCMO markedly modify it into such a core-shell form. The robustness of the PCMO matrix becomes fragile and melts at an external magnetic field (H) of ˜20 kOe. The analysis of magneto-transport data indicates the systematic reduction of the electron-electron and electron-magnon interactions in the presence of an external magnetic field in these nanostructures. The pronounced training effect appears in this phase separated compound, which was analyzed by considering the second order tunneling through the grain boundaries of the nanostructures. Additionally, the analysis of low field magnetoconductance data supports the second order tunneling and shows the close value of the universal limit (˜1.33).

Mn@Si14+: a singlet fullerene-like endohedrally doped silicon cluster.

PubMed

Ngan, Vu Thi; Pierloot, Kristine; Nguyen, Minh Tho

2013-04-21

The electronic structure of Mn@Si14(+) is determined using DFT and CASPT2/CASSCF(14,15) computations with large basis sets. The endohedrally Mn-doped Si cationic cluster has a D3h fullerene-like structure featuring a closed-shell singlet ground state with a singlet-triplet gap of ~1 eV. A strong stabilizing interaction occurs between the 3d(Mn) and the 2D-shell(Si14) orbitals, and a large amount of charge is transferred from the Si14 cage to the Mn dopant. The 3d(Mn) orbitals are filled by encapsulation, and the magnetic moment of Mn is completely quenched. Full occupation of [2S, 2P, 2D] shell orbitals by 18 delocalized electrons confers the doped Mn@Si14(+) cluster a spherically aromatic character.

Dependence of weak interaction rates on the nuclear composition during stellar core collapse

NASA Astrophysics Data System (ADS)

Furusawa, Shun; Nagakura, Hiroki; Sumiyoshi, Kohsuke; Kato, Chinami; Yamada, Shoichi

2017-02-01

We investigate the influences of the nuclear composition on the weak interaction rates of heavy nuclei during the core collapse of massive stars. The nuclear abundances in nuclear statistical equilibrium (NSE) are calculated by some equation of state (EOS) models including in-medium effects on nuclear masses. We systematically examine the sensitivities of electron capture and neutrino-nucleus scattering on heavy nuclei to the nuclear shell effects and the single-nucleus approximation. We find that the washout of the shell effect at high temperatures brings significant change to weak rates by smoothing the nuclear abundance distribution: the electron capture rate decreases by ˜20 % in the early phase and increases by ˜40 % in the late phase at most, while the cross section for neutrino-nucleus scattering is reduced by ˜15 % . This is because the open-shell nuclei become abundant instead of those with closed neutron shells as the shell effects disappear. We also find that the single-nucleus description based on the average values leads to underestimations of weak rates. Electron captures and neutrino coherent scattering on heavy nuclei are reduced by ˜80 % in the early phase and by ˜5 % in the late phase, respectively. These results indicate that NSE like EOS accounting for shell washout is indispensable for the reliable estimation of weak interaction rates in simulations of core-collapse supernovae.

Bis(aminoaryl) Carbon-Bridged Oligo(phenylenevinylene)s Expand the Limits of Electronic Couplings.

PubMed

Burrezo, Paula Mayorga; Lin, Nai-Ti; Nakabayashi, Koji; Ohkoshi, Shin-Ichi; Calzado, Eva M; Boj, Pedro G; Díaz García, María A; Franco, Carlos; Rovira, Concepciò; Veciana, Jaume; Moos, Michael; Lambert, Christoph; López Navarrete, Juan T; Tsuji, Hayato; Nakamura, Eiichi; Casado, Juan

2017-03-06

Carbon-bridged bis(aminoaryl) oligo(para-phenylenevinylene)s have been prepared and their optical, electrochemical, and structural properties analyzed. Their radical cations are class III and class II mixed-valence systems, depending on the molecular size, and they show electronic couplings which are among the largest for the self-exchange reaction of purely organic molecules. In their dication states, the antiferromagnetic coupling is progressively tuned with size from quinoidal closed-shell to open-shell biradicals. The data prove that the electronic coupling in the radical cations and the singlet-triplet gap in the dications show similar small attenuation factors, thus allowing charge/spin transfer over rather large distances. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation and recognition of surface molecularly imprinted core-shell microbeads for protein in aqueous solutions

NASA Astrophysics Data System (ADS)

Lu, Yan; Yan, Chang-Ling; Gao, Shu-Yan

2009-04-01

In this paper, a surface molecular imprinting technique was reported for preparing core-shell microbeads of protein imprinting, and bovine hemoglobin or bovine serum albumin were used as model proteins for studying the imprinted core-shell microbeads. 3-Aminophenylboronic acid (APBA) was polymerized onto the surface of polystyrene microbead in the presence of the protein templates to create protein-imprinted core-shell microbeads. The various samples were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and Brunauer-Emmett-Teller (BET) methods. The effect of pH on rebinding of the template hemoglobin, the specific binding and selective recognition were studied for the imprinted microbeads. The results show that the bovine hemoglobin-imprinted core-shell microbeads were successfully created. The shell was a sort of imprinted thin films with porous structure and larger surface areas. The imprinted microbeads have good selectivity for templates and high stability. Due to the recognition sites locating at or closing to the surface, these imprinted microbeads have good property of mass-transport. Unfortunately, the imprint technology was not successfully applied to imprinting bovine serum albumin (BSA).

The generator coordinate Dirac-Fock method for open-shell atomic systems

NASA Astrophysics Data System (ADS)

Malli, Gulzari L.; Ishikawa, Yasuyuki

1998-11-01

Recently we developed generator coordinate Dirac-Fock and Dirac-Fock-Breit methods for closed-shell systems assuming finite nucleus and have reported Dirac-Fock and Dirac-Fock-Breit energies for the atoms He through Nobelium (Z=102) [see Refs. Reference 10Reference 11Reference 12Reference 13]. In this paper, we generalize our earlier work on closed-shell systems and develop a generator coordinate Dirac-Fock method for open-shell systems. We present results for a number of representative open-shell heavy atoms (with nuclear charge Z>80) including the actinide and superheavy transactinide (with Z>103) atomic systems: Fr (Z=87), Ac (Z=89), and Lr (Z=103) to E113 (eka-thallium, Z=113). The high accuracy obtained in our open-shell Dirac-Fock calculations is similar to that of our closed-shell calculations, and we attribute it to the fact that the representation of the relativistic dynamics of an electron in a spherical ball finite nucleus near the origin in terms of our universal Gaussian basis set is as accurate as that provided by the numerical finite difference method. The DF SCF energies calculated by Desclaux [At. Data. Nucl. Data Tables 12, 311 (1973)] (apart from a typographic error for Fr pointed out here) are higher than those reported here for atoms of some of the superheavy transactinide elements by as much as 5 hartrees (136 eV). We believe that this is due to the use by Desclaux of much larger atomic masses than the currently accepted values for these elements.

Closed-Shell Polycyclic Aromatic Hydrocarbon Cations: A New Category of Interstellar Polycyclic Aromatic Hydrocarbons

NASA Technical Reports Server (NTRS)

Hudgins, Douglas M.; Bauschlicher, Charles W., Jr.; Allamandola, Louis J.; DeVincenzi, Donald (Technical Monitor)

2001-01-01

Density functional theory has been employed to calculate the harmonic frequencies and intensities of a range of polycyclic aromatic hydrocarbon (PAH) cations that explore both size and electronic structure effects of the infrared spectroscopic properties of these species. The sample extends the size range of PAH species considered to more than 50 carbon atoms and includes several representatives from each of two heretofore unexplored categories of PAH cations: (1) fully benzenoid PAH cations whose carbon skeleton is composed of an odd number of carbon atoms (C(sub odd) PAHs); and (2) protonated PAH cations (HPAH+). Unlike the radical electronic structures of the PAH cations that have been the subject of previous theoretical and experimental work, the species in these two classes have a closed-shell electronic configuration. The calculated spectra of circumcoronene, C54H18 in both neutral and (radical) cationic form are also reported and compared with those of the other species. Overall, the C(sub odd) PAHs spectra are dominated by strong CC stretching modes near 1600 cm(exp -1) and display spectra that are remarkably insensitive to molecular size. The HPAH+ species evince a more complex spectrum consistent with the added contributions of aliphatic modes and their generally lower symmetry. Finally, for both classes of closed-shell cations, the intensity of the aromatic CH stretching modes is found to increase with molecular size far out of proportion with the number of CH groups, approaching a value more typical of neutral PAHs for the largest species studied.

Efficient geometry optimization by Hellmann-Feynman forces with the anti-Hermitian contracted Schrödinger equation

NASA Astrophysics Data System (ADS)

Foley, Jonathan J.; Mazziotti, David A.

2010-10-01

An efficient method for geometry optimization based on solving the anti-Hermitian contracted Schrödinger equation (ACSE) is presented. We formulate a reduced version of the Hellmann-Feynman theorem (HFT) in terms of the two-electron reduced Hamiltonian operator and the two-electron reduced density matrix (2-RDM). The HFT offers a considerable reduction in computational cost over methods which rely on numerical derivatives. While previous geometry optimizations with numerical gradients required 2M evaluations of the ACSE where M is the number of nuclear degrees of freedom, the HFT requires only a single ACSE calculation of the 2-RDM per gradient. Synthesizing geometry optimization techniques with recent extensions of the ACSE theory to arbitrary electronic and spin states provides an important suite of tools for accurately determining equilibrium and transition-state structures of ground- and excited-state molecules in closed- and open-shell configurations. The ability of the ACSE to balance single- and multi-reference correlation is particularly advantageous in the determination of excited-state geometries where the electronic configurations differ greatly from the ground-state reference. Applications are made to closed-shell molecules N2, CO, H2O, the open-shell molecules B2 and CH, and the excited state molecules N2, B2, and BH. We also study the HCN ↔ HNC isomerization and the geometry optimization of hydroxyurea, a molecule which has a significant role in the treatment of sickle-cell anaemia.

On the Highest Oxidation States of Metal Elements in MO4 Molecules (M = Fe, Ru, Os, Hs, Sm, and Pu).

PubMed

Huang, Wei; Xu, Wen-Hua; Schwarz, W H E; Li, Jun

2016-05-02

Metal tetraoxygen molecules (MO4, M = Fe, Ru, Os, Hs, Sm, Pu) of all metal atoms M with eight valence electrons are theoretically studied using density functional and correlated wave function approaches. The heavier d-block elements Ru, Os, Hs are confirmed to form stable tetraoxides of Td symmetry in (1)A1 electronic states with empty metal d(0) valence shell and closed-shell O(2-) ligands, while the 3d-, 4f-, and 5f-elements Fe, Sm, and Pu prefer partial occupation of their valence shells and peroxide or superoxide ligands at lower symmetry structures with various spin couplings. The different geometric and electronic structures and chemical bonding types of the six iso-stoichiometric species are explained in terms of atomic orbital energies and orbital radii. The variations found here contribute to our general understanding of the periodic trends of oxidation states across the periodic table.

Nanoclusters as a new family of high temperature superconductors (Conference Presentation)

NASA Astrophysics Data System (ADS)

Halder, Avik; Kresin, Vitaly V.

2017-03-01

Electrons in metal clusters organize into quantum shells, akin to atomic shells in the periodic table. Such nanoparticles are referred to as "superatoms". The electronic shell levels are highly degenerate giving rise to sharp peaks in the density of states, which can enable exceptionally strong electron pairing in certain clusters containing tens to hundreds of atoms. A spectroscopic investigation of size - resolved aluminum nanoclusters has revealed a sharp rise in the density of states near the Fermi level as the temperature decreases towards 100 K. The effect is especially prominent in the closed-shell "magic" cluster Al66 [1, 2]. The characteristics of this behavior are fully consistent with a pairing transition, implying a high temperature superconducting state with Tc < 100K. This value exceeds that of bulk aluminum by two orders of magnitude. As a new class of high-temperature superconductors, such metal nanocluster particles are promising building blocks for high-Tc materials, devices, and networks. ---------- 1. Halder, A., Liang, A., Kresin, V. V. A novel feature in aluminum cluster photoionization spectra and possibility of electron pairing at T 100K. Nano Lett 15, 1410 - 1413 (2015) 2. Halder, A., Kresin, V. V. A transition in the density of states of metal "superatom" nanoclusters and evidence for superconducting pairing at T 100K. Phys. Rev. B 92, 214506 (2015).

Tuning the Rectification Ratio by Changing the Electronic Nature (Open-Shell and Closed-Shell) in Donor-Acceptor Self-Assembled Monolayers.

PubMed

Souto, Manuel; Yuan, Li; Morales, Dayana C; Jiang, Li; Ratera, Imma; Nijhuis, Christian A; Veciana, Jaume

2017-03-29

This Communication describes the mechanism of charge transport across self-assembled monolayers (SAMs) of two donor-acceptor systems consisting of a polychlorotriphenylmethyl (PTM) electron-acceptor moiety linked to an electron-donor ferrocene (Fc) unit supported by ultraflat template-stripped Au and contacted by a eutectic alloy of gallium and indium top contacts. The electronic and supramolecular structures of these SAMs were well characterized. The PTM unit can be switched between the nonradical and radical forms, which influences the rectification behavior of the junction. Junctions with nonradical units rectify currents via the highest occupied molecular orbital (HOMO) with a rectification ratio R = 99, but junctions with radical units have a new accessible state, a single-unoccupied molecular orbital (SUMO), which turns rectification off and drops R to 6.

Gamma-ray emission from the shell of supernova remnant W44 revealed by the Fermi LAT.

PubMed

Abdo, A A; Ackermann, M; Ajello, M; Baldini, L; Ballet, J; Barbiellini, G; Baring, M G; Bastieri, D; Baughman, B M; Bechtol, K; Bellazzini, R; Berenji, B; Blandford, R D; Bloom, E D; Bonamente, E; Borgland, A W; Bregeon, J; Brez, A; Brigida, M; Bruel, P; Burnett, T H; Buson, S; Caliandro, G A; Cameron, R A; Caraveo, P A; Casandjian, J M; Cecchi, C; Celik, O; Chekhtman, A; Cheung, C C; Chiang, J; Ciprini, S; Claus, R; Cognard, I; Cohen-Tanugi, J; Cominsky, L R; Conrad, J; Cutini, S; Dermer, C D; de Angelis, A; de Palma, F; Digel, S W; do Couto e Silva, E; Drell, P S; Dubois, R; Dumora, D; Espinoza, C; Farnier, C; Favuzzi, C; Fegan, S J; Focke, W B; Fortin, P; Frailis, M; Fukazawa, Y; Funk, S; Fusco, P; Gargano, F; Gasparrini, D; Gehrels, N; Germani, S; Giavitto, G; Giebels, B; Giglietto, N; Giordano, F; Glanzman, T; Godfrey, G; Grenier, I A; Grondin, M-H; Grove, J E; Guillemot, L; Guiriec, S; Hanabata, Y; Harding, A K; Hayashida, M; Hays, E; Hughes, R E; Jackson, M S; Jóhannesson, G; Johnson, A S; Johnson, T J; Johnson, W N; Kamae, T; Katagiri, H; Kataoka, J; Katsuta, J; Kawai, N; Kerr, M; Knödlseder, J; Kocian, M L; Kramer, M; Kuss, M; Lande, J; Latronico, L; Lemoine-Goumard, M; Longo, F; Loparco, F; Lott, B; Lovellette, M N; Lubrano, P; Lyne, A G; Madejski, G M; Makeev, A; Mazziotta, M N; McEnery, J E; Meurer, C; Michelson, P F; Mitthumsiri, W; Mizuno, T; Monte, C; Monzani, M E; Morselli, A; Moskalenko, I V; Murgia, S; Nakamori, T; Nolan, P L; Norris, J P; Noutsos, A; Nuss, E; Ohsugi, T; Omodei, N; Orlando, E; Ormes, J F; Paneque, D; Parent, D; Pelassa, V; Pepe, M; Pesce-Rollins, M; Piron, F; Porter, T A; Rainò, S; Rando, R; Razzano, M; Reimer, A; Reimer, O; Reposeur, T; Rochester, L S; Rodriguez, A Y; Romani, R W; Roth, M; Ryde, F; Sadrozinski, H F-W; Sanchez, D; Sander, A; Saz Parkinson, P M; Scargle, J D; Sgrò, C; Siskind, E J; Smith, D A; Smith, P D; Spandre, G; Spinelli, P; Stappers, B W; Stecker, F W; Strickman, M S; Suson, D J; Tajima, H; Takahashi, H; Takahashi, T; Tanaka, T; Thayer, J B; Thayer, J G; Theureau, G; Thompson, D J; Tibaldo, L; Tibolla, O; Torres, D F; Tosti, G; Tramacere, A; Uchiyama, Y; Usher, T L; Vasileiou, V; Venter, C; Vilchez, N; Vitale, V; Waite, A P; Wang, P; Winer, B L; Wood, K S; Yamazaki, R; Ylinen, T; Ziegler, M

2010-02-26

Recent observations of supernova remnants (SNRs) hint that they accelerate cosmic rays to energies close to ~10(15) electron volts. However, the nature of the particles that produce the emission remains ambiguous. We report observations of SNR W44 with the Fermi Large Area Telescope at energies between 2 x 10(8) electron volts and 3 x10(11) electron volts. The detection of a source with a morphology corresponding to the SNR shell implies that the emission is produced by particles accelerated there. The gamma-ray spectrum is well modeled with emission from protons and nuclei. Its steepening above approximately 10(9) electron volts provides a probe with which to study how particle acceleration responds to environmental effects such as shock propagation in dense clouds and how accelerated particles are released into interstellar space.

Efficient and accurate local single reference correlation methods for high-spin open-shell molecules using pair natural orbitals

NASA Astrophysics Data System (ADS)

Hansen, Andreas; Liakos, Dimitrios G.; Neese, Frank

2011-12-01

A production level implementation of the high-spin open-shell (spin unrestricted) single reference coupled pair, quadratic configuration interaction and coupled cluster methods with up to doubly excited determinants in the framework of the local pair natural orbital (LPNO) concept is reported. This work is an extension of the closed-shell LPNO methods developed earlier [F. Neese, F. Wennmohs, and A. Hansen, J. Chem. Phys. 130, 114108 (2009), 10.1063/1.3086717; F. Neese, A. Hansen, and D. G. Liakos, J. Chem. Phys. 131, 064103 (2009), 10.1063/1.3173827]. The internal space is spanned by localized orbitals, while the external space for each electron pair is represented by a truncated PNO expansion. The laborious integral transformation associated with the large number of PNOs becomes feasible through the extensive use of density fitting (resolution of the identity (RI)) techniques. Technical complications arising for the open-shell case and the use of quasi-restricted orbitals for the construction of the reference determinant are discussed in detail. As in the closed-shell case, only three cutoff parameters control the average number of PNOs per electron pair, the size of the significant pair list, and the number of contributing auxiliary basis functions per PNO. The chosen threshold default values ensure robustness and the results of the parent canonical methods are reproduced to high accuracy. Comprehensive numerical tests on absolute and relative energies as well as timings consistently show that the outstanding performance of the LPNO methods carries over to the open-shell case with minor modifications. Finally, hyperfine couplings calculated with the variational LPNO-CEPA/1 method, for which a well-defined expectation value type density exists, indicate the great potential of the LPNO approach for the efficient calculation of molecular properties.

Particle precipitation prior to large earthquakes of both the Sumatra and Philippine Regions: A statistical analysis

NASA Astrophysics Data System (ADS)

Fidani, Cristiano

2015-12-01

A study of statistical correlation between low L-shell electrons precipitating into the atmosphere and strong earthquakes is presented. More than 11 years of the Medium Energy Protons Electrons Detector data from the NOAA-15 Sun-synchronous polar orbiting satellite were analysed. Electron fluxes were analysed using a set of adiabatic coordinates. From this, significant electron counting rate fluctuations were evidenced during geomagnetic quiet periods. Electron counting rates were compared to earthquakes by defining a seismic event L-shell obtained radially projecting the epicentre geographical positions to a given altitude towards the zenith. Counting rates were grouped in every satellite semi-orbit together with strong seismic events and these were chosen with the L-shell coordinates close to each other. NOAA-15 electron data from July 1998 to December 2011 were compared for nearly 1800 earthquakes with magnitudes larger than or equal to 6, occurring worldwide. When considering 30-100 keV precipitating electrons detected by the vertical NOAA-15 telescope and earthquake epicentre projections at altitudes greater that 1300 km, a significant correlation appeared where a 2-3 h electron precipitation was detected prior to large events in the Sumatra and Philippine Regions. This was in physical agreement with different correlation times obtained from past studies that considered particles with greater energies. The Discussion below of satellite orbits and detectors is useful for future satellite missions for earthquake mitigation.

Direct Observation of the Growth of Au-Pd Core-Shell Nanoparticles Using in situ Low-Dose Liquid Cell STEM imaging

DOE PAGES

Bhattarai, Nabraj; Prozorov, Tanya

2016-07-25

Bimetallic core-shell nanoparticles are widely used as catalysts in several industrial reactions, with core-shell structures permitting facile surface modification and allowing increased stability and durability, and cost-effectiveness of the catalysts. We report, for the first time, on observing the early stages of the formation of Au-Pd core-shell bimetallic nanoparticles via the seed-mediated growth in the presence of reducing agent, while employing the low-dose scanning transmission electron microscopy imaging with the fluid cell in situ. Use of the continuous flow in situ fluid cell platform allows for delivery of reagent solutions and generation of near-native reaction environment in the reaction chamber,more » and permits direct visualization of the early stages of formation of Au-Pd core-shell structures at low dose rate (0.1 e -/(Å 2s)) in the presence of ascorbic acid. No core-shell structures were detected in the absence of reducing agent at the electron dose of 32.6 e -/Å 2. While the core-shell structures formed in situ under the low-dose imaging closely resemble those obtained in solution synthesis, the reaction kinetics in the fluid cell is affected by the radiolysis of liquid reagents induced by electron beam, altering the rate-determining reaction steps. The enhanced reduction of Pd ions leads to initial rapid growth of the nascent Pd shell along the <111> direction at the Au interface, followed by a slower rearrangement of the outer Pd layer. The latter becomes the rate-determining step in the in situ reaction and appears to follow the oriented attachment-like movement to yield a remodeled, compact and stable Au-Pd core-shell nanostructure. Our findings highlight the differences between the two reaction pathways and aid in understanding the mechanism of formation of the core-shell nanostructure in situ.« less

Reduced molybenum-oxide-based core-shell hybrids: "blue" electrons are delocalized on the shell.

PubMed

Todea, Ana Maria; Szakács, Julia; Konar, Sanjit; Bögge, Hartmut; Crans, Debbie C; Glaser, Thorsten; Rousselière, Hélène; Thouvenot, René; Gouzerh, Pierre; Müller, Achim

2011-06-06

The present study refers to a variety of reduced metal-oxide core-shell hybrids, which are unique with regard to their electronic structure, their geometry, and their formation. They contain spherical {Mo72Fe30} Keplerate-type shells encapsulating Keggin-type polyoxomolybdates based on very weak interactions. Studies on the encapsulation of molybdosilicate as well as on the earlier reported molybdophosphate, coupled with the use of several physical methods for the characterization led to unprecedented results (see title). Upon standing in air at room temperature, acidified aqueous solutions obtained by dissolving sodium molybdate, iron(II) chloride, acetic acid, and molybdosilicic acid led to the precipitation of monoclinic greenish crystals (1). A rhombohedral variant (2) has also been observed. Upon drying at room temperature, compound 3 with a layer structure was obtained from 1 in a solid-state reaction based on cross-linking of the shells. The compounds 1, 2, and 3 have been characterized by a combination of methods including single-crystal X-ray crystallography, magnetic studies, as well as IR, Mössbauer, (resonance) Raman, and electronic absorption spectroscopy. In connection with detailed studies of the guest-free two-electron-reduced {Mo72Fe30}-type Keplerate (4) and of the previously reported molybdophosphate-based hybrids (including 31P NMR spectroscopy results), it is unambiguously proved that 1, 2, and 3 contain non-reduced Keggin ion cores and reduced {Mo72Fe30}-type shells. The results are discussed in terms of redox considerations (the shell as well as the core can be reduced) including those related to the reduction of "molybdates" by FeII being of interdisciplinary including catalytic interest (the MoVI/MoV and FeIII/FeII couples have very close redox potentials!), while also referring to the special formation of the hybrids based on chemical Darwinism.

Discrimination Between Closed and Open Shell (Turkish) Pistachio Nuts Using Undecimated Wavelet Packet Transform

USDA-ARS?s Scientific Manuscript database

Due to low consumer acceptance and the possibility of immature kernels, closed-shell pistachio nuts should be separated from open-shell nuts before reaching the consumer. The feasibility of a system using impact acoustics as a means of classifying closed-shell nuts from open-shell nuts has already b...

Irreducible Brillouin conditions and contracted Schrödinger equations for n-electron systems. III. Systems of noninteracting electrons.

PubMed

Kutzelnigg, Werner; Mukherjee, Debashis

2004-04-22

We analyze the structure and the solutions of the irreducible k-particle Brillouin conditions (IBCk) and the irreducible contracted Schrödinger equations (ICSEk) for an n-electron system without electron interaction. This exercise is very instructive in that it gives one both the perspective and the strategies to be followed in applying the IBC and ICSE to physically realistic systems with electron interaction. The IBC1 leads to a Liouville equation for the one-particle density matrix gamma1=gamma, consistent with our earlier analysis that the IBC1 holds both for a pure and an ensemble state. The IBC1 or the ICSE1 must be solved subject to the constraints imposed by the n-representability condition, which is particularly simple for gamma. For a closed-shell state gamma is idempotent, i.e., all natural spin orbitals (NSO's) have occupation numbers 0 or 1, and all cumulants lambdak with k> or =2 vanish. For open-shell states there are NSO's with fractional occupation number, and at the same time nonvanishing elements of lambda2, which are related to spin and symmetry coupling. It is often useful to describe an open-shell state by a totally symmetric ensemble state. If one wants to treat a one-particle perturbation by means of perturbation theory, this mainly as a run-up for the study of a two-particle perturbation, one is faced with the problem that the perturbation expansion of the Liouville equation gives information only on the nondiagonal elements (in a basis of the unperturbed states) of gamma. There are essentially three possibilities to construct the diagonal elements of gamma: (i) to consider the perturbation expansion of the characteristic polynomial of gamma, especially the idempotency for closed-shell states, (ii) to rely on the ICSE1, which (at variance with the IBC1) also gives information on the diagonal elements, though not in a very efficient manner, and (iii) to formulate the perturbation theory in terms of a unitary transformation in Fock space. The latter is particularly powerful, especially, when one wishes to study realistic Hamiltonians with a two-body interaction. (c) 2004 American Institute of Physics

A code for analysis of the fine structure in near-rigid weakly-bonded open-shell complexes that consist of a diatomic radical in a Σ3 state and a closed-shell molecule

NASA Astrophysics Data System (ADS)

Fawzy, Wafaa M.

2010-10-01

A FORTRAN code is developed for simulation and fitting the fine structure of a planar weakly-bonded open-shell complex that consists of a diatomic radical in a Σ3 electronic state and a diatomic or a polyatomic closed-shell molecule. The program sets up the proper total Hamiltonian matrix for a given J value and takes account of electron-spin-electron-spin, electron-spin rotation interactions, and the quartic and sextic centrifugal distortion terms within the complex. Also, R-dependence of electron-spin-electron-spin and electron-spin rotation couplings are considered. The code does not take account of effects of large-amplitude internal rotation of the diatomic radical within the complex. It is assumed that the complex has a well defined equilibrium geometry so that effects of large amplitude motion are negligible. Therefore, the computer code is suitable for a near-rigid rotor. Numerical diagonalization of the matrix provides the eigenvalues and the eigenfunctions that are necessary for calculating energy levels, frequencies, relative intensities of infrared or microwave transitions, and expectation values of the quantum numbers within the complex. Goodness of all the quantum numbers, with exception of J and parity, depends on relative sizes of the product of the rotational constants and quantum numbers (i.e. BJ, CJ, and AK), electron-spin-electron-spin, and electron-spin rotation couplings, as well as the geometry of the complex. Therefore, expectation values of the quantum numbers are calculated in the eigenfunctions basis of the complex. The computational time for the least squares fits has been significantly reduced by using the Hellman-Feynman theory for calculating the derivatives. The computer code is useful for analysis of high resolution infrared and microwave spectra of a planar near-rigid weakly-bonded open-shell complex that contains a diatomic fragment in a Σ3 electronic state and a closed-shell molecule. The computer program was successfully applied to analysis and fitting the observed high resolution infrared spectra of the O 2sbnd HF/O 2sbnd DF and O 2sbnd N 2O complexes. Test input file for simulation and fitting the high resolution infrared spectrum of the O 2sbnd DF complex is provided. Program summaryProgram title: TSIG_COMP Catalogue identifier: AEGM_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEGM_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 10 030 No. of bytes in distributed program, including test data, etc.: 51 663 Distribution format: tar.gz Programming language: Fortran 90, free format Computer: SGI Origin 3400, workstations and PCs Operating system: Linux, UNIX and Windows (see Restrictions below) RAM: Case dependent Classification: 16.2 Nature of problem: TSIG_COMP calculates frequencies, relative intensities, and expectation values of the various quantum numbers and parities of bound states involved in allowed ro-vibrational transitions in semi-rigid planar weakly-bonded open-shell complexes. The complexes of interest contain a free radical in a Σ3 state and a closed-shell partner, where the electron-spin-electron-spin interaction, electron-spin rotation interaction, and centrifugal forces significantly modify the spectral patterns. To date, ab initio methods are incapable of taking these effects into account to provide accurate predictions for the ro-vibrational energy levels of the complexes of interest. In the TSIG_COMP program, the problem is solved by using the proper effective Hamiltonian and molecular basis set. Solution method: The program uses a Hamiltonian operator that takes into account vibration, end-over-end rotation, electron-spin-electron-spin and electron-spin rotation interactions as well as the various centrifugal distortion terms. The Hamiltonian operator and the molecular basis set are used to set up the Hamiltonian matrix in the inertial axis system of the complex of interest. Diagonalization of the Hamiltonian matrix provides the eigenvalues and the eigenfunctions for the bound ro-vibrational states. These eigenvalues and eigenfunctions are used to calculate frequencies and relative intensities of the allowed infrared or microwave transitions as well as expectation values of all the quantum numbers and parities of states involved in the transitions. The program employs the method of least squares fits to fit the observed frequencies to the calculated frequencies to provide the molecular parameters that determine the geometry of the complex of interest. Restrictions: The number of transitions and parameters included in the fits is limited to 80 parameters and 200 transitions. However, these numbers can be increased by adjusting dimensions of the arrays (not recommended). Running the program under MS windows is recommended for simulations of any number of transitions and for fitting a relatively small number of parameters and transitions (maximum 15 parameters and 82 transitions), for fitting larger number of parameters run time error may occur. Because spectra of weakly bonded complexes are recorded at low temperatures, in most of cases fittings can be performed under MS windows. Running time: Problem-dependent. The provided test input for Linux fits 82 transitions and 21 parameters, the actual run time is 62 minutes. The provided test input file for MS windows fits 82 transitions and 15 parameters; the actual runtime is 5 minutes.

Excited State Trends in Bidirectionally Expanded Closed-Shell PAH and PANH Anions

PubMed Central

Moore, Megan M.; Lee, Timothy J.

2018-01-01

Some anions are known to exhibit excited states independent of external forces such as dipole moments and induced polarizabilities. Such states exist simply as a result of the stabilization of valence accepting orbitals whereby the binding energy of the extra electron is greater than the valence excitation energy. Closed-shell anions are interesting candidates for such transitions since their ground-state, spin-paired nature makes the anions more stable from the beginning. Consequently, this work shows the point beyond which deprotonated, closed-shell polycyclic aromatic hydrocarbons (PAHs) and those PAHs containing nitrogen heteroatoms (PANHs) will exhibit valence excited states. This behavior has already been demonstrated in some PANHs and for anistropically-extended PAHs. This work establishes a general trend for PAHs/PANHs of arbitrary size and directional extension, whether in one dimension or two. Once seven six-membered rings make up a PAH/PANH, valence excited states are present. For most classes of PAHs/PANHs, this number is closer to four. Even though most of these excited states are weak absorbers, the sheer number of PAHs present in various astronomical environments should make them significant contributors to astronomical spectra. PMID:27585793

SHELL MICROSTRUCTURE OF GASTROPODS FROM LAKE TANGANYIKA, AFRICA: ADAPTATION, CONVERGENT EVOLUTION, AND ESCALATION.

PubMed

West, Kelly; Cohen, Andrew

1996-04-01

Gastropod shells from Lake Tanganyika, with their heavy calcification, coarse noded ribbing, spines, apertural lip thickening and repair scars, resemble marine shells more closely than they resemble other lacustrine shells. This convergence between Tanganyikan and marine gastropod shells, however, is not just superficial. Scanning electron microscope (SEM) studies reveal that the Tanganyikan shells are primarily layers of crossed-lamellar crystal architecture (that is, needle-like aragonite crystals arranged into laths that are packed into sheets such that the aragonite needles of adjacent laths are never parallel). The number of crossed-lamellar layers can vary from one to four between different Tanganyikan gastropod species. In species with two or more crossed-lamellar layers, the orientation of the lamellae is offset by approximately 90° between the different layers. The number of crossed-lamellar layers in the shell wall is positively correlated with shell strength and with predation resistance. Three and four crossed-lamellar layers in the shell wall evolved several times independently within the endemic thiarid gastropod radiation in Lake Tanganyika. Repeated origins of three and four crossed-lamellar layers suggest that they may be specific adaptations by Tanganyikan gastropods to strengthen their shells as a defense against shell-crushing predators. © 1996 The Society for the Study of Evolution.

Global molecular identification from graphs. Neutral and ionized main-group diatomic molecules.

PubMed

James, Bryan; Caviness, Ken; Geach, Jonathan; Walters, Chris; Hefferlin, Ray

2002-01-01

Diophantine equations and inequalities are presented for main-group closed-shell diatomic molecules. Specifying various bond types (covalent, dative, ionic, van der Waals) and multiplicities, it becomes possible to identify all possible molecules. While many of the identified species are probably unstable under normal conditions, they are interesting and present a challenge for computational or experimental analysis. Ionized molecules with net charges of -1, 1, and 2 are also identified. The analysis applies to molecules with atoms from periods 2 and 3 but can be generalized by substituting isovalent atoms. When closed-shell neutral diatomics are positioned in the chemical space (with axes enumerating the numbers of valence electrons of the free atoms), it is seen that they lie on a few parallel isoelectronic series.

Influence of dimensionality and interface type on optical and electronic properties of CdS/ZnS core-shell nanocrystals—A first-principles study

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

Kocevski, V., E-mail: vancho.vk@gmail.com, E-mail: vancho.kocevski@physics.uu.se; Eriksson, O.; Gerard, C.

2015-10-28

Semiconducting nanocrystals (NCs) have become one of the leading materials in a variety of applications, mainly due to their size tunable band gap and high intensity emission. Their photoluminescence (PL) properties can be notably improved by capping the nanocrystals with a shell of another semiconductor, making core-shell structures. We focus our study on the CdS/ZnS core-shell nanocrystals that are closely related to extensively studied CdSe/CdS NCs, albeit exhibiting rather different photoluminescence properties. We employ density functional theory to investigate the changes in the electronic and optical properties of these nanocrystals with size, core/shell ratio, and interface structure between the coremore » and the shell. We have found that both the lowest unoccupied eigenstate (LUES) and the highest occupied eigenstate (HOES) wavefunction (WF) are localized in the core of the NCs, with the distribution of the LUES WF being more sensitive to the size and the core/shell ratio. We show that the radiative lifetimes are increasing, and the Coulomb interaction energies decrease with increasing NC size. Furthermore, we investigated the electronic and optical properties of the NCs with different interfaces between the core and the shell and different core types. We find that the different interfaces and core types have rather small influence on the band gaps and the absorption indexes, as well as on the confinement of the HOES and LUES WFs. Also the radiative lifetimes are found to be only slightly influenced by the different structural models. In addition, we compare these results with the previous results for CdSe/CdS NCs, reflecting the different PL properties of these two types of NCs. We argue that the difference in their Coulomb interaction energies is one of the main reasons for their distinct PL properties.« less

Photoabsorption in sodium clusters: first principles configuration interaction calculations

NASA Astrophysics Data System (ADS)

Priya, Pradip Kumar; Rai, Deepak Kumar; Shukla, Alok

2017-05-01

We present systematic and comprehensive correlated-electron calculations of the linear photoabsorption spectra of small neutral closed- and open-shell sodium clusters (Nan, n = 2 - 6), as well as closed-shell cation clusters (Nan+, n = 3, 5). We have employed the configuration interaction (CI) methodology at the full CI (FCI) and quadruple CI (QCI) levels to compute the ground, and the low-lying excited states of the clusters. For most clusters, besides the minimum energy structures, we also consider their energetically close isomers. The photoabsorption spectra were computed under the electric-dipole approximation, employing the dipole-matrix elements connecting the ground state with the excited states of each isomer. Our calculations were tested rigorously for convergence with respect to the basis set, as well as with respect to the size of the active orbital space employed in the CI calculations. These calculations reveal that as far as electron-correlation effects are concerned, core excitations play an important role in determining the optimized ground state geometries of various clusters, thereby requiring all-electron correlated calculations. But, when it comes to low-lying optical excitations, only valence electron correlation effects play an important role, and excellent agreement with the experimental results is obtained within the frozen-core approximation. For the case of Na6, the largest cluster studied in this work, we also discuss the possibility of occurrence of plasmonic resonance in the optical absorption spectrum. Supplementary material in the form of one pdf file available from the Journal web page at http://https://doi.org/10.1140/epjd/e2017-70728-3

Electronic structures of Al-Si clusters and the magic number structure Al8Si4

NASA Astrophysics Data System (ADS)

Du, Ning; Su, Mingzhi; Chen, Hongshan

2018-02-01

The low-energy structures of Al8Sim (m = 1-6) have been determined by using the genetic algorithm combined with density functional theory and the Second-order Moller-Plesset perturbation theory (MP2) models. The results show that the close-packed structures are preferable in energy for Al-Si clusters and in most cases there exist a few isomers with close energies. The valence molecular orbitals, the orbital level structures and the electron localisation function (ELF) consistently demonstrate that the electronic structures of Al-Si clusters can be described by the jellium model. Al8Si4 corresponds to a magic number structure with pronounced stability and large energy gap; the 40 valence electrons form closed 1S21P61D102S21F142P6 shells. The ELF attractors also suggest weak covalent Si-Si, Si-Al and Al-Al bonding, and doping Si in aluminium clusters promotes the covalent interaction between Al atoms.

Ambient Stable Radical Cations, Diradicaloid π-Dimeric Dications, Closed-Shell Dications, and Diradical Dications of Methylthio-Capped Rylenes.

PubMed

Qi, Qingbiao; Burrezo, Paula Mayorga; Phan, Hoa; Herng, Tun Seng; Gopalakrishna, Tullimilli Y; Zeng, Wangdong; Ding, Jun; Casado, Juan; Wu, Jishan

2017-06-01

Radical cations and dications of π-conjugated systems play vital roles in organic electronic devices, organic conductors, and conducting polymers. Their structures, charge and spin distribution, and mechanism of charge transport are of great interest. In this article, radical cations and dications of a series of newly synthesized methylthio-capped rylenes were synthesized and isolated. Their ground-state structures, physical properties, and solid-state packing were systematically investigated by various experimental methods, such as X-ray crystallographic analysis, UV/Vis/NIR absorption spectroscopy, (spectro-)electrochemistry, nuclear magnetic resonance spectroscopy, electron spin resonance spectroscopy, superconducting quantum interference device, and Raman spectroscopy, assisted by DFT calculations. It was found that all the charged species show an exceptional stability under ambient air and light conditions due to the efficient spin and charge delocalization over the whole rylene backbone. The dication of hexarylene turned out to have an unusual open-shell singlet rather than closed-shell ground state, thus it can be described as a diradical dication. Dimerization was observed for the radical cations and even the dications in crystals due to the strong intermolecular antiferromagnetic spin-spin interaction and π-π interaction, which result in unique magnetic properties. Such intermolecular association was also observed in solution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The origin of the two-electron/four-centers C--C bond in pi-TCNE(2)2- dimers: electrostatic or dispersion?

PubMed

García-Yoldi, Iñigo; Mota, Fernando; Novoa, Juan J

2007-01-15

The structure and stability of the pi-TCNE(2)2- dimers in K2TCNE2 aggregates is revisited trying to find if the origin of their two-electron/four-centers C--C bond are the electrostatic K+-TCNE- interactions or the dispersion interactions between the anions. The study is done at the HF, B3LYP, CASSCF (2,2), and MCQDPT/CASSCF (2,2) levels using the 6-31+G(d) basis set. Our results show that the only minima of this aggregate that preserves the pi-TCNE(2)2- structure has the two K+ atoms placed in equatorial positions in between the two TCNE- planes. When the K+ atoms are placed along the D2h axis of the anions the structure is not a minimum. The main energetic component responsible for the stability of these aggregates comes from the cation-anion interactions. However, a proper accounting of the dispersion component (as done in the MCQDPT/CASSCF (2,2) calculations) is needed to make the closed-shell singlet more stable than the open-shell singlet. Thus, the bond results from the combination of the electrostatic and dispersion components, being the first the dominant one. The optimum geometry of the closed-shell singlet is very similar to the experimental one found in crystals. Copyright (c) 2006 Wiley Periodicals, Inc.

Shell effect on the electron and hole reorganization energy of core-shell II-VI nanoclusters

NASA Astrophysics Data System (ADS)

Cui, Xianhui; Wang, Xinqin; Yang, Fang; Cui, Yingqi; Yang, Mingli

2017-09-01

Density functional theory calculations were performed to study the effect of shell encapsulation on the geometrical and electronic properties of pure and hybrid core-shell CdSe nanoclusters. The CdSe cores are distorted by the shells, and the shells exhibit distinct surface activity from the cores, which leads to remarkable changes in their electron transition behaviors. Although the electron and hole reorganization energies, which are related to the formation and recombination of electron-hole pairs, vary in a complicated way, their itemized contributions, potentials of electron extraction, ionization and affinity, and hole extraction (HEP), are dependent on the cluster size, shell composition and/or solvent. Our calculations suggest that the behaviors of charge carriers, free electrons and holes, in the semiconductor core-shell nanoclusters can be modulated by selecting appropriate cluster size and controlling the chemical composition of the shells.

Redox-Active Bis(phenolate) N-Heterocyclic Carbene [OCO] Pincer Ligands Support Cobalt Electron Transfer Series Spanning Four Oxidation States.

PubMed

Harris, Caleb F; Bayless, Michael B; van Leest, Nicolaas P; Bruch, Quinton J; Livesay, Brooke N; Bacsa, John; Hardcastle, Kenneth I; Shores, Matthew P; de Bruin, Bas; Soper, Jake D

2017-10-16

A new family of low-coordinate Co complexes supported by three redox-noninnocent tridentate [OCO] pincer-type bis(phenolate) N-heterocyclic carbene (NHC) ligands are described. Combined experimental and computational data suggest that the charge-neutral four-coordinate complexes are best formulated as Co(II) centers bound to closed-shell [OCO] 2- dianions, of the general formula [(OCO)Co II L] (where L is a solvent-derived MeCN or THF). Cyclic voltammograms of the [(OCO)Co II L] complexes reveal three oxidations accessible at potentials below 1.2 V vs Fc + /Fc, corresponding to generation of formally Co(V) species, but the true physical/spectroscopic oxidation states are much lower. Chemical oxidations afford the mono- and dications of the imidazoline NHC-derived complex, which were examined by computational and magnetic and spectroscopic methods, including single-crystal X-ray diffraction. The metal and ligand oxidation states of the monocationic complex are ambiguous; data are consistent with formulation as either [( S OCO)Co III (THF) 2 ] + containing a closed-shell [ S OCO] 2- diphenolate ligand bound to a S = 1 Co(III) center, or [( S OCO • )Co II (THF) 2 ] + with a low-spin Co(II) ion ferromagnetically coupled to monoanionic [ S OCO • ] - containing a single unpaired electron distributed across the [OCO] framework. The dication is best described as [( S OCO 0 )Co II (THF) 3 ] 2+ , with a single unpaired electron localized on the d 7 Co(II) center and a doubly oxidized, charge-neutral, closed-shell S OCO 0 ligand. The combined data provide for the first time unequivocal and structural evidence for [OCO] ligand redox activity. Notably, varying the degree of unsaturation in the NHC backbone shifts the ligand-based oxidation potentials by up to 400 mV. The possible chemical origins of this unexpected shift, along with the potential utility of the [OCO] pincer ligands for base-metal-mediated organometallic coupling catalysis, are discussed.

Studies of Copper, Silver, and Gold Cluster Anions: Evidence of Electronic Shell Structure.

NASA Astrophysics Data System (ADS)

Pettiette, Claire Lynn

A new Ultraviolet Magnetic Time-of-Flight Photoelectron Spectrometer (MTOFPES) has been developed for the study of the electronic structure of clusters produced in a pulsed supersonic molecular beam. This is the first technique which has been successful in probing the valence electronic states of metal clusters. The ultraviolet photoelectron spectra of negative cluster ions of the noble metals have been taken at several different photon energies. These are presented along with the electron affinity and HOMO-LUMO gap measurements for Cu_6^- to Cu_ {41}^-, using 4.66 eV and 6.42 eV detachment energies; Ag_3^- to Ag_{21}^-, using 6.42 eV detachment energy; and Au_3^ - to Au_{21}^-, using 6.42 eV and 7.89 eV detachment energies. The spectra provide the first detailed probes of the s valence electrons of the noble metal clusters. In addition, the 6.42 eV and 7.89 eV spectra probe the first one to two electron volts of the molecular orbitals of the d valence electrons of copper and gold clusters. The electron affinity and HOMO-LUMO gap measurements of the noble metal clusters agree with the predictions of the ellipsoidal shell model for mono-valent metal clusters. In particular, cluster numbers 8, 20, and 40--which correspond to the spherical shell closings of this model--have low electron affinities and large HOMO-LUMO gaps. The spectra of the gold cluster ions indicate that the molecular orbital energies of the cluster valence electrons are more widely spaced for gold than for copper or silver. This is to be expected for the heavy atom clusters when relativistic effects are taken into account.

Structural and electronic properties for atomic clusters

NASA Astrophysics Data System (ADS)

Sun, Yan

We have studied the structural and electronic properties for different groups of atomic clusters by doing a global search on the potential energy surface using the Taboo Search in Descriptors Space (TSDS) method and calculating the energies with Kohn-Sham Density Functional Theory (KS-DFT). Our goal was to find the structural and electronic principles for predicting the structure and stability of clusters. For Ben (n = 3--20), we have found that the evolution of geometric and electronic properties with size reflects a change in the nature of the bonding from van der Waals to metallic and then bulk-like. The cluster sizes with extra stability agree well with the predictions of the jellium model. In the 4d series of transition metal (TM) clusters, as the d-type bonding becomes more important, the preferred geometric structure changes from icosahedral (Y, Zr), to distorted compact structures (Nb, Mo), and FCC or simple cubic crystal fragments (Tc, Ru, Rh) due to the localized nature of the d-type orbital. Analysis of relative isomer energies and their electronic density of states suggest that these clusters tend to follow a maximum hardness principle (MHP). For A4B12 clusters (A is divalent, B is monovalent), we found unusually large (on average 1.95 eV) HOMO-LUMO gap values. This shows the extra stability at an electronic closed shell (20 electrons) predicted by the jellium model. The importance of symmetry, closed electronic and ionic shells in stability is shown by the relative stability of homotops of Mg4Ag12 which also provides support for the hypothesis that clusters that satisfy more than one stability criterion ("double magic") should be particularly stable.

Theoretical investigation of gas-surface interactions

NASA Technical Reports Server (NTRS)

Dyall, Kenneth G.

1992-01-01

The investigation into the appearance of intruder states from the negative continuum when some of the two-electron integrals were omitted was completed. The work shows that, provided all integrals involving core contracted functions in an atomic general contraction are included, or that the core functions are radially localized, meaningful results are obtained and intruder states do not appear. In the area of program development, the Dirac-Hartree-Fock (DHF) program for closed-shell polyatomic molecules was extended to permit Kramers-restricted open-shell DHF calculations with one electron in an open shell or one hole in a closed shell, or state-averaged DHF calculations over several particle or hole doublet states. One application of the open-shell code was to the KO molecule. Another major area of program development is the transformation of integrals from the scalar basis in which they are generated to the 2-spinor basis employed in parts of the DHF program, and hence to supermatrix form. Particularly concerning the omission of small component integrals, and with increase in availability of disk space, it is now possible to consider transforming the integrals. The use of ordered integrals, either in the scalar basis or in the 2-spinor basis, would considerably speed up the construction of the Fock matrix, and even more so if supermatrices were constructed. A considerable amount of effort was spent on analyzing the integral ordering and tranformation for the DHF program. The work of assessing the reliability of the relativistic effective core potentials (RECPs) was continued with calculation of the group IV monoxides. The perturbation of the metal atom provided by oxygen is expected to be larger than that provided by hydrogen and thus provide a better test of the qualification of the RECPs. Calculations on some platinum hydrides were carried out at nonrelativistic (NR), perturbation theory (PT) and DHF levels. Reprints of four papers describing this work are included.

Seventeen-Coordinate Actinide Helium Complexes.

PubMed

Kaltsoyannis, Nikolas

2017-06-12

The geometries and electronic structures of molecular ions featuring He atoms complexed to actinide cations are explored computationally using density functional and coupled cluster theories. A new record coordination number is established, as AcHe 17 3+ , ThHe 17 4+ , and PaHe 17 4+ are all found to be true geometric minima, with the He atoms clearly located in the first shell around the actinide. Analysis of AcHe n 3+ (n=1-17) using the quantum theory of atoms in molecules (QTAIM) confirms these systems as having closed shell, charge-induced dipole bonding. Excellent correlations (R 2 >0.95) are found between QTAIM metrics (bond critical point electron densities and delocalization indices) and the average Ac-He distances, and also with the incremental He binding energies. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electronic structures of elements according to ionization energies.

PubMed

Zadeh, Dariush H

2017-11-28

The electronic structures of elements in the periodic table were analyzed using available experimental ionization energies. Two new parameters were defined to carry out the study. The first parameter-apparent nuclear charge (ANC)-quantified the overall charge of the nucleus and inner electrons observed by an outer electron during the ionization process. This parameter was utilized to define a second parameter, which presented the shielding ability of an electron against the nuclear charge. This second parameter-electron shielding effect (ESE)-provided an insight into the electronic structure of atoms. This article avoids any sort of approximation, interpolation or extrapolation. First experimental ionization energies were used to obtain the two aforementioned parameters. The second parameter (ESE) was then graphed against the electron number of each element, and was used to read the corresponding electronic structure. The ESE showed spikes/peaks at the end of each electronic shell, providing insight into when an electronic shell closes and a new one starts. The electronic structures of elements in the periodic table were mapped using this methodology. These graphs did not show complete agreement with the previously known "Aufbau" filling rule. A new filling rule was suggested based on the present observations. Finally, a new way to organize elements in the periodic table is suggested. Two earlier topics of effective nuclear charge, and shielding factor were also briefly discussed and compared numerically to demonstrate the capability of the new approach.

Analysis of liquid suspensions using scanning electron microscopy in transmission: estimation of the water film thickness using Monte-Carlo simulations.

PubMed

Xiao, J; Foray, G; Masenelli-Varlot, K

2018-02-01

Environmental scanning electron microscopy (ESEM) allows the observation of liquids under specific conditions of pressure and temperature. Moreover, when working in the transmission mode, that is in scanning transmission electron microscopy (STEM), nano-objects can be analysed inside a liquid. The contrast in the images is mass-thickness dependent as in STEM-in-TEM (transmission electron microscopy) using closed cells. However, in STEM-in-ESEM, as the liquid-vapour equilibrium is kept dynamically, the thickness of the water droplet remains unknown. In this paper, the contrasts measured in the experimental images are compared with calculations using Monte-Carlo simulations in order to estimate the thickness of water. Two examples are given. On gold nanoparticles, the thickness of a thick film can be estimated thanks to a contrast inversion. On core-shell latex particles, the grey level of the shell compared with those of the core and of the water film gives a relatively precise measurement of the water film thickness. © 2017 The Authors Journal of Microscopy © 2017 Royal Microscopical Society.

Following electron impact excitation of single (N, O, F, Ne, Na, Mg, Al, Si) atom L subshells ionization cross section calculations by using Lotz's equation

NASA Astrophysics Data System (ADS)

Aydinol, Mahmut

2017-02-01

L shell and L subshells ionization cross sections σL and σLi (i = 1, 2, 3) following electron impact on (N,O, F, Ne, Na, Mg, Al, Si) atoms calculated. By using Lotz' equation for nonrelativistic cases in Matlab σL and σLi cross section values obtained for ten electron impact(Eo) values in the range of ELi

Polarization and charge transfer in the hydration of chloride ions

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

Zhao Zhen; Rogers, David M.; Beck, Thomas L.

2010-01-07

A theoretical study of the structural and electronic properties of the chloride ion and water molecules in the first hydration shell is presented. The calculations are performed on an ensemble of configurations obtained from molecular dynamics simulations of a single chloride ion in bulk water. The simulations utilize the polarizable AMOEBA force field for trajectory generation and MP2-level calculations are performed to examine the electronic structure properties of the ions and surrounding waters in the external field of more distant waters. The ChelpG method is employed to explore the effective charges and dipoles on the chloride ions and first-shell waters.more » The quantum theory of atoms in molecules (QTAIM) is further utilized to examine charge transfer from the anion to surrounding water molecules. The clusters extracted from the AMOEBA simulations exhibit high probabilities of anisotropic solvation for chloride ions in bulk water. From the QTAIM analysis, 0.2 elementary charges are transferred from the ion to the first-shell water molecules. The default AMOEBA model overestimates the average dipole moment magnitude of the ion compared to the quantum mechanical value. The average magnitude of the dipole moment of the water molecules in the first shell treated at the MP2-level, with the more distant waters handled with an AMOEBA effective charge model, is 2.67 D. This value is close to the AMOEBA result for first-shell waters (2.72 D) and is slightly reduced from the bulk AMOEBA value (2.78 D). The magnitude of the dipole moment of the water molecules in the first solvation shell is most strongly affected by the local water-water interactions and hydrogen bonds with the second solvation shell, rather than by interactions with the ion.« less

A Statistical Correlation Between Low L-shell Electrons Measured by NOAA Satellites and Strong Earthquakes

NASA Astrophysics Data System (ADS)

Fidani, C.

2015-12-01

More than 11 years of the Medium Energy Protons Electrons Detector data from the NOAA polar orbiting satellites were analyzed. Significant electron counting rate fluctuations were evidenced during geomagnetic quiet periods by using a set of adiabatic coordinates. Electron counting rates were compared to earthquakes by defining a seismic event L-shell obtained radially projecting the epicenter geographical positions to a given altitude. Counting rate fluctuations were grouped in every satellite semi-orbit together with strong seismic events and these were chosen with the L-shell coordinates close to each other. Electron data from July 1998 to December 2011 were compared for nearly 1,800 earthquakes with magnitudes larger than or equal to 6, occurring worldwide. When considering 30 - 100 keV energy channels by the vertical NOAA telescopes and earthquake epicenter projections at altitudes greater that 1,300 km, a 4 sigma correlation appeared where time of particle precipitations Tpp occurred 2 - 3 hour prior time of large seismic events Teq. This was in physical agreement with different correlation times obtained from past studies that considered particles with greater energies. The correlation suggested a 4-8 hour advance in preparedness of strong earthquakes influencing the ionosphere. Considering this strong correlation between earthquakes and electron rate fluctuations, and the hypothesis that such fluctuations originated with magnetic disturbances generated underground, a small scale experiment with low cost at ground level is advisable. Plans exists to perform one or more unconventional experiments around an earthquake affected area by private investor in Italy.

75 FR 11169 - AES Sparrows Point LNG, LLC; Mid-Atlantic Express, LLC; Notice of Availability of the Revised...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-03-10

... LNG storage tanks; A closed-loop shell and tube heat exchanger vaporization system; Various ancillary..., there are three methods you can use to submit your comments to the Commission. In all instances please... encourages electronic filing of comments and has dedicated eFiling expert staff available to assist you at...

Restricted Closed Shell Hartree Fock Roothaan Matrix Method Applied to Helium Atom Using Mathematica

ERIC Educational Resources Information Center

Acosta, César R.; Tapia, J. Alejandro; Cab, César

2014-01-01

Slater type orbitals were used to construct the overlap and the Hamiltonian core matrices; we also found the values of the bi-electron repulsion integrals. The Hartree Fock Roothaan approximation process starts with setting an initial guess value for the elements of the density matrix; with these matrices we constructed the initial Fock matrix.…

Rapid Loss of Radiation Belt Relativistic Electrons by EMIC Waves

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

Su, Zhenpeng; Gao, Zhonglei; Zheng, Huinan

How relativistic electrons are lost is an important question surrounding the complex dynamics of the Earth's outer radiation belt. Radial loss to the magnetopause and local loss to the atmosphere are two main competing paradigms. Here on the basis of the analysis of a radiation belt storm event on 27 February 2014, we present new evidence for the electromagnetic ion cyclotron (EMIC) wave-driven local precipitation loss of relativistic electrons in the heart of the outer radiation belt. During the main phase of this storm, the radial profile of relativistic electron phase space density was quasi-monotonic, qualitatively inconsistent with the predictionmore » of radial loss theory. The local loss at low L shells was required to prevent the development of phase space density peak resulting from the radial loss process at high L shells. The rapid loss of relativistic electrons in the heart of outer radiation belt was observed as a dip structure of the electron flux temporal profile closely related to intense EMIC waves. Our simulations further confirm that the observed EMIC waves within a quite limited longitudinal region were able to reduce the off-equatorially mirroring relativistic electron fluxes by up to 2 orders of magnitude within about 1.5 h.« less

Rapid Loss of Radiation Belt Relativistic Electrons by EMIC Waves

DOE PAGES

Su, Zhenpeng; Gao, Zhonglei; Zheng, Huinan; ...

2017-08-31

How relativistic electrons are lost is an important question surrounding the complex dynamics of the Earth's outer radiation belt. Radial loss to the magnetopause and local loss to the atmosphere are two main competing paradigms. Here on the basis of the analysis of a radiation belt storm event on 27 February 2014, we present new evidence for the electromagnetic ion cyclotron (EMIC) wave-driven local precipitation loss of relativistic electrons in the heart of the outer radiation belt. During the main phase of this storm, the radial profile of relativistic electron phase space density was quasi-monotonic, qualitatively inconsistent with the predictionmore » of radial loss theory. The local loss at low L shells was required to prevent the development of phase space density peak resulting from the radial loss process at high L shells. The rapid loss of relativistic electrons in the heart of outer radiation belt was observed as a dip structure of the electron flux temporal profile closely related to intense EMIC waves. Our simulations further confirm that the observed EMIC waves within a quite limited longitudinal region were able to reduce the off-equatorially mirroring relativistic electron fluxes by up to 2 orders of magnitude within about 1.5 h.« less

Theory and practice of uncommon molecular electronic configurations.

PubMed

Gryn'ova, Ganna; Coote, Michelle L; Corminboeuf, Clemence

2015-01-01

The electronic configuration of the molecule is the foundation of its structure and reactivity. The spin state is one of the key characteristics arising from the ordering of electrons within the molecule's set of orbitals. Organic molecules that have open-shell ground states and interesting physicochemical properties, particularly those influencing their spin alignment, are of immense interest within the up-and-coming field of molecular electronics. In this advanced review, we scrutinize various qualitative rules of orbital occupation and spin alignment, viz., the aufbau principle, Hund's multiplicity rule, and dynamic spin polarization concept, through the prism of quantum mechanics. While such rules hold in selected simple cases, in general the spin state of a system depends on a combination of electronic factors that include Coulomb and Pauli repulsion, nuclear attraction, kinetic energy, orbital relaxation, and static correlation. A number of fascinating chemical systems with spin states that fluctuate between triplet and open-shell singlet, and are responsive to irradiation, pH, and other external stimuli, are highlighted. In addition, we outline a range of organic molecules with intriguing non-aufbau orbital configurations. In such quasi-closed-shell systems, the singly occupied molecular orbital (SOMO) is energetically lower than one or more doubly occupied orbitals. As a result, the SOMO is not affected by electron attachment to or removal from the molecule, and the products of such redox processes are polyradicals. These peculiar species possess attractive conductive and magnetic properties, and a number of them that have already been developed into molecular electronics applications are highlighted in this review. WIREs Comput Mol Sci 2015, 5:440-459. doi: 10.1002/wcms.1233 For further resources related to this article, please visit the WIREs website.

Inner-shell radiation from wire array implosions on the Zebra generator

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

Ouart, N. D.; Giuliani, J. L.; Dasgupta, A.

2014-03-15

Implosions of brass wire arrays on Zebra have produced L-shell radiation as well as inner-shell Kα and Kβ transitions. The L-shell radiation comes from ionization stages around the Ne-like charge state that is largely populated by a thermal electron energy distribution function, while the K-shell photons are a result of high-energy electrons ionizing or exciting an inner-shell (1s) electron from ionization stages around Ne-like. The K- and L-shell radiations were captured using two time-gated and two axially resolved time-integrated spectrometers. The electron beam was measured using a Faraday cup. A multi-zone non-local thermodynamic equilibrium pinch model with radiation transport ismore » used to model the x-ray emission from experiments for the purpose of obtaining plasma conditions. These plasma conditions are used to discuss some properties of the electron beam generated by runaway electrons. A simple model for runaway electrons is examined to produce the Kα radiation, but it is found to be insufficient.« less

Multishelled NiO Hollow Microspheres for High-performance Supercapacitors with Ultrahigh Energy Density and Robust Cycle Life

NASA Astrophysics Data System (ADS)

Qi, Xinhong; Zheng, Wenji; Li, Xiangcun; He, Gaohong

2016-09-01

Multishelled NiO hollow microspheres for high-performance supercapacitors have been prepared and the formation mechanism has been investigated. By using resin microspheres to absorb Ni2+ and subsequent proper calcinations, the shell numbers, shell spacing and exterior shell structure were facilely controlled via varying synthetic parameters. Particularly, the exterior shell structure that accurately associated with the ion transfer is finely controlled by forming a single shell or closed exterior double-shells. Among multishelled NiO hollow microspheres, the triple-shelled NiO with an outer single-shelled microspheres show a remarkable capacity of 1280 F g-1 at 1 A g-1, and still keep a high value of 704 F g-1 even at 20 A g-1. The outstanding performances are attributed to its fast ion/electron transfer, high specific surface area and large shell space. The specific capacitance gradually increases to 108% of its initial value after 2500 cycles, demonstrating its high stability. Importantly, the 3S-NiO-HMS//RGO@Fe3O4 asymmetric supercapacitor shows an ultrahigh energy density of 51.0 Wh kg-1 at a power density of 800 W kg-1, and 78.8% capacitance retention after 10,000 cycles. Furthermore, multishelled NiO can be transferred into multishelled Ni microspheres with high-efficient H2 generation rate of 598.5 mL H2 min-1 g-1Ni for catalytic hydrolysis of NH3BH3 (AB).

Synthesis of core-shell structured FAU/SBA-15 composite molecular sieves and their performance in catalytic cracking of polystyrene

NASA Astrophysics Data System (ADS)

Du, Jinlong; Shi, Chunwei; Wu, Wenyuan; Bian, Xue; Chen, Ping; Cui, Qingzhu; Cui, Zhixuan

2017-12-01

Composite molecular sieves, FAU/SBA-15, having core-shell structure were synthesized. The synthesized composite sieves were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), pyrolysis fourier transform infrared (Py-FTIR) spectroscopy, temperature programmed desorption spectra (NH3-TPD), UV Raman spectroscopy, nuclear magnetic resonance (NMR) and other techniques. XRD, SEM, TEM, N2 adsorption-desorption, mass spectrometry, NMR and EDS results showed that the composite molecular sieve contained two pore channels. Py-FTIR results showed that the addition of HY molecular sieves improved the acidity of the composite zeolite. The crystallization mechanism during the growth of FAU/SBA-15 shell was deduced from the influence of crystallization time on the synthesis of FAU/SBA-15 core-shell structured composite molecular sieve. HY dissociated partially in H2SO4 solution, and consisted of secondary structural units. This framework structure was more stable than its presence in the isolated form on the same ring or in the absence of Al. Thus it played a guiding role and connected with SBA-15 closely through the Si-O bond. This resulted in the gradual covering of the exterior surface of FAU phase by SBA-15 molecular sieves. The presence of SBA-15 restricted the formation of the other high mass components and increased the selectivity towards ethylbenzene.

Structural fluctuation governed dynamic diradical character in pentacene.

PubMed

Yang, Hongfang; Chen, Mengzhen; Song, Xinyu; Bu, Yuxiang

2015-06-07

We unravel intriguing dynamical diradical behavior governed by structural fluctuation in pentacene using ab initio molecular dynamics simulation. In contrast to static equilibrium configuration of pentacene with a closed-shell ground state without diradical character, due to structural fluctuation, some of its dynamical snapshot configurations exhibit an open-shell broken-symmetry singlet ground state with diradical character, and such diradical character presents irregular pulsing behavior in time evolution. Not all structural changes can lead to diradical character, only those involving the shortening of cross-linking C-C bonds and variations of the C-C bonds in polyacetylene chains are the main contributors. This scenario about diradicalization is distinctly different from that in long acenes. The essence is that structural distortion cooperatively raises the HOMO and lowers the LUMO, efficiently reducing the HOMO-LUMO and singlet-triplet energy gaps, which facilitate the formation of a broken-symmetry open-shell singlet state. The irregular pulsing behavior originates from the mixing of normal vibrations in pentacene. This fascinating behavior suggests the potential application of pentacene as a suitable building block in the design of new electronic devices due to its magnetism-controllability through energy induction. This work provides new insight into inherent electronic property fluctuation in acenes.

A generalized operational formula based on total electronic densities to obtain 3D pictures of the dual descriptor to reveal nucleophilic and electrophilic sites accurately on closed-shell molecules.

PubMed

Martínez-Araya, Jorge I

2016-09-30

By means of the conceptual density functional theory, the so-called dual descriptor (DD) has been adapted to be used in any closed-shell molecule that presents degeneracy in its frontier molecular orbitals. The latter is of paramount importance because a correct description of local reactivity will allow to predict the most favorable sites on a molecule to undergo nucleophilic or electrophilic attacks; on the contrary, an incomplete description of local reactivity might have serio us consequences, particularly for those experimental chemists that have the need of getting an insight about reactivity of chemical reagents before using them in synthesis to obtain a new compound. In the present work, the old approach based only on electronic densities of frontier molecular orbitals is replaced by the most accurate procedure that implies the use of total electronic densities thus keeping consistency with the essential principle of the DFT in which the electronic density is the fundamental variable and not the molecular orbitals. As a result of the present work, the DD will be able to properly describe local reactivities only in terms of total electronic densities. To test the proposed operational formula, 12 very common molecules were selected as the original definition of the DD was not able to describe their local reactivities properly. The ethylene molecule was additionally used to test the capability of the proposed operational formula to reveal a correct local reactivity even in absence of degeneracy in frontier molecular orbitals. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Electronic transport properties of inner and outer shells in near ohmic-contacted double-walled carbon nanotube transistors

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

Zhang, Yuchun; Zhou, Liyan; Zhao, Shangqian

2014-06-14

We investigate electronic transport properties of field-effect transistors based on double-walled carbon nanotubes, of which inner shells are metallic and outer shells are semiconducting. When both shells are turned on, electron-phonon scattering is found to be the dominant phenomenon. On the other hand, when outer semiconducting shells are turned off, a zero-bias anomaly emerges in the dependence of differential conductance on the bias voltage, which is characterized according to the Tomonaga-Luttinger liquid model describing tunneling into one-dimensional materials. We attribute these behaviors to different contact conditions for outer and inner shells of the double-walled carbon nanotubes. A simple model combiningmore » Luttinger liquid model for inner metallic shells and electron-phonon scattering in outer semiconducting shells is given here to explain our transport data at different temperatures.« less

Electrophobic interaction induced impurity clustering in metals

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

Zhou, Hong-Bo; Wang, Jin-Long; Jiang, W.

2016-10-01

We introduce the concept of electrophobic interaction, analogous to hydrophobic interaction, for describing the behavior of impurity atoms in a metal, a 'solvent of electrons'. We demonstrate that there exists a form of electrophobic interaction between impurities with closed electron shell structure, which governs their dissolution behavior in a metal. Using He, Be and Ar as examples, we predict by first-principles calculations that the electrophobic interaction drives He, Be or Ar to form a close-packed cluster with a clustering energy that follows a universal power-law scaling with the number of atoms (N) dissolved in a free electron gas, as wellmore » as W or Al lattice, as Ec is proportional to (N2/3-N). This new concept unifies the explanation for a series of experimental observations of close-packed inert-gas bubble formation in metals, and significantly advances our fundamental understanding and capacity to predict the solute behavior of impurities in metals, a useful contribution to be considered in future material design of metals for nuclear, metallurgical, and energy applications.« less

On the Role of Last Closed Drift Shell Dynamics in Driving Fast Losses and Van Allen Radiation Belt Extinction

NASA Astrophysics Data System (ADS)

Olifer, L.; Mann, I. R.; Morley, S. K.; Ozeke, L. G.; Choi, D.

2018-05-01

We present observations of very fast radiation belt loss as resolved using high time resolution electron flux data from the constellation of Global Positioning System (GPS) satellites. The time scale of these losses is revealed to be as short as ˜0.5-2 hr during intense magnetic storms, with some storms demonstrating almost total loss on these time scales and which we characterize as radiation belt extinction. The intense March 2013 and March 2015 storms both show such fast extinction, with a rapid recovery, while the September 2014 storm shows fast extinction but no recovery for around 2 weeks. By contrast, the moderate September 2012 storm which generated a three radiation belt morphology shows more gradual loss. We compute the last closed drift shell (LCDS) for each of these four storms and show a very strong correspondence between the LCDS and the loss patterns of trapped electrons in each storm. Most significantly, the location of the LCDS closely mirrors the high time resolution losses observed in GPS flux. The fast losses occur on a time scale shorter than the Van Allen Probes orbital period, are explained by proximity to the LCDS, and progress inward, consistent with outward transport to the LCDS by fast ultralow frequency wave radial diffusion. Expressing the location of the LCDS in L*, and not model magnetopause standoff distance in units of RE, clearly reveals magnetopause shadowing as the cause of the fast loss observed by the GPS satellites.

Atomistic tight-binding computations of the structural and optical properties of CdTe/CdX (X=S and Se)/ZnS core/shell/shell nanocrystals

NASA Astrophysics Data System (ADS)

Sukkabot, Worasak

2018-05-01

A study of CdTe/CdX (X=S and Se)/ZnS core/shell/shell nanocrystals is carried out using atomistic tight-binding theory and the configuration interaction method to provide information for applications in bioimaging, biolabeling, display devices and near-infrared electronic instruments. The calculations yield the dependences of the internal and external passivated shells on the natural behaviours of CdTe/CdX (X=S and Se)/ZnS core/shell/shell nanocrystals. The reduction of the optical band gaps is observed with increasing numbers of monolayers in the external ZnS shell due to quantum confinement. Interestingly, the optical band gaps of CdTe/CdS/ZnS core/shell/shell nanocrystals are greater than those of CdTe/CdSe/ZnS core/shell/shell nanocrystals. In the presence of an external ZnS-coated shell, electron-hole wave function overlaps, oscillation strengths, ground-state exchange energies and Stokes shift are improved, whereas ground-state coulomb energies and fine-structure splitting are reduced. The oscillation strengths, Stokes shift and fine-structure splitting are reduced with the increase in external ZnS shell thickness. The oscillation strengths, Stokes shift and fine-structure splitting of CdTe/CdS/ZnS core/shell/shell nanocrystals are larger than those of CdTe/CdSe/ZnS core/shell/shell nanocrystals. Reduction of the atomistic electron-hole interactions is observed with increasing external ZnS shell size. The strong electron-hole interactions are more probed in CdTe/CdS/ZnS core/shell/shell nanocrystals than in CdTe/CdSe/ZnS core/shell/shell nanocrystals.

Nano-scaling law: geometric foundation of thiolated gold nanomolecules.

PubMed

Dass, Amala

2012-04-07

Thiolated gold nanomolecules show a power correlation between the number of gold atoms and the thiolate ligands with a 2/3 scaling similar to Platonic and Archimedean solids. Nanomolecule stability is influenced by a universal geometric factor that is foundational to its stability through the Euclidean surface rule, in addition to the electronic shell closing factor and staple motif requirements. This journal is © The Royal Society of Chemistry 2012

Fine structural features of nanoscale zero-valent iron characterized by spherical aberration corrected scanning transmission electron microscopy (Cs-STEM).

PubMed

Liu, Airong; Zhang, Wei-xian

2014-09-21

An angstrom-resolution physical model of nanoscale zero-valent iron (nZVI) is generated with a combination of spherical aberration corrected scanning transmission electron microscopy (Cs-STEM), selected area electron diffraction (SAED), energy-dispersive X-ray spectroscopy (EDS) and electron energy-loss spectroscopy (EELS) on the Fe L-edge. Bright-field (BF), high-angle annular dark-field (HAADF) and secondary electron (SE) imaging of nZVI acquired by a Hitachi HD-2700 STEM show near atomic resolution images and detailed morphological and structural information of nZVI. The STEM-EDS technique confirms that the fresh nZVI comprises of a metallic iron core encapsulated with a thin layer of iron oxides or oxyhydroxides. SAED patterns of the Fe core suggest the polycrystalline structure in the metallic core and amorphous nature of the oxide layer. Furthermore, Fe L-edge of EELS shows varied structural features from the innermost Fe core to the outer oxide shell. A qualitative analysis of the Fe L(2,3) edge fine structures reveals that the shell of nZVI consists of a mixed Fe(II)/Fe(III) phase close to the Fe (0) interface and a predominantly Fe(III) at the outer surface of nZVI.

Effect of vertebral shell on injection pressure and intravertebral pressure in vertebroplasty.

PubMed

Baroud, Gamal; Vant, Christianne; Giannitsios, Demetri; Bohner, Marc; Steffen, Thomas

2005-01-01

An experimental biomechanical study conducted on osteoporotic cadaveric vertebrae. 1) To measure the intravertebral shell pressure and injection pressure; and 2) to determine the effect of the vertebral shell on the intravertebral shell pressure and on the injection pressure. Forces that govern cement flow are an essential component of the cement injection process in vertebroplasty. The vertebral shell may play a significant role in confining the flow of cement in the vertebral body and thereby affecting the intravertebral pressure and injection pressure. A small fenestration was created in the left lateral vertebral shell of 14 vertebrae. A valve to open and close the fenestration and a sensor to measure the intravertebral pressure were attached to the opening. A closed fenestration simulated an intact shell, whereas an open fenestration represented a vented shell. Injection pressure and intravertebral pressure at the shell were recorded during a controlled injection. A closed fenestration resulted in a significant increase in the intravertebral pressure at the shell. During the injection, the shell pressure increased on average to approximately 3.54 +/- 2.91 kPa. Conversely, an open fenestration resulted in an instant relaxation of the shell pressure to the ambient pressure of 0 kPa. Additionally, the injection pressure was approximately 97 times higher than the shell pressure. The presence of vertebral shell seems to be important for intravertebral pressure. However, the intravertebral shell pressure adds very little to the injection pressure.

Contributions from inner and outer shell electron energies to reaction heats for C/sub 1/, C/sub 2/, and C/sub 3/ hydrocarbons

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

George, P.; Bock, C.W.; Trachtman, M.

1979-04-01

The expectation energy values E/sub k/, V/sub ee/, V/sub nn/, V/sub en/, and E/sub T/ have been calculated for H/sub 2/ and the C/sub 1/, C/sub 2/, and C/sub 3/ hydrocarbons using a (9,5) basis set and the experimental geometries. Treating the theoretical reaction heat, ..delta..E/sub T/, as the resultant of the nuclear repulsion term, ..delta..V/sub nn/, and the net electron energy term, ..delta..E/sub elec/ = ..delta..E/sub k/ + ..delta..V/sub ee/ + ..delta..V/sub en/, the contribution of inner and outer shell electron energies to ..delta..E/sub elec/, and hence to ..delta..E/sub T/, has been calculated for a large number of hydrocarbonmore » reactions by evaluating the Coulson--Neilson energies eta/sub i/, where eta/sub i/ = E/sub elec/. For the vast majority of reactions, 67/84, the change in inner shell electron energy, (..delta sigma..eta/sub i/)/sub inner/, accounts for more than 10% of ..delta..E/sub elec/, in many cases being as high as 20-35%. Furthermore, in addition to these cases in which the change in inner shell electron energy serves to augment (significantly) the change in outer shell electron energy, there are other cases in which the change in inner shell electron energy either exceeds in magnitude the change in outer shell energy, or is even opposite in sign, indicative of inner and outer shell electrons acting contrariwise. Inner shell electron energies contribute to the reaction heats because they are structure dependent, like the more familiar orbital energies epsilon, but the dependence is of a different kind.« less

Electron-impact excitation of diatomic hydride cations - I. HeH+, CH+, ArH+

NASA Astrophysics Data System (ADS)

Hamilton, James R.; Faure, Alexandre; Tennyson, Jonathan

2016-01-01

R-matrix calculations combined with the adiabatic nuclei approximation are used to compute electron-impact rotational excitation rates for three closed-shell diatomic cations, HeH+, CH+, ArH+. Comparisons with previous studies show that an improved treatment of threshold effects leads to significant changes in the low temperature rates; furthermore the new calculations suggest that excitation of CH+ is dominated by ΔJ = 1 transitions as is expected for cations with a large dipole moment. A model for ArH+ excitation in the Crab nebula is presented which gives results consistent with the observations for electron densities in the range 2-3 × 103 cm-3.

Convective and diffusive ULF wave driven radiation belt electron transport

NASA Astrophysics Data System (ADS)

Degeling, A. W.; Rankin, R.; Elkington, S. R.

2011-12-01

The process of magnetospheric radiation belt electron transport driven by ULF waves is studied using a 2-D ideal MHD model for ULF waves in the equatorial plane including day/night asymmetry and a magnetopause boundary, and a test kinetic model for equatorially mirroring electrons. We find that ULF wave disturbances originating along the magnetopause flanks in the afternoon sector can act to periodically inject phase space density from these regions into the magnetosphere. Closely spaced drift-resonant surfaces for electrons with a given magnetic moment in the presence of the ULF waves create a layer of stochastic dynamics for L-shells above 6.5-7 in the cases examined, extending to the magnetopause. The phase decorrelation time scale for the stochastic region is estimated by the relaxation time for the diffusion coefficient to reach a steady value. This is found to be of the order of 10-15 wave periods, which is commensurate with the typical duration of observed ULF wave packets in the magnetosphere. For L-shells earthward of the stochastic layer, transport is limited to isolated drift-resonant islands in the case of narrowband ULF waves. We examine the effect of increasing the bandwidth of the ULF wave driver by summing together wave components produced by a set of independent runs of the ULF wave model. The wave source spectrum is given a flat-top amplitude of variable width (adjusted for constant power) and random phase. We find that increasing bandwidth can significantly enhance convective transport earthward of the stochastic layer and extend the stochastic layer to lower L-shells.

Multishelled NiO Hollow Microspheres for High-performance Supercapacitors with Ultrahigh Energy Density and Robust Cycle Life

PubMed Central

Qi, Xinhong; Zheng, Wenji; Li, Xiangcun; He, Gaohong

2016-01-01

Multishelled NiO hollow microspheres for high-performance supercapacitors have been prepared and the formation mechanism has been investigated. By using resin microspheres to absorb Ni2+ and subsequent proper calcinations, the shell numbers, shell spacing and exterior shell structure were facilely controlled via varying synthetic parameters. Particularly, the exterior shell structure that accurately associated with the ion transfer is finely controlled by forming a single shell or closed exterior double-shells. Among multishelled NiO hollow microspheres, the triple-shelled NiO with an outer single-shelled microspheres show a remarkable capacity of 1280 F g−1 at 1 A g−1, and still keep a high value of 704 F g−1 even at 20 A g−1. The outstanding performances are attributed to its fast ion/electron transfer, high specific surface area and large shell space. The specific capacitance gradually increases to 108% of its initial value after 2500 cycles, demonstrating its high stability. Importantly, the 3S-NiO-HMS//RGO@Fe3O4 asymmetric supercapacitor shows an ultrahigh energy density of 51.0 Wh kg−1 at a power density of 800 W kg−1, and 78.8% capacitance retention after 10,000 cycles. Furthermore, multishelled NiO can be transferred into multishelled Ni microspheres with high-efficient H2 generation rate of 598.5 mL H2 min−1 g−1Ni for catalytic hydrolysis of NH3BH3 (AB). PMID:27616420

The influence of MOVPE growth conditions on the shell of core-shell GaN microrod structures

NASA Astrophysics Data System (ADS)

Schimpke, Tilman; Avramescu, Adrian; Koller, Andreas; Fernando-Saavedra, Amalia; Hartmann, Jana; Ledig, Johannes; Waag, Andreas; Strassburg, Martin; Lugauer, Hans-Jürgen

2017-05-01

A core-shell geometry is employed for most next-generation, three-dimensional opto-electric devices based on III-V semiconductors and grown by metal organic vapor phase epitaxy (MOVPE). Controlling the shape of the shell layers is fundamental for device optimization, however no detailed analysis of the influence of growth conditions has been published to date. We study homogeneous arrays of gallium nitride core-shell microrods with height and diameter in the micrometer range and grown in a two-step selective area MOVPE process. Changes in shell shape and homogeneity effected by deliberately altered shell growth conditions were accurately assessed by digital analysis of high-resolution scanning electron microscope images. Most notably, two temperature regimes could be established, which show a significantly different behavior with regard to material distribution. Above 900 °C of wafer carrier temperature, the shell thickness along the growth axis of the rods was very homogeneous, however variations between vicinal rods increase. In contrast, below 830 °C the shell thickness is higher close to the microrod tip than at the base of the rods, while the lateral homogeneity between neighboring microrods is very uniform. This temperature effect could be either amplified or attenuated by changing the remaining growth parameters such as reactor pressure, structure distance, gallium precursor, carrier gas composition and dopant materials. Possible reasons for these findings are discussed with respect to GaN decomposition as well as the surface and gas phase diffusion of growth species, leading to an improved control of the functional layers in next-generation 3D V-III devices.

Magnesium Nanoparticles for Hydrogen Storage: Structure, Kinetics and Thermodynamics

NASA Astrophysics Data System (ADS)

Pasquini, L.; Brighi, M.; Montone, A.; Vittori Antisari, M.; Dam, B.; Palmisano, V.; Bonetti, E.

2012-08-01

Magnesium nanoparticles coated by a native oxide shell and decorated by palladium clusters were synthesized by the inert gas condensation technique. The kinetics and thermodynamics of hydrogen sorption were investigated by Sieverts measurements at high temperature and by optical hydrogenography close to ambient temperature. The structure and morphology of the nanoparticles were studied by electron microscopy and X-ray diffraction both in the as-prepared state and after hydrogen sorption cycles.

Synthesis of core–shell structured FAU/SBA-15 composite molecular sieves and their performance in catalytic cracking of polystyrene

PubMed Central

Du, Jinlong; Shi, Chunwei; Wu, Wenyuan; Bian, Xue; Chen, Ping; Cui, Qingzhu; Cui, Zhixuan

2017-01-01

Abstract Composite molecular sieves, FAU/SBA-15, having core-shell structure were synthesized. The synthesized composite sieves were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), pyrolysis fourier transform infrared (Py-FTIR) spectroscopy, temperature programmed desorption spectra (NH3-TPD), UV Raman spectroscopy, nuclear magnetic resonance (NMR) and other techniques. XRD, SEM, TEM, N2 adsorption-desorption, mass spectrometry, NMR and EDS results showed that the composite molecular sieve contained two pore channels. Py-FTIR results showed that the addition of HY molecular sieves improved the acidity of the composite zeolite. The crystallization mechanism during the growth of FAU/SBA-15 shell was deduced from the influence of crystallization time on the synthesis of FAU/SBA-15 core-shell structured composite molecular sieve. HY dissociated partially in H2SO4 solution, and consisted of secondary structural units. This framework structure was more stable than its presence in the isolated form on the same ring or in the absence of Al. Thus it played a guiding role and connected with SBA-15 closely through the Si-O bond. This resulted in the gradual covering of the exterior surface of FAU phase by SBA-15 molecular sieves. The presence of SBA-15 restricted the formation of the other high mass components and increased the selectivity towards ethylbenzene. PMID:29383044

Benchmark of Dynamic Electron Correlation Models for Seniority-Zero Wave Functions and Their Application to Thermochemistry.

PubMed

Boguslawski, Katharina; Tecmer, Paweł

2017-12-12

Wave functions restricted to electron-pair states are promising models to describe static/nondynamic electron correlation effects encountered, for instance, in bond-dissociation processes and transition-metal and actinide chemistry. To reach spectroscopic accuracy, however, the missing dynamic electron correlation effects that cannot be described by electron-pair states need to be included a posteriori. In this Article, we extend the previously presented perturbation theory models with an Antisymmetric Product of 1-reference orbital Geminal (AP1roG) reference function that allows us to describe both static/nondynamic and dynamic electron correlation effects. Specifically, our perturbation theory models combine a diagonal and off-diagonal zero-order Hamiltonian, a single-reference and multireference dual state, and different excitation operators used to construct the projection manifold. We benchmark all proposed models as well as an a posteriori Linearized Coupled Cluster correction on top of AP1roG against CR-CC(2,3) reference data for reaction energies of several closed-shell molecules that are extrapolated to the basis set limit. Moreover, we test the performance of our new methods for multiple bond breaking processes in the homonuclear N 2 , C 2 , and F 2 dimers as well as the heteronuclear BN, CO, and CN + dimers against MRCI-SD, MRCI-SD+Q, and CR-CC(2,3) reference data. Our numerical results indicate that the best performance is obtained from a Linearized Coupled Cluster correction as well as second-order perturbation theory corrections employing a diagonal and off-diagonal zero-order Hamiltonian and a single-determinant dual state. These dynamic corrections on top of AP1roG provide substantial improvements for binding energies and spectroscopic properties obtained with the AP1roG approach, while allowing us to approach chemical accuracy for reaction energies involving closed-shell species.

Design of WO3-SnO2 core-shell nanofibers and their enhanced gas sensing performance based on different work function

NASA Astrophysics Data System (ADS)

Li, Feng; Gao, Xing; Wang, Rui; Zhang, Tong

2018-06-01

In this work, core-shell WO3-SnO2 (CS-WS) nanofibers (NFs) have been successfully synthesized via a coaxial electrospinning approach. The structure and morphology characteristics of the resultant products were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectra (XPS). To investigate the sensing mechanism of the CS-WS NFs, sensors based on SnO2 NFs, WO3 NFs, and SnO2-WO3 composite NFs were fabricated respectively, and their gas sensing properties were investigated by using CO, ethanol, toluene, acetone, and ammonia as the test gas. The results indicated that the CS-WS NFs exhibited a good response to ethanol (5.09 at 10 ppm) and short response/recovery time (18.5 s and 282 s) compared with the other test gases. The enhanced ethanol sensing properties of CS-WS NFs compared with those of SnO2 NFs were closely associated with the CS structure and its derivative effect due to the different work function of SnO2 and WO3. The approach proposed in this study may contribute to the realization of more sensitive metal oxide semiconductor (MOS) core-shell heterostructure sensors.

Discovery of the Electronic Spectra of Hps and Dps

NASA Astrophysics Data System (ADS)

Grimminger, Robert A.; Wei, Jie; Ellis, Blaine; Clouthier, Dennis J.; Wang, Zhong; Sears, Trevor

2009-06-01

The hitherto unknown electronic spectrum of the closed shell transient molecule HPS has been observed in the 685 - 846 nm region by laser-induced fluorescence and single vibronic level emission techniques. HPS (and DPS) were produced in a pulsed electric discharge jet using a precursor mixture of 3% PH_3 and 1% H_2S (or PD_3 and D_2S) in high pressure argon. The weak set of observed bands are assigned to the à ^1A^''-X˜ ^1A^' electronic transition on the basis of chemical evidence, isotope shifts and the correspondence of the vibrational frequencies, excitation energy, and band contours with predictions based on our own high level ab initio calculations. Theory predicts that the HPS bond angle decreases on electronic excitation, contrary to expectations based on Walsh diagrams.

On the role of last closed drift shell dynamics in driving fast losses and Van Allen radiation belt extinction

DOE PAGES

Olifer, Leonid; Mann, Ian R.; Morley, Steven Karl; ...

2018-04-20

We present observations of very fast radiation belt loss as resolved using high time resolution electron flux data from the constellation of Global Positioning System (GPS) satellites. The time scale of these losses is revealed to be as short as ~0.5–2 hr during intense magnetic storms, with some storms demonstrating almost total loss on these time scales and which we characterize as radiation belt extinction. The intense March 2013 and March 2015 storms both show such fast extinction, with a rapid recovery, while the September 2014 storm shows fast extinction but no recovery for around 2 weeks. By contrast, themore » moderate September 2012 storm which generated a three radiation belt morphology shows more gradual loss. Here, we compute the last closed drift shell (LCDS) for each of these four storms and show a very strong correspondence between the LCDS and the loss patterns of trapped electrons in each storm. Most significantly, the location of the LCDS closely mirrors the high time resolution losses observed in GPS flux. The fast losses occur on a time scale shorter than the Van Allen Probes orbital period, are explained by proximity to the LCDS, and progress inward, consistent with outward transport to the LCDS by fast ultralow frequency wave radial diffusion. Expressing the location of the LCDS in L*, and not model magnetopause standoff distance in units of RE, clearly reveals magnetopause shadowing as the cause of the fast loss observed by the GPS satellites.« less

On the role of last closed drift shell dynamics in driving fast losses and Van Allen radiation belt extinction

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

Olifer, Leonid; Mann, Ian R.; Morley, Steven Karl

We present observations of very fast radiation belt loss as resolved using high time resolution electron flux data from the constellation of Global Positioning System (GPS) satellites. The time scale of these losses is revealed to be as short as ~0.5–2 hr during intense magnetic storms, with some storms demonstrating almost total loss on these time scales and which we characterize as radiation belt extinction. The intense March 2013 and March 2015 storms both show such fast extinction, with a rapid recovery, while the September 2014 storm shows fast extinction but no recovery for around 2 weeks. By contrast, themore » moderate September 2012 storm which generated a three radiation belt morphology shows more gradual loss. Here, we compute the last closed drift shell (LCDS) for each of these four storms and show a very strong correspondence between the LCDS and the loss patterns of trapped electrons in each storm. Most significantly, the location of the LCDS closely mirrors the high time resolution losses observed in GPS flux. The fast losses occur on a time scale shorter than the Van Allen Probes orbital period, are explained by proximity to the LCDS, and progress inward, consistent with outward transport to the LCDS by fast ultralow frequency wave radial diffusion. Expressing the location of the LCDS in L*, and not model magnetopause standoff distance in units of RE, clearly reveals magnetopause shadowing as the cause of the fast loss observed by the GPS satellites.« less

Core–shell-structured Li 3V 2(PO 4) 3 –LiVOPO 4 nanocomposites cathode for high-rate and long-life lithium-ion batteries

DOE PAGES

Sun, Pingping; Wang, Xiuzhen; Zhu, Kai; ...

2017-01-13

A facile strategy has been developed to construct unique core–shell-structured Li 2.7V 2.1(PO 4) 3 nanocomposites with a Li 3V 2(PO 4) 3 core and LiVOPO 4 shell by using nonstoichiometric design and high-energy ball milling (HEBM) treatment. The HEBM treatment supplies enough energy to drive the excess V atoms to the surface to form a V-enriched shell. Such kind of cathode can deliver a high reversible capacity of 131.5 mAhg $-$1 at 0.5 C, which is close to the theoretical capacity (133 mAhg $-$1 in 3.0–4.3 V). Even at 20 C, it still delivers an excellent discharge capacity ofmore » 116.3 mAhg $-$1, and a remarkable capacity of 111.0 mAhg $-$1 after 1000 cycles, corresponding to an ultra-small capacity-loss of 0.0046% per cycle. Finally, the significantly improved high-rate electrochemical performance can be attributed to the active shell of LiVOPO 4, which not only efficiently facilitates the electron and Li + ion transport during cycling processes, but also accommodates more Li+ ions to effectively compensate the capacity loss of the core.« less

Core–shell interaction and its impact on the optical absorption of pure and doped core-shell CdSe/ZnSe nanoclusters

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

Wang, Xinqin; Cui, Yingqi; Zeng, Qun

The structural, electronic, and optical properties of core-shell nanoclusters, (CdSe){sub x}@(CdSe){sub y} and their Zn-substituted complexes of x = 2–4 and y = 16–28, were studied with density functional theory calculations. The substitution was applied in the cores, the shells, and/or the whole clusters. All these clusters are characterized by their core-shell structures in which the core-shell interaction was found different from those in core or in shell, as reflected by their bondlengths, volumes, and binding energies. Moreover, the core and shell combine together to compose a new cluster with electronic and optical properties different from those of separated individuals,more » as reflected by their HOMO-LUMO gaps and optical absorptions. With the substitution of Cd by Zn, the structural, electronic, and optical properties of clusters change regularly. The binding energy increases with Zn content, attributed to the strong Zn–Se bonding. For the same core/shell, the structure with a CdSe shell/core has a narrower gap than that with a ZnSe shell/core. The optical absorption spectra also change accordingly with Zn substitution. The peaks blueshift with increasing Zn concentration, accompanying with shape variations in case large number of Cd atoms are substituted. Our calculations reveal the core-shell interaction and its influence on the electronic and optical properties of the core-shell clusters, suggesting a composition–structure–property relationship for the design of core-shell CdSe and ZnSe nanoclusters.« less

Reexamination of the interaction of atoms with a LiF(001) surface

NASA Astrophysics Data System (ADS)

Miraglia, J. E.; Gravielle, M. S.

2017-02-01

Pairwise additive potentials for multielectronic atoms interacting with a LiF(001) surface are revisited by including an improved description of the electron density associated with the different lattice sites, as well as nonlocal electron density contributions. Within this model, the electron distribution around each ionic site of the crystal is described by means of a so-called "onion" approach that accounts for the influence of the Madelung potential. From such densities, binary interatomic potentials are then derived by using well-known nonlocal functionals. Rumpling and long-range contributions due to projectile polarization and van der Waals forces are also included. We apply this pairwise additive approximation to evaluate the interaction potential between closed-shell (He, Ne, Ar, Kr, and Xe) and open-shell (N, S, and Cl) atoms and the LiF surface, analyzing the relative importance of the different contributions. The performance of the proposed potentials is assessed by contrasting angular positions of rainbow and supernumerary rainbow maxima produced by fast grazing incidence with available experimental data. One important result of our model is that both van der Waals contributions and thermal lattice vibrations play a negligible role for normal energies in the eV range.

Target electron ionization in Li2+-Li collisions: A multi-electron perspective

NASA Astrophysics Data System (ADS)

Śpiewanowski, M. D.; Gulyás, L.; Horbatsch, M.; Kirchner, T.

2015-05-01

The recent development of the magneto-optical trap reaction-microscope has opened a new chapter for detailed investigations of charged-particle collisions from alkali atoms. It was shown that energy-differential cross sections for ionization from the outer-shell in O8+-Li collisions at 1500 keV/amu can be readily explained with the single-active-electron approximation. Understanding of K-shell ionization, however, requires incorporating many-electron effects. An ionization-excitation process was found to play an important role. We present a theoretical study of target electron removal in Li2+-Li collisions at 2290 keV/amu. The results indicate that in outer-shell ionization a single-electron process plays the dominant part. However, the K-shell ionization results are more difficult to interpret. On one hand, we find only weak contributions from multi-electron processes. On the other hand, a large discrepancy between experimental and single-particle theoretical results indicate that multi-electron processes involving ionization from the outer shell may be important for a complete understanding of the process. Work supported by NSERC, Canada and the Hungarian Scientific Research Fund.

Copper fine-structure K-shell electron impact ionization cross sections for fast-electron diagnostic in laser-solid experiments

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

Palmeri, P., E-mail: patrick.palmeri@umons.ac.be; Quinet, P., E-mail: pascal.quinet@umons.ac.be; IPNAS, Université de Liège, B-4000 Liège

2015-03-15

The K-shell electron impact ionization (EII) cross section, along with the K-shell fluorescence yield, is one of the key atomic parameters for fast-electron diagnostic in laser-solid experiments through the K-shell emission cross section. In addition, copper is a material that has been often used in those experiments because it has a maximum total K-shell emission yield. Furthermore, in a campaign dedicated to the modeling of the K lines of astrophysical interest (Palmeri et al., 2012), the K-shell fluorescence yields for the K-vacancy fine-structure atomic levels of all the copper isonuclear ions have been calculated. In this study, the K-shell EII crossmore » sections connecting the ground and the metastable levels of the parent copper ions to the daughter ions K-vacancy levels considered in Palmeri et al. (2012) have been determined. The relativistic distorted-wave (DW) approximation implemented in the FAC atomic code has been used for the incident electron kinetic energies up to 10 times the K-shell threshold energies. Moreover, the resulting DW cross sections have been extrapolated at higher energies using the asymptotic form proposed by Davies et al. (2013)« less

Teaching Valence Shell Electron Pair Repulsion (VSEPR) Theory

ERIC Educational Resources Information Center

Talbot, Christopher; Neo, Choo Tong

2013-01-01

This "Science Note" looks at the way that the shapes of simple molecules can be explained in terms of the number of electron pairs in the valence shell of the central atom. This theory is formally known as valence shell electron pair repulsion (VSEPR) theory. The article explains the preferred shape of chlorine trifluoride (ClF3),…

Finalizing the DTAG: Implementation and Testing of Design Improvements for Reliability and Availability

DTIC Science & Technology

2015-09-30

acoustics and fine scale motion. The success of the Dtag has resulted in an increased demand for the instrument from researchers both within the...sensor blocks sound when the animal is close to the surface. The polyethylene shell was eliminated in the Dtag-3 design to improve acoustic ...into 3 main sub-assemblies (Figure 5): 1) foam sub-assembly, 2) sensor sub-assembly, and 3) Electronics sub-assembly. This separation enables rapid

Improving Effectiveness of Bioremediation at DNAPL Source Zone Sites by Applying Partitioning Electron Donors (PEDs)

DTIC Science & Technology

2014-07-01

at an effective concentration at the DNAPL:water interface for the growth of and consumption by dechlorinating biomass . In heterogeneous geological...the promotion of dechlorinating biomass growth close to the DNAPL, which results in sustained enhanced DNAPL dissolution rates. This approach...fine- grained sands with varying amounts of shell fragments, with a hydraulic conductivity of 3 ft/day in the 30 to 45 ft BLS interval; • 45 to 48 ft

Vanadium fine-structure K-shell electron impact ionization cross sections for fast-electron diagnostic in laser–solid experiments

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

Palmeri, P., E-mail: patrick.palmeri@umons.ac.be; Quinet, P., E-mail: pascal.quinet@umons.ac.be; IPNAS, Université de Liège, B-4000 Liège

2015-09-15

The K-shell electron impact ionization (EII) cross section, along with the K-shell fluorescence yield, is one of the key atomic parameters for fast-electron diagnostic in laser–solid experiments through the K-shell emission cross section. In addition, in a campaign dedicated to the modeling of the K lines of astrophysical interest (Palmeri et al. (2012)), the K-shell fluorescence yields for the K-vacancy fine-structure atomic levels of all the vanadium isonuclear ions have been calculated. In this study, the K-shell EII cross sections connecting the ground and the metastable levels of the parent vanadium ions to the daughter ions K-vacancy levels considered in Palmerimore » et al. (2012) have been determined. The relativistic distorted-wave (DW) approximation implemented in the FAC atomic code has been used for the incident electron kinetic energies up to 20 times the K-shell threshold energies. Moreover, the resulting DW cross sections have been extrapolated at higher energies using the asymptotic behavior of the modified relativistic binary encounter Bethe model (MRBEB) of Guerra et al. (2012) with the density-effect correction proposed by Davies et al. (2013)« less

Mesoscale studies of ionic closed membranes with polyhedral geometries

DOE PAGES

Olvera de la Cruz, Monica

2016-06-01

Large crystalline molecular shells buckle spontaneously into icosahedra while multicomponent shells buckle into various polyhedra. Continuum elastic theory explains the buckling of closed shells with one elastic component into icosahedra. A generalized elastic model, on the other hand, describes the spontaneous buckling of inhomogeneous shells into regular and irregular polyhedra. By coassembling water-insoluble anionic (–1) amphiphiles with cationic (3+) amphiphiles, we realized ionic vesicles. Results revealed that surface crystalline domains and the unusual shell shapes observed arise from the competition of ionic correlations with charge-regulation. We explain here the mechanism by which these ionic membranes generate a mechanically heterogeneous vesicle.

Mass Measurements Demonstrate a Strong N = 28 Shell Gap in Argon

DOE PAGES

Meisel, Z.; George, S.; Ahn, S.; ...

2015-01-15

We present results from recent time-of-flight nuclear mass measurements at the National Superconducting Cyclotron Laboratory at Michigan State University. We report the first mass measurements of 48Ar and 49Ar and find atomic mass excesses of -22.28(31) MeV and -17.8(1.1) MeV, respectively. These masses provide strong evidence for the closed shell nature of neutron number N = 28 in argon, which is therefore the lowest even-Z element exhibiting the N = 28 closed shell. The resulting trend in binding-energy differences, which probes the strength of the N = 28 shell, compares favorably with shell-model calculations in the sd-pf shell using SDPF-Umore » and SDPF-MU Hamiltonians.« less

Germanium Nanowires-in-Graphite Tubes via Self-Catalyzed Synergetic Confined Growth and Shell-Splitting Enhanced Li-Storage Performance.

PubMed

Sun, Yong; Jin, Shuaixing; Yang, Guowei; Wang, Jing; Wang, Chengxin

2015-04-28

Despite the high theoretical capacity, pure Ge has various difficulties such as significant volume expansion and electron and Li(+) transfer problems, when applied as anode materials in lithium ion battery (LIB), for which the solution would finally rely on rational design like advanced structures and available hybrid. Here in this work, we report a one-step synthesis of Ge nanowires-in-graphite tubes (GNIGTs) with the liquid Ge/C synergetic confined growth method. The structure exhibits impressing LIB behavior in terms of both cyclic stability and rate performance. We found the semiclosed graphite shell with thickness of ∼50 layers experience an interesting splitting process that was driven by electrolyte diffusion, which occurs before the Ge-Li alloying plateau begins. Two types of different splitting mechanism addressed as "inside-out"/zipper effect and "outside-in" dominate this process, which are resulted from the SEI layer growing longitudinally along the Ge-graphite interface and the lateral diffusion of Li(+) across the shell, respectively. The former mechanism is the predominant way driving the initial shell to split, which behaves like a zipper with SEI layer as invisible puller. After repeated Li(+) insertion/exaction, the GNIGTs configuration is finally reconstructed by forming Ge nanowires-thin graphite strip hybrid, both of which are in close contact, resulting in enormous enchantment to the electrons/Li(+) transport. These features make the structures perform well as anode material in LIB. We believe both the progress in 1D assembly and the structure evolution of this Ge-C composite would contribute to the design of advanced LIB anode materials.

A stable compound of helium and sodium at high pressure

DOE PAGES

Dong, Xiao; Oganov, Artem R.; Goncharov, Alexander F.; ...

2017-02-06

Helium is generally understood to be chemically inert and this is due to its extremely stable closed-shell electronic configuration, zero electron affinity and an unsurpassed ionization potential. It is not known to form thermodynamically stable compounds, except a few inclusion compounds. Here, using the ab initio evolutionary algorithm USPEX and subsequent high-pressure synthesis in a diamond anvil cell, we report the discovery of a thermodynamically stable compound of helium and sodium, Na 2He, which has a fluorite-type structure and is stable at pressures >113 GPa. We show that the presence of He atoms causes strong electron localization and makes thismore » material insulating. This phase is an electride, with electron pairs localized in interstices, forming eight-centre two-electron bonds within empty Na 8 cubes. As a result, we also predict the existence of Na 2HeO with a similar structure at pressures above 15 GPa.« less

A stable compound of helium and sodium at high pressure

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

Dong, Xiao; Oganov, Artem R.; Goncharov, Alexander F.

Helium is generally understood to be chemically inert and this is due to its extremely stable closed-shell electronic configuration, zero electron affinity and an unsurpassed ionization potential. It is not known to form thermodynamically stable compounds, except a few inclusion compounds. Here, using the ab initio evolutionary algorithm USPEX and subsequent high-pressure synthesis in a diamond anvil cell, we report the discovery of a thermodynamically stable compound of helium and sodium, Na 2He, which has a fluorite-type structure and is stable at pressures >113 GPa. We show that the presence of He atoms causes strong electron localization and makes thismore » material insulating. This phase is an electride, with electron pairs localized in interstices, forming eight-centre two-electron bonds within empty Na 8 cubes. We also predict the existence of Na 2HeO with a similar structure at pressures above 15 GPa.« less

A stable compound of helium and sodium at high pressure

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

Dong, Xiao; Oganov, Artem R.; Goncharov, Alexander F.

Helium is generally understood to be chemically inert and this is due to its extremely stable closed-shell electronic configuration, zero electron affinity and an unsurpassed ionization potential. It is not known to form thermodynamically stable compounds, except a few inclusion compounds. Here, using the ab initio evolutionary algorithm USPEX and subsequent high-pressure synthesis in a diamond anvil cell, we report the discovery of a thermodynamically stable compound of helium and sodium, Na 2He, which has a fluorite-type structure and is stable at pressures >113 GPa. We show that the presence of He atoms causes strong electron localization and makes thismore » material insulating. This phase is an electride, with electron pairs localized in interstices, forming eight-centre two-electron bonds within empty Na 8 cubes. As a result, we also predict the existence of Na 2HeO with a similar structure at pressures above 15 GPa.« less

Free Electrons to Molecular Bonds and Back: Closing the Energetic Oxygen Reduction (ORR)-Oxygen Evolution (OER) Cycle Using Core-Shell Nanoelectrocatalysts.

PubMed

Strasser, Peter

2016-11-15

Nanomaterial science and electrocatalytic science have entered a successful "nanoelectrochemical" symbiosis, in which novel nanomaterials offer new frontiers for studies on electrocatalytic charge transfer, while electrocatalytic processes give meaning and often practical importance to novel nanomaterial concepts. Examples of this fruitful symbiosis are dealloyed core-shell nanoparticle electrocatalysts, which often exhibit enhanced kinetic charge transfer rates at greatly improved atom-efficiency. As such, they represent ideal electrocatalyst architectures for the acidic oxygen reduction reaction to water (ORR) and the acidic oxygen evolution reaction from water (OER) that require scarce Pt- and Ir-based catalysts. Together, these two reactions constitute the "O-cycle", a key elemental process loop in the field of electrochemical energy interconversion between electricity (free electrons) and molecular bonds (H 2 O/O 2 ), realized in the combination of water electrolyzers and hydrogen/oxygen fuel cells. In this Account, we describe our recent efforts to design, synthesize, understand, and test noble metal-poor dealloyed Pt and Ir core-shell nanoparticles for deployment in acidic polymer electrolyte membrane (PEM) electrolyzers and PEM fuel cells. Spherical dealloyed Pt core-shell particles, derived from PtNi 3 precursor alloys, showed favorable ORR activity. More detailed size-activity correlation studies further revealed that the 6-8 nm diameter range is a most desirable initial particle size range in order to maximize the particle Ni content after ORR testing and to preserve performance stability. Similarly, dealloyed and oxidized IrO x core-shell particles derived from Ni-rich Ir-Ni precursor particles proved highly efficient oxygen evolution reaction (OER) catalysts in acidic conditions. In addition to the noble metal savings in the particle cores, the Pt core-shell particles are believed to benefit in terms of their mass-based electrochemical kinetics from surface lattice strain effects that tune the adsorption energies and barriers of elementary steps. The molecular mechanism of the kinetic benefit of the dealloyed IrO x particle needs more attention, but there is mounting evidence for ligand hole effects in defect-rich IrO x shells that generate preactive oxygen centers.

The radiation belts and ring current: the relationship between Dst and relativistic electron phase space density

NASA Astrophysics Data System (ADS)

Grande, M.; Carter, M.; Perry, C. H.

2002-03-01

We briefly review the radiation belts, before moving on to a more detailed examination of the relationship between the Disturbance Storm Time Index (Dst) and relativistic electron flux. We show that there is a strong correlation between the growth phase of storms, as represented by Dst, and dropouts in electron flux. Recovery is accompanied by growth of the electron flux. We calculate Electron Phase Space Density (PSD) as a function of adiabatic invariants using electron particle mesurements from the Imaging Electron Sensor (IES) and the High Sensitivity Telescope (HIST) on the CEPPAD experiment onboard POLAR. We present the time history of the phase space density through the year 1998 as L-sorted plots and look in detail at the May 98 storm. Comparison with the Tsyganenko 96 magnetic field model prediction for the last closed field line suggests that the loss of electrons may be directly caused by the opening of drift shells.

Effects of Drift-Shell Splitting by Chorus Waves on Radiation Belt Electrons

NASA Astrophysics Data System (ADS)

Chan, A. A.; Zheng, L.; O'Brien, T. P., III; Tu, W.; Cunningham, G.; Elkington, S. R.; Albert, J.

2015-12-01

Drift shell splitting in the radiation belts breaks all three adiabatic invariants of charged particle motion via pitch angle scattering, and produces new diffusion terms that fully populate the diffusion tensor in the Fokker-Planck equation. Based on the stochastic differential equation method, the Radbelt Electron Model (REM) simulation code allows us to solve such a fully three-dimensional Fokker-Planck equation, and to elucidate the sources and transport mechanisms behind the phase space density variations. REM has been used to perform simulations with an empirical initial phase space density followed by a seed electron injection, with a Tsyganenko 1989 magnetic field model, and with chorus wave and ULF wave diffusion models. Our simulation results show that adding drift shell splitting changes the phase space location of the source to smaller L shells, which typically reduces local electron energization (compared to neglecting drift-shell splitting effects). Simulation results with and without drift-shell splitting effects are compared with Van Allen Probe measurements.

Energy-dependent dynamics of keV to MeV electrons in the inner zone, outer zone, and slot regions.

PubMed

Reeves, Geoffrey D; Friedel, Reiner H W; Larsen, Brian A; Skoug, Ruth M; Funsten, Herbert O; Claudepierre, Seth G; Fennell, Joseph F; Turner, Drew L; Denton, Mick H; Spence, Harlan E; Blake, J Bernard; Baker, Daniel N

2016-01-01

We present observations of the radiation belts from the Helium Oxygen Proton Electron and Magnetic Electron Ion Spectrometer particle detectors on the Van Allen Probes satellites that illustrate the energy dependence and L shell dependence of radiation belt enhancements and decays. We survey events in 2013 and analyze an event on 1 March in more detail. The observations show the following: (a) at all L shells, lower energy electrons are enhanced more often than higher energies; (b) events that fill the slot region are more common at lower energies; (c) enhancements of electrons in the inner zone are more common at lower energies; and (d) even when events do not fully fill the slot region, enhancements at lower energies tend to extend to lower L shells than higher energies. During enhancement events the outer zone extends to lower L shells at lower energies while being confined to higher L shells at higher energies. The inner zone shows the opposite with an outer boundary at higher L shells for lower energies. Both boundaries are nearly straight in log(energy) versus L shell space. At energies below a few 100 keV, radiation belt electron penetration through the slot region into the inner zone is commonplace, but the number and frequency of "slot filling" events decreases with increasing energy. The inner zone is enhanced only at energies that penetrate through the slot. Energy- and L shell-dependent losses (that are consistent with whistler hiss interactions) return the belts to more quiescent conditions.

Energy-dependent dynamics of keV to MeV electrons in the inner zone, outer zone, and slot regions

DOE PAGES

Reeves, Geoffrey D.; Friedel, Reiner H. W.; Larsen, Brian A.; ...

2016-01-28

Here, we present observations of the radiation belts from the Helium Oxygen Proton Electron and Magnetic Electron Ion Spectrometer particle detectors on the Van Allen Probes satellites that illustrate the energy dependence and L shell dependence of radiation belt enhancements and decays. We survey events in 2013 and analyze an event on 1 March in more detail. The observations show the following: (a) at all L shells, lower energy electrons are enhanced more often than higher energies; (b) events that fill the slot region are more common at lower energies; (c) enhancements of electrons in the inner zone are moremore » common at lower energies; and (d) even when events do not fully fill the slot region, enhancements at lower energies tend to extend to lower L shells than higher energies. During enhancement events the outer zone extends to lower L shells at lower energies while being confined to higher L shells at higher energies. The inner zone shows the opposite with an outer boundary at higher L shells for lower energies. Both boundaries are nearly straight in log(energy) versus L shell space. At energies below a few 100 keV, radiation belt electron penetration through the slot region into the inner zone is commonplace, but the number and frequency of “slot filling” events decreases with increasing energy. The inner zone is enhanced only at energies that penetrate through the slot. Energy- and L shell-dependent losses (that are consistent with whistler hiss interactions) return the belts to more quiescent conditions.« less

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

Hall, J.; Richard, P.; Gray, T.J.

The systematics of single and double K-shell-vacancy production in titanium has been investigated in the limit of zero target thickness (approx.1 ..mu..g/cm/sup 2/) for incident C, N, O, F, Mg, Al, Si, S, and Cl ions over a maximum energy range of 0.5 to 6.5 MeV/amu. This corresponds to collision systems with 0.27< or =Z/sub 1//Z/sub 2/< or =0.77 and 0.24< or =v/sub 1//vK< or =0.85, where v/sub 1/ is the projectile nuclear velocity and vK is the mean velocity of an electron in the target K shell. The present work is divided into four major sections. (1) Single K-shell-vacancymore » production has been investigated by measuring K..cap alpha.. and K..beta.. p satellite x-ray-production cross sections for projectiles incident with no K-shell vacancies. For incident ions with Z/sub 1/> or =9, the contribution due to electron-transfer processes from the target K shell to outer shells of the projectile has also been noted. (2) Single K-shell--to--K-shell electron-transfer cross sections have been obtained indirectly by the measuring of the enhancement in the Ti K x-ray production cross section for bare incident projectiles over ions incident with no initial K-shell vacancies. (3) Double K-vacancy production has been investigated by measuring the K..cap alpha.. hypersatellite intensity in ratio to the total K..cap alpha.. intensity. (4) Double K-shell--to--K-shell electron-transfer cross sections have been obtained indirectly with the use of a procedure similar to that used for single K to K transfer. The measured cross sections have been compared to theoretical models for direct Coulomb ionization and inner-shell electron transfer and have been used to investigate the relative importance of these mechanisms for K-vacancy production in heavy-ion--atom collisions.« less

Carrier relaxation mechanisms in self-assembled (In,Ga)As/GaAs quantum dots: Efficient P→S Auger relaxation of electrons

NASA Astrophysics Data System (ADS)

Narvaez, Gustavo A.; Bester, Gabriel; Zunger, Alex

2006-08-01

We calculate the P -shell-to- S -shell decay lifetime τ(P→S) of electrons in lens-shaped self-assembled (In,Ga)As/GaAs dots due to Auger electron-hole scattering within an atomistic pseudopotential-based approach. We find that this relaxation mechanism leads to fast decay of τ(P→S)˜1-7ps for dots of different sizes. Our calculated Auger-type P -shell-to- S -shell decay lifetimes τ(P→S) compare well to data in (In,Ga)As/GaAs dots, showing that as long as both electrons and holes are present there is no need for an alternative polaron mechanism.

Interplay of spherical closed shells and N /Z asymmetry in quasifission dynamics

NASA Astrophysics Data System (ADS)

Mohanto, G.; Hinde, D. J.; Banerjee, K.; Dasgupta, M.; Jeung, D. Y.; Simenel, C.; Simpson, E. C.; Wakhle, A.; Williams, E.; Carter, I. P.; Cook, K. J.; Luong, D. H.; Palshetkar, C. S.; Rafferty, D. C.

2018-05-01

Background: Quasifission (QF) has gained tremendous importance in heavy-ion nuclear physics research because of its strong influence on superheavy-element synthesis. Collisions involving closed-shell nuclei in the entrance channel are found to affect the QF reaction mechanism. Hence, it is important to improve the understanding of their effect on QF. Apart from that, some recent studies show that the difference in N /Z of reaction partners influences the reaction dynamics. Since heavier doubly magic nuclei have different N /Z than lighter doubly magic nuclei, it is important to understand the effect of N /Z mismatch as well as the effect of shell closures. Purpose: To investigate the effect of entrance-channel shell closures and N /Z asymmetry on QF. The reactions were chosen to decouple these effects from the contributions of other entrance-channel parameters. Method: Fission fragment mass-angle distributions were measured using the CUBE fission spectrometer, consisting of two large area position-sensitive multi-wire proportional counters (MWPCs), for five reactions, namely, 50Cr+208Pb , 52Cr+Pb,208206 , 54Cr+Pb,208204 . Result: Two components were observed in the measured fragment mass angle distribution, a fast mass-asymmetric quasifission and a slow mass-symmetric component having a less significant mass-angle correlation. The ratio of these components was found to depend on spherical closed shells in the entrance channel nuclei and the magnitude of the N /Z mismatch between the two reaction partners, as well as the beam energy. Conclusions: Entrance-channel spherical closed shells can enhance compound nucleus formation provided the N /Z asymmetry is small. Increase in the N /Z asymmetry is expected to destroy the effect of entrance-channel spherical closed shells, through nucleon transfer reactions.

Enhancement of Fenton processes at initial circumneutral pH for the degradation of norfloxacin with Fe@Fe2O3 core-shell nanomaterials.

PubMed

Liu, Jingyi; Hu, Wenyong; Sun, Maogui; Xiong, Ouyang; Yu, Haibin; Feng, Haopeng; Wu, Xuan; Tang, Lin; Zhou, Yaoyu

2018-06-13

The degradation of norfloxacin by Fenton reagent with core-shell Fe@Fe 2 O 3 nanomaterials was studied under neutral conditions in a closed batch system. Norfloxacin was significantly degraded (90%) in the Fenton system with Fe@Fe 2 O 3 in 30 min at the initial pH 7.0, but slightly degraded in Fenton system without Fe@Fe 2 O 3 under the same experimental conditions. The intermediate products were investigated by gas chromatography-mass spectrometry, and the possible Fenton oxidation pathway of norfloxacin in the presence of Fe@Fe 2 O 3 nanowires was proposed. Electron spin resonance spectroscopy was used to identify and characterize the free radicals generated, and the mechanism for norfloxacin degradation was also revealed. Finally, the reusability and the stability of Fe@Fe 2 O 3 nanomaterials were studied using x-ray diffraction and scanning electron microscope, which indicated that Fe@Fe 2 O 3 is a stable catalyst and can be used repetitively in environmental pollution control.

Temperature dependent electron delocalization in CdSe/CdS type-I core-shell systems: An insight from scanning tunneling spectroscopy

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

Kundu, Biswajit; Chakrabarti, Sudipto; Pal, Amlan J., E-mail: sspajp@iacs.res.in

2016-03-14

Core-shell nanocrystals having a type-I band-alignment confine charge carriers to the core. In this work, we choose CdSe/CdS core-shell nano-heterostructures that evidence confinement of holes only. Such a selective confinement occurs in the core-shell nanocrystals due to a low energy-offset of conduction band (CB) edges resulting in delocalization of electrons and thus a decrease in the conduction band-edge. Since the delocalization occurs through a thermal assistance, we study temperature dependence of selective delocalization process through scanning tunneling spectroscopy. From the density of states (DOS), we observe that the electrons are confined to the core at low temperatures. Above a certainmore » temperature, they become delocalized up to the shell leading to a decrease in the CB of the core-shell system due to widening of quantum confinement effect. With holes remaining confined to the core due to a large offset in the valence band (VB), we record the topography of the core-shell nanocrystals by probing their CB and VB edges separately. The topographies recorded at different temperatures representing wave-functions of electrons and holes corresponded to the results obtained from the DOS spectra. The results evidence temperature-dependent wave-function delocalization of one-type of carriers up to the shell layer in core-shell nano-heterostructures.« less

Glass shell manufacturing in space

NASA Technical Reports Server (NTRS)

Downs, R. L.; Ebner, M. A.; Nolen, R. L., Jr.

1981-01-01

Highly-uniform, hollow glass spheres (shells), which are used for inertial confinement fusion targets, were formed from metal-organic gel powder feedstock in a vertical furnace. As a result of the rapid pyrolysis caused by the furnace, the gel is transformed to a shell in five distinct stages: (a) surface closure of the porous gel; (b) generation of a closed-cell foam structure in the gel; (c) spheridization of the gel and further expansion of the foam; (d) coalescence of the closed-cell foam to a single-void shell; and (e) fining of the glass shell. The heat transfer from the furnace to the falling gel particle was modeled to determine the effective heating rate of the gel. The model predicts the temperature history for a particle as a function of mass, dimensions, specific heat, and absorptance as well as furnace temperature profile and thermal conductivity of the furnace gas. A model was developed that predicts the gravity-induced degradation of shell concentricity in falling molten shells as a function of shell characteristics and time.

Development of Paper Products from Dried Sweetpotato Stems and Peanut Shells

NASA Technical Reports Server (NTRS)

McConnell, R.; Smith, R.; Jones, G.; Lu, J. Y.

1998-01-01

One of the goals of NASA's Advanced Life Support Program (ALS) for sustaining human life in space is to achieve a closed system in plant production and usage. That all inedible plant parts should be recycled or used in some way. A Tuskegee University team researching sweetpotato and peanut for ALS has developed paper products from dried sweet-potato stems and peanut shells. In this study, the sweet-potato stems and peanut shells were soaked separately in water for 48 hours. After 48 hours, researchers manually separated the pulp and the unusable parts. To form the paper, 160 g of pulp and water mixture was poured through a 15.1 cm (diameter) filtration funnel and the pulp was trapped on 15 cm (diameter) filter paper. The filter paper and pulp were dried in an air oven, and the filter paper was removed, An examination under a scanning electron microscope showed that the sweet-potato paper was composed of "fibers", whereas the peanut shell paper was composed of "blocks". Results of physical testing showed that the sweet-potato stem paper was stronger than the peanut shell paper. It is anticipated that there may be other uses of these products such as writing paper, bags and packaging material. Because of its biodegradability, it can be incorporated into the resource recycling system at the end of its use.

Enhanced Electron Mobility in Nonplanar Tensile Strained Si Epitaxially Grown on SixGe1-x Nanowires.

PubMed

Wen, Feng; Tutuc, Emanuel

2018-01-10

We report the growth and characterization of epitaxial, coherently strained Si x Ge 1-x -Si core-shell nanowire heterostructure through vapor-liquid-solid growth mechanism for the Si x Ge 1-x core, followed by an in situ ultrahigh-vacuum chemical vapor deposition for the Si shell. Raman spectra acquired from individual nanowire reveal the Si-Si, Si-Ge, and Ge-Ge modes of the Si x Ge 1-x core and the Si-Si mode of the shell. Because of the compressive (tensile) strain induced by lattice mismatch, the core (shell) Raman modes are blue (red) shifted compared to those of unstrained bare Si x Ge 1-x (Si) nanowires, in good agreement with values calculated using continuum elasticity model coupled with lattice dynamic theory. A large tensile strain of up to 2.3% is achieved in the Si shell, which is expected to provide quantum confinement for electrons due to a positive core-to-shell conduction band offset. We demonstrate n-type metal-oxide-semiconductor field-effect transistors using Si x Ge 1-x -Si core-shell nanowires as channel and observe a 40% enhancement of the average electron mobility compared to control devices using Si nanowires due to an increased electron mobility in the tensile-strained Si shell.

Modeling the Magnetopause Shadowing Loss during the October 2012 Dropout Event

NASA Astrophysics Data System (ADS)

Tu, Weichao; Cunningham, Gregory

2017-04-01

The relativistic electron flux in Earth's outer radiation belt are observed to drop by orders of magnitude on timescales of a few hours, which is called radiation belt dropouts. Where do the electrons go during the dropouts? This is one of the most important outstanding questions in radiation belt studies. Radiation belt electrons can be lost either by precipitation into the atmosphere or by transport across the magnetopause into interplanetary space. The latter mechanism is called magnetopause shadowing, usually combined with outward radial diffusion of electrons due to the sharp radial gradient it creates. In order to quantify the relative contribution of these two mechanisms to radiation belt dropout, we performed an event study on the October 2012 dropout event observed by Van Allen Probes. First, the precipitating MeV electrons observed by multiple NOAA POES satellites at low altitude did not show evidence of enhanced precipitation during the dropout, which suggested that precipitation was not the dominant loss mechanism for the event. Then, in order to simulate the magnetopause shadowing loss and outward radial diffusion during the dropout, we applied a radial diffusion model with electron lifetimes on the order of electron drift periods outside the last closed drift shell. In addition, realistic and event-specific inputs of radial diffusion coefficients (DLL) and last closed drift shell (LCDS) were implemented in the model. Specifically, we used the new DLL developed by Cunningham [JGR 2016] which were estimated in realistic TS04 [Tsyganenko and Sitnov, JGR 2005] storm time magnetic field model and included physical K (2nd adiabatic invariant) or pitch angle dependence. Event-specific LCDS traced in TS04 model with realistic K dependence was also implemented. Our simulation results showed that these event-specific inputs are critical to explain the electron dropout during the event. The new DLL greatly improved the model performance at low L* regions (L*<3.6) compared to empirical Kp-dependent DLL [Brautigam and Albert, JGR 2000] used in previous radial diffusion models. Combining the event-specific DLL and LCDS, our model well captured the magnetopause shadowing loss and reproduced the electron dropout at L*=4.0-4.5. In addition, we found the K-dependent LCDS is critical to reproduce the pitch angle dependence of the observed electron dropout.

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

Reeves, Geoffrey D.; Friedel, Reiner H. W.; Larsen, Brian A.

Here, we present observations of the radiation belts from the Helium Oxygen Proton Electron and Magnetic Electron Ion Spectrometer particle detectors on the Van Allen Probes satellites that illustrate the energy dependence and L shell dependence of radiation belt enhancements and decays. We survey events in 2013 and analyze an event on 1 March in more detail. The observations show the following: (a) at all L shells, lower energy electrons are enhanced more often than higher energies; (b) events that fill the slot region are more common at lower energies; (c) enhancements of electrons in the inner zone are moremore » common at lower energies; and (d) even when events do not fully fill the slot region, enhancements at lower energies tend to extend to lower L shells than higher energies. During enhancement events the outer zone extends to lower L shells at lower energies while being confined to higher L shells at higher energies. The inner zone shows the opposite with an outer boundary at higher L shells for lower energies. Both boundaries are nearly straight in log(energy) versus L shell space. At energies below a few 100 keV, radiation belt electron penetration through the slot region into the inner zone is commonplace, but the number and frequency of “slot filling” events decreases with increasing energy. The inner zone is enhanced only at energies that penetrate through the slot. Energy- and L shell-dependent losses (that are consistent with whistler hiss interactions) return the belts to more quiescent conditions.« less

Higher Order π-Conjugated Polycyclic Hydrocarbons with Open-Shell Singlet Ground State: Nonazethrene versus Nonacene.

PubMed

Huang, Rui; Phan, Hoa; Herng, Tun Seng; Hu, Pan; Zeng, Wangdong; Dong, Shao-Qiang; Das, Soumyajit; Shen, Yongjia; Ding, Jun; Casanova, David; Wu, Jishan

2016-08-17

Higher order acenes (i.e., acenes longer than pentacene) and extended zethrenes (i.e., zethrenes longer than zethrene) are theoretically predicted to have an open-shell singlet ground state, and the radical character is supposed to increase with extension of molecular size. The increasing radical character makes the synthesis of long zethrenes and acenes very challenging, and so far, the longest reported zethrene and acene derivatives are octazethrene and nonacene, respectively. In addition, there is a lack of fundamental understanding of the differences between these two closely related open-shell singlet systems. In this work, we report the first synthesis of a challenging nonazethrene derivative, HR-NZ, and its full structural and physical characterizations including variable temperature NMR, ESR, SQUID, UV-vis-NIR absorption and electrochemical measurements. Compound HR-NZ has an open-shell singlet ground state with a moderate diradical character (y0 = 0.48 based on UCAM-B3LYP calculation) and a small singlet-triplet gap (ΔES-T = -5.2 kcal/mol based on SQUID data), thus showing magnetic activity at room temperature. It also shows amphoteric redox behavior, with a small electrochemical energy gap (1.33 eV). Its electronic structure and physical properties are compared with those of Anthony's nonacene derivative JA-NA and other zethrene derivatives. A more general comparison between higher order acenes and extended zethrenes was also conducted on the basis of ab initio electronic structure calculations, and it was found that zethrenes and acenes have very different spatial localization of the unpaired electrons. As a result, a faster decrease of singlet-triplet energy gap and a faster increase of radical character with increase of the number of benzenoid rings were observed in zethrene series. Our studies reveal that spatial localization of the frontier molecular orbitals play a very important role on the nature of radical character as well as the excitation energy.

Core-shell nanophosphor architecture: toward efficient energy transport in inorganic/organic hybrid solar cells.

PubMed

Li, Qinghua; Yuan, Yongbiao; Chen, Zihan; Jin, Xiao; Wei, Tai-huei; Li, Yue; Qin, Yuancheng; Sun, Weifu

2014-08-13

In this work, a core-shell nanostructure of samarium phosphates encapsulated into a Eu(3+)-doped silica shell has been successfully fabricated, which has been confirmed by X-ray diffraction, transmission electron microscopy (TEM), and high-resolution TEM. Moreover, we report the energy transfer process from the Sm(3+) to emitters Eu(3+) that widens the light absorption range of the hybrid solar cells (HSCs) and the strong enhancement of the electron-transport of TiO2/poly(3-hexylthiophene) (P3HT) bulk heterojunction (BHJ) HSCs by introducing the unique core-shell nanoarchitecture. Furthermore, by applying femtosecond transient absorption spectroscopy, we successfully obtain the electron transport lifetimes of BHJ systems with or without incorporating the core-shell nanophosphors (NPs). Concrete evidence has been provided that the doping of core-shell NPs improves the efficiency of electron transfers from donor to acceptor, but the hole transport almost remains unchanged. In particular, the hot electron transfer lifetime was shortened from 30.2 to 16.7 ps, i.e., more than 44% faster than pure TiO2 acceptor. Consequently, a notable power conversion efficiency of 3.30% for SmPO4@Eu(3+):SiO2 blended TiO2/P3HT HSCs is achieved at 5 wt % as compared to 1.98% of pure TiO2/P3HT HSCs. This work indicates that the core-shell NPs can efficiently broaden the absorption region, facilitate electron-transport of BHJ, and enhance photovoltaic performance of inorganic/organic HSCs.

Corrosion on the acetabular liner taper from retrieved modular metal-on-metal total hip replacements.

PubMed

Gascoyne, Trevor C; Dyrkacz, Richard M; Turgeon, Thomas R; Burnell, Colin D; Wyss, Urs P; Brandt, Jan-M

2014-10-01

Eight retrieved metal-on-metal total hip replacements displayed corrosion damage along the cobalt-chromium alloy liner taper junction with the Ti alloy acetabular shell. Scanning electron microscopy indicated the primary mechanism of corrosion to be grain boundary and associated crevice corrosion, which was likely accelerated through mechanical micromotion and galvanic corrosion resulting from dissimilar alloys. Coordinate measurements revealed up to 4.3mm(3) of the cobalt-chromium alloy taper surface was removed due to corrosion, which is comparable to previous reports of corrosion damage on head-neck tapers. The acetabular liner-shell taper appears to be an additional source of metal corrosion products in modular total hip replacements. Patients with these prostheses should be closely monitored for signs of adverse reaction towards corrosion by-products. Copyright © 2014 Elsevier Inc. All rights reserved.

Bistable mixed-valence molecular architectures for bit storage

NASA Astrophysics Data System (ADS)

Guihery, Nathalie; Durand, Gérard; Lepetit, Marie-Bernadette

1994-05-01

The work examines the possible realization of bit storage at the molecular scale using mixed valence compounds i.e. the existence of two stable and degenerate forms associated with the 0 and 1 positions of the bit. The proposed systems are constituted of two donors (D) and acceptor (A), or one donor and two acceptors, juxtaposed in DAD or ADA architectures. Our proposals take advantage of the possibility of donor—acceptor complexes to exhibit either complete or partial charge transfer. The first system we propose has an essentially neutral ground state. However, the potential energy surface (PES) presents two degenerated minima associated with a partial charge transfer between the donor and one of the two acceptor molecules (A δ-D δ+1 A and AD δ+ A δ-). Systems presenting a complete charge transfer give rise to two stable, weakly coupled, and degenerate ionic electronic states, A - A + A and AD + A - for an ADA architecture and D + A -D and DA -D + for a DAD In these cases, the two forms differ by both their intramolecular geometries and the relative positions of their constituents. It seems rather difficult to conceive such bistable molecular systems using closed-shell molecules, while a donor radical and a closed-shell acceptor or an acceptor radical and closed-shell donor can generate very stable ionic states. It is assumed that the relative positions of the donor and acceptor molecules can be fixed using chemical bridges constituted of rigid or flexible ligands. The writing and reading processes are discussed for each system as well as the information stability when a large number of bits are juxtaposed on a surface.

Exploring the effect of band alignment and surface states on photoinduced electron transfer from CuInS2/CdS core/shell quantum dots to TiO2 electrodes.

PubMed

Sun, Mingye; Zhu, Dehua; Ji, Wenyu; Jing, Pengtao; Wang, Xiuying; Xiang, Weidong; Zhao, Jialong

2013-12-11

Photoinduced electron transfer (ET) processes from CuInS2/CdS core/shell quantum dots (QDs) with different core sizes and shell thicknesses to TiO2 electrodes were investigated by time-resolved photoluminescence (PL) spectroscopy. The ET rates and efficiencies from CuInS2/CdS QDs to TiO2 were superior to those of CuInS2/ZnS QDs. An enhanced ET efficiency was surprisingly observed for 2.0 nm CuInS2 core QDs after growth of the CdS shell. On the basis of the experimental and theoretical analysis, the improved performances of CuInS2/CdS QDs were attributed to the passivation of nonradiative traps by overcoating shell and enhanced delocalization of electron wave function from core to CdS shell due to lower conduction band offset. These results indicated that the electron distribution regulated by the band alignment between core and shell of QDs and the passivation of surface defect states could improve ET performance between donor and acceptor.

Model of resonant high harmonic generation in multi-electron systems

NASA Astrophysics Data System (ADS)

Redkin, P. V.; Ganeev, R. A.

2017-09-01

We extend the 4-step analytical model of resonant enhancement of high harmonic generation to the systems possessing resonant transitions of inner-shell electrons. Resonant enhancement is explained by lasing without inversion in a three-level system of ground, excited and shifted resonant states, which are coupled to the fundamental field and its high harmonics. The role of inelastic scattering is studied by simulation of an excited state’s population dynamics. It is shown that maximal gain is achieved when the energy shift between the excited state and resonant state is close to the energy of the fundamental photon. To prove the concept we demonstrate the enhancement of harmonics in the In plasma using different pumps.

Atomistic tight-binding theory of excitonic splitting energies in CdX(X = Se, S and Te)/ZnS core/shell nanocrystals

NASA Astrophysics Data System (ADS)

Sukkabot, Worasak; Pinsook, Udomsilp

2017-01-01

Using the atomistic tight-binding theory (TB) and a configuration interaction description (CI), we numerically compute the excitonic splitting of CdX(X = Se, S and Te)/ZnS core/shell nanocrystals with the objective to explain how types of the core materials and growth shell thickness can provide the detailed manipulation of the dark-dark (DD), dark-bright (DB) and bright-bright (BB) excitonic splitting, beneficial for the active application of quantum information. To analyze the splitting of the excitonic states, the optical band gaps, ground-state wave function overlaps and atomistic electron-hole interactions tend to be numerically demonstrated. Based on the atomistic computations, the single-particle and excitonic gaps are mainly reduced with the increasing ZnS shell thickness owing to the quantum confinement. In the range of the higher to lower energies, the order of the single-particle gaps is CdSe/ZnS, CdS/ZnS and CdTe/ZnS core/shell nanocrystals, while one of the excitonic gaps is CdS/ZnS, CdSe/ZnS and CdTe/ZnS core/shell nanocrystals because of the atomistic electron-hole interaction. The strongest electron-hole interactions are mainly observed in CdSe/ZnS core/shell nanocrystals. In addition, the computational results underline that the energies of the dark-dark (DD), dark-bright (DB) and bright-bright (BB) excitonic splitting are generally reduced with the increasing ZnS growth shell thickness as described by the trend of the electron-hole exchange interaction. The high-to-low splitting of the excitonic states is demonstrated in CdSe/ZnS, CdTe/ZnS and CdS/ZnS core/shell nanocrystals because of the fashion in the electron-hole exchange interaction and overlaps of the electron-hole wave functions. As the resulting calculations, it is expected that CdS/ZnS core/shell nanocrystals are the best candidates to be the source of entangled photons. Finally, the comprehensive information on the excitonic splitting can enable the use of suitable core/shell nanocrystals for the entangled photons in the application of quantum information.

Disorders of metal metabolism

PubMed Central

Ferreira, Carlos R.; Gahl, William A.

2017-01-01

Trace elements are chemical elements needed in minute amounts for normal physiology. Some of the physiologically relevant trace elements include iodine, copper, iron, manganese, zinc, selenium, cobalt and molybdenum. Of these, some are metals, and in particular, transition metals. The different electron shells of an atom carry different energy levels, with those closest to the nucleus being lowest in energy. The number of electrons in the outermost shell determines the reactivity of such an atom. The electron shells are divided in sub-shells, and in particular the third shell has s, p and d sub-shells. Transition metals are strictly defined as elements whose atom has an incomplete d sub-shell. This incomplete d sub-shell makes them prone to chemical reactions, particularly redox reactions. Transition metals of biologic importance include copper, iron, manganese, cobalt and molybdenum. Zinc is not a transition metal, since it has a complete d sub-shell. Selenium, on the other hand, is strictly speaking a nonmetal, although given its chemical properties between those of metals and nonmetals, it is sometimes considered a metalloid. In this review, we summarize the current knowledge on the inborn errors of metal and metalloid metabolism. PMID:29354481

Band engineered epitaxial 3D GaN-InGaN core-shell rod arrays as an advanced photoanode for visible-light-driven water splitting.

PubMed

Caccamo, Lorenzo; Hartmann, Jana; Fàbrega, Cristian; Estradé, Sonia; Lilienkamp, Gerhard; Prades, Joan Daniel; Hoffmann, Martin W G; Ledig, Johannes; Wagner, Alexander; Wang, Xue; Lopez-Conesa, Lluis; Peiró, Francesca; Rebled, José Manuel; Wehmann, Hergo-Heinrich; Daum, Winfried; Shen, Hao; Waag, Andreas

2014-02-26

3D single-crystalline, well-aligned GaN-InGaN rod arrays are fabricated by selective area growth (SAG) metal-organic vapor phase epitaxy (MOVPE) for visible-light water splitting. Epitaxial InGaN layer grows successfully on 3D GaN rods to minimize defects within the GaN-InGaN heterojunctions. The indium concentration (In ∼ 0.30 ± 0.04) is rather homogeneous in InGaN shells along the radial and longitudinal directions. The growing strategy allows us to tune the band gap of the InGaN layer in order to match the visible absorption with the solar spectrum as well as to align the semiconductor bands close to the water redox potentials to achieve high efficiency. The relation between structure, surface, and photoelectrochemical property of GaN-InGaN is explored by transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), Auger electron spectroscopy (AES), current-voltage, and open circuit potential (OCP) measurements. The epitaxial GaN-InGaN interface, pseudomorphic InGaN thin films, homogeneous and suitable indium concentration and defined surface orientation are properties demanded for systematic study and efficient photoanodes based on III-nitride heterojunctions.

A circumferential crack in a cylindrical shell under tension.

NASA Technical Reports Server (NTRS)

Duncan-Fama, M. E.; Sanders, J. L., Jr.

1972-01-01

A closed cylindrical shell under uniform internal pressure has a slit around a portion of its circumference. Linear shallow shell theory predicts inverse square-root-type singularities in certain of the stresses at the crack tips. This paper reports the computed strength of these singularities for different values of a dimensionless parameter based on crack length, shell radius and shell thickness.

Improving the In-Medium Similarity Renormalization Group via approximate inclusion of three-body effects

NASA Astrophysics Data System (ADS)

Morris, Titus; Bogner, Scott

2016-09-01

The In-Medium Similarity Renormalization Group (IM-SRG) has been applied successfully to the ground state of closed shell finite nuclei. Recent work has extended its ability to target excited states of these closed shell systems via equation of motion methods, and also complete spectra of the whole SD shell via effective shell model interactions. A recent alternative method for solving of the IM-SRG equations, based on the Magnus expansion, not only provides a computationally feasible route to producing observables, but also allows for approximate handling of induced three-body forces. Promising results for several systems, including finite nuclei, will be presented and discussed.

Footprints of electron correlation in strong-field double ionization of Kr close to the sequential-ionization regime

NASA Astrophysics Data System (ADS)

Li, Xiaokai; Wang, Chuncheng; Yuan, Zongqiang; Ye, Difa; Ma, Pan; Hu, Wenhui; Luo, Sizuo; Fu, Libin; Ding, Dajun

2017-09-01

By combining kinematically complete measurements and a semiclassical Monte Carlo simulation we study the correlated-electron dynamics in the strong-field double ionization of Kr. Interestingly, we find that, as we step into the sequential-ionization regime, there are still signatures of correlation in the two-electron joint momentum spectrum and, more intriguingly, the scaling law of the high-energy tail is completely different from early predictions on the low-Z atom (He). These experimental observations are well reproduced by our generalized semiclassical model adapting a Green-Sellin-Zachor potential. It is revealed that the competition between the screening effect of inner-shell electrons and the Coulomb focusing of nuclei leads to a non-inverse-square central force, which twists the returned electron trajectory at the vicinity of the parent core and thus significantly increases the probability of hard recollisions between two electrons. Our results might have promising applications ranging from accurately retrieving atomic structures to simulating celestial phenomena in the laboratory.

Energy‐dependent dynamics of keV to MeV electrons in the inner zone, outer zone, and slot regions

PubMed Central

Friedel, Reiner H. W.; Larsen, Brian A.; Skoug, Ruth M.; Funsten, Herbert O.; Claudepierre, Seth G.; Fennell, Joseph F.; Turner, Drew L.; Denton, Mick H.; Spence, Harlan E.; Blake, J. Bernard; Baker, Daniel N.

2016-01-01

Abstract We present observations of the radiation belts from the Helium Oxygen Proton Electron and Magnetic Electron Ion Spectrometer particle detectors on the Van Allen Probes satellites that illustrate the energy dependence and L shell dependence of radiation belt enhancements and decays. We survey events in 2013 and analyze an event on 1 March in more detail. The observations show the following: (a) at all L shells, lower energy electrons are enhanced more often than higher energies; (b) events that fill the slot region are more common at lower energies; (c) enhancements of electrons in the inner zone are more common at lower energies; and (d) even when events do not fully fill the slot region, enhancements at lower energies tend to extend to lower L shells than higher energies. During enhancement events the outer zone extends to lower L shells at lower energies while being confined to higher L shells at higher energies. The inner zone shows the opposite with an outer boundary at higher L shells for lower energies. Both boundaries are nearly straight in log(energy) versus L shell space. At energies below a few 100 keV, radiation belt electron penetration through the slot region into the inner zone is commonplace, but the number and frequency of “slot filling” events decreases with increasing energy. The inner zone is enhanced only at energies that penetrate through the slot. Energy‐ and L shell‐dependent losses (that are consistent with whistler hiss interactions) return the belts to more quiescent conditions. PMID:27818855

Low energy electron attenuation lengths in core–shell nanoparticles

DOE PAGES

Jacobs, Michael I.; Kostko, Oleg; Ahmed, Musahid; ...

2017-05-05

Here, a velocity map imaging spectrometer is used to measure photoemission from free core–shell nanoparticles, where a salt core is coated with a liquid hydrocarbon shell (i.e. squalane). By varying the radial thickness of the hydrocarbon shell, electron attenuation lengths (EALs) are determined by measuring the decay in photoemission intensity from the salt core. In squalane, electrons with kinetic energy (KE) above 2 eV are found to have EALs of 3–5 nm, whereas electrons with smaller KE (<2 eV) have significantly larger EALs of >15 nm. These results (in the context of other energy-resolved EAL measurements) suggest that the energymore » dependent behavior of low energy electrons is similar in dielectrics when KE > 2 eV. At this energy the EALs do not appear to exhibit strong energy dependence. However, at very low KE (<2 eV), the EALs diverge and appear to be extremely material dependent.« less

Approximate Theoretical Model for the Five Electronic States (Ω = 5/2, 3/2, 3/2, 1/2, 1/2) Arising from the Ground 3d9 Configuration in Nickel Halide Molecules and for Rotational Levels of the Two Ω = 1/2 States in that Manifold

NASA Astrophysics Data System (ADS)

Cheung, Allan S.-C.

2011-06-01

An effective Hamiltonian for a non-rotating diatomic molecule containing only crystal-field and spin-orbit operators has been set up to describe the energies of the five spin-orbit components that arise in the ground electronic configuration of the nickel monohalides. The model assumes that bonding in the nickel halides has the approximate form Ni+X-, with an electronic 3d9 configuration plus closed shells on the Ni+ moiety and a closed shell configuration on the X&- moiety. Least-squares fits of the observed five spin-orbit components of the three lowest electronic states in NiF and NiCl are then carried out in terms of the three crystal field parameters C0, C2, C4 and the spin-orbit coupling constant A. Following this, the usual effective Hamiltonian B(J-L-S)^2 for a rotating diatomic molecule is used to derive expressions for the unusually large Ω-type doubling parameter p in the two Ω = 1/2 states in the 3d9 manifold. These expressions show (for certain sign conventions) that the sum of the two p values should be -2B, but that their difference can vary between -10B and +10B. The theoretical magnitudes for p are in good agreement with the two observed p values for both NiF and NiCl, but the signs are not. The experimental signs can be brought into agreement with the theoretical signs by a fairly massive change in +/- parity assignments in the NiF and NiCl literature. The last part of the talk will focus on the theoretical and experimental implications of these parity changes.

Einstein observations of selected close binaries and shell stars

NASA Technical Reports Server (NTRS)

Guinan, E. F.; Koch, R. H.; Plavec, M. J.

1984-01-01

Several evolved close binaries and shell stars were observed with the IPC aboard the HEAO 2 Einstein Observatory. No eclipsing target was detected, and only two of the shell binaries were detected. It is argued that there is no substantial difference in L(X) for eclipsing and non-eclipsing binaries. The close binary and shell star CX Dra was detected as a moderately strong source, and the best interpretation is that the X-ray flux arises primarily from the corona of the cool member of the binary at about the level of Algol-like or RS CVn-type sources. The residual visible-band light curve of this binary has been modeled so as to conform as well as possible with this interpretation. HD 51480 was detected as a weak source. Substantial background information from IUE and ground scanner measurements are given for this binary. The positions and flux values of several accidentally detected sources are given.

Ocean acidification reduces the crystallographic control in juvenile mussel shells.

PubMed

Fitzer, Susan C; Cusack, Maggie; Phoenix, Vernon R; Kamenos, Nicholas A

2014-10-01

Global climate change threatens the oceans as anthropogenic carbon dioxide causes ocean acidification and reduced carbonate saturation. Future projections indicate under saturation of aragonite, and potentially calcite, in the oceans by 2100. Calcifying organisms are those most at risk from such ocean acidification, as carbonate is vital in the biomineralisation of their calcium carbonate protective shells. This study highlights the importance of multi-generational studies to investigate how marine organisms can potentially adapt to future projected global climate change. Mytilus edulis is an economically important marine calcifier vulnerable to decreasing carbonate saturation as their shells comprise two calcium carbonate polymorphs: aragonite and calcite. M. edulis specimens were cultured under current and projected pCO2 (380, 550, 750 and 1000μatm), following 6months of experimental culture, adults produced second generation juvenile mussels. Juvenile mussel shells were examined for structural and crystallographic orientation of aragonite and calcite. At 1000μatm pCO2, juvenile mussels spawned and grown under this high pCO2 do not produce aragonite which is more vulnerable to carbonate under-saturation than calcite. Calcite and aragonite were produced at 380, 550 and 750μatm pCO2. Electron back scatter diffraction analyses reveal less constraint in crystallographic orientation with increased pCO2. Shell formation is maintained, although the nacre crystals appear corroded and crystals are not so closely layered together. The differences in ultrastructure and crystallography in shells formed by juveniles spawned from adults in high pCO2 conditions may prove instrumental in their ability to survive ocean acidification. Copyright © 2014 Elsevier Inc. All rights reserved.

Electronically cloaked nanoparticles

NASA Astrophysics Data System (ADS)

Shen, Wenqing

The concept of electronic cloaking is to design objects invisible to conduction electrons. The approach of electronic cloaking has been recently suggested to design invisible nanoparticle dopants with electronic scattering cross section smaller than 1% of the physical cross section (pi a2), and therefore to enhance the carrier mobility of bulk materials. The proposed nanoparticles have core-shell structures. The dopants are incorporated inside the core, while the shell layer serves both as a spacer to separate the charge carriers from their parent atoms and as a cloaking shell to minimize the scattering cross section of the electrons from the ionized nanoparticles. Thermoelectric materials are usually highly doped to have enough carrier density. Using invisible dopants could achieve larger thermoelectric power factors by enhancing the electronic mobility. Core-shell nanoparticles show an advantage over one-layer nanoparticles, which are proposed in three-dimensional modulation doping. However designing such nanoparticles is not easy as there are too many parameters to be considered. This thesis first shows an approach to design hollow nanoparticles by applying constrains on variables. In the second part, a simple mapping approach is introduced where one can identify possible core-shell particles by comparing the dimensionless parameters of chosen materials with provided maps. In both parts of this work, several designs with realistic materials were made and proven to achieve electronic cloaking. Improvement in the thermoelectric power factor compared to the traditional impurity doping method was demonstrated in several cases.

Theoretical study of the H2 reaction with a Pt4 (111) cluster

NASA Astrophysics Data System (ADS)

Cruz, A.; Bertin, V.; Poulain, E.; Benitez, J. I.; Castillo, S.

2004-04-01

The Cs symmetry reaction of the H2 molecule on a Pt4 (111) clusters, has been studied using ab initio multiconfiguration self-consistent field plus extensive multireference configuration interaction variational and perturbative calculations. The H2 interaction by the vertex and by the base of a tetrahedral Pt4 cluster were studied in ground and excited triplet and singlet states (closed and open shells), where the reaction curves are obtained through many avoided crossings. The Pt4 cluster captures and activates the hydrogen molecule; it shows a similar behavior compared with other Ptn (n=1,2,3) systems. The Pt4 cluster in their lowest five open and closed shell electronic states: 3B2, 1B2, 1A1 3A1, 1A1, respectively, may capture and dissociate the H2 molecule without activation barriers for the hydrogen molecule vertex approach. For the threefolded site reaction, i.e., by the base, the situation is different, the hydrogen adsorption presents some barriers. The potential energy minima occur outside and inside the cluster, with strong activation of the H-H bond. In all cases studied, the Pt4 cluster does not absorb the hydrogen molecule.

The effects of the chemical composition and strain on the electronic properties of GaSb/InAs core-shell nanowires

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

Ning, Feng; Wang, Dan; Tang, Li-Ming, E-mail: lmtang@hnu.edu.cn

2014-09-07

The effects of the chemical composition and strain on the electronic properties of [111] zinc-blende (ZB) and [0001] wurtzite (WZ) GaSb/InAs core-shell nanowires (NWs) with different core diameters and shell thicknesses are studied using first-principles methods. The band structures of the [111] ZB GaSb/InAs core-shell NWs underwent a noticeable type-I/II band alignment transition, associated with a direct-to-indirect band gap transition under a compressive uniaxial strain. The band structures of the [0001] WZ GaSb/InAs core-shell NWs preserved the direct band gap under either compressive or tensile uniaxial strains. In addition, the band gaps and the effective masses of the carriers couldmore » be tuned by their composition. For the core-shell NWs with a fixed GaSb-core size, the band gaps decreased linearly with an increasing InAs-shell thickness, caused by the significant downshift of the conduction bands. For the [111] ZB GaSb/InAs core-shell NWs, the calculated effective masses indicated that the transport properties could be changed from hole-dominated conduction to electron-dominated conduction by changing the InAs-shell thickness.« less

Drastic difference between hole and electron injection through the gradient shell of CdxSeyZn1-xS1-y quantum dots.

PubMed

Abdellah, Mohamed; Poulsen, Felipe; Zhu, Qiushi; Zhu, Nan; Žídek, Karel; Chábera, Pavel; Corti, Annamaria; Hansen, Thorsten; Chi, Qijin; Canton, Sophie E; Zheng, Kaibo; Pullerits, Tõnu

2017-08-31

Ultrafast fluorescence spectroscopy was used to investigate the hole injection in Cd x Se y Zn 1-x S 1-y gradient core-shell quantum dot (CSQD) sensitized p-type NiO photocathodes. A series of CSQDs with a wide range of shell thicknesses was studied. Complementary photoelectrochemical cell measurements were carried out to confirm that the hole injection from the active core through the gradient shell to NiO takes place. The hole injection from the valence band of the QDs to NiO depends much less on the shell thickness when compared to the corresponding electron injection to n-type semiconductor (ZnO). We simulate the charge carrier tunneling through the potential barrier due to the gradient shell by numerically solving the Schrödinger equation. The details of the band alignment determining the potential barrier are obtained from X-ray spectroscopy measurements. The observed drastic differences between the hole and electron injection are consistent with a model where the hole effective mass decreases, while the gradient shell thickness increases.

Observation of hole accumulation in Ge/Si core/shell nanowires using off-axis electron holography.

PubMed

Li, Luying; Smith, David J; Dailey, Eric; Madras, Prashanth; Drucker, Jeff; McCartney, Martha R

2011-02-09

Hole accumulation in Ge/Si core/shell nanowires (NWs) has been observed and quantified using off-axis electron holography and other electron microscopy techniques. The epitaxial [110]-oriented Ge/Si core/shell NWs were grown on Si (111) substrates by chemical vapor deposition through the vapor-liquid-solid growth mechanism. High-angle annular-dark-field scanning transmission electron microscopy images and off-axis electron holograms were obtained from specific NWs. The excess phase shifts measured by electron holography across the NWs indicated the presence of holes inside the Ge cores. Calculations based on a simplified coaxial cylindrical model gave hole densities of (0.4 ± 0.2) /nm(3) in the core regions.

Electric current distribution of a multiwall carbon nanotube

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

Chen, Li-Ying; Chang, Chia-Seng, E-mail: jasonc@phys.sinica.edu.tw; Institute of Physics, Academia Sinica, Taipei 11529, Taiwan

2016-07-15

The electric current distribution in a multiwall carbon nanotube (MWCNT) was studied by in situ measuring the electric potential along an individual MWCNT in the ultra-high vacuum transmission electron microscope (TEM). The current induced voltage drop along each section of a side-bonded MWCNT was measured by a potentiometric probe in TEM. We have quantitatively derived that the current on the outermost shell depends on the applied current and the shell diameter. More proportion of the total electronic carriers hop into the inner shells when the applied current is increased. The larger a MWCNT’s diameter is, the easier the electronic carriersmore » can hop into the inner shells. We observed that, for an 8 nm MWCNT with 10 μA current applied, 99% of the total current was distributed on the outer two shells.« less

Green synthesis and characterization of size tunable silica-capped gold core-shell nanoparticles

NASA Astrophysics Data System (ADS)

Wangoo, Nishima; Shekhawat, Gajendra; Wu, Jin-Song; Bhasin, Aman K. K.; Suri, C. R.; Bhasin, K. K.; Dravid, Vinayak

2012-08-01

Silica-coated gold nanoparticles (Au@SiO2) with controlled silica-shell thickness were prepared by a modified Stober's method using 10-nm gold nanoparticles (AuNPs) as seeds. The AuNPs were silica-coated with a sol-gel reaction using tetraethylorthosilicate (TEOS) as a silica source and ammonia as a catalyst. An increase in TEOS concentration resulted in an increase in shell thickness. The NPs were characterized by transmission electron microscopy, selected area electron diffraction, energy-dispersive X-ray spectroscopy, scanning near-field ultrasound holography and scanning transmission electron microscopy. The method required no surface modification and the synthesized core shell nanoparticles can be used for various types of biological applications.

B(E2)↑ Measurements for Radioactive Neutron-Rich Ge Isotopes: Reaching the N=50 Closed Shell

NASA Astrophysics Data System (ADS)

Padilla-Rodal, E.; Galindo-Uribarri, A.; Baktash, C.; Batchelder, J. C.; Beene, J. R.; Bijker, R.; Brown, B. A.; Castaños, O.; Fuentes, B.; del Campo, J. Gomez; Hausladen, P. A.; Larochelle, Y.; Lisetskiy, A. F.; Mueller, P. E.; Radford, D. C.; Stracener, D. W.; Urrego, J. P.; Varner, R. L.; Yu, C.-H.

2005-03-01

The B(E2;0+1→2+1) values for the radioactive neutron-rich germanium isotopes 78,80Ge and the closed neutron shell nucleus 82Ge were measured at the HRIBF using Coulomb excitation in inverse kinematics. These data allow a study of the systematic trend between the subshell closures at N=40 and 50. The B(E2) behavior approaching N=50 is similar to the trend observed for heavier isotopic chains. A comparison of the experimental results with a shell model calculation demonstrates persistence of the N=50 shell gap and a strong sensitivity of the B(E2) values to the effective interaction.

The effects of staggered bandgap in the InP/CdSe and CdSe/InP core/shell quantum dots.

PubMed

Kim, Sunghoon; Park, Jaehyun; Kim, Sungwoo; Jung, Won; Sung, Jaeyoung; Kim, Sang-Wook

2010-06-15

New type-II structures of CdSe/InP and InP/CdSe core-shell nanocrystals which have staggered bandgap alignment were fabricated. Using a simple model for the wave function for electrons and holes in InP/CdSe and CdSe/InP core/shell nanocrystals showed the wave function of the electron and hole spread into the shell, respectively. The probability density of the InP/CdSe and CdSe/InP core/shell QDs also showed a similar tendency. As a result, the structure exhibits increased delocalization of electrons and holes, leading to a red-shift in absorption and emission. Quantum yield increased in the InP/CdSe, however decreased in the CdSe/InP. The reason may be due to the surface trap and high activation barrier for de-trapping in the InP shell. 2010 Elsevier Inc. All rights reserved.

Abnormal elastic modulus behavior in a crystalline-amorphous core-shell nanowire system.

PubMed

Lee, Jeong Hwan; Choi, Su Ji; Kwon, Ji Hwan; Van Lam, Do; Lee, Seung Mo; Kim, An Soon; Baik, Hion Suck; Ahn, Sang Jung; Hong, Seong Gu; Yun, Yong Ju; Kim, Young Heon

2018-06-13

We investigated the elastic modulus behavior of crystalline InAs/amorphous Al2O3 core-shell heterostructured nanowires with shell thicknesses varying between 10 and 90 nm by conducting in situ tensile tests inside a transmission electron microscope (TEM). Counterintuitively, the elastic modulus behaviors of InAs/Al2O3 core-shell nanowires differ greatly from those of bulk-scale composite materials, free from size effects. According to our results, the elastic modulus of InAs/Al2O3 core-shell nanowires increases, peaking at a shell thickness of 40 nm, and then decreases in the range of 50-90 nm. This abnormal behavior is attributed to the continuous decrease in the elastic modulus of the Al2O3 shell as the thickness increases, which is caused by changes in the atomic/electronic structure during the atomic layer deposition process and the relaxation of residual stress/strain in the shell transferred from the interfacial mismatch between the core and shell materials. A novel method for estimating the elastic modulus of the shell in a heterostructured core-shell system was suggested by considering these two effects, and the predictions from the suggested method coincided well with the experimental results. We also found that the former and latter effects account for 89% and 11% of the change in the elastic modulus of the shell. This study provides new insight by showing that the size dependency, which is caused by the inhomogeneity of the atomic/electronic structure and the residual stress/strain, must be considered to evaluate the mechanical properties of heterostructured nanowires.

Relativistic effects in electron impact ionization from the p-orbital

NASA Astrophysics Data System (ADS)

Haque, A. K. F.; Uddin, M. A.; Basak, A. K.; Karim, K. R.; Saha, B. C.; Malik, F. B.

2006-06-01

The parameters of our recent modification of BELI formula (MBELL) [A.K.F. Haque, M.A. Uddin, A.K. Basak, K.R. Karim, B.C. Saha, Phys. Rev. A 73 (2006) 012708] are generalized in terms of the orbital quantum numbers nl to evaluate the electron impact ionization (EII) cross sections of a wide range of isoelectronic targets (H to Ne series) and incident energies. For both the open and closed p-shell targets, the present MBELL results with a single parameter set, agree nicely with the experimental cross sections. The relativistic effect of ionization in the 2p subshell of U82+ for incident energies up to 250 MeV is well accounted for by the prescribed parameters of the model.

Electron impact ionization from p-orbital targets

NASA Astrophysics Data System (ADS)

Saha, Bidhan; Basak, Arun K.; Alfaz Uddin, M.

2006-05-01

Electron impact ionization cross sections are evaluated using a modified version [1] of the BELL formula [2] for a wide range of isoelectronic targets, ranging from Li to Ne targets with both the open and closed shell configurations. In this report the MBELL parameters are generalized for treating the orbital quantum numbers nl dependency; its accuracy has been tested by evaluating cross sections for a wider range of species and energies. Details will be presented at the meeting. [1] A. K. F. Haque, M. A. Uddin, A. K. Basak, K. R. Karim and B. C. Saha, Phys. Rev. A73, 012708 (2005). [2] K. L. Bell, H. B. Gilbody, J. G. Hughes, A. E. Kingston, and F. J. Smith, J. Phys. Chem. Ref. Data 12, 891 (1983).

a Theoretical Search for AN Electronic Spectrum of the He-BeO Complex

NASA Astrophysics Data System (ADS)

Gardner, Adrian; Heaven, Michael

2014-06-01

The surprisingly high dissociation energy of the He-Be bond in the He-BeO complex was first reported 25 years ago. Following which, a number of theoretical studies have investigated similar closed shell helium containing complexes. However, despite these investigations, a complex containing a strong He-X bond has thus far eluded experimental detection. In this work, potential energy surfaces of electronically excited states of the He-BeO complex have been calculated employing high level CASSCF+MRCI+Q methodologies and utilizing extended basis sets. Several excited states show strong interactions between helium and BeO lying in Franck-Condon accessible windows of electronic transitions arising from the vibrationless electronic ground state. It is hoped that the conclusions of this study will result in the observation an electronic spectrum of this long hypothesized strongly bound complex in the near future. W. Koch, J. R. Collins and G. Frenking, Chem. Phys. Lett. 1986, 132 330-333.

Electron affinity and excited states of methylglyoxal

NASA Astrophysics Data System (ADS)

Dauletyarov, Yerbolat; Dixon, Andrew R.; Wallace, Adam A.; Sanov, Andrei

2017-07-01

Using photoelectron imaging spectroscopy, we characterized the anion of methylglyoxal (X2A″ electronic state) and three lowest electronic states of the neutral methylglyoxal molecule: the closed-shell singlet ground state (X1A'), the lowest triplet state (a3A″), and the open-shell singlet state (A1A″). The adiabatic electron affinity (EA) of the ground state, EA(X1A') = 0.87(1) eV, spectroscopically determined for the first time, compares to 1.10(2) eV for unsubstituted glyoxal. The EAs (adiabatic attachment energies) of two excited states of methylglyoxal were also determined: EA(a3A″) = 3.27(2) eV and EA(A1A″) = 3.614(9) eV. The photodetachment of the anion to each of these two states produces the neutral species near the respective structural equilibria; hence, the a3A″ ← X2A″ and A1A″ ← X2A″ photodetachment transitions are dominated by intense peaks at their respective origins. The lowest-energy photodetachment transition, on the other hand, involves significant geometry relaxation in the X1A' state, which corresponds to a 60° internal rotation of the methyl group, compared to the anion structure. Accordingly, the X1A' ← X2A″ transition is characterized as a broad, congested band, whose vertical detachment energy, VDE = 1.20(4) eV, significantly exceeds the adiabatic EA. The experimental results are in excellent agreement with the ab initio predictions using several equation-of-motion methodologies, combined with coupled-cluster theory.

K-shell X-ray transition energies of multi-electron ions of silicon and sulfur

NASA Astrophysics Data System (ADS)

Beiersdorfer, P.; Brown, G. V.; Hell, N.; Santana, J. A.

2017-10-01

Prompted by the detection of K-shell absorption or emission features in the spectra of plasma surrounding high mass X-ray binaries and black holes, recent measurements using the Livermore electron beam ion trap have focused on the energies of the n = 2 to n = 1 K-shell transitions in the L-shell ions of lithiumlike through fluorinelike silicon and sulfur. In parallel, we have made calculations of these transitions using the Flexible Atomic Code and the multi-reference Møller-Plesset (MRMP) atomic physics code. Using this code we have attempted to produce sets of theoretical atomic data with spectroscopic accuracy for all the L-shell ions of silicon and sulfur. We present results of our calculations for oxygenlike and fluorinelike silicon and compare them to the recent electron beam ion trap measurements as well as previous calculations.

K-shell X-ray transition energies of multi-electron ions of silicon and sulfur

DOE PAGES

Beiersdorfer, P.; Brown, G. V.; Hell, N.; ...

2017-04-20

Prompted by the detection of K-shell absorption or emission features in the spectra of plasma surrounding high mass X-ray binaries and black holes, recent measurements using the Livermore electron beam ion trap have focused on the energies of the n = 2 to n = 1 K-shell transitions in the L-shell ions of lithiumlike through fluorinelike silicon and sulfur. In parallel, we have made calculations of these transitions using the Flexible Atomic Code and the multi-reference Møller-Plesset (MRMP) atomic physics code. Using this code we have attempted to produce sets of theoretical atomic data with spectroscopic accuracy for all themore » L-shell ions of silicon and sulfur. Here, we present results of our calculations for oxygenlike and fluorinelike silicon and compare them to the recent electron beam ion trap measurements as well as previous calculations.« less

Shannon entropies and Fisher information of K-shell electrons of neutral atoms

NASA Astrophysics Data System (ADS)

Sekh, Golam Ali; Saha, Aparna; Talukdar, Benoy

2018-02-01

We represent the two K-shell electrons of neutral atoms by Hylleraas-type wave function which fulfils the exact behavior at the electron-electron and electron-nucleus coalescence points and, derive a simple method to construct expressions for single-particle position- and momentum-space charge densities, ρ (r) and γ (p) respectively. We make use of the results for ρ (r) and γ (p) to critically examine the effect of correlation on bare (uncorrelated) values of Shannon information entropies (S) and of Fisher information (F) for the K-shell electrons of atoms from helium to neon. Due to inter-electronic repulsion the values of the uncorrelated Shannon position-space entropies are augmented while those of the momentum-space entropies are reduced. The corresponding Fisher information are found to exhibit opposite behavior in respect of this. Attempts are made to provide some plausible explanation for the observed response of S and F to electronic correlation.

Morphology and electronic structure of the oxide shell on the surface of iron nanoparticles.

PubMed

Wang, Chongmin; Baer, Donald R; Amonette, James E; Engelhard, Mark H; Antony, Jiji; Qiang, You

2009-07-01

An iron (Fe) nanoparticle exposed to air at room temperature will be instantly covered by an oxide shell that is typically approximately 3 nm thick. The nature of this native oxide shell, in combination with the underlying Fe(0) core, determines the physical and chemical behavior of the core-shell nanoparticle. One of the challenges of characterizing core-shell nanoparticles is determining the structure of the oxide shell, that is, whether it is FeO, Fe(3)O(4), gamma-Fe(2)O(3), alpha-Fe(2)O(3), or something else. The results of prior characterization efforts, which have mostly used X-ray diffraction and spectroscopy, electron diffraction, and transmission electron microscopic imaging, have been framed in terms of one of the known Fe-oxide structures, although it is not necessarily true that the thin layer of Fe oxide is a known Fe oxide. In this Article, we probe the structure of the oxide shell on Fe nanoparticles using electron energy loss spectroscopy (EELS) at the oxygen (O) K-edge with a spatial resolution of several nanometers (i.e., less than that of an individual particle). We studied two types of representative particles: small particles that are fully oxidized (no Fe(0) core) and larger core-shell particles that possess an Fe core. We found that O K-edge spectra collected for the oxide shell in nanoparticles show distinct differences from those of known Fe oxides. Typically, the prepeak of the spectra collected on both the core-shell and the fully oxidized particles is weaker than that collected on standard Fe(3)O(4). Given the fact that the origin of this prepeak corresponds to the transition of the O 1s electron to the unoccupied state of O 2p hybridized with Fe 3d, a weak pre-edge peak indicates a combination of the following four factors: a higher degree of occupancy of the Fe 3d orbital; a longer Fe-O bond length; a decreased covalency of the Fe-O bond; and a measure of cation vacancies. These results suggest that the coordination configuration in the oxide shell on Fe nanoparticles is defective as compared to that of their bulk counterparts. Implications of these defective structural characteristics on the properties of core-shell structured iron nanoparticles are discussed.

Ultraviolet Thomson Scattering from Direct-Drive Coronal Plasmas in Multilayer Targets

NASA Astrophysics Data System (ADS)

Henchen, R. J.; Goncharov, V. N.; Michel, D. T.; Follett, R. K.; Katz, J.; Froula, D. H.

2014-10-01

Ultraviolet (λ4 ω = 263 nm) Thomson scattering (TS) was used to probe ion-acoustic waves (IAW's) and electron plasma waves (EPW's) from direct-drive coronal plasmas. Fifty-nine drive beams (λ3 ω = 351 nm) illuminate a spherical target with a radius of ~ 860 μ m. A series of experiments studied the effect of higher electron temperature near the 3 ω quarter-critical surface (~ 2 . 5 ×1021 cm-3) on laser-plasma interactions resulting from a Si layer in the target. Electron temperatures and densities were measured from 150 to 400 μm from the initial target surface. Standard CH shells were compared to two-layered shells of CH and Si and three-layered shells of CH, Si, and CH. These multilayer targets have less hot-electron energy than standard CH shells as a result of higher electron temperature in the coronal plasmas. This material is based upon work supported by the Department of Energy National Nuclear Security Administration under Award Number DE-NA0001944.

Fabrication of core-shell micro/nanoparticles for programmable dual drug release by emulsion electrospraying

NASA Astrophysics Data System (ADS)

Wang, Yazhou; Zhang, Yiqiong; Wang, Bochu; Cao, Yang; Yu, Qingsong; Yin, Tieying

2013-06-01

The study aimed at constructing a novel drug delivery system for programmable multiple drug release controlled with core-shell structure. The core-shell structure consisted of chitosan nanoparticles as core and polyvinylpyrrolidone micro/nanocoating as shell to form core-shell micro/nanoparticles, which was fabricated by ionic gelation and emulsion electrospray methods. As model drug agents, Naproxen and rhodamine B were encapsulated in the core and shell regions, respectively. The core-shell micro/nanoparticles thus fabricated were characterized and confirmed by scanning electron microscope, transmission electron microscope, and fluorescence optical microscope. The core-shell micro/nanoparticles showed good release controllability through drug release experiment in vitro. It was noted that a programmable release pattern for dual drug agents was also achieved by adjusting their loading regions in the core-shell structures. The results indicate that emulsion electrospraying technology is a promising approach in fabrication of core-shell micro/nanoparticles for programmable dual drug release. Such a novel multi-drug delivery system has a potential application for the clinical treatment of cancer, tuberculosis, and tissue engineering.

Trends in Ionization Energy of Transition-Metal Elements

ERIC Educational Resources Information Center

Matsumoto, Paul S.

2005-01-01

A rationale for the difference in the periodic trends in the ionization energy of the transition-metal elements versus the main-group elements is presented. The difference is that in the transition-metal elements, the electrons enter an inner-shell electron orbital, while in the main-group elements, the electrons enter an outer-shell electron…

Structural and electronic properties of CdSe/ZnS and ZnS/CdSe core/shell nanowires via first principles study

NASA Astrophysics Data System (ADS)

Rehman, Shafiq Ur; Li, H. M.; Ding, Z. J.

2018-05-01

First principles calculations have been performed to predict the structural stability and electronic structures of hydrogen passivated wurtzite CdSe/ZnS and ZnS/CdSe core/shell nanowires (CSNWs) in the [0001] direction. The calculated binding energy shows that ZnS/CdSe CSNWs are more stable than CdSe/ZnS CSNWs and the stability of ZnS/CdSe CSNWs increases with increasing the thickness of ZnS shell. The modulated electronic band gap demonstrates an increase when the size of both CSNWs is reduced, as a result of the quantum confinement effect. The core-to-shell chemical composition of atoms shows that a strong composition effect also exists in these CSNWs, which in turn affects their electronic properties. Our simulated results show that the photoemission spectra of the CSNWs can be significantly improved by tuning the energy gap of CSNWs.

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

Anderson, Brian B.; Kirkegaard, Marie C.; Miskowiec, Andrew J.

Uranyl fluoride (UO 2F 2) is a hygroscopic powder with two main structural phases: an anhydrous crystal and a partially hydrated crystal of the same R¯3m symmetry. The formally closed-shell electron structure of anhydrous UO 2F 2 is amenable to density functional theory calculations. We use density functional perturbation theory (DFPT) to calculate the vibrational frequencies of the anhydrous crystal structure and employ complementary inelastic neutron scattering and temperature-dependent Raman scattering to validate those frequencies. As a model closed-shell actinide, we investigated the effect of LDA, GGA, and non-local vdW functionals as well as the spherically-averaged Hubbard +U correction onmore » vibrational frequencies, electronic structure, and geometry of anhydrous UO 2F 2. A particular choice of U eff = 5.5 eV yields the correct U Oyl bond distance and vibrational frequencies for the characteristic Eg and A1g modes that are within the resolution of experiment. Inelastic neutron scattering and Raman scattering suggest a degree of water coupling to the lattice vibrations in the more experimentally accessible partially hydrated UO 2F 2 system, with the symmetric O-U-O stretching vibration shifted approximately 47 cm -1 lower in energy compared to the anhydrous structure. Evidence of water interaction with the uranyl ion is present from a two-peak decomposition of the uranyl stretching vibration in the Raman spectra and anion hydrogen stretching vibrations in the inelastic neutron scattering spectra. A first-order dehydration phase transition temperature is definitively identified to be 125 °C using temperature-dependent Raman scattering.« less

Vibrational Properties of Anhydrous and Partially Hydrated Uranyl Fluoride

DOE PAGES

Anderson, Brian B.; Kirkegaard, Marie C.; Miskowiec, Andrew J.; ...

2017-01-01

Uranyl fluoride (UO 2F 2) is a hygroscopic powder with two main structural phases: an anhydrous crystal and a partially hydrated crystal of the same R¯3m symmetry. The formally closed-shell electron structure of anhydrous UO 2F 2 is amenable to density functional theory calculations. We use density functional perturbation theory (DFPT) to calculate the vibrational frequencies of the anhydrous crystal structure and employ complementary inelastic neutron scattering and temperature-dependent Raman scattering to validate those frequencies. As a model closed-shell actinide, we investigated the effect of LDA, GGA, and non-local vdW functionals as well as the spherically-averaged Hubbard +U correction onmore » vibrational frequencies, electronic structure, and geometry of anhydrous UO 2F 2. A particular choice of U eff = 5.5 eV yields the correct U Oyl bond distance and vibrational frequencies for the characteristic Eg and A1g modes that are within the resolution of experiment. Inelastic neutron scattering and Raman scattering suggest a degree of water coupling to the lattice vibrations in the more experimentally accessible partially hydrated UO 2F 2 system, with the symmetric O-U-O stretching vibration shifted approximately 47 cm -1 lower in energy compared to the anhydrous structure. Evidence of water interaction with the uranyl ion is present from a two-peak decomposition of the uranyl stretching vibration in the Raman spectra and anion hydrogen stretching vibrations in the inelastic neutron scattering spectra. A first-order dehydration phase transition temperature is definitively identified to be 125 °C using temperature-dependent Raman scattering.« less

Oxygen reduction kinetics on Pt monolayer shell highly affected by the structure of bimetallic AuNi cores

DOE PAGES

Chen, Guangyu; Kuttiyiel, Kurian A.; Su, Dong; ...

2016-07-12

Here, we describe pronounced effects of structural changes of the AuNi cores on the oxygen reduction reaction (ORR) activity of a Pt monolayer shell. The study of alloyed AuNi nanoparticles compared with AuNi core–shell structured nanoparticles revealed configurations having different electronic and electrochemical properties. Controlled alloying of Au with Ni was essential to tune the electronic properties of Au interacting with the Pt monolayer shell to achieve suitable adsorption of O 2 on Pt for expediting the ORR. The alloyed AuNi nanoparticles made the Pt shell more catalytically active for the ORR than the core–shell structured AuNi nanoparticles. The Ptmore » monolayer supported on the alloyed AuNi nanoparticles showed the Pt mass and specific activities as high as 1.52 A mg –1 and 1.18 mA cm –2, respectively, with almost no loss over 5 000 cycles of stability test. This high ORR activity is ascribed to the role of nonspecific steric configuration of Ni atoms changing the electronic properties of the alloy that affect the oxygen and water interaction with the Pt shell and facilitate increased ORR kinetics.« less

A revised MRCI-algorithm coupled to an effective valence-shell Hamiltonian. II. Application to the valence excitations of butadiene

NASA Astrophysics Data System (ADS)

Strodel, Paul; Tavan, Paul

2002-09-01

In Paper I of this work we have sketched an improved MRCI algorithm and its coupling to the effective valence-shell Hamiltonian OM2. To check the quality of the resulting OM2/MRCI approach, it is applied here to the excited valence states of all-trans butadiene. As is explained by a review of previous theoretical work, proper descriptions of these states posed severe problems within correlated ab initio treatments but seemed to be trivial within simple correlated pi-electron models. We now show that an extended MRCI treatment of the correlations among all valence electrons as described by OM2 closely reproduces the experimental evidence, placing the vertical 2 1Ag excitation by about 0.2 eV below the 1 1Bu excitation. By an analysis of sigma]-[pi interactions we explain the corresponding earlier success of correlated pi-electron theory. Exploiting the enhanced capabilities of the new approach we investigate the potential surfaces. Here, OM2/MRCI is shown to predict that the 2 1Ag state is energetically lowered about four times more strongly than the 1 1Bu state upon geometry relaxation constrained to the C2h symmetry. We conclude that OM2/MRCI should be well-suited for the study of excited state surfaces of organic dye molecules.

Probing the Influence of Disorder on Lanthanide Luminescence Using Eu-Doped LaPO4 Nanoparticles

PubMed Central

2017-01-01

Lanthanide-doped nanocrystals (NCs) differ from their bulk counterparts due to their large surface to volume ratio. It is generally assumed that the optical properties are not affected by size effects as electronic transitions occur within the well-shielded 4f shell of the lanthanide dopant ions. However, defects and disorder in the surface layer can affect the luminescence properties. Trivalent europium is a suitable ion to investigate the subtle influence of the surface, because of its characteristic luminescence and high sensitivity to the local environment. Here, we investigate the influence of disorder in NCs on the optical properties of lanthanide dopants by studying the inhomogeneous linewidth, emission intensity ratios, and luminescence decay curves for LaPO4:Eu3+ samples of different sizes (4 nm to bulk) and core–shell configurations (core, core–isocrystalline shell, and core–silica shell). We show that the emission linewidths increase strongly for NCs. The ratio of the intensities of the forced electric dipole (ED) and magnetic dipole (MD) transitions, a measure for the local symmetry distortion around Eu3+ ions, is higher for samples with a large fraction of Eu3+ ions close to the surface. Finally, we present luminescence decay curves revealing an increased nonradiative decay rate for Eu3+ in NCs. The effects are strongest in core and core–silica shell NCs and can be reduced by growth of an isocrystalline LaPO4 shell. The present systematic study provides quantitative insight into the role of surface disorder on the optical properties of lanthanide-doped NCs. These insights are important in emerging applications of lanthanide-doped nanocrystals. PMID:28919934

Use of nanoindentation technique for a better understanding of the fracture toughness of Strombus gigas conch shell

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

Romana, L., E-mail: laurence.romana@univ-ag.fr; Thomas, P.; Bilas, P.

2013-02-15

In this work the nanochemical properties of the composite organomineral biomaterial constituting Strombus gigas conch shell are studied by means of dynamic mechanical analyses associated to nanoidentation technique. The measurements are performed on shell samples presenting different surface orientations relative to the growth axis of the conch shell. The influence of the organic component of the biomaterial on its nanomechanical properties is also investigated by studying fresh and dried S. gigas conch shells. Monocrystalline aragonite is used as a reference. For the understanding of nanochemical behaviour, special attention is paid to the pop in events observed on the load/displacement curvesmore » which results from nanofractures' initiation and propagation occuring during the load process. In order to better understand the mechanical properties systematic studies of the structure and morphology are performed using scanning electron microscopy, atomic force microscopy and X-ray diffractometry. The hardness and Young's modulus values measured on bio aragonite samples are close to those of the aragonite mineral standard. This surprising result shows that, H and E values are not related to the bio composition and lamellar structure of the bio aragonite. However, it was found that the organic layer and the micro architecture strongly influence the nanofracture initiation and propagation processes in the samples. Statistic study of the pop-in events can help to predict the macroscopic mechanical behaviour of the material. - Highlights: ► Nanomechanical properties of Strombus gigas conch shell ► Low influence of the crossed lamellar structure on H and E values at the nano scale ► Strong influence of the crossed lamellar on nanocracks initiation ► Correlation between mechanical behaviors at the macro and nano scales.« less

Evaluating and interpreting the chemical relevance of the linear response kernel for atoms II: open shell.

PubMed

Boisdenghien, Zino; Fias, Stijn; Van Alsenoy, Christian; De Proft, Frank; Geerlings, Paul

2014-07-28

Most of the work done on the linear response kernel χ(r,r') has focussed on its atom-atom condensed form χAB. Our previous work [Boisdenghien et al., J. Chem. Theory Comput., 2013, 9, 1007] was the first effort to truly focus on the non-condensed form of this function for closed (sub)shell atoms in a systematic fashion. In this work, we extend our method to the open shell case. To simplify the plotting of our results, we average our results to a symmetrical quantity χ(r,r'). This allows us to plot the linear response kernel for all elements up to and including argon and to investigate the periodicity throughout the first three rows in the periodic table and in the different representations of χ(r,r'). Within the context of Spin Polarized Conceptual Density Functional Theory, the first two-dimensional plots of spin polarized linear response functions are presented and commented on for some selected cases on the basis of the atomic ground state electronic configurations. Using the relation between the linear response kernel and the polarizability we compare the values of the polarizability tensor calculated using our method to high-level values.

High-temperature investigation on morphology, phase and size of iron/iron-oxide core–shell nanoclusters for radiation nanodetector

NASA Astrophysics Data System (ADS)

Khanal, Lokendra Raj; Williams, Thomas; Qiang, You

2018-06-01

Iron/iron-oxide (Fe–Fe3O4) core–shell nanoclusters (NCs) synthesized by a cluster deposition technique were subjected to a study of their high temperature structural and morphological behavior. Annealing effects have been investigated up to 800 °C in vacuum, oxygen and argon environments. The ~18 nm average size of the as-prepared NCs increases slowly in temperatures up to 500 °C in all three environments. The size increases abruptly in the argon environment but slowly in vacuum and oxygen when annealed at 800 °C. The x-ray diffraction (XRD) studies have shown that the iron core remains in the core–shell NCs only when they were annealed in the vacuum. A dramatic change in the surface morphology, an island like structure and/or a network like pattern, was observed at the elevated temperature. The as-prepared and annealed samples were analyzed using XRD, scanning electron microscopy and imageJ software for a close inspection of the temperature aroused properties. This work presents the temperature induced size growth mechanism, oxidation kinetics and phase transformation of the NCs accompanied by cluster aggregation, particle coalescence, and diffusion.

PMMA/PS coaxial electrospinning: core-shell fiber morphology as a function of material parameters

NASA Astrophysics Data System (ADS)

Rahmani, Shahrzad; Arefazar, Ahmad; Latifi, Masoud

2017-03-01

Core-shell fibers of polymethyl methacrylate (PMMA) and polystyrene (PS) have been successfully electrospun by coaxial electrospinning. To evaluate the influence of the solvent on the final fiber morphology, four types of organic solvents were used in the shell solution while the core solvent was preserved. Morphological observations with scanning electron microscopy, transmission electron microscopy and optical microscopy revealed that both core and shell solvent properties were involved in the final fiber morphology. To explain this involvement, alongside a discussion of the Bagley solubility graph of PS and PMMA, a novel criterion based on solvent physical properties was introduced. A theoretical model based on the momentum conservation principle was developed and applied for describing the dependence of the core and shell diameters to their solvent combinations. Different concentrations of core and shell were also investigated in the coaxial electrospinning of PMMA/PS. The core-shell fiber morphologies with different core and shell concentrations were compared with their single electrospun fibers.

Absolute cross-section measurements of inner-shell ionization

NASA Astrophysics Data System (ADS)

Schneider, Hans; Tobehn, Ingo; Ebel, Frank; Hippler, Rainer

1994-12-01

Cross section ratios for K- and L-shell ionization of thin silver and gold targets by positron and electron impact have been determined at projectile energies of 30 70 keV. The experimental results are confirmed by calculations in plane wave Born approximation (PWBA) which include an electron exchange term and account for the deceleration or acceleration of the incident projectile in the nuclear field of the target atom. We report first absolute cross sections for K- and L-shell ionization of silver and gold targets by lepton impact in the threshold region. We have measured the corresponding cross sections for electron (e-) impact with an electron gun and the same experimental set-up.

Efficient G0W0 using localized basis sets: a benchmark for molecules

NASA Astrophysics Data System (ADS)

Koval, Petr; Per Ljungberg, Mathias; Sanchez-Portal, Daniel

Electronic structure calculations within Hedin's GW approximation are becoming increasingly accessible to the community. In particular, as it has been shown earlier and we confirm by calculations using our MBPT_LCAO package, the computational cost of the so-called G0W0 can be made comparable to the cost of a regular Hartree-Fock calculation. In this work, we study the performance of our new implementation of G0W0 to reproduce the ionization potentials of all 117 closed-shell molecules belonging to the G2/97 test set, using a pseudo-potential starting point provided by the popular density-functional package SIESTA. Moreover, the ionization potentials and electron affinities of a set of 24 acceptor molecules are compared to experiment and to reference all-electron calculations. PK: Guipuzcoa Fellow; PK,ML,DSP: Deutsche Forschungsgemeinschaft (SFB1083); PK,DSP: MINECO MAT2013-46593-C6-2-P.

The Non-innocent Phenalenyl Unit: An Electronic Nest to Modulate the Catalytic Activity in Hydroamination Reaction

PubMed Central

Mukherjee, Arup; Sen, Tamal K.; Ghorai, Pradip Kr; Mandal, Swadhin K.

2013-01-01

The phenalenyl unit has played intriguing role in different fields of research spanning from chemistry, material chemistry to device physics acting as key electronic reservoir which has not only led to the best organic single component conductor but also created the spin memory device of next generation. Now we show the non-innocent behaviour of phenalenyl unit in modulating the catalytic behaviour in a homogeneous organic transformation. The present study establishes that the cationic state of phenalenyl unit can act as an organic Lewis acceptor unit to influence the catalytic outcome of intermolecular hydroamination reaction of carbodiimides. For the present study, we utilized organoaluminum complexes of phenalenyl ligands in which the phenalenyl unit maintains the closed shell electronic state. The DFT calculation reveals that the energy of LUMO of the catalyst is mainly controlled by phenalenyl ligands which in turn determines the outcome of the catalysis. PMID:24084653

On Closed Shells in Nuclei

DOE R&D Accomplishments Database

Mayer, M. G.

1948-02-01

It has been suggested in the past that special numbers of neutrons or protons in the nucleus form a particularly stable configuration.{sup1} The complete evidence for this has never been summarized, nor is it generally recognized how convincing this evidence is. That 20 neutrons or protons (Ca{sup40}) form a closed shell is predicted by the Hartree model. A number of calculations support this fact.{sup2} These considerations will not be repeated here. In this paper, the experimental facts indicating a particular stability of shells of 50 and 82 protons and of 50, 82, and 126 neutrons will be listed.

Low-Energy Charged Particles in Saturn's Magnetosphere: Results from Voyager 1.

PubMed

Krimigis, S M; Armstrong, T P; Axford, W I; Bostrom, C O; Gloeckler, G; Keath, E P; Lanzerotti, L J; Carbary, J F; Hamilton, D C; Roelof, E C

1981-04-10

The low-energy charged particle instrument on Voyager 1 measured low-energy electrons and ions (energies >/= 26 and >/= 40 kiloelectron volts, respectively) in Saturn's magnetosphere. The first-order ion anisotropies on the dayside are generally in the corotation direction with the amplitude decreasing with decreasing distance to the planet. The ion pitch-angle distributions generally peak at 90 degrees , whereas the electron distributions tend to have field-aligned bidirectional maxima outside the L shell of Rhea. A large decrease in particle fluxes is seen near the L shell of Titan, while selective particle absorption (least affecting the lowest energy ions) is observed at the L shells of Rhea, Dione, and Tethys. The phase space density of ions with values of the first invariant in the range approximately 300 to 1000 million electron volts per gauss is consistent with a source in the outer magnetosphere. The ion population at higher energies (>/= 200 kiloelectron volts per nucleon) consists primarily of protons, molecular hydrogen, and helium. Spectra of all ion species exhibit an energy cutoff at energies >/= 2 million electron volts. The proton-to-helium ratio at equal energy per nucleon is larger (up to approximately 5 x 10(3)) than seen in other magnetospheres and is consistent with a local (nonsolar wind) proton source. In contrast to the magnetospheres of Jupiter and Earth, there are no lobe regions essentially devoid of particles in Saturn's nighttime magnetosphere. Electron pitch-angle distributions are generally bidirectional andfield-aligned, indicating closed field lines at high latitudes. Ions in this region are generally moving toward Saturn, while in the magnetosheath they exhibit strong antisunward streaming which is inconsistent with purely convective flows. Fluxes of magnetospheric ions downstream from the bow shock are present over distances >/= 200 Saturn radii from the planet. Novel features identified in the Saturnian magnetosphere include a mantle of low-energy particles extending inward from the dayside magnetopause to approximately 17 Saturn radii, at least two intensity dropouts occurring approximately 11 hours apart in the nighttime magnetosphere, and a pervasive population of energetic molecular hydrogen.

Observations on ichnology, taphonomy and epibiota in the freshwater realm

NASA Astrophysics Data System (ADS)

Lawfield, Andrew Martin William

Ichnology concerns the study of interactions between organisms and both soft and hard substrates. Actualistic observation of a modern day river channel molluscan assemblage including unionid and sphaeriid bivalves and gastropods within the Saint John River, Fredericton, New Brunswick, Canada reveals their production of almond shaped Lockeia like resting traces, together with varied, horizontally aligned furrowed, meandering, looping and spiral plan view locomotion/grazing traces. These traces occur within a shifting sand softground substrate. An emersion event associated with a low water level allowed collection of unionid samples, amongst which Elliptio complanata predominates, alongside Lampsilis radiata and Anodonta implicata. Detailed analysis of shell material, with methodologies including scanning electron microscopy (SEM) reveals microboring, various taphonomic signatures and the development of biofilm and extracellular polymeric substances (EPS). These are often associated with one another and their location closely influenced by the shell structure. Taphonomic decay of the shells was noted, with the external periostracum and prismatic aragonite layers decaying, particularly in the umbonal region. Physical puncturing and tearing penetrate the periostracum. Exposed regions of nacreous aragonite are smoothed by a combination of chemical interaction with the water column and physical abrasion from agitated silt and sand sediments. Surface pitting and circular to ovoid penetrations with morphologies comparable to Oichnus borings are noted and their formation is tentatively attributed to bacterial decay processes. In marine settings, the outer protective periostracum of molluscs often possesses physical and chemical defence mechanisms intended to inhibit the attachment of epibiota. Our observations suggest their absence from unionids, with final instar larval or pupal stage Trichoptera, including Goera, Neophylax and Helicopsyche selectively attached to regions of intact periostracum in preference to exposed aragonite on dead shells. In addition, live unionids can display thick growths of cyanobacterial or cyanophyte dominated microbial mat. Biofilm and extracellular polymeric substances, with bacterial, diatomaceous and filamentous components are also observed, often displaying a close association with both microboring and the shells conchiolin layers. Several styles of microboring are noted, with predominantly surficial and both simple tubular and complex network penetrative styles observed. Microborings may be attributed to cyanobacterial, cyanophyte and fungal activity.

Polaronic effects on the off-center donor impurity in AlAs/GaAs/SiO2 spherical core/shell quantum dots

NASA Astrophysics Data System (ADS)

El Haouari, M.; Feddi, E.; Dujardin, F.; Restrepo, R. L.; Mora-Ramos, M. E.; Duque, C. A.

2017-11-01

The ground state of a conduction electron coupled to an off-center impurity donor in a AlAS/GaAs spherical core/shell quantum dot is investigated theoretically. The image-charge effect and the influence of the electron-polar-LO-phonon interaction are considered. The electron-impurity binding energy is calculated via a variational procedure and is reported both as a function of the shell width and of the radial position of the donor atom. The polaronic effects on this quantity are particularly discussed.

Energetic-particle drift motions in the outer dayside magnetosphere

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

Buck, R.C.

1987-01-01

Models of the geomagnetic field predict that within a distance of approximately one earth radius inside the dayside magnetopause, magnetic fields produced by the Chapman-Ferraro magnetopause currents create high-latitude minimum-B pockets in the geomagnetic field. These pockets are theoretically capable of temporarily trapping azimuthally-drifting electrons and modifying electron directional distributions. The Lawrence Livermore National Laboratory's scanning electron spectrometer aboard the OGO-5 satellite provided detailed energetic (E > 70 keV) electron pitch-angle distributions throughout the magnetosphere. Distributions obtained in the outer dayside magnetosphere over a wide range of longitudes show unusual flux features. This study analyzes drift-shell branching caused by themore » minimum-B pockets, and interprets the observed flux features in terms of an adiabatic-shell branching and rejoining process. The author examines the shell-branching process for a static field in detail, using the Choe-Beard 1974 magnetospheric magnetic field mode. He finds that shell branching and rejoining conserves the particle mirror field B/sub M/, the fieldline integral invariant I, and the directional electron flux j. He also finds a good correlation between the itch angles that mark the transition from branched to unbranched shells in the model and the distinctive features of the OGO-5 distributions.« less

Defects in ion-implanted hcp-titanium: A first-principles study of electronic structures

NASA Astrophysics Data System (ADS)

Raji, Abdulrafiu T.; Mazzarello, Riccardo; Scandolo, Sandro; Nsengiyumva, Schadrack; Härting, Margit; Britton, David T.

2011-12-01

The electronic structures of hexagonal closed-packed (h.c.p) titanium containing a vacancy and krypton impurity atoms at various insertion sites are calculated by first-principles methods in the framework of the density-functional theory (DFT). The density of states (DOS) for titanium containing a vacancy defect shows resonance-like features. Also, the bulk electron density decreases from ˜0.15/Å 3 to ˜0.05/Å 3 at the vacancy centre. Electronic structure calculations have been performed to investigate what underlies the krypton site preference in titanium. The DOS of the nearest-neighbour (NN) titanium atoms to the octahedral krypton appears to be less distorted (relative to pure titanium) when compared to the NN titanium atoms to the tetrahedral krypton. The electronic density deformation maps show that polarization of the titanium atoms is stronger when the krypton atom is located at the tetrahedral site. Since krypton is a closed-shell atom, thus precluding any bonding with the titanium atoms, we may conclude that the polarization of the electrons in the vicinity of the inserted krypton atoms and the distortion of the DOS of the NN titanium atoms to the krypton serve to indicate which defect site is preferred when a krypton atom is inserted into titanium. Based on these considerations, we conclude that the substitutional site is the most favourable one, and the octahedral is the preferred interstitial site, in agreement with recent DFT calculations of the energetics of krypton impurity sites.

Stability of a Bifunctional Cu-Based Core@Zeolite Shell Catalyst for Dimethyl Ether Synthesis Under Redox Conditions Studied by Environmental Transmission Electron Microscopy and In Situ X-Ray Ptychography.

PubMed

Baier, Sina; Damsgaard, Christian D; Klumpp, Michael; Reinhardt, Juliane; Sheppard, Thomas; Balogh, Zoltan; Kasama, Takeshi; Benzi, Federico; Wagner, Jakob B; Schwieger, Wilhelm; Schroer, Christian G; Grunwaldt, Jan-Dierk

2017-06-01

When using bifunctional core@shell catalysts, the stability of both the shell and core-shell interface is crucial for catalytic applications. In the present study, we elucidate the stability of a CuO/ZnO/Al2O3@ZSM-5 core@shell material, used for one-stage synthesis of dimethyl ether from synthesis gas. The catalyst stability was studied in a hierarchical manner by complementary environmental transmission electron microscopy (ETEM), scanning electron microscopy (SEM) and in situ hard X-ray ptychography with a specially designed in situ cell. Both reductive activation and reoxidation were applied. The core-shell interface was found to be stable during reducing and oxidizing treatment at 250°C as observed by ETEM and in situ X-ray ptychography, although strong changes occurred in the core on a 10 nm scale due to the reduction of copper oxide to metallic copper particles. At 350°C, in situ X-ray ptychography indicated the occurrence of structural changes also on the µm scale, i.e. the core material and parts of the shell undergo restructuring. Nevertheless, the crucial core-shell interface required for full bifunctionality appeared to remain stable. This study demonstrates the potential of these correlative in situ microscopy techniques for hierarchically designed catalysts.

Specific formation of negative ions from leucine and isoleucine molecules

NASA Astrophysics Data System (ADS)

Papp, Peter; Shchukin, Pavel; Matejčík, Štefan

2010-01-01

Dissociative electron attachment (DEA) to gas phase leucine (Leu) and isoleucine (Ile) molecules was studied using experimental and quantum-chemical methods. The relative partial cross sections for DEA have been measured using crossed electron/molecular beams technique. Supporting ab initio calculations of the structure, energies of neutral molecules, fragments, and negative ions have been carried out at G3MP2 and B3LYP levels in order to interpret the experimental data. Leu and Ile exhibit several common features. The negative ionic fragments from both molecules are formed in the electron energy range from 0 to approximately 14 eV via three resonances (1.2, 5.5, and 8 eV). The relative partial cross sections for DEA Leu and Ile are very similar. The dominant negative ions formed were closed shell negative ions (M-H)- (m/z=130) formed preferentially via low electron energy resonance of 1.23 eV. Additional negative ions with m/z=115, 114, 113, 112, 84, 82, 74, 45, 26, and 17 have been detected.

Formation of energetic electron butterfly distributions by magnetosonic waves via Landau resonance

DOE PAGES

Li, Jinxing; Ni, Binbin; Ma, Qianli; ...

2016-03-06

Radiation belt electrons can exhibit different types of pitch angle distributions in response to various magnetospheric processes. Butterfly distributions, characterized by flux minima at pitch angles around 90°, are broadly observed in both the outer and inner belts and the slot region. Butterfly distributions close to the outer magnetospheric boundary have been attributed to drift shell splitting and losses to the magnetopause. However, their occurrence in the inner belt and the slot region has hitherto not been resolved. In this study, by analyzing the particle and wave data collected by the Van Allen Probes during a geomagnetic storm, we combinemore » test particle calculations and Fokker-Planck simulations to reveal that scattering by equatorial magnetosonic waves is a significant cause for the formation of energetic electron butterfly distributions in the inner magnetosphere. Finally, another event shows that a large-amplitude magnetosonic wave in the outer belt can create electron butterfly distributions in just a few minutes.« less

A Modern Periodic Table.

ERIC Educational Resources Information Center

Herrenden-Harker, B. D.

1997-01-01

Presents a modern Periodic Table based on the electron distribution in the outermost shell and the order of filling of the sublevels within the shells. Enables a student to read off directly the electronic configuration of the element and the order in which filling occurs. (JRH)

Synthesis, structure, and bonding of two lanthanum indium germanides with novel structures and properties

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

Guloy, A.M.; Corbett, J.D.

1996-04-24

The new tetragonal phases La{sub 3}In{sub 4}Ge and La{sub 3}InGe are obtained from high-temperature reactions of the elements in welded Ta followed by annealing. The structures of both were established by single-crystal X-ray diffraction in tetragonal space group I4/mcm (Z = 4 and 16, {alpha} = 8.5165(3) and 12.3083(2) {Angstrom}, c = 11.9024(4) and 16.0776(4) {Angstrom}, respectively). La{sub 3}In{sub 4}Ge contains layers or slabs of three-connected indium built of puckered 8-rings and 4-rings, or of squashed tetrahedra ({open_quotes}butterflies{close_quotes}) interlinked at all vertices, and these are separated by layers of La and isolated Ge. The phase is deficient of being amore » Zintl phase by three electrons per formula unit and is better described in terms of an alternate optimized and delocalized bonding picture and an open-shell metallic better described in terms of an alternate optimized and delocalized bonding picture and an open-shell metallic behavior for the In slabs. The more complex La{sub 3}InGe, isostructural with Gd{sub 3}Ga{sub 2}, is also layered. This phase contains pairs of mixed-occupancy (0.75 In, 0.25 Ge) sites separated by 3.020 {Angstrom}, as well as isolated In and Ge atoms. The former appear to be fully reduced closed-shell atoms (relative to the bonded Ga dimers in Gd{sub 3}Ga{sub 2}) that are held in somewhat close proximity by cation matrix effects. The compound appears to be semiconducting and thus is a classical Zintl phase, (La{sup +3}){sub 3}In{sup {minus}5}Ge{sup {minus}4} in the simplest oxidation state notation. High Coulomb energies are presumably important for the nature of the bonding and the stabilities of both compounds.« less

Approximate theoretical model for the five electronic states ( Ω = 5/2, 3/2, 3/2, 1/2, 1/2) arising from the ground 3d 9 configuration in nickel halide molecules and for rotational levels of the two Ω = 1/2 states in that manifold

NASA Astrophysics Data System (ADS)

Hougen, Jon T.

2011-05-01

In the first part of this paper an effective Hamiltonian for a non-rotating diatomic molecule containing only crystal-field and spin-orbit operators is set up to describe the energies of the five spin-orbit components that arise in the ground electronic configuration of the nickel monohalides. The model assumes that bonding in the nickel halides has the approximate form Ni +X -, with an electronic 3d 9 configuration plus closed shells on the Ni + moiety and a closed shell configuration on the X - moiety. From a crystal-field point of view, interactions of the positive d-hole with the cylindrically symmetrical electric charge distribution of the hypothetical NiX - closed-shell core can then be parameterized by three terms in a traditional expansion in spherical harmonics: C0 + C2Y20( θ, ϕ) + C4Y40( θ, ϕ). Interaction of the hole with the magnetic field generated by its own orbital motion can be parameterized by a traditional spin-orbit interaction operator A L · S. The Hamiltonian matrix is set up in a basis set consisting of the 10 Hund's case (a) basis functions | L, Λ; S , Σ> that arise when L = 2 and S = 1/2. Least-squares fits of the observed five spin-orbit components of the three lowest electronic states in NiF and NiCl are then carried out in terms of the four parameters C0, C2, C4, and A which lead to good agreement, except for the two | Ω| = 1/2 states. The large equal and opposite residuals of the | Ω| = 1/2 states can be reduced to values comparable with those for the | Ω| = 3/2 and | Ω| = 5/2 states by fixing A to its value in Ni + and then introducing an empirical correction factor for one off-diagonal orbital matrix element. In the second part of this paper the usual effective Hamiltonian B( J- L- S) 2 for a rotating diatomic molecule is used to derive expressions for the Ω-type doubling parameter p in the two | Ω| = 1/2 states. These expressions show (for certain sign conventions) that the sum of the two p values should be -2 B, but that their difference can vary between -10 B and +10 B. These theoretical results are in good agreement with the two observed p values for both NiF and NiCl. The present formalism should in principle be applicable to NiBr and NiI, and to the halides of palladium, since Pd + has a well isolated 4d 9 electronic ground configuration. Extension to metal halides having d n configurations with n < 9, or to platinum halides may present difficulties, since manifolds from the d n and d n-1s configurations may be heavily mixed, thus requiring "too many" parameters in the electronic part of the problem. Application to linear triatomic molecules may also present problems because of the large number of vibronic perturbations made possible by their four vibrational degrees of freedom.

Ab initio effective core potentials including relativistic effects and their application to the electronic structure calculations of heavy atoms and molecules

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

Lee, Y.S.

1977-11-01

The effects of the 4f shell of electrons and the relativity of valence electrons are compared. The effect of 4f shell (lanthanide contraction) is estimated from the numerical Hartree-Fock (HF) calculations of pseudo-atoms corresponding to Hf, Re, Au, Hg, Tl, Pb and Bi without 4f electrons and with atomic numbers reduced by 14. The relativistic effect estimated from the numerical Dirac-Hartree-Fock (DHF) calculations of those atoms is comparable in the magnitude with that of the 4f shell of electrons. Both are larger for 6s than for 5d or 6p electrons. The various relativistic effects on valence electrons are discussed inmore » detail to determine the proper level of the approximation for the valence electron calculations of systems with heavy elements. An effective core potential system has been developed for heavy atoms in which relativistic effects are included in the effective potentials.« less

Demonstration of Confined Electron Gas and Steep-Slope Behavior in Delta-Doped GaAs-AlGaAs Core-Shell Nanowire Transistors.

PubMed

Morkötter, S; Jeon, N; Rudolph, D; Loitsch, B; Spirkoska, D; Hoffmann, E; Döblinger, M; Matich, S; Finley, J J; Lauhon, L J; Abstreiter, G; Koblmüller, G

2015-05-13

Strong surface and impurity scattering in III-V semiconductor-based nanowires (NW) degrade the performance of electronic devices, requiring refined concepts for controlling charge carrier conductivity. Here, we demonstrate remote Si delta (δ)-doping of radial GaAs-AlGaAs core-shell NWs that unambiguously exhibit a strongly confined electron gas with enhanced low-temperature field-effect mobilities up to 5 × 10(3) cm(2) V(-1) s(-1). The spatial separation between the high-mobility free electron gas at the NW core-shell interface and the Si dopants in the shell is directly verified by atom probe tomographic (APT) analysis, band-profile calculations, and transport characterization in advanced field-effect transistor (FET) geometries, demonstrating powerful control over the free electron gas density and conductivity. Multigated NW-FETs allow us to spatially resolve channel width- and crystal phase-dependent variations in electron gas density and mobility along single NW-FETs. Notably, dc output and transfer characteristics of these n-type depletion mode NW-FETs reveal excellent drain current saturation and record low subthreshold slopes of 70 mV/dec at on/off ratios >10(4)-10(5) at room temperature.

The limits of hamiltonian structures in three-dimensional elasticity, shells, and rods

NASA Astrophysics Data System (ADS)

Ge, Z.; Kruse, H. P.; Marsden, J. E.

1996-01-01

This paper uses Hamiltonian structures to study the problem of the limit of three-dimensional (3D) elastic models to shell and rod models. In the case of shells, we show that the Hamiltonian structure for a three-dimensional elastic body converges, in a sense made precise, to that for a shell model described by a one-director Cosserat surface as the thickness goes to zero. We study limiting procedures that give rise to unconstrained as well as constrained Cosserat director models. The case of a rod is also considered and similar convergence results are established, with the limiting model being a geometrically exact director rod model (in the framework developed by Antman, Simo, and coworkers). The resulting model may or may not have constraints, depending on the nature of the constitutive relations and their behavior under the limiting procedure. The closeness of Hamiltonian structures is measured by the closeness of Poisson brackets on certain classes of functions, as well as the Hamiltonians. This provides one way of justifying the dynamic one-director model for shells. Another way of stating the convergence result is that there is an almost-Poisson embedding from the phase space of the shell to the phase space of the 3D elastic body, which implies that, in the sense of Hamiltonian structures, the dynamics of the elastic body is close to that of the shell. The constitutive equations of the 3D model and their behavior as the thickness tends to zero dictates whether the limiting 2D model is a constrained or an unconstrained director model. We apply our theory in the specific case of a 3D Saint Venant-Kirchhoff material and derive the corresponding limiting shell and rod theories. The limiting shell model is an interesting Kirchhoff-like shell model in which the stored energy function is explicitly derived in terms of the shell curvature. For rods, one gets (with an additional inextensibility constraint) a one-director Kirchhoff elastic rod model, which reduces to the well-known Euler elastica if one adds an additional single constraint that the director lines up with the Frenet frame.

Ab initio coupled-cluster and multi-reference configuration interaction studies of the low-lying electronic states of 1,2,3,4-cyclobutanetetraone

DOE PAGES

Hansen, Jared A.; Bauman, Nicholas P.; Shen, Jun; ...

2015-12-09

In this paper, the four, closely spaced, lowest energy electronic states of the challenging, D 4h-symmetric, 1,2,3,4-cyclobutanetetraone (C 4O 4) molecule have been investigated using high-level ab initio methods. The calculated states include the closed-shell singlet 8π( 1A 1g) state, the singlet 10π( 1A 1g) state, in which the π-type lowest unoccupied molecular orbital (LUMO) of the 8π( 1A 1g) reference is doubly occupied and the σ-type highest occupied molecular orbital (HOMO) is empty, and the open-shell singlet and triplet states, designated as 9π( 1B 2u) and 9π( 3B 2u), respectively, originating from single occupancy of the HOMO and LUMO.more » Our focus is on single-reference coupled-cluster (CC) approaches capable of handling electronic near-degeneracies in diradicals, especially the completely renormalised CR-CC(2,3) and active-space CCSDt methods, along with their CCSD and EOMCCSD counterparts. The internally contracted multi-reference configuration interaction calculations with a quasi-degenerate Davidson correction are performed as well. Our computations demonstrate that the state ordering is 9π( 3B 2u) < 8π( 1A 1g) < 9π( 1B 2u) < 10π( 1A 1g) and that the 8π( 1A 1g) - 9π( 3B 2u) gap is in the 7–11 kJ/mol range, in reasonable agreement with the negative ion photoelectron spectroscopy measurements, which give 6.27 ± 0.5 kJ/mol. Finally, in addition to the theory level used, geometry relaxation and basis set play a significant role in determining the state ordering and energy spacings. In particular, it is unsafe to use lower level, non-CC geometries and smaller basis sets.« less

Bandgap Engineering of InP QDs Through Shell Thickness and Composition

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

Dennis, Allison M.; Mangum, Benjamin D.; Piryatinski, Andrei

2012-06-21

Fields as diverse as biological imaging and telecommunications utilize the unique photophysical and electronic properties of nanocrystal quantum dots (NQDs). The development of new NQD compositions promises material properties optimized for specific applications, while addressing material toxicity. Indium phosphide (InP) offers a 'green' alternative to the traditional cadmium-based NQDs, but suffers from extreme susceptibility to oxidation. Coating InP cores with more stable shell materials significantly improves nanocrystal resistance to oxidation and photostability. We have investigated several new InP-based core-shell compositions, correlating our results with theoretical predictions of their optical and electronic properties. Specifically, we can tailor the InP core-shell QDsmore » to a type-I, quasi-type-II, or type-II bandgap structure with emission wavelengths ranging from 500-1300 nm depending on the shell material used (ZnS, ZnSe, CdS, or CdSe) and the thickness of the shell. Single molecule microscopy assessments of photobleaching and blinking are used to correlate NQD properties with shell thickness.« less

Achillea millefolium L. extract mediated green synthesis of waste peach kernel shell supported silver nanoparticles: Application of the nanoparticles for catalytic reduction of a variety of dyes in water.

PubMed

Khodadadi, Bahar; Bordbar, Maryam; Nasrollahzadeh, Mahmoud

2017-05-01

In this paper, silver nanoparticles (Ag NPs) are synthesized using Achillea millefolium L. extract as reducing and stabilizing agents and peach kernel shell as an environmentally benign support. FT-IR spectroscopy, UV-Vis spectroscopy, X-ray Diffraction (XRD), Field emission scanning electron microscopy (FESEM), Energy Dispersive X-ray Spectroscopy (EDS), Thermo gravimetric-differential thermal analysis (TG-DTA) and Transmission Electron Microscopy (TEM) were used to characterize peach kernel shell, Ag NPs, and Ag NPs/peach kernel shell. The catalytic activity of the Ag NPs/peach kernel shell was investigated for the reduction of 4-nitrophenol (4-NP), Methyl Orange (MO), and Methylene Blue (MB) at room temperature. Ag NPs/peach kernel shell was found to be a highly active catalyst. In addition, Ag NPs/peach kernel shell can be recovered and reused several times with no significant loss of its catalytic activity. Copyright © 2017 Elsevier Inc. All rights reserved.

Inner-shell chemistry under high pressure

NASA Astrophysics Data System (ADS)

Miao, Maosheng; Botana, Jorge; Pravica, Michael; Sneed, Daniel; Park, Changyong

2017-05-01

Chemistry at ambient conditions has implicit boundaries rooted in the atomic shell structure: the inner-shell electrons and the unoccupied outer-shell orbitals do not contribute as the major component to chemical reactions and in chemical bonds. These general rules govern our understanding of chemical structures and reactions. We review the recent progresses in high-pressure chemistry demonstrating that the above rules can be violated under extreme conditions. Using a first principles computation method and crystal structure search algorithm, we demonstrate that stable compounds involving inner shell electrons such as CsF3, CsF5, HgF3, and HgF4 can form under high external pressure and may present exotic properties. We also discuss experimental studies that have sought to confirm these predictions. Employing our recently developed hard X-ray photochemistry methods in a diamond anvil cell, we show promising early results toward realizing inner shell chemistry experimentally.

Are Pericentric Inversions Reorganizing Wedge Shell Genomes?

PubMed Central

García-Souto, Daniel; Pérez-García, Concepción

2017-01-01

Wedge shells belonging to the Donacidae family are the dominant bivalves in exposed beaches in almost all areas of the world. Typically, two or more sympatric species of wedge shells differentially occupy intertidal, sublittoral, and offshore coastal waters in any given locality. A molecular cytogenetic analysis of two sympatric and closely related wedge shell species, Donax trunculus and Donax vittatus, was performed. Results showed that the karyotypes of these two species were both strikingly different and closely alike; whilst metacentric and submetacentric chromosome pairs were the main components of the karyotype of D. trunculus, 10–11 of the 19 chromosome pairs were telocentric in D. vittatus, most likely as a result of different pericentric inversions. GC-rich heterochromatic bands were present in both species. Furthermore, they showed coincidental 45S ribosomal RNA (rRNA), 5S rRNA and H3 histone gene clusters at conserved chromosomal locations, although D. trunculus had an additional 45S rDNA cluster. Intraspecific pericentric inversions were also detected in both D. trunculus and D. vittatus. The close genetic similarity of these two species together with the high degree of conservation of the 45S rRNA, 5S rRNA and H3 histone gene clusters, and GC-rich heterochromatic bands indicate that pericentric inversions contribute to the karyotype divergence in wedge shells. PMID:29215567

Electron-capture Rates for pf-shell Nuclei in Stellar Environments and Nucleosynthesis

NASA Astrophysics Data System (ADS)

Suzuki, Toshio; Honma, Michio; Mori, Kanji; Famiano, Michael A.; Kajino, Toshitaka; Hidakai, Jun; Otsuka, Takaharu

Gamow-Teller strengths in pf-shell nuclei obtained by a new shell-model Hamltonian, GXPF1J, are used to evaluate electron-capture rates in pf-shell nuclei at stellar environments. The nuclear weak rates with GXPF1J, which are generally smaller than previous evaluations for proton-rich nuclei, are applied to nucleosynthesis in type Ia supernova explosions. The updated rates are found to lead to less production of neutron-rich nuclei such as 58Ni and 54Cr, thus toward a solution of the problem of over-production of neutron-rich isotopes of iron-group nuclei compared to the solar abundance.

Electronic properties of core-shell nanowire resonant tunneling diodes

PubMed Central

2014-01-01

The electronic sub-band structure of InAs/InP/InAs/InP/InAs core-shell nanowire resonant tunneling diodes has been investigated in the effective mass approximation by varying the core radius and the thickness of the InP barriers and InAs shells. A top-hat, double-barrier potential profile and optimal energy configuration are obtained for core radii and surface shells >10 nm, InAs middle shells <10 nm, and 5 nm InP barriers. In this case, two sub-bands exist above the Fermi level in the InAs middle shell which belongs to the m = 0 and m = 1 ladder of states that have similar wave functions and energies. On the other hand, the lowest m = 0 sub-band in the core falls below the Fermi level but the m = 1 states do not contribute to the current transport since they reside energetically well above the Fermi level. We compare the case of GaAs/AlGaAs/GaAs/AlGaAs/GaAs which may conduct current with smaller applied voltages due to the larger effective mass of electrons in GaAs and discuss the need for doping. PMID:25288912

Electronic properties of core-shell nanowire resonant tunneling diodes.

PubMed

Zervos, Matthew

2014-01-01

The electronic sub-band structure of InAs/InP/InAs/InP/InAs core-shell nanowire resonant tunneling diodes has been investigated in the effective mass approximation by varying the core radius and the thickness of the InP barriers and InAs shells. A top-hat, double-barrier potential profile and optimal energy configuration are obtained for core radii and surface shells >10 nm, InAs middle shells <10 nm, and 5 nm InP barriers. In this case, two sub-bands exist above the Fermi level in the InAs middle shell which belongs to the m = 0 and m = 1 ladder of states that have similar wave functions and energies. On the other hand, the lowest m = 0 sub-band in the core falls below the Fermi level but the m = 1 states do not contribute to the current transport since they reside energetically well above the Fermi level. We compare the case of GaAs/AlGaAs/GaAs/AlGaAs/GaAs which may conduct current with smaller applied voltages due to the larger effective mass of electrons in GaAs and discuss the need for doping.

Room-temperature ferromagnetic Cr-doped Ge/GeOx core-shell nanowires.

PubMed

Katkar, Amar S; Gupta, Shobhnath P; Seikh, Md Motin; Chen, Lih-Juann; Walke, Pravin S

2018-06-08

The Cr-doped tunable thickness core-shell Ge/GeO x nanowires (NWs) were synthesized and characterized using x-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, energy-dispersive x-ray spectroscopy, x-ray photoelectron spectroscopy and magnetization studies. The shell thickness increases with the increase in synthesis temperature. The presence of metallic Cr and Cr 3+ in core-shell structure was confirmed from XPS study. The magnetic property is highly sensitive to the core-shell thickness and intriguing room temperature ferromagnetism is realized only in core-shell NWs. The magnetization decreases with an increase in shell thickness and practically ceases to exist when there is no core. These NWs show remarkably high Curie temperature (T C  > 300 K) with the dominating values of its magnetic remanence (M R ) and coercivity (H C ) compared to germanium dilute magnetic semiconductor nanomaterials. We believe that our finding on these Cr-doped Ge/GeO X core-shell NWs has the potential to be used as a hard magnet for future spintronic devices, owing to their higher characteristic values of ferromagnetic ordering.

Room-temperature ferromagnetic Cr-doped Ge/GeOx core–shell nanowires

NASA Astrophysics Data System (ADS)

Katkar, Amar S.; Gupta, Shobhnath P.; Motin Seikh, Md; Chen, Lih-Juann; Walke, Pravin S.

2018-06-01

The Cr-doped tunable thickness core–shell Ge/GeOx nanowires (NWs) were synthesized and characterized using x-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, energy-dispersive x-ray spectroscopy, x-ray photoelectron spectroscopy and magnetization studies. The shell thickness increases with the increase in synthesis temperature. The presence of metallic Cr and Cr3+ in core–shell structure was confirmed from XPS study. The magnetic property is highly sensitive to the core–shell thickness and intriguing room temperature ferromagnetism is realized only in core–shell NWs. The magnetization decreases with an increase in shell thickness and practically ceases to exist when there is no core. These NWs show remarkably high Curie temperature (TC > 300 K) with the dominating values of its magnetic remanence (MR) and coercivity (HC) compared to germanium dilute magnetic semiconductor nanomaterials. We believe that our finding on these Cr-doped Ge/GeOX core–shell NWs has the potential to be used as a hard magnet for future spintronic devices, owing to their higher characteristic values of ferromagnetic ordering.

Catching the electron in action in real space inside a Ge-Si core-shell nanowire transistor.

PubMed

Jaishi, Meghnath; Pati, Ranjit

2017-09-21

Catching the electron in action in real space inside a semiconductor Ge-Si core-shell nanowire field effect transistor (FET), which has been demonstrated (J. Xiang, W. Lu, Y. Hu, Y. Wu, H. Yan and C. M. Lieber, Nature, 2006, 441, 489) to outperform the state-of-the-art metal oxide semiconductor FET, is central to gaining unfathomable access into the origin of its functionality. Here, using a quantum transport approach that does not make any assumptions on electronic structure, charge, and potential profile of the device, we unravel the most probable tunneling pathway for electrons in a Ge-Si core-shell nanowire FET with orbital level spatial resolution, which demonstrates gate bias induced decoupling of electron transport between the core and the shell region. Our calculation yields excellent transistor characteristics as noticed in the experiment. Upon increasing the gate bias beyond a threshold value, we observe a rapid drop in drain current resulting in a gate bias driven negative differential resistance behavior and switching in the sign of trans-conductance. We attribute this anomalous behavior in drain current to the gate bias induced modification of the carrier transport pathway from the Ge core to the Si shell region of the nanowire channel. A new experiment involving a four probe junction is proposed to confirm our prediction on gate bias induced decoupling.

Biomimetic synthesis of chiral erbium-doped silver/peptide/silica core-shell nanoparticles (ESPN)

NASA Astrophysics Data System (ADS)

Mantion, Alexandre; Graf, Philipp; Florea, Ileana; Haase, Andrea; Thünemann, Andreas F.; Mašić, Admir; Ersen, Ovidiu; Rabu, Pierre; Meier, Wolfgang; Luch, Andreas; Taubert, Andreas

2011-12-01

Peptide-modified silver nanoparticles have been coated with an erbium-doped silica layer using a method inspired by silica biomineralization. Electron microscopy and small-angle X-ray scattering confirm the presence of an Ag/peptide core and silica shell. The erbium is present as small Er2O3 particles in and on the silica shell. Raman, IR, UV-Vis, and circular dichroism spectroscopies show that the peptide is still present after shell formation and the nanoparticles conserve a chiral plasmon resonance. Magnetic measurements find a paramagnetic behavior. In vitro tests using a macrophage cell line model show that the resulting multicomponent nanoparticles have a low toxicity for macrophages, even on partial dissolution of the silica shell.Peptide-modified silver nanoparticles have been coated with an erbium-doped silica layer using a method inspired by silica biomineralization. Electron microscopy and small-angle X-ray scattering confirm the presence of an Ag/peptide core and silica shell. The erbium is present as small Er2O3 particles in and on the silica shell. Raman, IR, UV-Vis, and circular dichroism spectroscopies show that the peptide is still present after shell formation and the nanoparticles conserve a chiral plasmon resonance. Magnetic measurements find a paramagnetic behavior. In vitro tests using a macrophage cell line model show that the resulting multicomponent nanoparticles have a low toxicity for macrophages, even on partial dissolution of the silica shell. Electronic supplementary information (ESI) available: Figures S1 to S12, Tables S1 and S2. See DOI: 10.1039/c1nr10930h

Production of n-rich Nuclei along the Closed Shell N=126 in the collision 136Xe + 208Pb @E lab =870 MeV

NASA Astrophysics Data System (ADS)

Quero, D.; Vardaci, E.; Kozulin, E. M.; Zagrebaev, V. A.; Corradi, L.; Pulcini, A.; La Rana, G.; Itkis, I. M.; Knyazheva, G. N.; Novikov, K.; Harca, I.; Fioretto, E.; Stefanini, A. M.; Montanari, D.; Montagnoli, G.; Scarlassara, F.; Szilner, S.; Mijatović, T.; Trzaska, W. H.

2018-05-01

Multi-nucleon transfer reactions are nowadays the only known mean to produce neutron-rich nuclei in the Terra Incognita. The closed-shell region N=126 is crucial for both studying shell-quenching in exotic nuclei and the r-process, being its last “waiting-point”. The choice of suitable reactions is challenging and a favorable case is 136Xe+208Pb, near the Coulomb barrier, because their neutron shell-closures play a stabilizing role, favoring the proton-transfer from lead to xenon. TOF-TOF data were analyzed to reconstruct the mass-energy distribution of the primary fragments. Preliminary results of an experiment held at Laboratori Nazionali di Legnaro with PRISMA, aimed at A and Z identification of the products, will be shown.

Ultrastructure of Lymphocystis Virus

PubMed Central

Zwillenberg, Lutz O.; Wolf, Ken

1968-01-01

Lymphocystis virus obtained from bluegills (Lepomis macrochirus) was cultured in the permanent bluegill cell line BF-2 and examined by electron microscopy in ultrathin sections of cell cultures and in negative-contrast preparations from cells and from centrifuged culture medium. According to negative-contrast preparations, the icosahedral virions have an overall diameter close to but not exceeding 300 mμ. Delicate filaments seem to issue from the vertices. In collapsed virions, an ordered array of morphological units was seen. Positively contrasted virions in ultrathin sections show a shell with three dark (heavy metal-stained) layers alternating with and separated by two clear layers. The acquisition of an additional outer membrane during release from the cell, as found in African swine fever virus, was never seen. Morphologically, lymphocystis virus is considered to be closely related to Tipula iridescent virus. Images PMID:4986903

Core-shell SrTiO3/graphene structure by chemical vapor deposition for enhanced photocatalytic performance

NASA Astrophysics Data System (ADS)

He, Chenye; Bu, Xiuming; Yang, Siwei; He, Peng; Ding, Guqiao; Xie, Xiaoming

2018-04-01

Direct growth of high quality graphene on the surface of SrTiO3 (STO) was realized through chemical vapor deposition (CVD), to construct few-layer 'graphene shell' on every STO nanoparticle. The STO/graphene composite shows significantly enhanced UV light photocatalytic activity compared with the STO/rGO reference. Mechanism analysis confirms the role of special core-shell structure and chemical bond (Tisbnd C) for rapid interfacial electron transfer and effective electron-hole separation.

Effect of energy transfer from atomic electron shell to an α particle emitted by decaying nucleus

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

Igashov, S. Yu., E-mail: igashov@theor.mephi.ru; Tchuvil’sky, Yu. M.

2016-12-15

The process of energy transfer from the electron shell of an atom to an α particle propagating through the shell is formulated mathematically. Using the decay of the {sup 226}Ra nucleus as an example, it is demonstrated that this phenomenon increases the α-decay intensity in contrast with other known effects of similar type. Moreover, the α decay of the nucleus is more strongly affected by the energy transfer than by all other effects taken together.

Sn-Ag-Cu Nanosolders: Solder Joints Integrity and Strength

NASA Astrophysics Data System (ADS)

Roshanghias, Ali; Khatibi, Golta; Yakymovych, Andriy; Bernardi, Johannes; Ipser, Herbert

2016-08-01

Although considerable research has been dedicated to the synthesis and characterization of lead-free nanoparticle solder alloys, only very little has been reported on the reliability of the respective joints. In fact, the merit of nanoparticle solders with depressed melting temperatures close to the Sn-Pb eutectic temperature has always been challenged when compared with conventional solder joints, especially in terms of inferior solderability due to the oxide shell commonly present on the nanoparticles, as well as due to compatibility problems with common fluxing agents. Correspondingly, in the current study, Sn-Ag-Cu (SAC) nanoparticle alloys were combined with a proper fluxing vehicle to produce prototype nanosolder pastes. The reliability of the solder joints was successively investigated by means of electron microscopy and mechanical tests. As a result, the optimized condition for employing nanoparticles as a competent nanopaste and a novel procedure for surface treatment of the SAC nanoparticles to diminish the oxide shell prior to soldering are being proposed.

Calculation of catalyst crust thickness from full elemental laser-induced breakdown spectroscopy images

NASA Astrophysics Data System (ADS)

Sorbier, L.; Trichard, F.; Moncayo, S.; Lienemann, C. P.; Motto-Ros, V.

2018-01-01

We propose a methodology to compute the crust thickness of an element in an egg-shell catalyst from a two-dimensional elemental map. The methodology handles two important catalyst shapes: infinite extrudates of arbitrary section and spheres. The methodology is validated with synthetic analytical profiles on simple shapes (cylinder and sphere). Its relative accuracy is shown close to few percent with a decrease inversely proportional to the square root of the number of sampled pixels. The crust thickness obtained by this method from quantitative Pd maps acquired by laser-induced breakdown spectroscopy are comparable with values obtained from electron-probe microanalysis profiles. Some discrepancies are found and are explained by the heterogeneity of the crust thickness within a grain. As a full map is more representative than a single profile, fast mapping and the methodology exposed in this paper are expected to become valuable tools for the development of new generations of egg-shell deposited catalysts.

Strain relaxation and ambipolar electrical transport in GaAs/InSb core-shell nanowires.

PubMed

Rieger, Torsten; Zellekens, Patrick; Demarina, Natalia; Hassan, Ali Al; Hackemüller, Franz Josef; Lüth, Hans; Pietsch, Ullrich; Schäpers, Thomas; Grützmacher, Detlev; Lepsa, Mihail Ion

2017-11-30

The growth, crystal structure, strain relaxation and room temperature transport characteristics of GaAs/InSb core-shell nanowires grown using molecular beam epitaxy are investigated. Due to the large lattice mismatch between GaAs and InSb of 14%, a transition from island-based to layer-like growth occurs during the formation of the shell. High resolution transmission electron microscopy in combination with geometric phase analyses as well as X-ray diffraction with synchrotron radiation are used to investigate the strain relaxation and prove the existence of different dislocations relaxing the strain on zinc blende and wurtzite core-shell nanowire segments. While on the wurtzite phase only Frank partial dislocations are found, the strain on the zinc blende phase is relaxed by dislocations with perfect, Shockley partial and Frank partial dislocations. Even for ultrathin shells of about 2 nm thickness, the strain caused by the high lattice mismatch between GaAs and InSb is relaxed almost completely. Transfer characteristics of the core-shell nanowires show an ambipolar conductance behavior whose strength strongly depends on the dimensions of the nanowires. The interpretation is given based on an electronic band profile which is calculated for completely relaxed core/shell structures. The peculiarities of the band alignment in this situation implies simultaneously occupied electron and hole channels in the InSb shell. The ambipolar behavior is then explained by the change of carrier concentration in both channels by the gate voltage.

Evaluation of the Mechanical Properties and Effectiveness of Countermine Boots.

DTIC Science & Technology

1998-03-01

regarding comfort except that the 60 shanks overall length of approximately 5.7 in should allow normal flexure of the forefoot . Weight, however, is...When the electron beam strikes an element in the sample, electrons are ejected from inner atomic shells to outer shells resulting in ions in the

Photocatalytic activity of Ag/ZnO core-shell nanoparticles with shell thickness as controlling parameter under green environment

NASA Astrophysics Data System (ADS)

Rajbongshi, Himanshu; Bhattacharjee, Suparna; Datta, Pranayee

2017-02-01

Plasmonic Ag/ZnO core-shell nanoparticles have been synthesized via a simple two-step wet chemical method for application in Photocatalysis. The morphology, size, crystal structure, composition and optical properties of the nanoparticles are investigated by x-ray diffraction, transmission electron microscopy (TEM), FTIR spectroscopy, ultraviolet-visible (UV-Vis) absorption spectroscopy and photoluminescence (PL) spectroscopy. The shell thicknesses are varied by varying the concentration of zinc nitrate hexa-hydrate and triethanolamine. The ZnO shell coating over Ag core enhances the charge separation, whereas the larger shell thickness and increased refractive index of surrounding medium cause red shifts of surface Plasmon resonance (SPR) peak of Ag core. The photoluminescence (PL) spectra of Ag/ZnO core-shell show that the larger shell thickness quenches the near band edge UV emission of ZnO. The electrochemical impedance spectra (EIS) i.e. Nyquist plots also confirm the higher charge transfer efficiency of the Ag/ZnO core-shell nanoparticles. The Photocatalytic activities of Ag/ZnO core-shell nanoparticles are investigated by the degradation of methylene blue (MB) dye under direct sunlight irradiation. Compared to pure ZnO nanoparticles (NPs), Ag/ZnO core-shell NPs display efficient sunlight plasmonic photocatalytic activity because of the influence of SPR of Ag core and the electron sink effect. The photocatalytic activity of Ag/ZnO core-shell NPs is found to be enhanced with increase in shell thickness.

Low temperature nano-spin filtering using a diluted magnetic semiconductor core-shell quantum dot

NASA Astrophysics Data System (ADS)

Chattopadhyay, Saikat; Sen, Pratima; Andrews, Joshep Thomas; Sen, Pranay Kumar

2014-07-01

The spin polarized electron transport properties and spin polarized tunneling current have been investigated analytically in a diluted magnetic semiconductor core-shell quantum dot in the presence of applied electric and magnetic fields. Assuming the electron wave function to satisfy WKB approximation, the electron energy eigenvalues have been calculated. The spin polarized tunneling current and the spin dependent tunneling coefficient are obtained by taking into account the exchange interaction and Zeeman splitting. Numerical estimates made for a specific diluted magnetic semiconductor, viz., Zn1-xMnxSe/ZnS core-shell quantum dot establishes the possibility of a nano-spin filter for a particular biasing voltage and applied magnetic field. Influence of applied voltage on spin polarized electron transport has been investigated in a CSQD.

Population kinetics on K alpha lines of partially ionized Cl atoms.

PubMed

Kawamura, Tohru; Nishimura, Hiroaki; Koike, Fumihiro; Ochi, Yoshihiro; Matsui, Ryoji; Miao, Wen Yong; Okihara, Shinichiro; Sakabe, Shuji; Uschmann, Ingo; Förster, Eckhart; Mima, Kunioki

2002-07-01

A population kinetics code was developed to analyze K alpha emission from partially ionized chlorine atoms in hydrocarbon plasmas. Atomic processes are solved under collisional-radiative equilibrium for two-temperature plasmas. It is shown that the fast electrons dominantly contribute to ionize the K-shell bound electrons (i.e., inner-shell ionization) and the cold electrons to the outer-shell bound ones. Ratios of K alpha lines of partially ionized atoms are presented as a function of cold-electron temperature. The model was validated by observation of the K alpha lines from a chlorinated plastic target irradiated with 1 TW Ti:sapphire laser pulses at 1.5 x 10(17) W/cm(2), inferring a plasma temperature of about 100 eV on the target surface.

Calculated gadolinium atomic electron energy levels and Auger electron emission probability as a function of atomic number Z

NASA Astrophysics Data System (ADS)

Miloshevsky, G. V.; Tolkach, V. I.; Shani, Gad; Rozin, Semion

2002-06-01

Auger electron interaction with matter is gaining importance in particular in medical application of radiation. The production probability and energy spectrum is therefore of great importance. A good source of Auger electrons is the 157Gd(n,γ) 158Gd reaction. The present article describes calculations of electron levels in Gd atoms and provides missing data of outer electron energy levels. The energy of these electron levels missing in published tables, was found to be in the 23-24 and 6-7 eV energy ranges respectively. The probability of Auger emission was calculated as an interaction of wave function of the initial and final electron states. The wave functions were calculated using the Hartree-Fock-Slater approximation with relativistic correction. The equations were solved using a spherical symmetry potential. The error for inner shell level is less than 10%, it is increased to the order of 10-15% for the outer shells. The width of the Auger process changes from 0.1 to 1.2 eV for atomic number Z from 5 to 70. The fluorescence yield width changes five orders of magnitude in this range. Auger electron emission width from the K shell changes from 10 -2 to ˜1 eV with Z changing from 10 to 64, depending on the final state. For the L shell it changes from 0 to 0.25 when it Z changes from 20 to 64.

Fast-Response Single-Nanowire Photodetector Based on ZnO/WS2 Core/Shell Heterostructures.

PubMed

Butanovs, Edgars; Vlassov, Sergei; Kuzmin, Alexei; Piskunov, Sergei; Butikova, Jelena; Polyakov, Boris

2018-04-25

The surface plays an exceptionally important role in nanoscale materials, exerting a strong influence on their properties. Consequently, even a very thin coating can greatly improve the optoelectronic properties of nanostructures by modifying the light absorption and spatial distribution of charge carriers. To use these advantages, 1D/1D heterostructures of ZnO/WS 2 core/shell nanowires with a-few-layers-thick WS 2 shell were fabricated. These heterostructures were thoroughly characterized by scanning and transmission electron microscopy, X-ray diffraction, and Raman spectroscopy. Then, a single-nanowire photoresistive device was assembled by mechanically positioning ZnO/WS 2 core/shell nanowires onto gold electrodes inside a scanning electron microscope. The results show that a few layers of WS 2 significantly enhance the photosensitivity in the short wavelength range and drastically (almost 2 orders of magnitude) improve the photoresponse time of pure ZnO nanowires. The fast response time of ZnO/WS 2 core/shell nanowire was explained by electrons and holes sinking from ZnO nanowire into WS 2 shell, which serves as a charge carrier channel in the ZnO/WS 2 heterostructure. First-principles calculations suggest that the interface layer i-WS 2 , bridging ZnO nanowire surface and WS 2 shell, might play a role of energy barrier, preventing the backward diffusion of charge carriers into ZnO nanowire.

Advanced spectroscopic analysis of 0.8-1.0-MA Mo x pinches and the influence of plasma electron beams on L-shell spectra of Mo ions.

PubMed

Shlyaptseva, A S; Hansen, S B; Kantsyrev, V L; Fedin, D A; Ouart, N; Fournier, K B; Safronova, U I

2003-02-01

This paper presents a detailed investigation of the temporal, spatial, and spectroscopic properties of L-shell radiation from 0.8 to 1.0 MA Mo x pinches. Time-resolved measurements of x-ray radiation and both time-gated and time-integrated spectra and pinhole images are presented and analyzed. High-current x pinches are found to have complex spatial and temporal structures. A collisional-radiative kinetic model has been developed and used to interpret L-shell Mo spectra. The model includes the ground state of every ionization stage of Mo and detailed structure for the O-, F-, Ne-, Na-, and Mg-like ionization stages. Hot electron beams generated by current-carrying electrons in the x pinch are modeled by a non-Maxwellian electron distribution function and have significant influence on L-shell spectra. The results of 20 Mo x-pinch shots with wire diameters from 24 to 62 microm have been modeled. Overall, the modeled spectra fit the experimental spectra well and indicate for time-integrated spectra electron densities between 2 x 10(21) and 2 x 10(22) cm(-3), electron temperatures between 700 and 850 eV, and hot electron fractions between 3% and 7%. Time-gated spectra exhibit wide variations in temperature and density of plasma hot spots during the same discharge.

Cascading electron and hole transfer dynamics in a CdS/CdTe core-shell sensitized with bromo-pyrogallol red (Br-PGR): slow charge recombination in type II regime.

PubMed

Maity, Partha; Debnath, Tushar; Chopra, Uday; Ghosh, Hirendra Nath

2015-02-14

Ultrafast cascading hole and electron transfer dynamics have been demonstrated in a CdS/CdTe type II core-shell sensitized with Br-PGR using transient absorption spectroscopy and the charge recombination dynamics have been compared with those of CdS/Br-PGR composite materials. Steady state optical absorption studies suggest that Br-PGR forms strong charge transfer (CT) complexes with both the CdS QD and CdS/CdTe core-shell. Hole transfer from the photo-excited QD and QD core-shell to Br-PGR was confirmed by both steady state and time-resolved emission spectroscopy. Charge separation was also confirmed by detecting electrons in the conduction band of the QD and the cation radical of Br-PGR as measured from femtosecond transient absorption spectroscopy. Charge separation in the CdS/Br-PGR composite materials was found to take place in three different pathways, by transferring the photo-excited hole of CdS to Br-PGR, electron injection from the photo-excited Br-PGR to the CdS QD, and direct electron transfer from the HOMO of Br-PGR to the conduction band of the CdS QD. However, in the CdS/CdTe/Br-PGR system hole transfer from the photo-excited CdS to Br-PGR and electron injection from the photo-excited Br-PGR to CdS take place after cascading through the CdTe shell QD. Charge separation also takes place via direct electron transfer from the Br-PGR HOMO to the conduction band of CdS/CdTe. Charge recombination (CR) dynamics between the electron in the conduction band of the CdS QD and the Br-PGR cation radical were determined by monitoring the bleach recovery kinetics. The CR dynamics were found to be much slower in the CdS/CdTe/Br-PGR system than in the CdS/Br-PGR system. The formation of the strong CT complex and the separation of charges cascading through the CdTe shell help to slow down charge recombination in the type II regime.

An efficient parallel algorithm for the calculation of unrestricted canonical MP2 energies.

PubMed

Baker, Jon; Wolinski, Krzysztof

2011-11-30

We present details of our efficient implementation of full accuracy unrestricted open-shell second-order canonical Møller-Plesset (MP2) energies, both serial and parallel. The algorithm is based on our previous restricted closed-shell MP2 code using the Saebo-Almlöf direct integral transformation. Depending on system details, UMP2 energies take from less than 1.5 to about 3.0 times as long as a closed-shell RMP2 energy on a similar system using the same algorithm. Several examples are given including timings for some large stable radicals with 90+ atoms and over 3600 basis functions. Copyright © 2011 Wiley Periodicals, Inc.

Highly Stretchable and Transparent Supercapacitor by Ag-Au Core-Shell Nanowire Network with High Electrochemical Stability.

PubMed

Lee, Habeom; Hong, Sukjoon; Lee, Jinhwan; Suh, Young Duk; Kwon, Jinhyeong; Moon, Hyunjin; Kim, Hyeonseok; Yeo, Junyeob; Ko, Seung Hwan

2016-06-22

Stretchable and transparent electronics have steadily attracted huge attention in wearable devices. Although Ag nanowire is the one of the most promising candidates for transparent and stretchable electronics, its electrochemical instability has forbidden its application to the development of electrochemical energy devices such as supercapacitors. Here, we introduce a highly stretchable and transparent supercapacitor based on electrochemically stable Ag-Au core-shell nanowire percolation network electrode. We developed a simple solution process to synthesize the Ag-Au core-shell nanowire with excellent electrical conductivity as well as greatly enhanced chemical and electrochemical stabilities compared to pristine Ag nanowire. The proposed core-shell nanowire-based supercapacitor still possesses fine optical transmittance and outstanding mechanical stability up to 60% strain. The Ag-Au core-shell nanowire can be a strong candidate for future wearable electrochemical energy devices.

Time-resolved inner-shell photoelectron spectroscopy: From a bound molecule to an isolated atom

NASA Astrophysics Data System (ADS)

Brauße, Felix; Goldsztejn, Gildas; Amini, Kasra; Boll, Rebecca; Bari, Sadia; Bomme, Cédric; Brouard, Mark; Burt, Michael; de Miranda, Barbara Cunha; Düsterer, Stefan; Erk, Benjamin; Géléoc, Marie; Geneaux, Romain; Gentleman, Alexander S.; Guillemin, Renaud; Ismail, Iyas; Johnsson, Per; Journel, Loïc; Kierspel, Thomas; Köckert, Hansjochen; Küpper, Jochen; Lablanquie, Pascal; Lahl, Jan; Lee, Jason W. L.; Mackenzie, Stuart R.; Maclot, Sylvain; Manschwetus, Bastian; Mereshchenko, Andrey S.; Mullins, Terence; Olshin, Pavel K.; Palaudoux, Jérôme; Patchkovskii, Serguei; Penent, Francis; Piancastelli, Maria Novella; Rompotis, Dimitrios; Ruchon, Thierry; Rudenko, Artem; Savelyev, Evgeny; Schirmel, Nora; Techert, Simone; Travnikova, Oksana; Trippel, Sebastian; Underwood, Jonathan G.; Vallance, Claire; Wiese, Joss; Simon, Marc; Holland, David M. P.; Marchenko, Tatiana; Rouzée, Arnaud; Rolles, Daniel

2018-04-01

Due to its element and site specificity, inner-shell photoelectron spectroscopy is a widely used technique to probe the chemical structure of matter. Here, we show that time-resolved inner-shell photoelectron spectroscopy can be employed to observe ultrafast chemical reactions and the electronic response to the nuclear motion with high sensitivity. The ultraviolet dissociation of iodomethane (CH3I ) is investigated by ionization above the iodine 4 d edge, using time-resolved inner-shell photoelectron and photoion spectroscopy. The dynamics observed in the photoelectron spectra appear earlier and are faster than those seen in the iodine fragments. The experimental results are interpreted using crystal-field and spin-orbit configuration interaction calculations, and demonstrate that time-resolved inner-shell photoelectron spectroscopy is a powerful tool to directly track ultrafast structural and electronic transformations in gas-phase molecules.

Jammed elastic shells - a 3D experimental soft frictionless granular system

NASA Astrophysics Data System (ADS)

Jose, Jissy; Blab, Gerhard A.; van Blaaderen, Alfons; Imhof, Arnout

2015-03-01

We present a new experimental system of monodisperse, soft, frictionless, fluorescent labelled elastic shells for the characterization of structure, universal scaling laws and force networks in 3D jammed matter. The interesting fact about these elastic shells is that they can reversibly deform and therefore serve as sensors of local stress in jammed matter. Similar to other soft particles, like emulsion droplets and bubbles in foam, the shells can be packed to volume fractions close to unity, which allows us to characterize the contact force distribution and universal scaling laws as a function of volume fraction, and to compare them with theoretical predictions and numerical simulations. However, our shells, unlike other soft particles, deform rather differently at large stresses. They deform without conserving their inner volume, by forming dimples at contact regions. At each contact one of the shells buckled with a dimple and the other remained spherical, closely resembling overlapping spheres. We conducted 3D quantitative analysis using confocal microscopy and image analysis routines specially developed for these particles. In addition, we analysed the randomness of the process of dimpling, which was found to be volume fraction dependent.

First-principle interaction potentials for metastable He(3S) and Ne(3P) with closed-shell molecules: Application to Penning-ionizing systems

NASA Astrophysics Data System (ADS)

Hapka, Michał; Chałasiński, Grzegorz; Kłos, Jacek; Żuchowski, Piotr S.

2013-07-01

We present new interaction potential curves, calculated from first-principles, for the He(3S, 1s12s1)⋯H2 and He(3S)⋯Ar systems, relevant in recent Penning ionization experiments of Henson et al. [Science 338, 234 (2012), 10.1126/science.1229141]. Two different approaches were applied: supermolecular using coupled cluster (CC) theory and perturbational within symmetry-adapted perturbation theory (SAPT). Both methods gave consistent results, and the potentials were used to study the elastic scattering and determine the positions of shape resonances for low kinetic energy (up to 1 meV). We found a good agreement with the experiment. In addition, we investigated two other dimers composed of metastable Ne (3P, 2p53s1) and ground state He and Ar atoms. For the Ne(3P)⋯He system, a good agreement between CC and SAPT approaches was obtained. The Ne(3P)⋯Ar dimer was described only with SAPT, as CC gave divergent results. Ne* systems exhibit extremely small electronic orbital angular momentum anisotropy of the potentials. We attribute this effect to screening of an open 2p shell by a singly occupied 3s shell.

The Periodic Pyramid

ERIC Educational Resources Information Center

Hennigan, Jennifer N.; Grubbs, W. Tandy

2013-01-01

The chemical elements present in the modern periodic table are arranged in terms of atomic numbers and chemical periodicity. Periodicity arises from quantum mechanical limitations on how many electrons can occupy various shells and subshells of an atom. The shell model of the atom predicts that a maximum of 2, 8, 18, and 32 electrons can occupy…

Room-temperature fabrication of core-shell nano-ZnO/pollen grain biocomposite for adsorptive removal of organic dye from water

NASA Astrophysics Data System (ADS)

Tzvetkov, George; Kaneva, Nina; Spassov, Tony

2017-04-01

A new core-shell nano-ZnO/pollen grain (n-ZnO/PG) biocomposite has been successfully synthesized via simple and low-temperature two-step liquid precipitation method. The synthetic strategy consists of grafting the surface of pine pollen grains (PG) with Zn2+-organic complexes followed by a treatment in Zn(CH3COO)2/NaOH solution, thus producing a closed n-ZnO shell around the organic core, with a thickness of ∼450 nm. Scanning electron microscopy, X-ray diffraction, FTIR, XPS and UV-vis spectroscopy measurements along with N2 adsorption/desorption were used to characterize the resulting n-ZnO/PG biocomposite. The as-prepared core-shell microparticles are meso-/macro-porous with BET surface area of 25 m2 g-1 and total pore volume of 0.26 cm3 g-1. The adsorption properties of n-ZnO/PG were evaluated through adsorption of Malachite Green (MG) from aqueous medium at room temperature (25 °C). For the sake of comparison, the physico-chemical and adsorptive properties of the raw PG and pure n-ZnO were also examined. Results indicate that n-ZnO/PG is the most favorable for the adsorption of MG under the conditions used in this study. The adsorption kinetic data for PG, n-ZnO and n-ZnO/PG follow the pseudo-second order equation and the maximum adsorption capacity follows an order of n-ZnO/PG > n-ZnO > PG. For n-ZnO/PG an adsorption uptake up to 145.9 mg g-1 is observed. The as-prepared core-shell biocomposite material is a promising cost-effective and environmentally friendly adsorbent due to its textural properties, surface chemistry, adsorption capacity and recyclability.

Thioarsenides: A case for long-range Lewis acid-base-directed van der Waals interactions

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

Gibbs, Gerald V.; Wallace, Adam F.; Downs, R. T.

2011-04-01

Electron density distributions, bond paths, Laplacian and local energy density properties have been calculated for a number of As4Sn (n = 3,4,5) thioarsenide molecular crystals. On the basis of the distributions, the intramolecular As-S and As-As interactions classify as shared bonded interactions and the intermolecular As-S, As-As and S-S interactions classify as closed-shell van der Waals bonded interactions. The bulk of the intermolecular As-S bond paths link regions of locally concentrated electron density (Lewis base regions) with aligned regions of locally depleted electron density (Lewis acid regions) on adjacent molecules. The paths are comparable with intermolecular paths reported for severalmore » other molecular crystals that link aligned Lewis base and acid regions in a key-lock fashion, interactions that classified as long range Lewis acid-base directed van der Waals interactions. As the bulk of the intermolecular As-S bond paths (~70%) link Lewis acid-base regions on adjacent molecules, it appears that molecules adopt an arrangement that maximizes the number of As-S Lewis acid-base intermolecular bonded interactions. The maximization of the number of Lewis acid-base interactions appears to be connected with the close-packed array adopted by molecules: distorted cubic close-packed arrays are adopted for alacránite, pararealgar, uzonite, realgar and β-AsS and the distorted hexagonal close-packed arrays adopted by α- and β-dimorphite. A growth mechanism is proposed for thioarsenide molecular crystals from aqueous species that maximizes the number of long range Lewis acid-base vdW As-S bonded interactions with the resulting directed bond paths structuralizing the molecules as a molecular crystal.« less

Nonvolatile memory with Co-SiO2 core-shell nanocrystals as charge storage nodes in floating gate

NASA Astrophysics Data System (ADS)

Liu, Hai; Ferrer, Domingo A.; Ferdousi, Fahmida; Banerjee, Sanjay K.

2009-11-01

In this letter, we reported nanocrystal floating gate memory with Co-SiO2 core-shell nanocrystal charge storage nodes. By using a water-in-oil microemulsion scheme, Co-SiO2 core-shell nanocrystals were synthesized and closely packed to achieve high density matrix in the floating gate without aggregation. The insulator shell also can help to increase the thermal stability of the nanocrystal metal core during the fabrication process to improve memory performance.

Updating the Jovian Proton Radiation Environment - 2015

NASA Technical Reports Server (NTRS)

Garrett, Henry; Martinez-Sierra, Luz Maria; Evans, Robin

2015-01-01

Since publication in 1983 by N. Divine and H. Garrett, the Jet Propulsion Laboratory's plasma and radiation models have been the design standard for NASA's missions to Jupiter. These models consist of representations of the cold plasma and electrons, the warm and auroral electrons and protons, and the radiation environment (electron, proton, and heavy ions). To date, however, the high-energy proton model has been limited to an L-shell of 12. With the requirement to compute the effects of the high energy protons and other heavy ions on the proposed Europa mission, the extension of the high energy proton model from approximately 12 L-shell to approximately 50 L-shell has become necessary. In particular, a model of the proton environment over that range is required to estimate radiation effects on the solar arrays for the mission. This study describes both the steps taken to extend the original Divine proton model out to an approximately 50 L-shell and the resulting model developed to accomplish that goal. In addition to hydrogen, the oxygen, sulfur, and helium heavy ion environments have also been added between approximately 6 L-shell and approximately 50 L-shell. Finally, selected examples of the model's predictions are presented to illustrate the uses of the tool.

Use of the Bethe equation for inner-shell ionization by electron impact

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

Powell, Cedric J.; Llovet, Xavier; Salvat, Francesc

2016-05-14

We analyzed calculated cross sections for K-, L-, and M-shell ionization by electron impact to determine the energy ranges over which these cross sections are consistent with the Bethe equation for inner-shell ionization. Our analysis was performed with K-shell ionization cross sections for 26 elements, with L-shell ionization cross sections for seven elements, L{sub 3}-subshell ionization cross sections for Xe, and M-shell ionization cross sections for three elements. The validity (or otherwise) of the Bethe equation could be checked with Fano plots based on a linearized form of the Bethe equation. Our Fano plots, which display theoretical cross sections andmore » available measured cross sections, reveal two linear regions as predicted by de Heer and Inokuti [in Electron Impact Ionization, edited by T. D. Märk and G. H. Dunn, (Springer-Verlag, Vienna, 1985), Chap. 7, pp. 232–276]. For each region, we made linear fits and determined values of the two element-specific Bethe parameters. We found systematic variations of these parameters with atomic number for both the low- and the high-energy linear regions of the Fano plots. We also determined the energy ranges over which the Bethe equation can be used.« less

Influence of heat treatment on hole transfer dynamics in core-shell quantum dot/organic hole conductor hybrid films

NASA Astrophysics Data System (ADS)

Sun, Mingye; Zheng, Youjin; Zhang, Lei; Zhao, Liping; Zhang, Bing

2017-08-01

The influence of heat treatment on hole transfer (HT) processes from the CdSe/ZnS and CdSe/CdS/ZnS quantum dots (QDs) to 4,4‧,4″-Tris(carbazol-9-yl)-triphenylamine (TCTA) in QD/TCTA hybrid films has been researched with time-resolved photoluminescence (PL) spectroscopy. The PL dynamic results demonstrated a heat-treatment-temperature-dependent HT process from the core-shell CdSe QDs to TCTA. The HT rates and efficiencies can be effectively increased due to reduced distance between core-shell CdSe QDs and TCTA after heat treatment. The CdS shell exhibited a more obvious effect on HT from the core-shell CdSe QDs to TCTA than on electron transfer to TiO2, due to higher barrier for holes to tunnel through CdS shell and larger effective mass of holes in CdS than electrons. These results indicate that heat treatment would be an effective means to further optimize solid-state QD sensitized solar cells and rational design of CdS shell is significant.

Ni3Si(Al)/a-SiOx core shell nanoparticles: characterization, shell formation, and stability

NASA Astrophysics Data System (ADS)

Pigozzi, G.; Mukherji, D.; Gilles, R.; Barbier, B.; Kostorz, G.

2006-08-01

We have used an electrochemical selective phase dissolution method to extract nanoprecipitates of the Ni3Si-type intermetallic phase from two-phase Ni-Si and Ni-Si-Al alloys by dissolving the matrix phase. The extracted nanoparticles are characterized by transmission electron microscopy, energy-dispersive x-ray spectrometry, x-ray powder diffraction, and electron powder diffraction. It is found that the Ni3Si-type nanoparticles have a core-shell structure. The core maintains the size, the shape, and the crystal structure of the precipitates that existed in the bulk alloys, while the shell is an amorphous phase, containing only Si and O (SiOx). The shell forms around the precipitates during the extraction process. After annealing the nanoparticles in nitrogen at 700 °C, the tridymite phase recrystallizes within the shell, which remains partially amorphous. In contrast, on annealing in air at 1000 °C, no changes in the composition or the structure of the nanoparticles occur. It is suggested that the shell forms after dealloying of the matrix phase, where Si atoms, the main constituents of the shell, migrate to the surface of the precipitates.

Ni(3)Si(Al)/a-SiO(x) core-shell nanoparticles: characterization, shell formation, and stability.

PubMed

Pigozzi, G; Mukherji, D; Gilles, R; Barbier, B; Kostorz, G

2006-08-28

We have used an electrochemical selective phase dissolution method to extract nanoprecipitates of the Ni(3)Si-type intermetallic phase from two-phase Ni-Si and Ni-Si-Al alloys by dissolving the matrix phase. The extracted nanoparticles are characterized by transmission electron microscopy, energy-dispersive x-ray spectrometry, x-ray powder diffraction, and electron powder diffraction. It is found that the Ni(3)Si-type nanoparticles have a core-shell structure. The core maintains the size, the shape, and the crystal structure of the precipitates that existed in the bulk alloys, while the shell is an amorphous phase, containing only Si and O (SiO(x)). The shell forms around the precipitates during the extraction process. After annealing the nanoparticles in nitrogen at 700 °C, the tridymite phase recrystallizes within the shell, which remains partially amorphous. In contrast, on annealing in air at 1000 °C, no changes in the composition or the structure of the nanoparticles occur. It is suggested that the shell forms after dealloying of the matrix phase, where Si atoms, the main constituents of the shell, migrate to the surface of the precipitates.

Comparative study of the double-K -shell-vacancy production in single- and double-electron-capture decay

NASA Astrophysics Data System (ADS)

Ratkevich, S. S.; Gangapshev, A. M.; Gavrilyuk, Yu. M.; Karpeshin, F. F.; Kazalov, V. V.; Kuzminov, V. V.; Panasenko, S. I.; Trzhaskovskaya, M. B.; Yakimenko, S. P.

2017-12-01

Background: A double-K -electron capture is a rare nuclear-atomic process in which two K electrons are captured simultaneously from the atomic shell. A "hollow atom" is created as a result of this process. In single-K -shell electron-capture decays, there is a small probability that the second electron in the K shell is excited to an unoccupied level or can (mostly) be ejected to the continuum. In either case, a double vacancy is created in the K shell. The relaxation of the double-K -shell vacancy, accompanied by the emission of two K -fluorescence photons, makes it possible to perform experimental studies of such rare processes with the large-volume proportional gas chamber. Purpose: The purpose of the present analysis is to estimate a double-K -shell vacancy creation probability per K -shell electron capture PK K of 81Kr, as well as to measure the half-life of 78Kr relative to 2 ν 2 K capture. Method: Time-resolving current pulse from the large low-background proportional counter (LPC), filled with the krypton sample, was applied to detect triple coincidences of "shaked" electrons and two fluorescence photons. Results: The number of K -shell vacancies per the K -electron capture, produced as a result of the shake-off process, has been measured for the decay of 81Kr. The probability for this decay was found to be PK K=(5.7 ±0.8 ) ×10-5 with a systematic error of (ΔPKK) syst=±0.4 ×10-5 . For the 78Kr(2 ν 2 K ) decay, the comparative study of single- and double-capture decays allowed us to obtain the signal-to-background ratio up to 15/1. The half-life T1/2 2 ν 2 K(g .s .→g .s .) =[1 .9-0.7+1.3(stat) ±0.3 (syst) ] ×1022 y is determined from the analysis of data that have been accumulated over 782 days of live measurements in the experiment that used samples consisted of 170.6 g of 78Kr. Conclusions: The data collected during low background measurements using the LPC were analyzed to search the rare atomic and nuclear processes. We have determined PKK exp for the E C decay of 81Kr, which are in satisfactory agreement with Z-2 dependence of PK K predicted by Primakoff and Porter. This made possible to more accurately determine the background contribution in the energy region of our interest for the search for the 2 K capture in 78Kr. The general procedure of data analysis allowed us to determine the half-life of 78Kr relative to 2 ν 2 K transition with a greater statistical accuracy than in our previous works.

xLIPA: Promotion of Electrons from the K-shell to 2 GeV using 10 PW Laser Pulses

DTIC Science & Technology

2015-08-19

field [34]. Since then numerous analytical and numerical approaches have been employed with special emphasis on laser photoionization . Besides interest in... photoionization as a fundamental physical process there are many applications for photoelectrons. Knowledge of the electron properties, e.g., energy...Schwinger field. Photoionization of inner-shell electrons in high-Z atoms is another example where relativistic effects are important. Two analytical

Cargo-shell and cargo-cargo couplings govern the mechanics of artificially loaded virus-derived cages

NASA Astrophysics Data System (ADS)

Llauró, Aida; Luque, Daniel; Edwards, Ethan; Trus, Benes L.; Avera, John; Reguera, David; Douglas, Trevor; Pablo, Pedro J. De; Castón, José R.

2016-04-01

Nucleic acids are the natural cargo of viruses and key determinants that affect viral shell stability. In some cases the genome structurally reinforces the shell, whereas in others genome packaging causes internal pressure that can induce destabilization. Although it is possible to pack heterologous cargoes inside virus-derived shells, little is known about the physical determinants of these artificial nanocontainers' stability. Atomic force and three-dimensional cryo-electron microscopy provided mechanical and structural information about the physical mechanisms of viral cage stabilization beyond the mere presence/absence of cargos. We analyzed the effects of cargo-shell and cargo-cargo interactions on shell stability after encapsulating two types of proteinaceous payloads. While bound cargo to the inner capsid surface mechanically reinforced the capsid in a structural manner, unbound cargo diffusing freely within the shell cavity pressurized the cages up to ~30 atm due to steric effects. Strong cargo-cargo coupling reduces the resilience of these nanocompartments in ~20% when bound to the shell. Understanding the stability of artificially loaded nanocages will help to design more robust and durable molecular nanocontainers.Nucleic acids are the natural cargo of viruses and key determinants that affect viral shell stability. In some cases the genome structurally reinforces the shell, whereas in others genome packaging causes internal pressure that can induce destabilization. Although it is possible to pack heterologous cargoes inside virus-derived shells, little is known about the physical determinants of these artificial nanocontainers' stability. Atomic force and three-dimensional cryo-electron microscopy provided mechanical and structural information about the physical mechanisms of viral cage stabilization beyond the mere presence/absence of cargos. We analyzed the effects of cargo-shell and cargo-cargo interactions on shell stability after encapsulating two types of proteinaceous payloads. While bound cargo to the inner capsid surface mechanically reinforced the capsid in a structural manner, unbound cargo diffusing freely within the shell cavity pressurized the cages up to ~30 atm due to steric effects. Strong cargo-cargo coupling reduces the resilience of these nanocompartments in ~20% when bound to the shell. Understanding the stability of artificially loaded nanocages will help to design more robust and durable molecular nanocontainers. Electronic supplementary information (ESI) available: 6 figures, 3 tables and theory. See DOI: 10.1039/c6nr01007e

Structural and electronic properties of CdS/ZnS core/shell nanowires: A first-principles study

NASA Astrophysics Data System (ADS)

Kim, Hyo Seok; Kim, Yong-Hoon

2015-03-01

Carrying out density functional theory (DFT) calculation, we studied the relative effects of quantum confinement and strain on the electronic structures of II-IV semiconductor compounds with a large lattice-mismatch, CdS and ZnS, in the core/shell nanowire geometry. We considered different core radii and shell thickness of the CdS/ZnS core/shell nanowire, different surface facets, and various defects in the core/shell interface and surface regions. To properly describe the band level alignment at the core/shell boundary, we adopted the self-interaction correction (SIC)-DFT scheme. Implications of our findings in the context of device applications will be also discussed. This work was supported by the Basic Science Research Grant (No. 2012R1A1A2044793), Global Frontier Program (No. 2013-073298), and Nano-Material Technology Development Program (2012M3A7B4049888) of the National Research Foundation funded by the Ministry of Education, Science and Technology of Korea. Corresponding author

Copper nanowire-graphene core-shell nanostructure for highly stable transparent conducting electrodes.

PubMed

Ahn, Yumi; Jeong, Youngjun; Lee, Donghwa; Lee, Youngu

2015-03-24

A copper nanowire-graphene (CuNW-G) core-shell nanostructure was successfully synthesized using a low-temperature plasma-enhanced chemical vapor deposition process at temperatures as low as 400 °C for the first time. The CuNW-G core-shell nanostructure was systematically characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Raman, and X-ray photoelectron spectroscopy measurements. A transparent conducting electrode (TCE) based on the CuNW-G core-shell nanostructure exhibited excellent optical and electrical properties compared to a conventional indium tin oxide TCE. Moreover, it showed remarkable thermal oxidation and chemical stability because of the tight encapsulation of the CuNW with gas-impermeable graphene shells. The potential suitability of CuNW-G TCE was demonstrated by fabricating bulk heterojunction polymer solar cells. We anticipate that the CuNW-G core-shell nanostructure can be used as an alternative to conventional TCE materials for emerging optoelectronic devices such as flexible solar cells, displays, and touch panels.

Fabrication of Fe3O4@CuO core-shell from MOF based materials and its antibacterial activity

NASA Astrophysics Data System (ADS)

Rajabi, S. K.; Sohrabnezhad, Sh.; Ghafourian, S.

2016-12-01

Magnetic Fe3O4@CuO nanocomposite with a core/shell structure was successfully synthesized via direct calcinations of magnetic Fe3O4@HKUST-1 in air atmosphere. The morphology, structure, magnetic and porous properties of the as-synthesized nano composites were characterized by using scanning electron microscope (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (PXRD), and vibration sample magnetometer (VSM). The results showed that the nanocomposite material included a Fe3O4 core and a CuO shell. The Fe3O4@CuO core-shell can be separated easily from the medium by a small magnet. The antibacterial activity of Fe3O4-CuO core-shell was investigated against gram-positive and gram-negative bacteria. A new mechanism was proposed for inactivation of bacteria over the prepared sample. It was demonstrated that the core-shell exhibit recyclable antibacterial activity, acting as an ideal long-acting antibacterial agent.

Suppressed Blinking and Auger Recombination in Near-Infrared Type-II InP/CdS Nanocrystal Quantum Dots

PubMed Central

Dennis, Allison M.; Mangum, Benjamin D.; Piryatinski, Andrei; Park, Young-Shin; Hannah, Daniel C.; Casson, Joanna L.; Williams, Darrick J.; Schaller, Richard D.; Htoon, Han; Hollingsworth, Jennifer A.

2012-01-01

Non-blinking excitonic emission from near-infrared and type-II nanocrystal quantum dots (NQDs) is reported for the first time. To realize this unusual degree of stability at the single-dot level, novel InP/CdS core/shell NQDs were synthesized for a range of shell thicknesses (~1–11 monolayers of CdS). Ensemble spectroscopy measurements (photoluminescence peak position and radiative lifetimes) and electronic structure calculations established the transition from type-I to type-II band alignment in these heterostructured NQDs. More significantly, single-NQD studies revealed clear evidence for blinking suppression that was not strongly shell-thickness dependent, while photobleaching and biexciton lifetimes trended explicitly with extent of shelling. Specifically, very long biexciton lifetimes—up to >7 ns—were obtained for the thickest-shell structures, indicating dramatic suppression of non-radiative Auger recombination. This new system demonstrates that electronic structure and shell thickness can be employed together to effect control over key single-dot and ensemble NQD photophysical properties. PMID:23030497

Porphyrinoids as a platform of stable radicals

PubMed Central

Shimizu, Daiki

2018-01-01

The non-innocent ligand nature of porphyrins was observed for compound I in enzymatic cycles of cytochrome P450. Such porphyrin radicals were first regarded as reactive intermediates in catabolism, but recent studies have revealed that porphyrinoids, including porphyrins, ring-contracted porphyrins, and ring-expanded porphyrins, display excellent radical-stabilizing abilities to the extent that radicals can be handled like usual closed-shell organic molecules. This review surveys four types of stable porphyrinoid radical and covers their synthetic methods and properties such as excellent redox properties, NIR absorption, and magnetic properties. The radical-stabilizing abilities of porphyrinoids stem from their unique macrocyclic conjugated systems with high electronic and structural flexibilities. PMID:29675188

a Point-Like Picture of the Hydrogen Atom

NASA Astrophysics Data System (ADS)

Faghihi, F.; Jangjoo, A.; Khani, M.

A point-like picture of the Schrödinger solution for hydrogen atom is worked to emphasize that "point-like particles" may describe as "probability wave function". In each case, the three-dimensional shape of the |Ψnlm(rn, cosθ)|2 is plotted and the paths of the point-like electron (it is better to say reduced mass of the pair particles) are described in each closed shell. Finally, the orbital shape of the molecules are given according to the present simple model. In our opinion, "interpretations of the Correspondence Principle", which is a basic principle in all elementary quantum text, seems to be reviewed again!

Onion-like nanoscale structures and fullerene-type cages formed by electron irradiation on turbostratic B{sub x}C{sub 1{minus}x} (x<0.2)

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

Golberg, D.; Bando, Y.; Kurashima, K.

Flakes of CVD grown B{sub x}C{sub 1{minus}x} (x<0.2) films were exposed to intense electron irradiation (flux density up to {approximately}100 A/cm{sup 2}) in a 300 kV high resolution electron microscope equipped with a field emission gun. The starting flakes revealed a turbostratic B{sub x}C{sub 1{minus}x} structure. The composition of the starting materials and irradiated products was determined by using electron energy loss spectroscopy (EELS). Depending on the electron dose applied, irradiation of the turbostratic material led to formation of soap-bubble-like irregularly-shaped objects (linear dimensions of {approximately}2--5 nm), onion- and semi-onion-like structures (d{approximately}10nm), nested fullerenes (3--14 shells) and elementary fullerene-type cagesmore » (d{approximately}0.7 nm). It is thought that these curled and closed nanostructures arise from a continuous bending of the hexagonal B{sub x}C{sub 1{minus}x} sheets under electron irradiation. Finally, some possible structural models of B{sub x}C{sub 1{minus}x} fullerenes are considered.« less

Optimum hot electron production with low-density foams for laser fusion by fast ignition.

PubMed

Lei, A L; Tanaka, K A; Kodama, R; Kumar, G R; Nagai, K; Norimatsu, T; Yabuuchi, T; Mima, K

2006-06-30

We propose a foam cone-in-shell target design aiming at optimum hot electron production for the fast ignition. A thin low-density foam is proposed to cover the inner tip of a gold cone inserted in a fuel shell. An intense laser is then focused on the foam to generate hot electrons for the fast ignition. Element experiments demonstrate increased laser energy coupling efficiency into hot electrons without increasing the electron temperature and beam divergence with foam coated targets in comparison with solid targets. This may enhance the laser energy deposition in the compressed fuel plasma.

Preparation and Characterization of WS2@SiO2 and WS2@PANI Core-Shell Nanocomposites

PubMed Central

Sade, Hagit

2018-01-01

Two tungsten disulfide (WS2)-based core-shell nanocomposites were fabricated using readily available reagents and simple procedures. The surface was pre-treated with a surfactant couple in a layer-by-layer approach, enabling good dispersion of the WS2 nanostructures in aqueous media and providing a template for the polymerization of a silica (SiO2) shell. After a Stöber-like reaction, a conformal silica coating was achieved. Inspired by the resulting nanocomposite, a second one was prepared by reacting the surfactant-modified WS2 nanostructures with aniline and an oxidizing agent in an aqueous medium. Here too, a conformal coating of polyaniline (PANI) was obtained, giving a WS2@PANI nanocomposite. Both nanocomposites were analyzed by electron microscopy, energy dispersive X-ray spectroscopy (EDS) and FTIR, verifying the core-shell structure and the character of shells. The silica shell was amorphous and mesoporous and the surface area of the composite increases with shell thickness. Polyaniline shells slightly differ in their morphologies dependent on the acid used in the polymerization process and are amorphous like the silica shell. Electron paramagnetic resonance (EPR) spectroscopy of the WS2@PANI nanocomposite showed variation between bulk PANI and the PANI shell. These two nanocomposites have great potential to expand the use of transition metals dichalcogenides (TMDCs) for new applications in different fields. PMID:29534426

Electron cryo-tomographic structure of cystovirus phi 12.

PubMed

Hu, Guo-Bin; Wei, Hui; Rice, William J; Stokes, David L; Gottlieb, Paul

2008-03-01

Bacteriophage phi 12 is a member of the Cystoviridae virus family and contains a genome consisting of three segments of double-stranded RNA (dsRNA). This virus family contains eight identified members, of which four have been classified in regard to their complete genomic sequence and encoded viral proteins. A phospholipid envelope that contains the integral proteins P6, P9, P10, and P13 surrounds the viral particles. In species phi 6, host infection requires binding of a multimeric P3 complex to type IV pili. In species varphi8, phi 12, and phi 13, the attachment apparatus is a heteromeric protein assembly that utilizes the rough lipopolysaccharide (rlps) as a receptor. In phi 8 the protein components are designated P3a and P3b while in species phi 12 proteins P3a and P3c have been identified in the complex. The phospholipid envelope of the cystoviruses surrounds a nucleocapsid (NC) composed of two shells. The outer shell is composed of protein P8 with a T=13 icosahedral lattice while the primary component of the inner shell is a dodecahedral frame composed of dimeric protein P1. For the current study, the 3D architecture of the intact phi 12 virus was obtained by electron cryo-tomography. The nucleocapsid appears to be centered within the membrane envelope and possibly attached to it by bridging structures. Two types of densities were observed protruding from the membrane envelope. The densities of the first type were elongated, running parallel, and closely associated to the envelope outer surface. In contrast, the second density was positioned about 12 nm above the envelope connected to it by a flexible low-density stem. This second structure formed a torroidal structure termed "the donut" and appears to inhibit BHT-induced viral envelope fusion.

Solvation of carbonaceous molecules by para-H2 and ortho-D2 clusters. II. Fullerenes.

PubMed

Calvo, F; Yurtsever, E

2016-08-28

The coating of various fullerenes by para-hydrogen and ortho-deuterium molecules has been computationally studied as a function of the solvent amount. Rotationally averaged interaction potentials for structureless hydrogen molecules are employed to model their interaction with neutral or charged carbonaceous dopants containing between 20 and 240 atoms, occasionally comparing different fullerenes having the same size but different shapes. The solvation energy and the size of the first solvation shell obtained from path-integral molecular dynamics simulations at 2 K show only minor influence on the dopant charge and on the possible deuteration of the solvent, although the shell size is largest for ortho-D2 coating cationic fullerenes. Nontrivial finite size effects have been found with the shell size varying non-monotonically close to its completion limit. For fullerenes embedded in large hydrogen clusters, the shell size and solvation energy both follow linear scaling with the fullerene size. The shell sizes obtained for C60 (+) and C70 (+) are close to 49 and 51, respectively, and agree with mass spectrometry experiments.

Solvation of carbonaceous molecules by para-H2 and ortho-D2 clusters. II. Fullerenes

NASA Astrophysics Data System (ADS)

Calvo, F.; Yurtsever, E.

2016-08-01

The coating of various fullerenes by para-hydrogen and ortho-deuterium molecules has been computationally studied as a function of the solvent amount. Rotationally averaged interaction potentials for structureless hydrogen molecules are employed to model their interaction with neutral or charged carbonaceous dopants containing between 20 and 240 atoms, occasionally comparing different fullerenes having the same size but different shapes. The solvation energy and the size of the first solvation shell obtained from path-integral molecular dynamics simulations at 2 K show only minor influence on the dopant charge and on the possible deuteration of the solvent, although the shell size is largest for ortho-D2 coating cationic fullerenes. Nontrivial finite size effects have been found with the shell size varying non-monotonically close to its completion limit. For fullerenes embedded in large hydrogen clusters, the shell size and solvation energy both follow linear scaling with the fullerene size. The shell sizes obtained for C 60+ and C 70+ are close to 49 and 51, respectively, and agree with mass spectrometry experiments.

Basis set and electron correlation effects on the polarizability and second hyperpolarizability of model open-shell π-conjugated systems

NASA Astrophysics Data System (ADS)

Champagne, Benoı̂t; Botek, Edith; Nakano, Masayoshi; Nitta, Tomoshige; Yamaguchi, Kizashi

2005-03-01

The basis set and electron correlation effects on the static polarizability (α) and second hyperpolarizability (γ) are investigated ab initio for two model open-shell π-conjugated systems, the C5H7 radical and the C6H8 radical cation in their doublet state. Basis set investigations evidence that the linear and nonlinear responses of the radical cation necessitate the use of a less extended basis set than its neutral analog. Indeed, double-zeta-type basis sets supplemented by a set of d polarization functions but no diffuse functions already provide accurate (hyper)polarizabilities for C6H8 whereas diffuse functions are compulsory for C5H7, in particular, p diffuse functions. In addition to the 6-31G*+pd basis set, basis sets resulting from removing not necessary diffuse functions from the augmented correlation consistent polarized valence double zeta basis set have been shown to provide (hyper)polarizability values of similar quality as more extended basis sets such as augmented correlation consistent polarized valence triple zeta and doubly augmented correlation consistent polarized valence double zeta. Using the selected atomic basis sets, the (hyper)polarizabilities of these two model compounds are calculated at different levels of approximation in order to assess the impact of including electron correlation. As a function of the method of calculation antiparallel and parallel variations have been demonstrated for α and γ of the two model compounds, respectively. For the polarizability, the unrestricted Hartree-Fock and unrestricted second-order Møller-Plesset methods bracket the reference value obtained at the unrestricted coupled cluster singles and doubles with a perturbative inclusion of the triples level whereas the projected unrestricted second-order Møller-Plesset results are in much closer agreement with the unrestricted coupled cluster singles and doubles with a perturbative inclusion of the triples values than the projected unrestricted Hartree-Fock results. Moreover, the differences between the restricted open-shell Hartree-Fock and restricted open-shell second-order Møller-Plesset methods are small. In what concerns the second hyperpolarizability, the unrestricted Hartree-Fock and unrestricted second-order Møller-Plesset values remain of similar quality while using spin-projected schemes fails for the charged system but performs nicely for the neutral one. The restricted open-shell schemes, and especially the restricted open-shell second-order Møller-Plesset method, provide for both compounds γ values close to the results obtained at the unrestricted coupled cluster level including singles and doubles with a perturbative inclusion of the triples. Thus, to obtain well-converged α and γ values at low-order electron correlation levels, the removal of spin contamination is a necessary but not a sufficient condition. Density-functional theory calculations of α and γ have also been carried out using several exchange-correlation functionals. Those employing hybrid exchange-correlation functionals have been shown to reproduce fairly well the reference coupled cluster polarizability and second hyperpolarizability values. In addition, inclusion of Hartree-Fock exchange is of major importance for determining accurate polarizability whereas for the second hyperpolarizability the gradient corrections are large.

Synthesis of fullerene@gold core-shell nanostructures.

PubMed

Ren, Yupeng; Paira, Priyankar; Nayak, Tapas Ranjan; Ang, Wee Han; Pastorin, Giorgia

2011-07-21

A "direct encapsulation" method was developed for the synthesis of highly stable water-soluble fullerene@gold core-shell nanostructures, with gold nanoshells showing either closed or porous morphology. This gold nano-shell coating formed a "nano-oven", capable of decomposing encapsulated fullerene molecules rapidly when irradiated by laser. We envisaged this being a useful tool for chemical reactions as well as a novel scaffold for nano-material synthesis.

Ramsey method for Auger-electron interference induced by an attosecond twin pulse

NASA Astrophysics Data System (ADS)

Buth, Christian; Schafer, Kenneth J.

2015-02-01

We examine the archetype of an interference experiment for Auger electrons: two electron wave packets are launched by inner-shell ionizing a krypton atom using two attosecond light pulses with a variable time delay. This setting is an attosecond realization of the Ramsey method of separated oscillatory fields. Interference of the two ejected Auger-electron wave packets is predicted, indicating that the coherence between the two pulses is passed to the Auger electrons. For the detection of the interference pattern an accurate coincidence measurement of photo- and Auger electrons is necessary. The method allows one to control inner-shell electron dynamics on an attosecond timescale and represents a sensitive indicator for decoherence.

The Oscillations of Coronal Loops Including the Shell

NASA Astrophysics Data System (ADS)

Mikhalyaev, B. B.; Solov'ev, A. A.

2005-04-01

We investigate the MHD waves in a double magnetic flux tube embedded in a uniform external magnetic field. The tube consists of a dense hot cylindrical cord surrounded by a co-axial shell. The plasma and the magnetic field are taken to be uniform inside the cord and also inside the shell. Two slow and two fast magnetosonic modes can exist in the thin double tube. The first slow mode is trapped by the cord, the other is trapped by the shell. The oscillations of the second mode have opposite phases inside the cord and shell. The speeds of the slow modes propagating along the tube are close to the tube speeds inside the cord and the shell. The behavior of the fast modes depends on the magnitude of Alfvén speed inside the shell. If it is less than the Alfvén speed inside the cord and in the environment, then the fast mode is trapped by the shell and the other may be trapped under the certain conditions. In the opposite case when the Alfvén speed in the shell is greater than those inside the cord and in the environment, then the fast mode is radiated by the tube and the other may also be radiated under certain conditions. The oscillation of the cord and the shell with opposite phases is the distinctive feature of the process. The proposed model allows to explain the basic phenomena connected to the coronal oscillations: i) the damping of oscillations stipulated in the double tube model by the radiative loss, ii) the presence of two different modes of perturbations propagating along the loop with close speeds, iii) the opposite phases of oscillations of modulated radio emission, coming from the near coronal sources having sharply different densities.

Atomic level characterization of cadmium selenide nanocrystal systems using atomic number contrast scanning transmission electron microscopy and Rutherford backscattering spectroscopy

NASA Astrophysics Data System (ADS)

McBride, James R.

This project involved the characterization of CdSe nanocrystals. Through the use of Atomic Number Contrast Scanning Transmission Electron Microscopy (Z-STEM) and Rutherford Backscattering Spectroscopy (RBS), atomic level structure and chemical information was obtained. Specifically, CdSe nanocrystals produced using a mixture of hexadecylamine (HDA) and trioctylphosphine oxide (TOPO) were determined to be spherical compared to nanocrystals produced in TOPO only, which had elongated (101) facets. Additionally, the first Z-STEM images of CdSe/ZnS core/shell nanocrystals were obtained. From these images, the growth mechanism of the ZnS shell was determined and the existence of non-fluorescent ZnS particles was confirmed. Through collaboration with Quantum Dot Corp., core/shell nanocrystals with near unity quantum yield were developed. These core/shell nanocrystals included a US intermediate layer to improve shell coverage.

Type I band alignment in GaAs{sub 81}Sb{sub 19}/GaAs core-shell nanowires

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

Xu, T.; Key Laboratory of Advanced Display and System Application, Shanghai University, 149 Yanchang Road, Shanghai 200072; Wei, M. J.

2015-09-14

The composition and band gap of the shell that formed during the growth of axial GaAs/GaAs{sub 81}Sb{sub 19}/ GaAs heterostructure nanowires have been investigated by transmission electron microscopy combined with energy dispersion spectroscopy, scanning tunneling spectroscopy, and density functional theory calculations. On the GaAs{sub 81}Sb{sub 19} intermediate segment, the shell is found to be free of Sb (pure GaAs shell) and transparent to the tunneling electrons, despite the (110) biaxial strain that affects its band gap. As a result, a direct measurement of the core band gap allows the quantitative determination of the band offset between the GaAs{sub 81}Sb{sub 19}more » core and the GaAs shell and identifies it as a type I band alignment.« less

Ab Initio Simulations and Electronic Structure of Lithium-Doped Ionic Liquids: Structure, Transport, and Electrochemical Stability.

PubMed

Haskins, Justin B; Bauschlicher, Charles W; Lawson, John W

2015-11-19

Density functional theory (DFT), density functional theory molecular dynamics (DFT-MD), and classical molecular dynamics using polarizable force fields (PFF-MD) are employed to evaluate the influence of Li(+) on the structure, transport, and electrochemical stability of three potential ionic liquid electrolytes: N-methyl-N-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([pyr14][TFSI]), N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide ([pyr13][FSI]), and 1-ethyl-3-methylimidazolium boron tetrafluoride ([EMIM][BF4]). We characterize the Li(+) solvation shell through DFT computations of [Li(Anion)n]((n-1)-) clusters, DFT-MD simulations of isolated Li(+) in small ionic liquid systems, and PFF-MD simulations with high Li-doping levels in large ionic liquid systems. At low levels of Li-salt doping, highly stable solvation shells having two to three anions are seen in both [pyr14][TFSI] and [pyr13][FSI], whereas solvation shells with four anions dominate in [EMIM][BF4]. At higher levels of doping, we find the formation of complex Li-network structures that increase the frequency of four anion-coordinated solvation shells. A comparison of computational and experimental Raman spectra for a wide range of [Li(Anion)n]((n-1)-) clusters shows that our proposed structures are consistent with experiment. We then compute the ion diffusion coefficients and find measures from small-cell DFT-MD simulations to be the correct order of magnitude, but influenced by small system size and short simulation length. Correcting for these errors with complementary PFF-MD simulations, we find DFT-MD measures to be in close agreement with experiment. Finally, we compute electrochemical windows from DFT computations on isolated ions, interacting cation/anion pairs, and liquid-phase systems with Li-doping. For the molecular-level computations, we generally find the difference between ionization energy and electron affinity from isolated ions and interacting cation/anion pairs to provide upper and lower bounds, respectively, to experiment. In the liquid phase, we find the difference between the lowest unoccupied and highest occupied electronic levels in pure and hybrid functionals to provide lower and upper bounds, respectively, to experiment. Li-doping in the liquid-phase systems results in electrochemical windows little changed from the neat systems.

Green synthesis of CuInS2/ZnS core-shell quantum dots by facile solvothermal route with enhanced optical properties

NASA Astrophysics Data System (ADS)

Jindal, Shikha; Giripunje, Sushama M.; Kondawar, Subhash B.; Koinkar, Pankaj

2018-03-01

We report an eco-friendly green synthesis of highly luminescent CuInS2/ZnS core-shell quantum dots (QDs) with average particle size ∼ 3.9 nm via solvothermal process. The present study embodies the intensification of CuInS2/ZnS QDs properties by the shell growth on the CuInS2 QDs. The as-prepared CuInS2 core and CuInS2/ZnS core-shell QDs have been characterized using a range of optical and structural techniques. By adopting a low temperature growth of CuInS2 core and high temperature growth of CuInS2/ZnS core-shell growth, the tuning of absorption and photoluminescence emission spectra were observed. Optical absorption and photoluminescence spectroscopy probe the effect of ZnS passivation on the electronic structure of the CuInS2 dots. In addition, QDs have been scrutinized using ultra violet photoelectron spectroscopy (UPS) to explore their electronic band structure. The band level positions of CuInS2 and CuInS2/ZnS QDs suffices the demand of non-toxic acceptor material for electronic devices. The variation in electronic energy levels of CuInS2 core with the coating of wide band gap ZnS shell influence the removal of trap assisted recombination on the surface of the core. QDs exhibited tunable emission from red to orange region. These studies reveal the feasibility of QDs in photovoltaic and light emitting diodes.

Orbital-optimized MP2.5 and its analytic gradients: Approaching CCSD(T) quality for noncovalent interactions

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

Bozkaya, Uğur, E-mail: ugur.bozkaya@atauni.edu.tr; Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, and School of Computational Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332; Sherrill, C. David

2014-11-28

Orbital-optimized MP2.5 [or simply “optimized MP2.5,” OMP2.5, for short] and its analytic energy gradients are presented. The cost of the presented method is as much as that of coupled-cluster singles and doubles (CCSD) [O(N{sup 6}) scaling] for energy computations. However, for analytic gradient computations the OMP2.5 method is only half as expensive as CCSD because there is no need to solve λ{sub 2}-amplitude equations for OMP2.5. The performance of the OMP2.5 method is compared with that of the standard second-order Møller–Plesset perturbation theory (MP2), MP2.5, CCSD, and coupled-cluster singles and doubles with perturbative triples (CCSD(T)) methods for equilibrium geometries, hydrogenmore » transfer reactions between radicals, and noncovalent interactions. For bond lengths of both closed and open-shell molecules, the OMP2.5 method improves upon MP2.5 and CCSD by 38%–43% and 31%–28%, respectively, with Dunning's cc-pCVQZ basis set. For complete basis set (CBS) predictions of hydrogen transfer reaction energies, the OMP2.5 method exhibits a substantially better performance than MP2.5, providing a mean absolute error of 1.1 kcal mol{sup −1}, which is more than 10 times lower than that of MP2.5 (11.8 kcal mol{sup −1}), and comparing to MP2 (14.6 kcal mol{sup −1}) there is a more than 12-fold reduction in errors. For noncovalent interaction energies (at CBS limits), the OMP2.5 method maintains the very good performance of MP2.5 for closed-shell systems, and for open-shell systems it significantly outperforms MP2.5 and CCSD, and approaches CCSD(T) quality. The MP2.5 errors decrease by a factor of 5 when the optimized orbitals are used for open-shell noncovalent interactions, and comparing to CCSD there is a more than 3-fold reduction in errors. Overall, the present application results indicate that the OMP2.5 method is very promising for open-shell noncovalent interactions and other chemical systems with difficult electronic structures.« less

Structural Basis for Near Unity Quantum Yield Core/Shell Nanostructures

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

McBride, James; Treadway, Joe; Pennycook, Stephen J

2006-01-01

Aberration-corrected Z-contrast scanning transmission electron microscopy of core/shell nanocrystals shows clear correlations between structure and quantum efficiency. Uniform shell coverage is obtained only for a graded CdS/ZnS shell material and is found to be critical to achieving near 100% quantum yield. The sublattice sensitivity of the images confirms that preferential growth takes place on the anion-terminated surfaces. This explains the three-dimensional "nanobullet" shape observed in the case of core/shell nanorods.

78 FR 18605 - Agency Information Collection Activities; Proposed Collection; Comment Request; Prevention of...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-03-27

... Enteritidis in Shell Eggs During Production--Recordkeeping and Registration Provisions AGENCY: Food and Drug... registration requirements for shell egg producers. DATES: Submit either electronic or written comments on the... appropriate, and other forms of information technology. Prevention of Salmonella Enteritidis in Shell Eggs...

Building Atoms Shell by Shell.

ERIC Educational Resources Information Center

Sussman, Beverly

1993-01-01

Describes an atom-building activity where students construct three-dimensional models of atoms using a styrofoam ball as the nucleus and pom-poms, gum drops, minimarshmallows, or other small items of two different colors to represent protons and neutrons attached. Rings of various sizes with pom-poms attached represent electron shells and…

Synthesis of parallel and antiparallel core-shell triangular nanoparticles

NASA Astrophysics Data System (ADS)

Bhattacharjee, Gourab; Satpati, Biswarup

2018-04-01

Core-shell triangular nanoparticles were synthesized by seed mediated growth. Using triangular gold (Au) nanoparticle as template, we have grown silver (Ag) shellto get core-shell nanoparticle. Here by changing the chemistry we have grown two types of core-shell structures where core and shell is having same symmetry and also having opposite symmetry. Both core and core-shell nanoparticles were characterized using transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX) to know the crystal structure and composition of these synthesized core-shell nanoparticles. From diffraction pattern analysis and energy filtered TEM (EFTEM) we have confirmed the crystal facet in core is responsible for such two dimensional growth of core-shell nanostructures.

Ultrafast Molecular Three-Electron Auger Decay.

PubMed

Feifel, Raimund; Eland, John H D; Squibb, Richard J; Mucke, Melanie; Zagorodskikh, Sergey; Linusson, Per; Tarantelli, Francesco; Kolorenč, Přemysl; Averbukh, Vitali

2016-02-19

Three-electron Auger decay is an exotic and elusive process, in which two outer-shell electrons simultaneously refill an inner-shell double vacancy with emission of a single Auger electron. Such transitions are forbidden by the many-electron selection rules, normally making their decay lifetimes orders of magnitude longer than the few-femtosecond lifetimes of normal (two-electron) Auger decay. Here we present theoretical predictions and direct experimental evidence for a few-femtosecond three-electron Auger decay of a double inner-valence-hole state in CH_{3}F. Our analysis shows that in contrast to double core holes, double inner-valence vacancies in molecules can decay exclusively by this ultrafast three-electron Auger process, and we predict that this phenomenon occurs widely.

A coupled-cluster study of photodetachment cross sections of closed-shell anions

NASA Astrophysics Data System (ADS)

Cukras, Janusz; Decleva, Piero; Coriani, Sonia

2014-11-01

We investigate the performance of Stieltjes Imaging applied to Lanczos pseudo-spectra generated at the coupled cluster singles and doubles, coupled cluster singles and approximate iterative doubles and coupled cluster singles levels of theory in modeling the photodetachment cross sections of the closed shell anions H-, Li-, Na-, F-, Cl-, and OH-. The accurate description of double excitations is found to play a much more important role than in the case of photoionization of neutral species.

A coupled-cluster study of photodetachment cross sections of closed-shell anions.

PubMed

Cukras, Janusz; Decleva, Piero; Coriani, Sonia

2014-11-07

We investigate the performance of Stieltjes Imaging applied to Lanczos pseudo-spectra generated at the coupled cluster singles and doubles, coupled cluster singles and approximate iterative doubles and coupled cluster singles levels of theory in modeling the photodetachment cross sections of the closed shell anions H(-), Li(-), Na(-), F(-), Cl(-), and OH(-). The accurate description of double excitations is found to play a much more important role than in the case of photoionization of neutral species.

Closed solutions of singular equations of thermoelasticity of compositions of shells of revolution smoothly connected with each other

NASA Astrophysics Data System (ADS)

Belostochny, Grigory; Myltcina, Olga

2018-05-01

The paper deals with the main positions of strict continuum model of compositions of shells of revolution smoothly connected with each other. Solutions of singular equations of the membrane conduct thermoelasticity for different species of compositions obtained in a closed form. The ability to eliminate discontinuities of the first kind of one of the tangential force on the lines of the distortion has been proved by using the additional local force impact or temperature.

Inner-shell excitation and ionic fragmentation of molecules

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

Hitchcock, A.P.; Tyliszczak, T.; Cavell, R.G.

1997-04-01

Inner-shell excitation and associated decay spectroscopies are site specific probes of electronic and geometrical structure and photoionization dynamics. X-ray absorption probes the geometric and electronic structure, while time-of-flight mass spectrometry with multi-coincidence detection provides information on the photofragmentation dynamics of the initially produced inner-shell state. Auger decay of inner-shell excited and ionised states is an efficient source of multiply charged ions. The charge separation and fragmentation of these species, studied by photoelectron-photoion-photoion coincidence (also called charge separation mass spectrometry) gives insights into bonding and electronic structure. In molecules, the dependence of the fragmentation process on the X-ray energy can revealmore » cases of site and/or state selective fragmentation. At the ALS the authors have examined the soft X-ray spectroscopy and ionic fragmentation of a number of molecules, including carboranes, silylenes, phosphorus halides, SF{sub 6} and CO{sub 2}. Their work is illustrated using results from the carborane and PF{sub 3} studies.« less

Alloy and heterostructure architectures as promising tools for controlling electronic properties of semiconductor quantum dots

NASA Astrophysics Data System (ADS)

Vaxenburg, Roman; Lifshitz, Efrat

2012-02-01

Tunability of energy levels and wavefunctions of carriers in colloidal quantum dots (CQDs) has a marked effect on numerous physical aspects, such as Coulomb interactions and charge separation, which in turn has a direct impact on the functioning of CQD-based opto-electronic devices. The electronic properties of CQDs are conventionally controlled by variation of their size. Here we demonstrate a theoretical approach to engineer the electronic properties of IV-VI CQDs by introducing an alloy composition in core and core/shell heterostructures, having the general chemical formula PbSexS1-x/PbSeyS1-y (0 ≤ x ≤ 1, 0 ≤ y ≤ 1), while maintaining a constant size. The theoretical model considered an effective mass anisotropy and smooth potential step at the core/shell interface. The model revealed the influence induced by variation of chemical composition and core-to-shell division on the band-gap energy, remote states’ density, internal charge separation, electron-hole Coulomb interaction, and optical transition oscillator strength.

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

Jarrott, L. C.; McGuffey, C.; Beg, F. N.

Fast electron transport and spatial energy deposition are investigated in integrated cone-guided Fast Ignition experiments by measuring fast electron induced copper K-shell emission using a copper tracer added to deuterated plastic shells with a geometrically reentrant gold cone. Experiments were carried out at the Laboratory for Laser Energetics on the OMEGA/OMEGA-EP Laser where the plastic shells were imploded using 54 of the 60 OMEGA60 beams (3ω, 20 kJ), while the high intensity OMEGA-EP (BL2) beam (1 ω, 10 ps, 500 J, I peak > 10 19 W/cm 2) was focused onto the inner cone tip. Here, a retrograde analysis usingmore » the hybrid-PIC electron transport code, ZUMA, is performed to examine the sensitivity of the copper Kα spatial profile on the laser-produced fast electrons, facilitating the optimization of new target point designs and laser configurations to improve the compressed core areal density by a factor of 4 and the fast electron energy coupling by a factor of 3.5.« less

Strongly screening corrections to antineutrino energy loss by β --decay of nuclides 53Fe, 54Fe, 55Fe, and 56Fe in supernova

NASA Astrophysics Data System (ADS)

Liu, Jing-Jing; Liu, Dong-Mei

2018-06-01

Based on the p-f shell-model, we discuss and calculate β--decay half-lives of neutron-rich nuclei, with a consideration of shell and pair effects, the decay energy, and the nucleon numbers. According to the linear response theory model, we study the effect of electron screening on the electron energy, beta-decay threshold energy, and the antineutrino energy loss rate by β--decay of some iron isotopes. We find that the electron screening antineutrino energy loss rates increase by about two orders of magnitude due to the shell effects and the pairing effect. Beta-decay rates with Q-value corrections due to strong electron screening are higher than those without the Q-value corrections by more than two orders of magnitude. Our conclusions may be helpful for the research on numerical simulations of the cooling of stars.

Photophysical Properties of II-VI Semiconductor Nanocrystals

NASA Astrophysics Data System (ADS)

Gong, Ke

As it is well known, semiconductor nanocrystals (also called quantum dots, QDs) are being actively pursued for use in many different types of luminescent optical materials. These materials include the active media for luminescence downconversion in artificial lighting, lasers, luminescent solar concentrators and many other applications. Chapter 1 gives general introduction of QDs, which describe the basic physical properties and optical properties. Based on the experimental spectroscopic study, a semiquantitative method-effective mass model is employed to give theoretical prediction and guide. The following chapters will talks about several topics respectively. A predictive understanding of the radiative lifetimes is therefore a starting point for the understanding of the use of QDs for these applications. Absorption intensities and radiative lifetimes are fundamental properties of any luminescent material. Meantime, achievement of high efficiency with high working temperature and heterostructure fabrication with manipulation of lattice strain are not easy and need systematic investigation. To make accurate connections between extinction coefficients and radiative recombination rates, chapter 2 will consider three closely related aspects of the size dependent spectroscopy of II-VI QDs. First, it will consider the existing literature on cadmium selenide (CdSe) QD absorption spectra and extinction coefficients. From these results and fine structure considerations Boltzmann weighted radiative lifetimes are calculated. These lifetimes are compared to values measured on very high quality CdSe and CdSe coated with zinc selenide (ZnSe) shells. Second, analogous literature data are analyzed for cadmium telluride (CdTe) nanocrystals and compared to lifetimes measured for very high quality QDs. Furthermore, studies of the absorption and excitation spectra and measured radiative lifetimes for CdTe/CdSe Type-II core/shell QDs are reported. These results are also analyzed in terms of a Boltzmann population of exciton sublevels and calculated electron and hole wave functions. Much of the absorption data and fine structure calculations are already in the literature. These results are combined with new measurements of radiative lifetimes and electron-hole overlap calculations to produce an integrated picture of the II-VI QD spectroscopic fundamentals. Finally, we adopt recent synthetic advances to make very monodisperse zincblende CdSe/CdS quantum dots having near-unity photoluminescence quantum yields (PLQYs). Due the absence of nonradiative decay pathways, accurate values of the radiative lifetimes can be obtained from time resolved PL measurements. Radiative lifetimes can also be obtained from the Einstein relations, using the static absorption spectra and the relative thermal populations in the angular momentum sublevels. One of the inputs into these calculations is the shell thickness, and it is useful to be able to determine shell thickness from spectroscopic measurements. We use an empirically corrected effective mass model to produce a "map" of exciton wavelength as a function of core size and shell thickness. These calculations use an elastic continuum model and the known lattice and elastic constants to include the effect of lattice strain on the band gap energy. Radiative lifetimes calculated both experimentally and theoretically are checked and the size dependence is compared to previous studied Type-I, II and single component particles. However, it is not enough to just understanding these basic photophysics of absorption and emission. The emission intensities (related to QYs) also change with changes of the temperature. The temperature dependent PLs of II-VI QDs is extensively studied, but most of this work is at low temperatures. Temperatures well above ambient are of interest to lighting applications and in this regime both the reversible and irreversible loss of quantum yield (thermal quenching) are serious impediments to the implementation of QDs in commercial devices. Chapter 3 will elucidate the mechanism of static thermal quenching, in which the reduction of QYs does not affect the PL decay kinetics, on CdSe, CdTe and CdSe/ZnSe QDs as a function of particle sizes/shapes, surface composition and surface ligands. Through systematic experiments, this part of the dissertation discusses several possible mechanisms (e.g. structural, activated excited state, and electronic charging) and examines which the dominant cause for loss of QY at high temperature is. The more practical step is to develop the synthetic method of highly luminescent and stable core/shell QDs with minimum thermal quenching, which greatly enhance the energy efficiency of light emitting and photovoltaic devices. As the nonradiative Auger processed are induced by surface charging described in chapter 3, static and time-resolved fluorescence and high and low power transient absorption results on CdSe/CdS and CdSe/ZnSe core/shell particles are presented in chapter 4. Two CdS shell thicknesses were examined and all of the particles had either octadecylamine (ODA) and tributylphosphine (TBP) or just ODA ligands. The results can be understood in terms of a mechanism in which there is a thermal equilibrium between electrons being in the valence band or in chalcogenide localized surface states. Thermal promotion of a valence band electron to a surface state leaves the particle core positively charged. Photon absorption when the particle is in this state results in a positive trion, which undergoes a fast Auger recombination, making the particle nonluminescent. A lack of TBP ligands results in more empty surface orbitals and therefore shifts the equilibrium toward surface trapped electrons and hence trion formation. Low- and high-power transient absorption measurements give the trion and biexciton lifetimes and the ratio of the trion to biexciton Auger lifetimes are examined and compared to the degeneracies of Auger pathways. We also study the shell thickness and composition dependence of Auger times, which is compared to the scaling factors of effective volume and electron-hole overlap considerations. Core/shell QDs often exhibit much higher luminescence quantum yields (QYs), more stability, and are depicted as having a nearly spherical core and a shell of very nearly uniform thickness, which results in a very simple picture of surface passivation. The uniformity of the shell is crucial in obtaining QDs with well passivated surfaces. However, transmission electron microscope (TEM) images disprove the ideal situation. Defects and thickness inhomogeneity in shell materials are treated qualitatively as an analog to film thickness inhomogeneity in epitaxially grown thin films. More quantitatively, the extent to which the shell thickness of core/shell particles is constant can be determined by time-resolved PL studies that measure the dynamics of hole tunneling to acceptors that are adsorbed on the shell surface due that tunneling rates varies strongly with core-acceptor separation. Careful analysis of the hole transfer kinetics reveals the extent of shell thickness inhomogeneity, however, it may be complicated by the distribution of numbers of adsorbed acceptors. All the considerations can be incorporated into a model we establish in Chapter 5for the distribution of measured hole tunneling rates. From this analysis the distribution of shell thicknesses can be extracted from the luminescence kinetic results. This approach is therefore a sensitive measure of the distribution of tunneling distances. Thus, any defects or structural irregularities that allow the hole acceptors to adsorb closer to the particle core increases the hole tunneling rate and can be detected and quantified. A quantitative treatment of the lattice strain energy in determining the shell morphology of CdSe/CdS core/shell nanoparticles is presented in chapter 5. We use the inhomogeneity in hole tunneling rates through the shell to adsorbed hole acceptors to quantify the extent of shell thickness inhomogeneity. The results can be understood in terms of a model based on elastic continuum calculations, which indicate that the lattice strain energy depends on both core size and shell thickness. This model assumes thermodynamic equilibrium, i.e., that the shell morphology corresponds to a minimum total (lattice strain plus surface) energy. Comparison with the experimental results indicates that CdSe/CdS nanoparticles undergo an abrupt transition from smooth to rough shells when the total lattice strain energy exceeds about 27eV or the strain energy density exceeds 0.59 eV/nm2. The predictions of this model are not followed for CdSe/CdS nanoparticles when the shell is deposited at very low temperature and therefore equilibrium is not established. The effects of lattice strain on the spectroscopy and photoluminescence quantum yields of zincblende CdSe/CdS core/shell quantum dots are examined. The quantum yields are measured as a function of core size and shell thickness. High quantum yields are achieved as long as the lattice strain energy density is below ~0.85 eV/nm2, which is considerably greater than the limiting value of 0.59 eV/nm2 for thermodynamicstability of a smooth, defect free shell, as previously reported in chapter 5. Thus, core/shell quantum dots having strain energy densities between 0.59 and 0.85 eV/nm2 can have very high PL QYs, but are metastable with respect to surface defect formation. Such metastable core/shell QDs can be produced by shell deposition at comparatively low temperatures (< 140 °C). Annealing of these particles causes partial loss of core pressure, and a red shift of the spectrum.

Characterization of the multilayered shell of a limpet, Lottia kogamogai (Mollusca: Patellogastropoda), using SEM-EBSD and FIB-TEM techniques.

PubMed

Suzuki, Michio; Kameda, Jun; Sasaki, Takenori; Saruwatari, Kazuko; Nagasawa, Hiromichi; Kogure, Toshihiro

2010-08-01

The microstructure and its crystallographic aspect of the shell of a limpet, Lottiakogamogai, have been investigated, as the first step to clarify the mechanism of shell formation in limpet. The shell consists of five distinct layers stacked along the shell thickness direction. Transmission electron microscopy (TEM) with the focused ion beam (FIB) sample preparation technique was primarily adopted, as well as scanning electron microscopy (SEM) with electron back-scattered diffraction (EBSD). The five layers were termed as M+3, M+2, M+1, M, M-1 from the outside to the inside in previous works, where M means myostracum. The outmost M+3 layer consists of calcite with a "mosaic" structure; granular submicron sub-grains with small-angle grain boundaries often accompanying dislocation arrays. M+2 layer consists of flat prismatic aragonite crystals with a leaf-like cross section, stacked obliquely to the shell surface. It looks that the prismatic crystals are surrounded by organic sheets, forming a compartment structure. M+1 and M-1 layers adopt a crossed lamellar structure consisting of aragonite flat prisms with rectangular cross section. M layer has a prismatic structure of aragonite perpendicular to the shell surface and with irregular shaped cross sections. Distinct organic sheets were not observed between the crystals in M+1, M and M-1 layers. The {110} twins are common in all aragonite M+2, M+1, M and M-1 layers, with the twin boundaries parallel to the prisms. These results for the microstructure of each layer should be considered in the discussion of the formation mechanism of the limpet shell structure. Copyright 2010 Elsevier Inc. All rights reserved.

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

Wang Shumin; Tian Hongwei; Pei Yanhui

A novel hedgehog-like core/shell structure, consisting of a high density of vertically aligned graphene sheets and a thin graphene shell/a copper core (VGs-GS/CC), has been synthesized via a simple one-step synthesis route using radio-frequency plasma-enhanced chemical vapor deposition (RF-PECVD). Scanning and transmission electron microscopy investigations show that the morphology of this core/shell material could be controlled by deposition time. For a short deposition time, only multilayer graphene shell tightly surrounds the copper particle, while as the deposition time is relative long, graphene sheets extend from the surface of GS/CC. The GS can protect CC particles from oxidation. The growth mechanismmore » for the obtained GS/CC and VGs-GS/CC has been revealed. Compared to VGs, VGs-GS/CC material exhibits a better electron field emission property. This investigation opens a possibility for designing a core/shell structure of different carbon-metal hybrid materials for a wide variety of practical applications. - Graphical abstract: With increasing deposition time, graphene sheets extend from the surface of GS/CC, causing the multilayer graphene encapsulated copper to be converted into vertically aligned graphene sheets-graphene shell/copper core structure. Highlights: Black-Right-Pointing-Pointer A novel hedgehog-like core/shell structure has been synthesized. Black-Right-Pointing-Pointer The structure consists of vertical graphene sheets-graphene shell and copper core. Black-Right-Pointing-Pointer The morphology of VGs-GS/CC can be controlled by choosing a proper deposition time. Black-Right-Pointing-Pointer With increasing deposition time, graphene sheets extend from the surface of GS/CC. Black-Right-Pointing-Pointer VGs-GS/CC exhibits a better electron field emission property as compared with VGs.« less

Modeling the gain of inner-shell X-ray laser transitions in neon, argon, and copper driven by X-ray free electron laser radiation using photo-ionization and photo-excitation processes

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

Nilsen, Joseph

2015-12-16

Using an X-ray free electron laser (XFEL) at 960 eV to photo-ionize the 1s electron in neutral neon followed by lasing on the 2p-1s transition in singly-ionized neon, an inner-shell X-ray laser was demonstrated at 849 eV in singly-ionized neon gas several years ago. It took decades to demonstrate this scheme, because it required a very strong X-ray source that could photo-ionize the 1s (K shell) electron in neon on a timescale comparable to the intrinsic Auger lifetime in neon of 2 fs. In this paper, we model the neon inner shell X-ray laser under similar conditions to those usedmore » in the XFEL experiments at the SLAC Linac Coherent Light Source (LCLS), and show how we can improve the efficiency of the neon laser and reduce the drive requirements by tuning the XFEL to the 1s-3p transition in neutral neon in order to create gain on the 2p-1s line in neutral neon. We also show how the XFEL could be used to photo-ionize L-shell electrons to drive gain on n = 3–2 transitions in singly-ionized Ar and Cu plasmas. Furthermore, these bright, coherent, and monochromatic X-ray lasers may prove very useful for doing high-resolution spectroscopy and for studying non-linear process in the X-ray regime.« less

Understanding Bright 13 keV Kr K-shell X-ray Sources at the NIF

NASA Astrophysics Data System (ADS)

May, M. J.; Colvin, J. D.; Kemp, G. E.; Fournier, K. B.; Scott, H.; Patel, M.; Barrios, Widmann; Widmann, K.

2015-11-01

High x-ray conversion efficiency (CE) K-shell Kr sources are being investigated for High Energy Density experiments. These sources are 4.1 mm in diameter 4.4 mm tall hollow epoxy tubes having a 40 μm thick wall holding either 1.2 or 1.5 atm of Kr gas. The CE of K-shell Kr is dependent upon the peak electron temperature in the radiating plasma. In the NIF experiments, the available energy heats the source to Te = 6-7 keV, well below the temperature of Te ~25 keV needed to optimize the Kr CE. The CE is a steep function of the peak electron temperature. A spatially averaged electron temperature can be estimated from measured He(α) and Ly(α) line ratios. Some disagreement has been observed in the simulated and measured line ratios for some of these K-shell sources. Disagreements have been observed between the simulated and measured line ratios for some of these K-shell sources. To help understand this issue, Kr gas pipes have been shot with 3 ω light at ?750 kJ at ~210, ~140 TW and ~120 TW power levels with 3.7, 5.2 and 6.7 ns pulses, respectively. The power and pulse length scaling of the measured CE and K-shell line ratios and their comparison to simulations will be discussed. This work was performed under the auspic

Biomineral shell formation under ocean acidification: a shift from order to chaos.

PubMed

Fitzer, Susan C; Chung, Peter; Maccherozzi, Francesco; Dhesi, Sarnjeet S; Kamenos, Nicholas A; Phoenix, Vernon R; Cusack, Maggie

2016-02-15

Biomineral production in marine organisms employs transient phases of amorphous calcium carbonate (ACC) in the construction of crystalline shells. Increasing seawater pCO2 leads to ocean acidification (OA) with a reduction in oceanic carbonate concentration which could have a negative impact on shell formation and therefore survival. We demonstrate significant changes in the hydrated and dehydrated forms of ACC in the aragonite and calcite layers of Mytilus edulis shells cultured under acidification conditions (1000 μatm pCO2) compared to present day conditions (380 μatm pCO2). In OA conditions, Mytilus edulis has more ACC at crystalisation sites. Here, we use the high-spatial resolution of synchrotron X-ray Photo Emission Electron Microscopy (XPEEM) combined with X-ray Absorption Spectroscopy (XAS) to investigate the influence of OA on the ACC formation in the shells of adult Mytilus edulis. Electron Backscatter Diffraction (EBSD) confirms that OA reduces crystallographic control of shell formation. The results demonstrate that OA induces more ACC formation and less crystallographic control in mussels suggesting that ACC is used as a repair mechanism to combat shell damage under OA. However, the resultant reduced crystallographic control in mussels raises concerns for shell protective function under predation and changing environments.

Biomineral shell formation under ocean acidification: a shift from order to chaos

PubMed Central

Fitzer, Susan C.; Chung, Peter; Maccherozzi, Francesco; Dhesi, Sarnjeet S.; Kamenos, Nicholas A.; Phoenix, Vernon R.; Cusack, Maggie

2016-01-01

Biomineral production in marine organisms employs transient phases of amorphous calcium carbonate (ACC) in the construction of crystalline shells. Increasing seawater pCO2 leads to ocean acidification (OA) with a reduction in oceanic carbonate concentration which could have a negative impact on shell formation and therefore survival. We demonstrate significant changes in the hydrated and dehydrated forms of ACC in the aragonite and calcite layers of Mytilus edulis shells cultured under acidification conditions (1000 μatm pCO2) compared to present day conditions (380 μatm pCO2). In OA conditions, Mytilus edulis has more ACC at crystalisation sites. Here, we use the high-spatial resolution of synchrotron X-ray Photo Emission Electron Microscopy (XPEEM) combined with X-ray Absorption Spectroscopy (XAS) to investigate the influence of OA on the ACC formation in the shells of adult Mytilus edulis. Electron Backscatter Diffraction (EBSD) confirms that OA reduces crystallographic control of shell formation. The results demonstrate that OA induces more ACC formation and less crystallographic control in mussels suggesting that ACC is used as a repair mechanism to combat shell damage under OA. However, the resultant reduced crystallographic control in mussels raises concerns for shell protective function under predation and changing environments. PMID:26876022

Biomineral shell formation under ocean acidification: a shift from order to chaos

NASA Astrophysics Data System (ADS)

Fitzer, Susan C.; Chung, Peter; Maccherozzi, Francesco; Dhesi, Sarnjeet S.; Kamenos, Nicholas A.; Phoenix, Vernon R.; Cusack, Maggie

2016-02-01

Biomineral production in marine organisms employs transient phases of amorphous calcium carbonate (ACC) in the construction of crystalline shells. Increasing seawater pCO2 leads to ocean acidification (OA) with a reduction in oceanic carbonate concentration which could have a negative impact on shell formation and therefore survival. We demonstrate significant changes in the hydrated and dehydrated forms of ACC in the aragonite and calcite layers of Mytilus edulis shells cultured under acidification conditions (1000 μatm pCO2) compared to present day conditions (380 μatm pCO2). In OA conditions, Mytilus edulis has more ACC at crystalisation sites. Here, we use the high-spatial resolution of synchrotron X-ray Photo Emission Electron Microscopy (XPEEM) combined with X-ray Absorption Spectroscopy (XAS) to investigate the influence of OA on the ACC formation in the shells of adult Mytilus edulis. Electron Backscatter Diffraction (EBSD) confirms that OA reduces crystallographic control of shell formation. The results demonstrate that OA induces more ACC formation and less crystallographic control in mussels suggesting that ACC is used as a repair mechanism to combat shell damage under OA. However, the resultant reduced crystallographic control in mussels raises concerns for shell protective function under predation and changing environments.

Direct correlations of structural and optical properties of three-dimensional GaN/InGaN core/shell micro-light emitting diodes

NASA Astrophysics Data System (ADS)

Sadat Mohajerani, Matin; Müller, Marcus; Hartmann, Jana; Zhou, Hao; Wehmann, Hergo-H.; Veit, Peter; Bertram, Frank; Christen, Jürgen; Waag, Andreas

2016-05-01

Three-dimensional (3D) InGaN/GaN quantum-well (QW) core-shell light emitting diodes (LEDs) are a promising candidate for the future solid state lighting. In this contribution, we study direct correlations of structural and optical properties of the core-shell LEDs using highly spatially-resolved cathodoluminescence spectroscopy (CL) in combination with scanning electron microscopy (SEM) and scanning transmission electron microscopy (STEM). Temperature-dependent resonant photoluminescence (PL) spectroscopy has been performed to understand recombination mechanisms and to estimate the internal quantum efficiency (IQE).

A comparative study of a (0-3) connectivity type composite and core-shell structure of CoFe2O4 - BaTiO3 based on microstructure and magnetic property

NASA Astrophysics Data System (ADS)

Das, Avisek; Gorige, Venkataiah

2018-04-01

In this work CoFe2O4 (CFO)-BaTiO3 (BTO) composite and core-shell CFO-BTO have been prepared to investigate the effect of microstructure on the magnetic properties. Detailed microstructure analysis has been carried out using X-ray diffraction, field emission scanning electron microscope and transmission electron microscope. Although uniform distribution of CFO is found in BTO matrix for the composite sample, magnetization and coercivity values are more enhanced in core-shell CFO-BTO.

Radiative Properties of Carriers in Cdse-Cds Core-Shell Heterostructured Nanocrystals of Various Geometries

NASA Astrophysics Data System (ADS)

Zhou, S.; Dong, L.; Popov, S.; Friberg, A. T.

2013-07-01

We report a model on core-shell heterostructured nanocrystals with CdSe as the core and CdS as the shell. The model is based on one-band Schrödinger equation. Three different geometries, nanodot, nanorod, and nanobone, are implemented. The carrier localization regimes with these structures are simulated, compared, and analyzed. Based on the electron and hole wave functions, the carrier overlap integral that has a great impact on stimulated emission is further investigated numerically by a novel approach. Furthermore, the relation between the nanocrystal size and electron-hole recombination energy is also examined.

Transport and spatial energy deposition of relativistic electrons in copper-doped fast ignition plasmas

DOE PAGES

Jarrott, L. C.; McGuffey, C.; Beg, F. N.; ...

2017-10-24

Fast electron transport and spatial energy deposition are investigated in integrated cone-guided Fast Ignition experiments by measuring fast electron induced copper K-shell emission using a copper tracer added to deuterated plastic shells with a geometrically reentrant gold cone. Experiments were carried out at the Laboratory for Laser Energetics on the OMEGA/OMEGA-EP Laser where the plastic shells were imploded using 54 of the 60 OMEGA60 beams (3ω, 20 kJ), while the high intensity OMEGA-EP (BL2) beam (1 ω, 10 ps, 500 J, I peak > 10 19 W/cm 2) was focused onto the inner cone tip. Here, a retrograde analysis usingmore » the hybrid-PIC electron transport code, ZUMA, is performed to examine the sensitivity of the copper Kα spatial profile on the laser-produced fast electrons, facilitating the optimization of new target point designs and laser configurations to improve the compressed core areal density by a factor of 4 and the fast electron energy coupling by a factor of 3.5.« less

Structural and Magnetic Response in Bimetallic Core/Shell Magnetic Nanoparticles

PubMed Central

Nairan, Adeela; Khan, Usman; Iqbal, Munawar; Khan, Maaz; Javed, Khalid; Riaz, Saira; Naseem, Shahzad; Han, Xiufeng

2016-01-01

Bimagnetic monodisperse CoFe2O4/Fe3O4 core/shell nanoparticles have been prepared by solution evaporation route. To demonstrate preferential coating of iron oxide onto the surface of ferrite nanoparticles X-ray diffraction (XRD), High resolution transmission electron microscope (HR-TEM) and Raman spectroscopy have been performed. XRD analysis using Rietveld refinement technique confirms single phase nanoparticles with average seed size of about 18 nm and thickness of shell is 3 nm, which corroborates with transmission electron microscopy (TEM) analysis. Low temperature magnetic hysteresis loops showed interesting behavior. We have observed large coercivity 15.8 kOe at T = 5 K, whereas maximum saturation magnetization (125 emu/g) is attained at T = 100 K for CoFe2O4/Fe3O4 core/shell nanoparticles. Saturation magnetization decreases due to structural distortions at the surface of shell below 100 K. Zero field cooled (ZFC) and Field cooled (FC) plots show that synthesized nanoparticles are ferromagnetic till room temperature and it has been noticed that core/shell sample possess high blocking temperature than Cobalt Ferrite. Results indicate that presence of iron oxide shell significantly increases magnetic parameters as compared to the simple cobalt ferrite. PMID:28335200

M-shell electron capture and direct ionization of gold by 25-MeV carbon and 32-MeV oxygen ions

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

Andrews, M.C.; McDaniel, F.D.; Duggan, J.L.

1984-01-01

M-shell x-ray production cross sections have been measured for thin solid targets of Au for 25 MeV /sup 12/C/sup q+/ (q = 4, 5, 6) and for 32 MeV /sup 16/O/sup q+/ (q = 5, 7, 8). The microscopic cross sections were determined from measurements made with targets ranging in thickness from 0.5 to 100 ..mu..g/cm/sup 2/. For projectiles with one or two K-shell vacancies, the M-shell x-ray production cross sections are found to be enhanced over those by projectiles without a K-shell vacancy. The sum of direct ionization to the continuum (DI) and electron capture (EC) to the L,more » M, N ... shells and EC to the K-shell of the projectile have been extracted from the data. The results are compared to the predictions of first Born theories i.e. PWBA for DI and OBK of Nikolaev for EC and the ECPSSR approach that accounts for energy loss, Coulomb deflection and relativistic effects in the perturbed stationary state theory. 25 references, 3 figures, 1 table.« less

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

Müller, Alfred; Bernhardt, Dietrich; Borovik, Alexander

Single, double, and triple photoionization of Ne + ions by single photons have been investigated at the synchrotron radiation source PETRA III in Hamburg, Germany. Absolute cross-sections were measured by employing the photon-ion merged-beams technique. Photon energies were between about 840 and 930 eV, covering the range from the lowest-energy resonances associated with the excitation of one single K-shell electron up to double excitations involving one K- and one L-shell electron, well beyond the K-shell ionization threshold. Also, photoionization of neutral Ne was investigated just below the K edge. The chosen photon energy bandwidths were between 32 and 500 meV,more » facilitating the determination of natural line widths. The uncertainty of the energy scale is estimated to be 0.2 eV. For comparison with existing theoretical calculations, astrophysically relevant photoabsorption cross-sections were inferred by summing the measured partial ionization channels. Discussion of the observed resonances in the different final ionization channels reveals the presence of complex Auger-decay mechanisms. The ejection of three electrons from the lowest K-shell-excited Ne + (1s2s 2p 6 2S 1/2) level, for example, requires cooperative interaction of at least four electrons.« less

A new LiNbO{sub 3}-type polar oxide with closed-shell cations: ZnPbO{sub 3}

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

Yu, Runze, E-mail: yu.r.aa@m.titech.ac.jp, E-mail: mazuma@msl.titech.ac.jp; Hojo, Hajime; Azuma, Masaki, E-mail: yu.r.aa@m.titech.ac.jp, E-mail: mazuma@msl.titech.ac.jp

2015-09-07

A new lithium-niobate (LiNbO{sub 3})-type polar compound, namely, ZnPbO{sub 3} (a = 5.41605(7) Å and c = 14.33151(3) Å), with closed-shell ions only was synthesized under high pressure and high temperature (8 GPa and 1273 K). A point-charge-model calculation based on atomic positions refined by Rietveld analysis of synchrotron X-ray diffraction data gave an electrical ionic polarization of 77 μC/cm{sup 2} along the hexagonal c-axis. Detailed structural analysis indicated that the contribution of Pb{sup 4+} in ZnPbO{sub 3} to the polarization was almost twice as large as that of Sn{sup 4+} in ZnSnO{sub 3}. Transport measurement showed metallic behavior of ZnPbO{sub 3} from room temperature to lowmore » temperature despite the fact that both cations are closed-shell ions.« less

Switchable Opening and Closing of a Liquid Marble via Ultrasonic Levitation.

PubMed

Zang, Duyang; Li, Jun; Chen, Zhen; Zhai, Zhicong; Geng, Xingguo; Binks, Bernard P

2015-10-27

Liquid marbles have promising applications in the field of microreactors, where the opening and closing of their surfaces plays a central role. We have levitated liquid water marbles using an acoustic levitator and, thereby, achieved the manipulation of the particle shell in a controlled manner. Upon increasing the sound intensity, the stable levitated liquid marble changes from a quasi-sphere to a flattened ellipsoid. Interestingly, a cavity on the particle shell can be produced on the polar areas, which can be completely healed when decreasing the sound intensity, allowing it to serve as a microreactor. The integral of the acoustic radiation pressure on the part of the particle surface protruding into air is responsible for particle migration from the center of the liquid marble to the edge. Our results demonstrate that the opening and closing of the liquid marble particle shell can be conveniently achieved via acoustic levitation, opening up a new possibility to manipulate liquid marbles coated with non-ferromagnetic particles.

The close circumstellar environment of the semi-regular S-type star π 1 Gruis

NASA Astrophysics Data System (ADS)

Sacuto, S.; Jorissen, A.; Cruzalèbes, P.; Chesneau, O.; Ohnaka, K.; Quirrenbach, A.; Lopez, B.

2008-05-01

Aims: We study the close circumstellar environment of the nearby S-type star π1 Gruis using high spatial-resolution, mid-infrared observations from the ESO/VLTI. Methods: Spectra and visibilities were obtained with the MIDI interferometer on the VLT Auxiliary Telescopes. The cool M5III giant β Gruis was used as bright primary calibrator, and a dedicated spectro-interferometric study was undertaken to determine its angular diameter accurately. The MIDI measurements were fitted with the 1D numerical radiative transfer code DUSTY to determine the dust shell parameters of π1 Gruis. Taking into account the low spatial extension of the model in the 8-9 μm spectral band for the smallest projected baselines, we consider the possibility of a supplementary molecular shell. Results: The MIDI visibility and phase data are mostly dominated by the spherical 21 mas (694 R_⊙) central star, while the extended dusty environment is over-resolved even with the shortest baselines. No obvious departure from spherical symmetry is found on the milliarcsecond scale. The spectro-interferometric observations are well-fitted by an optically thin (τ_dust<0.01 in the N band) dust shell that is located at about 14 stellar radii with a typical temperature of 700 K and composed of 70% silicate and 30% of amorphous alumina grains. An optically thin (τ_mol<0.1 in the N band) H{2}O + SiO molecular shell extending from the photosphere of the star up to 4.4 stellar radii with a typical temperature of 1000 K is added to the model to improve the fit in the 8-9 μm spectral band. We discuss the probable binary origin of asymmetries as revealed by millimetric observations. Based on observations made with the Very Large Telescope Interferometer at Paranal Observatory under programs 077.D-0294(D/E/F). Reduced visibilities and differential phases are available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/cgi-bin/qcat?J/A+A/482/561

A divalent rare earth oxide semiconductor: Yttrium monoxide

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

Kaminaga, Kenichi; Sei, Ryosuke; Department of Chemistry, Tohoku University, Sendai 980-8578

Rare earth oxides are usually widegap insulators like Y{sub 2}O{sub 3} with closed shell trivalent rare earth ions. In this study, solid phase rock salt structure yttrium monoxide, YO, with unusual valence of Y{sup 2+} (4d{sup 1}) was synthesized in a form of epitaxial thin film by pulsed laser deposition method. YO has been recognized as gaseous phase in previous studies. In contrast with Y{sub 2}O{sub 3}, YO was dark-brown colored and narrow gap semiconductor. The tunable electrical conductivity ranging from 10{sup −1} to 10{sup 3} Ω{sup −1 }cm{sup −1} was attributed to the presence of oxygen vacancies serving as electron donor.more » Weak antilocalization behavior observed in magnetoresistance indicated significant role of spin-orbit coupling as a manifestation of 4d electron carrier.« less

Communication: Nuclear quadrupole moment-induced Cotton-Mouton effect in noble gas atoms

NASA Astrophysics Data System (ADS)

Fu, Li-juan; Rizzo, Antonio; Vaara, Juha

2013-11-01

New, high-sensitivity and high-resolution spectroscopic and imaging methods may be developed by exploiting nuclear magneto-optic effects. A first-principles electronic structure formulation of nuclear electric quadrupole moment-induced Cotton-Mouton effect (NQCME) is presented for closed-shell atoms. In NQCME, aligned quadrupole moments alter the index of refraction of the medium along with and perpendicular to the direction of nuclear alignment. The roles of basis-set convergence, electron correlation, and relativistic effects are investigated for three quadrupolar noble gas isotopes: 21Ne, 83Kr, and 131Xe. The magnitude of the resulting ellipticities is predicted to be 10-4-10-6 rad/(M cm) for fully spin-polarized nuclei. These should be detectable in the Voigt setup. Particularly interesting is the case of 131Xe, in which a high degree of spin polarization can be achieved via spin-exchange optical hyperpolarization.

Molecular structure, vibrational spectral assignments (FT-IR and FT-RAMAN), NMR, NBO, HOMO-LUMO and NLO properties of O-methoxybenzaldehyde based on DFT calculations

NASA Astrophysics Data System (ADS)

Vennila, P.; Govindaraju, M.; Venkatesh, G.; Kamal, C.

2016-05-01

Fourier transform - Infra red (FT-IR) and Fourier transform - Raman (FT-Raman) spectroscopic techniques have been carried out to analyze O-methoxy benzaldehyde (OMB) molecule. The fundamental vibrational frequencies and intensity of vibrational bands were evaluated using density functional theory (DFT). The vibrational analysis of stable isomer of OMB has been carried out by FT-IR and FT-Raman in combination with theoretical method simultaneously. The first-order hyperpolarizability and the anisotropy polarizability invariant were computed by DFT method. The atomic charges, hardness, softness, ionization potential, electronegativity, HOMO-LUMO energies, and electrophilicity index have been calculated. The 13C and 1H Nuclear magnetic resonance (NMR) have also been obtained by GIAO method. Molecular electronic potential (MEP) has been calculated by the DFT calculation method. Electronic excitation energies, oscillator strength and excited states characteristics were computed by the closed-shell singlet calculation method.

One-pot synthesis of iniferter-bound polystyrene core nanoparticles for the controlled grafting of multilayer shells

NASA Astrophysics Data System (ADS)

Marchyk, Nataliya; Maximilien, Jacqueline; Beyazit, Selim; Haupt, Karsten; Sum Bui, Bernadette Tse

2014-02-01

A novel approach using one-pot synthesis for the production of uniform, iniferter-bound polystyrene core nanoparticles of size 30-40 nm is described. Conventional oil-in-water emulsion polymerisation of styrene and divinylbenzene, combining a hybrid initiation system (thermal and UV), triggered sequentially, was employed to form the surface-bound thiocarbamate iniferters in situ. The iniferter cores were then used as seeds for re-initiating further polymerisation by UV irradiation to produce water-compatible core-shell nanoparticles. Grafting of various shell-types is demonstrated: linear polymers of poly(N-isopropylacrylamide) brushes, crosslinked polymers bearing different surface charges and molecularly imprinted polymers. The shell thickness was readily tuned by varying the monomers' concentration and polymerisation time. Our method is straightforward and in addition, gives access to the preparation of fluorescent seeds and the possibility of grafting nanosized multiple shells. The core-shell nanoparticles were fully characterised by dynamic light scattering, transmission electron microscopy, Fourier transform infrared spectroscopy and microelemental analysis.A novel approach using one-pot synthesis for the production of uniform, iniferter-bound polystyrene core nanoparticles of size 30-40 nm is described. Conventional oil-in-water emulsion polymerisation of styrene and divinylbenzene, combining a hybrid initiation system (thermal and UV), triggered sequentially, was employed to form the surface-bound thiocarbamate iniferters in situ. The iniferter cores were then used as seeds for re-initiating further polymerisation by UV irradiation to produce water-compatible core-shell nanoparticles. Grafting of various shell-types is demonstrated: linear polymers of poly(N-isopropylacrylamide) brushes, crosslinked polymers bearing different surface charges and molecularly imprinted polymers. The shell thickness was readily tuned by varying the monomers' concentration and polymerisation time. Our method is straightforward and in addition, gives access to the preparation of fluorescent seeds and the possibility of grafting nanosized multiple shells. The core-shell nanoparticles were fully characterised by dynamic light scattering, transmission electron microscopy, Fourier transform infrared spectroscopy and microelemental analysis. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr05295h

Exchange and Inelastic OH(+) + H Collisions on the Doublet and Quartet Electronic States.

PubMed

Bulut, Niyazi; Lique, François; Roncero, Octavio

2015-12-17

The exchange and inelastic state-to-state cross sections for the OH(+) + H collisions are computed from wave packet calculations using the doublet and quartet ground electronic potential energy surface (PES) correlating to the open shell reactants, for collision energies in the range of 1 meV to 0.7 eV. The doublet PES presents a deep insertion well, of ≈6 eV, but the exchange reaction has a rather low probability, showing that the mechanism is not statistical. This well is also responsible of a rather high rotational energy transfer, which makes the rigid-rotor approach overestimate the cross section for low Δj transitions and for high collisonal energies. The quartet PES, with a much shallower well, also presents a low exchange reaction cross section, but the inelastic state-to-state cross sections are very well reproduced by rigid-rotor calculations. When the electronic partition is used to obtain the total state-to-state cross section, the contribution of the doublet state becomes small, and the resulting total cross sections become close to those obtained for the quartet state. Thus, the total (quartet and doublet) cross sections for this open shell system can be reproduced rather satisfactorily by those obtained with the rigid-rotor approximation on the quartet state. Finally, we compare the new OH(+)-H cross sections with OH(+)-He ones recently computed. We found significant differences, especially for transitions with large Δj showing that specific OH(+)-H calculations had to be performed to accurately analyze the OH(+) emission from interstellar molecular clouds.

Nature of ground and electronic excited states of higher acenes

PubMed Central

Yang, Yang; Yang, Weitao

2016-01-01

Higher acenes have drawn much attention as promising organic semiconductors with versatile electronic properties. However, the nature of their ground state and electronic excited states is still not fully clear. Their unusual chemical reactivity and instability are the main obstacles for experimental studies, and the potentially prominent diradical character, which might require a multireference description in such large systems, hinders theoretical investigations. Here, we provide a detailed answer with the particle–particle random-phase approximation calculation. The 1Ag ground states of acenes up to decacene are on the closed-shell side of the diradical continuum, whereas the ground state of undecacene and dodecacene tilts more to the open-shell side with a growing polyradical character. The ground state of all acenes has covalent nature with respect to both short and long axes. The lowest triplet state 3B2u is always above the singlet ground state even though the energy gap could be vanishingly small in the polyacene limit. The bright singlet excited state 1B2u is a zwitterionic state to the short axis. The excited 1Ag state gradually switches from a double-excitation state to another zwitterionic state to the short axis, but always keeps its covalent nature to the long axis. An energy crossing between the 1B2u and excited 1Ag states happens between hexacene and heptacene. Further energetic consideration suggests that higher acenes are likely to undergo singlet fission with a low photovoltaic efficiency; however, the efficiency might be improved if a singlet fission into multiple triplets could be achieved. PMID:27528690

The mechanism of oxidation in chromophore maturation of wild-type green fluorescent protein: a theoretical study.

PubMed

Ma, Yingying; Sun, Qiao; Smith, Sean C

2017-05-24

Oxidation is viewed as the second and rate-limiting step in the chromophore maturation process of the wild-type green fluorescent protein (GFP) under aerobic conditions. Molecular oxygen is the necessary oxidant for GFP chromophore biosynthesis. In this study, density functional theory (DFT) calculations were employed to study the mechanism of oxidation. Our results indicate that the deprotonation of the Tyr66 α-carbon is probably the rate-limiting step in the oxidation step. Electron transfer from the enolate form of the five-membered heterocycle (EFMH) to molecular oxygen, generating the triplet radical complex [EFMH˙O 2 - ˙] T , is an important step. This complex undergoes intersystem crossing to form an open-shell singlet diradical complex before it forms the closed-shell singlet hydroperoxy adduct. The formation of the hydroperoxy adduct is a proton-coupled electron transfer process. The energy barrier of H 2 O 2 elimination is 16.5 kcal mol -1 . The oxidation product IFMHH 2 O 2 that we discovered is a hydroxylated cyclic imine structure, which is consistent with the crystal structure trapped in the colorless Y66L variant. The relative energy of the oxidation product is -48.7 kcal mol -1 , which is in accordance with the experimental observation that the thermodynamically unfavourable cyclized product is trapped by oxidation. The results herein support the cyclization-oxidation-dehydration mechanism for the chromophore maturation of GFP.

Structure determination in 55-atom Li-Na and Na-K nanoalloys.

PubMed

Aguado, Andrés; López, José M

2010-09-07

The structure of 55-atom Li-Na and Na-K nanoalloys is determined through combined empirical potential (EP) and density functional theory (DFT) calculations. The potential energy surface generated by the EP model is extensively sampled by using the basin hopping technique, and a wide diversity of structural motifs is reoptimized at the DFT level. A composition comparison technique is applied at the DFT level in order to make a final refinement of the global minimum structures. For dilute concentrations of one of the alkali atoms, the structure of the pure metal cluster, namely, a perfect Mackay icosahedron, remains stable, with the minority component atoms entering the host cluster as substitutional impurities. At intermediate concentrations, the nanoalloys adopt instead a core-shell polyicosahedral (p-Ih) packing, where the element with smaller atomic size and larger cohesive energy segregates to the cluster core. The p-Ih structures show a marked prolate deformation, in agreement with the predictions of jelliumlike models. The electronic preference for a prolate cluster shape, which is frustrated in the 55-atom pure clusters due to the icosahedral geometrical shell closing, is therefore realized only in the 55-atom nanoalloys. An analysis of the electronic densities of states suggests that photoelectron spectroscopy would be a sufficiently sensitive technique to assess the structures of nanoalloys with fixed size and varying compositions.

Electronic Structures and Optical Properties of α-Al2O3Nanowires

NASA Astrophysics Data System (ADS)

Wang, Zhiqiang; Li, Chunlei; Liu, Lijia; Sham, Tsun-Kong

2013-04-01

The electronic structure and optical properties of α-Al2O3 nanowires (NWs) have been investigated using X-ray absorption near-edge structures (XANES) and X-ray excited optical luminescence (XEOL). The XANES were recorded in total electron yield (TEY) and total fluorescence yield (TFY) across the K- and L3,2-edges of aluminium and the K-edge of oxygen. The results indicate that the NWs are of a core/shell structure with a single-crystalline core and an amorphous shell. The XEOL spectra of the NWs show an intense peak at 404 nm, which comes from the F centre located in the amorphous shell of the NWs. The implication of these findings and the sensitivity of XEOL for defect detection are discussed.

Diffraction data of core-shell nanoparticles from an X-ray free electron laser

DOE PAGES

Li, Xuanxuan; Chiu, Chun -Ya; Wang, Hsiang -Ju; ...

2017-04-11

X-ray free-electron lasers provide novel opportunities to conduct single particle analysis on nanoscale particles. Coherent diffractive imaging experiments were performed at the Linac Coherent Light Source (LCLS), SLAC National Laboratory, exposing single inorganic core-shell nanoparticles to femtosecond hard-X-ray pulses. Each facetted nanoparticle consisted of a crystalline gold core and a differently shaped palladium shell. Scattered intensities were observed up to about 7 nm resolution. Analysis of the scattering patterns revealed the size distribution of the samples, which is consistent with that obtained from direct real-space imaging by electron microscopy. Furthermore, scattering patterns resulting from single particles were selected and compiledmore » into a dataset which can be valuable for algorithm developments in single particle scattering research.« less

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

Richter, W. A.; Brown, B. Alex

Assignments are made between theory and experiment of corresponding levels in {sup 26}Mg levels based on energies, lifetimes, branching ratios, electron scattering form factors, and reduced electromagnetic transition strengths. Results based on the new sd-shell interactions USDA (universal sd-shell interaction A) and USDB (universal sd-shell interaction B), as well as the older USD interaction, are compared.

Effect of palladium doping on the stability and fragmentation patterns of cationic gold clusters

NASA Astrophysics Data System (ADS)

Ferrari, P.; Hussein, H. A.; Heard, C. J.; Vanbuel, J.; Johnston, R. L.; Lievens, P.; Janssens, E.

2018-05-01

We analyze in detail how the interplay between electronic structure and cluster geometry determines the stability and the fragmentation channels of single Pd-doped cationic Au clusters, PdA uN-1+ (N =2 -20 ). For this purpose, a combination of photofragmentation experiments and density functional theory calculations was employed. A remarkable agreement between the experiment and the calculations is obtained. Pd doping is found to modify the structure of the Au clusters, in particular altering the two-dimensional to three-dimensional transition size, with direct consequences on the stability of the clusters. Analysis of the electronic density of states of the clusters shows that depending on cluster size, Pd delocalizes one 4 d electron, giving an enhanced stability to PdA u6 + , or remains with all 4 d10 electrons localized, closing an electronic shell in PdA u9 + . Furthermore, it is observed that for most clusters, Au evaporation is the lowest-energy decay channel, although for some sizes Pd evaporation competes. In particular, PdA u7 + and PdA u9 + decay by Pd evaporation due to the high stability of the A u7 + and A u9 + fragmentation products.

Electrochemical oxygen reduction behavior of selectively deposited platinum atoms on gold nanoparticles.

PubMed

Sarkar, A; Kerr, J B; Cairns, E J

2013-07-22

Carbon-supported Pt@Au "core-shell" nanoparticles with varying surface concentration of platinum atoms have been synthesized using a novel redox-mediated synthesis approach. The synthesis technique allows for a selective deposition of platinum atoms on the surface of prefabricated gold nanoparticles. Energy dispersive spectroscopic analyses in a scanning electron microscope reveal that the platinum to gold atomic ratios are close to the nominal values, validating the synthesis scheme. X-ray diffraction data indicate an un-alloyed structure. The platinum to gold surface atomic ratio determined from cyclic voltammetry and copper under-potential deposition experiments reveal good agreement with the calculated values at low platinum concentration. However, there is an increase in non-uniformity in the deposition process upon increasing the platinum concentration. Koutecky-Levich analysis of the samples indicates a transition of the total number of electrons transferred (n) in the electrochemical oxygen reduction reaction from two to four electrons upon increasing the surface concentration of platinum atoms. Furthermore, the data indicate that isolated platinum atoms can reduce molecular oxygen but via a two-electron route. Moreover, successful four-electron reduction of molecular oxygen requires clusters of platinum atoms. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nuclear Data Evaluation for Mass Chain A=217:Odd-Proton Nuclei

PubMed Central

Nafee, Sherif S.; Shaheen, Salem A.; Al-Ramady, Amir M.

2016-01-01

Thallium (Tl81217), Bismuth (Bi83217), Astatine (At85217), Francium (Fr87217), Actinium (Ac89217) and Protactinium (Pa91217) are of odd-proton numbers among the mass chain A = 217. In the present work, the half-lives and gamma transitions for the six nuclei have been studied and adopted based on the recently published interactions or unevaluated nuclear data sets XUNDL. The Q (α) has been updated based on the recent published work of the Atomic Mass Evaluation AME2012 as well. Moreover, the total conversion electrons as well as the K-Shell to L-Shell, L-Shell to M-Shell and L-Shell to N-Shell Conversion Electron Ratios have been calculated using BrIcc code v2.3. An updated skeleton decay scheme for each of the above nuclei has been presented here. The decay hindrance factors (HF) calculated using the ALPHAD program, which is available from Brookhaven National Laboratory’s website, have been calculated for the α- decay data sets for 221Fr-, 221Ac- and 221Pa- α-decays. PMID:26761207

Dye-sensitized solar cells employing a SnO2-TiO2 core-shell structure made by atomic layer deposition.

PubMed

Karlsson, Martin; Jõgi, Indrek; Eriksson, Susanna K; Rensmo, Håkan; Boman, Mats; Boschloo, Gerrit; Hagfeldt, Anders

2013-01-01

This paper describes the synthesis and characterization of core-shell structures, based on SnO2 and TiO2, for use in dye-sensitized solar cells (DSC). Atomic layer deposition is employed to control and vary the thickness of the TiO2 shell. Increasing the TiO2 shell thickness to 2 nm improved the device performance of liquid electrolyte-based DSC from 0.7% to 3.5%. The increase in efficiency originates from a higher open-circuit potential and a higher short-circuit current, as well as from an improvement in the electron lifetime. SnO2-TiO2 core-shell DSC devices retain their photovoltage in darkness for longer than 500 seconds, demonstrating that the electrons are contained in the core material. Finally core-shell structures were used for solid-state DSC applications using the hole transporting material 2,2',7,7',-tetrakis(N, N-di-p-methoxyphenyl-amine)-9,9',-spirofluorene. Similar improvements in device performance were obtained for solid-state DSC devices.

Ultrafast Recombination Dynamics in Dye-Sensitized SnO2/TiO2 Core/Shell Films.

PubMed

Gish, Melissa K; Lapides, Alexander M; Brennaman, M Kyle; Templeton, Joseph L; Meyer, Thomas J; Papanikolas, John M

2016-12-15

Interfacial dynamics are investigated in SnO 2 /TiO 2 core/shell films derivatized with a Ru(II)-polypyridyl chromophore ([Ru II (bpy) 2 (4,4'-(PO 3 H 2 ) 2 bpy)] 2+ , RuP) using transient absorption methods. Electron injection from the chromophore into the TiO 2 shell occurs within a few picoseconds after photoexcitation. Loss of the oxidized dye through recombination occurs across time scales spanning 10 orders of magnitude. The majority (60%) of charge recombination events occur shortly after injection (τ = 220 ps), while a small fraction (≤20%) of the oxidized chromophores persists for milliseconds. The lifetime of long-lived charge-separated states (CSS) depends exponentially on shell thickness, suggesting that the injected electrons reside in the SnO 2 core and must tunnel through the TiO 2 shell to recombine with oxidized dyes. While the core/shell architecture extends the lifetime in a small fraction of the CSS, making water oxidation possible, the subnanosecond recombination process has profound implications for the overall efficiencies of dye-sensitized photoelectrosynthesis cells (DSPECs).

Ultrafast recombination dynamics in dye-sensitized SnO 2/TiO 2 core/shell films

DOE PAGES

Gish, Melissa K.; Lapides, Alexander M.; Brennaman, M. Kyle; ...

2016-12-02

In dye-sensitized photoelectrosynthesis cells (DSPECs), molecular chromophores and catalysts are integrated on a semiconductor surface to perform water oxidation or CO 2 reduction after a series of light-induced electron transfer events. Unfortunately, recombination of the charge separated state (CSS) is competitive with productive catalysis. To overcome this major obstacle, implementation of photoanodic core/shell films within these devices improve electrochemical behavior and slow recombination through the introduction of an energetic barrier between the semiconductor core and oxidized species on the surface. In this study, interfacial dynamics are investigated in SnO 2/TiO 2 core/shell films derivatized with a Ru(II)-polypyridyl chromophore ([RuII(bpy)2(4,4'-(PO 3Hmore » 2) 2bpy)] 2+, RuP) using transient absorption methods. Electron injection from the chromophore into the TiO 2 shell occurs within a few picoseconds after photoexcitation. Loss of the oxidized dye through recombination occurs across time scales spanning 10 orders of magnitude. The majority (60%) of charge recombination events occur shortly after injection (τ = 220 ps), while a small fraction (≤20%) of the oxidized chromophores persists for milliseconds. The lifetime of long-lived CSS depends exponentially on shell thickness, suggesting that the injected electrons reside in the SnO 2 core and must tunnel through the TiO 2 shell to recombine with oxidized dyes. While the core/shell architecture extends the lifetime in a small fraction of the CSS, making water oxidation possible, the subnanosecond recombination process has profound implications for the overall efficiencies of DSPECs.« less

Coulomb excitations for a short linear chain of metallic shells

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

Zhemchuzhna, Liubov, E-mail: lzhemchuzhna@unm.edu; Center for High Technology Materials, University of New Mexico, Albuquerque, New Mexico 87106; Gumbs, Godfrey

2015-03-15

A self-consistent-field theory is given for the electronic collective modes of a chain containing a finite number, N, of Coulomb-coupled spherical two-dimensional electron gases arranged with their centers along a straight line, for simulating electromagnetic response of a narrow-ribbon of metallic shells. The separation between nearest-neighbor shells is arbitrary and because of the quantization of the electron energy levels due to their confinement to the spherical surface, all angular momenta L of the Coulomb excitations, as well as their projections M on the quantization axis, are coupled. However, for incoming light with a given polarization, only one angular momentum quantummore » number is usually required. Therefore, the electromagnetic response of the narrow-ribbon of metallic shells is expected to be controlled externally by selecting different polarizations for incident light. We show that, when N = 3, the next-nearest-neighbor Coulomb coupling is larger than its value if they are located at opposite ends of a right-angle triangle forming the triad. Additionally, the frequencies of the plasma excitations are found to depend on the orientation of the line joining them with respect to the axis of quantization since the magnetic field generated from the induced oscillating electric dipole moment on one sphere can couple to the induced magnetic dipole moment on another. Although the transverse inter-shell electromagnetic coupling can be modeled by an effective dynamic medium, the longitudinal inter-shell Coulomb coupling, on the other hand, can still significantly modify the electromagnetic property of this effective medium between shells.« less

Localized surface plasmon mediated energy transfer in the vicinity of core-shell nanoparticle

NASA Astrophysics Data System (ADS)

Shishodia, Manmohan Singh; Juneja, Soniya

2016-05-01

Multipole spectral expansion based theory of energy transfer interactions between a donor and an acceptor molecule in the vicinity of a core-shell (nanoshell or core@shell) based plasmonic nanostructure is developed. In view of the diverse applications and rich plasmonic features such as tuning capability of surface plasmon (SP) frequencies, greater sensitivity to the change of dielectric environment, controllable redirection of electromagnetic radiation, closed form expressions for Energy Transfer Rate Enhancement Factor (ETREF) near core-shell particle are reported. The dependence of ETREF on different parameters is established through fitting equations, perceived to be of key importance for developing appropriate designs. The theoretical approach developed in the present work is capable of treating higher order multipoles, which, in turn, are also shown to play a crucial role in the present context. Moreover, closed form expressions derived in the present work can directly be used as formula, e.g., for designing SP based biosensors and estimating energy exchange between proteins and excitonic interactions in quantum dots.

Shape coexistence from lifetime and branching-ratio measurements in 68,70Ni

DOE PAGES

Crider, B. P.; Prokop, C. J.; Liddick, S. N.; ...

2016-10-15

Shape coexistence near closed-shell nuclei, whereby states associated with deformed shapes appear at relatively low excitation energy alongside spherical ones, is indicative of the rapid change in structure that can occur with the addition or removal of a few protons or neutrons. Near 68Ni (Z=28, N=40), the identification of shape coexistence hinges on hitherto undetermined transition rates to and from low-energy 0 + states. In 68,70Ni, new lifetimes and branching ratios have been measured. These data enable quantitative descriptions of the 0 + states through the deduced transition rates and serve as sensitive probes for characterizing their nuclear wave functions.more » The results are compared to, and consistent with, large-scale shell-model calculations which predict shape coexistence. With the firm identification of this phenomenon near 68Ni, shape coexistence is now observed in all currently accessible regions of the nuclear chart with closed proton shells and mid-shell neutrons.« less

Nanocrystalline p-hydroxyacetanilide (paracetamol) and gold core-shell structure as a model drug deliverable organic-inorganic hybrid nanostructure

NASA Astrophysics Data System (ADS)

Das, Subhojit; Paul, Anumita; Chattopadhyay, Arun

2013-09-01

We report on the generation of core-shell nanoparticles (NPs) having an organic nanocrystal (NC) core coated with an inorganic metallic shell, being dispersed in aqueous medium. First, NCs of p-hydroxyacetanilide (pHA)--known also as paracetamol--were generated in an aqueous medium. Transmission electron microscopy (TEM) and powder X-ray diffraction (XRD) evidenced the formation of pHA NCs and of their crystalline nature. The NCs were then coated with Au to form pHA@Au core-shell NPs, where the thickness of the Au shell was on the order of nanometers. The formation of Au nanoshell--surrounding pHA NC--was confirmed from its surface plasmon resonance (SPR) band in the UV/Vis spectrum and by TEM measurements. Further, on treatment of the core-shell particles with a solution comprising NaCl and HCl (pH < 3), the Au shell could be dissolved, subsequently releasing pHA molecules. The dissolution of Au shell was marked by a gradual diminishing of its SPR band, while the release of pHA molecules in the solution was confirmed from TEM and FTIR studies. The findings suggest that the core-shell NP could be hypothesized to be a model for encapsulating drug molecules, in their crystalline forms, for slow as well as targeted release.We report on the generation of core-shell nanoparticles (NPs) having an organic nanocrystal (NC) core coated with an inorganic metallic shell, being dispersed in aqueous medium. First, NCs of p-hydroxyacetanilide (pHA)--known also as paracetamol--were generated in an aqueous medium. Transmission electron microscopy (TEM) and powder X-ray diffraction (XRD) evidenced the formation of pHA NCs and of their crystalline nature. The NCs were then coated with Au to form pHA@Au core-shell NPs, where the thickness of the Au shell was on the order of nanometers. The formation of Au nanoshell--surrounding pHA NC--was confirmed from its surface plasmon resonance (SPR) band in the UV/Vis spectrum and by TEM measurements. Further, on treatment of the core-shell particles with a solution comprising NaCl and HCl (pH < 3), the Au shell could be dissolved, subsequently releasing pHA molecules. The dissolution of Au shell was marked by a gradual diminishing of its SPR band, while the release of pHA molecules in the solution was confirmed from TEM and FTIR studies. The findings suggest that the core-shell NP could be hypothesized to be a model for encapsulating drug molecules, in their crystalline forms, for slow as well as targeted release. Electronic supplementary information (ESI) available: See DOI: 10.1039/c3nr03566b

Magnetic response of hybrid ferromagnetic and antiferromagnetic core-shell nanostructures

NASA Astrophysics Data System (ADS)

Khan, U.; Li, W. J.; Adeela, N.; Irfan, M.; Javed, K.; Wan, C. H.; Riaz, S.; Han, X. F.

2016-03-01

The synthesis of FeTiO3-Ni(Ni80Fe20) core-shell nanostructures by a two-step method (sol-gel and DC electrodeposition) has been demonstrated. XRD analysis confirms the rhombohedral crystal structure of FeTiO3(FTO) with space group R3&cmb.macr;. Transmission electron microscopy clearly depicts better morphology of nanostructures with shell thicknesses of ~25 nm. Room temperature magnetic measurements showed significant enhancement of magnetic anisotropy for the permalloy (Ni80Fe20)-FTO over Ni-FTO core-shell nanostructures. Low temperature magnetic measurements of permalloy-FeTiO3 core-shell structure indicated a strong exchange bias mechanism with magnetic coercivity below the antiferromagnetic Neel temperature (TN = 59 K). The exchange bias is attributed to the alignment of magnetic moments in the antiferromagnetic material at low temperature. Our scheme opens a path towards optimum automotive systems and wireless communications wherein broader bandwidths and smaller sizes are required.The synthesis of FeTiO3-Ni(Ni80Fe20) core-shell nanostructures by a two-step method (sol-gel and DC electrodeposition) has been demonstrated. XRD analysis confirms the rhombohedral crystal structure of FeTiO3(FTO) with space group R3&cmb.macr;. Transmission electron microscopy clearly depicts better morphology of nanostructures with shell thicknesses of ~25 nm. Room temperature magnetic measurements showed significant enhancement of magnetic anisotropy for the permalloy (Ni80Fe20)-FTO over Ni-FTO core-shell nanostructures. Low temperature magnetic measurements of permalloy-FeTiO3 core-shell structure indicated a strong exchange bias mechanism with magnetic coercivity below the antiferromagnetic Neel temperature (TN = 59 K). The exchange bias is attributed to the alignment of magnetic moments in the antiferromagnetic material at low temperature. Our scheme opens a path towards optimum automotive systems and wireless communications wherein broader bandwidths and smaller sizes are required. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07946b

Synthesis and Plasmonic Understanding of Core/Satellite and Core Shell Nanostructures

NASA Astrophysics Data System (ADS)

Ruan, Qifeng

Localized surface plasmon resonance, which stems from the collective oscillations of conduction-band electrons, endows Au nanocrystals with unique optical properties. Au nanocrystals possess extremely large scattering/absorption cross-sections and enhanced local electromagnetic field, both of which are synthetically tunable. Moreover, when Au nanocrystals are closely placed or hybridized with semiconductors, the coupling and interaction between the individual components bring about more fascinating phenomena and promising applications, including plasmon-enhanced spectroscopies, solar energy harvesting, and cancer therapy. The continuous development in the field of plasmonics calls for further advancements in the preparation of high-quality plasmonic nanocrystals, the facile construction of hybrid plasmonic nanostructures with desired functionalities, as well as deeper understanding and efficient utilization of the interaction between plasmonic nanocrystals and semiconductor components. In this thesis, I developed a seed-mediated growth method for producing size-controlled Au nanospheres with high monodispersity and assembled Au nanospheres of different sizes into core/satellite nanostructures for enhancing Raman signals. For investigating the interactions between Au nanocrystals and semiconductors, I first prepared (Au core) (TiO2 shell) nanostructures, and then studied their synthetically controlled plasmonic properties and light-harvesting applications. Au nanocrystals with spherical shapes are desirable in plasmon-coupled systems owing to their high geometrical symmetry, which facilitates the analysis of electrodynamic responses in a classical electromagnetic framework and the investigation of quantum tunneling and nonlocal effects. I prepared remarkably uniform Au nanospheres with diameters ranging from 20 nm to 220 nm using a simple seed-mediated growth method associated with mild oxidation. Core/satellite nanostructures were assembled out of differently sized Au nanospheres with molecular linkers. The plasmon resonances of the core/satellite nanostructures undergo red shifts in comparison to those of the sole Au cores, which is consistent with Mie theory analysis. As predicted by finite-difference time-domain simulations, the assembled core/satellite nanostructures exhibit large enhancements for Raman scattering. The facile growth of Au nanospheres and assembly of core/satellite nanostructures blaze a new way to the design of nanoarchitectures with desired plasmonic properties and functions. Coating semiconductors onto Au nanocrystals to form core shell configurations can increase the interactions between the two materials, benefiting from their large active interfacial area. The shell can also protect the Au nanocrystal core from aggregation, reshaping, and chemical corrosion. In this thesis, (Au nanocrystal core) (titania shell) nanostructures with tunable shell thicknesses were prepared by a facile wetchemistry method. Au nanocrystals with strong and tunable plasmon resonances in the visible and near-infrared regions can enhance and broaden the light utilization of TiO2 through the scattering/absorption enhancement, sensitization, and hot-electron injection. The integration of Au nanocrystals therefore hold the prospect of breaking the light-harvesting limit of TiO2 arising from its wide band gap. The resultant (Au core) (TiO2 shell) nanostructures were examined to be capable of efficiently generating reactive oxygen species under near-infrared resonant excitation. On the other hand, the transverse plasmon modes of Au nanorods, which are often too weak to be observed on scattering spectra, are enhanced by the TiO2 shell through energy transfer. With the increment of the shell thickness, the intensity of the transverse plasmon mode increases significantly and even becomes comparable with the longitudinal plasmon mode. Interestingly, both the transverse and longitudinal modes of the (Au core) (TiO2 shell) nanostructures exhibit asymmetric Fano line shapes. The Fano resonances result from the coupling between the core and shell, as understood by the mechanical oscillator model. Besides varying the shell thickness, the plasmonic bands of the core shell nanostructures can also be tailored by employing Au nanorods with different aspect ratios. The synthetically tunable plasmonic properties and synergistic interactions between the gold core and the titania shell make the hybrid nanostructure a multifunctional nanomaterial and ideal system for studying the plasmonic hybrid nanostructures.

A magnetic field cloak for charged particle beams

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

Capobianco-Hogan, K. G.; Cervantes, R.; Deshpande, A.

Shielding charged particle beams from transverse magnetic fields is a common challenge for particle accelerators and experiments. In this study, we demonstrate that a magnetic field cloak is a viable solution. It allows for the use of dipole magnets in the forward regions of experiments at an Electron Ion Collider (EIC) and other facilities without interfering with the incoming beams. The dipoles can improve the momentum measurements of charged final state particles at angles close to the beam line and therefore increase the physics reach of these experiments. In contrast to other magnetic shielding options (such as active coils), amore » cloak requires no external powering. We discuss the design parameters, fabrication, and limitations of a magnetic field cloak and demonstrate that cylinders made from 45 layers of YBCO high-temperature superconductor, combined with a ferromagnetic shell made from epoxy and stainless steel powder, shield more than 99% of a transverse magnetic field of up to 0.45 T (95% shielding at 0.5 T) at liquid nitrogen temperature. Lastly, the ferromagnetic shell reduces field distortions caused by the superconductor alone by 90% at 0.45 T.« less

A magnetic field cloak for charged particle beams

NASA Astrophysics Data System (ADS)

Capobianco-Hogan, K. G.; Cervantes, R.; Deshpande, A.; Feege, N.; Krahulik, T.; LaBounty, J.; Sekelsky, R.; Adhyatman, A.; Arrowsmith-Kron, G.; Coe, B.; Dehmelt, K.; Hemmick, T. K.; Jeffas, S.; LaByer, T.; Mahmud, S.; Oliveira, A.; Quadri, A.; Sharma, K.; Tishelman-Charny, A.

2018-01-01

Shielding charged particle beams from transverse magnetic fields is a common challenge for particle accelerators and experiments. We demonstrate that a magnetic field cloak is a viable solution. It allows for the use of dipole magnets in the forward regions of experiments at an Electron Ion Collider (EIC) and other facilities without interfering with the incoming beams. The dipoles can improve the momentum measurements of charged final state particles at angles close to the beam line and therefore increase the physics reach of these experiments. In contrast to other magnetic shielding options (such as active coils), a cloak requires no external powering. We discuss the design parameters, fabrication, and limitations of a magnetic field cloak and demonstrate that cylinders made from 45 layers of YBCO high-temperature superconductor, combined with a ferromagnetic shell made from epoxy and stainless steel powder, shield more than 99% of a transverse magnetic field of up to 0.45 T (95% shielding at 0.5 T) at liquid nitrogen temperature. The ferromagnetic shell reduces field distortions caused by the superconductor alone by 90% at 0.45 T.

A magnetic field cloak for charged particle beams

DOE PAGES

Capobianco-Hogan, K. G.; Cervantes, R.; Deshpande, A.; ...

2017-10-02

Shielding charged particle beams from transverse magnetic fields is a common challenge for particle accelerators and experiments. In this study, we demonstrate that a magnetic field cloak is a viable solution. It allows for the use of dipole magnets in the forward regions of experiments at an Electron Ion Collider (EIC) and other facilities without interfering with the incoming beams. The dipoles can improve the momentum measurements of charged final state particles at angles close to the beam line and therefore increase the physics reach of these experiments. In contrast to other magnetic shielding options (such as active coils), amore » cloak requires no external powering. We discuss the design parameters, fabrication, and limitations of a magnetic field cloak and demonstrate that cylinders made from 45 layers of YBCO high-temperature superconductor, combined with a ferromagnetic shell made from epoxy and stainless steel powder, shield more than 99% of a transverse magnetic field of up to 0.45 T (95% shielding at 0.5 T) at liquid nitrogen temperature. Lastly, the ferromagnetic shell reduces field distortions caused by the superconductor alone by 90% at 0.45 T.« less

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

Yamaguchi, Hiroya; Badenes, Carles; Foster, Adam R.

Despite decades of intense efforts, many fundamental aspects of Type Ia supernovae (SNe Ia) remain elusive. One of the major open questions is whether the mass of an exploding white dwarf (WD) is close to the Chandrasekhar limit. Here, we report the detection of strong K-shell emission from stable Fe-peak elements in the Suzaku X-ray spectrum of the Type Ia supernova remnant (SNR) 3C 397. The high Ni/Fe and Mn/Fe mass ratios (0.11–0.24 and 0.018–0.033, respectively) in the hot plasma component that dominates the K-shell emission lines indicate a degree of neutronization in the supernova ejecta that can only bemore » achieved by electron capture in the dense cores of exploding WDs with a near-Chandrasekhar mass. This suggests a single-degenerate origin for 3C 397, since Chandrasekhar mass progenitors are expected naturally if the WD accretes mass slowly from a companion. Altogether with other results supporting the double-degenerate scenario, our work adds to the mounting evidence that both progenitor channels make a significant contribution to the SN Ia rate in star-forming galaxies.« less

Core-shell magnetite-silica composite nanoparticles enhancing DNA damage induced by a photoactive platinum-diimine complex in red light.

PubMed

Zhang, Zhigang; Chai, Aiyun

2012-12-01

Lack of solubility under physiological conditions poses an additional risk for toxicity and side effects for intravenous delivery of the photodynamic therapeutic agent in vivo. Employing magnetite-silica composite nanoparticles as carriers of the photodynamic therapeutic agents may be a promising way to solve the problem. In this study, core-shell magnetite-silica composite nanoparticles were prepared by a sol-gel method, and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy and dynamic light scattering, then they were used as carriers of a photoactive platinum diimine complex. The interactions of the photosensitizer-loaded magnetic composite nanoparticles with DNA in red light were monitored by agarose-gel electrophoresis. The results suggest that high doses of magnetite-silica composite nanoparticles might facilitate the transformation of covalently closed circular (ccc)-DNA band to open circular (oc)-DNA band though they are harmless to DNA at their low concentrations, therefore enhancing the extent of DNA damage caused by the metal complex in red light. Copyright © 2012 Elsevier Inc. All rights reserved.

Systematic Evaluation of Low-Frequency Hiss and Energetic Electron Injections

DOE PAGES

Shi, Run; Li, Wen; Ma, Qianli; ...

2017-10-05

Here, the excitation of low-frequency (LF) plasmaspheric hiss, over the frequency range from 20 Hz to 100 Hz, is systematically investigated by comparing the hiss wave properties with electron injections at energies from tens of keV to several hundreds of keV. Both particle and wave data from the Van Allen Probes during the period from September 2012 to June 2016 are used in the present study. Our results demonstrate that the intensity of LF hiss has a clear day-night asymmetry, and increases with increasing geomagnetic activity, similar to the behavior of normal hiss (approximately hundred of hertz to several kilohertz).more » The occurrence rate of LF hiss in association with electron injections is up to 80% in the outer plasmasphere ( L > 4) on the dayside, and the strong correlation extends to lower L shells for more active times. In contrast, at lower L shells ( L < 3.5), LF hiss is seldom associated with electron injections. The LF hiss with Poynting flux directed away from the equator is dominant at higher magnetic latitudes and higher L shells, suggesting a local amplification of LF hiss in the outer plasmasphere. The averaged electron fluxes are larger at higher L shells, where significant LF hiss wave events are observed. Our study suggests the importance of electron injections and their drift trajectories toward the dayside plasmasphere in locally amplifying the LF hiss waves detected by the Van Allen Probes.« less

Systematic Evaluation of Low-Frequency Hiss and Energetic Electron Injections

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

Shi, Run; Li, Wen; Ma, Qianli

Here, the excitation of low-frequency (LF) plasmaspheric hiss, over the frequency range from 20 Hz to 100 Hz, is systematically investigated by comparing the hiss wave properties with electron injections at energies from tens of keV to several hundreds of keV. Both particle and wave data from the Van Allen Probes during the period from September 2012 to June 2016 are used in the present study. Our results demonstrate that the intensity of LF hiss has a clear day-night asymmetry, and increases with increasing geomagnetic activity, similar to the behavior of normal hiss (approximately hundred of hertz to several kilohertz).more » The occurrence rate of LF hiss in association with electron injections is up to 80% in the outer plasmasphere ( L > 4) on the dayside, and the strong correlation extends to lower L shells for more active times. In contrast, at lower L shells ( L < 3.5), LF hiss is seldom associated with electron injections. The LF hiss with Poynting flux directed away from the equator is dominant at higher magnetic latitudes and higher L shells, suggesting a local amplification of LF hiss in the outer plasmasphere. The averaged electron fluxes are larger at higher L shells, where significant LF hiss wave events are observed. Our study suggests the importance of electron injections and their drift trajectories toward the dayside plasmasphere in locally amplifying the LF hiss waves detected by the Van Allen Probes.« less

Authentic Assessment Tool for the Measurement of Students' Understanding of the Valence Shell Electron Pair Repulsion Theory

ERIC Educational Resources Information Center

Wuttisela, Karntarat

2017-01-01

There are various types of instructional media related to Valence Shell Electron Pair Repulsion (VSEPR) but there is a lack of diversity of resources devoted to assessment. This research presents an assessment and comparison of students' understanding of VSEPR theory before and after tuition involving the use of the foam molecule model (FMM) and…

Strain distribution of confined Ge/GeO2 core/shell nanoparticles engineered by growth environments

NASA Astrophysics Data System (ADS)

Wei, Wenyan; Yuan, Cailei; Luo, Xingfang; Yu, Ting; Wang, Gongping

2016-02-01

The strain distributions of Ge/GeO2 core/shell nanoparticles confined in different host matrix grown by surface oxidation are investigated. The simulated results by finite element method demonstrated that the strains of the Ge core and the GeO2 shell strongly depend on the growth environments of the nanoparticles. Moreover, it can be found that there is a transformation of the strain on Ge core from tensile to compressive strain during the growth of Ge/GeO2 core/shell nanoparticles. And, the transformation of the strain is closely related with the Young's modulus of surrounding materials of Ge/GeO2 core/shell nanoparticles.

Characterization of core/shell structures based on CdTe and GaAs nanocrystalline layers deposited on SnO2 microwires

NASA Astrophysics Data System (ADS)

Ghimpu, L.; Ursaki, V. V.; Pantazi, A.; Mesterca, R.; Brâncoveanu, O.; Shree, Sindu; Adelung, R.; Tiginyanu, I. M.; Enachescu, M.

2018-04-01

We report the fabrication and characterization of SnO2/CdTe and SnO2/GaAs core/shell microstructures. CdTe or GaAs shell layers were deposited by radio-frequency (RF) magnetron sputtering on core SnO2 microwires synthesized by a flame-based thermal oxidation method. The produced structures were characterized by scanning electron microscopy (SEM), high-resolution scanning transmission electron microscope (HR-STEM), X-ray diffraction (XRD), Raman scattering and FTIR spectroscopy. It was found that the SnO2 core is of the rutile type, while the shells are composed of CdTe or GaAs nanocrystallites of zincblende structure with the dimensions of crystallites in the range of 10-20 nm. The Raman scattering investigations demonstrated that the quality of the porous nanostructured shell is improved by annealing at temperatures of 420-450 °C. The prospects of implementing these microstructures in intrinsic type fiber optic sensors are discussed.

Quantum transport through single and multilayer icosahedral fullerenes

NASA Astrophysics Data System (ADS)

Lovey, Daniel A.; Romero, Rodolfo H.

2013-10-01

We use a tight-binding Hamiltonian and Green functions methods to calculate the quantum transmission through single-wall fullerenes and bilayered and trilayered onions of icosahedral symmetry attached to metallic leads. The electronic structure of the onion-like fullerenes takes into account the curvature and finite size of the fullerenes layers as well as the strength of the intershell interactions depending on to the number of interacting atom pairs belonging to adjacent shells. Misalignment of the symmetry axes of the concentric iscosahedral shells produces breaking of the level degeneracies of the individual shells, giving rise some narrow quasi-continuum bands instead of the localized discrete peaks of the individual fullerenes. As a result, the transmission function for non symmetrical onions is rapidly varying functions of the Fermi energy. Furthermore, we found that most of the features of the transmission through the onions are due to the electronic structure of the outer shell with additional Fano-like antiresonances arising from coupling with or between the inner shells.

The microstructure and magnetic properties of Cu/CuO/Ni core/multi-shell nanowire arrays

NASA Astrophysics Data System (ADS)

Yang, Feng; Shi, Jie; Zhang, Xiaofeng; Hao, Shijie; Liu, Yinong; Feng, Chun; Cui, Lishan

2018-04-01

Multifunctional metal/oxide/metal core/multi-shell nanowire arrays were prepared mostly by physical or chemical vapor deposition. In our study, the Cu/CuO/Ni core/multi-shell nanowire arrays were prepared by AAO template-electrodeposition and oxidation processes. The Cu/Ni core/shell nanowire arrays were prepared by AAO template-electrodeposition method. The microstructure and chemical compositions of the core/multi-shell nanowires and core/shell nanowires have been characterized using transmission electron microscopy with HADDF-STEM and X-ray diffraction. Magnetization measurements revealed that the Cu/CuO/Ni and Cu/Ni nanowire arrays have high coercivity and remanence ratio.

Neoclassical Diffusion of Radiation-Belt Electrons Across Very Low L -shells

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

Cunningham, Gregory S.; Loridan, Vivien; Ripoll, Jean-Francois

In the presence of drift-shell splitting intrinsic to the IGRF magnetic field model, pitch-angle scattering from Coulomb collisions experienced by radiation-belt electrons in the upper atmosphere and ionosphere produces extra radial diffusion, a form of neoclassical diffusion. The strength of the neoclassical radial diffusion at L < 1.2 exceeds that expected there from radial-diffusion mechanisms traditionally considered, and decreases with increasing L-shell. In this study we construct a numerical model for this coupled (radial and pitch-angle) collisional diffusion process and apply it to simulate raw count-rate data observed aboard the Gemini spacecraft for several years after the 1962 Starfish nuclearmore » detonation. The data show apparent lifetimes 10-100 times as long as would have been expected from collisional pitch-angle diffusion and Coulomb drag alone. Our model reproduces apparent lifetimes for >0.5-MeV electrons in the region 1.14 < L < 1.26 to within a factor of two (comparable to the uncertainty quoted for the observations). We conclude that neoclassical radial diffusion (resulting from drift-shell splitting intrinsic to IGRF's azimuthal asymmetries) mitigates the decay expected from collisional pitch-angle diffusion and inelastic energy loss alone and thus contributes importantly to the long apparent lifetimes observed at these low L-shells.« less

Neoclassical Diffusion of Radiation-Belt Electrons Across Very Low L -shells

DOE PAGES

Cunningham, Gregory S.; Loridan, Vivien; Ripoll, Jean-Francois; ...

2018-03-30

In the presence of drift-shell splitting intrinsic to the IGRF magnetic field model, pitch-angle scattering from Coulomb collisions experienced by radiation-belt electrons in the upper atmosphere and ionosphere produces extra radial diffusion, a form of neoclassical diffusion. The strength of the neoclassical radial diffusion at L < 1.2 exceeds that expected there from radial-diffusion mechanisms traditionally considered, and decreases with increasing L-shell. In this study we construct a numerical model for this coupled (radial and pitch-angle) collisional diffusion process and apply it to simulate raw count-rate data observed aboard the Gemini spacecraft for several years after the 1962 Starfish nuclearmore » detonation. The data show apparent lifetimes 10-100 times as long as would have been expected from collisional pitch-angle diffusion and Coulomb drag alone. Our model reproduces apparent lifetimes for >0.5-MeV electrons in the region 1.14 < L < 1.26 to within a factor of two (comparable to the uncertainty quoted for the observations). We conclude that neoclassical radial diffusion (resulting from drift-shell splitting intrinsic to IGRF's azimuthal asymmetries) mitigates the decay expected from collisional pitch-angle diffusion and inelastic energy loss alone and thus contributes importantly to the long apparent lifetimes observed at these low L-shells.« less

Neoclassical Diffusion of Radiation-Belt Electrons Across Very Low L-Shells

NASA Astrophysics Data System (ADS)

Cunningham, Gregory S.; Loridan, Vivien; Ripoll, Jean-François; Schulz, Michael

2018-04-01

In the presence of drift-shell splitting intrinsic to the International Geomagnetic Reference Field magnetic field model, pitch angle scattering from Coulomb collisions experienced by radiation-belt electrons in the upper atmosphere and ionosphere produces extra radial diffusion, a form of neoclassical diffusion. The strength of the neoclassical radial diffusion at L < 1.2 exceeds that expected there from radial-diffusion mechanisms traditionally considered and decreases with increasing L-shell. In this work we construct a numerical model for this coupled (radial and pitch angle) collisional diffusion process and apply it to simulate raw count-rate data observed aboard the Gemini spacecraft for several years after the 1962 Starfish nuclear detonation. The data show apparent lifetimes 10-100 times as long as would have been expected from collisional pitch angle diffusion and Coulomb drag alone. Our model reproduces apparent lifetimes for >0.5-MeV electrons in the region 1.14 < L < 1.26 to within a factor of 2 (comparable to the uncertainty quoted for the observations). We conclude that neoclassical radial diffusion (resulting from drift-shell splitting intrinsic to International Geomagnetic Reference Field's azimuthal asymmetries) mitigates the decay expected from collisional pitch angle diffusion and inelastic energy loss alone and thus contributes importantly to the long apparent lifetimes observed at these low L-shells.

Electron impact action spectroscopy of mass/charge selected macromolecular ions: Inner-shell excitation of ubiquitin protein

NASA Astrophysics Data System (ADS)

Ranković, Miloš Lj.; Giuliani, Alexandre; Milosavljević, Aleksandar R.

2016-02-01

We have performed inner-shell electron impact action spectroscopy of mass and charge selected macromolecular ions. For this purpose, we have coupled a focusing electron gun with a linear quadrupole ion trap mass spectrometer. This experiment represents a proof of principle that an energy-tunable electron beam can be used in combination with radio frequency traps as an activation method in tandem mass spectrometry (MS2) and allows performing action spectroscopy. Electron impact MS2 spectra of multiply protonated ubiquitin protein ion have been recorded at incident electron energies around the carbon 1 s excitation. Both MS2 and single ionization energy dependence spectra are compared with literature data obtained using the soft X-ray activation conditions.

Computer Technology for Industry

NASA Technical Reports Server (NTRS)

1982-01-01

Shell Oil Company used a COSMIC program, called VISCEL to insure the accuracy of the company's new computer code for analyzing polymers, and chemical compounds. Shell reported that there were no other programs available that could provide the necessary calculations. Shell produces chemicals for plastic products used in the manufacture of automobiles, housewares, appliances, film, textiles, electronic equipment and furniture.

Electron-Electron and Electron-Phonon interactions effects on the tunnel electronic spectrum of PbS quantum dots

NASA Astrophysics Data System (ADS)

Wang, Hongyue; Lhuillier, Emmanuel; Yu, Qian; Mottaghizadeh, Alireza; Ulysse, Christian; Zimmers, Alexandre; Dubertret, Benoit; Aubin, Herve

2015-03-01

We present a tunnel spectroscopy study of the electronic spectrum of single PbS Quantum Dots (QDs) trapped between nanometer-spaced electrodes, measured at low temperature T=5 K. The carrier filling of the QD can be controlled either by the drain voltage in the shell filling regime or by a gate voltage. In the empty QD, the tunnel spectrum presents the expected signature of the 8x degenerated excited levels. In the drain controlled shell filling regime, the levels degeneracies are lifted by the global electrostatic Coulomb energy of the QD; in the gate controlled shell filling regime, the levels degeneracies are lifted by the intra-Coulomb interactions. In the charged quantum dot, electron-phonons interactions lead to the apparition of Franck-Condon side bands on the single excited levels and possibly Franck Condon blockade at low energy. The sharpening of excited levels at higher gate voltage suggests that the magnitude of electron-phonon interactions is decreased upon increasing the electron filling in the quantum dot. This work was supported by the French ANR Grants 10-BLAN-0409-01, 09-BLAN-0388-01, by the Region Ile-de-France in the framework of DIM Nano-K and by China Scholarship Council.

Synthesis characterisation series of newly fabricated type II CdSe CdSe/CdTe nanocrystals and their optical properties

NASA Astrophysics Data System (ADS)

Ahmed, A. S.; Christopher, W.

2018-03-01

Nanocrystalline semiconductors exhibit different properties due to two basic factors. They possess high surface to volume ratio and the actual size of particle can determine the electronic and physical properties of the material. The small size results in an observable quantum confinement effect, defined by the increasing bandgap accompanied by the quantization of the energy levels to discrete values. In present work we have synthesized the series of cadmium selenide/cadmium telluride (CdSe/CdTe) core/shell and CdSe/CdTe/CdS core/shell/shell to investigate the biexciton energy through transient absorption measurements. These structures are type II nanocrystals are with a hole in the shell and the electron confined to the core. We specifically investigate the effect of nanoparticle shape on the electronic structure and ultrafast electronic dynamics in the band-edge exciton states of CdSe quantum dots, nanorods, and nanoplatelets. Particle size was chosen to enable straightforward comparisons of the effects of particle shape on the spectra and dynamics without retuning the laser source. In our results the Uv-vis showed only a mild redshift in the first excitonic an elongated tail with increasing shell thickness. High resolution Transmission Electron Microscopy (HRTEM) shows the slight agglomeration of the nanocrystals but still the size distribution was calculate able. Spherical small crystals ranging from 5.9 nm to 10 nm are observed. CdTe/CdSe structures were quasi spherical with a rough diameter 6 nm with some little agglomerated structure. . The spherical nanocrystals could be peanut shaped oriented along the c axis or the spherical only, which could explain the two peak emission. p-XRD results indicate the predominant wurtzite structure throughout.

Enhanced Ethanol Gas Sensing Properties of SnO2-Core/ZnO-Shell Nanostructures

PubMed Central

Tharsika, T.; Haseeb, A. S. M. A.; Akbar, Sheikh A.; Sabri, Mohd Faizul Mohd; Hoong, Wong Yew

2014-01-01

An inexpensive single-step carbon-assisted thermal evaporation method for the growth of SnO2-core/ZnO-shell nanostructures is described, and the ethanol sensing properties are presented. The structure and phases of the grown nanostructures are investigated by field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) techniques. XRD analysis indicates that the core-shell nanostructures have good crystallinity. At a lower growth duration of 15 min, only SnO2 nanowires with a rectangular cross-section are observed, while the ZnO shell is observed when the growth time is increased to 30 min. Core-shell hierarchical nanostructures are present for a growth time exceeding 60 min. The growth mechanism for SnO2-core/ZnO-shell nanowires and hierarchical nanostructures are also discussed. The sensitivity of the synthesized SnO2-core/ZnO-shell nanostructures towards ethanol sensing is investigated. Results show that the SnO2-core/ZnO-shell nanostructures deposited at 90 min exhibit enhanced sensitivity to ethanol. The sensitivity of SnO2-core/ZnO-shell nanostructures towards 20 ppm ethanol gas at 400 °C is about ∼5-times that of SnO2 nanowires. This improvement in ethanol gas response is attributed to high active sensing sites and the synergistic effect of the encapsulation of SnO2 by ZnO nanostructures. PMID:25116903

Electron radiation belt dynamics during magnetic storms and in quiet time

NASA Astrophysics Data System (ADS)

Lazutin, Leonid; Dmitriev, Aleksey; Suvorova, Alla

2018-03-01

The paper discusses the dynamics of the outer electron belt, adiabatic and nonadiabatic mechanisms of replenishment and losses of energetic electrons. Under undisturbed conditions, the outer electron belt gradually empties: in the inner magnetosphere due to electron precipitation in the atmosphere and in the quasi-trapping region due to losses at the magnetopause because drift shells of electrons are not closed there. The latter process does not occur in normal years due to the masking replenishment by freshly accelerated particles, but in years of extremely low activity, it leads to a significant decrease in the electron population of the belt. During the magnetic storm main phase, the first reason for the decrease in the electron flux intensity is the adiabatic cooling associated with conservation of adiabatic invariants and complemented by precipitation of electrons into the atmosphere and their dropout at the magnetopause. Electron flux increases involve E×B electron injection by the induction electric field of substorm activation and by the large-scale solar wind electric field, with pitch energy diffusion along with adiabatic heating in the recovery phase. The rate of electron flux recovery after a storm is determined by the ratio of nonadiabatic increases and losses; hence the electron flux represents a continuous series from low to very high values. The combination of these processes determines the individual character of radiation belt development during each magnetic storm and the behavior of the belt in the quiet time.

Architecture of crossed-lamellar bivalve shells: the southern giant clam (Tridacna derasa, Röding, 1798).

PubMed

Agbaje, O B A; Wirth, R; Morales, L F G; Shirai, K; Kosnik, M; Watanabe, T; Jacob, D E

2017-09-01

Tridacna derasa shells show a crossed lamellar microstructure consisting of three hierarchical lamellar structural orders. The mineral part is intimately intergrown with 0.9 wt% organics, namely polysaccharides, glycosylated and unglycosylated proteins and lipids, identified by Fourier transform infrared spectrometry. Transmission electron microscopy shows nanometre-sized grains with irregular grain boundaries and abundant voids. Twinning is observed across all spatial scales and results in a spread of the crystal orientation angles. Electron backscatter diffraction analysis shows a strong fibre texture with the [001] axes of aragonite aligned radially to the shell surface. The aragonitic [100] and [010] axes are oriented randomly around [001]. The random orientation of anisotropic crystallographic directions in this plane reduces anisotropy of the Young's modulus and adds to the optimization of mechanical properties of bivalve shells.

Surfactant mediated hydrothermal synthesis, characterization and luminescent properties of GdPO{sub 4}: Ce{sup 3+}/Tb{sup 3+} @ GdPO{sub 4} core shell nanorods

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

Khajuria, Heena; Ladol, Jigmet; Khajuria, Sonika

Highlights: • Core shell nanorods were synthesised by surfactant assisted hydrothermal method. • Morphology of core shell nanorods resembles those of core nanorods indicating coating of shell on cores. • More uniform and non-aggregated core shell nanorods were prepared in presence of surfactants. • Surfactant assisted prepared core shell nanorods show intense emission as compared to uncoated core nanorods. - Abstract: Core shell GdPO{sub 4}: Ce{sup 3+}/Tb{sup 3+} @ GdPO{sub 4} nanorods were synthesized via hydrothermal route in the presence of different surfactants [cetyltrimethyl ammonium bromide (CTAB) and Sodium dodecyl sulphate (SDS)]. The nanorods were characterized by powder X-ray diffractionmore » (PXRD), fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS) and photoluminescence (PL) studies. The X-ray diffraction results indicate good crystallinity and effective doping in core and core shell nanorods. SEM and TEM micrographs show that all of the as prepared gadolinium phosphate products have rod like shape. The compositional analysis of GdPO{sub 4}: Ce{sup 3+}/Tb{sup 3+} core was done by EDS. The emission intensity of the GdPO{sub 4}: Ce{sup 3+}/Tb{sup 3+} @ GdPO{sub 4} core shell increased significantly with respect to those of GdPO{sub 4}: Ce{sup 3+}/Tb{sup 3+} core nanorods. The effect of surfactant on the uniformity, thickness and luminescence of the core shell nanorods was investigated.« less

Band bending at the heterointerface of GaAs/InAs core/shell nanowires monitored by synchrotron X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Khanbabaee, B.; Bussone, G.; Knutsson, J. V.; Geijselaers, I.; Pryor, C. E.; Rieger, T.; Demarina, N.; Grützmacher, D.; Lepsa, M. I.; Timm, R.; Pietsch, U.

2016-10-01

Unique electronic properties of semiconductor heterostructured nanowires make them useful for future nano-electronic devices. Here, we present a study of the band bending effect at the heterointerface of GaAs/InAs core/shell nanowires by means of synchrotron based X-ray photoelectron spectroscopy. Different Ga, In, and As core-levels of the nanowire constituents have been monitored prior to and after cleaning from native oxides. The cleaning process mainly affected the As-oxides and was accompanied by an energy shift of the core-level spectra towards lower binding energy, suggesting that the As-oxides turn the nanowire surfaces to n-type. After cleaning, both As and Ga core-levels revealed an energy shift of about -0.3 eV for core/shell compared to core reference nanowires. With respect to depth dependence and in agreement with calculated strain distribution and electron quantum confinement, the observed energy shift is interpreted by band bending of core-levels at the heterointerface between the GaAs nanowire core and the InAs shell.

Oscillator strengths and integral cross sections for the valence-shell excitations of nitric oxide studied by fast electron impact.

PubMed

Xu, Xin; Xu, Long-Quan; Xiong, Tao; Chen, Tao; Liu, Ya-Wei; Zhu, Lin-Fan

2018-01-28

The generalized oscillator strengths for the valence-shell excitations of A 2 Σ + , C 2 Π, and D 2 Σ + electronic-states of nitric oxide have been determined at an incident electron energy of 1500 eV with an energy resolution of 70 meV. The optical oscillator strengths for these transitions have been obtained by extrapolating the generalized oscillator strengths to the limit that the squared momentum transfer approaches to zero, which give an independent cross-check to the previous experimental and theoretical results. The integral cross sections for the valence-shell excitations of nitric oxide have been determined systematically from the threshold to 2500 eV with the aid of the newly developed BE-scaling method for the first time. The present optical oscillator strengths and integral cross sections of the valence-shell excitations of nitric oxide play an important role in understanding many physics and chemistry of the Earth's upper atmosphere such as the radiative cooling, ozone destruction, day glow, aurora, and so on.

Excited-state dynamics of size-dependent colloidal TiO2-Au nanocomposites

NASA Astrophysics Data System (ADS)

Karam, Tony E.; Khoury, Rami A.; Haber, Louis H.

2016-03-01

The ultrafast excited-state dynamics of size-dependent TiO2-Au nanocomposites synthesized by reducing gold nanoclusters to the surface of colloidal TiO2 nanoparticles are studied using pump-probe transient absorption spectroscopy with 400 nm excitation pulses. The results show that the relaxation processes of the plasmon depletion band, which are described by electron-phonon and phonon-phonon scattering lifetimes, are independent of the gold nanocluster shell size surrounding the TiO2 nanoparticle core. The dynamics corresponding to interfacial electron transfer between the gold nanoclusters and the TiO2 bandgap are observed to spectrally overlap with the gold interband transition signal, and the electron transfer lifetimes are shown to significantly decrease as the nanocluster shell size increases. Additionally, size-dependent periodic oscillations are observed and are attributed to acoustic phonons of a porous shell composed of aggregated gold nanoclusters around the TiO2 core, with frequencies that decrease and damping times that remain constant as the nanocluster shell size increases. These results are important for the development of improved catalytic nanomaterial applications.

Accurate Cross Sections for Microanalysis.

PubMed

Rez, Peter

2002-01-01

To calculate the intensity of x-ray emission in electron beam microanalysis requires a knowledge of the energy distribution of the electrons in the solid, the energy variation of the ionization cross section of the relevant subshell, the fraction of ionizations events producing x rays of interest and the absorption coefficient of the x rays on the path to the detector. The theoretical predictions and experimental data available for ionization cross sections are limited mainly to K shells of a few elements. Results of systematic plane wave Born approximation calculations with exchange for K, L, and M shell ionization cross sections over the range of electron energies used in microanalysis are presented. Comparisons are made with experimental measurement for selected K shells and it is shown that the plane wave theory is not appropriate for overvoltages less than 2.5 V.

Transmission electron microscopy of unstained hybrid Au nanoparticles capped with PPAA (plasma-poly-allylamine): structure and electron irradiation effects.

PubMed

Gontard, Lionel C; Fernández, Asunción; Dunin-Borkowski, Rafal E; Kasama, Takeshi; Lozano-Pérez, Sergio; Lucas, Stéphane

2014-12-01

Hybrid (organic shell-inorganic core) nanoparticles have important applications in nanomedicine. Although the inorganic components of hybrid nanoparticles can be characterized readily using conventional transmission electron microscopy (TEM) techniques, the structural and chemical arrangement of the organic molecular components remains largely unknown. Here, we apply TEM to the physico-chemical characterization of Au nanoparticles that are coated with plasma-polymerized-allylamine, an organic compound with the formula C3H5NH2. We discuss the use of energy-filtered TEM in the low-energy-loss range as a contrast enhancement mechanism for imaging the organic shells of such particles. We also study electron-beam-induced crystallization and amorphization of the shells and the formation of graphitic-like layers that contain both C and N. The resistance of the samples to irradiation by high-energy electrons, which is relevant for optical tuning and for understanding the degree to which such hybrid nanostructures are stable in the presence of biomedical radiation, is also discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Ultralow energy calibration of LUX detector using Xe 127 electron capture

DOE PAGES

Akerib, D. S.; Alsum, S.; Araújo, H. M.; ...

2017-12-01

We report an absolute calibration of the ionization yields(more » $$\\textit{Q$$_y$})$ and fluctuations for electronic recoil events in liquid xenon at discrete energies between 186 eV and 33.2 keV. The average electric field applied across the liquid xenon target is 180 V/cm. The data are obtained using low energy $$^{127}$$Xe electron capture decay events from the 95.0-day first run from LUX (WS2013) in search of Weakly Interacting Massive Particles (WIMPs). The sequence of gamma-ray and X-ray cascades associated with $$^{127}$$I de-excitations produces clearly identified 2-vertex events in the LUX detector. We observe the K- (binding energy, 33.2 keV), L- (5.2 keV), M- (1.1 keV), and N- (186 eV) shell cascade events and verify that the relative ratio of observed events for each shell agrees with calculations. The N-shell cascade analysis includes single extracted electron (SE) events and represents the lowest-energy electronic recoil $$\\textit{in situ}$$ measurements that have been explored in liquid xenon.« less

Ultralow energy calibration of LUX detector using Xe 127 electron capture

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

Akerib, D. S.; Alsum, S.; Araújo, H. M.

We report an absolute calibration of the ionization yields (Q y) and fluctuations for electronic recoil events in liquid xenon at discrete energies between 186 eV and 33.2 keV. The average electric field applied across the liquid xenon target is 180 V/cm. The data are obtained using low energy 127Xe electron capture decay events from the 95.0-day first run from LUX (WS2013) in search of weakly interacting massive particles. The sequence of gamma-ray and x-ray cascades associated with 127I deexcitations produces clearly identified two-vertex events in the LUX detector. We observe the K-(binding energy, 33.2 keV), L-(5.2 keV), M-(1.1 keV),more » and N-(186 eV) shell cascade events and verify that the relative ratio of observed events for each shell agrees with calculations. In conclusion, the N-shell cascade analysis includes single extracted electron (SE) events and represents the lowest-energy electronic recoil in situ measurements that have been explored in liquid xenon.« less

Ultralow energy calibration of LUX detector using Xe 127 electron capture

NASA Astrophysics Data System (ADS)

Akerib, D. S.; Alsum, S.; Araújo, H. M.; Bai, X.; Bailey, A. J.; Balajthy, J.; Beltrame, P.; Bernard, E. P.; Bernstein, A.; Biesiadzinski, T. P.; Boulton, E. M.; Brás, P.; Byram, D.; Cahn, S. B.; Carmona-Benitez, M. C.; Chan, C.; Currie, A.; Cutter, J. E.; Davison, T. J. R.; Dobi, A.; Druszkiewicz, E.; Edwards, B. N.; Fallon, S. R.; Fan, A.; Fiorucci, S.; Gaitskell, R. J.; Genovesi, J.; Ghag, C.; Gilchriese, M. G. D.; Hall, C. R.; Hanhardt, M.; Haselschwardt, S. J.; Hertel, S. A.; Hogan, D. P.; Horn, M.; Huang, D. Q.; Ignarra, C. M.; Jacobsen, R. G.; Ji, W.; Kamdin, K.; Kazkaz, K.; Khaitan, D.; Knoche, R.; Larsen, N. A.; Lenardo, B. G.; Lesko, K. T.; Lindote, A.; Lopes, M. I.; Manalaysay, A.; Mannino, R. L.; Marzioni, M. F.; McKinsey, D. N.; Mei, D.-M.; Mock, J.; Moongweluwan, M.; Morad, J. A.; Murphy, A. St. J.; Nehrkorn, C.; Nelson, H. N.; Neves, F.; O'Sullivan, K.; Oliver-Mallory, K. C.; Palladino, K. J.; Pease, E. K.; Rhyne, C.; Shaw, S.; Shutt, T. A.; Silva, C.; Solmaz, M.; Solovov, V. N.; Sorensen, P.; Sumner, T. J.; Szydagis, M.; Taylor, D. J.; Taylor, W. C.; Tennyson, B. P.; Terman, P. A.; Tiedt, D. R.; To, W. H.; Tripathi, M.; Tvrznikova, L.; Uvarov, S.; Velan, V.; Verbus, J. R.; Webb, R. C.; White, J. T.; Whitis, T. J.; Witherell, M. S.; Wolfs, F. L. H.; Xu, J.; Yazdani, K.; Young, S. K.; Zhang, C.

2017-12-01

We report an absolute calibration of the ionization yields (Qy ) and fluctuations for electronic recoil events in liquid xenon at discrete energies between 186 eV and 33.2 keV. The average electric field applied across the liquid xenon target is 180 V /cm . The data are obtained using low energy Xe 127 electron capture decay events from the 95.0-day first run from LUX (WS2013) in search of weakly interacting massive particles. The sequence of gamma-ray and x-ray cascades associated with I 127 deexcitations produces clearly identified two-vertex events in the LUX detector. We observe the K-(binding energy, 33.2 keV), L-(5.2 keV), M-(1.1 keV), and N-(186 eV) shell cascade events and verify that the relative ratio of observed events for each shell agrees with calculations. The N-shell cascade analysis includes single extracted electron (SE) events and represents the lowest-energy electronic recoil in situ measurements that have been explored in liquid xenon.

Electron Impact K-shell Ionization of Atomic Targets

NASA Astrophysics Data System (ADS)

Saha, Bidhan; Basak, Arun K.; Alfaz Uddin, M.; Patoary, A. A. R.

2008-05-01

In spite of considerable progress -both theoretically and experimentally- recently in evaluating accurate K-shell ionization cross sections that play a decisive role for quantitative analyses using (i) electron probe microanalysis, (ii) Auger electron spectroscopy and (iii) electron energy loss spectra, attempts are still continuing to search for a model that can easily generate reliable cross sections for a wide range of energies and for various targets needed for plasma modeling code We report few modifications of the widely used binary encounter approximation (BEA) [1,2] and have tested by evaluating the electron impact K-shell ionization of few neutral targets at various projectile energies. Details will be presented at the meeting. [1] M. Gryziniski, Phys. Rev. A 138, 336 (1965); [2] L. Vriens, Proc. Phys. Soc. (London) 89, 13, (1966). [3M. A. Uddin , A. K. F. Haque, M. M. Billah, A. K. Basak, K, R, Karim and B. C. Saha, ,Phys. Rev. A 71,032715 (2005); [4] M. A. Uddin, A. K. Basak, and B. C. Saha, Int. J. Quan. Chem 100, 184 (2004).

Ultralow energy calibration of LUX detector using Xe 127 electron capture

DOE PAGES

Akerib, D. S.; Alsum, S.; Araújo, H. M.; ...

2017-12-28

We report an absolute calibration of the ionization yields (Q y) and fluctuations for electronic recoil events in liquid xenon at discrete energies between 186 eV and 33.2 keV. The average electric field applied across the liquid xenon target is 180 V/cm. The data are obtained using low energy 127Xe electron capture decay events from the 95.0-day first run from LUX (WS2013) in search of weakly interacting massive particles. The sequence of gamma-ray and x-ray cascades associated with 127I deexcitations produces clearly identified two-vertex events in the LUX detector. We observe the K-(binding energy, 33.2 keV), L-(5.2 keV), M-(1.1 keV),more » and N-(186 eV) shell cascade events and verify that the relative ratio of observed events for each shell agrees with calculations. In conclusion, the N-shell cascade analysis includes single extracted electron (SE) events and represents the lowest-energy electronic recoil in situ measurements that have been explored in liquid xenon.« less

Fabrication of Fe{sub 3}O{sub 4}@CuO core-shell from MOF based materials and its antibacterial activity

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

Rajabi, S.K.; Sohrabnezhad, Sh., E-mail: sohrabnezhad@guilan.ac.ir; Ghafourian, S.

Magnetic Fe{sub 3}O{sub 4}@CuO nanocomposite with a core/shell structure was successfully synthesized via direct calcinations of magnetic Fe{sub 3}O{sub 4}@HKUST-1 in air atmosphere. The morphology, structure, magnetic and porous properties of the as-synthesized nano composites were characterized by using scanning electron microscope (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (PXRD), and vibration sample magnetometer (VSM). The results showed that the nanocomposite material included a Fe{sub 3}O{sub 4} core and a CuO shell. The Fe{sub 3}O{sub 4}@CuO core-shell can be separated easily from the medium by a small magnet. The antibacterial activity of Fe{sub 3}O{sub 4}-CuO core-shell was investigated againstmore » gram-positive and gram-negative bacteria. A new mechanism was proposed for inactivation of bacteria over the prepared sample. It was demonstrated that the core-shell exhibit recyclable antibacterial activity, acting as an ideal long-acting antibacterial agent. - Graphical abstract: Fe{sub 3}O{sub 4}@CuO core-shell release of copper ions. These Cu{sup 2+} ions were responsible for the exhibited antibacterial activity. - Highlights: • The Fe{sub 3}O{sub 4}@CuO core-shell was prepared by MOF method. • This is the first study of antibacterial activity of core-shell consist of CuO and Fe{sub 3}O{sub 4}. • The core-shell can be reused effectively. • Core-shell was separated from the reaction solution by external magnetic field.« less

Synthesis and cytotoxicity study of magnesium ferrite-gold core-shell nanoparticles.

PubMed

Nonkumwong, Jeeranan; Pakawanit, Phakkhananan; Wipatanawin, Angkana; Jantaratana, Pongsakorn; Ananta, Supon; Srisombat, Laongnuan

2016-04-01

In this work, the core-magnesium ferrite (MgFe2O4) nanoparticles were prepared by hydrothermal technique. Completed gold (Au) shell coating on the surfaces of MgFe2O4 nanoparticles was obtained by varying core/shell ratios via a reduction method. Phase identification, morphological evolution, optical properties, magnetic properties and cytotoxicity to mammalian cells of these MgFe2O4 core coated with Au nanoparticles were examined by using a combination of X-ray diffraction, scanning electron microscopy, transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy, UV-visible spectroscopy (UV-vis), vibrating sample magnetometry and resazurin microplate assay techniques. In general, TEM images revealed different sizes of the core-shell nanoparticles generated from various core/shell ratios and confirmed the completed Au shell coating on MgFe2O4 core nanoparticles via suitable core/shell ratio with particle size less than 100 nm. The core-shell nanoparticle size and the quality of coating influence the optical properties of the products. The UV-vis spectra of complete coated MgFe2O4-Au core-shell nanoparticles exhibit the absorption bands in the near-Infrared (NIR) region indicating high potential for therapeutic applications. Based on the magnetic property measurement, it was found that the obtained MgFe2O4-Au core-shell nanoparticles still exhibit superparamagnetism with lower saturation magnetization value, compared with MgFe2O4 core. Both of MgFe2O4 and MgFe2O4-Au core-shell also showed in vitro non-cytotoxicity to mouse areola fibroblast (L-929) cell line. Copyright © 2015 Elsevier B.V. All rights reserved.

Statistical mechanics of shell models for two-dimensional turbulence

NASA Astrophysics Data System (ADS)

Aurell, E.; Boffetta, G.; Crisanti, A.; Frick, P.; Paladin, G.; Vulpiani, A.

1994-12-01

We study shell models that conserve the analogs of energy and enstrophy and hence are designed to mimic fluid turbulence in two-dimensions (2D). The main result is that the observed state is well described as a formal statistical equilibrium, closely analogous to the approach to two-dimensional ideal hydrodynamics of Onsager [Nuovo Cimento Suppl. 6, 279 (1949)], Hopf [J. Rat. Mech. Anal. 1, 87 (1952)], and Lee [Q. Appl. Math. 10, 69 (1952)]. In the presence of forcing and dissipation we observe a forward flux of enstrophy and a backward flux of energy. These fluxes can be understood as mean diffusive drifts from a source to two sinks in a system which is close to local equilibrium with Lagrange multipliers (``shell temperatures'') changing slowly with scale. This is clear evidence that the simplest shell models are not adequate to reproduce the main features of two-dimensional turbulence. The dimensional predictions on the power spectra from a supposed forward cascade of enstrophy and from one branch of the formal statistical equilibrium coincide in these shell models in contrast to the corresponding predictions for the Navier-Stokes and Euler equations in 2D. This coincidence has previously led to the mistaken conclusion that shell models exhibit a forward cascade of enstrophy. We also study the dynamical properties of the models and the growth of perturbations.

In-medium similarity renormalization group for closed and open-shell nuclei

NASA Astrophysics Data System (ADS)

Hergert, H.

2017-02-01

We present a pedagogical introduction to the in-medium similarity renormalization group (IMSRG) framework for ab initio calculations of nuclei. The IMSRG performs continuous unitary transformations of the nuclear many-body Hamiltonian in second-quantized form, which can be implemented with polynomial computational effort. Through suitably chosen generators, it is possible to extract eigenvalues of the Hamiltonian in a given nucleus, or drive the Hamiltonian matrix in configuration space to specific structures, e.g., band- or block-diagonal form. Exploiting this flexibility, we describe two complementary approaches for the description of closed- and open-shell nuclei: the first is the multireference IMSRG (MR-IMSRG), which is designed for the efficient calculation of nuclear ground-state properties. The second is the derivation of non-empirical valence-space interactions that can be used as input for nuclear shell model (i.e., configuration interaction (CI)) calculations. This IMSRG+shell model approach provides immediate access to excitation spectra, transitions, etc, but is limited in applicability by the factorial cost of the CI calculations. We review applications of the MR-IMSRG and IMSRG+shell model approaches to the calculation of ground-state properties for the oxygen, calcium, and nickel isotopic chains or the spectroscopy of nuclei in the lower sd shell, respectively, and present selected new results, e.g., for the ground- and excited state properties of neon isotopes.

Expanding relativistic shells and gamma-ray burst temporal structure

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

Fenimore, E.E.; Madras, C.D.; Nayakshin, S.

1996-12-01

Many models of gamma-ray bursts (GRBs) involve a shell expanding at extreme relativistic speeds. The shell of material expands in a photon-quiet phase for a period {ital t}{sub 0} and then becomes gamma-ray active, perhaps due to inhomogeneities in the interstellar medium or the generation of shocks. Based on kinematics, we relate the envelope of the emission of the event to the characteristics of the photon-quiet and photon-active phases. We initially assume local spherical symmetry wherein, on average, the same conditions prevail over the shell`s surface within angles the order of {Gamma}{sup {minus}1}, where {Gamma} is the Lorentz factor formore » the bulk motion. The contribution of the curvature to the temporal structure is comparable to the contribution from the overall expansion. As a result, GRB time histories from a shell should have an envelope similar to {open_quotes}FRED{close_quotes} (fast rise, exponential decay) events in which the rise time is related to the duration of the photon-active phase and the fall time is related to the duration of the photon-quiet phase. This result depends only on local spherical symmetry and, since most GRBs do not have such envelopes, we introduce the {open_quotes}shell symmetry{close_quotes} problem: the observed time history envelopes of most GRBs do not agree with that expected for a relativistic expanding shell. Although FREDs have the signature of a relativistic shell, they may not be due to a single shell, as required by some cosmological models. Some FREDs have precursors in which the peaks are separated by more than the expansion time required to explain FRED shape. Such a burst is most likely explained by a central engine; that is, the separation of the multiple peaks occurs because the central site produced multiple releases of energy on timescales comparable to the duration of the event. (Abstract Truncated)« less

Coherent Extreme Ultraviolet Generation and Surface Studies Using Ultraviolet Excimer Lasers.

DTIC Science & Technology

1986-02-10

of Outer-Shell Electrons" 7. "A Theoretical Model of Inner-Shell ......................... 30 A Excitation by Outer-Snell Electrons" E. "Anomalous...rays are feasible. Our work involves a program of activities, involving both experimental and theoretical components, to explore the physical... theoretical effort con- centrating on the character of high order multiquantum coupling in the inten- sity regime above 1017 WcM2 . In addition

Photoionization of Ne Atoms and Ne + Ions Near the K Edge: PrecisionSpectroscopy and Absolute Cross-sections

DOE PAGES

Müller, Alfred; Bernhardt, Dietrich; Borovik, Alexander; ...

2017-02-17

Single, double, and triple photoionization of Ne + ions by single photons have been investigated at the synchrotron radiation source PETRA III in Hamburg, Germany. Absolute cross-sections were measured by employing the photon-ion merged-beams technique. Photon energies were between about 840 and 930 eV, covering the range from the lowest-energy resonances associated with the excitation of one single K-shell electron up to double excitations involving one K- and one L-shell electron, well beyond the K-shell ionization threshold. Also, photoionization of neutral Ne was investigated just below the K edge. The chosen photon energy bandwidths were between 32 and 500 meV,more » facilitating the determination of natural line widths. The uncertainty of the energy scale is estimated to be 0.2 eV. For comparison with existing theoretical calculations, astrophysically relevant photoabsorption cross-sections were inferred by summing the measured partial ionization channels. Discussion of the observed resonances in the different final ionization channels reveals the presence of complex Auger-decay mechanisms. The ejection of three electrons from the lowest K-shell-excited Ne + (1s2s 2p 6 2S 1/2) level, for example, requires cooperative interaction of at least four electrons.« less

Direct observation and analysis of york-shell materials using low-voltage high-resolution scanning electron microscopy: Nanometal-particles encapsulated in metal-oxide, carbon, and polymer

NASA Astrophysics Data System (ADS)

Asahina, Shunsuke; Suga, Mitsuo; Takahashi, Hideyuki; Young Jeong, Hu; Galeano, Carolina; Schüth, Ferdi; Terasaki, Osamu

2014-11-01

Nanometal particles show characteristic features in chemical and physical properties depending on their sizes and shapes. For keeping and further enhancing their features, the particles should be protected from coalescence or degradation. One approach is to encapsulate the nanometal particles inside pores with chemically inert or functional materials, such as carbon, polymer, and metal oxides, which contain mesopores to allow permeation of only chemicals not the nanometal particles. Recently developed low-voltage high-resolution scanning electron microscopy was applied to the study of structural, chemical, and electron state of both nanometal particles and encapsulating materials in yolk-shell materials of Au@C, Ru/Pt@C, Au@TiO2, and Pt@Polymer. Progresses in the following categories were shown for the yolk-shell materials: (i) resolution of topographic image contrast by secondary electrons, of atomic-number contrast by back-scattered electrons, and of elemental mapping by X-ray energy dispersive spectroscopy; (ii) sample preparation for observing internal structures; and (iii) X-ray spectroscopy such as soft X-ray emission spectroscopy. Transmission electron microscopy was also used for characterization of Au@C.

The microscopic Z-pinch process of current-carrying rarefied deuterium plasma shell

NASA Astrophysics Data System (ADS)

Ning, Cheng; Feng, Zhixing; Xue, Chuang; Li, Baiwen

2015-02-01

For insight into the microscopic mechanism of Z-pinch dynamic processes, a code of two-dimensional particle-in-cell (PIC) simulation has been developed in cylindrical coordinates. In principle, the Z-pinch of current-carrying rarefied deuterium plasma shell has been simulated by means of this code. Many results related to the microscopic processes of the Z-pinch are obtained. They include the spatio-temporal distributions of electromagnetic field, current density, forces experienced by the ions and electrons, positions and energy distributions of particles, and trailing mass and current. In radial direction, the electric and magnetic forces exerted on the electrons are comparable in magnitude, while the forces exerted on the ions are mainly the electric forces. So in the Z-pinch process, the electrons are first accelerated in Z direction and get higher velocities; then, they are driven inwards to the axis at the same time by the radial magnetic forces (i.e., Lorentz forces) of them. That causes the separations between the electrons and ions because the ion mass is much larger than the electron's, and in turn a strong electrostatic field is produced. The produced electrostatic field attracts the ions to move towards the electrons. When the electrons are driven along the radial direction to arrive at the axis, they shortly move inversely due to the static repellency among them and their tiny mass, while the ions continue to move inertially inwards, and later get into stagnation, and finally scatter outwards. Near the stagnation, the energies of the deuterium ions mostly range from 0.3 to 6 keV, while the electron energies are mostly from 5 to 35 keV. The radial components, which can contribute to the pinched plasma temperature, of the most probable energies of electron and ion at the stagnation are comparable to the Bennett equilibrium temperature (about 1 keV), and also to the highest temperatures of electron and ion obtained in one dimensional radiation magnetohydrodynamic simulation of the plasma shell Z-pinch. The trailing mass is about 20% of the total mass of the shell, and the maximum trailing current is about 7% of the driven current under our trailing definition. Our PIC simulation also demonstrates that the plasma shell first experiences a snow-plow like implosion process, which is relatively stable.

Sound Transmission through Two Concentric Cylindrical Sandwich Shells

NASA Technical Reports Server (NTRS)

Tang, Yvette Y.; Silcox, Richard J.; Robinson, Jay H.

1996-01-01

This paper solves the problem of sound transmission through a system of two infinite concentric cylindrical sandwich shells. The shells are surrounded by external and internal fluid media and there is fluid (air) in the annular space between them. An oblique plane sound wave is incident upon the surface of the outer shell. A uniform flow is moving with a constant velocity in the external fluid medium. Classical thin shell theory is applied to the inner shell and first-order shear deformation theory is applied to the outer shell. A closed form for transmission loss is derived based on modal analysis. Investigations have been made for the impedance of both shells and the transmission loss through the shells from the exterior into the interior. Results are compared for double sandwich shells and single sandwich shells. This study shows that: (1) the impedance of the inner shell is much smaller than that of the outer shell so that the transmission loss is almost the same in both the annular space and the interior cavity of the shells; (2) the two concentric sandwich shells can produce an appreciable increase of transmission loss over single sandwich shells especially in the high frequency range; and (3) design guidelines may be derived with respect to the noise reduction requirement and the pressure in the annular space at a mid-frequency range.

Influence of Shell Thickness on the Performance of NiO-Based All-Inorganic Quantum Dot Light-Emitting Diodes.

PubMed

Wang, Ting; Zhu, Bingyan; Wang, Shuangpeng; Yuan, Qilin; Zhang, Han; Kang, Zhihui; Wang, Rong; Zhang, Hanzhuang; Ji, Wenyu

2018-05-02

The effect of shell thickness on the performance of all-inorganic quantum dot light-emitting diodes (QLEDs) is explored by employing a series of green quantum dots (QDs) (Zn x Cd 1- x Se/ZnS core/shell QDs with different ZnS shell thicknesses) as the emitters. ZnO nanoparticles and sol-gel NiO are employed as the electron and hole transport materials, respectively. Time-resolved and steady-state photoluminescence results indicate that positive charging processes might occur for the QDs deposited on NiO, which results in emission quenching of QDs and poor device performance. The thick shell outside the core in QDs not only largely suppresses the QD emission quenching but also effectively preserves the excitons in QDs from dissociation of electron-hole pairs when they are subjected to an electric field. The peak efficiency of 4.2 cd/A and maximum luminance of 4205 cd/m 2 are achieved for the device based on QDs with the thickest shells (∼4.2 nm). We anticipate that these results will spur progress toward the design and realization of efficient all-inorganic QLEDs as a platform for the QD-based full-colored displays.

PMMA/PS coaxial electrospinning: a statistical analysis on processing parameters

NASA Astrophysics Data System (ADS)

Rahmani, Shahrzad; Arefazar, Ahmad; Latifi, Masoud

2017-08-01

Coaxial electrospinning, as a versatile method for producing core-shell fibers, is known to be very sensitive to two classes of influential factors including material and processing parameters. Although coaxial electrospinning has been the focus of many studies, the effects of processing parameters on the outcomes of this method have not yet been well investigated. A good knowledge of the impacts of processing parameters and their interactions on coaxial electrospinning can make it possible to better control and optimize this process. Hence, in this study, the statistical technique of response surface method (RSM) using the design of experiments on four processing factors of voltage, distance, core and shell flow rates was applied. Transmission electron microscopy (TEM), scanning electron microscopy (SEM), oil immersion and Fluorescent microscopy were used to characterize fiber morphology. The core and shell diameters of fibers were measured and the effects of all factors and their interactions were discussed. Two polynomial models with acceptable R-squares were proposed to describe the core and shell diameters as functions of the processing parameters. Voltage and distance were recognized as the most significant and influential factors on shell diameter, while core diameter was mainly under the influence of core and shell flow rates besides the voltage.

Palladium-platinum core-shell electrocatalysts for oxygen reduction reaction prepared with the assistance of citric acid

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

Zhang, Lulu; Su, Dong; Zhu, Shangqian

Core–shell structure is a promising alternative to solid platinum (Pt) nanoparticles as electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). A simple method of preparing palladium (Pd)–platinum (Pt) core–shell catalysts (Pd@Pt/C) in a gram-batch was developed with the assistance of citric acid. The Pt shell deposition involves three different pathways: galvanic displacement reaction between Pd atoms and Pt cations, chemical reduction by citric acid, and reduction by negative charges on Pd surfaces. The uniform ultrathin (~0.4 nm) Pt shell was characterized by in situ X-ray diffraction (XRD) and high-angle annular dark-field scanning transmission electron microscopymore » (HAADF-STEM) images combined with electron energy loss spectroscopy (EELS). Compared with state-of-the-art Pt/C, the Pd@Pt/C core–shell catalyst showed 4 times higher Pt mass activity and much better durability upon potential cycling. As a result, both the mass activity and durability were comparable to that of Pd@Pt/C synthesized by a Cu-mediated-Pt-displacement method, which is more complicated and difficult for mass production.« less

Core-shell structured SiO2@YVO4:Dy3+/Sm3+ phosphor particles: sol-gel preparation and characterization.

PubMed

Wang, H; Yu, M; Lin, C K; Lin, J

2006-08-01

Spherical SiO(2) particles have been coated with YVO(4):Dy(3+)/Sm(3+) phosphor layers by a Pechini sol-gel process, leading to the formation of core-shell structured SiO(2)@YVO(4):Dy(3+)/Sm(3+) particles. X-ray diffraction (XRD), Fourier-transform IR spectroscopy, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting SiO(2)@YVO(4):Dy(3+)/Sm(3+) core-shell phosphors. The obtained core-shell phosphors have perfect spherical shape with narrow size distribution (average size ca. 300 nm), smooth surface and non-agglomeration. The thickness of shells could be easily controlled by changing the number of deposition cycles (20 nm for one deposition cycle). The core-shell particles show strong characteristic emission from Dy(3+) for SiO(2)@YVO(4):Dy(3+) and from Sm(3+) for SiO(2)@YVO(4):Sm(3+) due to an efficient energy transfer from YVO(4) host to them. The PL intensity of Dy(3+) and Sm(3+) increases with raising the annealing temperature and the number of coating cycles.

Template-Free Hydrothermal Synthesis, Mechanism, and Photocatalytic Properties of Core-Shell CeO2 Nanospheres

NASA Astrophysics Data System (ADS)

Li, Huijie; Meng, Fanming; Gong, Jinfeng; Fan, Zhenghua; Qin, Rui

2018-03-01

CeO2 nanospheres with the core-shell nanostructure have been successfully synthesized by a template-free hydrothermal method. The structures, morphologies and optical properties of core-shell CeO2 nanospheres were analyzed by X-ray diffraction (XRD), TG, Fourier transform infrared spectroscopy, XRD, EDS, SAED, scanning electron microscopy and transmission electron microscopy, UV-Vis diffuse reflectance spectra, Raman analyses. The degradation efficiencies of core-shell CeO2 nanospheres for methyl orange were as high as 93.49, 95.67 and 98.28% within 160 min, and the rates of photo degradation of methyl orange by core-shell CeO2 nanospheres under UV-light were 0.01693, 0.01782 and 0.02375 min-1. Methyl orange was degraded in photocatalytic oxidation processes, which mainly gave the credit to a large number of reactive species including h+, surface superoxide species ·O2 -, and ·OH radicals. The core-shell structure, small crystallite size and the conversion between Ce3+ and Ce4+ of CeO2 nanospheres were of importance for its catalytic activity. These results demonstrated the possibility of improving the efficient catalysts of the earth abundant CeO2 catalysts.

Synthesis and thermal stability of W/WS{sub 2} inorganic fullerene-like nanoparticles with core-shell structure

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

Chang Lianxia; Yang Haibin; Fu Wuyou

W/WS{sub 2} inorganic fullerene-like (IF) nanoparticles with core-shell structure are synthesized by the reaction of tungsten nanospheres and sulfur at relatively low temperatures (380-600 deg. C) under hydrogen atmosphere, in which tungsten nanospheres were prepared by wire electrical explosion method. Images of transmission electron microscopy and high-resolution transmission electron microscopy show that the composite particles are of core-shell structure with spherical shape and the shell thickness is about 10 nm. X-ray powder diffraction results indicate that the interlayer spacing of IF-WS{sub 2} shell decreases and approaches that of 2H-WS{sub 2} with increasing annealing temperatures, representing an expansion of 3.3-1.6%. Amore » mechanism of IF-WS{sub 2} formation via sulfur diffusion into fullerene nanoparticles is discussed. Thermal analysis shows that the nanoparticles obtained at different temperatures exhibit similar thermal stability and the onset temperature of oxidization is about 410 deg. C. Encapsulating hard tungsten core into IF-WS{sub 2} and the spherical shape of the core-shell structures may enhance their performance in tribological applications.« less

Facile green in situ synthesis of Mg/CuO core/shell nanoenergetic arrays with a superior heat-release property and long-term storage stability.

PubMed

Zhou, Xiang; Xu, Daguo; Zhang, Qiaobao; Lu, Jian; Zhang, Kaili

2013-08-14

We report a facile green method for the in situ synthesis of Mg/CuO core/shell nanoenergetic arrays on silicon, with Mg nanorods as the core and CuO as the shell. Mg nanorods are first prepared by glancing angle deposition. CuO is then deposited around the Mg nanorods by reactive magnetron sputtering to realize the core/shell structure. Various characterization techniques are used to investigate the prepared Mg/CuO core/shell nanoenergetic arrays, including scanning electron microscopy, transmission electron microscopy, X-ray energy dispersive spectroscopy, X-ray diffraction, and thermal analysis. Uniform mixing and intimate contact between the Mg nanorods and CuO are confirmed from both visual inspection of the morphological images and analyses of the heat-release curves. The nanoenergetic arrays exhibit a low-onset reaction temperature (∼300 °C) and high heat of reaction (∼3400 J/g). Most importantly, the nanoenergetic arrays possess long-term storage stability resulting from the stable CuO shell. This study provides a potential general strategy for the synthesis of various Mg nanorod-based stable nanoenergetic arrays.

Palladium-platinum core-shell electrocatalysts for oxygen reduction reaction prepared with the assistance of citric acid

DOE PAGES

Zhang, Lulu; Su, Dong; Zhu, Shangqian; ...

2016-04-26

Core–shell structure is a promising alternative to solid platinum (Pt) nanoparticles as electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). A simple method of preparing palladium (Pd)–platinum (Pt) core–shell catalysts (Pd@Pt/C) in a gram-batch was developed with the assistance of citric acid. The Pt shell deposition involves three different pathways: galvanic displacement reaction between Pd atoms and Pt cations, chemical reduction by citric acid, and reduction by negative charges on Pd surfaces. The uniform ultrathin (~0.4 nm) Pt shell was characterized by in situ X-ray diffraction (XRD) and high-angle annular dark-field scanning transmission electron microscopymore » (HAADF-STEM) images combined with electron energy loss spectroscopy (EELS). Compared with state-of-the-art Pt/C, the Pd@Pt/C core–shell catalyst showed 4 times higher Pt mass activity and much better durability upon potential cycling. As a result, both the mass activity and durability were comparable to that of Pd@Pt/C synthesized by a Cu-mediated-Pt-displacement method, which is more complicated and difficult for mass production.« less

Introduction of biotin or folic acid into polypyrrole magnetite core-shell nanoparticles

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

Nan, Alexandrina; Turcu, Rodica; Liebscher, Jürgen

2013-11-13

In order to contribute to the trend in contemporary research to develop magnetic core shell nanoparticles with better properties (reduced toxicity, high colloidal and chemical stability, wide scope of application) in straightforward and reproducible methods new core shell magnetic nanoparticles were developed based on polypyrrole shells functionalized with biotin and folic acid. Magnetite nanoparticles stabilized by sebacic acid were used as magnetic cores. The morphology of magnetite was determined by transmission electron microscopy TEM, while the chemical structure investigated by FT-IR.

ELECTRON-CAPTURE AND β-DECAY RATES FOR sd-SHELL NUCLEI IN STELLAR ENVIRONMENTS RELEVANT TO HIGH-DENSITY O–NE–MG CORES

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

Suzuki, Toshio; Toki, Hiroshi; Nomoto, Ken’ichi, E-mail: suzuki@phys.chs.nihon-u.ac.jp

Electron-capture and β-decay rates for nuclear pairs in the sd-shell are evaluated at high densities and high temperatures relevant to the final evolution of electron-degenerate O–Ne–Mg cores of stars with initial masses of 8–10 M{sub ⊙}. Electron capture induces a rapid contraction of the electron-degenerate O–Ne–Mg core. The outcome of rapid contraction depends on the evolutionary changes in the central density and temperature, which are determined by the competing processes of contraction, cooling, and heating. The fate of the stars is determined by these competitions, whether they end up with electron-capture supernovae or Fe core-collapse supernovae. Since the competing processes aremore » induced by electron capture and β-decay, the accurate weak rates are crucially important. The rates are obtained for pairs with A = 20, 23, 24, 25, and 27 by shell-model calculations in the sd-shell with the USDB Hamiltonian. Effects of Coulomb corrections on the rates are evaluated. The rates for pairs with A = 23 and 25 are important for nuclear Urca processes that determine the cooling rate of the O–Ne–Mg core, while those for pairs with A = 20 and 24 are important for the core contraction and heat generation rates in the core. We provide these nuclear rates at stellar environments in tables with fine enough meshes at various densities and temperatures for studies of astrophysical processes sensitive to the rates. In particular, the accurate rate tables are crucially important for the final fates of not only O–Ne–Mg cores but also a wider range of stars, such as C–O cores of lower-mass stars.« less

Does the 4f-shell contribute to bonding in tetravalent lanthanide halides?

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

Ji, Wen-Xin; School of Chemistry and Chemical Engineering, Ningxia University, 750015 Yinchuan; Xu, Wei

2014-12-28

Lanthanide tetrahalide molecules LnX{sub 4} (Ln = Ce, Pr, Tb; X = F, Cl, Br, I) have been investigated by density functional theory at the levels of the relativistic Zero Order Regular Approximation and the relativistic energy-consistent pseudopotentials, using frozen small- and medium-cores. The calculated bond lengths and vibrational frequencies are close to the experimental data. Our calculations indicate 4f shell contributions to bonding in LnX{sub 4}, in particular for the early lanthanides, which show significant overlap between the Ln 4f-shell and the halogen np-shells. The 4f shells contribute to Ln-X bonding in LnX{sub 4} about one third more thanmore » in LnX{sub 3}.« less

On the shape and orientation control of an orbiting shallow spherical shell structure

NASA Technical Reports Server (NTRS)

Bainum, P. M.; Reddy, A. S. S. R.

1982-01-01

The dynamics of orbiting shallow flexible spherical shell structures under the influence of control actuators was studied. Control laws are developed to provide both attitude and shape control of the structure. The elastic modal frequencies for the fundamental and lower modes are closely grouped due to the effect of the shell curvature. The shell is gravity stabilized by a spring loaded dumbbell type damper attached at its apex. Control laws are developed based on the pole clustering techniques. Savings in fuel consumption can be realized by using the hybrid shell dumbbell system together with point actuators. It is indicated that instability may result by not including the orbital and first order gravity gradient effects in the plant prior to control law design.

THERMALLY SHIELDED MOISTURE REMOVAL DEVICE

DOEpatents

Miller, O.E.

1958-08-26

An apparatus is presented for removing moisture from the air within tanks by condensation upon a cartridge containing liquid air. An insulating shell made in two halves covers the cartridge within the evacuated system. The shell halves are hinged together and are operated by a system of levers from outside the tank with the motion translated through a sylphon bellows to cover and uncover the cartridge. When the condensation of moisture is in process, the insulative shell is moved away from the liquid air cartridge, and during that part of the process when there is no freezing out of moisture, the shell halves are closed on the cell so thnt the accumulated frost is not evaporated. This insulating shell greatly reduces the consumption of liquid air in this condensation process.

Selective isolation of the electron or hole in photocatalysis: ZnO-TiO2 and TiO2-ZnO core-shell structured heterojunction nanofibers via electrospinning and atomic layer deposition.

PubMed

Kayaci, Fatma; Vempati, Sesha; Ozgit-Akgun, Cagla; Donmez, Inci; Biyikli, Necmi; Uyar, Tamer

2014-06-07

Heterojunctions are a well-studied material combination in photocatalysis studies, the majority of which aim to improve the efficacy of the catalysts. Developing novel catalysts begs the question of which photo-generated charge carrier is more efficient in the process of catalysis and the associated mechanism. To address this issue we have fabricated core-shell heterojunction (CSHJ) nanofibers from ZnO and TiO2 in two combinations where only the 'shell' part of the heterojunction is exposed to the environment to participate in the photocatalysis. Core and shell structures were fabricated via electrospinning and atomic layer deposition, respectively which were then subjected to calcination. These CSHJs were characterized and studied for photocatalytic activity (PCA). These two combinations expose electrons or holes selectively to the environment. Under suitable illumination of the ZnO-TiO2 CSHJ, e/h pairs are created mainly in TiO2 and the electrons take part in catalysis (i.e. reduce the organic dye) at the conduction band or oxygen vacancy sites of the 'shell', while holes migrate to the core of the structure. Conversely, holes take part in catalysis and electrons diffuse to the core in the case of a TiO2-ZnO CSHJ. The results further revealed that the TiO2-ZnO CSHJ shows ∼1.6 times faster PCA when compared to the ZnO-TiO2 CSHJ because of efficient hole capture by oxygen vacancies, and the lower mobility of holes.

Electron impact action spectroscopy of mass/charge selected macromolecular ions: Inner-shell excitation of ubiquitin protein

DOE PAGES

Rankovic, Milos Lj.; Giuliani, Alexandre; Milosavljevic, Aleksandar R.

2016-02-11

In this study, we have performed inner-shell electron impact action spectroscopy of mass and charge selected macromolecular ions. For this purpose, we have coupled a focusing electron gun with a linear quadrupole ion trap mass spectrometer. This experiment represents a proof of principle that an energy-tunable electron beam can be used in combination with radio frequency traps as an activation method in tandem mass spectrometry (MS 2) and allows performing action spectroscopy. Electron impact MS 2 spectra of multiply protonated ubiquitin protein ion have been recorded at incident electron energies around the carbon 1s excitation. Both MS 2 and singlemore » ionization energy dependence spectra are compared with literature data obtained using the soft X-ray activation conditions.« less

Electron impact action spectroscopy of mass/charge selected macromolecular ions: Inner-shell excitation of ubiquitin protein

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

Rankovic, Milos Lj.; Giuliani, Alexandre; Milosavljevic, Aleksandar R.

In this study, we have performed inner-shell electron impact action spectroscopy of mass and charge selected macromolecular ions. For this purpose, we have coupled a focusing electron gun with a linear quadrupole ion trap mass spectrometer. This experiment represents a proof of principle that an energy-tunable electron beam can be used in combination with radio frequency traps as an activation method in tandem mass spectrometry (MS 2) and allows performing action spectroscopy. Electron impact MS 2 spectra of multiply protonated ubiquitin protein ion have been recorded at incident electron energies around the carbon 1s excitation. Both MS 2 and singlemore » ionization energy dependence spectra are compared with literature data obtained using the soft X-ray activation conditions.« less

Simulating Self-Assembly with Simple Models

NASA Astrophysics Data System (ADS)

Rapaport, D. C.

Results from recent molecular dynamics simulations of virus capsid self-assembly are described. The model is based on rigid trapezoidal particles designed to form polyhedral shells of size 60, together with an atomistic solvent. The underlying bonding process is fully reversible. More extensive computations are required than in previous work on icosahedral shells built from triangular particles, but the outcome is a high yield of closed shells. Intermediate clusters have a variety of forms, and bond counts provide a useful classification scheme

Magnetic field insensitive photoluminescence decay of ZnSe/CdS core/shell type-II colloidal quantum dots

NASA Astrophysics Data System (ADS)

Lee, Woojin; Park, Seongho; Murayama, Akihiro; Lee, Jong-soo; Kyhm, Kwangseuk

2018-06-01

We have synthesized ZnSe/CdS core/shell type-II colloidal quantum dots, where an electron and a hole are separated in the CdS shell and the ZnSe core, respectively. Our theoretical model has revealed that absorbance spectrum of bare ZnSe quantum dots in 2 nm radius becomes broadened with a large redshift (∼1.15 eV) when the electron in ZnSe core is separated by 3.2 nm CdS shell. Also, we found that our type-II QDs are insensitive to an external magnetic field up to 5 T in terms of central emission energy, degree of polarization, and photoluminescence decay time. This can be attributed to the electron–hole charge separation in a type-II structure, whereby the suppressed exchange interaction gives rise to a magnetic insensitivity with a small energy difference between the bright and dark exciton states.

Bubble nucleation and migration in a lead-iron hydr(oxide) core-shell nanoparticle

DOE PAGES

Niu, Kaiyang; Frolov, Timofey; Xin, Huolin L.; ...

2015-10-05

Iron hydroxide is found in a wide range of contexts ranging from biominerals to steel corrosion, and it can transform to anhydrous oxide via releasing O 2 gas and H 2O. However, it is not well understood how gases transport through a crystal lattice. Here, we present in situ observation of the nucleation and migration of gas bubbles in iron (hydr)oxide using transmission electron microscopy. We create Pb–FeOOH model core–shell nanoparticles in a liquid cell. Under electron irradiation, iron hydroxide transforms to iron oxide, during which bubbles are generated, and they migrate through the shell to the nanoparticle surface. Geometricmore » phase analysis of the shell lattice shows an inhomogeneous stain field at the bubbles. In conclusion, our modeling suggests that the elastic interaction between the core and the bubble provides a driving force for bubble migration.« less

Investigation of CuInSe2 nanowire arrays with core-shell structure electrodeposited at various duty cycles into anodic alumina templates

NASA Astrophysics Data System (ADS)

Cheng, Yu-Song; Wang, Na-Fu; Tsai, Yu-Zen; Lin, Jia-Jun; Houng, Mau-Phon

2017-02-01

Copper indium selenide (CuInSe2) nanowire (NW) arrays were prepared at various electrolyte duty cycles by filling anodic alumina templates through the pulsed electrodeposition technique. X-ray diffraction and scanning electron microscopy (SEM) images showed that the nucleation mechanism of CuInSe2 NW arrays was affected by the electrodeposition duty cycle. Moreover, SEM images showed that the diameter and length of the NWs were 80 nm and 2 μm, respectively. Furthermore, PEDOT/CuInSe2 NW core-shell arrays were fabricated using surfactant-modified CuInSe2 NW surfaces showing the lotus effect. Transmission electron microscopy images confirmed that a core-shell structure was achieved. Current-voltage plots revealed that the CuInSe2 NW arrays were p-type semiconductors; moreover, the core-shell structure improved the diode ideality factor from 3.91 to 2.63.

Bubble nucleation and migration in a lead–iron hydr(oxide) core–shell nanoparticle

PubMed Central

Niu, Kaiyang; Frolov, Timofey; Xin, Huolin L.; Wang, Junling; Asta, Mark; Zheng, Haimei

2015-01-01

Iron hydroxide is found in a wide range of contexts ranging from biominerals to steel corrosion, and it can transform to anhydrous oxide via releasing O2 gas and H2O. However, it is not well understood how gases transport through a crystal lattice. Here, we present in situ observation of the nucleation and migration of gas bubbles in iron (hydr)oxide using transmission electron microscopy. We create Pb–FeOOH model core–shell nanoparticles in a liquid cell. Under electron irradiation, iron hydroxide transforms to iron oxide, during which bubbles are generated, and they migrate through the shell to the nanoparticle surface. Geometric phase analysis of the shell lattice shows an inhomogeneous stain field at the bubbles. Our modeling suggests that the elastic interaction between the core and the bubble provides a driving force for bubble migration. PMID:26438864

Amplitude fluctuations driven by the density of electron pairs within nanosize granular structures inside strongly disordered superconductors: evidence for a shell-like effect.

PubMed

Ghosh, Sanjib; Mandal, Sudhansu S

2013-11-15

Motivated by the recent observation of the shell effect in a nanoscale pure superconductor by Bose et al. [Nat. Mater. 9, 550 (2010)], we explore the possible shell-like effect in a strongly disordered superconductor as it is known to produce nanosize superconducting puddles (SPs). We find a remarkable change in the texture of the pairing amplitudes that is responsible for forming the SP, upon monotonic tuning of the average electron density, , and keeping the disorder landscape unaltered. Both the spatially averaged pairing amplitude and the quasiparticle excitation gap oscillate with . This oscillation is due to a rapid change in the low-lying quasiparticle energy spectra and thereby a change in the shapes and positions of the SPs. We establish a correlation between the formation of SPs and the shell-like effect. The experimental consequences of our theory are also discussed.

Quantifying the Impact of Nanoparticle Coatings and Non-uniformities on XPS Analysis: Gold/silver Core-shell Nanoparticles

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

Wang, Yung-Chen Andrew; Engelhard, Mark H.; Baer, Donald R.

2016-03-07

Abstract or short description: Spectral modeling of photoelectrons can serve as a valuable tool when combined with X-ray photoelectron spectroscopy (XPS) analysis. Herein, a new version of the NIST Simulation of Electron Spectra for Surface Analysis (SESSA 2.0) software, capable of directly simulating spherical multilayer NPs, was applied to model citrate stabilized Au/Ag-core/shell nanoparticles (NPs). The NPs were characterized using XPS and scanning transmission electron microscopy (STEM) to determine the composition and morphology of the NPs. The Au/Ag-core/shell NPs were observed to be polydispersed in size, non-circular, and contain off-centered Au-cores. Using the average NP dimensions determined from STEM analysis,more » SESSA spectral modeling indicated that washed Au/Ag-core shell NPs were stabilized with a 0.8 nm l« less

Injection and trapping of tunnel-ionized electrons into laser-produced wakes.

PubMed

Pak, A; Marsh, K A; Martins, S F; Lu, W; Mori, W B; Joshi, C

2010-01-15

A method, which utilizes the large difference in ionization potentials between successive ionization states of trace atoms, for injecting electrons into a laser-driven wakefield is presented. Here a mixture of helium and trace amounts of nitrogen gas was used. Electrons from the K shell of nitrogen were tunnel ionized near the peak of the laser pulse and were injected into and trapped by the wake created by electrons from majority helium atoms and the L shell of nitrogen. The spectrum of the accelerated electrons, the threshold intensity at which trapping occurs, the forward transmitted laser spectrum, and the beam divergence are all consistent with this injection process. The experimental measurements are supported by theory and 3D OSIRIS simulations.

Correlated ab initio calculations of spectroscopic parameters of SnO within the framework of the higher-order generalized Douglas-Kroll transformation.

PubMed

Wolf, Alexander; Reiher, Markus; Hess, Bernd Artur

2004-05-08

The first molecular calculations with the generalized Douglas-Kroll method up to fifth order in the external potential (DKH5) are presented. We study the spectroscopic parameters and electron affinity of the tin oxide molecule SnO and its anion SnO(-) applying nonrelativistic as well as relativistic calculations with higher orders of the DK approximation. In order to guarantee highly accurate results close to the basis set limit, an all-electron basis for Sn of at least quintuple-zeta quality has been constructed and optimized. All-electron CCSD(T) calculations of the potential energy curves of both SnO and SnO(-) reproduce the experimental values very well. Relative energies and valence properties are already well described with the established standard second-order approximation DKH2 and the higher-order corrections DKH3-DKH5 hardly affect these quantities. However, an accurate description of total energies and inner-shell properties requires superior relativistic schemes up to DKH5. (c) 2004 American Institute of Physics.

Superthermal Electron Energy Interchange in the Ionosphere-Plasmasphere System

NASA Technical Reports Server (NTRS)

Khazanov, G. V.; Glocer, A.; Liemohn, M. W.; Himwich, E. W.

2013-01-01

A self-consistent approach to superthermal electron (SE) transport along closed field lines in the inner magnetosphere is used to examine the concept of plasmaspheric transparency, magnetospheric trapping, and SE energy deposition to the thermal electrons. The dayside SE population is generated both by photoionization of the thermosphere and by secondary electron production from impact ionization when the photoelectrons collide with upper atmospheric neutral particles. It is shown that a self-consistent approach to this problem produces significant changes, in comparison with other approaches, in the SE energy exchange between the plasmasphere and the two magnetically conjugate ionospheres. In particular, plasmaspheric transparency can vary by a factor of two depending on the thermal plasma content along the field line and the illumination conditions of the two conjugate ionospheres. This variation in plasmaspheric transparency as a function of thermal plasma and ionospheric conditions increases with L-shell, as the field line gets longer and the equatorial pitch angle extent of the fly-through zone gets smaller. The inference drawn from these results is that such a self-consistent approach to SE transport and energy deposition should be included to ensure robustness in ionosphere-magnetosphere modeling networks.

Enhanced flexibility and electron-beam-controlled shape recovery in alumina-coated Au and Ag core-shell nanowires

NASA Astrophysics Data System (ADS)

Vlassov, Sergei; Polyakov, Boris; Vahtrus, Mikk; Mets, Magnus; Antsov, Mikk; Oras, Sven; Tarre, Aivar; Arroval, Tõnis; Lõhmus, Rünno; Aarik, Jaan

2017-12-01

The proper choice of coating materials and methods in core-shell nanowire (NW) engineering is crucial to assuring improved characteristics or even new functionalities of the resulting composite structures. In this paper, we have reported electron-beam-induced reversible elastic-to-plastic transition in Ag/Al2O3 and Au/Al2O3 NWs prepared by the coating of Ag and Au NWs with Al2O3 by low-temperature atomic layer deposition. The observed phenomenon enabled freezing the bent core-shell NW at any arbitrary curvature below the yield strength of the materials and later restoring its initially straight profile by irradiating the NW with electrons. In addition, we demonstrated that the coating efficiently protects the core material from fracture and plastic yield, allowing it to withstand significantly higher deformations and stresses in comparison to uncoated NW.

Recombination of open-f-shell tungsten ions

NASA Astrophysics Data System (ADS)

Krantz, C.; Badnell, N. R.; Müller, A.; Schippers, S.; Wolf, A.

2017-03-01

We review experimental and theoretical efforts aimed at a detailed understanding of the recombination of electrons with highly charged tungsten ions characterised by an open 4f sub-shell. Highly charged tungsten occurs as a plasma contaminant in ITER-like tokamak experiments, where it acts as an unwanted cooling agent. Modelling of the charge state populations in a plasma requires reliable thermal rate coefficients for charge-changing electron collisions. The electron recombination of medium-charged tungsten species with open 4f sub-shells is especially challenging to compute reliably. Storage-ring experiments have been conducted that yielded recombination rate coefficients at high energy resolution and well-understood systematics. Significant deviations compared to simplified, but prevalent, computational models have been found. A new class of ab initio numerical calculations has been developed that provides reliable predictions of the total plasma recombination rate coefficients for these ions.

High-Energy Electron Shell in ECR Ion Source:

NASA Astrophysics Data System (ADS)

Niimura, M. G.; Goto, A.; Yano, Y.

1997-05-01

As an injector of cyclotrons and RFQ linacs, ECR ion source (ECRIS) is expected to deliver highly charged ions (HCI) at high beam-current (HBC). Injections of light gases and supplementary electrons have been employed for enhancement of HCI and HBC, respectively. Further amelioration of the performance may be feasible by investigating the hot-electron ring inside an ECRIS. Its existence has been granted because of the MeV of Te observable via X-ray diagnostics. However, its location, acceleration mechanism, and effects on the performance are not well known.We found them by deriving the radially negative potential distribution for an ECRIS from measured endloss-current data. It was evidenced from a hole-burning on the parabolic potential profile (by uniformly distributed warm-electron space charges of 9.5x10^5cm-3) and from a local minimum of the electrostatically-trapped ion distribution. A high-energy electron shell (HEES) was located right on the ECR-radius of 6 cm with shell-halfwidth of 1 cm. Such a thin shell around core plasma can only be generated by the Sadeev-Shapiro or v_phxBz acceleration mechanism that can raise Te up to a relativistic value. Here, v_ph is the phase velocity of ES Bernstein waves propagating backwards against incident microwave and Bz the axial mirror magnetic field. The HEES carries diamagnetic current which reduces the core magnetic pressure, thereby stabilizing the ECR surface against driftwave instabilities similarly to gas-mixing.

Localized surface plasmon mediated energy transfer in the vicinity of core-shell nanoparticle

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

Shishodia, Manmohan Singh, E-mail: manmohan@gbu.ac.in; Juneja, Soniya

2016-05-28

Multipole spectral expansion based theory of energy transfer interactions between a donor and an acceptor molecule in the vicinity of a core-shell (nanoshell or core@shell) based plasmonic nanostructure is developed. In view of the diverse applications and rich plasmonic features such as tuning capability of surface plasmon (SP) frequencies, greater sensitivity to the change of dielectric environment, controllable redirection of electromagnetic radiation, closed form expressions for Energy Transfer Rate Enhancement Factor (ETREF) near core-shell particle are reported. The dependence of ETREF on different parameters is established through fitting equations, perceived to be of key importance for developing appropriate designs. Themore » theoretical approach developed in the present work is capable of treating higher order multipoles, which, in turn, are also shown to play a crucial role in the present context. Moreover, closed form expressions derived in the present work can directly be used as formula, e.g., for designing SP based biosensors and estimating energy exchange between proteins and excitonic interactions in quantum dots.« less

Hexakis(3,6-di-tert-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)cyclohexane: Closed-shell [6]Radialene or Open-shell Hexa-radicaloid?

PubMed

Wu, Jishan; Feng, Jiaqi; Gopalakrishna, Tullimilli Y; Phan, Hoa

2018-04-19

We report a star-shaped hexaquinocyclohexane molecule 4c, which turns out to be a closed-shell extended [6]radialene with a twisted-boat conformation according to X-ray crystallographic analysis. It was formed by an unusually slow decay of its in situ generated open-shell valence isomer, the hexa-radicaloid 4o, with a half-life time of about 156 min at room temperature. Reaction progress kinetic analysis revealed a large energy barrier of about 95.5 ± 4.3 kJ/mol at room temperature from the hexa-radical form 4o to the contorted [6]radialene form 4c, because the transformation need overcome large steric repulsion between the neighbouring phenoxyl units. Compound 4c can be chemically reduced to radical anion and dianion, and the dianion is actually a diradical dianion, with a calculated diradical character of 71.9%. This study demonstrated the unique chemical bonding nature of contorted quinoidal π-conjugated molecules and a very unusual valence isomerization process. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Single molecule conductivity: the role of junction-orbital degeneracy in the artificially high currents predicted by ab initio approaches.

PubMed

Solomon, Gemma C; Reimers, Jeffrey R; Hush, Noel S

2004-10-08

A priori evaluations, using Hartree-Fock self-consistent-field (SCF) theory or density-functional theory (DFT), of the current passing between two electrodes through a single bridging molecule result in predicted conductivities that may be up to one to two orders of magnitude larger than observed ones. We demonstrate that this is, in part, often due to the improper application of the computational methods. Conductivity is shown to arise from tunneling between junction states of the electrodes through the molecule; these states are inherently either quasi two-fold or four-fold degenerate and always comprise the (highest occupied molecular orbital) HOMO band at the Fermi energy of the system. Frequently, in previous cluster based molecular conduction calculations, closed-shell SCF or Kohn-Sham DFT methods have been applied to systems that we demonstrate to be intrinsically open shell in nature. Such calculations are shown to induce artificial HOMO-LUMO (LUMO-lowest unoccupied molecular orbital) band splittings that Landauer-based formalisms for steady-state conduction interpret as arising from extremely rapid through-molecule tunneling at the Fermi energy, hence, overestimating the low-voltage conductivity. It is demonstrated that these shortcomings can be eliminated, dramatically reducing calculated current magnitudes, through the alternate use of electronic-structure calculations based on the spin-restricted open-shell formalism and related multiconfigurational SCF of DFT approaches. Further, we demonstrate that most anomalies arising in DFT implementations arise through the use of hybrid density functionals such as B3LYP. While the enhanced band-gap properties of these functionals have made them the defacto standard in molecular conductivity calculations, we demonstrate that it also makes them particularly susceptible to open-shell anomalies.

Structural and electrical properties of TiO{sub 2}/ZnO core–shell nanoparticles synthesized by hydrothermal method

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

Vlazan, P.; Ursu, D.H.; Irina-Moisescu, C.

TiO{sub 2}/ZnO core–shell nanoparticles were successfully synthesized by hydrothermal method in two stages: first stage is the hydrothermal synthesis of ZnO nanoparticles and second stage the obtained ZnO nanoparticles are encapsulated in TiO{sub 2}. The obtained ZnO, TiO{sub 2} and TiO{sub 2}/ZnO core–shell nanoparticles were investigated by means of X-ray diffraction, transmission electron microscopy, Brunauer, Emmett, Teller and resistance measurements. X-ray diffraction analysis revealed the presence of both, TiO{sub 2} and ZnO phases in TiO{sub 2}/ZnO core–shell nanoparticles. According to transmission electron microscopy images, ZnO nanoparticles have hexagonal shapes, TiO{sub 2} nanoparticles have a spherical shape, and TiO{sub 2}/ZnO core–shellmore » nanoparticles present agglomerates and the shape of particles is not well defined. The activation energy of TiO{sub 2}/ZnO core–shell nanoparticles was about 101 meV. - Graphical abstract: Display Omitted - Highlights: • TiO{sub 2}/ZnO core–shell nanoparticles were synthesized by hydrothermal method. • TiO{sub 2}/ZnO core–shell nanoparticles were investigated by means of XRD, TEM and BET. • Electrical properties of TiO{sub 2}/ZnO core–shell nanoparticles were investigated. • The activation energy of TiO{sub 2}/ZnO core–shell nanoparticles was about E{sub a} = 101 meV.« less

Vibration analysis of FG cylindrical shells with power-law index using discrete singular convolution technique

NASA Astrophysics Data System (ADS)

Mercan, Kadir; Demir, Çiǧdem; Civalek, Ömer

2016-01-01

In the present manuscript, free vibration response of circular cylindrical shells with functionally graded material (FGM) is investigated. The method of discrete singular convolution (DSC) is used for numerical solution of the related governing equation of motion of FGM cylindrical shell. The constitutive relations are based on the Love's first approximation shell theory. The material properties are graded in the thickness direction according to a volume fraction power law indexes. Frequency values are calculated for different types of boundary conditions, material and geometric parameters. In general, close agreement between the obtained results and those of other researchers has been found.

Planar CoB18- Cluster: a New Motif for - and Metallo-Borophenes

NASA Astrophysics Data System (ADS)

Chen, Teng-Teng; Jian, Tian; Lopez, Gary; Li, Wan-Lu; Chen, Xin; Li, Jun; Wang, Lai-Sheng

2016-06-01

Combined Photoelectron Spectroscopy (PES) and theoretical calculations have found that anion boron clusters (Bn-) are planar and quasi-planar up to B25-. Recent works show that anion pure boron clusters continued to be planar at B27-,B30-,B35- and B36-. B35- and B36- provide the first experimental evidence for the viability of the two-dimensional (2D) boron sheets (Borophene). The 2D to three-dimensional (3D) transitions are shown to happen at B40-,B39- and B28-, which possess cage-like structures. These fullerene-like boron cage clusters are named as Borospherene. Recently, borophenes or similar structures are claimed to be synthesized by several groups. Following an electronic design principle, a series of transition-metal-doped boron clusters (M©Bn-, n=8-10) are found to possess the monocyclic wheel structures. Meanwhile, CoB12- and RhB12- are revealed to adopt half-sandwich-type structures with the quasi-planar B12 moiety similar to the B12- cluster. Very lately, we show that the CoB16- cluster possesses a highly symmetric Cobalt-centered drum-like structure, with a new record of coordination number at 16. Here we report the CoB18- cluster to possess a unique planar structure, in which the Co atom is doped into the network of a planar boron cluster. PES reveals that the CoB18- cluster is a highly stable electronic system with the first adiabatic detachment energy (ADE) at 4.0 eV. Global minimum searches along with high-level quantum calculations show the global minimum for CoB18- is perfectly planar and closed shell (1A1) with C2v symmetry. The Co atom is bonded with 7 boron atoms in the closest coordination shell and the other 11 boron atoms in the outer coordination shell. The calculated vertical detachment energy (VDE) values match quite well with our experimental results. Chemical bonding analysis by the Adaptive Natural Density Partitioning (AdNDP) method shows the CoB18- cluster is π-aromatic with four 4-centered-2-electron (4c-2e) π bonds and one 19-centered-2-electron (19c-2e) π bond, 10 π electrons in total. This perfectly planar structure reveals the viability of creating a new class of hetero-borophenes and metallo-borophenes by doping metal atoms into the plane of monolayer boron atoms. This gives a new approach to design perspective hetero-borophenes and metallo-borophenes materials with tunable chemical, magnetic and optical properties.

On the structure and dynamics of the hydrated sulfite ion in aqueous solution--an ab initio QMCF MD simulation and large angle X-ray scattering study.

PubMed

Eklund, Lars; Hofer, Thomas S; Pribil, Andreas B; Rode, Bernd M; Persson, Ingmar

2012-05-07

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) formalism has been applied in conjunction to experimental large angle X-ray scattering to study the structure and dynamics of the hydrated sulfite ion in aqueous solution. The results show that there is a considerable effect of the lone electron-pair on sulfur concerning structure and dynamics in comparison with the sulfate ion with higher oxidation number and symmetry of the hydration shell. The S-O bond distance in the hydrated sulfite ion has been determined to 1.53(1) Å by both methods. The hydrogen bonds between the three water molecules bound to each sulfite oxygen are only slightly stronger than those in bulk water. The sulfite ion can therefore be regarded as a weak structure maker. The water exchange rate is somewhat slower for the sulfite ion than for the sulfate ion, τ(0.5) = 3.2 and 2.6 ps, respectively. An even more striking observation in the angular radial distribution (ARD) functions is that the for sulfite ion the water exchange takes place in close vicinity of the lone electron-pair directed at its sides, while in principle no water exchange did take place of the water molecules hydrogen bound to sulfite oxygens during the simulation time. This is also confirmed when detailed pathway analysis is conducted. The simulation showed that the water molecules hydrogen bound to the sulfite oxygens can move inside the hydration shell to the area outside the lone electron-pair and there be exchanged. On the other hand, for the hydrated sulfate ion in aqueous solution one can clearly see from the ARD that the distribution of exchange events is symmetrical around the entire hydration sphere.

Fabrication and investigation of effect of core size in heterostructure PbS/CdS core/shell nanoparticles

NASA Astrophysics Data System (ADS)

Das, D.; Hussain, A. M. P.

2018-04-01

PbS/CdS core/shell (CS) nanoparticles (NPs) were fabricated with three different concentrations of PbS core and CdS shell. Formation of core/shell heterostructure was confirmed from X-ray diffraction studies. The diffraction patterns exhibited formation of cubic phase and polycrystalline core/shell nanostructure. The crystalline sizes calculated from Williamson-Hall plot exhibited increase with molar concentration of precursors with decrease in strain. High resolution electron microscopy studies also confirm the formation of core/shell structure with particle size around 10 nm. A large blue-shift for PbS core compared to its bulk and small red-shift for the PbS/CdS core/shell as compared to the core is being observed in absorption spectra.

In-situ synthetize multi-walled carbon nanotubes@MnO2 nanoflake core-shell structured materials for supercapacitors

NASA Astrophysics Data System (ADS)

Zheng, Huajun; Wang, Jiaoxia; Jia, Yi; Ma, Chun'an

2012-10-01

A new type of core-shell structured material consisting of multi-walled carbon nanotubes (MWCNTs) and manganese dioxide (MnO2) nanoflake is synthesized using an in-situ co-precipitation method. By scanning electron microscopy and transition electron microscope, it is confirmed that the core-shell nanostructure is formed by the uniform incorporation of birnessite-type MnO2 nanoflake growth round the surface of the activated-MWCNTs. That core-shell structured material electrode presents excellent electrochemical capacitance properties with the specific capacitance reaching 380 F g-1 at the current density of 5 A g-1 in 0.5 M Na2SO4 electrolyte. In addition, the electrode also exhibits good performance (the power density: 11.28 kW kg-1 at 5 A g-1) and long-term cycling stability (retaining 82.7% of its initial capacitance after 3500 cycles at 5 A g-1). It mainly attributes to MWCNTs not only providing considerable specific surface area for high mass loading of MnO2 nanoflakes to ensure effective utilization of MnO2 nanoflake, but also offering an electron pathway to improve electrical conductivity of the electrode materials. It is clearly indicated that such core-shell structured materials including MWCNTs and MnO2 nanoflake may find important applications for supercapacitors.

Pt@Ag and Pd@Ag core/shell nanoparticles for catalytic degradation of Congo red in aqueous solution.

PubMed

Salem, Mohamed A; Bakr, Eman A; El-Attar, Heba G

2018-01-05

Platinum/silver (Pt@Ag) and palladium/silver (Pd@Ag) core/shell NPs have been synthesized in two steps reaction using the citrate method. The progress of nanoparticle formation was followed by the UV/Vis spectroscopy. Transmission electron microscopy revealed spherical shaped core/shell nanoparticles with average particle diameter 32.17nm for Pt@Ag and 8.8nm for Pd@Ag. The core/shell NPs were further characterized by FT-IR and XRD. Reductive degradation of the Congo red dye was chosen to demonstrate the excellent catalytic activity of these core/shell nanostructures. The nanocatalysts act as electron mediators for the transfer of electrons from the reducing agent (NaBH 4 ) to the dye molecules. Effect of reaction parameters such as nanocatalyst dose, dye and NaBH 4 concentrations on the dye degradation was investigated. A comparison between the catalytic activities of both nanocatalysts was made to realize which of them the best in catalytic performance. Pd@Ag was the higher in catalytic activity over Pt@Ag. Such greater activity is originated from the smaller particle size and larger surface area. Pd@Ag nanocatalyst was catalytically stable through four subsequent reaction runs under the utilized reaction conditions. These findings can thus be considered as possible economical alternative for environmental safety against water pollution by dyes. Copyright © 2017. Published by Elsevier B.V.

Pt@Ag and Pd@Ag core/shell nanoparticles for catalytic degradation of Congo red in aqueous solution

NASA Astrophysics Data System (ADS)

Salem, Mohamed A.; Bakr, Eman A.; El-Attar, Heba G.

2018-01-01

Platinum/silver (Pt@Ag) and palladium/silver (Pd@Ag) core/shell NPs have been synthesized in two steps reaction using the citrate method. The progress of nanoparticle formation was followed by the UV/Vis spectroscopy. Transmission electron microscopy revealed spherical shaped core/shell nanoparticles with average particle diameter 32.17 nm for Pt@Ag and 8.8 nm for Pd@Ag. The core/shell NPs were further characterized by FT-IR and XRD. Reductive degradation of the Congo red dye was chosen to demonstrate the excellent catalytic activity of these core/shell nanostructures. The nanocatalysts act as electron mediators for the transfer of electrons from the reducing agent (NaBH4) to the dye molecules. Effect of reaction parameters such as nanocatalyst dose, dye and NaBH4 concentrations on the dye degradation was investigated. A comparison between the catalytic activities of both nanocatalysts was made to realize which of them the best in catalytic performance. Pd@Ag was the higher in catalytic activity over Pt@Ag. Such greater activity is originated from the smaller particle size and larger surface area. Pd@Ag nanocatalyst was catalytically stable through four subsequent reaction runs under the utilized reaction conditions. These findings can thus be considered as possible economical alternative for environmental safety against water pollution by dyes.

Adsorption performance of coconut shell activated carbon for the removal of chlorate from chlor-alkali brine stream.

PubMed

Lakshmanan, Shyam; Murugesan, Thanapalan

2016-12-01

Activated carbon from coconut shell was used to investigate the adsorption of chlorate from a chlor-alkali plant's brine stream. The effect of pH, flowrate, chlorate and chloride concentration on the breakthrough curves were studied in small-scale column trials. The results obtained show enhanced adsorption at low flowrates, higher chlorate concentrations, and at a pH of 10. These studies show that introducing an activated carbon adsorption column just before the saturator would remove sufficient quantities of chlorate to allow more of the chlor-alkali plant's brine stream to be reused. From column dynamic studies, the Thomas model showed close approximation when the chlorate in the effluent was higher than breakthrough concentrations and there was close correlation at high influent concentration. The q o (maximum adsorption capacity) values were close to those obtained experimentally, indicating close representation of the breakthrough curve by the Thomas model.

Modeling the Magnetopause Shadowing and Drift Orbit Bifurcation Loss during the June 2015 Dropout Event

NASA Astrophysics Data System (ADS)

Tu, W.; Cunningham, G.

2017-12-01

The relativistic electron flux in Earth's radiation belt are observed to drop by orders of magnitude on timescale of a few hours. Where do the electrons go during the dropout? This is one of the most important outstanding questions in radiation belt studies. Here we will study the 22 June 2015 dropout event which occurred during one of the largest geomagnetic storms in the last decade. A sudden and nearly complete loss of all the outer zone relativistic and ultra-relativistic electrons were observed after a strong interplanetary shock. The Last Closed Drift Shell (LCDS) calculated using the TS04 model reached as low as L*=3.7 during the shock and stay below L*=4 for 1 hour. The unusually low LCDS values suggest that magnetopause shadowing and the associated outward radial diffusion can contribute significantly to the observed dropout. In addition, Drift Orbit Bifurcation (DOB) has been suggested as an important loss mechanism for radiation belt electrons, especially when the solar wind dynamic pressure is high, but its relative importance has not been quantified. Here, we will model the June 2015 dropout event using a radial diffusion model that includes physical and event-specific inputs. First, we will trace electron drift shells based on TS04 model to identify the LCDS and bifurcation regions as a function of the 2nd adiabatic invariant (K) and time. To model magnetopause shadowing, electron lifetimes in our model will be set to electron drift periods at L*>LCDS. Electron lifetimes inside the bifurcation region have been estimated by Ukhorskiy et al. [JGR 2011, doi:10.1029/2011JA016623] as a function of L* and K, which will also be implemented in the model. This will be the first effort to include the DOB loss in a comprehensive radiation belt model. Furthermore, to realistically simulate outward radial diffusion, the new radial diffusion coefficients that are calculated based on the realistic TS04 model and include physical K dependence [Cunningham, JGR 2016, doi:10.1002/2015JA021981] will be achieved and included here. With these event-specific and physical model inputs, we will test how well the observed fast dropout during the June 2015 event can be reproduced by our model, and quantify the relative contribution of magnetopause shadowing, outward radial diffusion, and DOB to the fast electron depletion.

Electronic stopping in oxides beyond Bragg additivity

NASA Astrophysics Data System (ADS)

Sigmund, P.; Schinner, A.

2018-01-01

We present stopping cross sections calculated by our PASS code for several ions in metal oxides and SiO2 over a wide energy range. Input takes into account changes in the valence structure by assigning two additional electrons to the 2p shell of oxygen and removing the appropriate number of electrons from the outer shells of the metal atom. Results are compared with tabulated experimental values and with two versions of Bragg's additivity rule. Calculated stopping cross sections are applied in testing a recently-proposed scaling rule, which relates the stopping cross section to the number of oxygen atoms per molecule.

High-efficiency and mechano-/photo- bi-catalysis of piezoelectric-ZnO@ photoelectric-TiO2 core-shell nanofibers for dye decomposition.

PubMed

You, Huilin; Wu, Zheng; Jia, Yanmin; Xu, Xiaoli; Xia, Yuntao; Han, Zichen; Wang, Yu

2017-09-01

A mechano-/photo- bi-catalyst of piezoelectric-ZnO@photoelectric-TiO 2 core-shell nanofibers was hydrothermally synthesized for Methyl Orange (10 mg L -1 ) decomposition. The mechano-/photo- bi-catalysis in ZnO@TiO 2 is superior to mechano- or photo-catalysis in decomposing Methyl Orange, which is mainly attributed to the synergy effect of the piezoelectric-ZnO core's mechano-catalysis and the thin photoelectric TiO 2 shell's photo-catalysis. The heterostructure of the piezoelectric-ZnO@photoelectric-TiO 2 core-shell interface, being helpful to reduce electron-hole pair recombination and to separate the piezoelectrically-/photoelectric ally- induced electrons and holes, may also make a great contribution to the enhanced catalysis performance. The mechano-/photo-bi-catalysis in ZnO@TiO 2 core-shell nanofibers possesses the advantages of high efficiency, non-toxicity and tractability and is potential in utilizing mechanical/solar energy to deal with dye wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

Microstructural and thermal study of Al-Si-Mg/melon shell ash particulate composite

NASA Astrophysics Data System (ADS)

Abdulwahab, M.; Umaru, O. B.; Bawa, M. A.; Jibo, H. A.

The microstructural study via scanning electron microscope (SEM) and thermal study via differential scanning calorimetric (DSC) study of Al-7%Si-0.3Mg/melon shell ash particulate composite has been carried out. The melon shell ash was used in the production of MMC ranging from 5% to 20% at interval of 5% addition using stir casting method. The melon shell ash was characterized using X-ray fluorescent (XRF) that reveal the presence of CaO, SiO2, Al2O3, MgO, and TiO2 as major compounds. The composite was machined and subjected to heat treatment. Microstructural analyses of the composite produced were done using scanning electron microscope (SEM). The microstructure obtained reveals a dark ceramic (reinforcer) and white metallic phase. Equally, the 5 wt% DSC result gives better thermal conductivity than other proportions (10 wt%, 15 wt%, and 20 wt%). These results showed that an improved property of Al-Si-Mg alloy was achieved using melon shell ash particles as reinforcement up to a maximum of 20 wt% for microstructural and 5% wt DSC respectively.

Electronic transport properties of 4f shell elements of liquid metal using hard sphere Yukawa system

NASA Astrophysics Data System (ADS)

Patel, H. P.; Sonvane, Y. A.; Thakor, P. B.

2018-04-01

The electronic transport properties are analyzed for 4f shell elements of liquid metals. To examine the electronic transport properties like electrical resistivity (ρ), thermal conductivity (σ) and thermo electrical power (Q), we used our own parameter free model potential with the Hard Sphere Yukawa (HSY) reference system. The screening effect on aforesaid properties has been examined by using different screening functions like Hartree (H), Taylor (T) and Sarkar (S). The correlations of our resultsand other data with available experimental values are intensely promising. Also, we conclude that our newly constructed parameter free model potential is capable of explaining the above mentioned electronic transport properties.

Methanol oxidation reaction on core-shell structured Ruthenium-Palladium nanoparticles: Relationship between structure and electrochemical behavior

NASA Astrophysics Data System (ADS)

Kübler, Markus; Jurzinsky, Tilman; Ziegenbalg, Dirk; Cremers, Carsten

2018-01-01

In this work the relationship between structural composition and electrochemical characteristics of Palladium(Pd)-Ruthenium(Ru) nanoparticles during alkaline methanol oxidation reaction is investigated. The comparative study of a standard alloyed and a precisely Ru-core-Pd-shell structured catalyst allows for a distinct investigation of the electronic effect and the bifunctional mechanism. Core-shell catalysts benefit from a strong electronic effect and an efficient Pd utilization. It is found that core-shell nanoparticles are highly active towards methanol oxidation reaction for potentials ≥0.6 V, whereas alloyed catalysts show higher current outputs in the lower potential range. However, differential electrochemical mass spectrometry (DEMS) experiments reveal that the methanol oxidation reaction on core-shell structured catalysts proceeds via the incomplete oxidation pathway yielding formaldehyde, formic acid or methyl formate. Contrary, the alloyed catalyst benefits from the Ru atoms at its surface. Those are found to be responsible for high methanol oxidation activity at lower potentials as well as for complete oxidation of CH3OH to CO2 via the bifunctional mechanism. Based on these findings a new Ru-core-Pd-shell-Ru-terrace catalyst was synthesized, which combines the advantages of the core-shell structure and the alloy. This novel catalyst shows high methanol electrooxidation activity as well as excellent selectivity for the complete oxidation pathway.

One-pot synthesis of BiOCl half-shells using microemulsion droplets as templates with highly photocatalytic performance for the degradation of ciprofloxacin

NASA Astrophysics Data System (ADS)

Mao, Danjun; Yu, Anqing; Ding, Shanshan; Wang, Fei; Yang, Shaogui; Sun, Cheng; He, Huan; Liu, Yazi; Yu, Kai

2016-12-01

Ultrathin BiOCl half-shells have been synthesized via an ionic liquid-in-water (IL/W) microemulsion, applying the liquid-liquid boundary of the emulsion system as a template. Surfactant TX-100 acted as the stabilizer of the IL-microemulsion, which is of critical importance for the formation of BiOCl half-shells. The hollow structures were characterized using X-ray diffraction, scanning and transmission electron microscopy, diffuse reflectance spectroscopy and specific surface area, respectively. Possible formation mechanisms for the BiOCl half-shells were discussed. Moreover, the ultrathin BiOCl half-shells exhibited distinctly enhanced photocatalytic efficiency toward the degradation of colourless ciprofloxacin (CIP, a representative broad-spectrum antibiotic agent) under solar light irradiation as compared to BiOCl nanosheets. The photogenerated reactive species are verified by scavenger experiments, which reveals that rad O2- and h+ were the two major photoactive species toward the photodegradation of CIP over ultrathin BiOCl half-shells under solar-light. The enhanced activities of ultrathin BiOCl half-shells were mainly ascribed to the synergistic effect of the increased light-harvesting, larger BET surface area, faster separation and transfer of electron-hole pairs. It is hoped that the ionic liquid microemulsion-mediated route can be extended to the purposive design and fabrication of other halogen-containing inorganic hollow materials.

Wave Function Engineering in CdSe/PbS Core/Shell Quantum Dots.

PubMed

Wieliczka, Brian M; Kaledin, Alexey L; Buhro, William E; Loomis, Richard A

2018-05-25

The synthesis of epitaxial CdSe/PbS core/shell quantum dots (QDs) is reported. The PbS shell grows in a rock salt structure on the zinc blende CdSe core, thereby creating a crystal structure mismatch through additive growth. Absorption and photoluminescence (PL) band edge features shift to lower energies with increasing shell thickness, but remain above the CdSe bulk band gap. Nevertheless, the profiles of the absorption spectra vary with shell growth, indicating that the overlap of the electron and hole wave functions is changing significantly. This leads to over an order of magnitude reduction of absorption near the band gap and a large, tunable energy shift, of up to 550 meV, between the onset of strong absorption and the band edge PL. While the bulk valence and conduction bands adopt an inverse type-I alignment, the observed spectroscopic behavior is consistent with a transition between quasi-type-I and quasi-type-II behavior depending on shell thickness. Three effective mass approximation models support this hypothesis and suggest that the large difference in effective masses between the core and shell results in hole localization in the CdSe core and a delocalization of the electron across the entire QD. These results show the tuning of wave functions and transition energies in CdSe/PbS nanoheterostructures with prospects for use in optoelectronic devices for luminescent solar concentration or multiexciton generation.

The study of hard x-ray emission and electron beam generation in wire array Z-pinch and X-pinch plasmas at university-scale generators

NASA Astrophysics Data System (ADS)

Shrestha, Ishor Kumar

The studies of hard x-ray (HXR) emission and electron beam generation in Z-pinch plasmas are very important for Inertial Confinement Fusion (ICF) research and HXR emission application for sources of K-shell and L-shell radiation. Energetic electron beams from Z-pinch plasmas are potentially a problem in the development of ICF. The electron beams and the accompanying HXR emission can preheat the fuel of a thermonuclear target, thereby preventing the fuel compression from reaching densities required for the ignition of a fusion reaction. The photons above 3-4 keV radiated from a Z pinch can provide detailed information about the high energy density plasmas produced at stagnation. Hence, the investigation of characteristics of hard x-rays and electron beams produced during implosions of wire array loads on university scale-generators may provide important data for future ICF, sources of K-shell and L-shell radiations and basic plasma research. This dissertation presents the results of experimental studies of HXR and electron beam generation in wire-array and X-pinch on the 1.7 MA, 100-ns current rise time Zebra generator at University of Nevada, Reno and 1-MA 100-ns current rise-time Cornell Beam Research Accelerator (COBRA) at Cornell University. The experimental study of characteristics of HXR produced by multi-planar wire arrays, compact cylindrical wire array (CCWA) and nested cylindrical wire array (NCWA) made from Al, Cu, Mo, Ag, W and Au were analyzed. The dependence of the HXR yield and power on geometry of the load, the wire material, and load mass was observed. The presence of aluminum wires in the load with the main material such as stainless steel, Cu, Mo, Ag, W or Au in combined wire array decreases HXR yield. The comparison of emission characteristics of HXR and generation of electron beams in CCWA and NCWA on both the high impedance Zebra generator and low impedance COBRA generator were investigated. Some of the "cold" K- shell spectral lines (0.7-2.3Á) and cold L-shell spectral lines (1-1.54Á) in the HXR region were observed only during the interaction of electron beam with load material and anode surface. These observations suggest that the mechanism of HXR emission should be associated with non-thermal mechanisms such as the interaction of the electron beam with the load material. In order to estimate the characteristics of the high-energetic electron beam in Z-pinch plasmas, a hard x-ray polarimeter (HXP) has been developed and used in experiments on the Zebra generator. The electron beams (energy more than 30keV) have been investigated with measurements of the polarization state of the emitted bremsstrahlung radiation from plasma. We also analyzed characteristics of energetic electron beams produced by implosions of multi-planar wire arrays, compact cylindrical and nested wire arrays as well as X-pinches. Direct indications of electron beams (electron cutoff energy EB from 42-250 keV) were obtained by using the measured current of a Faraday cup placed above the anode or mechanical damage observed in the anode surface. A comparison of total electron beam energy and the spatial and spectral analysis of the parameters of plasmas were investigated for different wire materials. The dependences of the total electron beam energy (E b) on the wire material and the geometry of the wire array load were studied.

Interface engineered ferrite@ferroelectric core-shell nanostructures: A facile approach to impart superior magneto-electric coupling

NASA Astrophysics Data System (ADS)

Abraham, Ann Rose; Raneesh, B.; Das, Dipankar; Oluwafemi, Oluwatobi Samuel; Thomas, Sabu; Kalarikkal, Nandakumar

2018-04-01

The electric field control of magnetism in multiferroics is attractive for the realization of ultra-fast and miniaturized low power device applications like nonvolatile memories. Room temperature hybrid multiferroic heterostructures with core-shell (0-0) architecture (ferrite core and ferroelectric shell) were developed via a two-step method. High-Resolution Transmission Electron Microscopy (HRTEM) images confirm the core-shell structure. The temperature dependant magnetization measurements and Mossbauer spectra reveal superparamagnetic nature of the core-shell sample. The ferroelectric hysteresis loops reveal leaky nature of the samples. The results indicate the promising applications of the samples for magneto-electric memories and spintronics.

Size-Dependent Specific Surface Area of Nanoporous Film Assembled by Core-Shell Iron Nanoclusters

DOE PAGES

Antony, Jiji; Nutting, Joseph; Baer, Donald R.; ...

2006-01-01

Nmore » anoporous films of core-shell iron nanoclusters have improved possibilities for remediation, chemical reactivity rate, and environmentally favorable reaction pathways. Conventional methods often have difficulties to yield stable monodispersed core-shell nanoparticles. We produced core-shell nanoclusters by a cluster source that utilizes combination of Fe target sputtering along with gas aggregations in an inert atmosphere at 7 ∘ C . Sizes of core-shell iron-iron oxide nanoclusters are observed with transmission electron microscopy (TEM). The specific surface areas of the porous films obtained from Brunauer-Emmett-Teller (BET) process are size-dependent and compared with the calculated data.« less

Analysis of the electron density features of small boron clusters and the effects of doping with C, P, Al, Si, and Zn: Magic B7P and B8Si clusters

NASA Astrophysics Data System (ADS)

Saha, P.; Rahane, A. B.; Kumar, V.; Sukumar, N.

2016-05-01

Boron atomic clusters show several interesting and unusual size-dependent features due to the small covalent radius, electron deficiency, and higher coordination number of boron as compared to carbon. These include aromaticity and a diverse array of structures such as quasi-planar, ring or tubular shaped, and fullerene-like. In the present work, we have analyzed features of the computed electron density distributions of small boron clusters having up to 11 boron atoms, and investigated the effect of doping with C, P, Al, Si, and Zn atoms on their structural and physical properties, in order to understand the bonding characteristics and discern trends in bonding and stability. We find that in general there are covalent bonds as well as delocalized charge distribution in these clusters. We associate the strong stability of some of these planar/quasiplanar disc-type clusters with the electronic shell closing with effectively twelve delocalized valence electrons using a disc-shaped jellium model. {{{{B}}}9}-, B10, B7P, and B8Si, in particular, are found to be exceptional with very large gaps between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, and these are suggested to be magic clusters.

Modeling of the L-shell copper X-pinch plasma produced by the compact generator of Ecole polytechnique using pattern recognition

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

Larour, Jean; Aranchuk, Leonid E.; Danisman, Yusuf

2016-03-15

Principal component analysis is applied and compared with the line ratios of special Ne-like transitions for investigating the electron beam effects on the L-shell Cu synthetic spectra. The database for the principal component extraction is created over a non Local Thermodynamic Equilibrium (non-LTE) collisional radiative L-shell Copper model. The extracted principal components are used as a database for Artificial Neural Network in order to estimate the plasma electron temperature, density, and beam fractions from a representative time-integrated spatially resolved L-shell Cu X-pinch plasma spectrum. The spectrum is produced by the explosion of 25-μm Cu wires on a compact LC (40more » kV, 200 kA, and 200 ns) generator. The modeled plasma electron temperatures are about T{sub e} ∼ 150 eV and N{sub e} = 5 × 10{sup 19} cm{sup −3} in the presence of the fraction of the beams with f ∼ 0.05 and a centered energy of ∼10 keV.« less

Transition-Metal Nitride Core@Noble-Metal Shell Nanoparticles as Highly CO Tolerant Catalysts

DOE PAGES

Garg, Aaron; Milina, Maria; Ball, Madelyn; ...

2017-05-25

Core–shell architectures offer an effective way to tune and enhance the properties of noble-metal catalysts. Herein, we demonstrate the synthesis of Pt shell on titanium tungsten nitride core nanoparticles (Pt/TiWN) by high temperature ammonia nitridation of a parent core–shell carbide material (Pt/TiWC). X-ray photoelectron spectroscopy revealed significant core-level shifts for Pt shells supported on TiWN cores, corresponding to increased stabilization of the Pt valence d-states. The modulation of the electronic structure of the Pt shell by the nitride core translated into enhanced CO tolerance during hydrogen electrooxidation in the presence of CO. In conclusion, the ability to control shell coveragemore » and vary the heterometallic composition of the shell and nitride core opens up attractive opportunities to synthesize a broad range of new materials with tunable catalytic properties.« less

Transition-Metal Nitride Core@Noble-Metal Shell Nanoparticles as Highly CO Tolerant Catalysts

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

Garg, Aaron; Milina, Maria; Ball, Madelyn

Core–shell architectures offer an effective way to tune and enhance the properties of noble-metal catalysts. Herein, we demonstrate the synthesis of Pt shell on titanium tungsten nitride core nanoparticles (Pt/TiWN) by high temperature ammonia nitridation of a parent core–shell carbide material (Pt/TiWC). X-ray photoelectron spectroscopy revealed significant core-level shifts for Pt shells supported on TiWN cores, corresponding to increased stabilization of the Pt valence d-states. The modulation of the electronic structure of the Pt shell by the nitride core translated into enhanced CO tolerance during hydrogen electrooxidation in the presence of CO. In conclusion, the ability to control shell coveragemore » and vary the heterometallic composition of the shell and nitride core opens up attractive opportunities to synthesize a broad range of new materials with tunable catalytic properties.« less

Swift heavy ion track formation in Gd2Zr2-xTixO7 pyrochlore: Effect of electronic energy loss

NASA Astrophysics Data System (ADS)

Lang, Maik; Toulemonde, Marcel; Zhang, Jiaming; Zhang, Fuxiang; Tracy, Cameron L.; Lian, Jie; Wang, Zhongwu; Weber, William J.; Severin, Daniel; Bender, Markus; Trautmann, Christina; Ewing, Rodney C.

2014-10-01

The morphology of swift heavy ion tracks in the Gd2Zr2-xTixO7 pyrochlore system has been investigated as a function of the variation in chemical composition and electronic energy loss, dE/dx, over a range of energetic ions: 58Ni, 101Ru, 129Xe, 181Ta, 197Au, 208Pb, and 238U of 11.1 MeV/u specific energy. Bright-field transmission electron microscopy, synchrotron X-ray diffraction, and Raman spectroscopy reveal an increasing degree of amorphization with increasing Ti-content and dE/dx. The size and morphology of individual ion tracks in Gd2Ti2O7 were characterized by high-resolution transmission electron microscopy revealing a core-shell structure with an outer defect-fluorite dominated shell at low dE/dx to predominantly amorphous tracks at high dE/dx. Inelastic thermal-spike calculations have been used together with atomic-scale characterization of ion tracks in Gd2Ti2O7 by high resolution transmission electron microscopy to deduce critical energy densities for the complex core-shell morphologies induced by ions of different dE/dx.

Processes of energy deposition by heavy-particle and electron impact. Final progress report

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

Salop, A.; Smith, F.T.

1978-04-18

Progress is reported in three areas of reasearch during the present period: K-shell ionization in high energy collisions of heavy ions with light target atoms using the sudden (Magnus) approximation, K-L level matching phenomena associated with K-shell vacancy production in heavy-ion collisions, and studies of low energy collisions of electrons with molecules using semi-classical perturbation theory. A brief discussion of each of these activities is given.

Structural transformation and photoluminescence modification of AgInS2 nanoparticles induced by ZnS shell formation

NASA Astrophysics Data System (ADS)

Hamanaka, Yasushi; Yukitoki, Daichi; Kuzuya, Toshihiro

2015-09-01

AgInS2 nanoparticles were capped by ZnS via a widely used procedure to fabricate core/shell nanoparticles with highly efficient luminescence. The nanoparticle structures were investigated by ultrahigh-resolution analytical electron microscopy. We found that Zn-Ag-In-S nanoparticles were created by ZnS capping at ˜480 K, which suggests that the luminescence enhancement reported for such core/shell nanoparticles is not caused by the passivation of surface defects by ZnS shells but by Zn doping. Quasi-core/shell nanoparticles could be obtained by ZnS capping without heating. However, their luminescence efficiency remained unchanged, indicating that surface passivation was ineffective when ZnS shells were formed at room temperature.

Temperature effect on the growth of Au-free InAs and InAs/GaSb heterostructure nanowires on Si substrate by MOCVD

NASA Astrophysics Data System (ADS)

Kakkerla, Ramesh Kumar; Anandan, Deepak; Hsiao, Chih-Jen; Yu, Hung Wei; Singh, Sankalp Kumar; Chang, Edward Yi

2018-05-01

We demonstrate the growth of vertically aligned Au-free InAs and InAs/GaSb heterostructure nanowires on Si (1 1 1) substrate by Metal Organic Chemical Vapor Deposition (MOCVD). The effect of growth temperature on the morphology and growth rate of the InAs and InAs/GaSb heterostructure nanowires (NWs) is investigated. Control over diameter and length of the InAs NWs and the GaSb shell thickness was achieved by using growth temperature. As the GaSb growth temperature increase, GaSb radial growth rate increases due to the increase in alkyl decomposition at the substrate surface. Diffusivity of the adatoms increases as the GaSb growth temperature increase which results in tapered GaSb shell growth. Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) measurements revealed that the morphology and shell thickness can be tuned by the growth temperature. Electron microscopy also shows the formation of GaSb both in radial and axial directions outside the InAs NW core can be controlled by the growth temperature. This study demonstrates the control over InAs NWs growth and the GaSb shell thickness can be achieved through proper growth temperature control, such technique is essential for the growth of nanowire for future nano electronic devices, such as Tunnel FET.

Velocity dependence of heavy-ion stopping below the maximum

NASA Astrophysics Data System (ADS)

Sigmund, P.; Schinner, A.

2015-01-01

In the slowing-down of heavy ions in materials, the standard description by Lindhard and Scharff assumes the electronic stopping cross section to be proportional to the projectile speed v up to close to a stopping maximum, which is related to the Thomas-Fermi speed vTF . It is well known that strict proportionality with v is rarely observed, but little is known about the systematics of observed deviations. In this study we try to identify factors that determine positive or negative curvature of stopping cross sections on the basis of experimental data and of binary stopping theory. We estimate the influence of shell structure of the target and of the equilibrium charge of the ion and comment the role of dynamic screening.

Penetration boundary of solar cosmic rays into the earth's magnetosphere during magnetically quiet times

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

Biryukov, A.S.; Ivanova, T.A.; Kovrygina, L.M.

1984-05-01

Data is used from the satellites Interkosmos-17 and Kosmos-900 to determine penetration boundaries at high latitudes in the earth's magnetosphere. Considered are the results of observations of the penetration boundary of solar cosmic ray (SCR) protons and electrons during an SCR increase on November 22-25, 1977. The position of the SCR penetration boundary during a single increase at practically all values of MLT in quiet conditions is examined. Magnetospheric structure is determined in the region of closed drift shells where the magnetic field is asymmetric. The authors can estimate how the solar wind pressure affects the magnetosphere by using datamore » on the penetration boundaries of solar protons obtained during quiet geomagnetic conditions.« less

Coupled mixed-field laminate theory and finite element for smart piezoelectric composite shell structures

NASA Technical Reports Server (NTRS)

Saravanos, Dimitris A.

1996-01-01

Mechanics for the analysis of laminated composite shells with piezoelectric actuators and sensors are presented. A new mixed-field laminate theory for piezoelectric shells is formulated in curvilinear coordinates which combines single-layer assumptions for the displacements and a layerwise representation for the electric potential. The resultant coupled governing equations for curvilinear piezoelectric laminates are described. Structural mechanics are subsequently developed and an 8-node finite-element is formulated for the static and dynamic analysis of adaptive composite structures of general laminations containing piezoelectric layers. Evaluations of the method and comparisons with reported results are presented for laminated piezoelectric-composite plates, a closed cylindrical shell with a continuous piezoceramic layer and a laminated composite semi-circular cantilever shell with discrete cylindrical piezoelectric actuators and/or sensors.

The relativistic theory of the chemical shift

NASA Astrophysics Data System (ADS)

Pyper, N. C.

1983-04-01

A relativistic theory of the NMR chemical shift for a closed-shell system is presented. The final expression for the shielding, derived by, applying two Gordon decompositions to the Dirac current operator, closely parallels the Ramsey non-relativistic result.

Direct observation of ring-opening dynamics in strong-field ionized selenophene using femtosecond inner-shell absorption spectroscopy

DOE PAGES

Lackner, Florian; Chatterley, Adam S.; Pemmaraju, C. D.; ...

2016-12-21

Femtosecond extreme ultraviolet transient absorption spectroscopy is used to explore strong-field ionization induced dynamics in selenophene (C 4H 4Se). The dynamics are monitored in real-time from the viewpoint of the Se atom by recording the temporal evolution of element-specific spectral features near the Se 3d inner-shell absorption edge (~58 eV). The interpretation of the experimental results is supported by first-principles time-dependent density functional theory calculations. The experiments simultaneously capture the instantaneous population of stable molecular ions, the emergence and decay of excited cation states, and the appearance of atomic fragments. The experiments reveal, in particular, insight into the strong-field inducedmore » ring-opening dynamics in the selenophene cation, which are traced by the emergence of non-cyclic molecules as well as the liberation of Se + ions within an overall time scale of approximately 170 fs. In this study, we propose that both products may be associated with dynamics on the same electronic surfaces but with different degrees of vibrational excitation. The time-dependent inner-shell absorption features provide direct evidence for a complex relaxation mechanism that may be approximated by a two-step model, whereby the initially prepared, excited cyclic cation decays within τ 1 = 80 ± 30 fs into a transient molecular species, which then gives rise to the emergence of bare Se + and ring-open cations within an additional τ 2 = 80 ± 30 fs. The combined experimental and theoretical results suggest a close relationship between σ* excited cation states and the observed ring-opening reactions. In conclusion, the findings demonstrate that the combination of femtosecond time-resolved core-level spectroscopy with ab initio estimates of spectroscopic signatures provide new insights into complex, ultrafast photochemical reactions such as ring-opening dynamics in organic molecules in real-time and with simultaneous sensitivity for electronic and structural rearrangements.« less

Measurement of L-shell transitions in M-shell ions in the laboratory and identification in stellar coronae

DOE PAGES

Lepson, J. K.; Beiersdorfer, P.; Hell, N.; ...

2017-04-04

Based on laboratory data from the Lawrence Livermore EBIT-I electron beam ion trap and calculations using the relativistic multi-reference Møller-Plesset (MRMP) perturbation theory approach, we identify L-shell transitions of M-shell iron ions in emission spectra of the nearby stars Capella and Procyon. In conclusion, these lines are weaker than the well known, prominent lines from Fe XVII. However, they need to be taken into account when modeling the spectra, especially of cool stars.

Design of an Ada expert system shell for the VHSIC avionic modular flight processor

NASA Technical Reports Server (NTRS)

Fanning, F. Jesse

1992-01-01

The Embedded Computer System Expert System Shell (ES Shell) is an Ada-based expert system shell developed at the Avionics Laboratory for use on the VHSIC Avionic Modular Processor (VAMP) running under the Ada Avionics Real-Time Software (AARTS) Operating System. The ES Shell provides the interface between the expert system and the avionics environment, and controls execution of the expert system. Testing of the ES Shell in the Avionics Laboratory's Integrated Test Bed (ITB) has demonstrated its ability to control a non-deterministic software application executing on the VAMP's which can control the ITB's real-time closed-loop aircraft simulation. The results of these tests and the conclusions reached in the design and development of the ES Shell have played an important role in the formulation of the requirements for a production-quality expert system inference engine, an ingredient necessary for the successful use of expert systems on the VAMP embedded avionic flight processor.

Gold core@silver semishell Janus nanoparticles prepared by interfacial etching

NASA Astrophysics Data System (ADS)

Chen, Limei; Deming, Christopher P.; Peng, Yi; Hu, Peiguang; Stofan, Jake; Chen, Shaowei

2016-07-01

Gold core@silver semishell Janus nanoparticles were prepared by chemical etching of Au@Ag core-shell nanoparticles at the air/water interface. Au@Ag core-shell nanoparticles were synthesized by chemical deposition of a silver shell onto gold seed colloids followed by the self-assembly of 1-dodecanethiol onto the nanoparticle surface. The nanoparticles then formed a monolayer on the water surface of a Langmuir-Blodgett trough, and part of the silver shell was selectively etched away by the mixture of hydrogen peroxide and ammonia in the water subphase, where the etching was limited to the side of the nanoparticles that was in direct contact with water. The resulting Janus nanoparticles exhibited an asymmetrical distribution of silver on the surface of the gold cores, as manifested in transmission electron microscopy, UV-vis absorption, and X-ray photoelectron spectroscopy measurements. Interestingly, the Au@Ag semishell Janus nanoparticles exhibited enhanced electrocatalytic activity in oxygen reduction reactions, as compared to their Au@Ag and Ag@Au core-shell counterparts, likely due to a synergistic effect between the gold cores and silver semishells that optimized oxygen binding to the nanoparticle surface.Gold core@silver semishell Janus nanoparticles were prepared by chemical etching of Au@Ag core-shell nanoparticles at the air/water interface. Au@Ag core-shell nanoparticles were synthesized by chemical deposition of a silver shell onto gold seed colloids followed by the self-assembly of 1-dodecanethiol onto the nanoparticle surface. The nanoparticles then formed a monolayer on the water surface of a Langmuir-Blodgett trough, and part of the silver shell was selectively etched away by the mixture of hydrogen peroxide and ammonia in the water subphase, where the etching was limited to the side of the nanoparticles that was in direct contact with water. The resulting Janus nanoparticles exhibited an asymmetrical distribution of silver on the surface of the gold cores, as manifested in transmission electron microscopy, UV-vis absorption, and X-ray photoelectron spectroscopy measurements. Interestingly, the Au@Ag semishell Janus nanoparticles exhibited enhanced electrocatalytic activity in oxygen reduction reactions, as compared to their Au@Ag and Ag@Au core-shell counterparts, likely due to a synergistic effect between the gold cores and silver semishells that optimized oxygen binding to the nanoparticle surface. Electronic supplementary information (ESI) available: Additional TEM, UV-vis, XPS, and electrochemical data. See DOI: 10.1039/c6nr03368g

Understanding the mechanisms of radiation belt dropouts observed by Van Allen Probes

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

Xiang, Zheng; Tu, Weichao; Li, Xinlin

To achieve a better understanding of the dominant loss mechanisms for the rapid dropouts of radiation belt electrons, three distinct radiation belt dropout events observed by Van Allen Probes are comprehensively investigated. For each event, observations of the pitch angle distribution of electron fluxes and electromagnetic ion cyclotron (EMIC) waves are analyzed to determine the effects of atmospheric precipitation loss due to pitch angle scattering induced by EMIC waves. Last closed drift shells (LCDS) and magnetopause standoff position are obtained to evaluate the effects of magnetopause shadowing loss. Evolution of electron phase space density (PSD) versus L* profiles and themore » μ and K (first and second adiabatic invariants) dependence of the electron PSD drops are calculated to further analyze the dominant loss mechanisms at different L*. Here, our findings suggest that these radiation belt dropouts can be classified into distinct classes in terms of dominant loss mechanisms: magnetopause shadowing dominant, EMIC wave scattering dominant, and combination of both mechanisms. Different from previous understanding, our results show that magnetopause shadowing can deplete electrons at L* < 4, while EMIC waves can efficiently scatter electrons at L* > 4. Compared to the magnetopause standoff position, it is more reliable to use LCDS to evaluate the impact of magnetopause shadowing. Finally, the evolution of electron PSD versus L* profile and the μ, K dependence of electron PSD drops can provide critical and credible clues regarding the mechanisms responsible for electron losses at different L* over the outer radiation belt.« less

Understanding the Mechanisms of Radiation Belt Dropouts Observed by Van Allen Probes

NASA Astrophysics Data System (ADS)

Xiang, Zheng; Tu, Weichao; Li, Xinlin; Ni, Binbin; Morley, S. K.; Baker, D. N.

2017-10-01

To achieve a better understanding of the dominant loss mechanisms for the rapid dropouts of radiation belt electrons, three distinct radiation belt dropout events observed by Van Allen Probes are comprehensively investigated. For each event, observations of the pitch angle distribution of electron fluxes and electromagnetic ion cyclotron (EMIC) waves are analyzed to determine the effects of atmospheric precipitation loss due to pitch angle scattering induced by EMIC waves. Last closed drift shells (LCDS) and magnetopause standoff position are obtained to evaluate the effects of magnetopause shadowing loss. Evolution of electron phase space density (PSD) versus L* profiles and the μ and K (first and second adiabatic invariants) dependence of the electron PSD drops are calculated to further analyze the dominant loss mechanisms at different L*. Our findings suggest that these radiation belt dropouts can be classified into distinct classes in terms of dominant loss mechanisms: magnetopause shadowing dominant, EMIC wave scattering dominant, and combination of both mechanisms. Different from previous understanding, our results show that magnetopause shadowing can deplete electrons at L* < 4, while EMIC waves can efficiently scatter electrons at L* > 4. Compared to the magnetopause standoff position, it is more reliable to use LCDS to evaluate the impact of magnetopause shadowing. The evolution of electron PSD versus L* profile and the μ, K dependence of electron PSD drops can provide critical and credible clues regarding the mechanisms responsible for electron losses at different L* over the outer radiation belt.

Understanding the mechanisms of radiation belt dropouts observed by Van Allen Probes

DOE PAGES

Xiang, Zheng; Tu, Weichao; Li, Xinlin; ...

2017-08-30

To achieve a better understanding of the dominant loss mechanisms for the rapid dropouts of radiation belt electrons, three distinct radiation belt dropout events observed by Van Allen Probes are comprehensively investigated. For each event, observations of the pitch angle distribution of electron fluxes and electromagnetic ion cyclotron (EMIC) waves are analyzed to determine the effects of atmospheric precipitation loss due to pitch angle scattering induced by EMIC waves. Last closed drift shells (LCDS) and magnetopause standoff position are obtained to evaluate the effects of magnetopause shadowing loss. Evolution of electron phase space density (PSD) versus L* profiles and themore » μ and K (first and second adiabatic invariants) dependence of the electron PSD drops are calculated to further analyze the dominant loss mechanisms at different L*. Here, our findings suggest that these radiation belt dropouts can be classified into distinct classes in terms of dominant loss mechanisms: magnetopause shadowing dominant, EMIC wave scattering dominant, and combination of both mechanisms. Different from previous understanding, our results show that magnetopause shadowing can deplete electrons at L* < 4, while EMIC waves can efficiently scatter electrons at L* > 4. Compared to the magnetopause standoff position, it is more reliable to use LCDS to evaluate the impact of magnetopause shadowing. Finally, the evolution of electron PSD versus L* profile and the μ, K dependence of electron PSD drops can provide critical and credible clues regarding the mechanisms responsible for electron losses at different L* over the outer radiation belt.« less

A generic double-curvature piezoelectric shell energy harvester: Linear/nonlinear theory and applications

NASA Astrophysics Data System (ADS)

Zhang, X. F.; Hu, S. D.; Tzou, H. S.

2014-12-01

Converting vibration energy to useful electric energy has attracted much attention in recent years. Based on the electromechanical coupling of piezoelectricity, distributed piezoelectric zero-curvature type (e.g., beams and plates) energy harvesters have been proposed and evaluated. The objective of this study is to develop a generic linear and nonlinear piezoelectric shell energy harvesting theory based on a double-curvature shell. The generic piezoelectric shell energy harvester consists of an elastic double-curvature shell and piezoelectric patches laminated on its surface(s). With a current model in the closed-circuit condition, output voltages and energies across a resistive load are evaluated when the shell is subjected to harmonic excitations. Steady-state voltage and power outputs across the resistive load are calculated at resonance for each shell mode. The piezoelectric shell energy harvesting mechanism can be simplified to shell (e.g., cylindrical, conical, spherical, paraboloidal, etc.) and non-shell (beam, plate, ring, arch, etc.) distributed harvesters using two Lamé parameters and two curvature radii of the selected harvester geometry. To demonstrate the utility and simplification procedures, the generic linear/nonlinear shell energy harvester mechanism is simplified to three specific structures, i.e., a cantilever beam case, a circular ring case and a conical shell case. Results show the versatility of the generic linear/nonlinear shell energy harvesting mechanism and the validity of the simplification procedures.

X-ray transitions studied for decelerated bare and H-like uranium ions at the ESR electron cooler

NASA Astrophysics Data System (ADS)

Gumberidze, A.; Stöhlker, Th.; Bednarz, G.; Beyer, H. F.; Bosch, F.; Cai, X.; Hagmann, S.; Klepper, O.; Kozhuharov, C.; Liesen, D.; Ma, X.; Mokler, P. H.; Sierpowski, D.; Stachura, Z.; Steck, M.; Toleikis, S.; Warczak, A.; Zou, Y.

2003-05-01

Here we report on X-ray spectra induced by spontaneous capture of free electrons into decelerated bare- and hydrogen-like uranium ions which we measured recently at the cooler section of the ESR storage ring. The most intense lines observed in spectra can be attributed to direct transition of electrons into the K shell of the projectile ions and to characteristic L → K (Lyα) transitions. Radiative recombination lines into the K shell of bare and H-like uranium can be exploited for measuring the two-electron contribution to the ground state binding energy in helium-like uranium. The goal is to probe for high-Z ions bound-state QED corrections which are of the order of α2. Besides the dominant characteristic L → K transitions, the strongly reduced Bremsstrahlung (due to the low cooler voltage applied to the decelerated ions) allowed us to observe for the very first time RR transitions into the L shell as well as the balmer radiation located at the low-energy part of the spectra.

Interfacial charge separation and recombination in InP and quasi-type II InP/CdS core/shell quantum dot-molecular acceptor complexes.

PubMed

Wu, Kaifeng; Song, Nianhui; Liu, Zheng; Zhu, Haiming; Rodríguez-Córdoba, William; Lian, Tianquan

2013-08-15

Recent studies of group II-VI colloidal semiconductor heterostuctures, such as CdSe/CdS core/shell quantum dots (QDs) or dot-in-rod nanorods, show that type II and quasi-type II band alignment can facilitate electron transfer and slow down charge recombination in QD-molecular electron acceptor complexes. To explore the general applicability of this wave function engineering approach for controlling charge transfer properties, we investigate exciton relaxation and dissociation dynamics in InP (a group III-V semiconductor) and InP/CdS core/shell (a heterostructure beween group III-V and II-VI semiconductors) QDs by transient absorption spectroscopy. We show that InP/CdS QDs exhibit a quasi-type II band alignment with the 1S electron delocalized throughout the core and shell and the 1S hole confined in the InP core. In InP-methylviologen (MV(2+)) complexes, excitons in the QD can be dissociated by ultrafast electron transfer to MV(2+) from the 1S electron level (with an average time constant of 11.4 ps) as well as 1P and higher electron levels (with a time constant of 0.39 ps), which is followed by charge recombination to regenerate the complex in its ground state (with an average time constant of 47.1 ns). In comparison, InP/CdS-MV(2+) complexes show similar ultrafast charge separation and 5-fold slower charge recombination rates, consistent with the quasi-type II band alignment in these heterostructures. This result demonstrates that wave function engineering in nanoheterostructures of group III-V and II-VI semiconductors provides a promising approach for optimizing their light harvesting and charge separation for solar energy conversion applications.

Towards a First-Principles Determination of Effective Coulomb Interactions in Correlated Electron Materials: Role of Intershell Interactions

NASA Astrophysics Data System (ADS)

Seth, Priyanka; Hansmann, Philipp; van Roekeghem, Ambroise; Vaugier, Loig; Biermann, Silke

2017-08-01

The determination of the effective Coulomb interactions to be used in low-energy Hamiltonians for materials with strong electronic correlations remains one of the bottlenecks for parameter-free electronic structure calculations. We propose and benchmark a scheme for determining the effective local Coulomb interactions for charge-transfer oxides and related compounds. Intershell interactions between electrons in the correlated shell and ligand orbitals are taken into account in an effective manner, leading to a reduction of the effective local interactions on the correlated shell. Our scheme resolves inconsistencies in the determination of effective interactions as obtained by standard methods for a wide range of materials, and allows for a conceptual understanding of the relation of cluster model and dynamical mean field-based electronic structure calculations.

Towards a First-Principles Determination of Effective Coulomb Interactions in Correlated Electron Materials: Role of Intershell Interactions.

PubMed

Seth, Priyanka; Hansmann, Philipp; van Roekeghem, Ambroise; Vaugier, Loig; Biermann, Silke

2017-08-04

The determination of the effective Coulomb interactions to be used in low-energy Hamiltonians for materials with strong electronic correlations remains one of the bottlenecks for parameter-free electronic structure calculations. We propose and benchmark a scheme for determining the effective local Coulomb interactions for charge-transfer oxides and related compounds. Intershell interactions between electrons in the correlated shell and ligand orbitals are taken into account in an effective manner, leading to a reduction of the effective local interactions on the correlated shell. Our scheme resolves inconsistencies in the determination of effective interactions as obtained by standard methods for a wide range of materials, and allows for a conceptual understanding of the relation of cluster model and dynamical mean field-based electronic structure calculations.

Intramolecular interactions of L-phenylalanine revealed by inner shell chemical shift

NASA Astrophysics Data System (ADS)

Ganesan, Aravindhan; Wang, Feng

2009-07-01

Intramolecular interactions of the functional groups, carboxylic acid, amino, and phenyl in L-phenylalanine have been revealed through inner shell chemical shift. The chemical shift and electronic structures are studied using its derivatives, 2-phenethylamine (PEA) and 3-phenylpropionic acid (PPA), through substitutions of the functional groups on the chiral carbon Cα, i.e., carboxylic acid (-COOH) and amino (-NH2) groups. Inner shell ionization spectra of L-phenylalanine are simulated using density functional theory based B3LYP/TZVP and LB94/et-pVQZ models, which achieve excellent agreement with the most recently available synchrotron sourced x-ray photoemission spectroscopy of L-phenylalanine (Elettra, Italy). The present study reveals insight into behavior of the peptide bond (CO-NH) through chemical shift of the C1-Cα-Cβ(-Cγ) chain and intramolecular interactions with phenyl. It is found that the chemical shift of the carbonyl C1(=O) site exhibits an apparently redshift (smaller energy) when interacting with the phenyl aromatic group. Removal of the amino group (-NH2) from L-phenylalanine (which forms PPA) brings this energy on C1 close to that in L-alanine (δ <0.01 eV). Chemical environment of Cα and Cβ exhibits more significant differences in L-alanine than in the aromatic species, indicating that the phenyl group indeed affects the peptide bond in the amino acid fragment. No direct evidences are found that the carbonyl acid and amino group interact with the phenyl ring through conventional hydrogen bonds.

Micro-Raman investigations of InN-GaN core-shell nanowires on Si (111) substrate

NASA Astrophysics Data System (ADS)

Sangeetha, P.; Jeganathan, K.; Ramakrishnan, V.

2013-06-01

The electron-phonon interactions in InN-GaN core-shell nanowires grown by plasma assisted- molecular beam epitaxy (MBE) on Si (111) substrate have been analysed using micro-Raman spectroscopic technique with the excitation wavelength of 633, 488 and 325 nm. The Raman scattering at 633 nm reveals the characteristic E2 (high) and A1 (LO) phonon mode of InN core at 490 and 590 cm-1 respectively and E2 (high) phonon mode of GaN shell at 573 cm-1. The free carrier concentration of InN core is found to be low in the order ˜ 1016 cm-3 due to the screening of charge carriers by thin GaN shell. Diameter of InN core evaluated using the spatial correlation model is consistent with the transmission electron microscopic measurement of ˜15 nm. The phonon-life time of core-shell nanowire structure is estimated to be ˜0.4 ps. The micro-Raman mapping and its corresponding localised spectra for 325 nm excitation exhibit intense E2 (high) phonon mode of GaN shell at 573 cm-1 as the decrease of laser interaction length and the signal intensity is quenched at the voids due to high spacing of NWs.

MHD Waves in Coronal Loops with a Shell

NASA Astrophysics Data System (ADS)

Mikhalyaev, B. B.; Solov'ev, A. A.

2004-04-01

We consider a model of a coronal loop in the form of a cord surrounded by a coaxial shell. Two slow magnetosonic waves longitudinally propagate within a thin flux tube on the m = 0 cylindrical mode with velocities close to the tube velocities in the cord and the shell. One wave propagates inside the cord, while the other propagates inside the shell. A peculiar feature of the second wave is that the plasma in the cord and the shell oscillates with opposite phases. There are two fast magnetosonic waves on each of the cylindrical modes with m > 0. If the plasma density in the shell is lower than that in the surrounding corona, then one of the waves is radiated into the corona, which causes the loop oscillations to be damped, while the other wave is trapped by the cord, but can also be radiated out under certain conditions. If the plasma density in the shell is higher than that in the cord, then one of the waves is trapped by the shell, while the other wave can also be trapped by the shell under certain conditions. In the wave trapped by the shell and the wave radiated by the tube, the plasma in the cord and the shell oscillates with opposite phases.

Growth of fullerene-like carbon nitride thin solid films consisting of cross-linked nano-onions

NASA Astrophysics Data System (ADS)

Czigány, Zs.; Brunell, I. F.; Neidhardt, J.; Hultman, L.; Suenaga, K.

2001-10-01

Fullerene-like CNx (x≈0.12) thin solid films were deposited by reactive magnetron sputtering of graphite in a nitrogen and argon discharge on cleaved NaCl and Si(001) substrates at 450 °C. As-deposited films consist of 5 nm diam CNx nano-onions with shell sizes corresponding to Goldberg polyhedra determined by high-resolution transmission electron microscopy. Electron energy loss spectroscopy revealed that N incorporation is higher in the core of the onions than at the perimeter. N incorporation promotes pentagon formation and provides reactive sites for interlinks between shells of the onions. A model is proposed for the formation of CNx nano-onions by continuous surface nucleation and growth of hemispherical shells.

Self-consistent calculations for the electronic structure of a vacancy in copper. A solution of the embedding problem

NASA Astrophysics Data System (ADS)

Zeller, R.; Braspenning, P. J.

1982-06-01

The charge density and the local density of states for a vacancy in Cu and for the first shell of Cu neighbours are calculated by the KKR-Green's function technique. The muffin-tin potentials for the vacancy and the neighbour shell atoms are determined self-consistently in the local density approximation of density functional theory. By the use of the proper host Green's function the embedding of this cluster of 13 perturbed muffin-tins into the infinite array of bulk Cu muffin-tin potentials is described rigorously, thus representing a solution of the embedding problem. The calculations demonstrate a rather large charge transfer of 1.1 electrons from the first neighbour shell to the vacancy.

Sound Transmission through Cylindrical Shell Structures Excited by Boundary Layer Pressure Fluctuations

NASA Technical Reports Server (NTRS)

Tang, Yvette Y.; Silcox, Richard J.; Robinson, Jay H.

1996-01-01

This paper examines sound transmission into two concentric cylindrical sandwich shells subject to turbulent flow on the exterior surface of the outer shell. The interior of the shells is filled with fluid medium and there is an airgap between the shells in the annular space. The description of the pressure field is based on the cross-spectral density formulation of Corcos, Maestrello, and Efimtsov models of the turbulent boundary layer. The classical thin shell theory and the first-order shear deformation theory are applied for the inner and outer shells, respectively. Modal expansion and the Galerkin approach are used to obtain closed-form solutions for the shell displacements and the radiation and transmission pressures in the cavities including both the annular space and the interior. The average spectral density of the structural responses and the transmitted interior pressures are expressed explicitly in terms of the summation of the cross-spectral density of generalized force induced by the boundary layer turbulence. The effects of acoustic and hydrodynamic coincidences on the spectral density are observed. Numerical examples are presented to illustrate the method for both subsonic and supersonic flows.

Charge and spin control of ultrafast electron and hole dynamics in single CdSe/ZnSe quantum dots

NASA Astrophysics Data System (ADS)

Hinz, C.; Gumbsheimer, P.; Traum, C.; Holtkemper, M.; Bauer, B.; Haase, J.; Mahapatra, S.; Frey, A.; Brunner, K.; Reiter, D. E.; Kuhn, T.; Seletskiy, D. V.; Leitenstorfer, A.

2018-01-01

We study the dynamics of photoexcited electrons and holes in single negatively charged CdSe/ZnSe quantum dots with two-color femtosecond pump-probe spectroscopy. An initial characterization of the energy level structure is performed at low temperatures and magnetic fields of up to 5 T. Emission and absorption resonances are assigned to specific transitions between few-fermion states by a theoretical model based on a configuration interaction approach. To analyze the dynamics of individual charge carriers, we initialize the quantum system into excited trion states with defined energy and spin. Subsequently, the time-dependent occupation of the trion ground state is monitored by spectrally resolved differential transmission measurements. We observe subpicosecond dynamics for a hole excited to the D shell. The energy dependence of this D -to-S shell intraband transition is investigated in quantum dots of varying size. Excitation of an electron-hole pair in the respective p shells leads to the formation of singlet and triplet spin configurations. Relaxation of the p -shell singlet is observed to occur on a time scale of a few picoseconds. Pumping of p -shell triplet transitions opens up two pathways with distinctly different scattering times. These processes are shown to be governed by the mixing of singlet and triplet states due to exchange interactions enabling simultaneous electron and hole spin flips. To isolate the relaxation channels, we align the spin of the residual electron by a magnetic field and employ laser pulses of defined helicity. This step provides ultrafast preparation of a fully inverted trion ground state of the quantum dot with near unity probability, enabling deterministic addition of a single photon to the probe pulse. Therefore our experiments represent a significant step towards using single quantum emitters with well-controled inversion to manipulate the photon statistics of ultrafast light pulses.

Controlled synthesis of magnetic iron oxides@SnO2 quasi-hollow core-shell heterostructures: formation mechanism, and enhanced photocatalytic activity

NASA Astrophysics Data System (ADS)

Wu, Wei; Zhang, Shaofeng; Ren, Feng; Xiao, Xiangheng; Zhou, Juan; Jiang, Changzhong

2011-11-01

Iron oxide/SnO2 magnetic semiconductor core-shell heterostructures with high purity were synthesized by a low-cost, surfactant-free and environmentally friendly hydrothermal strategy via a seed-mediated method. The morphology and structure of the hybrid nanostructures were characterized by means of high-resolution transmission electron microscopy and X-ray diffraction. The morphology evolution investigations reveal that the Kirkendall effect directs the diffusion and causes the formation of iron oxide/SnO2 quasi-hollow particles. Significantly, the as-obtained iron oxides/SnO2 core-shell heterostructures exhibited enhanced visible light or UV photocatalytic abilities, remarkably superior to as-used α-Fe2O3 seeds and commercial SnO2 products, mainly owing to the effective electron hole separation at the iron oxides/SnO2 interfaces.Iron oxide/SnO2 magnetic semiconductor core-shell heterostructures with high purity were synthesized by a low-cost, surfactant-free and environmentally friendly hydrothermal strategy via a seed-mediated method. The morphology and structure of the hybrid nanostructures were characterized by means of high-resolution transmission electron microscopy and X-ray diffraction. The morphology evolution investigations reveal that the Kirkendall effect directs the diffusion and causes the formation of iron oxide/SnO2 quasi-hollow particles. Significantly, the as-obtained iron oxides/SnO2 core-shell heterostructures exhibited enhanced visible light or UV photocatalytic abilities, remarkably superior to as-used α-Fe2O3 seeds and commercial SnO2 products, mainly owing to the effective electron hole separation at the iron oxides/SnO2 interfaces. Electronic supplementary information (ESI) available: TEM and HRTEM images of hematite seeds and iron oxide/SnO2 (12 h and 36 h). See DOI: 10.1039/c1nr10728c

Physical mechanism causing rapid changes in ultrarelativistic electron pitch angle distributions right after a shock arrival: Evaluation of an electron dropout event: Drift Shell Splitting on the Dayside

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

Zhang, X. -J.; Li, W.; Thorne, R. M.

Three mechanisms have been proposed to explain relativistic electron flux depletions (dropouts) in the Earth's outer radiation belt during storm times: adiabatic expansion of electron drift shells due to a decrease in magnetic field strength, magnetopause shadowing and subsequent outward radial diffusion, and precipitation into the atmosphere (driven by EMIC wave scattering). Which mechanism predominates in causing electron dropouts commonly observed in the outer radiation belt is still debatable. In the present study, we evaluate the physical mechanism that may be primarily responsible for causing the sudden change in relativistic electron pitch angle distributions during a dropout event observed bymore » Van Allen Probes during the main phase of the 27 February 2014 storm. During this event, the phase space density of ultrarelativistic (>1MeV) electrons was depleted by more than 1 order of magnitude over the entire radial extent of the outer radiation belt (3 < L* < 5) in less than 6 h after the passage of an interplanetary shock. We model the electron pitch angle distribution under a compressed magnetic field topology based on actual solar wind conditions. Although these ultrarelativistic electrons exhibit highly anisotropic (peaked in 90°), energy-dependent pitch angle distributions, which appear to be associated with the typical EMIC wave scattering, comparison of the modeled electron distribution to electron measurements indicates that drift shell splitting is responsible for this rapid change in electron pitch angle distributions. This further indicates that magnetopause loss is the predominant cause of the electron dropout right after the shock arrival.« less

Physical mechanism causing rapid changes in ultrarelativistic electron pitch angle distributions right after a shock arrival: Evaluation of an electron dropout event: Drift Shell Splitting on the Dayside

DOE PAGES

Zhang, X. -J.; Li, W.; Thorne, R. M.; ...

2016-08-13

Three mechanisms have been proposed to explain relativistic electron flux depletions (dropouts) in the Earth's outer radiation belt during storm times: adiabatic expansion of electron drift shells due to a decrease in magnetic field strength, magnetopause shadowing and subsequent outward radial diffusion, and precipitation into the atmosphere (driven by EMIC wave scattering). Which mechanism predominates in causing electron dropouts commonly observed in the outer radiation belt is still debatable. In the present study, we evaluate the physical mechanism that may be primarily responsible for causing the sudden change in relativistic electron pitch angle distributions during a dropout event observed bymore » Van Allen Probes during the main phase of the 27 February 2014 storm. During this event, the phase space density of ultrarelativistic (>1MeV) electrons was depleted by more than 1 order of magnitude over the entire radial extent of the outer radiation belt (3 < L* < 5) in less than 6 h after the passage of an interplanetary shock. We model the electron pitch angle distribution under a compressed magnetic field topology based on actual solar wind conditions. Although these ultrarelativistic electrons exhibit highly anisotropic (peaked in 90°), energy-dependent pitch angle distributions, which appear to be associated with the typical EMIC wave scattering, comparison of the modeled electron distribution to electron measurements indicates that drift shell splitting is responsible for this rapid change in electron pitch angle distributions. This further indicates that magnetopause loss is the predominant cause of the electron dropout right after the shock arrival.« less

Stereo and scanning electron microscopy of in-shell Brazil nut (Bertholletia excelsa H.B.K.): part two-surface sound nut fungi spoilage susceptibility.

PubMed

Scussel, Vildes M; Manfio, Daniel; Savi, Geovana D; Moecke, Elisa H S

2014-11-01

This work reports the in-shell Brazil nut spoilage susceptible morpho-histological characteristics and fungi infection (shell, edible part, and brown skin) through stereo and scanning electron microscopies (SEM). The following characteristics related to shell (a) morphology-that allow fungi and insects' entrance to inner nut, and (b) histology-that allow humidity absorption, improving environment conditions for living organisms development, were identified. (a.1) locule in testae-the nut navel, which is a cavity formed during nut detaching from pods (located at 1.0 to 2.0/4th of the shell B&C nut faces linkage). It allows the nut brown skin (between shell and edible part) first contact to the external environment, through the (a.2) nut channel-the locule prolongation path, which has the water/nutrients cambium function for their transport and distribution to the inner seed (while still on the tree/pod). Both, locule followed by the channel, are the main natural entrance of living organisms (fungi and insects), including moisture to the inner seed structures. In addition, the (a.3) nut shell surface-which has a crinkled and uneven surface morphology-allows water absorption, thus adding to the deterioration processes too. The main shell histological characteristic, which also allows water absorption (thus improving environment conditions for fungi proliferation), is the (b.1) cell wall porosity-the multilayered wall and porous rich cells that compose the shell faces double tissue layers and the (b.2) soft tissue-the mix of tissues 2 faces corner/linkage. This work also shows in details the SEM nut spoilage susceptible features highly fungi infected with hyphae and reproductive structures distribution. © 2014 Institute of Food Technologists®

Buckling of circular cylindrical shells under dynamically applied axial loads

NASA Technical Reports Server (NTRS)

Tulk, J. D.

1972-01-01

A theoretical and experimental study was made of the buckling characteristics of perfect and imperfect circular cylindrical shells subjected to dynamic axial loading. Experimental data included dynamic buckling loads (124 data points), high speed photographs of buckling mode shapes and observations of the dynamic stability of shells subjected to rapidly applied sub-critical loads. A mathematical model was developed to describe the dynamic behavior of perfect and imperfect shells. This model was based on the Donnell-Von Karman compatibility and equilibrium equations and had a wall deflection function incorporating five separate modes of deflection. Close agreement between theory and experiment was found for both dynamic buckling strength and buckling mode shapes.

Influence of an asymmetric ring on the modeling of an orthogonally stiffened cylindrical shell

NASA Technical Reports Server (NTRS)

Rastogi, Naveen; Johnson, Eric R.

1994-01-01

Structural models are examined for the influence of a ring with an asymmetrical cross section on the linear elastic response of an orthogonally stiffened cylindrical shell subjected to internal pressure. The first structural model employs classical theory for the shell and stiffeners. The second model employs transverse shear deformation theories for the shell and stringer and classical theory for the ring. Closed-end pressure vessel effects are included. Interacting line load intensities are computed in the stiffener-to-skin joints for an example problem having the dimensions of the fuselage of a large transport aircraft. Classical structural theory is found to exaggerate the asymmetric response compared to the transverse shear deformation theory.

High throughput chemical munitions treatment system

DOEpatents

Haroldsen, Brent L [Manteca, CA; Stofleth, Jerome H [Albuquerque, NM; Didlake, Jr., John E.; Wu, Benjamin C-P [San Ramon, CA

2011-11-01

A new High-Throughput Explosive Destruction System is disclosed. The new system is comprised of two side-by-side detonation containment vessels each comprising first and second halves that feed into a single agent treatment vessel. Both detonation containment vessels further comprise a surrounding ventilation facility. Moreover, the detonation containment vessels are designed to separate into two half-shells, wherein one shell can be moved axially away from the fixed, second half for ease of access and loading. The vessels are closed by means of a surrounding, clam-shell type locking seal mechanisms.

Understanding and Calibrating Density-Functional-Theory Calculations Describing the Energy and Spectroscopy of Defect Sites in Hexagonal Boron Nitride.

PubMed

Reimers, Jeffrey R; Sajid, A; Kobayashi, Rika; Ford, Michael J

2018-03-13

Defect states in 2-D materials present many possible uses but both experimental and computational characterization of their spectroscopic properties is difficult. We provide and compare results from 13 DFT and ab initio computational methods for up to 25 excited states of a paradigm system, the V N C B defect in hexagonal boron nitride (h-BN). Studied include: (i) potentially catastrophic effects for computational methods arising from the multireference nature of the closed-shell and open-shell states of the defect, which intrinsically involves broken chemical bonds, (ii) differing results from DFT and time-dependent DFT (TDDFT) calculations, (iii) comparison of cluster models to periodic-slab models of the defect, (iv) the starkly differing effects of nuclear relaxation on the various electronic states that control the widths of photoabsorption and photoemission spectra as broken bonds try to heal, (v) the effect of zero-point energy and entropy on free-energy differences, (vi) defect-localized and conduction/valence-band transition natures, and (vii) strategies needed to ensure that the lowest-energy state of a defect can be computationally identified. Averaged state-energy differences of 0.3 eV are found between CCSD(T) and MRCI energies, with thermal effects on free energies sometimes also being of this order. However, DFT-based methods can perform very poorly. Simple generalized-gradient functionals like PBE fail at the most basic level and should never be applied to defect states. Hybrid functionals like HSE06 work very well for excitations within the triplet manifold of the defect, with an accuracy equivalent to or perhaps exceeding the accuracy of the ab initio methods used. However, HSE06 underestimates triplet-state energies by on average of 0.7 eV compared to closed-shell singlet states, while open-shell singlet states are predicted to be too low in energy by 1.0 eV. This leads to misassignment of the ground state of the V N C B defect. Long-range corrected functionals like CAM-B3LYP are shown to work much better and to represent the current entry level for DFT calculations on defects. As significant differences between cluster and periodic-slab models are also found, the widespread implementation of such functionals in periodic codes is in urgent need.

Two-component relativistic coupled-cluster methods using mean-field spin-orbit integrals

NASA Astrophysics Data System (ADS)

Liu, Junzi; Shen, Yue; Asthana, Ayush; Cheng, Lan

2018-01-01

A novel implementation of the two-component spin-orbit (SO) coupled-cluster singles and doubles (CCSD) method and the CCSD augmented with the perturbative inclusion of triple excitations [CCSD(T)] method using mean-field SO integrals is reported. The new formulation of SO-CCSD(T) features an atomic-orbital-based algorithm for the particle-particle ladder term in the CCSD equation, which not only removes the computational bottleneck associated with the large molecular-orbital integral file but also accelerates the evaluation of the particle-particle ladder term by around a factor of 4 by taking advantage of the spin-free nature of the instantaneous electron-electron Coulomb interaction. Benchmark calculations of the SO splittings for the thallium atom and a set of diatomic 2Π radicals as well as of the bond lengths and harmonic frequencies for a set of closed-shell diatomic molecules are presented. The basis-set and core-correlation effects in the calculations of these properties have been carefully analyzed.

Prolate spheroidal hematite particles equatorially belt with drug-carrying layered double hydroxide disks: Ring Nebula-like nanocomposites.

PubMed

Nedim Ay, Ahmet; Konuk, Deniz; Zümreoglu-Karan, Birgul

2011-02-03

A new nanocomposite architecture is reported which combines prolate spheroidal hematite nanoparticles with drug-carrying layered double hydroxide [LDH] disks in a single structure. Spindle-shaped hematite nanoparticles with average length of 225 nm and width of 75 nm were obtained by thermal decomposition of hydrothermally synthesized hematite. The particles were first coated with Mg-Al-NO3-LDH shell and then subjected to anion exchange with salicylate ions. The resulting bio-nanohybrid displayed a close structural resemblance to that of the Ring Nebula. Scanning electron microscope and transmission electron microscopy images showed that the LDH disks are stacked around the equatorial part of the ellipsoid extending along the main axis. This geometry possesses great structural tunability as the composition of the LDH and the nature of the interlayer region can be tailored and lead to novel applications in areas ranging from functional materials to medicine by encapsulating various guest molecules.

Prolate spheroidal hematite particles equatorially belt with drug-carrying layered double hydroxide disks: Ring Nebula-like nanocomposites

PubMed Central

2011-01-01

A new nanocomposite architecture is reported which combines prolate spheroidal hematite nanoparticles with drug-carrying layered double hydroxide [LDH] disks in a single structure. Spindle-shaped hematite nanoparticles with average length of 225 nm and width of 75 nm were obtained by thermal decomposition of hydrothermally synthesized hematite. The particles were first coated with Mg-Al-NO3-LDH shell and then subjected to anion exchange with salicylate ions. The resulting bio-nanohybrid displayed a close structural resemblance to that of the Ring Nebula. Scanning electron microscope and transmission electron microscopy images showed that the LDH disks are stacked around the equatorial part of the ellipsoid extending along the main axis. This geometry possesses great structural tunability as the composition of the LDH and the nature of the interlayer region can be tailored and lead to novel applications in areas ranging from functional materials to medicine by encapsulating various guest molecules. PMID:21711652

A low-cost approach to electronic excitation energies based on the driven similarity renormalization group

NASA Astrophysics Data System (ADS)

Li, Chenyang; Verma, Prakash; Hannon, Kevin P.; Evangelista, Francesco A.

2017-08-01

We propose an economical state-specific approach to evaluate electronic excitation energies based on the driven similarity renormalization group truncated to second order (DSRG-PT2). Starting from a closed-shell Hartree-Fock wave function, a model space is constructed that includes all single or single and double excitations within a given set of active orbitals. The resulting VCIS-DSRG-PT2 and VCISD-DSRG-PT2 methods are introduced and benchmarked on a set of 28 organic molecules [M. Schreiber et al., J. Chem. Phys. 128, 134110 (2008)]. Taking CC3 results as reference values, mean absolute deviations of 0.32 and 0.22 eV are observed for VCIS-DSRG-PT2 and VCISD-DSRG-PT2 excitation energies, respectively. Overall, VCIS-DSRG-PT2 yields results with accuracy comparable to those from time-dependent density functional theory using the B3LYP functional, while VCISD-DSRG-PT2 gives excitation energies comparable to those from equation-of-motion coupled cluster with singles and doubles.

Communication: Nuclear quadrupole moment-induced Cotton-Mouton effect in noble gas atoms

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

Fu, Li-juan; Vaara, Juha, E-mail: juha.vaara@iki.fi; Rizzo, Antonio

New, high-sensitivity and high-resolution spectroscopic and imaging methods may be developed by exploiting nuclear magneto-optic effects. A first-principles electronic structure formulation of nuclear electric quadrupole moment-induced Cotton-Mouton effect (NQCME) is presented for closed-shell atoms. In NQCME, aligned quadrupole moments alter the index of refraction of the medium along with and perpendicular to the direction of nuclear alignment. The roles of basis-set convergence, electron correlation, and relativistic effects are investigated for three quadrupolar noble gas isotopes: {sup 21}Ne, {sup 83}Kr, and {sup 131}Xe. The magnitude of the resulting ellipticities is predicted to be 10{sup −4}–10{sup −6} rad/(M cm) for fully spin-polarized nuclei.more » These should be detectable in the Voigt setup. Particularly interesting is the case of {sup 131}Xe, in which a high degree of spin polarization can be achieved via spin-exchange optical hyperpolarization.« less

Autoionizing resonances in electron-impact ionization of O5+ ions

NASA Astrophysics Data System (ADS)

Müller, A.; Teng, H.; Hofmann, G.; Phaneuf, R. A.; Salzborn, E.

2000-12-01

We report on a detailed experimental and theoretical study of electron-impact ionization of O5+ ions. A high-resolution scan measurement of the K-shell excitation threshold region has been performed with statistical uncertainties as low as 0.03%. At this level of precision a wealth of features in the cross section arising from indirect ionization processes becomes visible, and even interference of direct ionization with resonant-excitation/auto-double-ionization (READI) is clearly observed. The experimental results are compared with R-matrix calculations that include both direct and indirect processes in a unified way. Radiative damping of autoionizing Li-like states is found to be about 10-15 %. The calculations almost perfectly reproduce most of the experimental resonance features found in the present measurement including READI. They also agree with the direct-ionization converged close-coupling results of I. Bray [J. Phys. B 28, L247 (1995)] and the absolute total ionization cross section measurement of K. Rinn et al. [Phys. Rev. A 36, 595 (1987)].

A Systematic Theoretical Study of UC6: Structure, Bonding Nature, and Spectroscopy.

PubMed

Du, Jiguang; Jiang, Gang

2017-11-20

The study of uranium carbides has received renewed attention in recent years due to the potential use of these compounds as fuels in new generations of nuclear reactors. The isomers of the UC 6 cluster were determined by DFT and ab initio methods. The structures obtained using SC-RECP for U were generally consistent with those obtained using an all-electron basis set (ZORA-SARC). The CCSD(T) calculations indicated that two isomers had similar energies and may coexist in laser evaporation experiments. The nature of the U-C bonds in the different isomers was examined via a topological analysis of the electron density, and the results indicated that the U-C bonds are predominantly closed-shell (ionic) interactions with a certain degree of covalent character in all cases, particularly in the linear species. The IR and UV-vis spectra of the isomers were theoretically simulated to provide information that can be used to identify the isomers of UC 6 in future experiments.

Growth and Characterisation of GaAs/AlGaAs Core-shell Nanowires for Optoelectronic Device Applications

NASA Astrophysics Data System (ADS)

Jiang, Nian

III-V semiconductor nanowires have been investigated as key components for future electronic and optoelectronic devices and systems due to their direct band gap and high electron mobility. Amongst the III-V semiconductors, the planar GaAs material system has been extensively studied and used in industries. Accordingly, GaAs nanowires are the prime candidates for nano-scale devices. However, the electronic performance of GaAs nanowires has yet to match that of state-of-the-art planar GaAs devices. The present deficiency of GaAs nanowires is typically attributed to the large surface-to- volume ratio and the tendency for non-radiative recombination centres to form at the surface. The favoured solution of this problem is by coating GaAs nanowires with AlGaAs shells, which replaces the GaAs surface with GaAs/AlGaAs interface. This thesis presents a systematic study of GaAs/AlGaAs core-shell nanowires grown by metal organic chemical vapour deposition (MOCVD), including understanding the growth, and characterisation of their structural and optical properties. The structures of the nanowires were mainly studied by scanning electron microscopy and transmis- sion electron microscopy (TEM). A procedure of microtomy was developed to prepare the cross-sectional samples for the TEM studies. The optical properties were charac- terised by photoluminescence (PL) spectroscopy. Carrier lifetimes were measured by time-resolved PL. The growth of AlGaAs shell was optimised to obtain the best optical properties, e.g. the strongest PL emission and the longest minority carrier lifetimes. (Abstract shortened by ProQuest.).

Equation-of-motion coupled-cluster method for doubly ionized states with spin-orbit coupling.

PubMed

Wang, Zhifan; Hu, Shu; Wang, Fan; Guo, Jingwei

2015-04-14

In this work, we report implementation of the equation-of-motion coupled-cluster method for doubly ionized states (EOM-DIP-CC) with spin-orbit coupling (SOC) using a closed-shell reference. Double ionization potentials (DIPs) are calculated in the space spanned by 2h and 3h1p determinants with the EOM-DIP-CC approach at the CC singles and doubles level (CCSD). Time-reversal symmetry together with spatial symmetry is exploited to reduce computational effort. To circumvent the problem of unstable dianion references when diffuse basis functions are included, nuclear charges are scaled. Effect of this stabilization potential on DIPs is estimated based on results from calculations using a small basis set without diffuse basis functions. DIPs and excitation energies of some low-lying states for a series of open-shell atoms and molecules containing heavy elements with two unpaired electrons have been calculated with the EOM-DIP-CCSD approach. Results show that this approach is able to afford a reliable description on SOC splitting. Furthermore, the EOM-DIP-CCSD approach is shown to provide reasonable excitation energies for systems with a dianion reference when diffuse basis functions are not employed.

Equation-of-motion coupled-cluster method for doubly ionized states with spin-orbit coupling

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

Wang, Zhifan; Hu, Shu; Guo, Jingwei

2015-04-14

In this work, we report implementation of the equation-of-motion coupled-cluster method for doubly ionized states (EOM-DIP-CC) with spin-orbit coupling (SOC) using a closed-shell reference. Double ionization potentials (DIPs) are calculated in the space spanned by 2h and 3h1p determinants with the EOM-DIP-CC approach at the CC singles and doubles level (CCSD). Time-reversal symmetry together with spatial symmetry is exploited to reduce computational effort. To circumvent the problem of unstable dianion references when diffuse basis functions are included, nuclear charges are scaled. Effect of this stabilization potential on DIPs is estimated based on results from calculations using a small basis setmore » without diffuse basis functions. DIPs and excitation energies of some low-lying states for a series of open-shell atoms and molecules containing heavy elements with two unpaired electrons have been calculated with the EOM-DIP-CCSD approach. Results show that this approach is able to afford a reliable description on SOC splitting. Furthermore, the EOM-DIP-CCSD approach is shown to provide reasonable excitation energies for systems with a dianion reference when diffuse basis functions are not employed.« less

A Chandrasekhar Mass Progenitor for the Type Ia Supernova Remnant 3C 397 from the Enhanced Abundances of Nickel and Manganese

NASA Technical Reports Server (NTRS)

Yamaguchi, Hiroya; Badenes, Carles; Foster, Adam R.; Bravo, Eduardo; Williams, Brian J.; Maeda, Keiichi; Nobukawa, Masayoshi; Eriksen, Kristoffer A.; Brickhouse, Nancy S.; Petre, Robert;

First study of vitellogenesis of the broad fish tapeworm Diphyllobothrium latum (Cestoda, Diphyllobothriidea), a human parasite with extreme fecundity.

PubMed

Yoneva, Aneta; Kuchta, Roman; Scholz, Tomáš

2014-12-01

In the present study, the process of vitellogenesis of one of the most prolific organisms, the broad tapeworm, Diphyllobothrium latum, the causative agent of human diphyllobothriosis, was studied for the first time using transmission electron microscopy. Cytochemical staining with periodic acid-thiosemicarbazide-silver proteinate for detection of glycogen was applied. Starting from the periphery toward the center of the vitelline follicle four stages of vitellocytes are differentiated: immature vitellocytes, early maturing vitellocytes, advanced maturing and mature vitellocytes. Differentiation into mature vitellocytes involves the formation of shell globule clusters containing shell globules, large amount of saturated lipid droplets and glycogen. A peculiar ultrastructural feature of D. latum vitellogenesis is the presence of lamellar bodies in the cytoplasm of mature vitellocytes. This feature is similar to that present in the closely related caryophyllideans and spathebothriideans. Despite the great similarity observed in the embryonic development of diphylobothriideans, caryophyllideans and spathebothriideans, and the fact that their vitellocytes share a feature not reported from other cestode groups, there are substantial differences in the morphology of vitelline clusters, types, amount and localization of their nutritive reserves. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Bonding and structure of copper nitrenes.

PubMed

Cundari, Thomas R; Dinescu, Adriana; Kazi, Abul B

2008-11-03

Copper nitrenes are of interest as intermediates in the catalytic aziridination of olefins and the amination of C-H bonds. However, despite advances in the isolation and study of late-transition-metal multiply bonded complexes, a bona fide structurally characterized example of a terminal copper nitrene has, to our knowledge, not been reported. In anticipation of such a report, terminal copper nitrenes are studied from a computational perspective. The nitrene complexes studied here are of the form (beta-diketiminate)Cu(NPh). Density functional theory (DFT), complete active space self-consistent-field (CASSCF) electronic structure techniques, and hybrid quantum mechanical/molecular mechanical (QM/MM) methods are employed to study such species. While DFT methods indicate that a triplet (S = 1) is the ground state, CASSCF calculations indicate that a singlet (S = 0) is the ground state, with only a small energy gap between the singlet and triplet. Moreover, the ground-state (open-shell) singlet copper nitrene is found to be highly multiconfigurational (i.e., biradical) and to possess a bent geometry about the nitrene nitrogen, contrasting with the linear nitrene geometry of the triplet copper nitrenes. CASSCF calculations also reveal the existence of a closed-shell singlet state with some degree of multiple bonding character for the copper-nitrene bond.

Improved open-circuit voltage in polymer/oxide-nanoarray hybrid solar cells by formation of homogeneous metal oxide core/shell structures.

PubMed

Wu, Fan; Cui, Qi; Qiu, Zeliang; Liu, Changwen; Zhang, Hui; Shen, Wei; Wang, Mingtai

2013-04-24

Incorporation of vertically aligned nanorod/nanowire arrays of metal oxide (oxide-NAs) with a polymer can produce efficient hybrid solar cells with an ideal bulk-heterojunction architecture. However, polymer/oxide-NAs solar cells still suffer from a rather low (normally, < 0.4 V) open-circuit voltage (Voc). Here we demonstrate, for the first time, a novel strategy to improve the Voc in polymer/oxide-NAs solar cells by formation of homogeneous core/shell structures and reveal the intrinsic principles involved therein. A feasible hydrothermal-solvothermal combined method is developed for preparing homogeneous core/shell nanoarrays of metal oxides with a single-crystalline nanorod as core and the aggregation layer of corresponding metal oxide quantum dots (QDs) as shell, and the shell thickness (L) is easily controlled by the solvothermal reaction time for growing QDs on the nanorod. The core/shell formation dramatically improves the device Voc up to ca. 0.7-0.8 V depending on L. Based on steady-state and dynamic measurements, as well as modeling by space-charge-limited current method, it is found that the improved Voc originates from the up-shifted conduction band edge in the core by the interfacial dipole field resulting from the decreased mobility difference between photogenerated electrons and holes after the shell growth, which increases the energy difference between the quasi-Fermi levels of photogenerated electrons in the core and holes in the polymer for a higher Voc. Our results indicate that increasing Voc by the core/shell strategy seems not to be dependent on the kinds of metal oxides.

Enhance the photoluminescence and radioluminescence of La2Zr2O7:Eu3+ core nanoparticles by coating with a thin Y2O3 shell

NASA Astrophysics Data System (ADS)

Pokhrel, Madhab; Burger, Arnold; Groza, Michael; Mao, Yuanbing

2017-06-01

We report the generation of La2Zr2O7:5%Eu3+@Y2O3 (LZO5E@YO) core@shell crystalline inorganic-inorganic heterogeneous nanoparticles (NPs). The Y2O3 (YO) shell coating process based on a chemical sol-gel method led to the growth of a thin YO shell on the ordered pyrochlore La2Zr2O7:5%Eu3+ (LZO5E) core NPs. Photoluminescence (PL) analyses demonstrated a blue shift of 15 nm on charge transfer (CT) excitation band of the core@shell NPs from that of the core NPs. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) along x-ray diffraction (XRD), Fourier-transform Infrared spectroscopy (FTIR) and x-ray photoelectron spectroscopy (XPS) studies confirmed the formation of the thin YO layer over the LZO5E core NPs. The PL intensity of the LZO5E@YO core@shell NPs was enhanced by three fold compared to that of the LZO5E core NPs, and higher quantum yield (QY) was observed for the former compared to the original NPs by more than 70%. Higher radioluminescence (RL) emission was also observed for the core@shell NPs compared to the core NPs. Our ability of obtaining near-perfect core@shell heterostructure with enhanced luminescence performance opens the door for the development of efficient La2Zr2O7:5%Eu3+@Y2O3 NPs for both optical and x-ray scintillation applications.

Electron Shell as a Resonator

NASA Astrophysics Data System (ADS)

Karpeshin, F. F.

2002-11-01

Main principles of the resonance effect arising in the electron shells in interaction of the nuclei with electromagnetic radiation are analyzed and presented in the historical aspect. Principles of NEET are considered from a more general position, as compared to how this is usually presented. Characteristic features of NEET and its reverse, TEEN, as internal conversion processes are analyzed, and ways are offered of inducing them by laser radiation. The ambivalent role of the Pauli exclusion principles in NEET and TEEN processes is investigated.

Spectroscopy of M-shell x-ray transitions in Zn-like through Co-like W

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

Clementson, J; Beiersdorfer, P; Brown, G V

2009-07-08

The M-shell x-ray emission of highly charged tungsten ions has been investigated at the Livermore electron beam ion trap facility. Using the SuperEBIT electron beam ion trap and a NASA x-ray calorimeter array, transitions connecting the ground configurations in the 1500-3600 eV spectral range of zinc-like W{sup 44+} through cobalt-like W{sup 47+} have been measured. The measured spectra are compared with theoretical line positions and emissivities calculated using the FAC code.

X-Ray Laser Program Report for FY 1989

DTIC Science & Technology

1990-05-24

theoretical photopumped x-ray laser program also involves the use of a neon lasant plasma. However, that is the only similarity to the Na/Ne scheme described...K-shell neon Z pinch photons of energy hv > 900 eV, photoionize inner K-shell electrons from the neutral neon, leading to Auger decay from Ne II to...is generated by electrons which are produced in the photoionization of Ne I. For example, ionization by the Ly-a line produces 150-eV photoelectrons

Green synthesis and characterization of Au@Pt core-shell bimetallic nanoparticles using gallic acid

NASA Astrophysics Data System (ADS)

Zhang, Guojun; Zheng, Hongmei; Shen, Ming; Wang, Lei; Wang, Xiaosan

2015-06-01

In this study, we developed a facile and benign green synthesis approach for the successful fabrication of well-dispersed urchin-like Au@Pt core-shell nanoparticles (NPs) using gallic acid (GA) as both a reducing and protecting agent. The proposed one-step synthesis exploits the differences in the reduction potentials of AuCl4- and PtCl62-, where the AuCl4- ions are preferentially reduced to Au cores and the PtCl62- ions are then deposited continuously onto the Au core surface as a Pt shell. The as-prepared Au@Pt NPs were characterized by transmission electron microscope (TEM); high-resolution transmission electron microscope (HR-TEM); scanning electron microscope (SEM); UV-vis absorption spectra (UV-vis); X-ray diffraction (XRD); Fourier transmission infrared spectra (FT-IR). We systematically investigated the effects of some experimental parameters on the formation of the Au@Pt NPs, i.e., the reaction temperature, the molar ratios of HAuCl4/H2PtCl6, and the amount of GA. When polyvinylpyrrolidone K-30 (PVP) was used as a protecting agent, the Au@Pt core-shell NPs obtained using this green synthesis method were better dispersed and smaller in size. The as-prepared Au@Pt NPs exhibited better catalytic activity in the reaction where NaBH4 reduced p-nitrophenol to p-aminophenol. However, the results showed that the Au@Pt bimetallic NPs had a lower catalytic activity than the pure Au NPs obtained by the same method, which confirmed the formation of Au@Pt core-shell nanostructures because the active sites on the surfaces of the Au NPs were covered with a Pt shell.

Eosin-Y sensitized core-shell TiO2-ZnO nano-structured photoanodes for dye-sensitized solar cell applications.

PubMed

Manikandan, V S; Palai, Akshaya K; Mohanty, Smita; Nayak, Sanjay K

2018-06-01

In the current investigation, TiO 2 and TiO 2 -ZnO (core-shell) spherical nanoparticles were synthesized by simple combined hydrolysis and refluxing method. A TiO 2 core nanomaterial on the shell material of ZnO was synthesized by utilizing variable ratios of ZnO. The structural characterization of TiO 2 -ZnO core/shell nanoparticles were done by XRD analysis. The spherical structured morphology of the TiO 2 -ZnO has been confirmed through field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) studies. The UV-visible spectra of TiO 2 -ZnO nanostructures were also compared with the pristine TiO 2 to investigate the shift of wavelength. The TiO 2 -ZnO core/shell nanoparticles at the interface efficiently collect the photogenarated electrons from ZnO and also ZnO act a barrier for reduced charge recombination of electrolyte and dye-nanoparticles interface. This combination improved the light absorption which induced the charge transfer ability and dye loading capacity of core-shell nanoparticles. An enhancement in the short circuit current (J sc ) from 1.67 mA/cm 2 to 2.1 mA/cm 2 has been observed for TiO 2 -ZnObased photoanode (with platinum free counter electrode), promises an improvement in the energy conversion efficiency by 57% in comparison with that of the DSSCs based on the pristine TiO 2 . Henceforth, TiO 2 -ZnO photoelectrode in ZnO will effectively act as barrier at the interface of TiO 2 -ZnO and TiO 2 , ensuring the potential for DSSC application. Copyright © 2018 Elsevier B.V. All rights reserved.

Interactions of stars and interstellar matter in Scorpio Centaurus

NASA Technical Reports Server (NTRS)

De Geus, E. J.

1992-01-01

The interaction of the stars in the Scorpio-Centaurus OB association with the ambient interstellar medium is investigated. Large H I loops in the fourth galactic quadrant are parts of expanding shells surrounding the subgroups of the association. The energy output of the original stellar population of the subgroups is calculated. Comparison with the kinetic energy of the shells shows that the energy output of the stars in the subgroups is sufficient to form the shells. The masses of the shells are consistent with those of giant molecular clouds GMCs, suggesting that the shells consist of swept-up, original GMC material. The influence of the expanding shell around the young Upper-Scorpius subgroup on the morphology of the Ophiuchus molecular clouds is investigated. The interaction of the shell with the Ophiuchus clouds accounts for the presence of a slow shock and for the shape of the elongated dark clouds connected to the Rho Oph dense cloud. The close passage of the trajectory of the runaway star Zeta Oph by the center of the Upper-Scorpius shell, combined with the time scale of formation of the shell, strongly suggests that the star has originated in the Upper-Scorpius subgroup.

Electron and Nucleon Localization Functions of Oganesson: Approaching the Thomas-Fermi Limit

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

Jerabek, Paul; Schuetrumpf, Bastian; Schwerdtfeger, Peter

Fermion localization functions are used to discuss electronic and nucleonic shell structure effects in the superheavy element oganesson, the heaviest element discovered to date. Spin-orbit splitting in the 7p electronic shell becomes so large (~10 eV) that Og is expected to show uniform-gas-like behavior in the valence region with a rather large dipole polarizability compared to the lighter rare gas elements. The nucleon localization in Og is also predicted to undergo a transition to the Thomas-Fermi gas behavior in the valence region. Finally, this effect, particularly strong for neutrons, is due to the high density of single-particle orbitals.

Electron and Nucleon Localization Functions of Oganesson: Approaching the Thomas-Fermi Limit

DOE PAGES

Jerabek, Paul; Schuetrumpf, Bastian; Schwerdtfeger, Peter; ...

2018-01-31

Fermion localization functions are used to discuss electronic and nucleonic shell structure effects in the superheavy element oganesson, the heaviest element discovered to date. Spin-orbit splitting in the 7p electronic shell becomes so large (~10 eV) that Og is expected to show uniform-gas-like behavior in the valence region with a rather large dipole polarizability compared to the lighter rare gas elements. The nucleon localization in Og is also predicted to undergo a transition to the Thomas-Fermi gas behavior in the valence region. Finally, this effect, particularly strong for neutrons, is due to the high density of single-particle orbitals.

Correlated Optical Spectroscopy and Transmission Electron Microscopy of Individual Hollow Nanoparticles and their Dimers

PubMed Central

Yang, Linglu; Yan, Bo; Reinhard, Björn M.

2009-01-01

The optical spectra of individual Ag-Au alloy hollow particles were correlated with the particles’ structures obtained by transmission electron microscopy (TEM). The TEM provided direct experimental access to the dimension of the cavity, thickness of the metal shell, and the interparticle distance of hollow particle dimers with high spatial resolution. The analysis of correlated spectral and structural information enabled the quantification of the influence of the core-shell structure on the resonance energy, plasmon lifetime, and plasmon coupling efficiency. Electron beam exposure during TEM inspection was observed to affect plasmon wavelength and lifetime, making optical inspection prior to structural characterization mandatory. PMID:19768108

Electron and Nucleon Localization Functions of Oganesson: Approaching the Thomas-Fermi Limit

NASA Astrophysics Data System (ADS)

Jerabek, Paul; Schuetrumpf, Bastian; Schwerdtfeger, Peter; Nazarewicz, Witold

2018-02-01

Fermion localization functions are used to discuss electronic and nucleonic shell structure effects in the superheavy element oganesson, the heaviest element discovered to date. Spin-orbit splitting in the 7 p electronic shell becomes so large (˜10 eV ) that Og is expected to show uniform-gas-like behavior in the valence region with a rather large dipole polarizability compared to the lighter rare gas elements. The nucleon localization in Og is also predicted to undergo a transition to the Thomas-Fermi gas behavior in the valence region. This effect, particularly strong for neutrons, is due to the high density of single-particle orbitals.

First Principles Simulations fo the Supercritical Behavior of Ore Forming Fluids

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

Weare, John H

2013-04-19

Abstract of Selected Research Progress: I. First-principles simulation of solvation structure and deprotonation reactions of ore forming metal ions in very nonideal solutions: Advances in algorithms and computational performance achieved in this grant period have allowed the atomic level dynamical simulation of complex nanoscale materials using interparticle forces calculated directly from an accurate density functional solution to the electronic Schr dinger equation (ab-initio molecular dynamics, AIMD). Focus of this program was on the prediction and analysis of the properties of environmentally important ions in aqueous solutions. AIMD methods have provided chemical interpretations of these very complex systems with an unprecedentedmore » level of accuracy and detail. The structure of the solvation region neighboring a highly charged metal ion (e.g., 3+) in an aqueous solution is very different from that of bulk water. The many-body behaviors (polarization, charge transfer, etc.) of the ion-water and water-water interactions in this region are difficult to capture with conventional empirical potentials. However, a large numbers of waters (up to 128 waters) are required to fully describe chemical events in the extended hydrations shells and long simulation times are needed to reliably sample the system. Taken together this makes simulation at the 1st principles level a very large computational problem. Our AIMD simulation results using these methods agree with the measured octahedral structure of the 1st solvation shell of Al3+ at the 1st shell boundary and a calculated radius of 1.937 (exp. 1.9). Our calculated average 2nd shell radius agrees remarkably well with the measured radius, 4.093 calculated vs. the measured value of 4.0-4.15 . Less can be experimentally determined about the structure of the 2nd shell. Our simulations show that this shell contains roughly 12 water molecules, which are trigonally coordinated to the 1st shell waters. This structure cannot be measured directly. However, the number of 2nd shell water molecules predicted by the simulation is consistent with experimental estimates. Tetrahedral bulk water coordination reappears just after the 2nd shell. Simulations with 128 waters are close to the maximum size that can effectively be performed with present day methods. While the time scale of our simulation are not long enough to observe transfers of waters from the 1st to the 2nd shell, we do see transfers occurring on a picosecond time scale between the 2nd shell and 3rd shell via an associative mechanism. This is faster than, but consistent with, the results of measurements on the more tightly bound Cr3+ system. For high temperature simulations, proton transfers occur in the solvation shells leading to transient hydrolysis species. The reaction coordinate for proton transfer involves the coordinates of neighboring solvent waters as in the Grotis mechanism for proton transfer in bulk water. Directly removing a proton from the hexaqua Al3+ ion leads to a much more labile solvation shell and to a five coordinated Al3+ ion. This is consistent with very recent rate measurements of ligand exchange and the conjugate base labilization effect. For the Al3+-H2O system results for high but subcritical temperatures are qualitatively similar to room temperature simulations. However, preliminary simulations for supercritical temperatures (750K) suggest that there may be a dramatic change in behavior in the hydration structure of ions for these temperatures. For transition metal ions the presence of d valence electrons plays a significant role in the behavior of the system. Our preliminary results for the Fe3+ ion suggest that this ion which is larger radius than the Al3+ ion has somewhat less rigid 1st and 2nd solvation shell. II. Gibbs Ensemble Monte Carlo Simulation of Vapor/Liquid and Metastable Liquid/Liquid Phase Equilibria in the CO2-CH4-N2 System Many fluid inclusions have compositions in the system CO2-CH4-N2. Estimates of the saturation pressures, compositions and volumetric properties of coexisting phases in the unaries, binaries and the ternary of this system have been obtained from simulations using the Gibbs Ensemble Monte Carlo method. The temperature and pressure range considered include liquid/vapor, gas/gas and metastable liquid/liquid regions. All the molecular interactions in the system were described with two-body Lennard-Jones potentials requiring only two temperature independent parameters for interactions between like molecules. The Berthhelot-Lorentz rules are used to define the Lennard-Jones interactions for unlike molecules with one additional temperature independent mixing parameter. The equilibrium compositions and molar volumes of the coexisting phases in all the mixtures are predicted with accuracy close to that of the data. These results, particularly for the phase densities and critical parameters, are considerably closer to the observed values than those that have been reported using equation of state methods(116). For very low temperatures liquid/metastable liquid/vapor coexistence was observed for the CO2-N2 and the CH4-CO2 systems, e.g. the L1L2V line. The possibility of gas-gas coexistence for the binary N2-CO2 at high temperatures and pressures was also investigated but not observed.« less

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

Ford, A.L.; Reading, J.F.; Becker, R.L.

Theoretical methods used previously for H/sup +/, He/sup 2 +/, and C/sup 6 +/ collisions with neutral argon atoms have been applied to collisions of H/sup +/, He/sup 2 +/, and Li/sup 3 +/ projectiles with neon, and to collisions of H/sup +/ with carbon targets. The energy range covered by the calculations is 0.4 to 4.0 MeV/amu for the neon target, and 0.2 to 2.0 MeV/amu for carbon. We calculate single-electron amplitudes for target K-shell ionization and target K- and L-shell, to projectile K-shell, charge transfer. These single-electron amplitudes are used, in an independent-particle model that allows for multielectronmore » processes, to compute K-shell vacancy production cross sections sigma/sup IPM//sub V/K, and cross sections sigma/sup IPM//sub C/,VK for producing a charge-transfer state of the projectile in the coincidence with a K-shell vacancy in the target. These cross sections are in reasonable agreement with the recent experiments of Rodbro et al. at Aarhus. In particular, the calculated, as well as the experimental, sigma/sub C/,VK scale with projectile nuclear charge Z/sub p/ less strongly than the Z/sup 5//sub p/ of the Oppenheimer-Brinkman-Kramers (OBK) approximation. For He/sup 2 +/ and Li/sup 3 +/ projectiles at collision energies below where experimental data are available, our calculated multielectron corrections to the single-electron approximation for sigma/sub C/,VK are large.« less

Characterization of the organic ligand shell of semiconductor quantum dots by fluorescence quenching experiments.

PubMed

Boldt, Klaus; Jander, Sebastian; Hoppe, Kathrin; Weller, Horst

2011-10-25

We present the characterization of the organic ligand shell of CdSe/Cd(x)Zn(1-x)S/ZnS nanoparticles by means of fluorescence quenching experiments. Both electron scavengers and acceptors for resonance energy transfer were employed as probes. Different quenching behavior for short and long chain thiol ligands in water was found. It could be shown that poly(ethylene oxide) (PEO)-capping of the particles comprises a densely packed inner shell and a loosely packed outer shell in which ions and small molecules diffuse unhindered. A quantitative uptake of quencher molecules into the PEO shell was observed, through which the particle volume including the ligand sphere could be determined.

ZnO/ZnSxSe1-x core/shell nanowire arrays as photoelectrodes with efficient visible light absorption

NASA Astrophysics Data System (ADS)

Wang, Zhenxing; Zhan, Xueying; Wang, Yajun; Safdar, Muhammad; Niu, Mutong; Zhang, Jinping; Huang, Ying; He, Jun

2012-08-01

ZnO/ZnSxSe1-x core/shell nanowires have been synthesized on n+-type silicon substrate via a two-step chemical vapor deposition method. Transmission electron microscopy reveals that ZnSxSe1-x can be deposited on the entire surface of ZnO nanowire, forming coaxial heterojunction along ZnO nanowire with very smooth shell surface and high shell thickness uniformity. The photoelectrode after deposition of the ternary alloy shell significantly improves visible light absorption efficiency. Electrochemical impedance spectroscopy results explicitly indicate that the introduction of ZnSxSe1-x shell to ZnO nanowires effectively improves the photogenerated charge separation process. Our finding opens up an efficient means for achieving high efficient energy conversion devices.

Domain model for Ca2(+)-inactivation of Ca2+ channels at low channel density.

PubMed Central

Sherman, A; Keizer, J; Rinzel, J

1990-01-01

The "shell" model for Ca2(+)-inactivation of Ca2+ channels is based on the accumulation of Ca2+ in a macroscopic shell beneath the plasma membrane. The shell is filled by Ca2+ entering through open channels, with the elevated Ca2+ concentration inactivating both open and closed channels at a rate determined by how fast the shell is filled. In cells with low channel density, the high concentration Ca2+ "shell" degenerates into a collection of nonoverlapping "domains" localized near open channels. These domains form rapidly when channels open and disappear rapidly when channels close. We use this idea to develop a "domain" model for Ca2(+)-inactivation of Ca2+ channels. In this model the kinetics of formation of an inactivated state resulting from Ca2+ binding to open channels determines the inactivation rate, a mechanism identical with that which explains single-channel recordings on rabbit-mesenteric artery Ca2+ channels (Huang Y., J. M. Quayle, J. F. Worley, N. B. Standen, and M. T. Nelson. 1989. Biophys. J. 56:1023-1028). We show that the model correctly predicts five important features of the whole-cell Ca2(+)-inactivation for mouse pancreatic beta-cells (Plants, T. D. 1988. J. Physiol. 404:731-747) and that Ca2(+)-inactivation has only minor effects on the bursting electrical activity of these cells. PMID:2174274

Plasmonic Photovoltaic Cells with Dual-Functional Gold, Silver, and Copper Half-Shell Arrays.

PubMed

Wu, Ling; Kim, Gyu Min; Nishi, Hiroyasu; Tatsuma, Tetsu

2017-09-12

Solid-state photovoltaic cells based on plasmon-induced charge separation (PICS) have attracted growing attention during the past decade. However, the power conversion efficiency (PCE) of the previously reported devices, which are generally loaded with dispersed metal nanoparticles as light absorbers, has not been sufficiently high. Here we report simpler plasmonic photovoltaic cells with interconnected Au, Ag, and Cu half-shell arrays deposited on SiO 2 @TiO 2 colloidal crystals, which serve both as a plasmonic light absorber and as a current collector. The well-controlled and easily prepared plasmonic structure allows precise comparison of the PICS efficiency between different plasmonic metal species. The cell with the Ag half-shell array has higher photovoltaic performance than the cells with Au and Cu half-shell arrays because of the high population of photogenerated energetic electrons, which gives a high electron injection efficiency and suppressed charge recombination probability, achieving the highest PCE among the solid-state PICS devices even without a hole transport layer.

Synthesis of core-shell iron nanoparticles via a new (novel) approach

NASA Astrophysics Data System (ADS)

Chaudhary, Rakesh P.; Koymen, Ali R.

2014-03-01

Carbon-encapsulated iron (Fe) nanoparticles were synthesized by a newly developed method in toluene. Transmission Electron Microscopy (TEM) and High Resolution Transmission Electron Microscopy (HRTEM) of the as prepared sample reveal that core-shell nanostructures have been formed with Fe as core and graphitic carbon as shell. Fe nanoparticles with diameter 11nm to 102 nm are encapsulated by 6-8 nm thick graphitic carbon layers. There was no iron carbide formation observed between the Fe core and the graphitic shell. The Fe nanoparticles have body centered cubic (bcc) crystal structure. The magnetic hysteresis loop of the as synthesized powder at room temperature showed a saturation magnetization of 9 Am2 kg-1. After thermal treatment crystalline order of the samples improved and hence saturation magnetization increased to 24 Am2kg-1. We foresee that the carbon-encapsulated Fe nanoparticles are biologically friendly and could have potential applications in Magnetic Resonance Imaging (MRI) and Photothermal cancer therapy.

Detailed Investigation of Core-Shell Precipitates in a Cu-Containing High Entropy Alloy

NASA Astrophysics Data System (ADS)

Alam, T.; Gwalani, B.; Viswanathan, G.; Fraser, H.; Banerjee, R.

2018-05-01

Due to the competing influences of configurational entropy and enthalpy of mixing, in recent years, secondary (including intermetallic) phases have been reported in many high entropy alloy (HEA) systems. These secondary phases offer great potential in terms of strengthening the HEA beyond the solid solution strengthening effects, and as such are of great interest in regards to alloy design for engineering applications. The present research investigates novel nano-scale core-shell precipitates forming within the disordered bcc matrix phase of an Al2CrCuFeNi2 HEA, utilizing complementary high-resolution microscopy techniques of atom probe tomography (APT) and transmission electron microscopy (TEM). The size, morphology, and local chemistry of these core-shell precipitates was measured by APT, and the composition was further corroborated by high-resolution scanning transmission electron microscopy-energy dispersive spectroscopy in an aberration-corrected TEM. Furthermore, high-resolution TEM imaging of the core-shell structure indicates that the Cu-rich core exhibits a bcc crystal structure.

Tuning electrocatalytic activity of Pt monolayer shell by bimetallic Ir-M (M=Fe, Co, Ni or Cu) cores for the oxygen reduction reaction

DOE PAGES

Kuttiyiel, Kurian A.; Choi, YongMan; Sasaki, Kotaro; ...

2016-05-18

Here, platinum monolayer electrocatalyst are known to exhibit excellent oxygen reduction reaction (ORR) activity depending on the type of substrate used. Here we demonstrate a relationship between the ORR electrocatalytic activity and the surface electronic structure of Pt monolayer shell induced by various IrM bimetallic cores (M=Fe, Co, Ni or Cu). The relationship is rationalized by comparing density functional theory calculations and experimental results. For an efficient Pt monolayer electrocatalyst, the core should induce sufficient contraction to the Pt shell leading to a downshift of the d-band center with respect to the Fermi level. Depending on the structure of themore » IrM, relative to that of pure Ir, this interaction not only alters the electronic and geometric structure but also induces segregation effects. Combined these effects significantly enhance the ORR activities of the Pt monolayer shell on bimetallic Ir cores electrocatalysts.« less

Magnetically Recoverable Pd/Fe 3O 4 Core-Shell Nanowire Clusters with Increased Hydrogenation Activity

DOE PAGES

Watt, John; Kotula, Paul G.; Huber, Dale L.

2017-02-06

Core-shell nanostructures are promising candidates for the next generation of catalysts due to synergistic effects which can arise from having two active species in close contact, leading to increased activity. Likewise, catalysts displaying added functionality, such as a magnetic response, can increase their scientific and industrial potential. Here, we synthesize Pd/Fe 3O 4 core-shell nanowire clusters and apply them as hydrogenation catalysts for an industrially important hydrogenation reaction; the conversion of acetophenone to 1-phenylethanol. During synthesis, the palladium nanowires self-assemble into clusters which act as a high surface area framework for the growth of a magnetic iron oxide shell. Wemore » demonstrate excellent catalytic activity due to the presence of palladium while the strong magnetic properties provided by the iron oxide shell enable facile catalyst recovery.« less

Exact solutions for laminated composite cylindrical shells in cylindrical bending

NASA Technical Reports Server (NTRS)

Yuan, F. G.

1992-01-01

Analytic elasticity solutions for laminated composite cylindrical shells under cylindrical bending are presented. The material of the shell is assumed to be general cylindrically anisotropic. Based on the theory of cylindrical anisotropic elasticity, coupled governing partial differential equations are developed. The general expressions for the stresses and displacements in the laminated composite cylinders are discussed. The closed form solutions based on Classical Shell Theory (CST) and Donnell's (1933) theory are also derived for comparison purposes. Three examples illustrate the effect of radius-to-thickness ratio, coupling and stacking sequence. The results show that, in general, CST yields poor stress and displacement distributions for thick-section composite shells, but converges to the exact elasticity solution as the radius-to-thickness ratio increases. It is also shown that Donnell's theory significantly underestimates the stress and displacement response.

Low-frequency vibrations of a cylindrical shell rotating on rollers

NASA Astrophysics Data System (ADS)

Filippov, S. B.

2018-05-01

Small free low-frequency vibrations of a rotating closed cylindrical shell which is in a contact with rigid cylindrical rollers are considered. Assumptions of semi-momentless shell theory are used. By means of the expansion of solutions in truncated Fourier series in circumference coordinate the system of the algebraic equations for the approximate calculation of the vibration frequencies and the mode shapes is obtained. The algorithm for the evaluation of frequencies and vibration modes based on analytical solution is developed. In particular, the lowest frequencies of thin cylindrical shell, representing greatest interest for applications, were found. Approximate results are compared with results of numerical calculations carried out by the Finite Elements Analysis. It is shown that the semi-momentless theory can be used for the evaluation of the low frequencies of a cylindrical shell rotating on rollers.

Focused Research Group in Correlated Electron and Complex Materials

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

Wang, Ziqiang

While the remarkable physical properties of correlated and complex electronic materials hold great promise for technological applications, one of the key values of the research in this field is its profound impact on fundamental physics. The transition metal oxides, pnictides, and chalcogenides play a key role and occupy an especially important place in this field. The basic reason is that the outer shell of transition metals contains the atomic d-orbitals that have small spatial extent, but not too small to behave as localized orbtials. These d-electrons therefore have a small wave function overlap in a solid, e.g. in an octahedralmore » environment, and form energy bands that are relatively narrow and on the scale of the short-range intra-atomic Coulomb repulsion (Hubbard U). In this intermediate correlation regime lies the challenge of the many-body physics responsible for new and unconventional physical properties. The study of correlated electron and complex materials represents both the challenge and the vitality of condensed matter and materials physics and often demands close collaborations among theoretical and experimental groups with complementary techniques. Our team has a track record and a long-term research goal of studying the unusual complexities and emergent behaviors in the charge, spin, and orbital sectors of the transition metal compounds in order to gain basic knowledge of the quantum electronic states of matter. During the funding period of this grant, the team continued their close collaborations between theory, angle-resolved photoemission spectroscopy, and scanning tunneling microscopy and made significant progress and contributions to the field of iron-based superconductors, copper-oxide high-temperature superconductors, triangular lattice transition metal oxide cobaltates, strontium ruthenates, spin orbital coupled iridates, as well as topological insulators and other topological quantum states of matter. These results include both new discoveries and the resolution to outstanding and unresolved issues. It should be emphasized that the DOE funding provided the crucial support for the close and meaningful collaborations of the focused research group that go far beyond simply putting the research papers from each group together. Indeed, the majority of the publications involved multiple PIs and collaborations between theory and experiments.« less

Fast synthesis, formation mechanism, and control of shell thickness of CuS–polystyrene core–shell microspheres

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

Zhao, Li-min, E-mail: zhaolimin@lcu.ecu.cn; Shao, Xin; Yin, Yi-bin

2012-09-15

Graphical abstract: Core–shell structure PSt/CuS were prepared using polystyrene which were modified by 3-methacryloxypropyltrimethoxysilane as template. The coating thickness of CuS can be controlled by the amount of 3-methacryloxypropyltrimethoxysilane and the UV–vis absorption intensity of PSt/CuS composite also changed with the coating thickness of CuS. Highlights: ► Core–shell structure PSt/CuS were prepared using silanol-modified polystyrene microspheres as template. ► The coating thickness of core–shell structure PSt/CuS can be controlled by a simple method. ► The UV–vis absorption intensity of PSt/CuS composite also changed with the coating thickness of CuS. -- Abstract: The silanol-modified polystyrene microspheres were prepared through dispersion polymerization.more » Then copper sulfide particles were grown on silanol-modified polystyrene through sonochemical deposition in an aqueous bath containing copper acetate and sulfide, released through the hydrolysis of thioacetamide. The resulting particles were continuous and uniform as characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Fourier transform infrared, thermogravimetric analysis and UV–vis absorption spectroscopy were used to characterize the structure and properties of core–shell particles. The results showed the coating thickness of CuS shell can be controlled by the amount of silanol and the UV–vis absorption intensity of PSt/CuS composite also changed with the coating thickness of CuS.« less

On Closed Shells in Nuclei. II

DOE R&D Accomplishments Database

Mayer, M. G.

1949-04-01

Discussion on the use of spins and magnetic moments of the even-odd nuclei by Feenberg and Nordheim to determine the angular momentum of the eigenfunction of the odd particle; discussion of prevalence of isomerism in certain regions of the isotope chart; tabulated data on levels of square well potential, spectroscopic levels, spin term, number of states, shells and known spins and orbital assignments.

Changes in Benthos Associated with Mussel (Mytilus edulis L.) Farms on the West-Coast of Scotland

PubMed Central

Wilding, Thomas A.; Nickell, Thomas D.

2013-01-01

Aquaculture, as a means of food production, is growing rapidly in response to an increasing demand for protein and the over-exploitation of wild fisheries. This expansion includes mussels (family Mytilidae) where production currently stands at 1.5 million tonnes per annum. Mussel culture is frequently perceived as having little environmental impact yet mussel biodeposits and shell debris accumulate around the production site and are linked to changes in the benthos. To assess the extent and nature of changes in benthos associated with mussel farming grab and video sampling around seven mussel farms was conducted. Grab samples were analysed for macrofauna and shell-hash content whilst starfish were counted and the shell-hash cover estimated from video imaging. Shell-hash was patchily distributed and occasionally dominated sediments (maximum of 2116 g per 0.1 m2 grab). Mean shell-hash content decreased rapidly at distances >5 m from the line and, over the distance 1–64 m, decreased by three orders of magnitude. The presence of shell-hash and the distance-from-line influenced macrofaunal assemblages but this effect differed between sites. There was no evidence that mussel farming was associated with changes in macrobenthic diversity, species count or feeding strategy. However, total macrofaunal count was estimated to be 2.5 times higher in close proximity to the lines, compared with 64 m distance, and there was evidence that this effect was conditional on the presence of shell-hash. Starfish density varied considerably between sites but, overall, they were approximately 10 times as abundant close to the mussel-lines compared with 64 m distance. There was no evidence that starfish were more abundant in the presence of shell-hash visible on the sediment surface. In terms of farm-scale benthic impacts these data suggest that mussel farming is a relatively benign way of producing food, compared with intensive fish-farming, in similar environments. PMID:23874583

Understanding to Hierarchical Microstructures of Crab (Chinese hairy) Shell as a Natural Architecture

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

Chuanqiang, Zhou; Xiangxiang, Gong; School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou

This work was done to better understand the microstructures, composition and mechanical properties of Chinese hairy crab shell. For fully revealing its hierarchical microstructure, the crab shell was observed with electron microscope under different magnifications from different facets. XRD, EDS, FTIR and TGA techniques have been used to characterize the untreated and chemically-treated crab shells, which provided enough information to determine the species and relative content of components in this biomaterial. Combined the microstructures with constituents analysis, the structural principles of crab shell was detailedly realized from different structural levels beyond former reports. To explore the relationship between structure andmore » function, the mechanical properties of shell have been measured through performing tensile tests. The contributions of organics and minerals in shell to the mechanical properties were also discussed by measuring the tensile strength of de-calcification samples treated with HCl solution.« less

Fossil shell emission in dying radio loud AGNs

NASA Astrophysics Data System (ADS)

Kino, M.; Ito, H.; Kawakatu, N.; Orienti, M.; Nagai, H.; Wajima, K.; Itoh, R.

2016-02-01

We investigate shell emission associated with dying radio loud AGNs. First, based on our recent work by Ito et al. (2015), we describe the dynamical and spectral evolution of shells after stopping the jet energy injection. We find that the shell emission overwhelms that of the radio lobes soon after stopping the jet energy injection because fresh electrons are continuously supplied into the shell via the forward shock, while the radio lobes rapidly fade out without jet energy injection. We find that such fossil shells can be a new class of target sources for SKA telescope. Next, we apply the model to the nearby radio source 3C84. Then, we find that the fossil shell emission in 3C84 is less luminous in the radio band while it is bright in the TeV γ-ray band and can be detectable by CTA. Data from STELLA

Multiple shell fusion targets

DOEpatents

Lindl, J.D.; Bangerter, R.O.

1975-10-31

Multiple shell fusion targets for use with electron beam and ion beam implosion systems are described. The multiple shell targets are of the low-power type and use a separate relatively low Z, low density ablator at large radius for the outer shell, which reduces the focusing and power requirements of the implosion system while maintaining reasonable aspect ratios. The targets use a high Z, high density pusher shell placed at a much smaller radius in order to obtain an aspect ratio small enough to protect against fluid instability. Velocity multiplication between these shells further lowers the power requirements. Careful tuning of the power profile and intershell density results in a low entropy implosion which allows breakeven at low powers. For example, with ion beams as a power source, breakeven at 10-20 Terrawatts with 10 MeV alpha particles for imploding a multiple shell target can be accomplished.

Ultrasonic approach to the synthesis of HMX@TATB core-shell microparticles with improved mechanical sensitivity.

PubMed

Huang, Bing; Hao, Xiaofei; Zhang, Haobin; Yang, Zhijian; Ma, Zhigang; Li, Hongzhen; Nie, Fude; Huang, Hui

2014-07-01

To improve the safety of sensitive explosive HMX while maintaining explosion performance, a moderately powerful but insensitive explosive TATB was used to coat HMX microparticles via a facile ultrasonic method. By using Estane as surface modifier and nano-sized TATB as the shell layer, the HMX@TATB core-shell microparticles with a monodisperse size and compact shell structure were successfully constructed. Both scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) results confirmed the formation of perfect core-shell structured composites. Based on a systematic and comparative study of the effect of experimental conditions, a possible formation mechanism of core-shell structure was proposed in detail. Moreover, the perfect core-shell HMX@TATB microparticles exhibited a unique thermal behavior and significantly improved mechanical sensitivity compared with that of the physical mixture. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis, Characterization, and Mechanism of Formation of Janus-Like Nanoparticles of Tantalum Silicide-Silicon (TaSi2/Si)

PubMed Central

Nomoev, Andrey V.; Bardakhanov, Sergey P.; Schreiber, Makoto; Bazarova, Dashima Zh.; Baldanov, Boris B.; Romanov, Nikolai A.

2014-01-01

Metal-semiconductor Janus-like nanoparticles with the composition tantalum silicide-silicon (TaSi2/Si) were synthesized for the first time by means of an evaporation method utilizing a high-power electron beam. The composition of the synthesized particles were characterized using high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), selective area electron diffraction (SAED), and energy dispersive X-ray fluorescence (EDX) analysis. The system is compared to previously synthesized core-shell type particles in order to show possible differences responsible for the Janus-like structure forming instead of a core-shell architecture. It is proposed that the production of Janus-like as opposed to core-shell or monophase particles occurs due to the ability of Ta and Si to form compounds and the relative content of Ta and Si atoms in the produced vapour. Based on the results, a potential mechanism of formation for the TaSi2/Si nanoparticles is discussed. PMID:28346996

Synthesis, Characterization, and Mechanism of Formation of Janus-Like Nanoparticles of Tantalum Silicide-Silicon (TaSi₂/Si).

PubMed

Nomoev, Andrey V; Bardakhanov, Sergey P; Schreiber, Makoto; Bazarova, Dashima Zh; Baldanov, Boris B; Romanov, Nikolai A

2014-12-25

Metal-semiconductor Janus-like nanoparticles with the composition tantalum silicide-silicon (TaSi₂/Si) were synthesized for the first time by means of an evaporation method utilizing a high-power electron beam. The composition of the synthesized particles were characterized using high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), selective area electron diffraction (SAED), and energy dispersive X-ray fluorescence (EDX) analysis. The system is compared to previously synthesized core-shell type particles in order to show possible differences responsible for the Janus-like structure forming instead of a core-shell architecture. It is proposed that the production of Janus-like as opposed to core-shell or monophase particles occurs due to the ability of Ta and Si to form compounds and the relative content of Ta and Si atoms in the produced vapour. Based on the results, a potential mechanism of formation for the TaSi₂/Si nanoparticles is discussed.

Dielectronic Satellite Spectra of Na-like Mo Ions Benchmarked by LLNL EBIT with Application to HED Plasmas

NASA Astrophysics Data System (ADS)

Stafford, A.; Safronova, A. S.; Kantsyrev, V. L.; Safronova, U. I.; Petkov, E. E.; Shlyaptseva, V. V.; Childers, R.; Shrestha, I.; Beiersdorfer, P.; Hell, H.; Brown, G. V.

2017-10-01

Dielectronic recombination (DR) is an important process for astrophysical and laboratory high energy density (HED) plasmas and the associated satellite lines are frequently used for plasma diagnostics. In particular, K-shell DR satellite lines were studied in detail in low-Z plasmas. L-shell Na-like spectral features from Mo X-pinches considered here represent the blend of DR and inner shell satellites and motivated the detailed study of DR at the EBIT-1 electron beam ion trap at LLNL. In these experiments the beam energy was swept between 0.6 - 2.4 keV to produce resonances at certain electron beam energies. The advantages of using an electron beam ion trap to better understand atomic processes with highly ionized ions in HED Mo plasma are highlighted. This work was supported by NNSA under DOE Grant DE-NA0002954. Work at LLNL was performed under the auspices of the U.S. DOE under Contract No. DE-AC52-07NA27344.

Density functional theory study of the structural and bonding mechanism of molecular oxygen (O2) with C3Si

NASA Astrophysics Data System (ADS)

Parida, Saroj K.; Behera, C.; Sahu, Sridhar

2018-07-01

The investigations of pure and heteroatom doped carbon clusters have created great interest because of their enormous prospective applications in various research zones, for example, optoelectronics, semiconductors, material science, energy storage devices, astro-science and so on. In this article, the interaction of molecular oxygen (O2) with C3Si has explored within a density functional theory (DFT). Different possible types of structure for C3SiO2 have collected. Among five different kinds of structure, the structure-1a, 1A1 is more energetically stable. The nature of the bonding of O2 and C3Si, in C3SiO2 has been studied by using Bader's topological analysis of the electron charge density distribution ρ(r) , Laplacian ∇2 ρ(r) and total energy density H(r) at the bond critical points (BCPs) of the structures within the framework of the atoms in molecules theory (AIM). The bonding mechanism of O2 and C3Si in C3SiO2 prompts to the fundamental understanding of the interaction of C3Si with oxygen molecule. It is interesting to note that, two types of bonding mechanism are established in same C3SiO2 system such as (i) shared-kind interactions (ii) closed-shell interactions. From various kinds of structure, Csbnd C bonds in all structures are shown as shared-kind interactions whereas Csbnd Si, Osbnd O bonds are classified as closed-shell type interactions with a certain degree of covalent character.

Twin density of aragonite in molluscan shells characterized using X-ray diffraction and transmission electron microscopy

NASA Astrophysics Data System (ADS)

Kogure, Toshihiro; Suzuki, Michio; Kim, Hyejin; Mukai, Hiroki; Checa, Antonio G.; Sasaki, Takenori; Nagasawa, Hiromichi

2014-07-01

{110} twin density in aragonites constituting various microstructures of molluscan shells has been characterized using X-ray diffraction (XRD) and transmission electron microscopy (TEM), to find the factors that determine the density in the shells. Several aragonite crystals of geological origin were also investigated for comparison. The twin density is strongly dependent on the microstructures and species of the shells. The nacreous structure has a very low twin density regardless of the shell classes. On the other hand, the twin density in the crossed-lamellar (CL) structure has large variation among classes or subclasses, which is mainly related to the crystallographic direction of the constituting aragonite fibers. TEM observation suggests two types of twin structures in aragonite crystals with dense {110} twins: rather regulated polysynthetic twins with parallel twin planes, and unregulated polycyclic ones with two or three directions for the twin planes. The former is probably characteristic in the CL structures of specific subclasses of Gastropoda. The latter type is probably related to the crystal boundaries dominated by (hk0) interfaces in the microstructures with preferred orientation of the c-axis, and the twin density is mainly correlated to the crystal size in the microstructures.

All zinc-blende GaAs/(Ga,Mn)As core-shell nanowires with ferromagnetic ordering.

PubMed

Yu, Xuezhe; Wang, Hailong; Pan, Dong; Zhao, Jianhua; Misuraca, Jennifer; von Molnár, Stephan; Xiong, Peng

2013-04-10

Combining self-catalyzed vapor-liquid-solid growth of GaAs nanowires and low-temperature molecular-beam epitaxy of (Ga,Mn)As, we successfully synthesized all zinc-blende (ZB) GaAs/(Ga,Mn)As core-shell nanowires on Si(111) substrates. The ZB GaAs nanowire cores are first fabricated at high temperature by utilizing the Ga droplets as the catalyst and controlling the triple phase line nucleation, then the (Ga,Mn)As shells are epitaxially grown on the side facets of the GaAs core at low temperature. The growth window for the pure phase GaAs/(Ga,Mn)As core-shell nanowires is found to be very narrow. Both high-resolution transmission electron microscopy and scanning electron microscopy observations confirm that all-ZB GaAs/(Ga,Mn)As core-shell nanowires with smooth side surface are obtained when the Mn concentration is not more than 2% and the growth temperature is 245 °C or below. Magnetic measurements with different applied field directions provide strong evidence for ferromagnetic ordering in the all-ZB GaAs/(Ga,Mn)As nanowires. The hybrid nanowires offer an attractive platform to explore spin transport and device concepts in fully epitaxial all-semiconductor nanospintronic structures.

Gamow-Teller Strength Distributions for pf-shell Nuclei and its Implications in Astrophysics

NASA Astrophysics Data System (ADS)

Rahman, M.-U.; Nabi, J.-U.

2009-08-01

The {pf}-shell nuclei are present in abundance in the pre-supernova and supernova phases and these nuclei are considered to play an important role in the dynamics of core collapse supernovae. The B(GT) values are calculated for the {pf}-shell nuclei 55Co and 57Zn using the pn-QRPA theory. The calculated B(GT) strengths have differences with earlier reported shell model calculations, however, the results are in good agreement with the experimental data. These B(GT) strengths are used in the calculations of weak decay rates which play a decisive role in the core-collapse supernovae dynamics and nucleosynthesis. Unlike previous calculations the so-called Brink's hypothesis is not assumed in the present calculation which leads to a more realistic estimate of weak decay rates. The electron capture rates are calculated over wide grid of temperature ({0.01} × 109 - 30 × 109 K) and density (10-1011 g-cm-3). Our rates are enhanced compared to the reported shell model rates. This enhancement is attributed partly to the liberty of selecting a huge model space, allowing consideration of many more excited states in the present electron capture rates calculations.

Highly exothermic and superhydrophobic Mg/fluorocarbon core/shell nanoenergetic arrays.

PubMed

Zhou, Xiang; Xu, Daguo; Yang, Guangcheng; Zhang, Qiaobao; Shen, Jinpeng; Lu, Jian; Zhang, Kaili

2014-07-09

Mg/fluorocarbon core/shell nanoenergetic arrays are prepared onto silicon substrate, with Mg nanorods as the core and fluorocarbon as the shell. Mg nanorods are deposited by the glancing angle deposition technique, and the fluorocarbon layer is then prepared as a shell to encase the Mg nanorods by the magnetron sputtering deposition process. Scanning electron microscopy and transmission electron microscopy show the core/shell structure of the Mg/fluorocarbon arrays. X-ray energy-dispersive spectroscopy, X-ray diffraction, and Fourier transform infrared spectroscopy are used to characterize the structural composition of the Mg/fluorocarbon. It is found that the as-prepared fluorocarbon layer consists of shorter molecular chains compared to that of bulk polytetrafluoroethylene, which is proven beneficial to the low onset reaction temperature of Mg/fluorocarbon. Water contact angle test demonstrates the superhydrophobicity of the Mg/fluorocarbon arrays, and a static contact angle as high as 162° is achieved. Thermal analysis shows that the Mg/fluorocarbon material exhibits a very low onset reaction temperature of about 270 °C as well as an ultrahigh heat of reaction approaching 9 kJ/g. A preliminary combustion test reveals rapid combustion wave propagation, and a convective mechanism is adopted to explain the combustion behaviors.

PbSe-Based Colloidal Core/Shell Heterostructures for Optoelectronic Applications

PubMed Central

Zaiats, Gary; Yanover, Diana; Vaxenburg, Roman; Tilchin, Jenya; Sashchiuk, Aldona; Lifshitz, Efrat

2014-01-01

Lead-based (IV–VI) colloidal quantum dots (QDs) are of widespread scientific and technological interest owing to their size-tunable band-gap energy in the near-infrared optical region. This article reviews the synthesis of PbSe-based heterostructures and their structural and optical investigations at various temperatures. The review focuses on the structures consisting of a PbSe core coated with a PbSexS1–x (0 ≤ x ≤ 1) or CdSe shell. The former-type shells were epitaxially grown on the PbSe core, while the latter-type shells were synthesized using partial cation-exchange. The influence of the QD composition and the ambient conditions, i.e., exposure to oxygen, on the QD optical properties, such as radiative lifetime, Stokes shift, and other temperature-dependent characteristics, was investigated. The study revealed unique properties of core/shell heterostructures of various compositions, which offer the opportunity of fine-tuning the QD electronic structure by changing their architecture. A theoretical model of the QD electronic band structure was developed and correlated with the results of the optical studies. The review also outlines the challenges related to potential applications of colloidal PbSe-based heterostructures. PMID:28788244

Hollow Pd/MOF Nanosphere with Double Shells as Multifunctional Catalyst for Hydrogenation Reaction.

PubMed

Wan, Mingming; Zhang, Xinlu; Li, Meiyan; Chen, Bo; Yin, Jie; Jin, Haichao; Lin, Lin; Chen, Chao; Zhang, Ning

2017-10-01

A new type of hollow nanostructure featured double metal-organic frameworks shells with metal nanoparticles (MNPs) is designed and fabricated by the methods of ship in a bottle and bottle around the ship. The nanostructure material, hereinafter denoted as Void@HKUST-1/Pd@ZIF-8, is confirmed by the analyses of photograph, transmission electron microscopy, scanning electron microscopy, powder X-ray diffraction, inductively coupled plasma, and N 2 sorption. It possesses various multifunctionally structural characteristics such as hollow cavity which can improve mass transfer, the adjacent of the inner HKUST-1 shell to the void which enables the matrix of the shell to host and well disperse MNPs, and an outer ZIF-8 shell which acts as protective layer against the leaching of MNPs and a sieve to guarantee molecular-size selectivity. This makes the material eligible candidates for the heterogeneous catalyst. As a proof of concept, the liquid-phase hydrogenation of olefins with different molecular sizes as a model reaction is employed. It demonstrates the efficient catalytic activity and size-selectivity of Void@HKUST-1/Pd@ZIF-8. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Low energy dipole strength from large scale shell model calculations

NASA Astrophysics Data System (ADS)

Sieja, Kamila

2017-09-01

Low energy enhancement of radiative strength functions has been deduced from experiments in several mass regions of nuclei. Such an enhancement is believed to impact the calculated neutron capture rates which are crucial input for reaction rates of astrophysical interest. Recently, shell model calculations have been performed to explain the upbend of the γ-strength as due to the M1 transitions between close-lying states in the quasi-continuum in Fe and Mo nuclei. Beyond mean-↓eld calculations in Mo suggested, however, a non-negligible role of electric dipole in the low energy enhancement. So far, no calculations of both dipole components within the same theoretical framework have been presented in this context. In this work we present newly developed large scale shell model appraoch that allows to treat on the same footing natural and non-natural parity states. The calculations are performed in a large sd - pf - gds model space, allowing for 1p{1h excitations on the top of the full pf-shell con↓guration mixing. We restrict the discussion to the magnetic part of the dipole strength, however, we calculate for the ↓rst time the magnetic dipole strength between states built of excitations going beyond the classical shell model spaces. Our results corroborate previous ↓ndings for the M1 enhancement for the natural parity states while we observe no enhancement for the 1p{1h contributions. We also discuss in more detail the e↑ects of con↓guration mixing limitations on the enhancement coming out from shell model calculations.

Dielectronic recombination of the 4p and 4d open sub-shell tungsten ions

NASA Astrophysics Data System (ADS)

Li, M. J.; Fu, Y. B.; Zhang, G. D.; Zhang, Y. Z.; Dong, C. Z.; Koike, F.

2014-04-01

Dielectronic recombination rate coefficients are given theoretically for several highly charged tungsten ions. As 4p open sub-shell ions, Ga-, Ge-, As-, Br-, Kr-like ions are considered. Rb-like ion is further considered as a 4d open sub-shell ion. Theoretical calculations are carried out using a relativistic atomic code FAC. The effect of configuration interaction is taking into account. Inner-shell electron excitations play a significant role for the dielectronic recombination process. Simple analytical formulae are given for the total rate coefficients by fitting to the presently obtained numerical results.