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Sample records for actinide electronic structure

  1. Actinide electronic structure and atomic forces

    NASA Astrophysics Data System (ADS)

    Albers, R. C.; Rudin, Sven P.; Trinkle, Dallas R.; Jones, M. D.

    2000-07-01

    We have developed a new method[1] of fitting tight-binding parameterizations based on functional forms developed at the Naval Research Laboratory.[2] We have applied these methods to actinide metals and report our success using them (see below). The fitting procedure uses first-principles local-density-approximation (LDA) linear augmented plane-wave (LAPW) band structure techniques[3] to first calculate an electronic-structure band structure and total energy for fcc, bcc, and simple cubic crystal structures for the actinide of interest. The tight-binding parameterization is then chosen to fit the detailed energy eigenvalues of the bands along symmetry directions, and the symmetry of the parameterization is constrained to agree with the correct symmetry of the LDA band structure at each eigenvalue and k-vector that is fit to. By fitting to a range of different volumes and the three different crystal structures, we find that the resulting parameterization is robust and appears to accurately calculate other crystal structures and properties of interest.

  2. Theoretical Studies of the Electronic Structure of the Compounds of the Actinide Elements

    SciTech Connect

    Kaltsoyannis, Nikolas; Hay, P. Jeffrey; Li, Jun; Blaudeau, Jean-Philippe; Bursten, Bruce E.

    2006-02-02

    In this chapter, we will present an overview of the theoretical and computational developments that have increased our understanding of the electronic structure of actinide-containing molecules and ions. The application of modern electronic structure methodologies to actinide systems remains one of the great challenges in quantum chemistry; indeed, as will be discussed below, there is no other portion of the periodic table that leads to the confluence of complexity with respect to the calculation of ground- and excited-state energies, bonding descriptions, and molecular properties. But there is also no place in the periodic table in which effective computational modeling of electronic structure can be more useful. The difficulties in creating, isolating, and handling many of the actinide elements provide an opportunity for computational chemistry to be an unusually important partner in developing the chemistry of these elements. The importance of actinide electronic structure begins with the earliest studies of uranium chemistry and predates the discovery of quantum mechanics. The fluorescence of uranyl compounds was observed as early as 1833 (Jørgensen and Reisfeld, 1983), a presage of the development of actinometry as a tool for measuring photochemical quantum yields. Interest in nuclear fuels has stimulated tremendous interest in understanding the properties, including electronic properties, of small actinide-containing molecules and ions, especially the oxides and halides of uranium and plutonium. The synthesis of uranocene in 1968 (Streitwieser and Mu¨ ller-Westerhoff, 1968) led to the flurry of activity in the organometallic chemistry of the actinides that continues today. Actinide organometallics (or organoactinides) are nearly always molecular systems and are often volatile, which makes them amenable to an arsenal of experimental probes of molecular and electronic structure (Marks and Fischer, 1979). Theoretical and computational studies of the electronic

  3. The Dirac equation in electronic structure calculations: Accurate evaluation of DFT predictions for actinides

    SciTech Connect

    Wills, John M; Mattsson, Ann E

    2012-06-06

    Brooks, Johansson, and Skriver, using the LMTO-ASA method and considerable insight, were able to explain many of the ground state properties of the actinides. In the many years since this work was done, electronic structure calculations of increasing sophistication have been applied to actinide elements and compounds, attempting to quantify the applicability of DFT to actinides and actinide compounds and to try to incorporate other methodologies (i.e. DMFT) into DFT calculations. Through these calculations, the limits of both available density functionals and ad hoc methodologies are starting to become clear. However, it has also become clear that approximations used to incorporate relativity are not adequate to provide rigorous tests of the underlying equations of DFT, not to mention ad hoc additions. In this talk, we describe the result of full-potential LMTO calculations for the elemental actinides, comparing results obtained with a full Dirac basis with those obtained from scalar-relativistic bases, with and without variational spin-orbit. This comparison shows that the scalar relativistic treatment of actinides does not have sufficient accuracy to provide a rigorous test of theory and that variational spin-orbit introduces uncontrolled errors in the results of electronic structure calculations on actinide elements.

  4. Probing Actinide Electronic Structure through Pu Cluster Calculations

    DOE PAGES

    Ryzhkov, Mickhail V.; Mirmelstein, Alexei; Yu, Sung-Woo; ...

    2013-02-26

    The calculations for the electronic structure of clusters of plutonium have been performed, within the framework of the relativistic discrete-variational method. Moreover, these theoretical results and those calculated earlier for related systems have been compared to spectroscopic data produced in the experimental investigations of bulk systems, including photoelectron spectroscopy. Observation of the changes in the Pu electronic structure as a function of size provides powerful insight for aspects of bulk Pu electronic structure.

  5. Comparative Study of f-Element Electronic Structure across a Series of Multimetallic Actinide, Lanthanide-Actinide and Lanthanum-Actinide Complexes Possessing Redox-Active Bridging Ligands

    SciTech Connect

    Schelter, Eric J.; Wu, Ruilian; Veauthier, Jacqueline M.; Bauer, Eric D.; Booth, Corwin H.; Thomson, Robert K.; Graves, Christopher R.; John, Kevin D.; Scott, Brian L.; Thompson, Joe D.; Morris, David E.; Kiplinger, Jaqueline L.

    2010-02-24

    A comparative examination of the electronic interactions across a series of trimetallic actinide and mixed lanthanide-actinide and lanthanum-actinide complexes is presented. Using reduced, radical terpyridyl ligands as conduits in a bridging framework to promote intramolecular metal-metal communication, studies containing structural, electrochemical, and X-ray absorption spectroscopy are presented for (C{sub 5}Me{sub 5}){sub 2}An[-N=C(Bn)(tpy-M{l_brace}C{sub 5}Me4R{r_brace}{sub 2})]{sub 2} (where An = Th{sup IV}, U{sup IV}; Bn = CH{sub 2}C{sub 6}H{sub 5}; M = La{sup III}, Sm{sup III}, Yb{sup III}, U{sup III}; R = H, Me, Et) to reveal effects dependent on the identities of the metal ions and R-groups. The electrochemical results show differences in redox energetics at the peripheral 'M' site between complexes and significant wave splitting of the metal- and ligand-based processes indicating substantial electronic interactions between multiple redox sites across the actinide-containing bridge. Most striking is the appearance of strong electronic coupling for the trimetallic Yb{sup III}-U{sup IV}-Yb{sup III}, Sm{sup III}-U{sup IV}-Sm{sup III}, and La{sup III}-U{sup IV}-La{sup III} complexes, [8]{sup -}, [9b]{sup -} and [10b]{sup -}, respectively, whose calculated comproportionation constant K{sub c} is slightly larger than that reported for the benchmark Creutz-Taube ion. X-ray absorption studies for monometallic metallocene complexes of U{sup III}, U{sup IV}, and U{sup V} reveal small but detectable energy differences in the 'white-line' feature of the uranium L{sub III}-edges consistent with these variations in nominal oxidation state. The sum of this data provides evidence of 5f/6d-orbital participation in bonding and electronic delocalization in these multimetallic f-element complexes. An improved, high-yielding synthesis of 4{prime}-cyano-2,2{prime}:6{prime},2{double_prime}-terpyridine is also reported.

  6. Electronic Structure of Transition Metal Clusters and Actinide Complexes and Their Reactivity

    SciTech Connect

    Balasubramanian, K

    2008-10-06

    Our research in this area since October 2007 has resulted in seven completed publications and more papers of the completed work are in progress. Our work during this period principally focused on actinide complexes with secondary emphasis on spectroscopic properties and electronic structure of metal complexes. As the publications are available online with all of the details of the results, tables and figures, we are providing here only a brief summary of major highlights, in each of the categories.

  7. Electronic, structural and transport properties of (almost) rare-earth-like actinide hydrides

    SciTech Connect

    Ward, J.W.; Cort, B.; Goldstone, J.A.; Lawson, A.C.; Cox, L.E. ); Haire, R.G. )

    1990-01-01

    By the virtue of broad-band, hybridized 5f-electron behavior, the hydride systems for Pa and U exhibit unique properties and structures, the actinide metal atoms existing in different states. A sudden change at Np to more rare-earth-like behavior implies a major change in electronic structure. There are both many parallels but also enigmas for the Np + H and Pu + H systems. Electrical resistivities are large and complex with temperature. Low-temperature structural transitions as studied by neutron diffraction help elucidate some of these effects. Phonon spectra are quite rare-earth-like, and XPS data imply a metal atom with mostly d-screened core levels. Then it is at americium, where fully localized and corelike 5f electrons are found, that we look finally for true rare-earth-like behavior, which should include a large drop in electrical resistivity. 33 refs., 7 figs., 1 tab.

  8. Comparative study of f-element electronic structure across a series of multimetallic actinide and lanthanoid-actinide complexes possessing redox-active bridging ligands.

    PubMed

    Schelter, Eric J; Wu, Ruilian; Veauthier, Jacqueline M; Bauer, Eric D; Booth, Corwin H; Thomson, Robert K; Graves, Christopher R; John, Kevin D; Scott, Brian L; Thompson, Joe D; Morris, David E; Kiplinger, Jaqueline L

    2010-02-15

    A comparative examination of the electronic interactions across a series of trimetallic actinide and mixed lanthanide-actinide and lanthanum-actinide complexes is presented. Using reduced, radical terpyridyl ligands as conduits in a bridging framework to promote intramolecular metal-metal communication, studies containing structural, electrochemical, and X-ray absorption spectroscopy are reported for (C(5)Me(5))(2)An[-N horizontal lineC(Bn)(tpy-M{C(5)Me(4)R}(2))](2) (where An = Th(IV), U(IV); Bn = CH(2)C(6)H(5); M = La(III), Sm(III), Yb(III), U(III); R = H, Me, Et) to reveal effects dependent on the identities of the metal ions and R-groups. The electrochemical results show differences in redox energetics at the peripheral "M" site between complexes and significant wave splitting of the metal- and ligand-based processes indicating substantial electronic interactions between multiple redox sites across the actinide-containing bridge. Most striking is the appearance of strong electronic coupling for the trimetallic Yb(III)-U(IV)-Yb(III), Sm(III)-U(IV)-Sm(III), and La(III)-U(IV)-La(III) complexes, [8](-), [9b](-), and [10b](-), respectively, whose calculated comproportionation constant K(c) is slightly larger than that reported for the benchmark Creutz-Taube ion. X-ray absorption studies for monometallic metallocene complexes of U(III), U(IV), and U(V) reveal small but detectable energy differences in the "white-line" feature of the uranium L(III)-edges consistent with these variations in nominal oxidation state. The sum of these data provides evidence of 5f/6d-orbital participation in bonding and electronic delocalization in these multimetallic f-element complexes. An improved, high-yielding synthesis of 4'-cyano-2,2':6',2''-terpyridine is also reported.

  9. Relativistic Multireference Quantum Chemical Study of the Electronic Structure of Actinide Trioxide Molecules.

    PubMed

    Kovács, Attila

    2017-03-17

    Actinide trioxide (AnO3, An = U, Np, Pu, Am, Cm) molecules have been investigated by relativistic multireference quantum chemical calculations with the goal to elucidate their electronic structures. The molecular geometries of the ground and selected excited electronic states have been optimized at the spin-orbit-free complete active space second-order perturbation theory (SF-CASPT2) level. The low-lying vertical excitation states have been computed and characterized by CASPT2 calculations taking into account spin-orbit coupling. The reason for the considerable lengthening of the equatorial An-O bond in AmO3 and CmO3 with respect to the other trioxides has been analyzed on the basis of valence molecular orbitals of the SF ground electronic states. For the bond in question a singly occupied π orbital has been identified, this orbital is doubly occupied in the other (An = U, Np, Pu) trioxides. The clarified electronic structures of the investigated AnO3 molecules confirmed the pentavalent character of Am and Cm in their trioxides in contrast to the hexavalent character of U, Np, and Pu.

  10. Probing the chemistry, electronic structure and redox energetics in pentavalent organometallic actinide complexes

    SciTech Connect

    Graves, Christopher R; Vaughn, Anthony E; Morris, David E; Kiplinger, Jaqueline L

    2008-01-01

    Complexes of the early actinides (Th-Pu) have gained considerable prominence in organometallic chemistry as they have been shown to undergo chemistries not observed with their transition- or lanthanide metal counterparts. Further, while bonding in f-element complexes has historically been considered to be ionic, the issue of covalence remains a subject of debate in the area of actinide science, and studies aimed at elucidating key bonding interactions with 5f-orbitals continue to garner attention. Towards this end, our interests have focused on the role that metal oxidation state plays in the structure, reactivity and spectral properties of organouranium complexes. We report our progress in the synthesis of substituted U{sup V}-imido complexes using various routes: (1) Direct oxidation of U{sup IV}-imido complexes with copper(I) salts; (2) Salt metathesis with U{sup V}-imido halides; (3) Protonolysis and insertion of an U{sup V}-imido alkyl or aryl complex with H-N{double_bond}CPh{sub 2} or N{triple_bond}C-Ph, respectively, to form a U{sup V}-imido ketimide complex. Further, we report and compare the crystallographic, electrochemical, spectroscopic and magnetic characterization of the pentavalent uranium (C{sub 5}Me{sub 5}){sub 2}U({double_bond}N-Ar)(Y) series (Y = OTf, SPh, C{triple_bond}C-Ph, NPh{sub 2}, OPh, N{double_bond}CPh{sub 2}) to further interrogate the molecular, electronic, and magnetic structures of this new class of uranium complexes.

  11. Electronic Structure of AC-Clusters and High-Resolution X-ray Spectra of Actinides in Solids

    SciTech Connect

    Kulagin, Nicolay Alex

    2007-07-01

    Ab initio calculations using SCF approach for and analysis of results of investigation of the electronic structure of the clusters RAn+:[L]k with rare earths or actinides were carried out for the clusters in solids and liquids. Theoretical results for the electronic structure, radial integrals and energy of X- ray lines are presented for AC ions with unoccupied 5f-shell in the clusters in oxides, chlorides and fluorides environment. Possibility of collapse of nf-shell for the separate clusters and identification of electronic state of ions with unstable nuclei, are discussed, too. (author)

  12. Electronic Structure of Transition Metal Clusters, Actinide Complexes and Their Reactivities

    SciTech Connect

    Krishnan Balasubramanian

    2009-07-18

    This is a continuing DOE-BES funded project on transition metal and actinide containing species, aimed at the electronic structure and spectroscopy of transition metal and actinide containing species. While a long term connection of these species is to catalysis and environmental management of high-level nuclear wastes, the immediate relevance is directly to other DOE-BES funded experimental projects at DOE-National labs and universities. There are a number of ongoing gas-phase spectroscopic studies of these species at various places, and our computational work has been inspired by these experimental studies and we have also inspired other experimental and theoretical studies. Thus our studies have varied from spectroscopy of diatomic transition metal carbides to large complexes containing transition metals, and actinide complexes that are critical to the environment. In addition, we are continuing to make code enhancements and modernization of ALCHEMY II set of codes and its interface with relativistic configuration interaction (RCI). At present these codes can carry out multi-reference computations that included up to 60 million configurations and multiple states from each such CI expansion. ALCHEMY II codes have been modernized and converted to a variety of platforms such as Windows XP, and Linux. We have revamped the symbolic CI code to automate the MRSDCI technique so that the references are automatically chosen with a given cutoff from the CASSCF and thus we are doing accurate MRSDCI computations with 10,000 or larger reference space of configurations. The RCI code can also handle a large number of reference configurations, which include up to 10,000 reference configurations. Another major progress is in routinely including larger basis sets up to 5g functions in thee computations. Of course higher angular momenta functions can also be handled using Gaussian and other codes with other methods such as DFT, MP2, CCSD(T), etc. We have also calibrated our RECP

  13. Comparative electronic structure of a lanthanide and actinide diatomic oxide: Nd versus U

    NASA Astrophysics Data System (ADS)

    Krauss, M.; Stevens, W. J.

    2003-01-01

    Using a modified version of the Alchemy electronic structure code and relativistic pseudopotentials, the electronic structure of the ground and low lying excited states of UO, NdO, and NdO + have been calculated at the Hartree-Fock (HF) and multiconfiguration self-consistent field (MCSCF) levels of theory. Including results from an earlier study of UO + this provides the information for a comparative analysis of a lanthanide and an actinide diatomic oxide. UO and NdO are both described formally as M +2 O -2 and the cations as M +3 O -2 , but the HF and MCSCF calculations show that these systems are considerably less ionic due to large charge back-transfer in the πorbitals. The electronic states putatively arise from the ligand field (oxygen anion) perturbed f 4 , sf 3 , df 3 , sdf 2 , or s 2 f 2 states of M +2 and f 3 , sf 2 or df 2 states of M +3 . Molecular orbital results show a substantial stabilization of the sf 3 or s 2 f 2 configurations relative to the f 4 or df 3 configurations that are the even or odd parity ground states in the M +2 free ion. The compact f and d orbitals are more destabilized by the anion field than the diffuse s orbital. The ground states of the neutral species are dominated by orbitals arising from the M +2 sf 3 term, and all the potential energy curves arising from this configuration are similar, which allows an estimate of the vibrational frequencies for UO and NdO of 862 cm -1 and 836 cm -1 , respectively. For NdO + and UO + the excitation energies for the Ωstates were calculated with a valence configuration interaction method using ab initio effective spin-orbit operators to couple the molecular orbital configurations. The results for NdO + are very comparable with the results for UO + , and show the vibrational and electronic states to be interleaved.

  14. Core-hole effect on XANES and electronic structure of minor actinide dioxides with fluorite structure

    NASA Astrophysics Data System (ADS)

    Suzuki, Chikashi; Nishi, Tsuyoshi; Nakada, Masami; Akabori, Mitsuo; Hirata, Masaru; Kaji, Yoshiyuki

    2012-02-01

    The authors investigated theoretically core-hole effects on X-ray absorption near-edge structures (XANES) of Np and Am LIII in neptunium dioxide (NpO2) and americium dioxide (AmO2) with CaF2-type crystal lattices using the all-electron full-potential linearized augmented plane-wave (FP-LAPW) method. The peak creation mechanism of XANES was shown by examining the electronic structures of these oxides, which indicated that core-hole screening was more marked for AmO2 than for NpO2 because of the difference in the charge transfer between these oxides. Furthermore, the results of charge density analysis suggested that the white line was assigned to the quasi-bound state composed of the localized Np d or Am d components and O components, and that the tail structure was created as a result of delocalized standing waves between the Np or Am atoms.

  15. Rare-earth metal π-complexes of reduced arenes, alkenes, and alkynes: bonding, electronic structure, and comparison with actinides and other electropositive metals.

    PubMed

    Huang, Wenliang; Diaconescu, Paula L

    2015-09-21

    Rare-earth metal complexes of reduced π ligands are reviewed with an emphasis on their electronic structure and bonding interactions. This perspective discusses reduced carbocyclic and acyclic π ligands; in certain categories, when no example of a rare-earth metal complex is available, a closely related actinide analogue is discussed. In general, rare-earth metals have a lower tendency to form covalent interactions with π ligands compared to actinides, mainly uranium. Despite predominant ionic interactions in rare-earth chemistry, covalent bonds can be formed with reduced carbocyclic ligands, especially multiply reduced arenes.

  16. Pressure induced structural phase transition and electronic properties of actinide monophospides: Ab-initio calculations

    NASA Astrophysics Data System (ADS)

    Makode, Chandrabhan; Sanyal, Sankar P.

    2011-09-01

    We have investigated the structural and electronic properties of monophospides of thorium, uranium and neptunium. The total energy as a function of volume is obtained by means of the self-consistent tight binding linear muffin-tin-orbital (TB-LMTO) method within the local density approximation (LDA). From the present study with the help of total energy calculations it is found that ThP, UP and NpP are stable in NaCl-type structure at ambient pressure. The structural stability of ThP, UP and NpP changes under the application of pressure. We predict a structural phase transition from NaCl-type (B 1-phase) structure to CsCl-type (B 2-phase) structure for these phospides in the pressure range of 37.0-24.0 GPa (ThP-NpP). We also calculate lattice parameter ( a0), bulk modulus ( B0), band structure and density of states. From energy band diagram it is observed that ThP, UP and NpP exhibit metallic behavior. The calculated equilibrium lattice parameters and bulk modulus are in good agreement with experimental and theoretical work.

  17. The effect of actinide thin films on the electronic structure and reactivity of various elements

    SciTech Connect

    Gouder, T.; Colmenares, C.

    1994-12-08

    This report summarizes the experimental work carried out at the Lawrence Livermore National Laboratory on the electronic structure and reactivity of uranium thin films on Pd, Pt, Si, graphite, Cu, and Au substrates from 1990 to 1993. The U-Pd system was studied in the most detail because it was the first to be chosen right after the completion of the experimental equipment. We first studied and characterized clean U overlayers and the possible surface reactions between this metal and the substrates studied. We then subjected these systems to reactive conditions such as heating and adsorbing corrosive gases (O{sub 2}, CO, CO{sub 2}, and C{sub 2}H{sub 4}). Finally we investigated the diffusion of U metal and some of its compounds into the substrates. A new technique was developed, based on Auger Electron Spectroscopy, to follow in real time the diffusion of U overlayers into the substrate. The temperature of the sample is ramped linearly up to 900{degrees}C while following the Auger peak intensities of the two components for a given system. Diffusion rates are obtained by differentiating the measured intensity curves, then peaks result corresponding to diffusion processes with different activation energies. This technique bears a strong similarity to thermal desorption spectroscopy (TDS), where the sample is heated linearly and the rate of desorption is measured as a function of temperature and heating rate.

  18. Electronic Structure of PA^{n+; n=1-4} Ions: Looking for Clarity in Actinide Electronic Structure

    NASA Astrophysics Data System (ADS)

    Mrozik, Michael; Pitzer, Russell M.; Bursten, Bruce E.

    2009-06-01

    Since the identification of f-orbital contribution to the bonding in PaO^{+}, investigation into Pa cations have hoped to characterize as many of the electronic states possible.^{1} Electronic states of the Pa^{n+; n=1-4} ions have been investigated using multi-reference spin-orbit configuration interaction (MR-SOCI). Each additional electron in the series adds increased complexity and difficulty in evaluation of electronic states. Comparison of results with data at NIST and its institutional analog in France, or lack there of, indicate that L-S coupling does not adequately describe all the complexity present in these ions. Instead of L-S or a {ω-ω} coupling we propose that states of the Pa^{n+; n=1-4} ions would be better described using a J-j labeling of states. (1) Gibson et. al. Organometallics 2007, 26, 3947-3956.

  19. First principles study of structural, electronic, mechanical and magnetic properties of actinide nitrides AnN (An = U, Np and Pu)

    NASA Astrophysics Data System (ADS)

    Murugan, A.; Priyanga, G. Sudha; Rajeswarapalanichamy, R.; Santhosh, M.; Iyakutti, K.

    2016-09-01

    The electronic, structural, mechanical and magnetic properties of Actinide nitrides AnN (An = U, Np and Pu) are investigated in three cubic phases, namely, NaCl (B1), CsCl (B2) and zinc blende (B3). At normal pressure, UN is stable in antiferromagnetic state while the other two nitrides are stable in the ferromagnetic state with NaCl (B1) structure. A pressure induced structural phase transition from B1 to B3 phase is predicted in these nitrides. The electronic structure reveals that these nitrides are metallic in nature. The magnetic phase transition from antiferromagnetic to non-magnetic state is observed in UN at a pressure of 127 GPa while ferromagnetic to non-magnetic state is observed in NpN and PuN at the pressures of 67 GPa and 102.3 GPa respectively. The computed structural parameters, bulk modulus density of states and charge density distributions are compared with experimental and other theoretical calculations.

  20. Actinides-1981

    SciTech Connect

    Not Available

    1981-09-01

    Abstracts of 134 papers which were presented at the Actinides-1981 conference are presented. Approximately half of these papers deal with electronic structure of the actinides. Others deal with solid state chemistry, nuclear physic, thermodynamic properties, solution chemistry, and applied chemistry.

  1. Actinide Spectroscopy Workshop

    SciTech Connect

    Tobin, J.G.; Shuh, D.K.

    2004-12-05

    Actinide materials present an extreme scientific challenge to the materials research community. The complex electronic structures of actinide materials result in many unusual and unique properties that have yet to be fully understood. The difficulties in handling, preparing, and characterizing actinide materials has frequently precluded investigations and has the limited the detailed understanding of these relevant, complex materials. However, modern experiments with actinide materials have the potential to provide key, fundamental information about many long-standing issues concerning actinide materials. This workshop focused on the scientific and technical challenges posed by actinide materials and the potential that synchrotron radiation approaches available at the ALS can contribute to improving the fundamental understanding of actinides materials. Fundamental experimental approaches and results, as well as theoretical modeling and computational simulations, were part of the workshop program.

  2. Magnetic structures of actinide materials by pulsed neutron diffraction

    SciTech Connect

    Lawson, A.C.; Goldstone, J.A.; Huber, J.G.; Giorgi, A.L.; Conant, J.W.; Severing, A.; Cort, B.; Robinson, R.A.

    1990-01-01

    We describe some attempts to observe magnetic structure in various actinide (5f-electron) materials. Our experimental technique is neutron powder diffraction as practiced at a spallation (pulsed) neutron source. We will discuss our investigations of {alpha}-Pu, {delta}-Pu, {alpha}-UD{sub 3} and {beta}-UD{sub 3}. {beta}-UD{sub 3} is a simple ferromagnet: surprisingly, the moments on the two non-equivalent uranium atoms are the same within experimental error. {alpha}-UD{sub 3}, {alpha}-Pu and {delta}-Pu are non-magnetic, within the limits of our observations. Our work with pulsed neutron diffraction shows that it is a useful technique for research on magnetic materials.

  3. Theoretical studies of the crystal structure of rare earths and actinides at zero temperature

    SciTech Connect

    Wills, J.M.; Eriksson, O.

    1993-07-01

    Accurate total energy electronic structure calculations have recently been carried out over a range of volumes for selected rare-earth and actinide elements in crystal structures, experimentally observed in these elements. Correct zero temperature crystal structures are obtained, and calculated equilibrium properties are in reasonable agreement with experiment. Results of these calculations indicate that the interactions underlying crystal structure stability are similar in itinerant f-electron metals and transition metals. The stable crystal structure at a particular volume is determined by a balance between one-electron bandwidths and band fillings and the electrostatic energy of the crystal lattice. Broad bands favor high-symmetry, close-packed structures while narrow bands favor low-symmetry, open structures; allowing for expansion as well as contraction, both transition and actinide elements can be stabilized in both low- and high-symmetry crystal structures.

  4. Theoretical studies of the crystal structure of rare earths and actinides at zero temperature

    SciTech Connect

    Wills, J.M. ); Eriksson, O. . Dept. of Physics)

    1993-01-01

    Accurate total energy electronic structure calculations have recently been carried out over a range of volumes for selected rare-earth and actinide elements in crystal structures, experimentally observed in these elements. Correct zero temperature crystal structures are obtained, and calculated equilibrium properties are in reasonable agreement with experiment. Results of these calculations indicate that the interactions underlying crystal structure stability are similar in itinerant f-electron metals and transition metals. The stable crystal structure at a particular volume is determined by a balance between one-electron bandwidths and band fillings and the electrostatic energy of the crystal lattice. Broad bands favor high-symmetry, close-packed structures while narrow bands favor low-symmetry, open structures; allowing for expansion as well as contraction, both transition and actinide elements can be stabilized in both low- and high-symmetry crystal structures.

  5. New cubic structure compounds as actinide host phases

    NASA Astrophysics Data System (ADS)

    Stefanovsky, S. V.; Yudintsev, S. V.; Livshits, T. S.

    2010-03-01

    Various compounds with fluorite (cubic zirconia) and fluorite-derived (pyrochlore, zirconolite) structures are considered as promising actinide host phases at immobilization of actinide-bearing nuclear wastes. Recently some new cubic compounds — stannate and stannate-zirconate pyrochlores, murataite and related phases, and actinide-bearing garnet structure compounds were proposed as perspective matrices for complex actinide wastes. Zirconate pyrochlore (ideally Gd2Zr2O7) has excellent radiation resistance and high chemical durability but requires high temperatures (at least 1500 °C) to be produced by hot-pressing from sol-gel derived precursor. Partial Sn4+ substitution for Zr4+ reduces production temperature and the compounds REE2ZrSnO7 may be hot-pressed or cold pressed and sintered at ~1400 °C. Pyrochlore, A2B2O7-x (two-fold elementary fluorite unit cell), and murataite, A3B6C2O20-y (three-fold fluorite unit cell), are end-members of the polysomatic series consisting of the phases whose structures are built from alternating pyrochlore and murataite blocks (nano-sized modules) with seven- (2C/3C/2C), five- (2C/3C), eight- (3C/2C/3C) and three-fold (3C — murataite) fluorite unit cells. Actinide content in this series reduces in the row: 2C (pyrochlore) > 7C > 5C > 8C > 3C (murataite). Due to congruent melting murataite-based ceramics may be produced by melting and the firstly segregated phase at melt crystallization is that with the highest fraction of the pyrochlore modules in its structure. The melts containing up to 10 wt. % AnO2 (An = Th, U, Np, Pu) or REE/An fraction of HLW form at crystallization zoned grains composed sequentially of the 5C → 8C → 3C phases with the highest actinide concentration in the core and the lowest — in the rim of the grains. Radiation resistance of the "murataite" is comparable to titanate pyrochlores. One more promising actinide hosts are ferrites with garnet structure. The matrices containing sometime complex fluorite

  6. Chemical effects of lanthanides and actinides in glasses determined with electron energy loss spectroscopy

    SciTech Connect

    Fortner, J.A.; Buck, E.C.; Ellison, A.J.G.; Bates, J.K.

    1996-07-01

    Chemical and structural environments of f-electron elements in glasses are the origin of many of the important properties of materials with these elements; thus oxidation state and chemical coordination of lanthanides and actinides in host materials is an important design consideration in optically active glasses, magnetic materials, perovskite superconductors, and nuclear waste materials. We have made use of the line shapes of Ce to determine its oxidation state in alkali borosilicate glasses being developed for immobilization of Pu. Examination of several prototype waste glass compositions with EELS shows that the redox state of Ce doped to 7 wt% could be varied by suitable choice of alkali elements. EELS for a Pu-doped glass illustrate the small actinide N{sub 4}/N{sub 5} intensity ratio and show that the Pu-N{sub 4,5} white line cross section is comparable to that of Gd M{sub 4,5}.

  7. Effect of pressure on f-electron delocalization and oxidation in actinide dioxides

    NASA Astrophysics Data System (ADS)

    Petit, L.; Szotek, Z.; Temmerman, W. M.; Stocks, G. M.; Svane, A.

    2014-08-01

    Using first principles calculations, we have investigated f-electron delocalization and oxidation in the actinide dioxides under pressure. Whilst UO2 is found on the verge of an insulator to metal transition at the equilibrium volume, increasingly larger pressures are required to delocalize f-electrons in NpO2, PuO2, and AmO2, respectively 49, 112, and 191 GPa. Compared to this broad range of pressures, the experimentally observed structural transitions, in all four dioxides, occur between 30 and 40 GPa, which leads us to conclude that the associated volume collapse is not due to f-electron delocalization. In contrast, oxidation of the dioxides is found to be linked to the degree of f-electron localization, but it emerges that for naturally occurring pressures (<10 GPa), higher oxides only exist for UO2.

  8. High-quality single crystal growth and strongly correlated electronic states in rare earth and actinide compounds

    NASA Astrophysics Data System (ADS)

    Ōnuki, Yoshichika; Honda, Fuminori; Hirose, Yusuke; Settai, Rikio; Takeuchi, Tetsuya

    2016-11-01

    We review the nature of strongly correlated electronic states in rare earth and actinide compounds, focusing on localized versus itinerant electronic states in CeRhIn5, quantum critical phenomena in YbIr2Zn20, residual resistivity in CeCu6, metamagnetism in heavy fermion compounds, and unconventional superconductivity in CeIrSi3 without inversion symmetry in the crystal structure, emphasizing that sample quality is essentially important to clarify the characteristic features for the heavy fermion compounds.

  9. The electronic, magnetic and thermal properties of actinide monocarbides: A first principles study

    NASA Astrophysics Data System (ADS)

    Soni, Pooja; Pagare, Gitanjali; Rajagopalan, M.; Sanyal, Sankar P.

    2012-06-01

    A theoretical study on structural, electronic, magnetic and thermal properties of actinide monocarbides AnCs (An= Np and Cm), which crystallize in NaCl-type structure, has been performed using self consistent tight binding linear muffin tin orbital (TB-LMTO) method at ambient as well as at high pressure. Both non-spin and spin polarized calculations have been performed to check the magnetic stability. We observe that both the compounds are metallic in nature and ferro-magnetically stable at ambient pressure. The calculated ground state properties such as lattice constants and bulk modulus are compared with the available results. The Debye temperature is also estimated for the first time.

  10. Electronic structure and spectroscopic properties of mixed sodium actinide oxides Na2AnO4 (An = U, Np, Pu, Am)

    NASA Astrophysics Data System (ADS)

    Kovács, Attila

    2017-03-01

    Multireference relativistic post-HF and DFT calculations have been performed on four Na2AnO4 (An = U, Np, Pu, Am) molecules. Beyond the electronic characteristics of the ground and excited electronic states, the molecular geometries and vibrational frequencies have been determined.

  11. Electron affinities for rare gases and some actinides from local-spin-density-functional theory

    SciTech Connect

    Guo, Y.; Wrinn, M.C.; Whitehead, M.A. )

    1989-12-01

    The negative ions of the rare gases (He, Ne, Ar, Kr, Xe, and Rn) and some actinides (Pu, Am, Bk, Cf, and Es) have been calculated self-consistently by the generalized exchange local-spin-density-functional theory with self-interaction correction and correlation. The electron affinities were obtained as the differences between the statistical total energies of the negative ions and neutral atoms; the electron affinities were positive around several millirydbergs. Consequently, the negative ions are predicted stable for the rare gases and actinides.

  12. Thermodynamic and Structural Investigation of Synthetic Actinide-Peptide Scaffolds.

    PubMed

    Safi, Samir; Jeanson, Aurélie; Roques, Jérome; Solari, Pier Lorenzo; Charnay-Pouget, Florence; Den Auwer, Christophe; Creff, Gaëlle; Aitken, David J; Simoni, Eric

    2016-01-19

    The complexation of uranium and europium, in oxidation states +VI and +III, respectively, was investigated with pertinent bio-inorganic systems. Three aspartate-rich pentapeptides with different structural properties were selected for study to rationalize the structure-affinity relationships. Thermodynamic results, crosschecked by both isothermal titration calorimetry and time-resolved laser fluorescence spectroscopy, showed different affinity depending on the peptide for both Eu(III) and U(VI). The thermodynamic aspects were correlated to structural predictions, which were acquired by density functional theory quantum chemical calculations and from IR and extended X-ray absorption fine structure experiments. The combination of these microscopic properties revealed that carbonyl-metal interactions affected the entropy in the case of europium, while the larger uranyl cation was mostly affected by preorganization and steric effects, so that the affinity was enhanced through enthalpy. The approach described here revealed various microscopic aspects governing peptide actinide affinity. Highlighting these mechanisms should certainly contribute to the rational synthesis of higher affinity biomimetic aspartic ligands.

  13. Understanding the O4,5 edge structure of actinide metals

    SciTech Connect

    Butterfield, M; Moore, K; der Laan, G v; Wall, M; Haire, D

    2007-12-12

    Using electron energy-loss spectroscopy (EELS) and many-electron atomic spectral calculations, we examine the O{sub 4,5} (5d {yields} 5f) edge structure of the ground-state {alpha} phase of Th, U, Np, Pu, Am, and Cm metal. Results show that the dipole-allowed transitions are contained within the giant resonance and that the small pre-peak in the actinide 5d {yields} 5f transition should not be labeled the O{sub 5} peak, but rather the {Delta}S=1 peak. Lastly, we present for the first time the O{sub 4,5} EELS spectra for Np, Am, and Cm metal.

  14. The Electronic Structure of Heavy Element Complexes

    SciTech Connect

    Bursten, Bruce E.

    2000-07-25

    The area of study is the bonding in heavy element complexes, and the application of more sophisticated electronic structure theories. Progress is recounted in several areas: (a) technological advances and current methodologies - Relativistic effects are extremely important in gaining an understanding of the electronic structure of compounds of the actinides, transactinides, and other heavy elements. Therefore, a major part of the continual benchmarking was the proper inclusion of the appropriate relativistic effects for the properties under study. (b) specific applications - These include organoactinide sandwich complexes, CO activation by actinide atoms, and theoretical studies of molecules of the transactinide elements. Finally, specific directions in proposed research are described.

  15. Measuring the Cosmic Particle Radiation from electrons to actinides - CALET

    NASA Astrophysics Data System (ADS)

    Mitchell, John; Calet Collaboration; Hnx/Tigeriss Collaboration

    2017-01-01

    CALET (Calorimetric Electron Telescope) was installed on the Exposed Facility of the Japanese Experiment Module (Kibo) on for 24 August 2015. CALET measures the high-energy spectra of electrons, nuclei, and gamma-rays. CALET will extend direct measurements of the total electron spectrum into the trans-TeV energy range for the first time. In this paper, we well present the science and current status of CALET and initial observations from its first 1.5 years in orbit.

  16. Application of chemical structure and bonding of actinide oxide materials for forensic science

    SciTech Connect

    Wilkerson, Marianne Perry

    2010-01-01

    We are interested in applying our understanding of actinide chemical structure and bonding to broaden the suite of analytical tools available for nuclear forensic analyses. Uranium- and plutonium-oxide systems form under a variety of conditions, and these chemical species exhibit some of the most complex behavior of metal oxide systems known. No less intriguing is the ability of AnO{sub 2} (An: U, Pu) to form non-stoichiometric species described as AnO{sub 2+x}. Environmental studies have shown the value of utilizing the chemical signatures of these actinide oxide materials to understand transport following release into the environment. Chemical speciation of actinide-oxide samples may also provide clues as to the age, source, or process history of the material. The scientific challenge is to identify, measure and understand those aspects of speciation of actinide analytes that carry information about material origin and history most relevant to forensics. Here, we will describe our efforts in material synthesis and analytical methods development that we will use to provide the fundamental science to characterize actinide oxide molecular structures for forensic science. Structural properties and initial results to measure structural variability of uranium oxide samples using synchrotron-based X-ray Absorption Fine Structure will be discussed.

  17. Experimental level-structure determination in odd-odd actinide nuclei

    SciTech Connect

    Hoff, R.W.

    1985-04-04

    The status of experimental determination of level structure in odd-odd actinide nuclei is reviewed. A technique for modeling quasiparticle excitation energies and rotational parameters in odd-odd deformed nuclei is applied to actinide species where new experimental data have been obtained by use of neutron-capture gamma-ray spectroscopy. The input parameters required for the calculation are derived from empirical data on single-particle excitations in neighboring odd-mass nuclei. Calculated configuration-specific values for the Gallagher-Moszkowski splittings are used. Calculated and experimental level structures for /sup 238/Np, /sup 244/Am, and /sup 250/Bk are compared, as well as those for several nuclei in the rare-earth region. The agreement for the actinide species is excellent, with bandhead energies deviating 22 keV and rotational parameters 5%, on the average. Applications of this modeling technique are discussed.

  18. Predictive Modeling in Actinide Chemistry and Catalysis

    SciTech Connect

    Yang, Ping

    2016-05-16

    These are slides from a presentation on predictive modeling in actinide chemistry and catalysis. The following topics are covered in these slides: Structures, bonding, and reactivity (bonding can be quantified by optical probes and theory, and electronic structures and reaction mechanisms of actinide complexes); Magnetic resonance properties (transition metal catalysts with multi-nuclear centers, and NMR/EPR parameters); Moving to more complex systems (surface chemistry of nanomaterials, and interactions of ligands with nanoparticles); Path forward and conclusions.

  19. QED and electron collisions in the super strong fields of K-shell actinide ions

    SciTech Connect

    Beiersdorfer, P

    2006-01-25

    Atomic physics of high-Z, heavy ions is very different from that encountered in low-Z or medium-Z ions. The reason is the ultra strong nuclear field found only in the heaviest ions. The highest-Z atomic systems available to physical investigation, the actinides, therefore, offer rich new physics that cannot be studied any other way. This ranges from new dominating forces in electron-ion collisions to tests of fundamental theories. A measurement of the two-loop Lamb shift in uranium is by many considered to be the ''holy grail'' of high-field QED tests of atomic systems. Such measurements have been attempted at heavy-ion accelerator facilities but have yet to succeed because of the difficulty to make measurements with the required accuracy. Also, electron collisions behave very differently in such tightly bound systems. The magnetic interaction between the ion and the incoming free electron (the so-called generalized Breit interaction) is essentially non-existent in collisions involving low and medium-Z ions. This interaction is therefore missing in essentially all electron collision codes. But in heavy, highly charged ions like uranium, the generalized Breit interaction readily is the dominant force, changing electron collision cross sections by a factor of two. This has never been experimentally observed. In fact, no K-shell emission spectrum of any heavy high-Z ion higher than krypton (Z=36) has ever been recorded from a collisional source. By studying the heaviest actinides such fundamental science can be extended to regimes where the highest precision tests can be made.

  20. A moving target: responding to magnetic and structural disorder in lanthanide- and actinide-based superconductors

    SciTech Connect

    Bauer, Eric D; Mitchell, Jeremy N; Booth, C H

    2009-01-01

    The effects of various chemical substitutions and induced lattice disorder in the Ce- and Pu-based 115 superconductors are reviewed, with particular emphasis on results from x-ray absorption fine structure (XAFS) measurements. The competition between spin, charge, and lattice interactions is at the heart of many of the strongly-correlated ground states in materials of current interest, such as in colossal magnetoresistors and high-temperature superconductors. This relationship is particularly strong in the CeTIn{sub 5} and PuTGa{sub 5} series (T = Co, Rh, Ir) of heavy-fermion superconductors. In these systems (figure 1), competition between bulk magnetic and non-magnetic ground states, as well as between superconducting and normal states, are directly related to local properties around the lanthanide or actinide ion, such as the nearest-neighbor bond lengths and the local density of states at the Fermi level. Tiny changes in the latter values can easily tip the balance from one ground state to another. This paper reviews recent work by the authors exploring the relationship between local crystal and electronic structure and ground state magnetic and conducting properties in the Ce- and Pu-based 115 materials.

  1. Actinide-specific complexing agents: their structural and solution chemistry

    SciTech Connect

    Raymond, K.N.; Freeman, G.E.; Kappel, M.J.

    1983-07-01

    The synthesis of a series of tetracatecholate ligands designed to be specific for Pu(IV) and other actinide(IV) ions has been achieved. Although these compounds are very effective as in vivo plutonium removal agents, potentiometric and voltammetric data indicate that at neutral pH full complexation of the Pu(IV) ion by all four catecholate groups does not occur. Spectroscopic results indicate that the tetracatecholates, 3,4,3-LICAMS and 3,4,3-LICAMC, complex Am(III). The Am(IV)/(III)-catecholate couple (where catecholate = 3,4,3-LICAMS or 3,4,3-LICAMC) is not observed, but may not be observable due to the large currents associated with ligand oxidation. However, within the potential range where ligand oxidation does not occur, these experiments indicate that the reduction potential of free Am(IV)/(III) is probably greater than or equal to + 2.6 V vs NHE or higher. Proof of the complexation of americium in the trivalent oxidation state by 3,4,3-LICAMS and 3,4,3-LICAMC elimates the possibility of tetracatholates stabilizing Am(IV) in vivo.

  2. Actinides and Rare Earths Topical Conference (Code AC)

    SciTech Connect

    Tobin, J G

    2009-11-24

    Actinide and the Rare Earth materials exhibit many unique and diverse physical, chemical and magnetic properties, in large part because of the complexity of their f electronic structure. This Topical Conference will focus upon the chemistry, physics and materials science in Lanthanide and Actinide materials, driven by 4f and 5f electronic structure. Particular emphasis will be placed upon 4f/5f magnetic structure, surface science and thin film properties. For the actinides, fundamental actinide science and its role in resolving technical challenges posed by actinide materials will be stressed. Both basic and applied experimental approaches, including synchrotron-radiation-based investigations, as well as theoretical modeling and computational simulations, are planned to be part of the Topical Conference. Of particular importance are the issues related to the potential renaissance in Nuclear Fuels, including synthesis, oxidation, corrosion, intermixing, stability in extreme environments, prediction of properties via benchmarked simulations, separation science, environmental impact and disposal of waste products.

  3. Molecular models for actinide speciation

    SciTech Connect

    Clark, D.L.; Watkin, J.G.; Morris, D.E.; Berg, J.M.

    1994-06-01

    Much effort has been devoted to the development of sensitive spectroscopic techniques for the study of actinide speciation based on the sensitivity of f-f electronic absorption bands to oxidation state and ligation of the actinide ions. These efforts assume that data obtained in such studies will be interpretable in terms of changes in complexation of the metal center. However, the current understanding of 5f electronic structure is based on data from solid state doped single crystals. In those studies, the local coordination geometry about the central actinide ion is maintained in an almost perfect high-symmetry environment and will have little relevance for species in solution where deviations from perfect high symmetry tend to be the rule rather than the exception. The authors have developed a vigorous research program in the systematic preparation and spectroscopic characterization of synthetic actinide complexes (Th, U, Np, and Pu) in which they can control nuclearity, oxidation state, and molecular structure. These complexes have been used to determine how observable electronic transitions are perturbed in response to structural changes in the complex in solution. From the spectra obtained for these model complexes, the authors have found that the f-f transitions naturally fall into obvious groupings by coordination number and symmetry by which they can now differentiate between monomeric, dimeric, and trimeric species in solution. The study of radionuclide speciation is fundamentally important to the determination of radionuclide solubility in the groundwater at Yucca Mountain.

  4. Structural Properties of Lanthanide and Actinide Compounds within the Plane Wave Pseudopotential Approach

    NASA Astrophysics Data System (ADS)

    Pickard, Chris J.; Winkler, Björn; Chen, Roger K.; Payne, M. C.; Lee, M. H.; Lin, J. S.; White, J. A.; Milman, V.; Vanderbilt, David

    2000-12-01

    We show that plane wave ultrasoft pseudopotential methods readily extend to the calculation of the structural properties of lanthanide and actinide containing compounds. This is demonstrated through a series of calculations performed on UO, UO2, UO3, U3O8, UC2, α-CeC2, CeB6, CeSe, CeO2, NdB6, TmOI, LaBi, LaTiO3, YbO, and elemental Lu.

  5. Structural properties of lanthanide and actinide compounds within the plane wave pseudopotential approach

    PubMed

    Pickard; Winkler; Chen; Payne; Lee; Lin; White; Milman; Vanderbilt

    2000-12-11

    We show that plane wave ultrasoft pseudopotential methods readily extend to the calculation of the structural properties of lanthanide and actinide containing compounds. This is demonstrated through a series of calculations performed on UO, UO2, UO3, U3O8, UC2, alpha-CeC2, CeB6, CeSe, CeO2, NdB6, TmOI, LaBi, LaTiO3, YbO, and elemental Lu.

  6. Electronic Structure Methods Based on Density Functional Theory

    DTIC Science & Technology

    2010-01-01

    L. Nordström, L. Tongming, and B. Johansson, “Relativistic Effects on the Thermal Expansion of the Actinide Elements ”, Phys. Rev. B 42, 1990, p 4544...In-house 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 62102F 6. AUTHOR(S) Christopher F. Woodward (AFRL/RXLMD) 5d. PROJECT NUMBER 4347 5e...in valence electrons change the structure of the core electrons. For example in the actinides , where the f-electrons are coupled to the core states

  7. An investigation on the structural transition and stability of some actinide nitrides under pressure

    NASA Astrophysics Data System (ADS)

    Shareef M., Faisal; Bhardwaj, Purvee; Singh, Sadhna

    2014-06-01

    A theoretical study of the structural and related properties of some actinide nitrides under high pressure has been carried out using three-body interaction (TBI) potential model. The present TBI model constitutes the long range Coulombic, three body interaction forces with inclusion of covalency effect, van der Waals' interaction and short range overlap repulsive forces operative up-to next nearest neighbor ions. The covalency effect is introduced to explain the partial covalent nature of the present compounds. Using this static simulation technique we have investigated the phase transition pressures, volume collapses and elastic behaviour of ThN, NpN and CmN at high-pressures. A detailed discussion of stability criteria using various theories has also been done. The results found are well agreed with available experimental and other data.

  8. First-principles DFT+DMFT calculations of structural properties of actinides: Role of Hund's exchange, spin-orbit coupling, and crystal structure

    NASA Astrophysics Data System (ADS)

    Amadon, Bernard

    2016-09-01

    We utilize a combination of an ab initio calculation of effective Coulomb interactions and a DFT+DMFT calculation of total energy to study the structural properties of pure actinides. We first show that the effective direct Coulomb interactions in plutonium and americium are much smaller than usually expected. Secondly, we emphasize the key role of Hund's exchange in combination with the spin-orbit coupling in determining the structural parameters of δ -plutonium and americium. Thirdly, using this ab initio description, we reproduce the experimental transition from low volume early actinides (uranium, neptunium, α -plutonium) to high-volume late actinides (δ -plutonium, americium, and curium) without the need of an artificial magnetism. Finally, we compare the energies and structural properties of α , γ , ɛ , and δ phases of plutonium to experimental data.

  9. Dynamic Recovery in Silicate-Apatite Structures Under Irradiation and Implications for Long-Term Immobilization of Actinides

    SciTech Connect

    Weber, William J.; Zhang, Yanwen; Xiao, Haiyan Y.; Wang, Lumin M.

    2011-11-14

    The irradiation responses of Ca{sub 2}La{sub 8}(SiO{sub 4}){sub 6}O{sub 2} and Sr{sub 2}Nd{sub 8}(SiO{sub 4}){sub 6}O{sub 2} with the apatite structure are investigated to predict their long-term behaviour as host phases for immobilization of actinide elements from the nuclear fuel cycle. Different ions and energies are used to study the effects of dose, temperature, atomic displacement rate and ionization rate on irradiation-induced amorphization and recrystallization. The dose for amorphization increases with temperature in two stages, below and above 150 K. In the high temperature stage relevant to actinide immobilization, the increase of amorphization dose with temperature exhibits a strong dependence on the ratio of ionization rate to displacement rate for the different ions. Data analysis using a dynamic model for amorphization reveals that ionization-induced processes, with activation energy of 0.15 {+-} 0.02 eV, dominate dynamic recovery for ions from Ne through Xe. For heavier Au ions or for alpha-recoil nuclei emitted in alpha decay of actinides, ionization becomes less dominant and dynamic recovery is controlled primarily by thermally-driven processes. In post-irradiation annealing studies of amorphous samples, epitaxial thermal recrystallization is observed at 1123 K, and irradiation-enhanced nucleation of nanocrystallites is observed under irradiation with heavier ions. The recrystallization temperature under irradiation decreases with increasing ion mass to a value of {approx} 823 K, which also defines the thermally-driven critical temperature for amorphization under irradiation with heavy ions. Some partial recovery due to alpha particle irradiation at 300 K is observed that suggests a self-healing mechanism in apatite phases containing actinides. Based on the results and dynamic model, the temperature and time dependences of amorphization in silicate-apatite host phases for actinide immobilization are predicted.

  10. Dynamic recovery in silicate-apatite structures under irradiation and implications for long-term immobilization of actinides

    SciTech Connect

    Weber, William J; Zhang, Yanwen; Xiao, Haiyan; Wang, Prof. Lumin

    2012-01-01

    The irradiation responses of Ca2La8(SiO4)6O2 and Sr2Nd8(SiO4)6O2 with the apatite structure are investigated to predict their long-term behaviour as host phases for immobilization of actinide elements from the nuclear fuel cycle. Different ions and energies are used to study the effects of dose, temperature, atomic displacement rate and ionization rate on irradiation-induced amorphization and recrystallization. The dose for amorphization increases with temperature in two stages, below and above 150 K. In the high temperature stage relevant to actinide immobilization, the increase of amorphization dose with temperature exhibits a strong dependence on the ratio of ionization rate to displacement rate for the different ions. Data analysis using a dynamic model for amorphization reveals that ionization-induced processes, with activation energy of 0.15 0.02 eV, dominate dynamic recovery for ions from Ne through Xe. For heavier Au ions or for alpha-recoil nuclei emitted in alpha decay of actinides, ionization becomes less dominant and dynamic recovery is controlled primarily by thermally-driven processes. In post-irradiation annealing studies of amorphous samples, epitaxial thermal recrystallization is observed at 1123 K, and irradiation-enhanced nucleation of nanocrystallites is observed under irradiation with heavier ions. The recrystallization temperature under irradiation decreases with increasing ion mass to a value of ~ 823 K, which also defines the thermally-driven critical temperature for amorphization under irradiation with heavy ions. Some partial recovery due to alpha particle irradiation at 300 K is observed that suggests a self-healing mechanism in apatite phases containing actinides. Based on the results and dynamic model, the temperature and time dependences of amorphization in silicate-apatite host phases for actinide immobilization are predicted.

  11. Synthesis, structure and bonding of actinide disulphide dications in the gas phase.

    PubMed

    Lucena, Ana F; Bandeira, Nuno A G; Pereira, Cláudia C L; Gibson, John K; Marçalo, Joaquim

    2017-04-11

    Actinide disulphide dications, AnS2(2+), were produced in the gas phase for An = Th and Np by reaction of An(2+) cations with the sulfur-atom donor COS, in a sequential abstraction process of two sulfur atoms, as examined by FTICR mass spectrometry. For An = Pu and Am, An(2+) ions were unreactive with COS and did not yield any sulphide species. High level multiconfigurational (CASPT2) calculations were performed to assess the structures and bonding of the new AnS2(2+) species obtained for An = Th, Np, as well as for An = Pu to examine trends along the An series, and for An = U to compare with a previous experimental study and DFT computational scrutiny of US2(2+). The CASPT2 results showed that, like in the case of uranium, the new AnS2(2+) ions have ground states with triangular geometries, corresponding to the presence of a persulphide in the case of thorium that formally leads to a stable Th(IV)S2(2+) species, while a supersulphide appears to be present in the case of U, Np and Pu, formally leading to a An(III)S2(2+) species. The computations also revealed that linear thioactinyl structures are higher in energy, with a difference that increases fourfold upon moving from U to Pu, apparently indicating that it will be even more pronounced for Am.

  12. Systematic view of optical absorption spectra in the actinide series

    SciTech Connect

    Carnall, W.T.

    1985-01-01

    In recent years sufficient new spectra of actinides in their numerous valence states have been measured to encourage a broader scale analysis effort than was attempted in the past. Theoretical modelling in terms of effective operators has also undergone development. Well established electronic structure parameters for the trivalent actinides are being used as a basis for estimating parameters in other valence states and relationships to atomic spectra are being extended. Recent contributions to our understanding of the spectra of 4+ actinides have been particularly revealing and supportive of a developing general effort to progress beyond a preoccupation with modelling structure to consideration of the much broader area of structure-bonding relationships. We summarize here both the developments in modelling electronic structure and the interpretation of apparent trends in bonding. 60 refs., 9 figs., 1 tab.

  13. Actinide science with soft x-ray synchrotron radiation

    NASA Astrophysics Data System (ADS)

    Shuh, David K.

    2000-07-01

    The primary methods for the experimental investigation of actinide materials in the VUV/soft x-ray region are the complementary photoelectron spectroscopies, near-edge x-ray absorption fine structure (NEXAFS), and x-ray emission spectroscopy (XES) techniques. Resonant photoemission techniques capable of resolving the 5f electron contributions to actinide bonding along with angle-resolving measurements for band structure and surface structure determinations, have clear and immediate applications. Venerable angle-integrating core and valence band photoelectron spectroscopy are valuable for characterization and analytical purposes. Combined with results from NEXAFS measurements, these techniques will provide the information needed to develop improved understandings of the electronic structure of actinide materials and their surface chemistries/physics.

  14. Measuring the Cosmic Particle Radiation from electrons to actinides - HNX/TIGERISS

    NASA Astrophysics Data System (ADS)

    Mitchell, John

    2017-01-01

    The Heavy Nuclei eXplorer (HNX) mission will measure the abundances of nuclei from Carbon (Z =6) to Curium (Z =96) in the cosmic radiation with the resolution to identify the atomic number of each detected nucleus. HNX will measure a significant number of actinides. HNX utilizes two high-precision instruments, the Extremely-heavy Cosmic-ray Composition Observer (ECCO) and the Cosmic-Ray Trans-Iron Galactic Element Recorder (CosmicTIGER), located in a SpaceX DragonLab capsule orbiting the Earth. This talk will discuss the motivating science, the HNX mission, the design and performance of the HNX instruments, and another new instrument, TIGERISS (Trans-Iron Galactic Element Recorder on the ISS), that will be proposed as an intermediate between SuperTIGER and HNX.

  15. The low-energy dipole structure of 232Th , 236U and 238U actinide nuclei

    NASA Astrophysics Data System (ADS)

    Kuliev, A. A.; Guliyev, E.; Ertugral, F.; Özkan, S.

    2010-03-01

    In this study, ensuremath I^{π} = 1+ and ensuremath I^{π} = 1- dipole mode excitations are systematically investigated within the rotational and translational + Galilean invariant quasiparticle random-phase approximation for 232Th , 236U , and 238U actinide nuclei. It is shown that the investigated nuclei reach a B( M1) strength structure, which corresponds to the scissors mode. The calculated mean excitation energies as well as the summed B( M1) value of the scissors mode excitations are consistent with the available experimental data. The results of calculations indicate large differences to the rare-earth nuclei as is the case for the experiment: a doubling of the observed dipole strengths and a shift of the energy centroid to the lower energies by about 800keV. The calculations indicate the presence of a few prominent negative-parity ensuremath K^{π} = 1- states in the 2.0-4.0MeV energy interval. The occurrence of the negative-parity dipole states with the rather high B( E1) value less than 4MeV shows the necessity of explicit parity measurements for the correct determination of the scissors mode strength in 232Th , 236U , and 238U isotopes.

  16. Semi-empirical models of actinide alloying

    NASA Astrophysics Data System (ADS)

    Gibson, John K.; Haire, Richard G.; Ogawa, Toru

    1999-07-01

    Alloys of Np have been studied less than those of the neighboring elements, U and Pu; the higher actinides have received even less attention. Recent interest in 237Np, 241Am and other actinide isotopes as significant, long-lived and highly radiotoxic nuclear waste components, and particularly the roles of metallic materials in new handling/separations and remediation technologies, demands that this paucity of information concerning alloy behaviors be addressed. An additional interest in these materials arises from the possibility of revealing fundamental properties and bonding interactions, which would further characterize the unique electronic structures (e.g., 5f electrons) of the actinide elements. The small empirical knowledge basis presently available for understanding and modeling the alloying behavior of Np is summarized here, with emphasis on our recent results for the Np-Am, Np-Zr and Np-Fe phase diagrams. In view of the limited experimental data base for neptunium and the transplutonium metals, the value of semi-empirical intermetallic bonding models for predicting actinide alloy thermodynamics is evaluated.

  17. Local structure in solid solutions of stabilised zirconia with actinide dioxides (UO{sub 2}, NpO{sub 2})

    SciTech Connect

    Walter, Marcus; Somers, Joseph; Bouexiere, Daniel; Rothe, Joerg

    2011-04-15

    The local structure of (Zr,Lu,U)O{sub 2-x} and (Zr,Y,Np)O{sub 2-x} solid solutions has been investigated by extended X-ray absorption fine structure (EXAFS). Samples were prepared by mixing reactive (Zr,Lu)O{sub 2-x} and (Zr,Y)O{sub 2-x} precursor materials with the actinide oxide powders, respectively. Sintering at 1600 {sup o}C in Ar/H{sub 2} yields a fluorite structure with U(IV) and Np(IV). As typical for stabilised zirconia the metal-oxygen and metal-metal distances are characteristic for the different metal ions. The bond lengths increase with actinide concentration, whereas highest adaptation to the bulk stabilised zirconia structure was observed for U---O and Np---O bonds. The Zr---O bond shows only a slight increase from 2.14 A at 6 mol% actinide to 2.18 A at infinite dilution in UO{sub 2} and NpO{sub 2}. The short interatomic distance between Zr and the surrounding oxygen and metal atoms indicate a low relaxation of Zr with respect to the bulk structure, i.e. a strong Pauling behaviour. -- Graphical abstract: Metal-oxygen bond distances in (Zr,Lu,U)O{sub 2-x} solid solutions with different oxygen vacancy concentrations (Lu/Zr=1 and Lu/Zr=0.5). Display Omitted Research Highlights: {yields} EXAFS indicates high U and Np adaption to the bulk structure of stabilised zirconia. {yields} Zr---O bond length is 2.18 A at infinite Zr dilution in UO{sub 2} and NpO{sub 2}. {yields} Low relaxation (strong Pauling behaviour) of Zr explains its low solubility in UO{sub 2}.

  18. Theoretical investigation on multiple bonds in terminal actinide nitride complexes.

    PubMed

    Wu, Qun-Yan; Wang, Cong-Zhi; Lan, Jian-Hui; Xiao, Cheng-Liang; Wang, Xiang-Ke; Zhao, Yu-Liang; Chai, Zhi-Fang; Shi, Wei-Qun

    2014-09-15

    A series of actinide (An) species of L-An-N compounds [An = Pa-Pu, L = [N(CH2CH2NSiPr(i)3)3](3-), Pr(i) = CH(CH3)2] have been investigated using scalar relativistic density functional theory (DFT) without considering spin-orbit coupling effects. The ground state geometric and electronic structures and natural bond orbital (NBO) analysis of actinide compounds were studied systematically in neutral and anionic forms. It was found that with increasing actinide atomic number, the bond length of terminal multiple An-N1 bond decreases, in accordance with the actinide contraction. The Mayer bond order of An-N1 decreases gradually from An = Pa to Pu, which indicates a decrease in bond strength. The terminal multiple bond for L-An-N compounds contains one σ and two π molecular orbitals, and the contributions of the 6d orbital to covalency are larger in magnitude than the 5f orbital based on NBO analysis and topological analysis of electron density. This work may help in understanding of the bonding nature of An-N multiple bonds and elucidating the trends and electronic structure changes across the actinide series. It can also shed light on the construction of novel An-N multiple bonds.

  19. Microscopic theory of the insulating electronic ground states of the actinide dioxides AnO2 (An = U, Np, Pu, Am, and Cm)

    NASA Astrophysics Data System (ADS)

    Suzuki, M.-T.; Magnani, N.; Oppeneer, P. M.

    2013-11-01

    The electronic states of the actinide dioxides AnO2 (with An = U, Np, Pu, Am, and Cm) are investigated employing first-principles calculations within the framework of the local density approximation +U (LDA+U) approach, implemented in a full-potential linearized augmented plane-wave scheme. A systematic analysis of the An-5f states is performed which provides intuitive connections between the electronic structures and the local crystalline fields of the f states in the AnO2 series. Particularly the mechanisms leading to the experimentally observed insulating ground states are investigated. These are found to be caused by the strong spin-orbit and Coulomb interactions of the 5f orbitals; however, as a result of the different configurations, this mechanism works in distinctly different ways for each of the AnO2 compounds. In agreement with experimental observations, the nonmagnetic states of plutonium and curium dioxide are computed to be insulating, whereas those of uranium, neptunium, and americium dioxides require additional symmetry breaking to reproduce the insulator ground states, a condition which is met with magnetic phase transitions. We show that the occupancy of the An-f orbitals is closely connected to each of the appearing insulating mechanisms. We furthermore investigate the detailed constitution of the noncollinear multipolar moments for transverse 3q magnetic ordered states in UO2 and longitudinal 3q high-rank multipolar ordered states in NpO2 and AmO2.

  20. Actinide redox-active ligand complexes: reversible intramolecular electron-transfer in U(dpp-BIAN)2/U(dpp-BIAN)2(THF).

    PubMed

    Schelter, Eric J; Wu, Ruilian; Scott, Brian L; Thompson, Joe D; Cantat, Thibault; John, Kevin D; Batista, Enrique R; Morris, David E; Kiplinger, Jaqueline L

    2010-02-01

    Actinide complexes of the redox-active ligand (dpp-BIAN)(2-) (dpp-BIAN = 1,2-bis(2,6-diisopropylphenylimino)acenaphthylene), U(dpp-BIAN)(2) (1), U(dpp-BIAN)(2)(THF) (1-THF), and Th(dpp-BIAN)(2)(THF) (2-THF), have been prepared. Solid-state magnetic and single-crystal X-ray data for complex 1 indicate a ground-state U(IV)-pi*(4) configuration, whereas a (dpp-BIAN)(2-)-to-uranium electron transfer occurs for 1-THF, resulting in a U(III)-pi*(3) ground configuration. The solid-state magnetic data also indicate that interconversion between the two forms of the complex is possible, limited only by the ability of tetrahydrofuran (THF) vapor to penetrate the solid upon cooling of the sample. In contrast to those in the solid state, spectroscopic data acquired in THF indicate only the presence of the U(IV)-pi*(4) form for 1-THF in solution, evidenced by electronic absorption spectra and by measurement of the solution magnetic moment in THF-d(8) using the Evans method. Also reported is the electrochemistry of the complexes collected in CH(2)Cl(2), CF(3)C(6)H(5), and THF. As expected from the solution spectroscopic data, only small differences are observed in half-wave potentials of ligand-based processes in the presence of THF, consistent with the solution U(IV)-pi*(4) configuration of the complexes in all cases. Density functional theory calculations were undertaken for complexes 1 and 1-THF to determine if intrinsic energetic or structural factors underlie the observed charge-transfer process. While the calculated optimized geometries agree well with experimental results, it was not possible to arrive at a convergent solution for 1-THF in the U(III)-pi*(3) configuration. However, perturbations in the orbital energies in 1 versus 1-THF for the U(IV)-pi*(4) configuration do point to a diminished highest occupied molecular orbital-lowest unoccupied molecular orbital energy gap in 1-THF, consistent with the solid-state magnetic data. These results represent the first example

  1. Actinide (An = Th-Pu) dimetallocenes: promising candidates for metal-metal multiple bonds.

    PubMed

    Wang, Cong-Zhi; Gibson, John K; Lan, Jian-Hui; Wu, Qun-Yan; Zhao, Yu-Liang; Li, Jun; Chai, Zhi-Fang; Shi, Wei-Qun

    2015-10-21

    Synthesis of complexes with direct actinide-actinide (An-An) bonding is an experimental 'holy grail' in actinide chemistry. In this work, a series of actinide dimetallocenes An2Cp (Cp(*) = C5(CH3)5, An = Th-Pu) with An-An multiple bonds have been systematically investigated using quantum chemical calculations. The coaxial Cp(*)-An-An-Cp(*) structures are found to be the most stable species for all the dimetallocenes. A Th-Th triple bond is predicted in the Th2Cp complex, and the calculated An-An bond orders decrease across the actinide series from Pa to Pu. The covalent character of the An-An bonds is analyzed by using natural bond orbitals (NBO), molecular orbitals (MO), the quantum theory of atoms in molecules (QTAIM), and electron density difference (EDD). While Th 6d orbitals dominate the Th-Th bonds in Th2Cp, the An 6d-orbital characters decrease and 5f-orbital characters increase for complexes from Pa2Cp to Pu2Cp. All these actinide dimetallocenes are stable in the gas phase relative to the AnCp(*) reference at room temperature. Based on the reactions of AnCp and An, Th2Cp, Pa2Cp and possibly also U2Cp should be accessible as isolated molecules under suitable synthetic conditions. Our results shed light on the molecular design of ligands for stabilizing actinide-actinide multiple bonds.

  2. A new opportunity: coincident spectroscopy in neutron-deficient actinides

    NASA Astrophysics Data System (ADS)

    Gothe, Oliver; Gates, J. M.; Gregorich, K. E.; Baartman, B.; Fallon, P.; Esker, N. E.; Kwarsick, J.; Machiavelli, A. O.; Mudder, P. R.; Olive, D. T.; Pang, G.; Rissanen, J.; Nitsche, H.

    2014-09-01

    Due to high γ-ray background rates heavy element production facilities are usually not sensitive to the electron capture decay of neutron deficient actinides. We have developed new capabilities at the Berkeley Gas Filled Separator (BGS) that allow us to study these isotopes. The highly selective and efficient separation of compound nucleus evaporation residue products using the BGS couple with a rapid delivery to a low-background detector facility, opens up many new possibilities for nuclear decay and structure studies in the neutron deficient actinides. The decay of these actinides produces vacancies in the K-shell resulting in x-rays uniquely identifying the Z of the decay products. We present the first results of this new methodology in studying the nuclear structure of fermium-254 by observing the gamma rays in coincidence with fermium x-rays. Coincident gamma-decay spectroscopy gives us a new tool to study the nuclear structure of previously inaccessible systems.

  3. Adventures in Actinide Chemistry: A Year of Exploring Uranium and Thorium in Los Alamos

    SciTech Connect

    Pagano, Justin

    2016-01-08

    The first part of this collection of slides is concerned with considerations when working with actinides. The topics discussed in the document as a whole are the following: Actinide chemistry vs. transition metal chemistry--tools we can use; New synthetic methods to obtain actinide hydrides; Actinide metallacycles: synthesis, structure, and properties; and Reactivity of actinide metallacycles.

  4. First structural characterization of Pa(iv) in aqueous solution and quantum chemical investigations of the tetravalent actinides up to Bk(IV): the evidence of a curium break.

    PubMed

    Banik, Nidhu lal; Vallet, Valérie; Réal, Florent; Belmecheri, Réda Mohamed; Schimmelpfennig, Bernd; Rothe, Jörg; Marsac, Rémi; Lindqvist-Reis, Patric; Walther, Clemens; Denecke, Melissa A; Marquardt, Christian M

    2016-01-14

    More than a century after its discovery the structure of the Pa(4+) ion in acidic aqueous solution has been investigated for the first time experimentally and by quantum chemistry. The combined results of EXAFS data and quantum chemically optimized structures suggest that the Pa(4+) aqua ion has an average of nine water molecules in its first hydration sphere at a mean Pa-O distance of 2.43 Å. The data available for the early tetravalent actinide (An) elements from Th(4+) to Bk(4+) show that the An-O bonds have a pronounced electrostatic character, with bond distances following the same monotonic decreasing trend as the An(4+) ionic radii, with a decrease of the hydration number from nine to eight for the heaviest ions Cm(4+) and Bk(4+). Being the first open-shell tetravalent actinide, Pa(4+) features a coordination chemistry very similar to its successors. The electronic configuration of all open-shell systems corresponds to occupation of the valence 5f orbitals, without contribution from the 6d orbitals. Our results thus demonstrate that Pa(iv) resembles its early actinide neighbors.

  5. An instrument for the investigation of actinides with spin resolved photoelectron spectroscopy and bremsstrahlung isochromat spectroscopy

    SciTech Connect

    Yu, S.-W.; Tobin, J. G.; Chung, B. W.

    2011-01-01

    A new system for spin resolved photoelectron spectroscopy and bremsstrahlung isochromat spectroscopy has been built and commissioned at Lawrence Livermore National Laboratory for the investigation of the electronic structure of the actinides.Actinide materials are very toxic and radioactive and therefore cannot be brought to most general user facilities for spectroscopic studies. The technical details of the new system and preliminary data obtained therein will be presented and discussed.

  6. Sulfonate complexes of actinide ions: structural diversity in uranyl complexes with 2-sulfobenzoate.

    PubMed

    Thuéry, Pierre

    2013-01-07

    The reaction of uranyl nitrate hexahydrate with 2-sulfobenzoate (SB(2-)) in the presence of various amines gave the series of complexes [UO(2)(SB)(H(2)O)] (1), [UO(2)(SB)(H(2)O)](2)·pyz (2), [2,2'-bipyH](2)[UO(2)(SB)(2)(H(2)O)]·4H(2)O (3), [4,4'-bipyH(2)](2)[UO(2)(SB)(2)](2) (4), [4,4'-bipyH](2)[(UO(2))(2)(SB)(3)(H(2)O)]·4H(2)O (5), [NMe(4)](2)[(UO(2))(2)(SB)(3)(H(2)O)(1.15)]·1.35H(2)O (6), [NMe(4)](2)[(UO(2))(3)(SB)(2)O(2)] (7), and [H(2)DABCO](2)[(UO(2))(5)(SB)(4)O(2)(OH)(2)]·4H(2)O (8), where pyz = pyrazine, bipy = bipyridine, and DABCO = 1,4-diazabicyclo[2.2.2]octane, with all compounds but 5 having been obtained under hydrothermal conditions. The crystal structures of these complexes display a common motif in which uranyl is chelated by the carboxylate and sulfonate groups of SB, giving a seven-membered ring. Structure-directing effects due to the amine and the presence in 7 and 8 of additional μ(3)-oxo or μ(2)-hydroxo bridges result in much structural variety, with different bridging by the carboxylate and sulfonate groups giving rise to zero- (3, 4), one- (1, 5-8), or two-dimensional (2) assemblies. Some unusual uranyl secondary building units are observed, such as the pentanuclear [(UO(2))(5)O(2)(OH)(2)] discrete motif. Addition of 3d-block metal cations (Cu(2+), Ni(2+)) in the presence of nitrogen donors gave the heterometallic molecular complex [UO(2)Cu(SB)(2)(2,2'-bipy)(2)](2)·2H(2)O (9), the heterogeneous compound [Cu(4,4'-bipy)(H(2)O)(3)](2)[UO(2)(SB)(2)](2)·2H(2)O (10), in which molecular uranyl dimers are encompassing copper-containing chains, and the heterometallic one-dimensional polymers [(UO(2))(2)Cu(2)(SB)(4)(bipym)(H(2)O)(4)] (11) and [UO(2)Ni(SB)(2)(bipym)(H(2)O)(2)]·3H(2)O (12), where bipym = bipyrimidine. The latter two complexes display two different arrangements: in 11, bipym bridges two [UO(2)Cu(SB)(2)] chains to give a ladderlike assembly, while the uranyl cations are merely decorating species in 12. In contrast to those of

  7. Magnetic exchange coupling in actinide-containing molecules.

    PubMed

    Rinehart, Jeffrey D; Harris, T David; Kozimor, Stosh A; Bartlett, Bart M; Long, Jeffrey R

    2009-04-20

    Recent progress in the assembly of actinide-containing coordination clusters has generated systems in which the first glimpses of magnetic exchange coupling can be recognized. Such systems are of interest owing to the prospects for involving 5f electrons in stronger magnetic exchange than has been observed for electrons in the more contracted 4f orbitals of the lanthanide elements. Here, we survey the actinide-containing molecules thought to exhibit magnetic exchange interactions, including multiuranium, uranium-lanthanide, uranium-transition metal, and uranium-radical species. Interpretation of the magnetic susceptibility data for compounds of this type is complicated by the combination of spin-orbit coupling and ligand-field effects arising for actinide ions. Nevertheless, for systems where analogues featuring diamagnetic replacement components for the non-actinide spin centers can be synthesized, a data subtraction approach can be utilized to probe the presence of exchange coupling. In addition, methods have been developed for employing the resulting data to estimate lower and upper bounds for the exchange constant. Emphasis is placed on evaluation of the linear clusters (cyclam)M[(mu-Cl)U(Me(2)Pz)(4)](2) (M = Co, Ni, Cu, Zn; cyclam = 1,4,8,11-tetraazacyclotetradecane; Me(2)Pz(-) = 3,5-dimethylpyrazolate), for which strong ferromagnetic exchange with 15 cm(-1) < or = J < or = 48 cm(-1) is observed for the Co(II)-containing species. Owing to the modular synthetic approach employed, this system in particular offers numerous opportunities for adjusting the strength of the magnetic exchange coupling and the total number of unpaired electrons. To this end, the prospects of such modularity are discussed through the lens of several new related clusters. Ultimately, it is hoped that this research will be of utility in the development of electronic structure models that successfully describe the magnetic behavior of actinide compounds and will perhaps even lead to new

  8. Effect of pressure on f-electron delocalization and oxidation in actinide dioxides

    SciTech Connect

    Petit, Leon; Szotek, Zdzislawa; Temmerman, Walter M; Stocks, George Malcolm; Svane, Axel

    2014-08-01

    Using rstprinciplescalculations,wehaveinvestigatedf-electrondelocalizationandoxidationintheactinidedioxidesunderpressure.WhilstUO2isfoundonthevergeofaninsulatortometaltransitionattheequilibriumvolume,increasinglylargerpressuresarerequiredtodelocalizef-electronsinNpO2,PuO2,andAmO2,respectively49,112,and191GPa.Comparedtothisbroadrangeofpressures,theexper-imentallyobservedstructuraltransitions,inallfourdioxides,occurbetween30and40GPa,whichleadsustoconcludethattheassociatedvolumecollapseisnotduetof-electrondelocalization.Incontrast,oxi-dationofthedioxidesisfoundtobelinkedtothedegreeoff-electronlocalization,butitemergesthatfornaturallyoccurringpressures(<10GPa),higheroxidesonlyexistforUO2.

  9. Chemistry of the actinide elements. Second edition

    SciTech Connect

    Katz, J.J.; Seaborg, G.T.; Morss, L.R.

    1987-01-01

    This is an exhaustive, updated discourse on the chemistry of Actinides, Volume 1 contains a systematic coverage of the elements Ac, Th, Pa, U, Np, and Pu, which constitutes Part 1 of the work. The characterization of each element is discussed in terms of its nuclear properties, occurrence, preparation, atomic and metallic properties, chemistry of specific compounds, and solution chemistry. The first part of Volume 2 follows the same format as Volume 1 but is confined to the elements Am, Cm, Bk, Cf, and Es, plus a more condensed coverage of the Transeinsteinium elements (Fm, Md, No, Lw, and 104-109). Part 2 of this volume is devoted to a discussion of the actinide elements in general, with a specific focus on electronic spectra, thermodynamic and magnetic properties, the metallic state, structural chemistry, solution kinetics, organometallic chemistry for /sigma/- and /pi/-bonded compounds, and some concluding remarks on the superheavy elements.

  10. Patterns in the stability of the lower oxidation states of the actinides and lanthanides

    SciTech Connect

    Mikheev, N.B.; Auerman, L.N.; Ionova, G.V.; Korshunov, B.G.; Spitsyn, V.I.

    1986-09-01

    The authors compare the first half of the lanthanides and the second half of the actinides by considering the specifics of the electronic structure of the valence atoms of the f-, d-, and s-orbitals, consisting of he following: The lanthanides from praseodymium to europium and from dysprosium to ytterbium, as well as the actinides from californium to nobelium, have the same electronic configuration f /SUP n/ s/sub 2/ in the state of free neutral atoms, which corresponds to their divalent state. On the basis of a consideration of the energy characteristics of the valence orbitals of the elements of the lanthanide and actinide famililies and as a result of an experimental determination of the standard oxidation potential of these elements, the authors consider the profound similarity between the elements of the first half of the lanthanide family and the second half of the actinide family to be established.

  11. Pressure Induced Structural Phase Transition in Actinide Monophospides: Ab Initio Calculations

    NASA Astrophysics Data System (ADS)

    Makode, Chandrabhan; Sanyal, Sankar P.

    2011-07-01

    The structural and electronic properties of monophospides of Thorium, Uranium and Neptunium have been investigated using tight binding linear muffin-in-orbital (TB-LMTO) method within the local density approximation (LDA). From present study with the help of total energy calculations it is found that ThP, UP and NpP are stable in NaCl- type structure under ambient pressure. The structure stability of ThP, UP and NpP changes under the application of pressure. We predict a structural phase transition from NaCl-type (B1-phase) structure to CsCl-type (B2-phase) structure for these phospides in the pressure range of 37.0-24.0 GPa (ThP to NpP). The calculated equilibrium lattice parameters and bulk modulus are in good agreement with experimental and theoretical work.

  12. Pressure induced structural phase transition in actinide mono-bismuthides: Ab initio calculations

    NASA Astrophysics Data System (ADS)

    Pataiya, J.; Makode, C.; Aynyas, M.; Sanyal, Sankar P.

    2013-06-01

    The structural and electronic properties of mono-bismuthides of Plutonium and Americium have been investigated using tight binding linear muffin-tin-orbital (TB-LMTO) method within the local density approximation (LDA). From present study with the help of total energy calculations it is found that PuBi and AmBi are stable in NaCl - type structure under ambient pressure. The structure stability of PuBi and AmBi changes under the application of pressure. We predict a structural phase transition from NaCl-type (B1-phase) structure to CsCl-type (B2-phase) structure for these phospides in the pressure range of 45 - 4.5 GPa for PuBi and AmBi respectively. The calculated equilibrium lattice parameters and bulk modulus are in good agreement with experimental and theoretical work.

  13. Gas-phase reactions of doubly charged actinide cations with alkanes and alkenes--probing the chemical activity of 5f electrons from Th to Cm.

    PubMed

    Marçalo, Joaquim; Santos, Marta; Gibson, John K

    2011-11-07

    Small alkanes (methane, ethane, propane, n-butane) and alkenes (ethene, propene, 1-butene) were used to probe the gas-phase reactivity of doubly charged actinide cations, An(2+) (An = Th, Pa, U, Np, Pu, Am, Cm), by means of Fourier transform ion cyclotron resonance mass spectrometry. Different combinations of doubly and singly charged ions were observed as reaction products, comprising species formed via metal-ion induced eliminations of small molecules, simple adducts and ions resulting from electron, hydride or methide transfer channels. Th(2+), Pa(2+), U(2+) and Np(2+) preferentially yielded doubly charged products of hydrocarbon activation, while Pu(2+), Am(2+) and Cm(2+) reacted mainly through transfer channels. Cm(2+) was also capable of forming doubly charged products with some of the hydrocarbons whereas Pu(2+) and Am(2+) were not, these latter two ions conversely being the only for which adduct formation was observed. The product distributions and the reaction efficiencies are discussed in relation to the electronic configurations of the metal ions, the energetics of the reactions and similar studies previously performed with doubly charged lanthanide and transition metal cations. The conditions for hydrocarbon activation to occur as related to the accessibility of electronic configurations with one or two 5f and/or 6d unpaired electrons are examined and the possible chemical activity of the 5f electrons in these early actinide ions, particularly Pa(2+), is considered.

  14. Vapor pressure and thermodynamics of actinide metals

    SciTech Connect

    Ward, J.W.; Kleinschmidt, P.D.; Haire, R.G.; Brown, D.

    1980-01-01

    Precise vapor pressure measurements by target collection/mass spectrometric Knudsen effusion techniques were combined with crystal entropy estimates to produce self-consistent free-enrgy functions, permitting calculation of heats, entropies and free energies from 298/sup 0/K to the highest temperatures of measurement. The vapor pressures and thermodyamics of vaporization of americium, curium, berkelium, and californium are compared in terms of electronic structure and bonding trends in the trans-plutonium elements. These resuslts are contrasted with the behavior of the early actinides, with attention to energy states and possible effects of f-electron bonding. 9 figures, 4 tables.

  15. Narrowing the Range of Possible Solutions to the Pu Electronic Structure Problem: Developing a New Bremstrahlung Isohromat Spectroscopy Capability

    SciTech Connect

    Tobin, J G; Yu, S; Chung, B; Waddill, G; Kutepov, A

    2009-06-08

    Bremstrahlung Isochromat Spectroscopy (BIS) has a proven record for the probing of unoccupied electronic structure, including feasibility studies of actinides such as U and Th. A description of the BIS or Inverse Photoelectron Spectroscopy (IPES) process and of our reasoning concerning the potential importance of extending the application of BIS related techniques to the actinides, will be provided. To put this into the proper context, our past successes, using soft x-ray techniques to interrogate the electronic structure of Pu, will be briefly reviewed. Finally, the initial results of the calibration of the BIS device, including preliminary spectra from of the surrogate system CeOxide, will be presented.

  16. Electron Structure of Francium

    NASA Astrophysics Data System (ADS)

    Koufos, Alexander

    2012-02-01

    This talk presents the first calculations of the electronic structure of francium for the bcc, fcc and hcp structures, using the Augmented Plane Wave (APW) method in its muffin-tin and linearized general potential forms. Both the Local Density Approximation (LDA) and Generalized Gradient Approximation (GGA), were used to calculate the electronic structure and total energy of francium (Fr). The GGA and LDA both found the total energy of the hcp structure slightly below that of the fcc and bcc structure, respectively. This is in agreement with similar results for the other alkali metals using the same methodology. The equilibrium lattice constant, bulk modulus and superconductivity parameters were calculated. We found that under pressures, in the range of 1-5 GPa, Fr could be a superconductor at a critical temperature of about 4K.

  17. High pressure phase transformations in yttrium and scandium: Relation to rare earths and actinides crystal structures

    NASA Astrophysics Data System (ADS)

    Grosshans, W. A.; Vohra, Y. K.; Holzapfel, W. B.

    1982-10-01

    The phase transformations in the 4d transition metal yttrium (Y) and the 3d transition metal scandium (Sc) have been studied under pressures up to 45 GPa by energy dispersive X-ray diffraction. The metal Y shows the complete rare earth crystal structure sequence i.e. hcp→Sm-type→dhcp→fcc with increasing pressure. This establishes experimentally the similarity of Y with heavy lanthanides, and that the rare earth crystal structure sequence is driven by s→d transfer without any significant contribution from 4f electrons. The metal Sc does not undergo the rare earth crystal structure sequence with pressure but shows above 20 GPa β-Neptunium (Np) structure (tetragonal, 4 atoms/cell). This structure remains stable up to the highest pressure of 45 GPa. The occurence of the high temperature β-Np structure in trivalent Sc combined with large thermal expansions of Np and plutonium (Pu) suggest that itinerant 5f electrons become localized at high temperature in Np and Pu close to melting. This Mott transition with temperature is similar to the one observed between Pu and americium (Am).

  18. The first case of actinide triple helices: pH-dependent structural evolution and kinetically-controlled transformation of two supramolecular conformational isomers.

    PubMed

    An, Shu-wen; Mei, Lei; Wang, Cong-zhi; Xia, Chuan-qin; Chai, Zhi-fang; Shi, Wei-qun

    2015-05-28

    The first actinide triple helices, including two supramolecular conformational isomers of uranium(VI), have been synthesized with the aid of a flexible V-shaped ligand and a rigid aromatic base. The isomers exhibit an intriguing pH-dependent structural evolution and a kinetically-controlled transformation via a novel conformational rearrangement of the organic base.

  19. Density functional theory studies of actinide(III) motexafins (An-Motex2+, An = Ac, Cm, Lr). Structure, stability, and comparison with lanthanide(III) motexafins.

    PubMed

    Cao, Xiaoyan; Li, Quansong; Moritz, Anna; Xie, Zhizhong; Dolg, Michael; Chen, Xuebo; Fang, Weihai

    2006-04-17

    Newly developed relativistic energy-consistent 5f-in-core actinide pseudopotentials and corresponding (7s6p5d1f)/[5s4p3d1f] basis sets in the segmented contraction scheme, combined with density functional theory methods, have been used to study the molecular structure and chemical properties of selected actinide(III) motexafins (An-Motex2+, An = Ac, Cm, Lr). Structure and stability are discussed, and a comparison to the lanthanide(III) motexafins (Ln-Motex2+, Ln = La, Gd, Lu) is made. The actinide element is found to reside above the mean N5 motexafin plane, and the larger the cation, the greater the observed out-of-plane displacement. It is concluded that the actinium(III), curium(III), and lawrencium(III) cations are tightly bound to the macrocyclic skeleton, yielding stable structures. However, the calculated metal-ligand gas-phase binding energy for An-Motex2+ is about 1-2 eV lower than that of Ln-Motex2+, implying a lower stability of An-Motex2+ compared to Ln-Motex2+. Results including solvent effects imply that Ac-Motex2+ is the most stable complex in aqueous solution and should be the best candidate for experimentalists to get stable actinide(III) motexafin complexes.

  20. Loading Actinides in Multilayered Structures for Nuclear Waste Treatment: The First Case Study of Uranium Capture with Vanadium Carbide MXene.

    PubMed

    Wang, Lin; Yuan, Liyong; Chen, Ke; Zhang, Yujuan; Deng, Qihuang; Du, Shiyu; Huang, Qing; Zheng, Lirong; Zhang, Jing; Chai, Zhifang; Barsoum, Michel W; Wang, Xiangke; Shi, Weiqun

    2016-06-29

    Efficient nuclear waste treatment and environmental management are important hurdles that need to be overcome if nuclear energy is to become more widely used. Herein, we demonstrate the first case of using two-dimensional (2D) multilayered V2CTx nanosheets prepared by HF etching of V2AlC to remove actinides from aqueous solutions. The V2CTx material is found to be a highly efficient uranium (U(VI)) sorbent, evidenced by a high uptake capacity of 174 mg g(-1), fast sorption kinetics, and desirable selectivity. Fitting of the sorption isotherm indicated that the sorption followed a heterogeneous adsorption model, most probably due to the presence of heterogeneous adsorption sites. Density functional theory calculations, in combination with X-ray absorption fine structure characterizations, suggest that the uranyl ions prefer to coordinate with hydroxyl groups bonded to the V-sites of the nanosheets via forming bidentate inner-sphere complexes.

  1. Functionalization of borate networks by the incorporation of fluoride: Syntheses, crystal structures; and nonlinear optical properties of novel actinide fluoroborates

    SciTech Connect

    Wang, Shuao; Alekseev, Evgeny V.; Diwu, Juan; Miller, Hannah M.; Oliver, Allen G.; Liu, Guokui; Depmeier, Wulf; Albrecht-Schmitt, Thomas E.

    2011-06-14

    The boric acid flux reactions of uranyl nitrate with sodium, potassium, rubidium, or thallium fluoride result in the formation of a novel family of uranyl(VI) fluoroborate materials. These compounds are Na[(UO₂)B₅O₈(OH)F]·H₂O (NaUBOF-1), K[(UO₂)B₅O₈(OH)F] (KUBOF-1), K₁₁[(UO₂)₆B₂₄O₃₆F₂₂)](H₂BO₃) (KUBOF-2), Rb[(UO₂)B₅O₈(OH)F] (RbUBOF-1), and Tl[(UO₂)B₅O₈(OH)F] (TlUBOF-1). A new neptunium(VI) fluoroborate that is isotypic with NaUBOF-1, Na[(NpO₂)B₅O₈(OH)F]·H₂O (NaNpBOF-1), was synthesized via the boric acid flux reaction of neptunium(VI) nitrate with sodium fluoride. These new actinide fluoroborates share a common structural motif consisting of a linear actinyl (U(Np)O₂2+) cation surrounded by BO₃ triangles and BO₄ tetrahedra to create an U(Np)O₈ hexagonal bipyramidal environment around uranium or neptunium. The borate anions bridge between actinyl units to create layers. B–F bonds were formed during the reactions to yield BO₃F tetrahedral units. The BO3F tetrahedra and additional BO₃ triangles extend from the actinyl polyborate layers and are directed approximately perpendicular to the layers. A novel actinyl borate layered topology was found in K₁₁[(UO₂)₆B₂₄O₃₆F₂₂)](H₂BO₃) (KUBOF-2). Except for K[(UO₂)B₅O₈(OH)F] (KUBOF-1) and K₁₁[(UO₂)₆B₂₄O₃₆F₂₂)](H₂BO₃) (KUBOF-2), all of the other actinide fluoroborate phases adopt noncentrosymmetric space groups. Tl[(UO₂)B₅O₈(OH)F] (TlUBOF-1), which can be obtained as a pure phase, displays second-harmonic generation of 532-nm light from 1064-nm light.

  2. Actinide metal processing

    DOEpatents

    Sauer, N.N.; Watkin, J.G.

    1992-03-24

    A process for converting an actinide metal such as thorium, uranium, or plutonium to an actinide oxide material by admixing the actinide metal in an aqueous medium with a hypochlorite as an oxidizing agent for sufficient time to form the actinide oxide material and recovering the actinide oxide material is described together with a low temperature process for preparing an actinide oxide nitrate such as uranyl nitrate. Additionally, a composition of matter comprising the reaction product of uranium metal and sodium hypochlorite is provided, the reaction product being an essentially insoluble uranium oxide material suitable for disposal or long term storage.

  3. Actinide metal processing

    DOEpatents

    Sauer, Nancy N.; Watkin, John G.

    1992-01-01

    A process of converting an actinide metal such as thorium, uranium, or plnium to an actinide oxide material by admixing the actinide metal in an aqueous medium with a hypochlorite as an oxidizing agent for sufficient time to form the actinide oxide material and recovering the actinide oxide material is provided together with a low temperature process of preparing an actinide oxide nitrate such as uranyl nitrte. Additionally, a composition of matter comprising the reaction product of uranium metal and sodium hypochlorite is provided, the reaction product being an essentially insoluble uranium oxide material suitable for disposal or long term storage.

  4. Actinides and Life's Origins

    NASA Astrophysics Data System (ADS)

    Adam, Zachary

    2007-12-01

    There are growing indications that life began in a radioactive beach environment. A geologic framework for the origin or support of life in a Hadean heavy mineral placer beach has been developed, based on the unique chemical properties of the lower-electronic actinides, which act as nuclear fissile and fertile fuels, radiolytic energy sources, oligomer catalysts, and coordinating ions (along with mineralogically associated lanthanides) for prototypical prebiotic homonuclear and dinuclear metalloenzymes. A four-factor nuclear reactor model was constructed to estimate how much uranium would have been required to initiate a sustainable fission reaction within a placer beach sand 4.3 billion years ago. It was calculated that about 1-8 weight percent of the sand would have to have been uraninite, depending on the weight percent, uranium enrichment, and quantity of neutron poisons present within the remaining placer minerals. Radiolysis experiments were conducted with various solvents with the use of uranium- and thorium-rich minerals (metatorbernite and monazite, respectively) as proxies for radioactive beach sand in contact with different carbon, hydrogen, oxygen, and nitrogen reactants. Radiation bombardment ranged in duration of exposure from 3 weeks to 6 months. Low levels of acetonitrile (estimated to be on the order of parts per billion in concentration) were conclusively identified in 2 setups and tentatively indicated in a 3rd by gas chromatography/mass spectrometry. These low levels have been interpreted within the context of a Hadean placer beach prebiotic framework to demonstrate the promise of investigating natural nuclear reactors as power production sites that might have assisted the origins of life on young rocky planets with a sufficiently differentiated crust/mantle structure. Future investigations are recommended to better quantify the complex relationships between energy release, radioactive grain size, fissionability, reactant phase, phosphorus

  5. Actinides and Life's Origins.

    PubMed

    Adam, Zachary

    2007-12-01

    There are growing indications that life began in a radioactive beach environment. A geologic framework for the origin or support of life in a Hadean heavy mineral placer beach has been developed, based on the unique chemical properties of the lower-electronic actinides, which act as nuclear fissile and fertile fuels, radiolytic energy sources, oligomer catalysts, and coordinating ions (along with mineralogically associated lanthanides) for prototypical prebiotic homonuclear and dinuclear metalloenzymes. A four-factor nuclear reactor model was constructed to estimate how much uranium would have been required to initiate a sustainable fission reaction within a placer beach sand 4.3 billion years ago. It was calculated that about 1-8 weight percent of the sand would have to have been uraninite, depending on the weight percent, uranium enrichment, and quantity of neutron poisons present within the remaining placer minerals. Radiolysis experiments were conducted with various solvents with the use of uraniumand thorium-rich minerals (metatorbernite and monazite, respectively) as proxies for radioactive beach sand in contact with different carbon, hydrogen, oxygen, and nitrogen reactants. Radiation bombardment ranged in duration of exposure from 3 weeks to 6 months. Low levels of acetonitrile (estimated to be on the order of parts per billion in concentration) were conclusively identified in 2 setups and tentatively indicated in a 3(rd) by gas chromatography/mass spectrometry. These low levels have been interpreted within the context of a Hadean placer beach prebiotic framework to demonstrate the promise of investigating natural nuclear reactors as power production sites that might have assisted the origins of life on young rocky planets with a sufficiently differentiated crust/mantle structure. Future investigations are recommended to better quantify the complex relationships between energy release, radioactive grain size, fissionability, reactant phase, phosphorus

  6. Electronic structure and bonding in transuranics: comparison with lanthanides

    SciTech Connect

    Ward, J.W.

    1983-01-01

    The physico-chemical properties of the actinide metals, alloys, and compounds show interesting parallels and contrasts with the rare earths, beyond uranium. At first there is a transition region where the unique bonding properties of the early actinides become less prominent, due to progressive f-electron localization. Nevertheless, in contrast to the rare earths, f-electron energies remain close to the Fermi level, resulting in complex behavior as a function of temperature, pressure and structure. Particularly interesting in this region are the metallic hydrides, whose chemistry is clearly rare-earth like, but whose electronic properties are entirely different. At americium a major localization and f-band narrowing occurs, but the explanation of americium behavior is obscured by the occurrence of the unique f/sup 6/ non-magnetic solid-state configuration. Beyond americium, it would appear that real rare-earth-like behavior finally begins; this has been born out by recent studies on the thermodynamics and cohesive energies of curium, berkelium, californium and einsteinium metals. However, a new complication arises almost immediately, in the onset of incipient stabilization of the divalent state, which already appears in californium, whose physico-chemical properties are remarkably similar to samarium. Einsteinium appears to be fully divalent, thus heralding the beginning of a mini-series of truly divalent metals.

  7. A moving target: responding to magnetic and structural disorder in lanthanide- and actinide-based superconductors

    SciTech Connect

    Booth, Corwin H.; Bauer, Eric D.; Mitchel, Jeremy N.

    2010-02-10

    The effects of various chemical substitutions and induced lattice disorder in the Ce- and Pu-based 115 superconductors are reviewed, with particular emphasis on results from x-ray absorption fine structure (XAFS) measurements. The PuCoGa{sub 5} system offers the opportunity to follow changes in magnetic and electronic properties due to lattice disorder as a function of time in the same samples, in addition to the more traditional approach of perturbing the superconducting state through chemical substitutions. The reviewed work establishes a baseline for such future studies by determining the intrinsic lattice order in the 115 system, successfully understanding disorder as introduced through chemical substitutions in the Ce-based 115s, and beginning to explore the surprisingly large role of self-irradiation damage directly on the PuCoGa{sub 5} lattice. These studies lay the foundation for the harder future work toward measuring chemical substitutions in PuCoGa{sub 5}, correlating effects with non-Fermi liquid behavior, and obtaining a better structural picture of the distortions induced by {alpha}-decay of the plutonium nucleus.

  8. Theoretical atomic volumes of the light actinides

    SciTech Connect

    Jones, M. D.; Boettger, J. C.; Albers, R. C.; Singh, D. J.

    2000-02-15

    The zero-pressure zero-temperature equilibrium volumes and bulk moduli are calculated for the light actinides Th through Pu using two independent all-electron, full-potential, electronic-structure methods: the full-potential linear augmented-plane-wave method and the linear combinations of Gaussian-type orbitals-fitting function method. The results produced by these two distinctly different electronic-structure techniques are in good agreement with each other, but differ significantly from previously published calculations using the full-potential linear muffin-tin-orbital (FP-LMTO) method. The theoretically calculated equilibrium volumes are in some cases nearly 10% larger than the previous FP-LMTO calculations, bringing them much closer to the experimentally observed volumes. We also discuss the anomalous upturn in equilibrium volume seen experimentally for {alpha}-Pu. (c) 2000 The American Physical Society.

  9. Actinide-ion sensor

    DOEpatents

    Li, Shelly X; Jue, Jan-fong; Herbst, Ronald Scott; Herrmann, Steven Douglas

    2015-01-13

    An apparatus for the real-time, in-situ monitoring of actinide-ion concentrations. A working electrolyte is positioned within the interior of a container. The working electrolyte is separated from a reference electrolyte by a separator. A working electrode is at least partially in contact with the working electrolyte. A reference electrode is at least partially in contact with the reference electrolyte. A voltmeter is electrically connected to the working electrode and the reference electrode. The working electrolyte comprises an actinide-ion of interest. The separator is ionically conductive to the actinide-ion of interest. The separator comprises an actinide, Zr, and Nb. Preferably, the actinide of the separator is Am or Np, more preferably Pu. In one embodiment, the actinide of the separator is the actinide of interest. In another embodiment, the separator further comprises P and O.

  10. Actinide biocolloid formation in brine by halophilic bacteria

    SciTech Connect

    Gillow, J.B.; Francis, A.J.; Dodge, C.J.; Harris, R.; Beveridge, T.J.; Brady, P.V.; Papenguth, H.W.

    1998-12-31

    The authors examined the ability of a halophilic bacterium (WIPP 1A) isolated from the Waste Isolation Pilot Plant (WIPP) site to accumulate uranium in order to determine the potential for biocolloid facilitated actinide transport. The bacterial cell surface functional groups involved in the complexation of the actinide were determined by titration. Uranium, added as uranyl nitrate, was removed from solution at pH 5 by cells but at pH 7 and 9 very little uranium was removed due to its limited solubility. Although present as soluble species, uranyl citrate at pH 5, 7, and 9, and uranyl carbonate at pH 9 were not removed by the bacterium because they were not bioavailable due to their neutral or negative charge. Addition of uranyl EDTA to brine at pH 5, 7, and 9 resulted in the immediate precipitation of U. Transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) analysis revealed that uranium was not only associated with the cell surface but also accumulated intracellularly as uranium-enriched granules. Extended X-ray absorption fine structure (EXAFS) analysis of the bacterial cells indicated the bulk sample contained more than one uranium phase. Nevertheless these results show the potential for the formation of actinide bearing bacterial biocolloids that are strictly regulated by the speciation and bioavailability of the actinide.

  11. Actinide Biocolloid Formation in Brine by Halophilic Bacteria

    SciTech Connect

    Gillow, J.B.; Francis, A.J.; Dodge, C.J.; Harris, R.; Beveridge, T.J.; Brady, P.V.; Papenguth, H.W.

    1999-07-28

    We examined the ability of a halophilic bacterium (WFP 1A) isolated from the Waste Isolation Pilot Plant (WIPP) site to accumulate uranium in order to determine the potential for biocolloid facilitated actinide transport. The bacterial cell Surface functional groups involved in the complexation of the actinide were determined by titration. Uranium, added as uranyl nitrate, was removed from solution at pH 5 by cells but at pH 7 and 9 very little uranium was removed due to its limited volubility. Although present as soluble species, uranyl citrate at pH 5, 7, and 9, and uranyl carbonate at pH 9 were not removed by the bacterium because they were not bioavailable due to their neutral or negative charge. Addition of uranyl EDTA to brine at pH 5, 7, and 9 resulted in the immediate precipitation of U. Transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) analysis revealed that uranium was not only associated with the cell surface but also accumulated intracellulary as uranium-enriched granules. Extended X-ray absorption fine structure (EXAFS) analysis, of the bacterial cells indicated the bulk sample contained more than one uranium phase. Nevertheless these results show the potential for the formation of actinide bearing bacterial biocolloids that are strictly regulated by the speciation and bioavailability of the actinide.

  12. ACTINIDE BIOCOLLOID FORMATION IN BRINE BY HALOPHILIC BACTERIA

    SciTech Connect

    GILLOW,J.B.; FRANCIS,A.J.; DODGE,C.J.; HARRIS,R.; BEVERIDGE,T.J.; BRADY,P.B.; PAPENGUTH,H.W.

    1998-11-09

    The authors examined the ability of a halophilic bacterium (WIPP 1A) isolated from the Waste Isolation Pilot Plant (WIPP) site to accumulate uranium in order to determine the potential for biocolloid facilitated actinide transport. The bacterial cell surface functional groups involved in the complexation of the actinide were determined by titration. Uranium, added as uranyl nitrate, was removed from solution at pH 5 by cells but at pH 7 and 9 very little uranium was removed due to its limited solubility. Although present as soluble species, uranyl citrate at pH 5, 7, and 9, and uranyl carbonate at pH 9 were not removed by the bacterium because they were not bioavailable due to their neutral or negative charge. Addition of uranyl EDTA to brine at pH 5, 7, and 9 resulted in the immediate precipitation of U. Transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) analysis revealed that uranium was not only associated with the cell surface but also accumulated intracellularly as uranium-enriched granules. Extended X-ray absorption fine structure (EXAFS) analysis of the bacterial cells indicated the bulk sample contained more than one uranium phase. Nevertheless these results show the potential for the formation of actinide bearing bacterial biocolloids that are strictly regulated by the speciation and bioavailability of the actinide.

  13. Chemical properties of the heavier actinides and transactinides

    SciTech Connect

    Hulet, E.K.

    1981-01-01

    The chemical properties of each of the elements 99 (Es) through 105 are reviewed and their properties correlated with the electronic structure expected for 5f and 6d elements. A major feature of the heavier actinides, which differentiates them from the comparable lanthanides, is the increasing stability of the divalent oxidation state with increasing atomic number. The divalent oxidation state first becomes observable in the anhydrous halides of californium and increases in stability through the series to nobelium, where this valency becomes predominant in aqueous solution. In comparison with the analogous 4f electrons, the 5f electrons in the latter part of the series are more tightly bound. Thus, there is a lowering of the 5f energy levels with respect to the Fermi level as the atomic number increases. The metallic state of the heavier actinides has not been investigated except from the viewpoint of the relative volatility among members of the series. In aqueous solutions, ions of these elements behave as a normal trivalent actinides and lanthanides (except for nobelium). Their ionic radii decrease with increasing nuclear charge which is moderated because of increased screening of the outer 6p electrons by the 5f electrons. The actinide series of elements is completed with the element lawrencium (Lr) in which the electronic configuration is 5f/sup 14/7s/sup 2/7p. From Mendeleev's periodicity and Dirac-Fock calculations, the next group of elements is expected to be a d-transition series corresponding to the elements Hf through Hg. The chemical properties of elements 104 and 105 only have been studied and they indeed appear to show the properties expected of eka-Hf and eka-Ta. However, their nuclear lifetimes are so short and so few atoms can be produced that a rich variety of chemical information is probably unobtainable.

  14. First principles study of the electron-phonon coupling on the light-actinides Ac-Th alloy: effect of spin-orbit coupling

    NASA Astrophysics Data System (ADS)

    de La Peña Seaman, Omar; de Coss-Martinez, Romeo; Gonzalez-Castelazo, Paola; Heid, Rolf; Bohnen, Klaus-Peter

    We have studied the electronic, lattice dynamics, and electron-phonon (e-ph) properties of the Ac1-xThx actinide alloy. This system have been studied within the framework of density functional perturbation theory, using a mixed-basis pseudopotential method and the virtual crystal approximation (VCA) for modeling the alloy. The electronic density of states (DOS), the full-phonon dispersion as well as the Eliashberg spectral function (α2 F (ω)) and the electron-phonon coupling (λ) parameter have been calculated with and without the inclusion of spin-orbit coupling (SOC). For Ac the observed effects of SOC on α2 F (ω) are very minor. However, as Th-content increases on the alloy the SOC influence is more important. Such evolution has its roots on a continuous increase of density of states at the Fermi level (N (EF)) difference between schemes, as well as a steady hardening of the SOC full phonon dispersion. The evolution of λ as a function of Th-content for both schemes is presented and discussed on the light of SOC effects on the electronic and vibrational properties. This research was supported by Conacyt-México under Project No. 221807.

  15. Electronic structure and magnetic state of transuranium metals under pressure.

    PubMed

    Lukoyanov, A V; Shorikov, A O; Bystrushkin, V B; Dyachenko, A A; Kabirova, L R; Tsiovkin, Yu Yu; Povzner, A A; Dremov, V V; Korotin, M A; Anisimov, V I

    2010-12-15

    The electronic structures of bcc Np, fcc Pu, Am, and Cm pure metals under pressure have been investigated employing the LDA + U method with spin-orbit coupling (LDA + U + SO). The magnetic state of the actinide ions was analyzed in both LS and jj coupling schemes to reveal the applicability of corresponding coupling bases. It was demonstrated that whereas Pu and Am are well described within the jj coupling scheme, Np and Cm can be described appropriately neither in a {mσ}, nor in a {jmj} basis, due to intermediate coupling scheme realization in these metals that requires some finer treatment. The LDA + U + SO results for the considered transuranium metals reveal band broadening and gradual 5f electron delocalization under pressure.

  16. Emergence of californium as the second transitional element in the actinide series

    SciTech Connect

    Cary, Samantha K.; Vasiliu, Monica; Baumbach, Ryan E.; Stritzinger, Jared T.; Green, Thomas D.; Diefenbach, Kariem; Cross, Justin N.; Knappenberger, Kenneth L.; Liu, Guokui; Silver, Mark A.; DePrince, A. Eugene; Polinski, Matthew J.; Van Cleve, Shelley M.; House, Jane H.; Kikugawa, Naoki; Gallagher, Andrew; Arico, Alexandra A.; Dixon, David A.; Albrecht-Schmitt, Thomas E.

    2015-04-16

    A break in periodicity occurs in the actinide series between plutonium and americium as the result of the localization of 5f electrons. The subsequent chemistry of later actinides is thought to closely parallel lanthanides in that bonding is expected to be ionic and complexation should not substantially alter the electronic structure of the metal ions. Here we demonstrate that ligation of californium(III) by a pyridine derivative results in significant deviations in the properties of the resultant complex with respect to that predicted for the free ion. We expand on this by characterizing the americium and curium analogues for comparison, and show that these pronounced effects result from a second transition in periodicity in the actinide series that occurs, in part, because of the stabilization of the divalent oxidation state. As a result, the metastability of californium(II) is responsible for many of the unusual properties of californium including the green photoluminescence.

  17. Emergence of californium as the second transitional element in the actinide series

    DOE PAGES

    Cary, Samantha K.; Vasiliu, Monica; Baumbach, Ryan E.; ...

    2015-04-16

    A break in periodicity occurs in the actinide series between plutonium and americium as the result of the localization of 5f electrons. The subsequent chemistry of later actinides is thought to closely parallel lanthanides in that bonding is expected to be ionic and complexation should not substantially alter the electronic structure of the metal ions. Here we demonstrate that ligation of californium(III) by a pyridine derivative results in significant deviations in the properties of the resultant complex with respect to that predicted for the free ion. We expand on this by characterizing the americium and curium analogues for comparison, andmore » show that these pronounced effects result from a second transition in periodicity in the actinide series that occurs, in part, because of the stabilization of the divalent oxidation state. As a result, the metastability of californium(II) is responsible for many of the unusual properties of californium including the green photoluminescence.« less

  18. Emergence of californium as the second transitional element in the actinide series

    PubMed Central

    Cary, Samantha K.; Vasiliu, Monica; Baumbach, Ryan E.; Stritzinger, Jared T.; Green, Thomas D.; Diefenbach, Kariem; Cross, Justin N.; Knappenberger, Kenneth L.; Liu, Guokui; Silver, Mark A.; DePrince, A. Eugene; Polinski, Matthew J.; Van Cleve, Shelley M.; House, Jane H.; Kikugawa, Naoki; Gallagher, Andrew; Arico, Alexandra A.; Dixon, David A.; Albrecht-Schmitt, Thomas E.

    2015-01-01

    A break in periodicity occurs in the actinide series between plutonium and americium as the result of the localization of 5f electrons. The subsequent chemistry of later actinides is thought to closely parallel lanthanides in that bonding is expected to be ionic and complexation should not substantially alter the electronic structure of the metal ions. Here we demonstrate that ligation of californium(III) by a pyridine derivative results in significant deviations in the properties of the resultant complex with respect to that predicted for the free ion. We expand on this by characterizing the americium and curium analogues for comparison, and show that these pronounced effects result from a second transition in periodicity in the actinide series that occurs, in part, because of the stabilization of the divalent oxidation state. The metastability of californium(II) is responsible for many of the unusual properties of californium including the green photoluminescence. PMID:25880116

  19. Emergence of californium as the second transitional element in the actinide series.

    PubMed

    Cary, Samantha K; Vasiliu, Monica; Baumbach, Ryan E; Stritzinger, Jared T; Green, Thomas D; Diefenbach, Kariem; Cross, Justin N; Knappenberger, Kenneth L; Liu, Guokui; Silver, Mark A; DePrince, A Eugene; Polinski, Matthew J; Van Cleve, Shelley M; House, Jane H; Kikugawa, Naoki; Gallagher, Andrew; Arico, Alexandra A; Dixon, David A; Albrecht-Schmitt, Thomas E

    2015-04-16

    A break in periodicity occurs in the actinide series between plutonium and americium as the result of the localization of 5f electrons. The subsequent chemistry of later actinides is thought to closely parallel lanthanides in that bonding is expected to be ionic and complexation should not substantially alter the electronic structure of the metal ions. Here we demonstrate that ligation of californium(III) by a pyridine derivative results in significant deviations in the properties of the resultant complex with respect to that predicted for the free ion. We expand on this by characterizing the americium and curium analogues for comparison, and show that these pronounced effects result from a second transition in periodicity in the actinide series that occurs, in part, because of the stabilization of the divalent oxidation state. The metastability of californium(II) is responsible for many of the unusual properties of californium including the green photoluminescence.

  20. Studies of electronic configurations in the emission spectra of lanthanides and actinides: application to the interpretation of Es I and Es II, predictions for Fm I

    SciTech Connect

    Wyart, Jean-Francois . E-mail: jean-francois.wyart@lac.u-psud.fr; Blaise, Jean; Worden, Earl F.

    2005-02-15

    The interpretation of the spectra of free atoms and gaseous ions in the 4f{sup N} and 5f{sup N} periods became less active after critical compilations of energy levels appeared. However, several spectra are still under study and the application of the Racah-Slater and HFR methods to extended sets of configurations leads to revisions and additions. In doubly charged ions of lanthanides, the treatment of configuration interaction by means of effective parameters and by extension of the basis of states are both important. Concerning actinides, calculations of several observables (Lande factors and isotope shifts in Pu I, hyperfine constants, transition probabilities) prove the quality of eigenfunctions. The classification of Es I and Es II has been extended and radial parameters for fine and hyperfine structures have been derived. Level predictions for the next element fermium are supported by parameter extrapolations.

  1. Actinide extraction methods

    DOEpatents

    Peterman, Dean R [Idaho Falls, ID; Klaehn, John R [Idaho Falls, ID; Harrup, Mason K [Idaho Falls, ID; Tillotson, Richard D [Moore, ID; Law, Jack D [Pocatello, ID

    2010-09-21

    Methods of separating actinides from lanthanides are disclosed. A regio-specific/stereo-specific dithiophosphinic acid having organic moieties is provided in an organic solvent that is then contacted with an acidic medium containing an actinide and a lanthanide. The method can extend to separating actinides from one another. Actinides are extracted as a complex with the dithiophosphinic acid. Separation compositions include an aqueous phase, an organic phase, dithiophosphinic acid, and at least one actinide. The compositions may include additional actinides and/or lanthanides. A method of producing a dithiophosphinic acid comprising at least two organic moieties selected from aromatics and alkyls, each moiety having at least one functional group is also disclosed. A source of sulfur is reacted with a halophosphine. An ammonium salt of the dithiophosphinic acid product is precipitated out of the reaction mixture. The precipitated salt is dissolved in ether. The ether is removed to yield the dithiophosphinic acid.

  2. Electronic energy level and intensity correlations in the spectra of the trivalent actinide aquo ions. III. Bk/sup 3 +/

    SciTech Connect

    Carnall, W.T.; Beitz, J.V.; Crosswhite, H.

    1984-03-15

    The solution absorption spectrum of Bk/sup 3 +/(aquo) was measured and the observed band structure interpreted in terms of a free-ion energy level model. The band intensities were successfully analyzed using the Judd--Ofelt theory for transitions within the f/sup tsN/ configuration. Parameters of the theory were then used to compute fluorescence branching ratios from most probable fluorescing states, and an experimental search was successful in yielding evidence for a transition from one excited state to the ground state in D/sub 2/O solvent. Absorption bands attributed to f ..-->.. d transitions were observed and an interpretation of the electronic structure is presented. Band intensities were compared to those observed for Tb/sup 3 +/(aquo).

  3. Specific sequestering agents for the actinides. VI. Synthetic and structural chemistry of tetrakis(N-alkylalkanehydroxamato)thorium(IV) complexes

    SciTech Connect

    Smith, W.L.; Raymond, K.N.

    1981-06-17

    Hydroxamate complexes of the actinides have been investigated as structural archetypes in the design of actinide-specific sequestering agents. The complexes Th((CH/sub 3/)/sub 2/CHN(O)O(O)R)/sub 4/ have been prepared (R = C(CH/sub 3/)/sub 3/ (1) or CH/sub 2/C(CH/sub 3/)/sub 3/ (2) The uranium(IV) analogue of 1 was also prepared. The tert-butyl groups of 1 dominate the stereochemistry of the complex by assuming a tetrahedral disposition around the metal. The coordination polyhedron of 1, which has 4 (S/sub 4/) crystallographic symmetry, is nearly cubic. The localization of charge on the nitrogen oxygen of the hydroxamate group makes this ligand unsymmetrical, and this gives rise to a 0.14-A difference in R(Th-O/sub N/) (2.357(3) A) and R(Th-O/sub C/) (2.492 (3) A). The sterically less constrained neopentyl derivative 2 shows a more typical eight-coordinate geometry - the D/sub 2d/ trigonal-faced (mmmm) dodecahedron. The average R(Th-O/sub N/) (2.36 (1) A) is again shorter than R(Th-O/sub C/) (2.46 (2) A). There is apparently no sorting of sites by ligand charge, since the O/sub N/ and O/sub C/ atoms are equally distributed between the A and B sites of the dodecahedron. Crystals of 1 conform to space group I4/sub 1//a with a = 17.338 (4) A and c = 12.706 (4) A. For 4 formula units per cell the calculated density d/sub calcd/ is 1.50 g cm/sup -3/ and d/sub obsd/ is 1.50 (1) g cm/sup -3/. Crystals of 2 conform to space group P1 with a = 9.777 (2) A, b = 14.633 (2) A, c = 18.515 (1) A, ..cap alpha.. = 74.061/sub 0/ (8), ..beta.. = 88.41 (1)/sup 0/, and ..gamma.. = 74.71 (2)/sup 0/. For 2 formula units per cell d/sub calcd/ = 1.30 g cm/sup -3/ and d/sub obsd/ = 1.19 g cm/sup -3/. Full-matrix least-squares refinement of both structures using all averaged, independent data with F/sup 2/ > 3sigma(F)/sup 2/ gave for 1 with 1798 data and 117 variables R = 0.027 and R/sub w/ = 0.032 and for 2 with 6978 data and 467 variables R = 0.034, R/sub w/ = 0.042. 10 figures, 11 tables.

  4. Magnetic properties of actinide elements having the 5f/sup 6/ and 5f/sup 7/ electronic configurations

    SciTech Connect

    Nave, S.E.; Haire, R.G.; Huray, P.G.

    1983-09-01

    Magnetic susceptibility measurements have been made on multimicrogram quantities of /sup 243/AmF/sub 3/, /sup 248/CmF/sub 4/, /sup 248/CmO/sub 2/, and /sup 248/CmBaO/sub 3/ samples (nominally the 5f/sup 6/ electronic configuration) and on /sup 248/Cm/sub 2/O/sub 3/, /sup 248/CmF/sub 3/, /sup 249/BkF/sub 4/, and /sup 249/BkO/sub 2/ (nominally the 5f/sup 7/ electronic configuration) in the temperature range 4.2--300 K and in magnetic fields up to 1650 G. The experimentally determined effective magnetic moments and the Curie-Weiss constants for these compounds are presented. The deviation of the moments for the 5f/sup 6/ compounds from those expected from classic theory is discussed in terms of low-lying excited states, chemical composition, crystal-field perturbations, and realistic electronic structure.

  5. Research in actinide chemistry

    SciTech Connect

    Choppin, G.R.

    1993-01-01

    This research studies the behavior of the actinide elements in aqueous solution. The high radioactivity of the transuranium actinides limits the concentrations which can be studied and, consequently, limits the experimental techniques. However, oxidation state analogs (trivalent lanthanides, tetravalent thorium, and hexavalent uranium) do not suffer from these limitations. Behavior of actinides in the environment are a major USDOE concern, whether in connection with long-term releases from a repository, releases from stored defense wastes or accidental releases in reprocessing, etc. Principal goal of our research was expand the thermodynamic data base on complexation of actinides by natural ligands (e.g., OH[sup [minus

  6. Nano-focused Bremstrahlung Isochromat Spectroscopy (nBIS) Determination of the Unoccupied Electronic Structure of Pu

    SciTech Connect

    Tobin, J G; Butterfield, M; Teslich, N; Bliss, A; Chung, B; Gross, J; McMahan, A; Schwartz, A

    2006-12-20

    While chemically toxic and highly radioactive, Pu may be the most scientifically interesting element in the periodic table. It's properties include the following: six different phases, close to each other in energy and sensitive to variations of temperature, pressure and chemistry; the face-centered-cubic phase (delta) is the least dense; Pu expands when it solidifies from the melt; and it is clearly the nexus of the actinide binary phase diagrams of the actinides. In a sense, it is the boundary between the light (ostensibly delocalized 5f electrons) and heavy (ostensibly localized or correlated 5f electrons) actinide elements, but this is an over-simplification. The localized atomic 5f states are naturally correlated, but important regimes of correlated electron states are conceivable as extended states on the delocalized side of the possible Mott transition between conductive and insulating behavior. The proximity to this crossover may be the driving force behind all these exotic properties. Pu remains of immense scientific and technological importance and the advancement to a firm, scientific understanding of the electronic structure of Pu and its compounds, mixtures, alloys and solutions is a crucial issue. Moreover, while there are a number of ongoing experimental efforts directed at determining the occupied (valence band, below the Fermi Energy) electronic structure of Pu, there is essential no experimental data on the unoccupied (conduction band, above the Fermi Energy) electronic structure of Pu. Our objective is to determine the conduction band (unoccupied) electronic structure of Pu and other actinides (and possibly rare earths as well), in a phase specific fashion and emphasizing bulk contributions. This is world-class science directed at issue that is central to LLNL and DOE: Pu structure property relationships.

  7. Recent progress in actinide borate chemistry.

    PubMed

    Wang, Shuao; Alekseev, Evgeny V; Depmeier, Wulf; Albrecht-Schmitt, Thomas E

    2011-10-21

    The use of molten boric acid as a reactive flux for synthesizing actinide borates has been developed in the past two years providing access to a remarkable array of exotic materials with both unusual structures and unprecedented properties. [ThB(5)O(6)(OH)(6)][BO(OH)(2)]·2.5H(2)O possesses a cationic supertetrahedral structure and displays remarkable anion exchange properties with high selectivity for TcO(4)(-). Uranyl borates form noncentrosymmetric structures with extraordinarily rich topological relationships. Neptunium borates are often mixed-valent and yield rare examples of compounds with one metal in three different oxidation states. Plutonium borates display new coordination chemistry for trivalent actinides. Finally, americium borates show a dramatic departure from plutonium borates, and there are scant examples of families of actinides compounds that extend past plutonium to examine the bonding of later actinides. There are several grand challenges that this work addresses. The foremost of these challenges is the development of structure-property relationships in transuranium materials. A deep understanding of the materials chemistry of actinides will likely lead to the development of advanced waste forms for radionuclides present in nuclear waste that prevent their transport in the environment. This work may have also uncovered the solubility-limiting phases of actinides in some repositories, and allows for measurements on the stability of these materials.

  8. Recent progress in actinide borate chemistry

    SciTech Connect

    Wang, Shuao; Alekseev, Evgeny V.; Depmeier, Wulf; Albrecht-Schmitt, Thomas E.

    2011-01-01

    The use of molten boric acid as a reactive flux for synthesizing actinide borates has been developed in the past two years providing access to a remarkable array of exotic materials with both unusual structures and unprecedented properties. [ThB₅O₆(OH)₆][BO(OH)₂]·2.5H₂O possesses a cationic supertetrahedral structure and displays remarkable anion exchange properties with high selectivity for TcO4- Uranyl borates form noncentrosymmetric structures with extraordinarily rich topological relationships. Neptunium borates are often mixed-valent and yield rare examples of compounds with one metal in three different oxidation states. Plutonium borates display new coordination chemistry for trivalent actinides. Finally, americium borates show a dramatic departure from plutonium borates, and there are scant examples of families of actinides compounds that extend past plutonium to examine the bonding of later actinides. There are several grand challenges that this work addresses. The foremost of these challenges is the development of structure-property relationships in transuranium materials. A deep understanding of the materials chemistry of actinides will likely lead to the development of advanced waste forms for radionuclides present in nuclear waste that prevent their transport in the environment. This work may have also uncovered the solubility-limiting phases of actinides in some repositories, and allows for measurements on the stability of these materials.

  9. Chemistry of the heaviest actinides: fermium, mendelevium, nobelium, and lawrencium

    SciTech Connect

    Hulet, E.K.

    1980-01-01

    The chemical properties of the heavy actinides systematically deviate from those of their lanthanide counterparts. The differences between the later elements of the 4f and 5f series can be generally interpreted on the basis of subtle changes in electronic structure. The most important change is a lowering of the 5f energy levels with respect to the Fermi level and a wider separation between the 5f ground states and the first excited states in the 6d or 7p levels. It was concluded that these shifts toward greater stabilization of 5f orbitals with increasing atomic number are mainly supported by the appearance of the divalent oxidation state well before the end of the actinide series and the predominance of the divalent state in the next to last element in the series. The chemistry of fermium, mendelevium, nobelium, and lawrencium was discussed. 8 figures 4 tables. (DP)

  10. All-electron density functional theory calculations of the zero-pressure properties of plutonium dioxide

    NASA Astrophysics Data System (ADS)

    Boettger, Jonathan C.; Ray, Asok K.

    2000-07-01

    The fluorite structure light-actinide dioxides, uranium dioxide and plutonium dioxide, are both known to be prototypical Mott-Hubbard insulators, with band gaps produced by strong Coulomb correlation effects that are not adequately accounted for in traditional density functional theory (DFT) calculations. Indeed, DFT electronic structure calculations for these two actinide dioxides have been shown to incorrectly predict metallic behavior. The highly-correlated electron effects exhibited by the actinide dioxides, combined with the large relativistic effects (including spin-orbit coupling) expected for any actinide compound, provide an extreme challenge for electronic structure theorists. For this reason, few fully-self-consistent DFT calculations have been carried out for the actinide dioxides, in general, and only one for plutonium dioxide. In that calculation, the troublesome 5f electrons were treated as core electrons, and spin-orbit coupling was ignored.

  11. Actinide recovery process

    DOEpatents

    Muscatello, Anthony C.; Navratil, James D.; Saba, Mark T.

    1987-07-28

    Process for the removal of plutonium polymer and ionic actinides from aqueous solutions by absorption onto a solid extractant loaded on a solid inert support such as polystyrenedivinylbenzene. The absorbed actinides can then be recovered by incineration, by stripping with organic solvents, or by acid digestion. Preferred solid extractants are trioctylphosphine oxide and octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide and the like.

  12. Computational Modeling of Actinide Ions in Aqueous Solution

    NASA Astrophysics Data System (ADS)

    Atta-Fynn, Raymond

    2014-03-01

    Unraveling the chemical behavior of actinide species is difficult owing to the complex electronic structure of these species, the fact that many of these species can occur in multiple oxidation states, and the difficulties encountered in their experimental studies. First principles dynamical modeling, although computationally costly, allows us to gain rich insights into the behavior of actinide species. In this talk, we present results of the hydration shell structure and x-ray absorption spectra of aqueous actinides in different oxidation states including U(VI), U(V), U(IV), and Cm(III) using relativistic ab initiomolecular dynamics at 300 K. We also probed the thermodynamics of hydrolysis by calculating the first acidity constant for uranium in all three oxidation states (IV, V, and VI). We predicted, for the first time, that UO2+ is a weak acid in solution with a pKa value of 8.5. This result is particularly important since no thermodynamic data are available for hydrolyzed species of U(V). In our most recent work on concentrated Cm(III) solutions, we showed that counter-ions can strengthen or weaken the solvent structure itself rather than just the water coordination number. These new results are better explained in terms of the hydrogen bond lifetimes of the solvents.

  13. Thermodynamic Properties of Actinides and Actinide Compounds

    NASA Astrophysics Data System (ADS)

    Konings, Rudy J. M.; Morss, Lester R.; Fuger, Jean

    The necessity of obtaining accurate thermodynamic quantities for the actinide elements and their compounds was recognized at the outset of the Manhattan Project, when a dedicated team of scientists and engineers initiated the program to exploit nuclear energy for military purposes. Since the end of World War II, both fundamental and applied objectives have motivated a great deal of further study of actinide thermodynamics. This chapter brings together many research papers and critical reviews on this subject. It also seeks to assess, to systematize, and to predict important properties of the actinide elements, ions, and compounds, especially for species in which there is significant interest and for which there is an experimental basis for the prediction.

  14. Electronic and geometric structure of Pu metal: A high-resolution photoelectron spectromicroscopy study

    NASA Astrophysics Data System (ADS)

    Terry, J.; Schulze, R. K.; Zocco, T.; Lashley, Jason; Farr, J. D.; Heinzelman, K.; Rotenberg, E.; Shuh, D. K.; Blau, M.; Tobin, J.

    2000-07-01

    Soft x-ray techniques (photon energy in the range of 10-1000 eV) such as photoelectron; x-ray emission; and near-edge, x-ray absorption spectroscopies have been used to determine the electronic structure of many (in fact most) materials. However, these techniques have not been fully utilized on the actinides. The safety issues involved in handling the actinides make it necessary to minimize the amount of radioactive materials used in the measurements. To our knowledge, the only synchrotron radiation source in the world where soft x-ray measurements have been performed on plutonium is the Spectromicroscopy Facility at Beam Line 7.0.1 at the Advanced Light Source (ALS). We performed core-level photoemission, valence band photoemission, and near-edge x-ray absorption spectroscopy on both polycrystalline α-plutonium and δ-plutonium microcrystals.

  15. "Computational Modeling of Actinide Complexes"

    SciTech Connect

    Balasubramanian, K

    2007-03-07

    We will present our recent studies on computational actinide chemistry of complexes which are not only interesting from the standpoint of actinide coordination chemistry but also of relevance to environmental management of high-level nuclear wastes. We will be discussing our recent collaborative efforts with Professor Heino Nitsche of LBNL whose research group has been actively carrying out experimental studies on these species. Computations of actinide complexes are also quintessential to our understanding of the complexes found in geochemical, biochemical environments and actinide chemistry relevant to advanced nuclear systems. In particular we have been studying uranyl, plutonyl, and Cm(III) complexes are in aqueous solution. These studies are made with a variety of relativistic methods such as coupled cluster methods, DFT, and complete active space multi-configuration self-consistent-field (CASSCF) followed by large-scale CI computations and relativistic CI (RCI) computations up to 60 million configurations. Our computational studies on actinide complexes were motivated by ongoing EXAFS studies of speciated complexes in geo and biochemical environments carried out by Prof Heino Nitsche's group at Berkeley, Dr. David Clark at Los Alamos and Dr. Gibson's work on small actinide molecules at ORNL. The hydrolysis reactions of urnayl, neputyl and plutonyl complexes have received considerable attention due to their geochemical and biochemical importance but the results of free energies in solution and the mechanism of deprotonation have been topic of considerable uncertainty. We have computed deprotonating and migration of one water molecule from the first solvation shell to the second shell in UO{sub 2}(H{sub 2}O){sub 5}{sup 2+}, UO{sub 2}(H{sub 2}O){sub 5}{sup 2+}NpO{sub 2}(H{sub 2}O){sub 6}{sup +}, and PuO{sub 2}(H{sub 2}O){sub 5}{sup 2+} complexes. Our computed Gibbs free energy(7.27 kcal/m) in solution for the first time agrees with the experiment (7.1 kcal

  16. NMR Spectroscopy and Structural Characterization of Dithiophosphinates Relevant to Minor Actinide Extraction Processes

    SciTech Connect

    Scott R. Daly; Kevin S. Boland; John R. Klaehn; Stosh A. Kozimor; Molly M. MacInnes; Dean R. Peterman; Brian L. Scott

    2012-02-01

    Synthetic routes to alkyl and aryl substituted dithiophosphinate salts that contain non-coordinating PPh{sub 4}{sup 1+} counter cations are reported. In general, these compounds can be prepared via a multi-step procedure that starts with reacting secondary phosphines, i.e. HPR{sub 2}, with two equivalents elemental S. This transformation proceeds in two steps - first oxidation of the phosphine and second insertion of S into the H-P bond - and has been used to synthesize a series of dithiophoshinic acids, which were fully characterized, namely HS{sub 2}P(p-CF{sub 3}C{sub 6}H{sub 4}){sub 2}, HS{sub 2}P(m-CF{sub 3}C{sub 6}H{sub 4}){sub 2}, HS{sub 2}P(o-MeC{sub 6}H{sub 4}){sub 2}, and HS{sub 2}P(o-MeOC{sub 6}H{sub 4}){sub 2}. Although the insertion step was found to be much slower than the oxidation reaction, the formation of (NH{sub 4})S{sub 2}PR{sub 2} from HPSR{sub 2} occurs almost instantaneous upon addition of NH{sub 4}OH. Subsequent cation exchange reactions proceed readily with PPh{sub 4}Cl in water, under air, and at ambient conditions to provide analytically pure samples of [PPh{sub 4}][S{sub 2}PR{sub 2}] (R = p-CF{sub 3}C{sub 6}H{sub 4}, m-CF{sub 3}C{sub 6}H{sub 4}, o-CF{sub 3}C{sub 6}H{sub 4}, o-MeC{sub 6}H{sub 4}, o-MeOC{sub 6}H{sub 4}, Ph, and Me, 1b-7b, respectively), which were characterized by elemental analysis, multinuclear NMR, and IR spectroscopy. In addition the S{sub 2}PMe{sub 2}{sup 1-}, S{sub 2}PPh{sub 2}{sup 1-}, and dithiophosphinates with ortho-substituted arene rings were characterized by X-ray crystallography. Structural analysis show that, as opposed to the acids which have short P=S double bonds and long P-SH single bonds, the metric parameters for the S atoms in S{sub 2}PR{sub 2}{sup 1-} are equivalent. In addition, the presence of large non-coordinating PPh{sub 4}{sup 1+} cations guard against intermolecular P-S {hor_ellipsis} X interactions and insure that the P-S bond is isolated. Overall, this synthetic procedure provides high

  17. Method for preparing actinide nitrides

    DOEpatents

    Bryan, G.H.; Cleveland, J.M.; Heiple, C.R.

    1975-12-01

    Actinide nitrides, and particularly plutonium and uranium nitrides, are prepared by reacting an ammonia solution of an actinide compound with an ammonia solution of a reactant or reductant metal, to form finely divided actinide nitride precipitate which may then be appropriately separated from the solution. The actinide nitride precipitate is particularly suitable for forming nuclear fuels.

  18. PREFACE: Actinides 2009

    NASA Astrophysics Data System (ADS)

    Rao, Linfeng; Tobin, James G.; Shuh, David K.

    2010-07-01

    This volume of IOP Conference Series: Materials Science and Engineering consists of 98 papers that were presented at Actinides 2009, the 8th International Conference on Actinide Science held on 12-17 July 2009 in San Francisco, California, USA. This conference was jointly organized by Lawrence Livermore National Laboratory and Lawrence Berkeley National Laboratory. The Actinides conference series started in Baden-Baden, Germany (1975) and this first conference was followed by meetings at Asilomar, CA, USA (1981), Aix-en-Provence, France (1985), Tashkent, USSR (1989), Santa Fe, NM, USA (1993), Baden-Baden, Germany (1997), Hayama, Japan (2001), and Manchester, UK (2005). The Actinides conference series provides a regular venue for the most recent research results on the chemistry, physics, and technology of the actinides and heaviest elements. Actinides 2009 provided a forum spanning a diverse range of scientific topics, including fundamental materials science, chemistry, physics, environmental science, and nuclear fuels. Of particular importance was a focus on the key roles that basic actinide chemistry and physics research play in advancing the worldwide renaissance of nuclear energy. Editors Linfeng Rao Lawrence Berkeley National Laboratory (lrao@lbl.gov) James G Tobin Lawrence Livermore National Laboratory (tobin1@llnl.gov) David K Shuh Lawrence Berkeley National Laboratory (dkshuh@lbl.gov)

  19. Structural and electronic properties of uranium-encapsulated Au14 cage

    PubMed Central

    Gao, Yang; Dai, Xing; Kang, Seung-gu; Jimenez-Cruz, Camilo Andres; Xin, Minsi; Meng, Yan; Han, Jie; Wang, Zhigang; Zhou, Ruhong

    2014-01-01

    The structural properties of the uranium-encapsulated nano-cage U@Au14 are predicted using density functional theory. The presence of the uranium atom makes the Au14 structure more stable than the empty Au14-cage, with a triplet ground electronic state for U@Au14. Analysis of the electronic structure shows that the two frontier single-occupied molecular orbital electrons of U@Au14 mainly originate from the 5f shell of the U atom after charge transfer. Meanwhile, the bonding orbitals and charge population indicate that the designed U@Au14 nano-cage structure is stabilized by ionocovalent interactions. The current findings provide theoretical basis for future syntheses and further study of actinide doped gold nanoclusters, which might subsequently facilitate applications of such structure in radio-labeling, nanodrug carrier and other biomedical applications. PMID:25069968

  20. Research in actinide chemistry

    SciTech Connect

    Not Available

    1991-01-01

    This report contains research results on studies of inorganic and organic complexes of actinide and lanthanide elements. Special attention is given to complexes of humic acids and to spectroscopic studies.

  1. PRODUCTION OF ACTINIDE METAL

    DOEpatents

    Knighton, J.B.

    1963-11-01

    A process of reducing actinide oxide to the metal with magnesium-zinc alloy in a flux of 5 mole% of magnesium fluoride and 95 mole% of magnesium chloride plus lithium, sodium, potassium, calcium, strontium, or barium chloride is presented. The flux contains at least 14 mole% of magnesium cation at 600-- 900 deg C in air. The formed magnesium-zinc-actinide alloy is separated from the magnesium-oxide-containing flux. (AEC)

  2. Actinide recovery process

    DOEpatents

    Muscatello, A.C.; Navratil, J.D.; Saba, M.T.

    1985-06-13

    Process for the removal of plutonium polymer and ionic actinides from aqueous solutions by absorption onto a solid extractant loaded on a solid inert support such as polystyrene-divinylbenzene. The absorbed actinides can then be recovered by incineration, by stripping with organic solvents, or by acid digestion. Preferred solid extractants are trioctylphosphine oxide and octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide and the like. 2 tabs.

  3. Thermochemistry of the actinides

    SciTech Connect

    Kleinschmidt, P.D.

    1993-10-01

    The measurement of equilibria by Knudsen effusion techniques and the enthalpy of formation of the actinide atoms is briefly discussed. Thermochemical data on the sublimation of the actinide fluorides is used to calculate the enthalpies of formation and entropies of the gaseous species. Estimates are made for enthalpies and entropies of the tetrafluorides and trifluorides for those systems where data is not available. The pressure of important species in the tetrafluoride sublimation processes is calculated based on this thermochemical data.

  4. Subsurface Biogeochemistry of Actinides

    SciTech Connect

    Kersting, Annie B.; Zavarin, Mavrik

    2016-06-29

    A major scientific challenge in environmental sciences is to identify the dominant processes controlling actinide transport in the environment. It is estimated that currently, over 2200 metric tons of plutonium (Pu) have been deposited in the subsurface worldwide, a number that increases yearly with additional spent nuclear fuel (Ewing et al., 2010). Plutonium has been shown to migrate on the scale of kilometers, giving way to a critical concern that the fundamental biogeochemical processes that control its behavior in the subsurface are not well understood (Kersting et al., 1999; Novikov et al., 2006; Santschi et al., 2002). Neptunium (Np) is less prevalent in the environment; however, it is predicted to be a significant long-term dose contributor in high-level nuclear waste. Our focus on Np chemistry in this Science Plan is intended to help formulate a better understanding of Pu redox transformations in the environment and clarify the differences between the two long-lived actinides. The research approach of our Science Plan combines (1) Fundamental Mechanistic Studies that identify and quantify biogeochemical processes that control actinide behavior in solution and on solids, (2) Field Integration Studies that investigate the transport characteristics of Pu and test our conceptual understanding of actinide transport, and (3) Actinide Research Capabilities that allow us to achieve the objectives of this Scientific Focus Area (SFA and provide new opportunities for advancing actinide environmental chemistry. These three Research Thrusts form the basis of our SFA Science Program (Figure 1).

  5. Strong correlations in actinide redox reactions

    NASA Astrophysics Data System (ADS)

    Horowitz, S. E.; Marston, J. B.

    2011-02-01

    Reduction-oxidation (redox) reactions of the redox couples An(VI)/An(V), An(V)/An(IV), and An(IV)/An(III), where An is an element in the family of early actinides (U, Np, and Pu), as well as Am(VI)/Am(V) and Am(V)/Am(III), are modeled by combining density functional theory with a generalized Anderson impurity model that accounts for the strong correlations between the 5f electrons. Diagonalization of the Anderson impurity model yields improved estimates for the redox potentials and the propensity of the actinide complexes to disproportionate.

  6. Strong correlations in actinide redox reactions.

    PubMed

    Horowitz, S E; Marston, J B

    2011-02-14

    Reduction-oxidation (redox) reactions of the redox couples An(VI)/An(V), An(V)/An(IV), and An(IV)/An(III), where An is an element in the family of early actinides (U, Np, and Pu), as well as Am(VI)/Am(V) and Am(V)/Am(III), are modeled by combining density functional theory with a generalized Anderson impurity model that accounts for the strong correlations between the 5f electrons. Diagonalization of the Anderson impurity model yields improved estimates for the redox potentials and the propensity of the actinide complexes to disproportionate.

  7. Theoretical electronic structure of structurally modified graphene

    NASA Astrophysics Data System (ADS)

    Dvorak, Marc David

    Graphene has emerged as a promising replacement for silicon in next-generation electronics and optoelectronic devices. If graphene is to be used in semiconductor devices, however, it must acquire an electronic band gap. Numerous approaches have been proposed to control the band gap of graphene, including the periodic patterning of defects. However, the mechanism for band gap opening and the associated physics in graphene patterned with defects remain unclear. Using both analytic theory and first-principles calculations, we show that periodic patterning of defects on graphene can open a large and tunable band gap, induce strong absorption peaks at optical wavelengths, and host a giant band gap quantum spin Hall phase. First, a geometric rule is analytically derived for the arrangements of defects that open a band gap in graphene, with one ninth of all possible patterns opening a band gap. Next, we perform ab-initio density functional calculations to compare the effects of structural vacancies, hexagonal BN dopants, and passivants on the electronic structure of graphene. Qualitatively, these three types of structural defects behave the same, with only slight differences in their resulting band structures. By adjusting the shape of structural defects, we show how to move the Dirac cones in reciprocal space in accordance with the tight-binding model for the anisotropic honeycomb lattice, while the fundamental mechanism for band gap opening remains the same. To quantitatively predict the band gap and optical properties of these materials, we employ many-body perturbation theory with Green's functions (GW/Bethe-Salpeter equation) to directly include electron-electron and electron-hole interactions. Structurally modified graphene shows a strong renormalization of the fundamental band gap over single particle descriptions, and a strong electron-hole interaction as indicated by strong exciton binding energies (> 0.5 eV). Finally, we show that structurally modified graphene

  8. Nonaqueous actinide hydride dissolution and production of actinide $beta$- diketonates

    DOEpatents

    Crisler, L.R.

    1975-11-11

    Actinide beta-diketonate complex molecular compounds are produced by reacting a beta-diketone compound with a hydride of the actinide material in a mixture of carbon tetrachloride and methanol. (auth)

  9. Diglycolamide-functionalized calix[4]arenes showing unusual complexation of actinide ions in room temperature ionic liquids: role of ligand structure, radiolytic stability, emission spectroscopy, and thermodynamic studies.

    PubMed

    Mohapatra, Prasanta K; Sengupta, Arijit; Iqbal, Mudassir; Huskens, Jurriaan; Verboom, Willem

    2013-03-04

    Diglycolamide-functionalized calix[4]arenes (C4DGAs) with varying structural modifications were evaluated for actinide complexation from their extraction behavior toward actinide ions such as UO2(2+), Pu(4+), PuO2(2+), and Am(3+) in the room temperature ionic liquid (RTIL) 1-n-octyl-3-methylimidazolium bis(trifluoromethane)sulfonamide (C8mimNTf2). The formation constants were calculated for Am(3+) which showed a significant role of ligand structure, nature of substituents, and spacer length. Although the alkyl substituents on the amidic nitrogen increase the extraction efficiency of americium at lower acidity because of the inductive effect of the alkyl groups, at higher acidity the steric crowding around the ligating site determines the extraction efficiency. All C4DGAs formed 1:1 complexes with Am(3+) while for the analogous Eu(3+) complexes no inner sphere water molecules were detected and the asymmetry of the metal ligand complex differed from one another as proved by time-resolved laser induced fluorescence spectroscopy (TRLIFS). Thermodynamic studies indicated that the extraction process, predominant by the Am(3+)-C4DGA complexation reaction, is exothermic. The unique role of the medium on Am(3+) complexation with the C4DGA molecules with varying spacer length, L-IV and L-V, was noticed for the first time with a reversal in the trend observed in the RTIL compared to that seen in a nonpolar molecular diluent like n-dodecane. Various factors leading to a more preorganized structure were responsible for favorable metal ion complexation. The solvent systems show promise to be employed for nuclear waste remediation, and sustainability options were evaluated from radiolytic stability as well as stripping studies.

  10. Electronic Structure Principles and Aromaticity

    ERIC Educational Resources Information Center

    Chattaraj, P. K.; Sarkar, U.; Roy, D. R.

    2007-01-01

    The relationship between aromaticity and stability in molecules on the basis of quantities such as hardness and electrophilicity is explored. The findings reveal that aromatic molecules are less energetic, harder, less polarizable, and less electrophilic as compared to antiaromatic molecules, as expected from the electronic structure principles.

  11. Electron Scattering and Nuclear Structure

    ERIC Educational Resources Information Center

    Trower, W. P.; Ficenec, J. R.

    1971-01-01

    Presents information about the nucleus gained by studies of electron scattering. Discusses what can be implied about the shape of the charge distribution, the nucleus positions, the vibrational modes of the nucleus, the momentum of the nucleus, and the granularity and core structures of the nucleus. (DS)

  12. Density functional theory calculations of the redox potentials of actinide(VI)/actinide(V) couple in water.

    PubMed

    Steele, Helen M; Guillaumont, Dominique; Moisy, Philippe

    2013-05-30

    The measured redox potential of an actinide at an electrode surface involves the transfer of a single electron from the electrode surface on to the actinide center. Before electron transfer takes place, the complexing ligands and molecules of solvation need to become structurally arranged such that the electron transfer is at its most favorable. Following the electron transfer, there is further rearrangement to obtain the minimum energy structure for the reduced state. As such, there are three parts to the total energy cycle required to take the complex from its ground state oxidized form to its ground state reduced form. The first part of the energy comes from the structural rearrangement and solvation energies of the actinide species before the electron transfer or charge transfer process; the second part, the energy of the electron transfer; the third part, the energy required to reorganize the ligands and molecules of solvation around the reduced species. The time resolution of electrochemical techniques such as cyclic voltammetry is inadequate to determine to what extent bond and solvation rearrangement occurs before or after electron transfer; only for a couple to be classed as reversible is it fast in terms of the experimental time. Consequently, the partitioning of the energy theoretically is of importance to obtain good experimental agreement. Here we investigate the magnitude of the instantaneous charge transfer through calculating the fast one electron reduction energies of AnO2(H2O)n(2+), where An = U, Np, and Pu, for n = 4-6, in solution without inclusion of the structural optimization energy of the reduced form. These calculations have been performed using a number of DFT functionals, including the recently developed functionals of Zhao and Truhlar. The results obtained for calculated electron affinities in the aqueous phase for the AnO2(H2O)5(2+/+) couples are within 0.04 V of accepted experimental redox potentials, nearly an order of magnitude

  13. RELATIVISTIC EFFECTS ON THE EQUATION OF STATE OF THE LIGHT ACTINIDES

    SciTech Connect

    Landa, A; Soderlind, P

    2005-11-04

    The effect of the relativistic spin-orbit (SO) interaction on the bonding in the early actinides has been investigated by means of electronic-structure calculations. Specifically, the equation of state (EOS) for the face-centered cubic (fcc) model systems of these metals have been calculated from the first-principles density-functional theory (DFT). Traditionally, the SO interaction in electronic-structure methods is implemented as a perturbation to the Hamiltonian that is solved for basis functions that explicitly do not depend on SO coupling. Here this approximation is shown to compare well with the fully relativistic Dirac treatment. It is further shown that SO coupling has a gradually increasing effect on the EOS as one proceeds through the actinides and the effect is diminished as density increases.

  14. Structural Dynamics of Electronic Systems

    NASA Astrophysics Data System (ADS)

    Suhir, E.

    2013-03-01

    The published work on analytical ("mathematical") and computer-aided, primarily finite-element-analysis (FEA) based, predictive modeling of the dynamic response of electronic systems to shocks and vibrations is reviewed. While understanding the physics of and the ability to predict the response of an electronic structure to dynamic loading has been always of significant importance in military, avionic, aeronautic, automotive and maritime electronics, during the last decade this problem has become especially important also in commercial, and, particularly, in portable electronics in connection with accelerated testing of various surface mount technology (SMT) systems on the board level. The emphasis of the review is on the nonlinear shock-excited vibrations of flexible printed circuit boards (PCBs) experiencing shock loading applied to their support contours during drop tests. At the end of the review we provide, as a suitable and useful illustration, the exact solution to a highly nonlinear problem of the dynamic response of a "flexible-and-heavy" PCB to an impact load applied to its support contour during drop testing.

  15. Synthesis and structure of Ce1-xEuxPO4 solid solutions for minor actinides immobilization

    NASA Astrophysics Data System (ADS)

    Wang, Xiaohuan; Teng, Yuancheng; Huang, Yi; Wu, Lang; Zeng, Pan

    2014-08-01

    Ce1-xEuxPO4 (x = 0-1) solid solutions were synthesized by the solid state reaction process using europium (Eu) as the surrogate for trivalent minor actinide americium (Am). The effects of calcination temperature, holding time and Eu content on the crystalline phase, microstructure and morphology of Ce1-xEuxPO4 (x = 0-1) were investigated. The monazite-type EuPO4 and CePO4 coexisted after being calcined at 1000 °C for 4 h, suggesting the CePO4 and EuPO4 phases would form initially separately. Pure and single-phase monazite-type Ce1-xEuxPO4 (x = 0-1) powders were obtained at 1300 °C for 4 h. The results of the XRD patterns Rietveld refinement and μ-Raman analysis confirmed the formation of a Ce1-xEuxPO4 (x = 0-1) continuous solid solution. The grain size of Ce0.5Eu0.5PO4 increased obviously as the holding time extended. The Ce, Eu, P and O elements were almost distributed homogeneously in the Ce0.5Eu0.5PO4 solid solution.

  16. Activation energetics of actinide diffusion in UO2 from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Wang, Jianwei; Becker, Udo

    2013-02-01

    Diffusion of actinides in uranium dioxide plays an important role in determining thermodynamic and mechanic properties of the material. Activation energies of Th, U, Np, and Pu diffusion in uranium dioxide were systematically studied using first-principles calculations. The generalized gradient approximation and projector-augmented wave methods with on-site Coulomb repulsive interaction were applied within Density Functional Theory and Plane Wave framework. Two diffusion paths, one along the lattice <1 1 0> direction and the other along the lattice <1 0 0> direction, were examined in the face-centered cubic UO2 structure. The results show that the <1 1 0> path has lower migration energy than the <1 0 0> path. Under the assumption of a vacancy-assisted jump diffusion mechanism, the major contribution to the activation energy is the migration energy, followed by the vacancy formation energy and vacancy binding energy, where the last has the lowest contribution. However, differences in the activation energies among different actinides stem from both the migration and vacancy binding energies, both of which decrease with atomic number. While discrepancies between the absolute values of the calculated and experimentally observed activation energies remain, this study shows a correlation between activation energy and atomic number and an asymptotic relation between activation energy and ionic radius of the actinides. The present study suggests that the migration of the actinides through the uranium dioxide lattice is closely correlated to the number of 5f electrons and the size of the diffusing atoms.

  17. Electronic structure investigations of quasicrystals

    NASA Astrophysics Data System (ADS)

    Rotenberg, E.; Theis, W.; Horn, K.

    2004-08-01

    We present a review of the determination of density of states (DOS) of quasicrystals using valence band photoemission spectroscopy. The absence of fine or spiky structure in the angle-integrated DOS of quasicrystals suggests the possibility of delocalized electronic states. These were confirmed with angle-resolved photoemission studies, which clearly establish the presence of dispersing features attributed to momentum-dependent bandstructure. Such dispersing states are observed not only for deeper-lying sp states, but also for d-derived bands near the Fermi level. Data from three different high symmetry surfaces of decagonal Al-Ni-Co, an ideal model system, are presented. We find that only a few dominant reciprocal lattice vectors are sufficient to describe the quasiperiodic potential, and the implications for electronic properties are discussed.

  18. Chemistry of tetravalent actinide phosphates-Part I

    SciTech Connect

    Brandel, V. . E-mail: vbrandel@neuf.fr; Dacheux, N. . E-mail: dacheux@ipno.in2p3.fr

    2004-12-01

    The chemistry and crystal structure of phosphates of tetravalent cations, including that of actinides was reviewed several times up to 1985. Later, new compounds were synthesized and characterized. In more recent studies, it was found that some of previously reported phases, especially those of thorium, uranium and neptunium, were wrongly identified. In the light of these new facts an update review and classification of the tetravalent actinide phosphates is proposed in the two parts of this paper. Their crystal structure and some chemical properties are also compared to non-actinide cation phosphates.

  19. Electronic instrumentation for smart structures

    NASA Astrophysics Data System (ADS)

    Blanar, George J.

    1995-04-01

    The requirements of electronic instrumentation for smart structures are similar to those of data acquisition systems at our national particle physics laboratories. Modern high energy and heavy ion physics experiments may have tens of thousands of channels of data sources producing data that must be converted to digital form, compacted, stored and interpreted. In parallel, multiple sensors distributed in and around smart structures generate either binary or analog signals that are voltage, charge, or time like in their information content. In all cases, they must be transmitted, converted and preserved into a unified digital format for real-time processing. This paper will review the current status of practical large scale electronic measurement systems with special attention to architectures and physical organization. Brief surveys of the current state of the art will include preamplifiers and amplifiers, comparators and discriminators, voltage or charge analog-to-digital converters, time internal meters or time-to-digital converters, and finally, counting or scalar systems. The paper will conclude by integrating all of these ideas in a concept for an all-digital readout of a smart structure using the latest techniques used in physics research today.

  20. The electronic structure of Lu

    NASA Astrophysics Data System (ADS)

    Tibbetts, T. A.; Harmon, B. N.

    1982-12-01

    The electronic structure of hcp Lu has been calculated using a linearized augmented plane wave (LAPW) method and the Hedin-Lundqvist local density approximation for exchange and correlation. Although complete self-consistency was hindered by the proximity of the 4f levels to the Fermi energy, the valence bands were converged and the calculation yielded a Fermi surface remarkably similar to that calculated by Keeton and Loucks. Comparison is made with recent de Haas-van Alphen and neutron magnetic form factor experiments.

  1. IMPORTANCE OF FULL COULOMB INTERACTIONS FOR UNDERSTANDING THE ELECTRONIC STRUCTURE OF DELTA-Pu

    SciTech Connect

    Gorelov, E; Kolorenc, J; Wehling, T; Hafermann, H; Lichtenstein, A I; Shick, A B; Rubtsov, A N; Katsnelson, M I; Landa, A; McMahan, A K

    2010-04-01

    The solid-state properties of most elements are now well understood on the basis of quantum physics - with few exceptions, notably the element number 94, plutonium. Plutonium has six crystalline phases at ambient pressure, some of which are separated by unusual phase transitions with large discontinuities in volume, exhibit negative thermal expansion coefficients, or form exotic low-symmetry structures. The main challenge to explain these anomalous properties is that the characteristic ingredient of actinides, the 5f electronic states, are in the cross-over regime between the localized and delocalized (itinerant) behaviour in Pu. The early part of the actinide series with the 5f states being itinerant, i.e. part of the metallic bond, culminates with Pu; starting with Am (Z = 95), the 5f states are localized, nonbonding, and resemble the 4f states in lanthanides. Both itinerant and localized regimes are well covered by existing theories, but they cannot be simply interpolated due to the importance of dynamical electron-electron correlations. Here we present accurate quantum Monte Carlo calculations achieving previously inaccessible resolution. Obtained results demonstrate that interplay of the full Coulomb interaction vertex with spin-orbital coupling is crucial for understanding the experimentally observed spectral properties of plutonium near the Fermi level.

  2. Electronic structure quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Bajdich, Michal; Mitas, Lubos

    2009-04-01

    Quantum Monte Carlo (QMC) is an advanced simulation methodology for studies of manybody quantum systems. The QMC approaches combine analytical insights with stochastic computational techniques for efficient solution of several classes of important many-body problems such as the stationary Schrödinger equation. QMC methods of various flavors have been applied to a great variety of systems spanning continuous and lattice quantum models, molecular and condensed systems, BEC-BCS ultracold condensates, nuclei, etc. In this review, we focus on the electronic structure QMC, i.e., methods relevant for systems described by the electron-ion Hamiltonians. Some of the key QMC achievements include direct treatment of electron correlation, accuracy in predicting energy differences and favorable scaling in the system size. Calculations of atoms, molecules, clusters and solids have demonstrated QMC applicability to real systems with hundreds of electrons while providing 90-95% of the correlation energy and energy differences typically within a few percent of experiments. Advances in accuracy beyond these limits are hampered by the so-called fixed-node approximation which is used to circumvent the notorious fermion sign problem. Many-body nodes of fermion states and their properties have therefore become one of the important topics for further progress in predictive power and efficiency of QMC calculations. Some of our recent results on the wave function nodes and related nodal domain topologies will be briefly reviewed. This includes analysis of few-electron systems and descriptions of exact and approximate nodes using transformations and projections of the highly-dimensional nodal hypersurfaces into the 3D space. Studies of fermion nodes offer new insights into topological properties of eigenstates such as explicit demonstrations that generic fermionic ground states exhibit the minimal number of two nodal domains. Recently proposed trial wave functions based on Pfaffians with

  3. Actinide halide complexes

    SciTech Connect

    Avens, L.R.; Zwick, B.D.; Sattelberger, A.P.; Clark, D.L.; Watkin, J.G.

    1991-02-07

    A compound of the formula MX{sub n}L{sub m} wherein M = Th, Pu, Np,or Am thorium, X = a halide atom, n = 3 or 4, L is a coordinating ligand selected from the group consisting of aprotic Lewis bases having an oxygen-, nitrogen-, sulfur-, or phosphorus-donor, and m is 3 or 4 for monodentate ligands or is 2 for bidentate ligands, where n + m = 7 or 8 for monodentate ligands or 5 or 6 for bidentate ligands, a compound of the formula MX{sub n} wherein M, X, and n are as previously defined, and a process of preparing such actinide metal compounds including admixing the actinide metal in an aprotic Lewis base as a coordinating solvent in the presence of a halogen-containing oxidant, are provided.

  4. The nature of chemical bonding in actinide and lanthanide ferrocyanides determined by X-ray absorption spectroscopy and density functional theory.

    PubMed

    Dumas, Thomas; Guillaumont, Dominique; Fillaux, Clara; Scheinost, Andreas; Moisy, Philippe; Petit, Sébastien; Shuh, David K; Tyliszczak, Tolek; Den Auwer, Christophe

    2016-01-28

    The electronic properties of actinide cations are of fundamental interest to describe intramolecular interactions and chemical bonding in the context of nuclear waste reprocessing or direct storage. The 5f and 6d orbitals are the first partially or totally vacant states in these elements, and the nature of the actinide ligand bonds is related to their ability to overlap with ligand orbitals. Because of its chemical and orbital selectivities, X-ray absorption spectroscopy (XAS) is an effective probe of actinide species frontier orbitals and for understanding actinide cation reactivity toward chelating ligands. The soft X-ray probes of the light elements provide better resolution than actinide L3-edges to obtain electronic information from the ligand. Thus coupling simulations to experimental soft X-ray spectral measurements and complementary quantum chemical calculations yields quantitative information on chemical bonding. In this study, soft X-ray XAS at the K-edges of C and N, and the L2,3-edges of Fe was used to investigate the electronic structures of the well-known ferrocyanide complexes K4Fe(II)(CN)6, thorium hexacyanoferrate Th(IV)Fe(II)(CN)6, and neodymium hexacyanoferrate KNd(III)Fe(II)(CN)6. The soft X-ray spectra were simulated based on quantum chemical calculations. Our results highlight the orbital overlapping effects and atomic effective charges in the Fe(II)(CN)6 building block. In addition to providing a detailed description of the electronic structure of the ferrocyanide complex (K4Fe(II)(CN)6), the results strongly contribute to confirming the actinide 5f and 6d orbital oddity in comparison to lanthanide 4f and 5d.

  5. Environmental behavior of actinides

    NASA Astrophysics Data System (ADS)

    Choppin, G. R.

    2006-01-01

    Since the plutonium concentration in ocean waters is quite low, most of the plutonium deposited in marine waters has been sorbed onto plants and sediments. Actinides in natural waters usually are not in a state of thermodynamic equilibrium for long time periods as their solubility and migration behavior is strongly related to the form in which the nuclides are introduced initially into the aquatic system for long time periods. Their solubility depends on pH (hydrolysis), E H (oxidation state), reaction with complexants (e.g., carbonate, phosphate, humic acid, etc.), sorption to surfaces of minerals and/or colloids, etc. The primary variable is the oxidation state of the actinide cation. Actinides can be present in more than one oxidation state which complicates modeling actinide environmental behavior. Np(V)O 2 + and Pu(V)O 2 + are weakly complexing and resistant to hydrolysis and subsequent precipitation, but both can undergo reduction to the IV oxidation state. The solubility of NpO 2 + can be as high as 10-4M, while that of PuO 2 + is more limited as the very low solubility of Pu(OH)4 promotes reduction to Pu(IV). The solubility of hexavalent UO 2 2+ in sea water is limited by hydrolysis, but has a relatively high concentration due to carbonate complexation. Americium(III) hydroxocarbonate, Am(CO3)(OH), is the limiting species for the solubility of Am(III) in sea water. Thorium has a very low solubility due to the formation of Th(OH)4.

  6. Spectroscopic investigation of actinide speciation in concentrated chloride solution

    SciTech Connect

    Runde, W.; Neu, M.P.; Conradson, S.D.; Clark, D.L.; Palmer, P.D.; Reilly, S.D.; Scott, B.L.; Tait, C.D.

    1997-12-31

    The proposed disposal of nuclear waste in geological salt formations, e.g., the Waste Isolation Pilot Plant (USA) and the Gorleben site (Germany), raises a fundamental question: To what degree actinides will be solubilized and mobilized upon interaction with chloride ions? Actinide solubilities in highly concentrated chloride solutions are about one order of magnitude higher than in similar inert electrolyte (NaClO{sub 4}) solutions. This increased solubility is due to interactions between actinide and chloride ions. Contradictory results exist regarding the interaction mechanism between actinide and chloride ions. Specifically, both inner-sphere complex formation and ion pair association have been implicated in the interpretation of spectrophotometric and extraction data. To address this controversy, the authors investigated the interaction between actinide ions in the (III), (IV), (V) and (VI) oxidation states and chloride ions using a multi-method approach. Spectroscopic techniques (TRLFS, Raman, UV-Vis absorption, EXAFS) were used to distinguish between changes in the inner coordination sphere of the actinide ion and effects of ion pairing, X-ray absorption spectroscopy and single crystal X-ray diffraction were used to determine structural details of the actinide chloro complexes formed in solution and solid states.

  7. In vitro removal of actinide (IV) ions

    DOEpatents

    Weitl, Frederick L.; Raymond, Kenneth N.

    1982-01-01

    A compound of the formula: ##STR1## wherein X is hydrogen or a conventional electron-withdrawing group, particularly --SO.sub.3 H or a salt thereof; n is 2, 3, or 4; m is 2, 3, or 4; and p is 2 or 3. The present compounds are useful as specific sequestering agents for actinide (IV) ions. Also described is a method for the 2,3-dihydroxybenzamidation of azaalkanes.

  8. Electronic transport in nanoscale structures

    NASA Astrophysics Data System (ADS)

    Lagerqvist, Johan

    In this dissertation electronic transport in nanoscale structures is discussed. An expression for the shot noise, a fluctuation in current due to the discreteness of charge, is derived directly from the wave functions of a nanoscale system. Investigation of shot noise is of particular interest due to the rich fundamental physics involved. For example, the study of shot noise can provide fundamental insight on the nature of electron transport in a nanoscale junction. We report calculations of the shot noise properties of parallel wires in the regime in which the interwire distance is much smaller than the inelastic mean free path. The validity of quantized transverse momenta in a nanoscale structure and its effect on shot noise is also discussed. We theoretically propose and show the feasibility of a novel protocol for DNA sequencing based on the electronic signature of single-stranded DNA while it translocates through a nanopore. We find that the currents for the bases are sufficiently different to allow for efficient sequencing. Our estimates reveal that sequencing of an entire human genome could be done with very high accuracy in a matter of hours, e.g., orders of magnitude faster than present techniques. We also find that although the overall magnitude of the current may change dramatically with different detection conditions, the intrinsic distinguishability of the bases is not significantly affected by pore size and transverse field strength. Finally, we study the ability of water to screen charges in nanopores by using all-atom molecular dynamics simulations coupled to electrostatic calculations. Due to the short length scales of the nanopore geometry and the large local field gradient of a single ion, the energetics of transporting an ion through the pore is strongly dependent on the microscopic details of the electric field. We show that as long as the pore allows the first hydration shell to stay intact, e.g., ˜6 nearby water molecules, the electric field

  9. Synthesis, phase structure and microstructure of monazite-type Ce1-xPrxPO4 solid solutions for immobilization of minor actinide neptunium

    NASA Astrophysics Data System (ADS)

    Zeng, Pan; Teng, Yuancheng; Huang, Yi; Wu, Lang; Wang, Xiaohuan

    2014-09-01

    Praseodymium was used as the surrogate for trivalent minor actinide neptunium, and a complete series of pure monazite-type Ce1-xPrxPO4 (x = 0-1) solid solutions were successfully prepared by the solid state reaction. The effects of calcining temperature, holding time and Pr content on the structure of Ce1-xPrxPO4 solid solutions were investigated. The results show that although Pr6O11 (Pr23+Pr44+O11) exists two stabilized oxidation states, there has been no tetravalent praseodymium phosphate during the synthesis process. The optimized temperature for the synthesis of Ce0.8Pr0.2PO4 solid solution is more than 1100 °C, and a hypothetical reaction mechanism is also proposed. Besides, the crystalline grains coarsen as the increasing of holding time. The linear variation of unit cell parameters and a gradual hypsochromic shift in the Raman spectra are observed with the increase of Pr content, indicating that cerium is progressively replaced by praseodymium and Ce1-xPrxPO4 solid solutions were prepared.

  10. Circularly polarized luminescence of curium: a new characterization of the 5f actinide complexes.

    PubMed

    Law, Ga-Lai; Andolina, Christopher M; Xu, Jide; Luu, Vinh; Rutkowski, Philip X; Muller, Gilles; Shuh, David K; Gibson, John K; Raymond, Kenneth N

    2012-09-19

    A key distinction between the lanthanide (4f) and the actinide (5f) transition elements is the increased role of f-orbital covalent bonding in the latter. Circularly polarized luminescence (CPL) is an uncommon but powerful spectroscopy which probes the electronic structure of chiral, luminescent complexes or molecules. While there are many examples of CPL spectra for the lanthanides, this report is the first for an actinide. Two chiral, octadentate chelating ligands based on orthoamide phenol (IAM) were used to complex curium(III). While the radioactivity kept the amount of material limited to micromole amounts, spectra of the highly luminescent complexes showed significant emission peak shifts between the different complexes, consistent with ligand field effects previously observed in luminescence spectra.

  11. PROCESS OF PRODUCING ACTINIDE METALS

    DOEpatents

    Magel, T.T.

    1959-07-14

    The preparation of actinide metals in workable, coherent form is described. In general, the objects of the invention are achieved by heating a mixture of an oxide and a halide of an actinide metal such as uranium with an alkali metal on alkaline earth metal reducing agent in the presence of iodine.

  12. Microbial Transformations of Actinides and Other Radionuclides

    SciTech Connect

    Francis,A.J.; Dodge, C. J.

    2009-01-07

    Microorganisms can affect the stability and mobility of the actinides and other radionuclides released from nuclear fuel cycle and from nuclear fuel reprocessing plants. Under appropriate conditions, microorganisms can alter the chemical speciation, solubility and sorption properties and thus could increase or decrease the concentrations of radionuclides in solution in the environment and the bioavailability. Dissolution or immobilization of radionuclides is brought about by direct enzymatic action or indirect non-enzymatic action of microorganisms. Although the physical, chemical, and geochemical processes affecting dissolution, precipitation, and mobilization of radionuclides have been extensively investigated, we have only limited information on the effects of microbial processes and biochemical mechanisms which affect the stability and mobility of radionuclides. The mechanisms of microbial transformations of the major and minor actinides U, Pu, Cm, Am, Np, the fission products and other radionuclides such as Ra, Tc, I, Cs, Sr, under aerobic and anaerobic conditions in the presence of electron donors and acceptors are reviewed.

  13. Electronic processes in multilayer memory structures

    NASA Astrophysics Data System (ADS)

    Plotnikov, A. F.

    The papers presented in this volume contain results of recent theoretical and experimental research related to electron processes in optoelectronic memory media based on structures consisting of a metal, an amorphous insulating layer, and a semiconductor. Topics discussed include photostimulated electron processes in metal-insulator-semiconductor structures, electron transfer phenomena in amorphous dielectric layers, degradation phenomena in MNOS memory elements under prolonged charge injection into the dielectric layer, and characteristics of charge relaxation in MNOS structures following multiple reprogramming.

  14. Electrorecovery of actinides at room temperature

    SciTech Connect

    Stoll, Michael E; Oldham, Warren J; Costa, David A

    2008-01-01

    There are a large number of purification and processing operations involving actinide species that rely on high-temperature molten salts as the solvent medium. One such application is the electrorefining of impure actinide metals to provide high purity material for subsequent applications. There are some drawbacks to the electrodeposition of actinides in molten salts including relatively low yields, lack of accurate potential control, maintaining efficiency in a highly corrosive environment, and failed runs. With these issues in mind we have been investigating the electrodeposition of actinide metals, mainly uranium, from room temperature ionic liquids (RTILs) and relatively high-boiling organic solvents. The RTILs we have focused on are comprised of 1,3-dialkylimidazolium or quaternary ammonium cations and mainly the {sup -}N(SO{sub 2}CF{sub 3}){sub 2} anion [bis(trif1uoromethylsulfonyl)imide {equivalent_to} {sup -}NTf{sub 2}]. These materials represent a class of solvents that possess great potential for use in applications employing electrochemical procedures. In order to ascertain the feasibility of using RTILs for bulk electrodeposition of actinide metals our research team has been exploring the electron transfer behavior of simple coordination complexes of uranium dissolved in the RTIL solutions. More recently we have begun some fundamental electrochemical studies on the behavior of uranium and plutonium complexes in the organic solvents N-methylpyrrolidone (NMP) and dimethylsulfoxide (DMSO). Our most recent results concerning electrodeposition will be presented in this account. The electrochemical behavior of U(IV) and U(III) species in RTILs and the relatively low vapor pressure solvents NMP and DMSO is described. These studies have been ongoing in our laboratory to uncover conditions that will lead to the successful bulk electrodeposition of actinide metals at a working electrode surface at room temperature or slightly elevated temperatures. The RTILs we

  15. 237Np Mössbauer studies on actinide superconductors and related materials

    NASA Astrophysics Data System (ADS)

    Colineau, Eric; Gaczyński, Piotr; Griveau, Jean-Christophe; Eloirdi, Rachel; Caciuffo, Roberto

    2012-03-01

    Actinide materials play a special role in condensed matter physics, spanning behaviours of itinerant d-electron and localized 4f-electron materials. This duality of the 5f electrons confer to actinide-based intermetallic compounds a broad variety of physical properties such as magnetic or multipolar ordering, heavy fermion behaviour, quantum criticality, unconventional superconductivity... 237Np Mössbauer spectroscopy is a unique microscopic tool for gaining information on the electronic and magnetic properties of Np systems.

  16. Actinide halide complexes

    DOEpatents

    Avens, L.R.; Zwick, B.D.; Sattelberger, A.P.; Clark, D.L.; Watkin, J.G.

    1992-11-24

    A compound is described of the formula MX[sub n]L[sub m] wherein M is a metal atom selected from the group consisting of thorium, plutonium, neptunium or americium, X is a halide atom, n is an integer selected from the group of three or four, L is a coordinating ligand selected from the group consisting of aprotic Lewis bases having an oxygen-, nitrogen-, sulfur-, or phosphorus-donor, and m is an integer selected from the group of three or four for monodentate ligands or is the integer two for bidentate ligands, where the sum of n+m equals seven or eight for monodentate ligands or five or six for bidentate ligands. A compound of the formula MX[sub n] wherein M, X, and n are as previously defined, and a process of preparing such actinide metal compounds are described including admixing the actinide metal in an aprotic Lewis base as a coordinating solvent in the presence of a halogen-containing oxidant.

  17. Actinide halide complexes

    DOEpatents

    Avens, Larry R.; Zwick, Bill D.; Sattelberger, Alfred P.; Clark, David L.; Watkin, John G.

    1992-01-01

    A compound of the formula MX.sub.n L.sub.m wherein M is a metal atom selected from the group consisting of thorium, plutonium, neptunium or americium, X is a halide atom, n is an integer selected from the group of three or four, L is a coordinating ligand selected from the group consisting of aprotic Lewis bases having an oxygen-, nitrogen-, sulfur-, or phosphorus-donor, and m is an integer selected from the group of three or four for monodentate ligands or is the integer two for bidentate ligands, where the sum of n+m equals seven or eight for monodentate ligands or five or six for bidentate ligands, a compound of the formula MX.sub.n wherein M, X, and n are as previously defined, and a process of preparing such actinide metal compounds including admixing the actinide metal in an aprotic Lewis base as a coordinating solvent in the presence of a halogen-containing oxidant, are provided.

  18. Electronic correlation contributions to structural energies

    NASA Astrophysics Data System (ADS)

    Haydock, Roger

    2015-03-01

    The recursion method is used to calculate electronic excitation spectra including electron-electron interactions within the Hubbard model. The effects of correlation on structural energies are then obtained from these spectra and applied to stacking faults. http://arxiv.org/abs/1405.2288 Supported by the Richmond F. Snyder Fund and Gifts.

  19. MOLECULAR SPECTROSCPY AND REACTIONS OF ACTINIDES IN THE GAS PHASE AND CRYOGENIC MATRICES

    SciTech Connect

    Heaven, Michael C.; Gibson, John K.; Marcalo, Joaquim

    2009-02-01

    temperature or below. For many spectroscopic measurements, low temperatures have been achieved by co-condensing the actinide vapor in rare gas or inert molecule host matrices. Spectra recorded in matrices are usually considered to be minimally perturbed. Trapping the products from gas-phase reactions that occur when trace quantities of reactants are added to the inert host gas has resulted in the discovery of many new actinide species. Selected aspects of the matrix isolation data were discussed in chapter 17. In the present chapter we review the spectroscopic matrix data in terms of its relationship to gas-phase measurements, and update the description of the new reaction products found in matrices to reflect the developments that have occurred during the past two years. Spectra recorded in matrix environments are usually considered to be minimally perturbed, and this expectation is borne out for many closed shell actinide molecules. However, there is growing evidence that significant perturbations can occur for open shell molecules, resulting in geometric distortions and/or electronic state reordering. Studies of actinide reactions in the gas phase provide an opportunity to probe the relationship between electronic structure and reactivity. Much of this work has focused on the reactions of ionic species, as these may be selected and controlled using various forms of mass spectrometry. As an example of the type of insight derived from reaction studies, it has been established that the reaction barriers for An+ ions are determined by the promotion energies required to achieve the 5fn6d7s configuration. Gas-phase reaction studies also provide fundamental thermodynamic properties such as bond dissociation and ionization energies. In recent years, an increased number of gas-phase ion chemistry studies of bare (atomic) and ligated (molecular) actinide ions have appeared, in which relevant contributions to fundamental actinide chemistry have been made. These studies were initiated

  20. 5f band dispersion in the highly correlated electronic structure of uranium compounds

    NASA Astrophysics Data System (ADS)

    Moore, D. P.; Joyce, J. J.; Arko, A. J.; Morales, L.; Sarrao, J.

    2000-07-01

    Despite the fact that the 5f shell of the light actinides is less than half filled, the relatively short radial extent of 5f-electron wave functions yields at most minimal f-f overlap (the critical actinide-actinide spacing for which f-f overlap is no longer viable was first quantified by H. Hill and found to be 3.4 Å. The spacing for both USb2 and UAsSe is about 4.5. Å) and results in a myriad of phenomena collectively called correlated electron behavior. We present data from angle resolved photoemission studies of USb2 and UAsSe on correlated electron behavior.

  1. Electronic structure of lithium tetraborate

    NASA Astrophysics Data System (ADS)

    Wooten, David J.

    Due to many of its attributes, Li2B4O7 provides a possible material for incorporation as either a primary or companion material in future solid state neutron detectors. There is however a lack of fundamental characterization information regarding this useful material, particularly its electronic configuration. To address this, an investigation of Li2B4O7(110) and Li2B 4O7(100) was undertaken, utilizing photoemission and inverse photoemission spectroscopic techniques. The measured band gap depended on crystallographic direction with the band gaps ranging from 8.9+/-0.5 eV to 10.1+/-0.5 eV. The measurement yielded a density of states that qualitatively agreed with the theoretical results from model bulk band structure calculations for Li2B4O7; albeit with a larger band gap than predicted, but consistent with the known deficiencies of Local Density Approximation and Density Functional Theory calculations. The occupied states of both surfaces were extremely flat; to the degree that resolving periodic dispersion of the occupied states was inconclusive, within the resolution of the system. However, both surfaces demonstrated clear periodic dispersion within the empty states very close to theoretical Brillouin zone values. These attributes also translated to a lighter charge carrier effective mass in the unoccupied states. Of the two surfaces, Li2B4O 7(110) yielded the more consistent values in orthogonal directions for energy states. The presence of a bulk band gap surface state and image potential state in Li2B4O7(110) was indicative of a defect-free surface. The absence of both in the more polar, more dielectric Li2B4O7(100) was attributed to the presence of defects determined to be O vacancies. The results from Li2B 4O7(110) were indicative of a more stable surface than Li 2B4O7(100). In addition, Li 1s bulk and surface core level components were determined at the binding energies of -56.5+0.4 and -53.7+0.5 eV. Resonance features were observed along the [001

  2. Managing Inventories of Heavy Actinides

    SciTech Connect

    Wham, Robert M; Patton, Bradley D

    2011-01-01

    The Department of Energy (DOE) has stored a limited inventory of heavy actinides contained in irradiated targets, some partially processed, at the Savannah River Site (SRS) and Oak Ridge National Laboratory (ORNL). The 'heavy actinides' of interest include plutonium, americium, and curium isotopes; specifically 242Pu and 244Pu, 243Am, and 244/246/248Cm. No alternate supplies of these heavy actinides and no other capabilities for producing them are currently available. Some of these heavy actinide materials are important for use as feedstock for producing heavy isotopes and elements needed for research and commercial application. The rare isotope 244Pu is valuable for research, environmental safeguards, and nuclear forensics. Because the production of these heavy actinides was made possible only by the enormous investment of time and money associated with defense production efforts, the remaining inventories of these rare nuclear materials are an important part of the legacy of the Nuclear Weapons Program. Significant unique heavy actinide inventories reside in irradiated Mark-18A and Mark-42 targets at SRS and ORNL, with no plans to separate and store the isotopes for future use. Although the costs of preserving these heavy actinide materials would be considerable, for all practical purposes they are irreplaceable. The effort required to reproduce these heavy actinides today would likely cost billions of dollars and encompass a series of irradiation and chemical separation cycles for at least 50 years; thus, reproduction is virtually impossible. DOE has a limited window of opportunity to recover and preserve these heavy actinides before they are disposed of as waste. A path forward is presented to recover and manage these irreplaceable National Asset materials for future use in research, nuclear forensics, and other potential applications.

  3. Nuclear waste forms for actinides.

    PubMed

    Ewing, R C

    1999-03-30

    The disposition of actinides, most recently 239Pu from dismantled nuclear weapons, requires effective containment of waste generated by the nuclear fuel cycle. Because actinides (e.g., 239Pu and 237Np) are long-lived, they have a major impact on risk assessments of geologic repositories. Thus, demonstrable, long-term chemical and mechanical durability are essential properties of waste forms for the immobilization of actinides. Mineralogic and geologic studies provide excellent candidate phases for immobilization and a unique database that cannot be duplicated by a purely materials science approach. The "mineralogic approach" is illustrated by a discussion of zircon as a phase for the immobilization of excess weapons plutonium.

  4. Actinide Burning in CANDU Reactors

    SciTech Connect

    Hyland, B.; Dyck, G.R.

    2007-07-01

    Actinide burning in CANDU reactors has been studied as a method of reducing the actinide content of spent nuclear fuel from light water reactors, and thereby decreasing the associated long term decay heat load. In this work simulations were performed of actinides mixed with natural uranium to form a mixed oxide (MOX) fuel, and also mixed with silicon carbide to form an inert matrix (IMF) fuel. Both of these fuels were taken to a higher burnup than has previously been studied. The total transuranic element destruction calculated was 40% for the MOX fuel and 71% for the IMF. (authors)

  5. Electronic Structure of Lithium Tetraborate

    DTIC Science & Technology

    2010-06-01

    binding energies of -56.5+0.4 and -53.7+0.5 eV. Resonance features were observed along the [001] direction and were attributed to a Coster- Kronig ...could be theoretically explained as an Auger electron [12] or Coster- Kronig process [13] of a Li 1s electron photoexcitation to an unoccupied 2p...Coster Kronig , which requires only one Li atom. Such a Coster Kronig mechanism is pictorially displayed below in Figure 7.9. 128 Figure 7.9

  6. Electron tomography of dislocation structures

    SciTech Connect

    Liu, G.S.; House, S.D.; Kacher, J.; Tanaka, M.; Higashida, K.; Robertson, I.M.

    2014-01-15

    Recent developments in the application of electron tomography for characterizing microstructures in crystalline solids are described. The underlying principles for electron tomography are presented in the context of typical challenges in adapting the technique to crystalline systems and in using diffraction contrast imaging conditions. Methods for overcoming the limitations associated with the angular range, the number of acquired images, and uniformity of image contrast are introduced. In addition, a method for incorporating the real space coordinate system into the tomogram is presented. As the approach emphasizes development of experimental solutions to the challenges, the solutions developed and implemented are presented in the form of examples.

  7. Electron gun controlled smart structure

    DOEpatents

    Martin, Jeffrey W.; Main, John Alan; Redmond, James M.; Henson, Tammy D.; Watson, Robert D.

    2001-01-01

    Disclosed is a method and system for actively controlling the shape of a sheet of electroactive material; the system comprising: one or more electrodes attached to the frontside of the electroactive sheet; a charged particle generator, disposed so as to direct a beam of charged particles (e.g. electrons) onto the electrode; a conductive substrate attached to the backside of the sheet; and a power supply electrically connected to the conductive substrate; whereby the sheet changes its shape in response to an electric field created across the sheet by an accumulation of electric charge within the electrode(s), relative to a potential applied to the conductive substrate. Use of multiple electrodes distributed across on the frontside ensures a uniform distribution of the charge with a single point of e-beam incidence, thereby greatly simplifying the beam scanning algorithm and raster control electronics, and reducing the problems associated with "blooming". By placing a distribution of electrodes over the front surface of a piezoelectric film (or other electroactive material), this arrangement enables improved control over the distribution of surface electric charges (e.g. electrons) by creating uniform (and possibly different) charge distributions within each individual electrode. Removal or deposition of net electric charge can be affected by controlling the secondary electron yield through manipulation of the backside electric potential with the power supply. The system can be used for actively controlling the shape of space-based deployable optics, such as adaptive mirrors and inflatable antennae.

  8. Effects of 5f-elements on electronic structures and spectroscopic properties of gold superatom model

    NASA Astrophysics Data System (ADS)

    Gao, Yang; Wang, Zhigang

    2016-08-01

    5f-elements encaged in a gold superatomic cluster are capable of giving rise to unique optical properties due to their hyperactive valence electrons and great radial components of 5f/6d orbitals. Herein, we review our first-principles studies on electronic structures and spectroscopic properties of a series of actinide-embedded gold superatomic clusters with different dimensions. The three-dimensional (3D) and two-dimensional (2D) superatom clusters possess the 18-electron configuration of 1S21P61D10 and 10-electron configuration of 1S21P41D4, respectively. Importantly, their electronic absorption spectra can also be effectively explained by the superatom orbitals. Specifically, the charge transfer (CT) transitions involved in surface-enhance Raman spectroscopy (SERS) spectra for 3D and 2D structures are both from the filled 1D orbitals, providing the enhancement factors of the order of ˜ 104 at 488 nm and ˜ 105 at 456 nm, respectively. This work implies that the superatomic orbital transitions involved in 5f-elements can not only lead to a remarkable spectroscopic performance, but also a new direction for optical design in the future. Project supported by the National Natural Science Foundation of China (Grant No. 11374004), the Science and Technology Development Program of Jilin Province, China (Grant No. 20150519021JH), the Fok Ying Tung Education Foundation, China (Grant No. 142001), and the Support from the High Performance Computing Center (HPCC) of Jilin University, China.

  9. Complex structures of dense lithium: Electronic origin

    NASA Astrophysics Data System (ADS)

    Degtyareva, V. F.

    2016-11-01

    Lithium—the lightest alkali metal exhibits unexpected structures and electronic behavior at high pressures. Like the heavier alkali metals, Li is bcc at ambient pressure and transforms first to fcc (at 7.5 GPa). The post-fcc high-pressure form Li-cI 16 (at 40-60 GPa) is similar to Na-cI 16 and related to more complex structures of heavy alkalis Rb-oC52 and Cs- oC84. The other high pressure phases for Li (oC88, oC40, oC24) observed at pressures up to 130 GPa are found only in Li. The different route of Li high-pressure structures correlates with its special electronic configuration containing the only 3 electrons (at 1s and 2s levels). Crystal structures for Li are analyzed within the model of Fermi sphere-Brillouin zone interactions. Stability of post-fcc structures for Li are supported by the Hume-Rothery arguments when new diffraction plains appear close to the Fermi level producing pseudogaps near the Fermi level and decreasing the crystal energy. The filling of Brillouin-Jones zones by electron states for a given structure defines the physical properties as optical reflectivity, electrical resistivity and superconductivity. To understand the complexity of structural and physical properties of Li above 60 GPa it is necessary to assume the valence electron band overlap with the core electrons and increase the valence electron count under compression.

  10. Electronic Structure of Small Lanthanide Containing Molecules

    NASA Astrophysics Data System (ADS)

    Kafader, Jared O.; Ray, Manisha; Topolski, Josey E.; Chick Jarrold, Caroline

    2016-06-01

    Lanthanide-based materials have unusual electronic properties because of the high number of electronic degrees of freedom arising from partial occupation of 4f orbitals, which make these materials optimal for their utilization in many applications including electronics and catalysis. Electronic spectroscopy of small lanthanide molecules helps us understand the role of these 4f electrons, which are generally considered core-like because of orbital contraction, but are energetically similar to valence electrons. The spectroscopy of small lanthanide-containing molecules is relatively unexplored and to broaden this understanding we have completed the characterization of small cerium, praseodymium, and europium molecules using photoelectron spectroscopy coupled with DFT calculations. The characterization of PrO, EuH, EuO/EuOH, and CexOy molecules have allowed for the determination of their electron affinity, the assignment of numerous anion to neutral state transitions, modeling of anion/neutral structures and electron orbital occupation.

  11. Actinide Dioxides in Water: Interactions at the Interface

    SciTech Connect

    Alexandrov, Vitaly; Shvareva, Tatiana Y.; Hayun, Shmuel; Asta, Mark; Navrotsky, Alexandra

    2011-12-15

    A comprehensive understanding of chemical interactions between water and actinide dioxide surfaces is critical for safe operation and storage of nuclear fuels. Despite substantial previous research, understanding the nature of these interactions remains incomplete. In this work, we combine accurate calorimetric measurements with first-principles computational studies to characterize surface energies and adsorption enthalpies of water on two fluorite-structured compounds, ThO₂ and CeO₂, that are relevant for understanding the behavior of water on actinide oxide surfaces more generally. We determine coverage-dependent adsorption enthalpies and demonstrate a mixed molecular and dissociative structure for the first hydration layer. The results show a correlation between the magnitude of the anhydrous surface energy and the water adsorption enthalpy. Further, they suggest a structural model featuring one adsorbed water molecule per one surface cation on the most stable facet that is expected to be a common structural signature of water adsorbed on actinide dioxide compounds.

  12. Environmental research on actinide elements

    SciTech Connect

    Pinder, J.E. III; Alberts, J.J.; McLeod, K.W.; Schreckhise, R.G.

    1987-08-01

    The papers synthesize the results of research sponsored by DOE's Office of Health and Environmental Research on the behavior of transuranic and actinide elements in the environment. Separate abstracts have been prepared for the 21 individual papers. (ACR)

  13. Actinide transmutation in nuclear reactors

    SciTech Connect

    Ganev, I.K.; Lopatkin, A.V.; Naumov, V.V.; Tocheny, L.V.

    1993-12-31

    Of some interest is the comparison between the actinide nuclide burning up (fission) rates such as americium 241, americium 242, curium 244, and neptunium 237, in the reactors with fast or thermal neutron spectra.

  14. Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes

    NASA Astrophysics Data System (ADS)

    King, David M.; Cleaves, Peter A.; Wooles, Ashley J.; Gardner, Benedict M.; Chilton, Nicholas F.; Tuna, Floriana; Lewis, William; McInnes, Eric J. L.; Liddle, Stephen T.

    2016-12-01

    Determining the electronic structure of actinide complexes is intrinsically challenging because inter-electronic repulsion, crystal field, and spin-orbit coupling effects can be of similar magnitude. Moreover, such efforts have been hampered by the lack of structurally analogous families of complexes to study. Here we report an improved method to U≡N triple bonds, and assemble a family of uranium(V) nitrides. Along with an isoelectronic oxo, we quantify the electronic structure of this 5f1 family by magnetometry, optical and electron paramagnetic resonance (EPR) spectroscopies and modelling. Thus, we define the relative importance of the spin-orbit and crystal field interactions, and explain the experimentally observed different ground states. We find optical absorption linewidths give a potential tool to identify spin-orbit coupled states, and show measurement of UV...UV super-exchange coupling in dimers by EPR. We show that observed slow magnetic relaxation occurs via two-phonon processes, with no obvious correlation to the crystal field.

  15. Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes

    PubMed Central

    King, David M.; Cleaves, Peter A.; Wooles, Ashley J.; Gardner, Benedict M.; Chilton, Nicholas F.; Tuna, Floriana; Lewis, William; McInnes, Eric J. L.; Liddle, Stephen T.

    2016-01-01

    Determining the electronic structure of actinide complexes is intrinsically challenging because inter-electronic repulsion, crystal field, and spin–orbit coupling effects can be of similar magnitude. Moreover, such efforts have been hampered by the lack of structurally analogous families of complexes to study. Here we report an improved method to U≡N triple bonds, and assemble a family of uranium(V) nitrides. Along with an isoelectronic oxo, we quantify the electronic structure of this 5f1 family by magnetometry, optical and electron paramagnetic resonance (EPR) spectroscopies and modelling. Thus, we define the relative importance of the spin–orbit and crystal field interactions, and explain the experimentally observed different ground states. We find optical absorption linewidths give a potential tool to identify spin–orbit coupled states, and show measurement of UV···UV super-exchange coupling in dimers by EPR. We show that observed slow magnetic relaxation occurs via two-phonon processes, with no obvious correlation to the crystal field. PMID:27996007

  16. In pursuit of homoleptic actinide alkyl complexes.

    PubMed

    Seaman, Lani A; Walensky, Justin R; Wu, Guang; Hayton, Trevor W

    2013-04-01

    This Forum Article describes the pursuit of isolable homoleptic actinide alkyl complexes, starting with the pioneering work of Gilman during the Manhattan project. The initial reports in this area suggested that homoleptic uranium alkyls were too unstable to be isolated, but Wilkinson demonstrated that tractable uranium alkyls could be generated by purposeful "ate" complex formation, which serves to saturate the uranium coordination sphere and provide the complexes with greater kinetic stability. More recently, we reported the solid-state molecular structures of several homoleptic uranium alkyl complexes, including [Li(THF)4][U(CH2(t)Bu)5], [Li(TMEDA)]2[UMe6], [K(THF)]3[K(THF)2][U(CH2Ph)6]2, and [Li(THF)4][U(CH2SiMe3)6], by employing Wilkinson's strategy. Herein, we describe our attempts to extend this chemistry to thorium. The treatment of ThCl4(DME)2 with 5 equiv of LiCH2(t)Bu or LiCH2SiMe3 at -25 °C in THF affords [Th(CH2(t)Bu)5] (1) and [Li(DME)2][Th(CH2SiMe3)5 (2), respectively, in moderate yields. Similarly, the treatment of ThCl4(DME)2 with 6 equiv of K(CH2Ph) produces [K(THF)]2[Th(CH2Ph)6] (3), in good yield. Complexes 1-3 have been fully characterized, while the structures of 1 and 3 were confirmed by X-ray crystallography. Additionally, the electronic properties of 1 and 3 were explored by density functional theory.

  17. Structural physiology based on electron crystallography

    PubMed Central

    Fujiyoshi, Yoshinori

    2011-01-01

    There are many questions in brain science, which are extremely interesting but very difficult to answer. For example, how do education and other experiences during human development influence the ability and personality of the adult? The molecular mechanisms underlying such phenomena are still totally unclear. However, technological and instrumental advancements of electron microscopy have facilitated comprehension of the structures of biological components, cells, and organelles. Electron crystallography is especially good for studying the structure and function of membrane proteins, which are key molecules of signal transduction in neural and other cells. Electron crystallography is now an established technique to analyze the structures of membrane proteins in lipid bilayers, which are close to their natural biological environment. By utilizing cryo-electron microscopes with helium cooled specimen stages, which were developed through a personal motivation to understand functions of neural systems from a structural point of view, structures of membrane proteins were analyzed at a resolution higher than 3 Å. This review has four objectives. First, it is intended to introduce the new research field of structural physiology. Second, it introduces some of the personal struggles, which were involved in developing the cryo-electron microscope. Third, it discusses some of the technology for the structural analysis of membrane proteins based on cryo-electron microscopy. Finally, it reviews structural and functional analyses of membrane proteins. PMID:21416541

  18. Laboratory actinide partitioning - Whitlockite/liquid and influence of actinide concentration levels

    NASA Technical Reports Server (NTRS)

    Benjamin, T. M.; Jones, J. H.; Heuser, W. R.; Burnett, D. S.

    1983-01-01

    The partition coefficients between synthetic whitlockite (beta Ca-phosphate) and coexisting silicate melts are determined for the actinide elements Th, U and Pu. Experiments were performed at 1 bar pressure and 1250 C at oxygen fugacities from 10 to the -8.5 to 10 to the -0.7 bars, and partitioning was determined from trace element radiography combined with conventional electron microprobe analysis. Results show Pu to be more readily incorporated into crystalline phases than U or Th under reducing conditions, which is attributed to the observation that Pu exists primarily in the trivalent state, while U and Th are tetravalent. Corrected partition coefficients for whitlockite of 3.6, less than or equal to 0.6, 1.2, 0.5 and less than or equal to 0.002 are estimated for Pu(+3), Pu(+4), Th(+4), U(+4) and U(+6), respectively. Experiments performed at trace levels and percent levels of UO2 indicate that Si is involved in U substitution in whitlockite, and show a reduced partition coefficient at higher concentrations of U that can be explained by effects on melt structure or the fraction of tetravalent U.

  19. Instructional Approach to Molecular Electronic Structure Theory

    ERIC Educational Resources Information Center

    Dykstra, Clifford E.; Schaefer, Henry F.

    1977-01-01

    Describes a graduate quantum mechanics projects in which students write a computer program that performs ab initio calculations on the electronic structure of a simple molecule. Theoretical potential energy curves are produced. (MLH)

  20. Computational Chemistry Using Modern Electronic Structure Methods

    ERIC Educational Resources Information Center

    Bell, Stephen; Dines, Trevor J.; Chowdhry, Babur Z.; Withnall, Robert

    2007-01-01

    Various modern electronic structure methods are now days used to teach computational chemistry to undergraduate students. Such quantum calculations can now be easily used even for large size molecules.

  1. Controlling the Electronic Structure of Bilayer Graphene

    NASA Astrophysics Data System (ADS)

    Ohta, Taisuke; Bostwick, Aaron; Seyller, Thomas; Horn, Karsten; Rotenberg, Eli

    2006-08-01

    We describe the synthesis of bilayer graphene thin films deposited on insulating silicon carbide and report the characterization of their electronic band structure using angle-resolved photoemission. By selectively adjusting the carrier concentration in each layer, changes in the Coulomb potential led to control of the gap between valence and conduction bands. This control over the band structure suggests the potential application of bilayer graphene to switching functions in atomic-scale electronic devices.

  2. Pressure-induced changes in the electronic structure of americium metal

    SciTech Connect

    Soderlind, P; Moore, K T; Landa, A; Bradley, J A

    2011-02-25

    We have conducted electronic-structure calculations for Am metal under pressure to investigate the behavior of the 5f-electron states. Density-functional theory (DFT) does not reproduce the experimental photoemission spectra for the ground-state phase where the 5f electrons are localized, but the theory is expected to be correct when 5f delocalization occurs under pressure. The DFT prediction is that peak structures of the 5f valence band will merge closer to the Fermi level during compression indicating presence of itinerant 5f electrons. Existence of such 5f bands is argued to be a prerequisite for the phase transitions, particularly to the primitive orthorhombic AmIV phase, but does not agree with modern dynamical-mean-field theory (DMFT) results. Our DFT model further suggests insignificant changes of the 5f valence under pressure in agreement with recent resonant x-ray emission spectroscopy, but in contradiction to the DMFT predictions. The influence of pressure on the 5f valency in the actinides is discussed and is shown to depend in a non-trivial fashion on 5f band position and occupation relative to the spd valence bands.

  3. Synthesis and characterization of a tetrathiafulvalene-salphen actinide complex.

    PubMed

    Bejger, Christopher; Tian, Yong-Hui; Barker, Beau J; Boland, Kevin S; Scott, Brian L; Batista, Enrique R; Kozimor, Stosh A; Sessler, Jonathan L

    2013-05-21

    A new tetrathiafulvalene-salphen uranyl complex has been prepared. The system was designed to study the electronic coupling between actinides and a redox active ligand framework. Theoretical and experimental methods--including DFT calculations, single crystal X-ray analysis, cyclic voltammetry, NMR and IR spectroscopies--were used to characterize this new uranyl complex.

  4. Foil support structure for large electron guns

    SciTech Connect

    Brucker, J.P.; Rose, E.A.

    1993-08-01

    This paper describes a novel support structure for a vacuum diode used to pump a gaseous laser with an electron beam. Conventional support structures are designed to hold a foil flat and rigid. This new structure takes advantage of the significantly greater strength of metals in pure tension, utilizing curved shapes for both foil and support structure. The shape of the foil is comparable to the skin of a balloon, and the shape of the support structures is comparable to the cables of a suspension bridge. This design allows a significant reduction in foil thickness and support structure mass, resulting in a lower electron-beam loss between diode and laser gas. In addition, the foil is pre-formed in the support structure at pressures higher than operating pressure. Therefore, the foil is operated far from the yield point. Increased reliability is anticipated.

  5. Unique Four-Electron Metal-to-Cage Charge Transfer of Th to a C82 Fullerene Cage: Complete Structural Characterization of Th@C3v(8)-C82.

    PubMed

    Wang, Yaofeng; Morales-Martínez, Roser; Zhang, Xingxing; Yang, Wei; Wang, Yaxing; Rodríguez-Fortea, Antonio; Poblet, Josep M; Feng, Lai; Wang, Shuao; Chen, Ning

    2017-03-31

    Endohedral metallofullerenes (EMFs) containing lanthanides have been intensively studied in recent years. By contrast, actinide endohedral fullerenes remain largely unexplored. Herein, for the first time, we report the single crystal structure and full characterization of an actinide endohedral fullerene, Th@C82, which exhibits remarkably different electronic and spectroscopic properties compared to those of lanthanide EMFs. Single crystal X-ray crystallography unambiguously established the molecular structure as Th@C3v(8)-C82. Combined experimental and theoretical studies reveal that Th@C3v(8)-C82 is the first example of an isolated monometallofullerene with four electrons transferred from the metal to the cage, with a surprisingly large electrochemical band gap of 1.51 eV. Moreover, Th@C3v(8)-C82 displays a strong vibrationally coupled photoluminescence signal in the visible region, an extremely rare feature for both fullerenes and thorium compounds.

  6. Mathematical modeling of the effects of aerobic and anaerobic chelate bioegradation on actinide speciation.

    SciTech Connect

    Banaszak, J.E.; VanBriesen, J.; Rittmann, B.E.; Reed, D.T.

    1998-03-19

    Biodegradation of natural and anthropogenic chelating agents directly and indirectly affects the speciation, and, hence, the mobility of actinides in subsurface environments. We combined mathematical modeling with laboratory experimentation to investigate the effects of aerobic and anaerobic chelate biodegradation on actinide [Np(IV/V), Pu(IV)] speciation. Under aerobic conditions, nitrilotriacetic acid (NTA) biodegradation rates were strongly influenced by the actinide concentration. Actinide-chelate complexation reduced the relative abundance of available growth substrate in solution and actinide species present or released during chelate degradation were toxic to the organisms. Aerobic bio-utilization of the chelates as electron-donor substrates directly affected actinide speciation by releasing the radionuclides from complexed form into solution, where their fate was controlled by inorganic ligands in the system. Actinide speciation was also indirectly affected by pH changes caused by organic biodegradation. The two concurrent processes of organic biodegradation and actinide aqueous chemistry were accurately linked and described using CCBATCH, a computer model developed at Northwestern University to investigate the dynamics of coupled biological and chemical reactions in mixed waste subsurface environments. CCBATCH was then used to simulate the fate of Np during anaerobic citrate biodegradation. The modeling studies suggested that, under some conditions, chelate degradation can increase Np(IV) solubility due to carbonate complexation in closed aqueous systems.

  7. Quantum Mechanical Studies of the Early Actinide Compounds

    NASA Astrophysics Data System (ADS)

    Obodo, Kingsley Onyebuchi

    This study involves the investigation of the early actinide systems using ab initio techniques based on density functional theory (DFT). It was motivated by: (i) the incomplete description of these systems using conventional DFT because they are strongly correlated, (ii) the usefulness of these systems in nuclear energy generation, (iii) the complexity that arises in experimentally studying these systems due to their inherent radioactive nature and (iv) their limited availability. The results obtained from this study are divided into two broad sections. The first comprises chapters 3 and 4 while the second comprises chapters 5 and 6. Thorium based compounds are studied in chapters 3 and 4. In the first section, the Hubbard U parameter is not necessary to accurately describe the electronic, elastic and mechanical properties of these systems. In the second, the inclusion of the Hubbard U parameter is shown to be paramount for the accurate description of most compounds considered. Chapter 3 presents the electronic, structural and bonding character of thorium based nitrides. We obtained the result that Th2N2 NH, which is crystallographically equivalent to metallic Th2N 3, is insulating. Chapter 4 demonstrates that the formation of a meta-stable thorium-titanium based alloy is plausible and also further information on bonding, electronic and elastic properties of the determined meta-stable alloy is provided. This has provided important new knowledge about these bulk systems. In Chapter 5 the DFT + U based study on Pa and its oxides is presented. The electronic, structural and bonding character of these systems was studied. We found that PaO2 is a Mott-Hubbard insulator with an indirect band gap of 3.48 eV within the generalized gradient approximation GGA + U. Chapter 6 discusses various actinide nitrides. We explored the electronic properties, elastic properties, lattice dynamics and the energetics of the various compounds using GGA + U. Also, we investigated the effect

  8. Kinetics of actinide complexation reactions

    SciTech Connect

    Nash, K.L.; Sullivan, J.C.

    1997-09-01

    Though the literature records extensive compilations of the thermodynamics of actinide complexation reactions, the kinetics of complex formation and dissociation reactions of actinide ions in aqueous solutions have not been extensively investigated. In light of the central role played by such reactions in actinide process and environmental chemistry, this situation is somewhat surprising. The authors report herein a summary of what is known about actinide complexation kinetics. The systems include actinide ions in the four principal oxidation states (III, IV, V, and VI) and complex formation and dissociation rates with both simple and complex ligands. Most of the work reported was conducted in acidic media, but a few address reactions in neutral and alkaline solutions. Complex formation reactions tend in general to be rapid, accessible only to rapid-scan and equilibrium perturbation techniques. Complex dissociation reactions exhibit a wider range of rates and are generally more accessible using standard analytical methods. Literature results are described and correlated with the known properties of the individual ions.

  9. 33rd Actinide Separations Conference

    SciTech Connect

    McDonald, L M; Wilk, P A

    2009-05-04

    Welcome to the 33rd Actinide Separations Conference hosted this year by the Lawrence Livermore National Laboratory. This annual conference is centered on the idea of networking and communication with scientists from throughout the United States, Britain, France and Japan who have expertise in nuclear material processing. This conference forum provides an excellent opportunity for bringing together experts in the fields of chemistry, nuclear and chemical engineering, and actinide processing to present and discuss experiences, research results, testing and application of actinide separation processes. The exchange of information that will take place between you, and other subject matter experts from around the nation and across the international boundaries, is a critical tool to assist in solving both national and international problems associated with the processing of nuclear materials used for both defense and energy purposes, as well as for the safe disposition of excess nuclear material. Granlibakken is a dedicated conference facility and training campus that is set up to provide the venue that supports communication between scientists and engineers attending the 33rd Actinide Separations Conference. We believe that you will find that Granlibakken and the Lake Tahoe views provide an atmosphere that is stimulating for fruitful discussions between participants from both government and private industry. We thank the Lawrence Livermore National Laboratory and the United States Department of Energy for their support of this conference. We especially thank you, the participants and subject matter experts, for your involvement in the 33rd Actinide Separations Conference.

  10. Fundamental aspects of actinide-zirconium pyrochlore oxides: Systematic comparison of the Pu, Am, Cm, Bk and Cf systems

    NASA Astrophysics Data System (ADS)

    Haire, R. G.; Raison, P. E.

    2000-07-01

    Zirconium- and hafnium-based oxide materials have gained attraction for various nuclear applications. These materials have features in common with one of the early, well-publicized inorganic ceramics for immobilizing nuclear waste. Our interests have addressed the fundamental structural and chemical properties of these oxide systems. We pursued both the crystal chemical constraints of the oxide matrices, as well as the importance of the chemistry of the f-elements. By incorporating five actinide elements in our studies, we were able to compare systematically the materials science of these materials with the fundamental chemistry and electronic configurations of these actinides employed. It is expected that this basic information will be useful technologically in the realm of tailor-made materials for different applications.

  11. Ab Initio Enhanced calphad Modeling of Actinide-Rich Nuclear Fuels

    SciTech Connect

    Morgan, Dane; Yang, Yong Austin

    2013-10-28

    The process of fuel recycling is central to the Advanced Fuel Cycle Initiative (AFCI), where plutonium and the minor actinides (MA) Am, Np, and Cm are extracted from spent fuel and fabricated into new fuel for a fast reactor. Metallic alloys of U-Pu-Zr-MA are leading candidates for fast reactor fuels and are the current basis for fast spectrum metal fuels in a fully recycled closed fuel cycle. Safe and optimal use of these fuels will require knowledge of their multicomponent phase stability and thermodynamics (Gibbs free energies). In additional to their use as nuclear fuels, U-Pu-Zr-MA contain elements and alloy phases that pose fundamental questions about electronic structure and energetics at the forefront of modern many-body electron theory. This project will validate state-of-the-art electronic structure approaches for these alloys and use the resulting energetics to model U-Pu-Zr-MA phase stability. In order to keep the work scope practical, researchers will focus on only U-Pu-Zr-{Np,Am}, leaving Cm for later study. The overall objectives of this project are to: Provide a thermodynamic model for U-Pu-Zr-MA for improving and controlling reactor fuels; and, Develop and validate an ab initio approach for predicting actinide alloy energetics for thermodynamic modeling.

  12. Siderocalin-mediated recognition, sensitization, and cellular uptake of actinides

    PubMed Central

    Allred, Benjamin E.; Rupert, Peter B.; Gauny, Stacey S.; An, Dahlia D.; Ralston, Corie Y.; Sturzbecher-Hoehne, Manuel; Strong, Roland K.; Abergel, Rebecca J.

    2015-01-01

    Synthetic radionuclides, such as the transuranic actinides plutonium, americium, and curium, present severe health threats as contaminants, and understanding the scope of the biochemical interactions involved in actinide transport is instrumental in managing human contamination. Here we show that siderocalin, a mammalian siderophore-binding protein from the lipocalin family, specifically binds lanthanide and actinide complexes through molecular recognition of the ligands chelating the metal ions. Using crystallography, we structurally characterized the resulting siderocalin–transuranic actinide complexes, providing unprecedented insights into the biological coordination of heavy radioelements. In controlled in vitro assays, we found that intracellular plutonium uptake can occur through siderocalin-mediated endocytosis. We also demonstrated that siderocalin can act as a synergistic antenna to sensitize the luminescence of trivalent lanthanide and actinide ions in ternary protein–ligand complexes, dramatically increasing the brightness and efficiency of intramolecular energy transfer processes that give rise to metal luminescence. Our results identify siderocalin as a potential player in the biological trafficking of f elements, but through a secondary ligand-based metal sequestration mechanism. Beyond elucidating contamination pathways, this work is a starting point for the design of two-stage biomimetic platforms for photoluminescence, separation, and transport applications. PMID:26240330

  13. Siderocalin-mediated recognition, sensitization, and cellular uptake of actinides.

    PubMed

    Allred, Benjamin E; Rupert, Peter B; Gauny, Stacey S; An, Dahlia D; Ralston, Corie Y; Sturzbecher-Hoehne, Manuel; Strong, Roland K; Abergel, Rebecca J

    2015-08-18

    Synthetic radionuclides, such as the transuranic actinides plutonium, americium, and curium, present severe health threats as contaminants, and understanding the scope of the biochemical interactions involved in actinide transport is instrumental in managing human contamination. Here we show that siderocalin, a mammalian siderophore-binding protein from the lipocalin family, specifically binds lanthanide and actinide complexes through molecular recognition of the ligands chelating the metal ions. Using crystallography, we structurally characterized the resulting siderocalin-transuranic actinide complexes, providing unprecedented insights into the biological coordination of heavy radioelements. In controlled in vitro assays, we found that intracellular plutonium uptake can occur through siderocalin-mediated endocytosis. We also demonstrated that siderocalin can act as a synergistic antenna to sensitize the luminescence of trivalent lanthanide and actinide ions in ternary protein-ligand complexes, dramatically increasing the brightness and efficiency of intramolecular energy transfer processes that give rise to metal luminescence. Our results identify siderocalin as a potential player in the biological trafficking of f elements, but through a secondary ligand-based metal sequestration mechanism. Beyond elucidating contamination pathways, this work is a starting point for the design of two-stage biomimetic platforms for photoluminescence, separation, and transport applications.

  14. Crystal growth methods dedicated to low solubility actinide oxalates

    NASA Astrophysics Data System (ADS)

    Tamain, C.; Arab-Chapelet, B.; Rivenet, M.; Grandjean, S.; Abraham, F.

    2016-04-01

    Two novel crystal growth syntheses dedicated to low solubility actinide-oxalate systems and adapted to glove box handling are described. These methods based on the use of precursors of either actinide metal or oxalic acid have been optimized on lanthanide systems (analogue of actinides(III)) and then assessed on real actinide systems. They allow the synthesis of several actinide oxalate single crystals, Am2(C2O4)3(H2O)3·xH2O, Th(C2O4)2·6H2O, M2+x[PuIV2-xPuIIIx(C2O4)5]·nH2O and M1-x[PuIII1-xPuIVx(C2O4)2·H2O]·nH2O. It is the first time that these well-known compounds are formed by crystal growth methods, thus enabling direct structural studies on transuranic element systems and acquisition of basic data beyond deductions from isomorphic (or not) lanthanide compounds. Characterizations by X-ray diffraction, UV-visible solid spectroscopy, demonstrate the potentialities of these two crystal growth methods to obtain oxalate compounds.

  15. Improving electronic structure methods to predict nano-optoelectronics and nano-catalyst functions.

    SciTech Connect

    Nielsen, Ida Marie B.; Marzari, Nicola; Shelnutt, John Allen; Kulik, Heather J.; Medforth, Craig John; Leung, Kevin

    2009-10-01

    This report focuses on quantum chemistry and ab initio molecular dynamics (AIMD) calculations applied to elucidate the mechanism of the multi-step, 2-electron, electrochemical reduction of the green house gas molecule carbon dioxide (CO{sub 2}) to carbon monoxide (CO) in aqueous media. When combined with H{sub 2} gas to form synthesis ('syn') gas, CO becomes a key precursor to methane, methanol, and other useful hydrocarbon products. To elucidate the mechanism of this reaction, we apply computational electrochemistry which is a fledgling, important area of basic science critical to energy storage. This report highlights several approaches, including the calculation of redox potentials, the explicit depiction of liquid water environments using AIMD, and free energy methods. While costly, these pioneering calculations reveal the key role of hydration- and protonation-stabilization of reaction intermediates, and may inform the design of CO{sub 2}-capture materials as well as its electrochemical reduction. In the course of this work, we have also dealt with the challenges of identifying and applying electronic structure methods which are sufficiently accurate to deal with transition metal ion complex-based catalyst. Such electronic structure methods are also pertinent to the accurate modeling of actinide materials and therefore to nuclear energy research. Our multi-pronged effort towards achieving this titular goal of the LDRD is discussed.

  16. Electronic structure and polarizability of metallic nanoshells

    NASA Astrophysics Data System (ADS)

    Prodan, E.; Nordlander, P.

    2002-01-01

    An efficient method for the calculation of the electronic structure of metallic nanoshells is developed. The method is applied to a large nanoshell (of 10 nm in diameter) containing more than 2.5×10 4 conduction electrons. The calculations show that the density of states of the nanoshell is relatively bulk-like. The frequency dependent polarizability is calculated and shown to display strong confinement effects and features similar to what is predicted by semi-classical electrodynamic theory.

  17. Nuclear waste forms for actinides

    PubMed Central

    Ewing, Rodney C.

    1999-01-01

    The disposition of actinides, most recently 239Pu from dismantled nuclear weapons, requires effective containment of waste generated by the nuclear fuel cycle. Because actinides (e.g., 239Pu and 237Np) are long-lived, they have a major impact on risk assessments of geologic repositories. Thus, demonstrable, long-term chemical and mechanical durability are essential properties of waste forms for the immobilization of actinides. Mineralogic and geologic studies provide excellent candidate phases for immobilization and a unique database that cannot be duplicated by a purely materials science approach. The “mineralogic approach” is illustrated by a discussion of zircon as a phase for the immobilization of excess weapons plutonium. PMID:10097054

  18. 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.

  19. Defect Induced Electronic Structure of Uranofullerene

    PubMed Central

    Dai, Xing; Cheng, Cheng; Zhang, Wei; Xin, Minsi; Huai, Ping; Zhang, Ruiqin; Wang, Zhigang

    2013-01-01

    The interaction between the inner atoms/cluster and the outer fullerene cage is the source of various novel properties of endohedral metallofullerenes. Herein, we introduce an adatom-type spin polarization defect on the surface of a typical endohedral stable U2@C60 to predict the associated structure and electronic properties of U2@C61 based on the density functional theory method. We found that defect induces obvious changes in the electronic structure of this metallofullerene. More interestingly, the ground state of U2@C61 is nonet spin in contrast to the septet of U2@C60. Electronic structure analysis shows that the inner U atoms and the C ad-atom on the surface of the cage contribute together to this spin state, which is brought about by a ferromagnetic coupling between the spin of the unpaired electrons of the U atoms and the C ad-atom. This discovery may provide a possible approach to adapt the electronic structure properties of endohedral metallofullerenes. PMID:23439318

  20. Preliminary considerations concerning actinide solubilities

    SciTech Connect

    Newton, T.W.; Bayhurst, B.P.; Daniels, W.R.; Erdal, B.R.; Ogard, A.E.

    1980-01-01

    Work at the Los Alamos Scientific Laboratory on the fundamental solution chemistry of the actinides has thus far been confined to preliminary considerations of the problems involved in developing an understanding of the precipitation and dissolution behavior of actinide compounds under environmental conditions. Attempts have been made to calculate solubility as a function of Eh and pH using the appropriate thermodynamic data; results have been presented in terms of contour maps showing lines of constant solubility as a function of Eh and pH. Possible methods of control of the redox potential of rock-groundwater systems by the use of Eh buffers (redox couples) is presented.

  1. Actinide chemistry in ionic liquids.

    PubMed

    Takao, Koichiro; Bell, Thomas James; Ikeda, Yasuhisa

    2013-04-01

    This Forum Article provides an overview of the reported studies on the actinide chemistry in ionic liquids (ILs) with a particular focus on several fundamental chemical aspects: (i) complex formation, (ii) electrochemistry, and (iii) extraction behavior. The majority of investigations have been dedicated to uranium, especially for the 6+ oxidation state (UO2(2+)), because the chemistry of uranium in ordinary solvents has been well investigated and uranium is the most abundant element in the actual nuclear fuel cycles. Other actinides such as thorium, neptunium, plutonium, americium, and curiumm, although less studied, are also of importance in fully understanding the nuclear fuel engineering process and the safe geological disposal of radioactive wastes.

  2. Actinide Thermodynamics at Elevated Temperatures

    SciTech Connect

    Friese, Judah I.; Rao, Linfeng; Xia, Yuanxian; Bachelor, Paula P.; Tian, Guoxin

    2007-11-16

    The postclosure chemical environment in the proposed Yucca Mountain repository is expected to experience elevated temperatures. Predicting migration of actinides is possible if sufficient, reliable thermodynamic data on hydrolysis and complexation are available for these temperatures. Data are scarce and scattered for 25 degrees C, and nonexistent for elevated temperatures. This collaborative project between LBNL and PNNL collects thermodynamic data at elevated temperatures on actinide complexes with inorganic ligands that may be present in Yucca Mountain. The ligands include hydroxide, fluoride, sulfate, phosphate and carbonate. Thermodynamic parameters of complexation, including stability constants, enthalpy, entropy and heat capacity of complexation, are measured with a variety of techniques including solvent extraction, potentiometry, spectrophotometry and calorimetry

  3. Boron Fullerenes: An Electronic Structure Study

    NASA Astrophysics Data System (ADS)

    Sadrzadeh, Arta; Pupysheva, Olga; Boustani, Ihsan; Yakobson, Boris

    2008-03-01

    Using ab initio calculations, we study electronic structure and frequency modes of B80, a member of boron fullerene family made from boron isomorphs of carbon fullerenes with additional atoms in the centers of hexagons. We also investigate geometrical and electronic structural properties of double-rings with various diameters, which are important as building blocks of boron nanotubes, and as the most stable clusters among the studied isomers with no more than 36 atoms. Double-rings also appear as building blocks of B80. Furthermore, we investigate the possibility of further stabilizing some of fullerenes by depleting them.

  4. Complete recovery of actinides from UREX-like raffinates using a combination of hard and soft donor ligands. II. soft donor structure variation

    DOE PAGES

    Zalupski, Peter R.; Klaehn, John R.; Peterman, Dean R.

    2015-07-30

    The feasibility of simultaneous separation of uranium, neptunium, plutonium, americium, and curium from a simulated dissolved used fuel simulant adjusted to 1.0 M nitric acid is investigated using a mixture of the soft donor bis(bis-3,5-trifluoromethyl)phenyl) dithiophosphinic acid (“0”) and the hard donor synergist trioctylphosphine oxide (TOPO) dissolved in toluene. The results reported in this work are compared to our recent demonstration of a complete actinide recovery from a simulated dissolved fuel solution using a synergistic combination of bis(o-trifluoromethylphenyl)dithiophosphinic acid (“1”) and TOPO dissolved in either toluene or trifluoromethylphenyl sulfone. While the extraction efficiency of americium was enhanced for the liquid-liquidmore » system containing “0”, enabling to accomplish a trivalent An/Ln separation at 1.0 M HNO3, the extraction of neptunium was drastically diminished, relative to “1”. The partitioning behavior of curium was also negatively impacted, introducing an effective opportunity for americium/curium separation. Radiometric and spectrophotometric studies demonstrate that the complete actinide recovery using the solvent based upon “0” and TOPO is not feasible. Additionally, the importance of radiolytic degradation processes is discussed through the comparisons of extraction properties of liquid-liquid systems based on both soft donor reagents.« less

  5. Complete recovery of actinides from UREX-like raffinates using a combination of hard and soft donor ligands. II. soft donor structure variation

    SciTech Connect

    Zalupski, Peter R.; Klaehn, John R.; Peterman, Dean R.

    2015-07-30

    The feasibility of simultaneous separation of uranium, neptunium, plutonium, americium, and curium from a simulated dissolved used fuel simulant adjusted to 1.0 M nitric acid is investigated using a mixture of the soft donor bis(bis-3,5-trifluoromethyl)phenyl) dithiophosphinic acid (“0”) and the hard donor synergist trioctylphosphine oxide (TOPO) dissolved in toluene. The results reported in this work are compared to our recent demonstration of a complete actinide recovery from a simulated dissolved fuel solution using a synergistic combination of bis(o-trifluoromethylphenyl)dithiophosphinic acid (“1”) and TOPO dissolved in either toluene or trifluoromethylphenyl sulfone. While the extraction efficiency of americium was enhanced for the liquid-liquid system containing “0”, enabling to accomplish a trivalent An/Ln separation at 1.0 M HNO3, the extraction of neptunium was drastically diminished, relative to “1”. The partitioning behavior of curium was also negatively impacted, introducing an effective opportunity for americium/curium separation. Radiometric and spectrophotometric studies demonstrate that the complete actinide recovery using the solvent based upon “0” and TOPO is not feasible. Additionally, the importance of radiolytic degradation processes is discussed through the comparisons of extraction properties of liquid-liquid systems based on both soft donor reagents.

  6. Utilizing Nano-focussed Bremstrahlung Isochromat Spectroscopy (nBIS) to Determine the Unoccupied Electronic Structure of Pu

    SciTech Connect

    Butterfield, M T; Tobin, J G; Teslich, N E; Bliss, R A; Wall, M A; McMahan, A K; Chung, B W; Schwartz, A J; Kutepov, A L

    2005-11-01

    Understanding the behavior of 5f electrons remains an unrealized ambition of condensed matter physics [1,2]. Recently, there has been a large amount of interest in the actinides, particularly plutonium, driven by the complex and intriguing behavior of Pu and several of its compounds [3-5]. This has prompted both theoretical and experimental investigations of 5f metals and compounds. Of the different allotropes of Pu, the d-phase is of particular interest because of the high symmetry crystal structure and the stability of the phase to low temperatures when alloyed with small amounts of trivalent elements. Consequently much of the recent experimental and theoretical work has focused on this allotrope. From an experimental point of view, the reactivity and radioactivity of Pu, and the complexity of the phase diagram, make it exceedingly complicated to collect high-quality data. Investigations of these complex behaviors all point back to being caused by the intriguing interplay of the various electron states and in particular the behavior of the 5f states. While there are a number of ongoing experimental efforts directed at determining the occupied electronic structure of Pu, there is essentially no experimental data on the unoccupied electronic structure of Pu. We aim to determine the conduction band (unoccupied) electronic structure of Pu and other actinides in a phase specific fashion and emphasizing bulk contributions by using Nano-focussed Bremstrahlung Isochromat Spectroscopy (nBIS). Bremstrahlung Isochromat Spectroscopy (BIS) is the high-energy variant of inverse photoelectron spectroscopy (IPES: electron in, photon out), which is essentially the time reversal of photoelectron spectroscopy (photon in, electron out). IPES can be used to follow the dispersion of electronic states in ordered samples. Owing to its low energies, IPES is usually very surface sensitive. However, by working at higher energies (>200 eV), we will sample preferentially for bulk properties

  7. Separations of actinides, lanthanides and other metals

    DOEpatents

    Smith, Barbara F.; Jarvinen, Gordon D.; Ensor, Dale D.

    1995-01-01

    An organic extracting solution comprised of a bis(acylpyrazolone or a substituted bis(acylpyrazolone) and an extraction method useful for separating certain elements of the actinide series of the periodic table having a valence of four from one other, and also from one or more of the substances in a group consisting of hexavalent actinides, trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals and also from one or more of the substances in a group consisting of hexavalent actinides, trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals and also useful for separating hexavalent actinides from one or more of the substances in a group consisting of trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals.

  8. Electronic and structural properties of functional nanostructures

    NASA Astrophysics Data System (ADS)

    Yang, Teng

    In this Thesis, I present a study of electronic and structural properties of functional nanostructures such as MoSxIy nanowires, self-assembled monolayer on top of metallic surfaces and structural changes induced in graphite by photo excitations. MoSxI y nanowires, which can be easily synthesized in one step, show many advantages over conventional carbon nanotubes in molecular electronics and many other applications. But how to self-assemble them into desired pattern for practical electronic network? Self-assembled monolayers of polymers on metallic surfaces may help to guide pattern formation of some nanomaterials such as MoSxIy nanowires. I have investigated the physical properties of these nanoscale wires and microscopic self-assembly mechanisms of patterns by total energy calculations combined with molecular dynamics simulations and structure optimization. First, I studied the stability of novel Molybdenum chaicohalide nanowires, a candidate for molecular electronics applications. Next, I investigated the self-assembly of nanoparticles into ordered arrays with the aid of a template. Such templates, I showed, can be formed by polymer adsorption on surfaces such as highly ordered pyrolytic graphite and Ag(111). Finally, I studied the physical origin of of structural changes induced in graphite by light in form of a femtosecond laser pulse.

  9. Structure refinement from precession electron diffraction data.

    PubMed

    Palatinus, Lukáš; Jacob, Damien; Cuvillier, Priscille; Klementová, Mariana; Sinkler, Wharton; Marks, Laurence D

    2013-03-01

    Electron diffraction is a unique tool for analysing the crystal structures of very small crystals. In particular, precession electron diffraction has been shown to be a useful method for ab initio structure solution. In this work it is demonstrated that precession electron diffraction data can also be successfully used for structure refinement, if the dynamical theory of diffraction is used for the calculation of diffracted intensities. The method is demonstrated on data from three materials - silicon, orthopyroxene (Mg,Fe)(2)Si(2)O(6) and gallium-indium tin oxide (Ga,In)(4)Sn(2)O(10). In particular, it is shown that atomic occupancies of mixed crystallographic sites can be refined to an accuracy approaching X-ray or neutron diffraction methods. In comparison with conventional electron diffraction data, the refinement against precession diffraction data yields significantly lower figures of merit, higher accuracy of refined parameters, much broader radii of convergence, especially for the thickness and orientation of the sample, and significantly reduced correlations between the structure parameters. The full dynamical refinement is compared with refinement using kinematical and two-beam approximations, and is shown to be superior to the latter two.

  10. Electronic structure of Mn and Fe oxides

    NASA Astrophysics Data System (ADS)

    Harrison, Walter

    2008-03-01

    We present a clear, simple tight-binding representation of the electronic structure and cohesive energy (energy of atomization) of MnO, Mn2O3, and MnO2, in which the formal charge states Mn^2+, Mn^3+, and Mn^4+, respectively, occur. It is based upon localized cluster orbitals for each Mn and its six oxygen neighbors. This approach is fundamentally different from local-density theory (or LDA+U), and perhaps diametrically opposite to Dynamical Mean Field Theory. Electronic states were calculated self-consistently using existing parameters [1], but it is found that the charge density is quite insensitive to charge state, so that the starting parameters are adequate. The cohesive energy per Mn is dominated by the transfer of two s electrons to oxygen p states, the same for all three compounds. The differing transfer of majority d electrons to oxygen p states, and the coupling between them, accounts for the observed variation in cohesion in the series. The same description applies to the perovskites, such as LaxSr1-xMnO3, and can be used for FeO, Fe2O3 (and FeO2), Because the formulation is local, it is equally applicable to impurities, defects and surfaces. [1] Walter A. Harrison, Elementary Electronic Structure, World Scientific (Singapore, 1999), revised edition (2004).

  11. Main Group Metal-Actinide Magnetic Coupling and Structural Response Upon U(4+) Inclusion Into Bi, Tl/Bi, or Pb/Bi Cages.

    PubMed

    Lichtenberger, Niels; Wilson, Robert J; Eulenstein, Armin R; Massa, Werner; Clérac, Rodolphe; Weigend, Florian; Dehnen, Stefanie

    2016-07-27

    The encapsulation of actinide ions in intermetalloid clusters has long been proposed but was never realized synthetically. We report the isolation and experimental, as well as quantum chemical, characterization of the uranium-centered clusters [U@Bi12](3-), [U@Tl2Bi11](3-), [U@Pb7Bi7](3-), and [U@Pb4Bi9](3-), upon reaction of (EE'Bi2)(2-) (E = Ga, Tl, E' = Bi; E = E' = Pb) and [U(C5Me4H)3] or [U(C5Me4H)3Cl] in 1,2-diaminoethane. For [U@Bi12](3-), magnetic susceptibility measurements rationalize an unprecedented antiferromagnetic coupling between a magnetic U(4+) site and a unique radical Bi12(7-) shell.

  12. Electronic structure engineering of various structural phases of phosphorene.

    PubMed

    Kaur, Sumandeep; Kumar, Ashok; Srivastava, Sunita; Tankeshwar, K

    2016-07-21

    We report the tailoring of the electronic structures of various structural phases of phosphorene (α-P, β-P, γ-P and δ-P) based homo- and hetero-bilayers through in-plane mechanical strains, vertical pressure and transverse electric field by employing density functional theory. In-plane biaxial strains have considerably modified the electronic bandgap of both homo- and hetero-bilayers while vertical pressure induces metallization in the considered structures. The γ-P homo-bilayer structure showed the highest ultimate tensile strength (UTS ∼ 6.21 GPa) upon in-plane stretching. Upon application of a transverse electric field, the variation in the bandgap of hetero-bilayers was found to be strongly dependent on the polarity of the applied field which is attributed to the counterbalance between the external electric field and the internal field induced by different structural phases and heterogeneity in the arrangements of atoms of each surface of the hetero-bilayer system. Our results demonstrate that the electronic structures of the considered hetero- and homo-bilayers of phosphorene could be modified by biaxial strain, pressure and electric field to achieve the desired properties for future nano-electronic devices.

  13. [Structured electronic consultation letter for shoulder disorders].

    PubMed

    Paloneva, Juha; Oikari, Marjo; Ylinen, Jari; Ingalsuo, Minna; Ilkka, Kunnamo; Ilkka, Kiviranta

    2012-01-01

    Referral to a specialist has a significant influence on management of the patient and costs associated with the treatments. However, development and research of the process by which patients are referred has been almost neglected. Expectations considering the purpose, contents, and timing of the referral of the consulting physician and the consultant do not always meet. A structured, electronic consultation letter was developed to respond this need. Functionality and interactivity are the key elements of the referral, including (1) an electronic referral letter to a specialist, (2) interactive education in clinical examination and management of shoulder disorders, and (3) an instrument of clinical examination and documentation of shoulder disorders.

  14. The role of transferrin in actinide(IV) uptake: comparison with iron(III).

    PubMed

    Jeanson, Aurélie; Ferrand, M; Funke, Harald; Hennig, Christoph; Moisy, Philippe; Solari, Pier Lorenzo; Vidaud, Claude; Den Auwer, Christophe

    2010-01-25

    The impact of actinides on living organisms has been the subject of numerous studies since the 1950s. From a general point of view, these studies show that actinides are chemical poisons as well as radiological hazards. Actinides in plasma are assumed to be mainly complexed to transferrin, the iron carrier protein. This paper casts light on the uptake of actinides(IV) (thorium, neptunium, plutonium) by transferrin, focusing on the pH dependence of the interaction and on a molecular description of the cation binding site in the protein. Their behavior is compared with that of iron(III), the endogenous transferrin cation, from a structural point of view. Complementary spectroscopic techniques (UV/Vis spectrophotometry, microfiltration coupled with gamma spectrometry, and X-ray absorption fine structure) have been combined in order to propose a structural model for the actinide-binding site in transferrin. Comparison of our results with data available on holotransferrin suggests some similarities between the behavior of Fe(III) and Np(IV)/Pu(IV)/ Np(IV) is not complexed at pH <7, whereas at pH approximately 7.4 complexation can be regarded as quantitative. This pH effect is consistent with the in vivo transferrin "cycle". Pu(IV) also appears to be quantitatively bound by apotransferrin at around pH approximately 7.5, whereas Th(IV) was never complexed under our experimental conditions. EXAFS data at the actinide edge have allowed a structural model of the actinide binding site to be elaborated: at least one tyrosine residue could participate in the actinide coordination sphere (two for iron), forming a mixed hydroxo-transferrin complex in which actinides are bound with transferrin both through An-tyrosine and through An--OH bonds. A description of interatomic distances is provided.

  15. The electronic structure of nonpolyhex carbon nanotubes.

    PubMed

    László, István

    2004-01-01

    Generalizing the folding method to any periodic two-dimensional planar carbon structures we have calculated the corresponding electronic structures in the framework of the one orbital one site tight-binding (Bloch-Hückel) method by solving the eigenvalue problems in a numerical way. We discussed the metallic or the nonmetallic behavior of the nanotubes by applying the folding vectors of parameters (m, n). We extended the topological coordinate method to two-dimensional periodic planar structures as well. Nearly regular hexagonal, pentagonal, and heptagonal polygons were obtained. The curvatures of the final relaxed structures can be read from the sizes of the polygons. Thus relying only on the topological information we could describe the shape of the tubular structures and their conductivity behaviors.

  16. Probing Structural and Electronic Dynamics with Ultrafast Electron Microscopy

    SciTech Connect

    Plemmons, DA; Suri, PK; Flannigan, DJ

    2015-05-12

    In this Perspective, we provide an overview,of the field of ultrafast electron microscopy (UEM). We begin by briefly discussing the emergence of methods for probing ultrafast structural dynamics and the information that can be obtained. Distinctions are drawn between the two main types a probes for femtosecond (fs) dynamics fast electrons and X-ray photons and emphasis is placed on hour the nature of charged particles is exploited in ultrafast electron-based' experiments:. Following this, we describe the versatility enabled by the ease with which electron trajectories and velocities can be manipulated with transmission electron microscopy (TEM): hardware configurations, and we emphasize how this is translated to the ability to measure scattering intensities in real, reciprocal, and energy space from presurveyed and selected rianoscale volumes. Owing to decades of ongoing research and development into TEM instrumentation combined with advances in specimen holder technology, comprehensive experiments can be conducted on a wide range of materials in various phases via in situ methods. Next, we describe the basic operating concepts, of UEM, and we emphasize that its development has led to extension of several of the formidable capabilities of TEM into the fs domain, dins increasing the accessible temporal parameter spade by several orders of magnitude. We then divide UEM studies into those conducted in real (imaging), reciprocal (diffraction), and energy (spectroscopy) spate. We begin each of these sections by providing a brief description of the basic operating principles and the types of information that can be gathered followed by descriptions of how these approaches are applied in UM, the type of specimen parameter space that can be probed, and an example of the types of dynamics that can be resolved. We conclude with an Outlook section, wherein we share our perspective on some future directions of the field pertaining to continued instrument development and

  17. Actinide geochemistry: from the molecular level to the real system.

    PubMed

    Geckeis, Horst; Rabung, Thomas

    2008-12-12

    Geochemical processes leading to either mobilization or retention of radionuclides in an aquifer system are significantly influenced by their interaction with rock, sediment and colloid surfaces. Therefore, a sound safety assessment of nuclear waste disposal requires the elucidation and quantification of those processes. State-of-the-art analytical techniques as e.g. laser- and X-ray spectroscopy are increasingly applied to study solid-liquid interface reactions to obtain molecular level speciation insight. We have studied the sorption of trivalent lanthanides and actinides onto aluminium oxides, hydroxides and purified clay minerals by the time-resolved laser fluorescence spectroscopy and X-ray-absorption spectroscopy. Chemical constitution and structure of surface bound actinides are proposed based on spectroscopic information. Open questions still remain with regard to the exact nature of mineral surface ligands and the mineral/water interface. Similarities of spectroscopic data obtained for M(III) sorbed onto gamma-alumina, and clay minerals suggest the formation of very comparable inner-sphere surface complexes such as S-O-An(III)(OH)x(2-x)(H2O)5-x at pH > 5. Those speciation data are found consistent with those predicted by surface complexation modelling. The applicability of data obtained for pure mineral phases to actinide sorption onto heterogeneously composed natural clay rock is examined by experiments and by geochemical modelling. Good agreement of experiment and model calculations is found for U(VI) and trivalent actinide/lanthanide sorption to natural clay rock. The agreement of spectroscopy, geochemical modelling and batch experiments with natural rock samples and purified minerals increases the reliability in model predictions. The assessment of colloid borne actinide migration observed in various laboratory and field studies calls for detailed information on actinide-colloid interaction. Kinetic stabilization of colloid bound actinides can be due

  18. Electronic structure of worm-eaten graphene

    NASA Astrophysics Data System (ADS)

    Negishi, Hayato; Takeda, Kyozaburo

    2017-02-01

    We theoretically study the electronic structure of graphenes having several kinds of imperfections such as atomic vacancies and heteroatom replacements. We consider 12 different configurations of vacancies and 39 different geometries of heteroatom replacements in order to approximately take into account the random conformations of imperfections. To systematically provide a perspective understanding of the defect π and σ states caused by atomistic voids and/or vacancies and heteroatom replacements, we have carried out a tight-binding (TB) calculation. We study the orbital hybridization to clarify the origin and formation of π and σ defect states arising from such imperfections. We also discuss the electronic structure around the Fermi level through the TB band calculation.

  19. Electronic structure investigation of biphenylene films

    NASA Astrophysics Data System (ADS)

    Totani, R.; Grazioli, C.; Zhang, T.; Bidermane, I.; Lüder, J.; de Simone, M.; Coreno, M.; Brena, B.; Lozzi, L.; Puglia, C.

    2017-02-01

    Photoelectron Spectroscopy (PS) and Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy have been used to investigate the occupied and empty density of states of biphenylene films of different thicknesses, deposited onto a Cu(111) crystal. The obtained results have been compared to previous gas phase spectra and single molecule Density Functional Theory (DFT) calculations to get insights into the possible modification of the molecular electronic structure in the film induced by the adsorption on a surface. Furthermore, NEXAFS measurements allowed characterizing the variation of the molecular arrangement with the film thickness and helped to clarify the substrate-molecule interaction.

  20. Atomic and Electronic Structure of Solids

    NASA Astrophysics Data System (ADS)

    Kaxiras, Efthimios

    2003-01-01

    Preface; Acknowledgements; Part I. Crystalline Solids: 1. Atomic structure of crystals; 2. The single-particle approximation; 3. Electrons in crystal potential; 4. Band structure of crystals; 5. Applications of band theory; 6. Lattice vibrations; 7. Magnetic behaviour of solids; 8. Superconductivity; Part II. Defects, Non-Crystalline Solids and Finite Structures: 9. Defects I: point defects; 10. Defects II: line defects; 11. Defects III: surfaces and interfaces; 12. Non-crystalline solids; 13. Finite structures; Part III. Appendices: A. Elements of classical electrodynamics; B. Elements of quantum mechanics; C. Elements of thermodynamics; D. Elements of statistical mechanics; E. Elements of elasticity theory; F. The Madelung energy; G. Mathematical tools; H. Nobel Prize citations; I. Units and symbols; References; Index.

  1. Controlling the Electronic Structure of Bilayer Graphene

    NASA Astrophysics Data System (ADS)

    Ohta, Taisuke; Bostwick, Aaron; McChesney, Jessica; Seyller, Thomas; Horn, Karsten; Rotenberg, Eli

    2007-03-01

    Carbon-based materials such as carbon nanotubes, graphite intercalation compounds, fullerenes, and ultrathin graphite films exhibit many exotic phenomena such as superconductivity and an anomalous quantum Hall effect. These findings have caused renewed interest in the electronic structure of ultrathin layers of graphene: a single honeycomb carbon layer that is the building block for these materials. There is a strong motivation to incorporate graphene multilayers into atomic-scale devices, spurred on by rapid progress in their fabrication and manipulation. We have synthesized bilayer graphene thin films deposited on insulating silicon carbide and characterized their electronic band structure using angle-resolved photoemission. By selectively adjusting the carrier concentration in each layer, changes in the Coulomb potential led to control of the gap between valence and conduction bands [1]. This control over the band structure suggests the potential application of bilayer graphene to switching functions in atomic scale electronic devices. [1] T. Ohta, A. Bostwick, T. Seyller, K. Horn, E. Rotenberg, Science, 313, 951 (2006).

  2. MICROBIAL TRANSFORMATIONS OF PLUTONIUM AND OTHER ACTINIDES IN TRANSURANIC AND MIXED WASTES.

    SciTech Connect

    FRANCIS,A.J.

    2003-07-06

    The presence of the actinides Th, U, Np, Pu, and Am in transuranic (TRU) and mixed wastes is a major concern because of their potential for migration from the waste repositories and long-term contamination of the environment. The toxicity of the actinide elements and the long half-lives of their isotopes are the primary causes for concern. In addition to the radionuclides the TRU waste consists a variety of organic materials (cellulose, plastic, rubber, chelating agents) and inorganic compounds (nitrate and sulfate). Significant microbial activity is expected in the waste because of the presence of organic compounds and nitrate, which serve as carbon and nitrogen sources and in the absence of oxygen the microbes can use nitrate and sulfate as alternate electron acceptors. Biodegradation of the TRU waste can result in gas generation and pressurization of containment areas, and waste volume reduction and subsidence in the repository. Although the physical, chemical, and geochemical processes affecting dissolution, precipitation, and mobilization of actinides have been investigated, we have only limited information on the effects of microbial processes. Microbial activity could affect the chemical nature of the actinides by altering the speciation, solubility and sorption properties and thus could increase or decrease the concentrations of actinides in solution. Under appropriate conditions, dissolution or immobilization of actinides is brought about by direct enzymatic or indirect non-enzymatic actions of microorganisms. Dissolution of actinides by microorganisms is brought about by changes in the Eh and pH of the medium, by their production of organic acids, such as citric acid, siderophores and extracellular metabolites. Immobilization or precipitation of actinides is due to changes in the Eh of the environment, enzymatic reductive precipitation (reduction from higher to lower oxidation state), biosorption, bioaccumulation, biotransformation of actinides complexed

  3. Actinide Partitioning and Radiation Effects in U(VI)-Solids: Thermodynamic & Mechanistic Study

    SciTech Connect

    Clark, Sue B.; Ewing, Rodney C.

    2010-05-20

    In most environmental systems, the mobility of a contaminant metal cation depends on its partitioning between the solid and solution phase. At the molecular level, partitioning to the solid phase is controlled by the coordination requirements of the contaminant cation. In this work, we developed linear free energy relationships (LFERs) to describe the partitioning of non-U actinide cations to U(VI) solid phases in a radiation environment; the LFERs are based on knowledge of the actinide coordination environment in or on the surface of the U(VI) solid, and the impact of ionizing radiation on the atomic interactions of the non-U actinide cations. LFERs were established for predicting (1) free energies of formation of pure U(VI) solids and solid solutions with non-U actinide cations, and (2) the adsorption of non-U actinide cations to pure U(VI) solids. We demonstrated the application of LFERs developed from knowledge of molecular structures of U(VI) solid phases to predict the predominance of U(VI) oxide hydrate and silicate solid phases as a function of geochemical conditions. We extended our efforts to define LFERs for U(VI) phosphate solids, and included the impact of actinide self-radiation on all LFERs for free energies of formation for U(VI) solids. We also defined LFERs for the formation of solid solutions between the U(VI) solids and non-U actinide cations such as Th, Np, Pu, Am, and Cm. We demonstrated the importance of nanocrystalline solids in the solid phase partitioning of these non-U actinide cations. For those solid solutions formed, we investigated the impact of ionizing radiation on the stability of those phases, and the release of the non-U actinide cations from the solids. Finally, developed LFERs to predict the adsorption of the non-U actinide cations to the surfaces of U(VI) oxide hydrates and U(VI) phosphates. We determined adsorption constants and coordination requirements for actinide adsorption to U(VI) solid phases. We determined

  4. Actinide recovery techniques utilizing electromechanical processes

    SciTech Connect

    Westphal, B.R.; Benedict, R.W.

    1994-01-01

    Under certain conditions, the separation of actinides using electromechanical techniques may be an effective means of residue processing. The separation of granular mixtures of actinides and other materials discussed in this report is based on appreciable differences in the magnetic and electrical properties of the actinide elements. In addition, the high density of actinides, particularly uranium and plutonium, may render a simultaneous separation based on mutually complementary parameters. Both high intensity magnetic separation and electrostatic separation have been investigated for the concentration of an actinide waste stream. Waste stream constituents include an actinide metal alloy and broken quartz shards. The investigation of these techniques is in support of the Integral Fast Reactor (IFR) concept currently being developed at Argonne National Laboratory under the auspices of the Department of Energy.

  5. Actinide Recovery Method for Large Soil Samples

    SciTech Connect

    Maxwell, S.L. III; Nichols, S.

    1998-11-01

    A new Actinide Recovery Method has been developed by the Savannah River Site Central Laboratory to preconcentrate actinides in very large soil samples. Diphonix Resin(r) is used eliminate soil matrix interferences and preconcentrate actinides after soil leaching or soil fusion. A rapid microwave digestion technique is used to remove the actinides from the Diphonix Resin(r). After the resin digestion, the actinides are recovered in a small volume of nitric acid which can be easily loaded onto small extraction-chromatography columns, such as TEVA Resin(r), U-TEVA Resin(r) or TRU Resin(r) (Eichrom Industries). This method enables the application of small, selective extraction-columns to recover actinides from very large soil samples with high selectivity, consistent tracer recoveries and minimal liquid waste.

  6. Process for recovering actinide values

    DOEpatents

    Horwitz, E. Philip; Mason, George W.

    1980-01-01

    A process for rendering actinide values recoverable from sodium carbonate scrub waste solutions containing these and other values along with organic compounds resulting from the radiolytic and hydrolytic degradation of neutral organophosphorous extractants such as tri-n butyl phosphate (TBP) and dihexyl-N,N-diethyl carbamylmethylene phosphonate (DHDECAMP) which have been used in the reprocessing of irradiated nuclear reactor fuels. The scrub waste solution is preferably made acidic with mineral acid, to form a feed solution which is then contacted with a water-immiscible, highly polar organic extractant which selectively extracts the degradation products from the feed solution. The feed solution can then be processed to recover the actinides for storage or recycled back into the high-level waste process stream. The extractant is recycled after stripping the degradation products with a neutral sodium carbonate solution.

  7. Actinide abundances in ordinary chondrites

    NASA Technical Reports Server (NTRS)

    Hagee, B.; Bernatowicz, T. J.; Podosek, F. A.; Johnson, M. L.; Burnett, D. S.

    1990-01-01

    Measurements of actinide and light REE (LREE) abundances and of phosphate abundances in equilibrated ordinary chondrites were obtained and were used to define the Pu abundance in the solar system and to determine the degree of variation of actinide and LREE abundances. The results were also used to compare directly the Pu/U ratio with the earlier obtained ratio determined indirectly, as (Pu/Nd)x(Nd/U), assuming that Pu behaves chemically as a LREE. The data, combined with high-accuracy isotope-dilution data from the literature, show that the degree of gram-scale variability of the Th, U, and LREE abundances for equilibrated ordinary chondrites is a factor of 2-3 for absolute abundances and up to 50 percent for relative abundances. The observed variations are interpreted as reflecting the differences in the compositions and/or proportions of solar nebula components accreted to ordinary chondrite parent bodies.

  8. Electronic structure theory of the superheavy elements

    NASA Astrophysics Data System (ADS)

    Eliav, Ephraim; Fritzsche, Stephan; Kaldor, Uzi

    2015-12-01

    High-accuracy calculations of atomic properties of the superheavy elements (SHE) up to element 122 are reviewed. The properties discussed include ionization potentials, electron affinities and excitation energies, which are associated with the spectroscopic and chemical behavior of these elements, and are therefore of considerable interest. Accurate predictions of these quantities require high-order inclusion of relativity and electron correlation, as well as large, converged basis sets. The Dirac-Coulomb-Breit Hamiltonian, which includes all terms up to second order in the fine-structure constant α, serves as the framework for the treatment; higher-order Lamb shift terms are considered in some selected cases. Electron correlation is treated by either the multiconfiguration self-consistent-field approach or by Fock-space coupled cluster theory. The latter is enhanced by the intermediate Hamiltonian scheme, allowing the use of larger model (P) spaces. The quality of the calculations is assessed by applying the same methods to lighter homologs of the SHEs and comparing with available experimental information. Very good agreement is obtained, within a few hundredths of an eV, and similar accuracy is expected for the SHEs. Many of the properties predicted for the SHEs differ significantly from what may be expected by straightforward extrapolation of lighter homologs, demonstrating that the structure and chemistry of SHEs are strongly affected by relativity. The major scientific challenge of the calculations is to find the electronic structure and basic atomic properties of the SHE and assign its proper place in the periodic table. Significant recent developments include joint experimental-computational studies of the excitation spectrum of Fm and the ionization energy of Lr, with excellent agreement of experiment and theory, auguring well for the future of research in the field.

  9. Colloid-borne forms of tetravalent actinides: a brief review.

    PubMed

    Zänker, Harald; Hennig, Christoph

    2014-02-01

    Tetravalent actinides, An(IV), are usually assumed to be little mobile in near-neutral environmental waters because of their low solubility. However, there are certain geochemical scenarios during which mobilization of An(IV) in a colloid-borne (waterborne) form cannot be ruled out. A compilation of colloid-borne forms of tetravalent actinides described so far for laboratory experiments together with several examples of An(IV) colloids observed in field experiments and real-world scenarios are given. They are intended to be a knowledge base and a tool for those who have to interpret actinide behavior under environmental conditions. Synthetic colloids containing structural An(IV) and synthetic colloids carrying adsorbed An(IV) are considered. Their behavior is compared with the behavior of An(IV) colloids observed after the intentional or unintentional release of actinides into the environment. A list of knowledge gaps as to the behavior of An(IV) colloids is provided and items which need further research are highlighted.

  10. Electronic bandstructure of semiconductor dilute bismide structures

    NASA Astrophysics Data System (ADS)

    Erucar, T.; Nutku, F.; Donmez, O.; Erol, A.

    2017-02-01

    In this work electronic band structure of dilute bismide GaAs/GaAs1-xBix quantum well structures with 1.8% and 3.75% bismuth compositions have been investigated both experimentally and theoretically. Photoluminescence (PL) measurements reveal that effective bandgap of the samples decreases approximately 65 meV per bismuth concentration. Temperature dependence of the effective bandgap is obtained to be higher for the sample with higher bismuth concentration. Moreover, both asymmetric characteristic at the low energy tail of the PL and full width at half maximum (FWHM) of PL peak increase with increasing bismuth composition as a result of increased Bi related defects located above valence band (VB). In order to explain composition dependence of the effective bandgap quantitatively, valence band anti-crossing (VBAC) model is used. Bismuth composition and temperature dependence of effective bandgap in a quantum well structure is modeled by solving Schrödinger equation and compared with experimental PL data.

  11. Electronic structure interpolation via atomic orbitals.

    PubMed

    Chen, Mohan; Guo, G-C; He, Lixin

    2011-08-17

    We present an efficient scheme for accurate electronic structure interpolation based on systematically improvable optimized atomic orbitals. The atomic orbitals are generated by minimizing the spillage value between the atomic basis calculations and the converged plane wave basis calculations on some coarse k-point grid. They are then used to calculate the band structure of the full Brillouin zone using the linear combination of atomic orbitals algorithms. We find that usually 16-25 orbitals per atom can give an accuracy of about 10 meV compared to the full ab initio calculations, and the accuracy can be systematically improved by using more atomic orbitals. The scheme is easy to implement and robust, and works equally well for metallic systems and systems with complicated band structures. Furthermore, the atomic orbitals have much better transferability than Shirley's basis and Wannier functions, which is very useful for perturbation calculations.

  12. Thermal transfer structures coupling electronics card(s) to coolant-cooled structure(s)

    DOEpatents

    David, Milnes P; Graybill, David P; Iyengar, Madhusudan K; Kamath, Vinod; Kochuparambil, Bejoy J; Parida, Pritish R; Schmidt, Roger R

    2014-12-16

    Cooling apparatuses and coolant-cooled electronic systems are provided which include thermal transfer structures configured to engage with a spring force one or more electronics cards with docking of the electronics card(s) within a respective socket(s) of the electronic system. A thermal transfer structure of the cooling apparatus includes a thermal spreader having a first thermal conduction surface, and a thermally conductive spring assembly coupled to the conduction surface of the thermal spreader and positioned and configured to reside between and physically couple a first surface of an electronics card to the first surface of the thermal spreader with docking of the electronics card within a socket of the electronic system. The thermal transfer structure is, in one embodiment, metallurgically bonded to a coolant-cooled structure and facilitates transfer of heat from the electronics card to coolant flowing through the coolant-cooled structure.

  13. Lauriston S. Taylor Lecture: the quest for therapeutic actinide chelators.

    PubMed

    Durbin, Patricia W

    2008-11-01

    All of the actinides are radioactive. Taken into the body, they damage and induce cancer in bone and liver, and in the lungs if inhaled, and U(VI) is a chemical kidney poison. Containment of radionuclides is fundamental to radiation protection, but if it is breached accidentally or deliberately, decontamination of exposed persons is needed to reduce the consequences of radionuclide intake. The only known way to reduce the health risks of internally deposited actinides is to accelerate their excretion with chelating agents. Ethylendiaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) were introduced in the 1950's. DTPA is now clinically accepted, but its oral activity is low, it must be injected as a Ca(II) or Zn(II) chelate to avoid toxicity, and it is structurally unsuitable for chelating U(VI) or Np(V). Actinide penetration into the mammalian iron transport and storage systems suggested that actinide ions would form stable complexes with the Fe(III)-binding units found in potent selective natural iron chelators (siderophores). Testing of that biomimetic approach began in the late 1970's with the design, production, and assessment for in vivo Pu(IV) chelation of synthetic multidentate ligands based on the backbone structures and Fe(III)-binding groups of siderophores. New efficacious actinide chelators have emerged from that program, in particular, octadentate 3,4,3-LI(1,2-HOPO) and tetradentate 5-LIO(Me-3,2-HOPO) have potential for clinical acceptance. Both are much more effective than CaNa3-DTPA for decorporation of Pu(IV), Am(III), U(VI), and Np(IV,V), they are orally active, and toxicity is acceptably low at effective dosage.

  14. Redox chemistry of actinide ions in Wells-Dawson heteropolyoxoanion complexes.

    SciTech Connect

    Chiang, M.-H.; Soderholm, L.; Antonio, M. R.; Chemistry

    2003-08-18

    The redox behavior has been characterized for several actinide (An) complexes with the monovacant Wells-Dawson anion, of the form [An{sup n+}({alpha}-2-P{sub 2}W{sub 17}O{sub 61}){sub 2}]{sup n-20} (An = Th{sup 4+}, U{sup 4+}, Np{sup 4+}, Pu{sup 4+}, and Am{sup 3+}). Two complexes, with An = U{sup 4+} and Am{sup 3+}, show redox activity under oxidizing conditions, which is attributed to the actinide oxidation. Am{sup 3+} is oxidized to Am{sup 4+} with an E{sub 1/2} = +1.21{+-}0.01 V, and U{sup 4+} oxidizes to U{sup 5+} with a measured E{sub 1/2} = +0.55{+-}0.01 V vs. Ag/AgCl. Although the cyclic voltammetry (CV) data are consistent with a reversible redox couple, bulk oxidative electrolysis of [U{sup 4+}({alpha}-2-P{sub 2}W{sub 17}O{sub 61}){sub 2}]{sup 16-} results in the decomposition of this complex to produce uranyl acetate and the free monovacant Wells-Dawson anion. In contrast, all of the CV data from the actinide coordination complexes differ from equivalent data obtained from the [{alpha}-2-P{sub 2}W{sub 17}O{sub 61}]{sup 10-} ligand itself. There are two complexed An{sup 4+} ions, Np and Pu, that undergo reduction over the same potential range as the ligands themselves. In situ X-ray spectroelectrochemistry is used to quantify the actinide response. The Np{sup 4+}/Np{sup 3+} redox behavior is a classically single ion process, with a formal potential of -0.84{+-}0.01 V that was determined from a Nernst plot of X-ray absorption near-edge structure (XANES) data. The Pu{sup 4+}/Pu{sup 3+} formal reduction potential in the complex [Pu({alpha}-2-P{sub 2}W{sub 17}O{sub 61}){sub 2}]{sup n-} was determined to be -0.17{+-}0.01 V using the same methodology. However, in this latter case, the slope of the Nernst plot indicates that 0.72{+-}0.03 electrons are involved in the reduction. This is a significant deviation from the 1 electron expected for the Pu couple, and is discussed in terms of the concomitant reduction of the P-W-O framework of the Wells-Dawson anion.

  15. Extraordinary electronic properties in uncommon structure types

    NASA Astrophysics Data System (ADS)

    Ali, Mazhar Nawaz

    In this thesis I present the results of explorations into several uncommon structure types. In Chapter 1 I go through the underlying idea of how we search for new compounds with exotic properties in solid state chemistry. The ideas of exploring uncommon structure types, building up from the simple to the complex, using chemical intuition and thinking by analogy are discussed. Also, the history and basic concepts of superconductivity, Dirac semimetals, and magnetoresistance are briefly reviewed. In chapter 2, the 1s-InTaS2 structural family is introduced along with the discovery of a new member of the family, Ag0:79VS2; the synthesis, structure, and physical properties of two different polymorphs of the material are detailed. Also in this chapter, we report the observation of superconductivity in another 1s structure, PbTaSe2. This material is especially interesting due to it being very heavy (resulting in very strong spin orbit coulping (SOC)), layered, and noncentrosymmetric. Electronic structure calculations reveal the presence of a bulk 3D Dirac cone (very similar to graphene) that is gapped by SOC originating from the hexagonal Pb layer. In Chapter 3 we show the re-investigation of the crystal structure of the 3D Dirac semimetal, Cd3As2. It is found to be centrosymmetric, rather than noncentrosymmetric, and as such all bands are spin degenerate and there is a 4-fold degenerate bulk Dirac point at the Fermi level, making Cd3As2 a 3D electronic analog to graphene. Also, for the first time, scanning tunneling microscopy experiments identify a 2x2 surface reconstruction in what we identify as the (112) cleavage plane of single crystals; needle crystals grow with a [110] long axis direction. Lastly, in chapter 4 we report the discovery of "titanic" (sadly dubbed ⪉rge, nonsaturating" by Nature editors and given the acronym XMR) magnetoresistance (MR) in the non-magnetic, noncentrosymmetric, layered transition metal dichalcogenide WTe2; over 13 million% at 0.53 K in

  16. Pu electronic structure and photoelectron spectroscopy

    SciTech Connect

    Joyce, John J; Durakiewicz, Tomasz; Graham, Kevin S; Bauer, Eric D; Moore, David P; Mitchell, Jeremy N; Kennison, John A; Martin, Richard L; Roy, Lindsay E; Scuseria, G. E.

    2010-01-01

    The electronic structure of PuCoGa{sub 5}, Pu metal, and PuO{sub 2} is explored using photoelectron spectroscopy. Ground state electronic properties are inferred from temperature dependent photoemission near the Fermi energy for Pu metal. Angle-resolved photoemission details the energy vs. crystaJ momentum landscape near the Fermi energy for PuCoGa{sub 5} which shows significant dispersion in the quasiparticle peak near the Fermi energy. For the Mott insulators AnO{sub 2}(An = U, Pu) the photoemission results are compared against hybrid functional calculations and the model prediction of a cross over from ionic to covalent bonding is found to be reasonable.

  17. Structural and electronic properties of fluorographene.

    PubMed

    Samarakoon, Duminda K; Chen, Zhifan; Nicolas, Chantel; Wang, Xiao-Qian

    2011-04-04

    The structural and electronic characteristics of fluorinated graphene are investigated based on first-principles density-functional calculations. A detailed analysis of the energy order for stoichiometric fluorographene membranes indicates that there exists prominent chair and stirrup conformations, which correlate with the experimentally observed in-plane lattice expansion contrary to a contraction in graphane. The optical response of fluorographene is investigated using the GW-Bethe-Salpeter equation approach. The results are in good conformity with the experimentally observed optical gap and reveal predominant charge-transfer excitations arising from strong electron-hole interactions. The appearance of bounded excitons in the ultraviolet region can result in an excitonic Bose-Einstein condensate in fluorographene.

  18. Electronic Structure of Buried Interfaces - Oral Presentation

    SciTech Connect

    Porter, Zachary

    2015-08-25

    In the electronics behind computer memory storage, the speed and size are dictated by the performance of permanent magnets inside devices called read heads. Complicated magnets made of stacked layers of thin films can be engineered to have properties that yield more energy storage and faster switching times compared to conventional iron or cobalt magnets. The reason is that magnetism is a result of subtle interactions amongst electrons; just how neurons come together on large scales to make cat brains and dog brains, ensembles of electrons interact and become ferromagnets and paramagnets. These interactions make magnets too difficult to study in their entirety, so I focus on the interfaces between layers, which are responsible for the coupling materials physicists hope to exploit to produce next-generation magnets. This project, I study a transition metal oxide material called LSCO, Lanthanum Cobaltite, which can be a paramagnet or a ferromagnet depending on how you tweak the electronic structure. It exhibits an exciting behavior: its sum is greater than the sum of its parts. When another similar material called a LSMO, Lanthanum Manganite, is grown on top of it, their interface has a different type of magnetism from the LSCO or the LSMO! I hope to explain this by demonstrating differently charged ions in the interface. The typical method for quantifying this is x-ray absorption, but all conventional techniques look at every layer simultaneously, averaging the interfaces and the LSCO layers that we want to characterize separately. Instead, I must use a new reflectivity technique, which tracks the intensity of reflected x-rays at different angles, at energies near the absorption peaks of certain elements, to track changes in the electronic structure of the material. The samples were grown by collaborators at the Takamura group at U.C. Davis and probed with this “resonant reflectivity” technique on Beamline 2-1 at the Stanford Synchrotron Radiation Lightsource

  19. Molecular Characterization of Actinide Oxocations from Protactinium to Plutonium

    SciTech Connect

    Den Auwer, C.; Guilbaud, P.; Guillaumont, D.; Moisy, P.; Hennig, C.; Scheinost, A.; Conradson, S. D.

    2007-02-02

    This presentation addresses the structural characterization by EXAFS of actinide cations at oxidation states (V) and (VI) as one walks across the periodic table from Z = 91 (protactinium) to Z = 94 (plutonium). A structural comparison between Pa, U, Np and Pu oxocations in aqueous solution at formal oxidation states (V) and (VI) is carried out. These results are corroborated by quantum chemical and molecular dynamics calculations.

  20. Surface structure and electronic properties of materials

    NASA Technical Reports Server (NTRS)

    Siekhaus, W. J.; Somorjai, G. A.

    1975-01-01

    A surface potential model is developed to explain dopant effects on chemical vapor deposition. Auger analysis of the interaction between allotropic forms of carbon and silicon films has shown Si-C formation for all forms by glassy carbon. LEED intensity measurements have been used to determine the mean square displacement of surface atoms of silicon single crystals, and electron loss spectroscopy has shown the effect of structure and impurities on surface states located within the band gap. A thin film of Al has been used to enhance film crystallinity at low temperature.

  1. Structural, electronic and optical properties of carbonnitride

    SciTech Connect

    Cohen, Marvin L.

    1996-01-31

    Carbon nitride was proposed as a superhard material and a structural prototype, Beta-C3N4, was examined using several theoretical models. Some reports claiming experimental verifications have been made recently. The current status of the theory and experiment is reviewed, and a detailed discussion is presented of calculations of the electronic and optical properties of this material. These calculations predict that Beta-C3N4 will have a minimum gap which is indirect at 6.4 plus or minus 0.5 eV. A discussion of the possibility of carbon nitride nanotubes is also presented.

  2. Archetypes for actinide-specific chelating agents

    SciTech Connect

    Smith, W.L.

    1980-01-01

    The complexes of uranium and thorium with monomeric hydroxamic acids can serve as archetypes for an optimized macrochelate designed for tetravalent actinides. The eight-coordinate complexes, Th(i-PrN(O)C(O)R)/sub 4/, where R = tert-butyl or R = neopentyl, have been synthesized and their structures have been determined by x-ray diffraction. The bulky alkyl substituents impart remarkable volatility and hydrocarbon solubility to these complexes, and the steric interactions of these substituents largely determine the structures. When R = tert-butyl, the substituents occupy the corners of a tetrahedron and force the complex into a distorted cubic geometry with crystallographic S/sub 4/ symmetry. Insertion of a methylene group between the carbonyl carbon and the tert-butyl group relaxes the steric requirements, and the coordination polyhedron of the neopentyl derivative is close to the mmmm isomer of the trigonal-faced dodecahedron. Uranium tetrachloride was quantitatively oxidized via an oxygen transfer reaction with two equivalents of N-phenylbenzohydroxamic acid anion (PBHA) in tetrahydrofuran (THF) to form UO/sub 2/ Cl(PBHA)(THF)/sub 2/ and benzanilide. The structure of the uranyl complex has been determined from x-ray diffraction data; the linear uranyl ion is surrounded by a planar pentagonal array composed of two hydroxamate oxygen atoms, a chloride ion and two THF oxygens, such that the chloride ion is opposite the hydroxamate group. That the THF and phenyl rings are twisted from this equatorial plane limits the molecular geometry to that of the C/sub 1/ point group. Some aspects of the chemistry of hydroxamic acids and of their incorporation into molecules that may serve as precursors of tetravalent actinide specific sequestering agents have also been investigated.

  3. The INE-Beamline for actinide science at ANKA

    SciTech Connect

    Rothe, J.; Dardenne, K.; Denecke, M. A.; Kienzler, B.; Loeble, M.; Metz, V.; Steppert, M.; Vitova, T.; Geckeis, H.; Butorin, S.; Seibert, A.; Walther, C.

    2012-04-15

    Since its inauguration in 2005, the INE-Beamline for actinide research at the synchrotron source ANKA (KIT North Campus) provides dedicated instrumentation for x-ray spectroscopic characterization of actinide samples and other radioactive materials. R and D work at the beamline focuses on various aspects of nuclear waste disposal within INE's mission to provide the scientific basis for assessing long-term safety of a final nuclear waste repository. The INE-Beamline is accessible for the actinide and radiochemistry community through the ANKA proposal system and the European Union Integrated Infrastructure Initiative ACTINET-I3. Experiments with activities up to 1 x 10{sup +6} times the European exemption limit are feasible within a safe but flexible containment concept. Measurements with monochromatic radiation are performed at photon energies varying between {approx}2.1 keV (P K-edge) and {approx}25 keV (Pd K-edge), including the lanthanide L-edges and the actinide M- and L3-edges up to Cf. The close proximity of the INE-Beamline to INE controlled area labs offers infrastructure unique in Europe for the spectroscopic and microscopic characterization of actinide samples. The modular beamline design enables sufficient flexibility to adapt sample environments and detection systems to many scientific questions. The well-established bulk techniques x-ray absorption fine structure (XAFS) spectroscopy in transmission and fluorescence mode have been augmented by advanced methods using a microfocused beam, including (confocal) XAFS/x-ray fluorescence detection and a combination of (micro-)XAFS and (micro-)x-ray diffraction. Additional instrumentation for high energy-resolution x-ray emission spectroscopy has been successfully developed and tested.

  4. The CECAM Electronic Structure Library: community-driven development of software libraries for electronic structure simulations

    NASA Astrophysics Data System (ADS)

    Oliveira, Micael

    The CECAM Electronic Structure Library (ESL) is a community-driven effort to segregate shared pieces of software as libraries that could be contributed and used by the community. Besides allowing to share the burden of developing and maintaining complex pieces of software, these can also become a target for re-coding by software engineers as hardware evolves, ensuring that electronic structure codes remain at the forefront of HPC trends. In a series of workshops hosted at the CECAM HQ in Lausanne, the tools and infrastructure for the project were prepared, and the first contributions were included and made available online (http://esl.cecam.org). In this talk I will present the different aspects and aims of the ESL and how these can be useful for the electronic structure community.

  5. Electronic-structural dynamics in graphene.

    PubMed

    Gierz, Isabella; Cavalleri, Andrea

    2016-09-01

    We review our recent time- and angle-resolved photoemission spectroscopy experiments, which measure the transient electronic structure of optically driven graphene. For pump photon energies in the near infrared ([Formula: see text]), we have discovered the formation of a population-inverted state near the Dirac point, which may be of interest for the design of THz lasing devices and optical amplifiers. At lower pump photon energies ([Formula: see text]), for which interband absorption is not possible in doped samples, we find evidence for free carrier absorption. In addition, when mid-infrared pulses are made resonant with an infrared-active in-plane phonon of bilayer graphene ([Formula: see text]), a transient enhancement of the electron-phonon coupling constant is observed, providing interesting perspective for experiments that report light-enhanced superconductivity in doped fullerites in which a similar lattice mode was excited. All the studies reviewed here have important implications for applications of graphene in optoelectronic devices and for the dynamical engineering of electronic properties with light.

  6. Electronic-structural dynamics in graphene

    PubMed Central

    Gierz, Isabella; Cavalleri, Andrea

    2016-01-01

    We review our recent time- and angle-resolved photoemission spectroscopy experiments, which measure the transient electronic structure of optically driven graphene. For pump photon energies in the near infrared (ℏωpump=950 meV), we have discovered the formation of a population-inverted state near the Dirac point, which may be of interest for the design of THz lasing devices and optical amplifiers. At lower pump photon energies (ℏωpump<400 meV), for which interband absorption is not possible in doped samples, we find evidence for free carrier absorption. In addition, when mid-infrared pulses are made resonant with an infrared-active in-plane phonon of bilayer graphene (ℏωpump=200 meV), a transient enhancement of the electron-phonon coupling constant is observed, providing interesting perspective for experiments that report light-enhanced superconductivity in doped fullerites in which a similar lattice mode was excited. All the studies reviewed here have important implications for applications of graphene in optoelectronic devices and for the dynamical engineering of electronic properties with light. PMID:27822486

  7. Electron beam coupling to a metamaterial structure

    SciTech Connect

    French, David M.; Shiffler, Don; Cartwright, Keith

    2013-08-15

    Microwave metamaterials have shown promise in numerous applications, ranging from strip lines and antennas to metamaterial-based electron beam driven devices. In general, metamaterials allow microwave designers to obtain electromagnetic characteristics not typically available in nature. High Power Microwave (HPM) sources have in the past drawn inspiration from work done in the conventional microwave source community. In this article, the use of metamaterials in an HPM application is considered by using an effective medium model to determine the coupling of an electron beam to a metamaterial structure in a geometry similar to that of a dielectric Cerenkov maser. Use of the effective medium model allows for the analysis of a wide range of parameter space, including the “mu-negative,”“epsilon-negative,” and “double negative” regimes of the metamaterial. The physics of such a system are modeled analytically and by utilizing the particle-in-cell code ICEPIC. For this geometry and effective medium representation, optimum coupling of the electron beam to the metamaterial, and thus the optimum microwave or RF production, occurs in the epsilon negative regime of the metamaterial. Given that HPM tubes have been proposed that utilize a metamaterial, this model provides a rapid method of characterizing a source geometry that can be used to quickly understand the basic physics of such an HPM device.

  8. Analysis of boron carbides' electronic structure

    NASA Technical Reports Server (NTRS)

    Howard, Iris A.; Beckel, Charles L.

    1986-01-01

    The electronic properties of boron-rich icosahedral clusters were studied as a means of understanding the electronic structure of the icosahedral borides such as boron carbide. A lower bound was estimated on bipolaron formation energies in B12 and B11C icosahedra, and the associated distortions. While the magnitude of the distortion associated with bipolaron formation is similar in both cases, the calculated formation energies differ greatly, formation being much more favorable on B11C icosahedra. The stable positions of a divalent atom relative to an icosahedral borane was also investigated, with the result that a stable energy minimum was found when the atom is at the center of the borane, internal to the B12 cage. If incorporation of dopant atoms into B12 cages in icosahedral boride solids is feasible, novel materials might result. In addition, the normal modes of a B12H12 cluster, of the C2B10 cage in para-carborane, and of a B12 icosahedron of reduced (D sub 3d) symmetry, such as is found in the icosahedral borides, were calculated. The nature of these vibrational modes will be important in determining, for instance, the character of the electron-lattice coupling in the borides, and in analyzing the lattice contribution to the thermal conductivity.

  9. Experimental Benchmarking of Pu Electronic Structure

    SciTech Connect

    Tobin, J.G.; Moore, K.T.; Chung, B.W.; Wall, M.A.; Schwartz, A.J.; Ebbinghaus, B.B.; Butterfield, M.T.; Teslich, Jr., N.E.; Bliss, R.A.; Morton, S.A.; Yu, S.W.; Komesu, T.; Waddill, G.D.; van der Laan, G.; Kutepov, A.L.

    2008-10-30

    The standard method to determine the band structure of a condensed phase material is to (1) obtain a single crystal with a well defined surface and (2) map the bands with angle resolved photoelectron spectroscopy (occupied or valence bands) and inverse photoelectron spectroscopy (unoccupied or conduction bands). Unfortunately, in the case of Pu, the single crystals of Pu are either nonexistent, very small and/or having poorly defined surfaces. Furthermore, effects such as electron correlation and a large spin-orbit splitting in the 5f states have further complicated the situation. Thus, we have embarked upon the utilization of unorthodox electron spectroscopies, to circumvent the problems caused by the absence of large single crystals of Pu with well-defined surfaces. Our approach includes the techniques of resonant photoelectron spectroscopy, x-ray absorption spectroscopy, electron energy loss spectroscopy, Fano Effect measurements, and Bremstrahlung Isochromat Spectroscopy, including the utilization of micro-focused beams to probe single-crystallite regions of polycrystalline Pu samples.

  10. Experimental Benchmarking of Pu Electronic Structure

    SciTech Connect

    Tobin, J G; Moore, K T; Chung, B W; Wall, M A; Schwartz, A J; Ebbinghaus, B B; Butterfield, M T; Teslich, Jr., N E; Bliss, R A; Morton, S A; Yu, S W; Komesu, T; Waddill, G D; der Laan, G v; Kutepov, A L

    2005-10-13

    The standard method to determine the band structure of a condensed phase material is to (1) obtain a single crystal with a well defined surface and (2) map the bands with angle resolved photoelectron spectroscopy (occupied or valence bands) and inverse photoelectron spectroscopy (unoccupied or conduction bands). Unfortunately, in the case of Pu, the single crystals of Pu are either nonexistent, very small and/or having poorly defined surfaces. Furthermore, effects such as electron correlation and a large spin-orbit splitting in the 5f states have further complicated the situation. Thus, we have embarked upon the utilization of unorthodox electron spectroscopies, to circumvent the problems caused by the absence of large single crystals of Pu with well-defined surfaces. Our approach includes the techniques of resonant photoelectron spectroscopy [1], x-ray absorption spectroscopy [1,2,3,4], electron energy loss spectroscopy [2,3,4], Fano Effect measurements [5], and Bremstrahlung Isochromat Spectroscopy [6], including the utilization of micro-focused beams to probe single-crystallite regions of polycrystalline Pu samples. [2,3,6

  11. Complexation of actinides with derivatives of oxydiaceticacid

    SciTech Connect

    Rao, Linfeng; Tian, Guoxin

    2006-01-04

    Complexation of Np(V), U(VI) and Nd(III) with dimethyl-3-oxa-glutaramic acid (DMOGA) and tetramethyl-3-oxa-glutaramide (TMOGA) was studied in comparison with the complexation with oxydiacetic acid (ODA). Stability constants and enthalpy of complexation were determined by potentiometry, spectrophotometry and calorimetry. Thermodynamic parameters, in conjunction with structural information of solid compounds, indicate that DMOGA and TMOGA form tridentate complexes with the ether-oxygen participating in bonding with actinide/lanthanide ions. The trends in the stability constants, enthalpy and entropy of complexation are discussed in terms of the difference in the hydration of the amide groups and carboxylate groups and the difference in the charge density of the metal ions.

  12. Structure and navigation for electronic publishing

    NASA Astrophysics Data System (ADS)

    Tillinghast, John; Beretta, Giordano B.

    1998-01-01

    The sudden explosion of the World Wide Web as a new publication medium has given a dramatic boost to the electronic publishing industry, which previously was a limited market centered around CD-ROMs and on-line databases. While the phenomenon has parallels to the advent of the tabloid press in the middle of last century, the electronic nature of the medium brings with it the typical characteristic of 4th wave media, namely the acceleration in its propagation speed and the volume of information. Consequently, e-publications are even flatter than print media; Shakespeare's Romeo and Juliet share the same computer screen with a home-made plagiarized copy of Deep Throat. The most touted tool for locating useful information on the World Wide Web is the search engine. However, due to the medium's flatness, sought information is drowned in a sea of useless information. A better solution is to build tools that allow authors to structure information so that it can easily be navigated. We experimented with the use of ontologies as a tool to formulate structures for information about a specific topic, so that related concepts are placed in adjacent locations and can easily be navigated using simple and ergonomic user models. We describe our effort in building a World Wide Web based photo album that is shared among a small network of people.

  13. Multigrid Methods in Electronic Structure Calculations

    NASA Astrophysics Data System (ADS)

    Briggs, Emil

    1996-03-01

    Multigrid techniques have become the method of choice for a broad range of computational problems. Their use in electronic structure calculations introduces a new set of issues when compared to traditional plane wave approaches. We have developed a set of techniques that address these issues and permit multigrid algorithms to be applied to the electronic structure problem in an efficient manner. In our approach the Kohn-Sham equations are discretized on a real-space mesh using a compact representation of the Hamiltonian. The resulting equations are solved directly on the mesh using multigrid iterations. This produces rapid convergence rates even for ill-conditioned systems with large length and/or energy scales. The method has been applied to both periodic and non-periodic systems containing over 400 atoms and the results are in very good agreement with both theory and experiment. Example applications include a vacancy in diamond, an isolated C60 molecule, and a 64-atom cell of GaN with the Ga d-electrons in valence which required a 250 Ry cutoff. A particular strength of a real-space multigrid approach is its ready adaptability to massively parallel computer architectures. The compact representation of the Hamiltonian is especially well suited to such machines. Tests on the Cray-T3D have shown nearly linear scaling of the execution time up to the maximum number of processors (512). The MPP implementation has been used for studies of a large Amyloid Beta Peptide (C_146O_45N_42H_210) found in the brains of Alzheimers disease patients. Further applications of the multigrid method will also be described. (in collaboration D. J. Sullivan and J. Bernholc)

  14. Electronic Structure and Bonding in Complex Biomolecule

    NASA Astrophysics Data System (ADS)

    Ouyang, Lizhi

    2005-03-01

    For over a century vitamin B12 and its enzyme cofactor derivates have persistently attracted research efforts for their vital biological role, unique Co-C bonding, rich red-ox chemistry, and recently their candidacies as drug delivery vehicles etc. However, our understanding of this complex metalorganic molecule's efficient enzyme activated catalytic power is still controversial. We have for the first time calculated the electronic structure, Mulliken effective charge and bonding of a whole Vitamin B12 molecule without any structural simplification by first- principles approaches based on density functional theory using structures determined by high resolution X-ray diffraction. A partial density of states analysis shows excellent agreement with X-ray absorption data and has been used successfully to interpret measured optical absorption spectra. Mulliken bonding analysis of B12 and its derivatives reveal noticeable correlations between the two axial ligands which could be exploited by the enzyme to control the catalytic process. Our calculated X-ray near edge structure of B12 and its derivates using Slater's transition state theory are also in good agreement with experiments. The same approach has been applied to other B12 derivatives, ferrocene peptides, and recently DNA molecules.

  15. Analysis of large soil samples for actinides

    DOEpatents

    Maxwell, III; Sherrod L.

    2009-03-24

    A method of analyzing relatively large soil samples for actinides by employing a separation process that includes cerium fluoride precipitation for removing the soil matrix and precipitates plutonium, americium, and curium with cerium and hydrofluoric acid followed by separating these actinides using chromatography cartridges.

  16. Prompt fission neutron spectra of actinides

    DOE PAGES

    Capote, R.; Chen, Y. -J.; Hambsch, F. -J.; ...

    2016-01-06

    Here, the energy spectrum of prompt neutrons emitted in fission (PFNS) plays a very important role in nuclear science and technology. A Coordinated Research Project (CRP) "Evaluation of Prompt Fission Neutron Spectra of Actinides" was established by the IAEA Nuclear Data Section in 2009, with the major goal to produce new PFNS evaluations with uncertainties for actinide nuclei.

  17. Prompt fission neutron spectrum of actinides

    SciTech Connect

    Capote, R.; Chen, Y. -J.; Hambsch, F. J.; Jurado, B.; Lestone, J. P.; Litaize, O.; Morillon, B.; Neudecker, D.; Oberstedt, S.; Ohsawa, T.; Otuka, N.; Pronyaev, V. G.; Saxena, A.; Schmidt, K. H.; Shcherbakov, O. A.; Shu, N. -C.; Smith, D. L.; Talou, P.; Trkov, A.; Tudora, A. C.; Vogt, R.; Vorobyev, A. S.

    2016-01-06

    Here, the energy spectrum of prompt neutron emitted in fission (PFNS) plays a very important role in nuclear science and technology. A Coordinated Research Project (CRP) "Evaluation of Prompt Fission Neutron Spectra of Actinides" was established by the IAEA Nuclear Data Section in 2009, with the major goal to produce new PFNS evaluations with uncertainties for actinide nuclei.

  18. Computational Chemistry for Nuclear Waste Characterization and Processing: Relativistic Quantum Chemistry of Actinides

    SciTech Connect

    Harrison, Robert J.; Bernholdt, David E.; Bursten, Bruce E.; De Jong, Wibe A.; Dixon, David A.; Dyall, Kenneth G.; Ermler, Walter V.; Fann, George I.; Hay, P. J.; Ismail Buchner, Nina; Kendall, Ricky A.; Li, Jun; Marino, Maria M.; Marsden, Colin J.; Martin, Richard L.; Minkoff, Michael; Nichols, Jeffrey A.; Nieplocha, Jarek; Pitzer, Russell M.; Pratt, Lawrence R.; Schreckenbach, Hans Georg; Seth, Michael C.; Shepard, Ron; Stevens, Rick L.; Tilson, Jeffrey L.; Wagner, Albert F.; Wang, Qi; Windus, Theresa L.; Wong, Adrian; Zhang, Zhiyong

    2002-08-02

    In the course of the 3 years we have conducted calculations on molecular structures containing actinides, lanthanides, and other heavy elements. Our calculations were done at the relativistically-correct, all-electron, 4-component calculations (DHF, MP2, and CCSD(T)), using density functional theory (DFT) with relativistic effective core potentials (RECPs), and various other methodologies. We studied the ground- and excited state structures, energetics, vibrational frequencies, and NMR, excitation and ionization spectra. In addition a considerable amount of codes and methodologies have been developed during the GC3 period, enabling us to do the extensive research described in this final report, and providing researchers worldwide with new computational chemistry tools. In this section we will give a brief overview of our activities and accomplishments, grouped by each research institution. A more extensive overview can be found in the appendices containing the full yearly reports.

  19. Electronic structure of Ca, Sr, and Ba under pressure.

    NASA Technical Reports Server (NTRS)

    Animalu, A. O. E.; Heine, V.; Vasvari, B.

    1967-01-01

    Electronic band structure calculations phase of Ca, Sr and Ba over wide range of atomic volumes under pressure electronic band structure calculations for fcc phase of Ca, Sr and Ba over wide range of atomic volumes under pressure electronic band structure calculations for fcc phase of Ca, Sr and Ba over wide range of atomic volumes under pressure

  20. Pulsed photothermal spectroscopy applied to lanthanide and actinide speciation

    SciTech Connect

    Berg, J.M.; Morris, D.E.; Clark, D.L.; Tait, C.D.; Woodruff, W.H. ); Ven Der Sluys, W.G. . Dept. of Chemistry)

    1991-01-01

    Several key elements important for the application of laser-based photothermal spectroscopies to the study of the complexation chemistry of lanthanides and actinides in solution have been demonstrated. The sensitivity of f-f electronic transition energies and band intensities to subtle changes in complexation was illustrated through comparison of visible and near infra-red absorption spectra of well-characterized U(IV) dimers with alkoxide ligands. Significant improvements in spectroscopic band resolution and energy measurement precision for solution species were shown to be achievable through work in frozen glasses at 77 K using a very simple cryogenic apparatus. A pulsed-laser photothermal spectroscopy apparatus was constructed and shown to be sensitive to optical density changes of 10{sup {minus}5} in an aqueous Nd{sup 3+} solution. In addition, the capability of obtaining photothermal lensing spectra of dilute actinide solutions in frozen glasses at 77 K was demonstrated. 6 refs., 5 figs.

  1. Minor Actinides Recycling in PWRs

    SciTech Connect

    Delpech, M.; Golfier, H.; Vasile, A.; Varaine, F.; Boucher, L.; Greneche, D.

    2006-07-01

    Recycling of minor actinides in current and near future PWR is considered as one of the options of the general waste management strategy. This paper presents the analysis of this option both from the core physics and fuel cycle point of view. A first indicator of the efficiency of different neutron spectra for transmutation purposes is the capture to fission cross sections ratio which is less favourable by a factor between 5 to 10 in PWRs compared to fast reactors. Another indicator presented is the production of high ranking isotopes like Curium, Berkelium or Californium in the thermal or epithermal spectrum conditions of PWR cores by successive neutron captures. The impact of the accumulation of this elements on the fabrication process of such PWR fuels strongly penalizes this option. The main constraint on minor actinides loadings in PWR (or fast reactors) fuels are related to their direct impact (or the impact of their transmutation products) on the reactivity coefficients, the reactivity control means and the core kinetics parameters. The main fuel cycle physical parameters like the neutron source, the alpha decay power, the gamma and neutrons dose rate and the criticality aspects are also affected. Recent neutronic calculations based on a reference core of the Evolutionary Pressurized Reactor (EPR), indicates typical maximum values of 1 % loadings. Different fuel design options for minor actinides transmutation purposes in PWRs are presented: UOX and MOX, homogeneous and heterogeneous assemblies. In this later case, Americium loading is concentrated in specific pins of a standard UOX assembly. Recycling of Neptunium in UOX and MOX fuels was also studied to improve the proliferation resistance of the fuel. The impact on the core physics and penalties on Uranium enrichment were underlined in this case. (authors)

  2. Actinide abundances in ordinary chondrites

    USGS Publications Warehouse

    Hagee, B.; Bernatowicz, T.J.; Podosek, F.A.; Johnson, M.L.; Burnett, D.S.; Tatsumoto, M.

    1990-01-01

    Measurements of 244Pu fission Xe, U, Th, and light REE (LREE) abundances, along with modal petrographic determinations of phosphate abundances, were carried out on equilibrated ordinary chondrites in order to define better the solar system Pu abundance and to determine the degree of variation of actinide and LREE abundances. Our data permit comparison of the directly measured Pu/ U ratio with that determined indirectly as (Pu/Nd) ?? (Nd/U) assuming that Pu behaves chemically as a LREE. Except for Guaren??a, and perhaps H chondrites in general, Pu concentrations are similar to that determined previously for St. Se??verin, although less precise because of higher trapped Xe contents. Trapped 130Xe 136Xe ratios appear to vary from meteorite to meteorite, but, relative to AVCC, all are similar in the sense of having less of the interstellar heavy Xe found in carbonaceous chondrite acid residues. The Pu/U and Pu/Nd ratios are consistent with previous data for St. Se??verin, but both tend to be slightly higher than those inferred from previous data on Angra dos Reis. Although significant variations exist, the distribution of our Th/U ratios, along with other precise isotope dilution data for ordinary chondrites, is rather symmetric about the CI chondrite value; however, actinide/(LREE) ratios are systematically lower than the CI value. Variations in actinide or LREE absolute and relative abundances are interpreted as reflecting differences in the proportions and/or compositions of more primitive components (chondrules and CAI materials?) incorporated into different regions of the ordinary chondrite parent bodies. The observed variations of Th/U, Nd/U, or Ce/U suggest that measurements of Pu/U on any single equilibrated ordinary chondrite specimen, such as St. Se??verin, should statistically be within ??20-30% of the average solar system value, although it is also clear that anomalous samples exist. ?? 1990.

  3. Interactions of microbial exopolymers with actinides

    NASA Astrophysics Data System (ADS)

    Johnson, Mitchell T.; Chitwood, Dawn J.; He, Lee; Neu, Mary P.

    2000-07-01

    The development of viable bioremediation strategies for radionuclide contaminated soils, sediments and ground waters at DOE sites is a formidable challenge. Ubiquitous microorganisms can absorb, oxidize, reduce and/or precipitate actinides and thereby affect the speciation, solubility, bioavailability, and migration of these toxic metals. Actinides can interact directly with microorganisms, i.e., via sorption to the cell wall, and indirectly via reaction with their byproducts, such as extracellular polymers. However, very little is known about the fundamental chemistry of any microbial-actinide interactions or their impact on environmental processes. Our goal is to fully characterize specific microbial-actinide interactions and determine how they may be exploited to effect environmental actinide mobility/immobility and remediation efforts.

  4. Actinide ion sensor for pyroprocess monitoring

    DOEpatents

    Jue, Jan-fong; Li, Shelly X.

    2014-06-03

    An apparatus for real-time, in-situ monitoring of actinide ion concentrations which comprises a working electrode, a reference electrode, a container, a working electrolyte, a separator, a reference electrolyte, and a voltmeter. The container holds the working electrolyte. The voltmeter is electrically connected to the working electrode and the reference electrode and measures the voltage between those electrodes. The working electrode contacts the working electrolyte. The working electrolyte comprises an actinide ion of interest. The reference electrode contacts the reference electrolyte. The reference electrolyte is separated from the working electrolyte by the separator. The separator contacts both the working electrolyte and the reference electrolyte. The separator is ionically conductive to the actinide ion of interest. The reference electrolyte comprises a known concentration of the actinide ion of interest. The separator comprises a beta double prime alumina exchanged with the actinide ion of interest.

  5. Exploring actinide materials through synchrotron radiation techniques.

    PubMed

    Shi, Wei-Qun; Yuan, Li-Yong; Wang, Cong-Zhi; Wang, Lin; Mei, Lei; Xiao, Cheng-Liang; Zhang, Li; Li, Zi-Jie; Zhao, Yu-Liang; Chai, Zhi-Fang

    2014-12-10

    Synchrotron radiation (SR) based techniques have been utilized with increasing frequency in the past decade to explore the brilliant and challenging sciences of actinide-based materials. This trend is partially driven by the basic needs for multi-scale actinide speciation and bonding information and also the realistic needs for nuclear energy research. In this review, recent research progresses on actinide related materials by means of various SR techniques were selectively highlighted and summarized, with the emphasis on X-ray absorption spectroscopy, X-ray diffraction and scattering spectroscopy, which are powerful tools to characterize actinide materials. In addition, advanced SR techniques for exploring future advanced nuclear fuel cycles dealing with actinides are illustrated as well.

  6. Reversible Hydrogen Storage Materials – Structure, Chemistry, and Electronic Structure

    SciTech Connect

    Robertson, Ian M.; Johnson, Duane D.

    2014-06-21

    To understand the processes involved in the uptake and release of hydrogen from candidate light-weight metal hydride storage systems, a combination of materials characterization techniques and first principle calculation methods have been employed. In addition to conventional microstructural characterization in the transmission electron microscope, which provides projected information about the through thickness microstructure, electron tomography methods were employed to determine the three-dimensional spatial distribution of catalyst species for select systems both before and after dehydrogenation. Catalyst species identification as well as compositional analysis of the storage material before and after hydrogen charging and discharging was performed using a combination of energy dispersive spectroscopy, EDS, and electron energy loss spectroscopy, EELS. The characterization effort was coupled with first-principles, electronic-structure and thermodynamic techniques to predict and assess meta-stable and stable phases, reaction pathways, and thermodynamic and kinetic barriers. Systems studied included:NaAlH4, CaH2/CaB6 and Ca(BH4)2, MgH2/MgB2, Ni-Catalyzed Magnesium Hydride, TiH2-Catalyzed Magnesium Hydride, LiBH4, Aluminum-based systems and Aluminum

  7. Separation of actinides from lanthanides

    DOEpatents

    Smith, Barbara F.; Jarvinen, Gordon D.; Ryan, Robert R.

    1989-01-01

    An organic extracting solution and an extraction method useful for separating elements of the actinide series of the periodic table from elements of the lanthanide series, where both are in trivalent form. The extracting solution consists of a primary ligand and a secondary ligand, preferably in an organic solvent. The primary ligand is a substituted monothio-1,3-dicarbonyl, which includes a substituted 4-acyl-2-pyrazolin-5-thione, such as 4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-thione (BMPPT). The secondary ligand is a substituted phosphine oxide, such as trioctylphosphine oxide (TOPO).

  8. Electronic band structure of defect chalcopyrites

    NASA Astrophysics Data System (ADS)

    Jiang, Xiaoshu; Lambrecht, Walter R. L.

    2001-03-01

    The defect chalcopyrites of chemical composition II-III-VI4 in which II, III and VI mean group-II elements such as Cd or Hg, group-III elements such as Al and Ga and group-VI elements such as S, Se, Te, form an interesting family of semiconductor compounds with potential nonlinear optical applications. They can be thought of as derived from the regular I-III-VI2 chalcopyrites by doubling the formula unit and replacing the group I element, for example, Ag by the group-II element and a vacancy in an ordered manner. The chalcopyrites themselves are derived from II-VI compounds by replacing the group-II by a group I and a group-III element. In this contribution we present electronic band structure calculations of some of these compounds, calculated using the linear muffin-tin orbital method combined with the local density functional approximation. We discuss the relation of the band structures of the corresponding zincblende, chalcopyrite and defect chalcopyrite compounds. In particular, the role of the group I or group II d-band energy will be shown to be important. The trends with chemical substutions and the effects of structural distortions c/a and internal parameters accompanying the chemical distortion will be discussed.

  9. Electronic structures of ytterbocene-imine complexes

    SciTech Connect

    Da Re, R. E.; Kuehl, C. J.; John, K. D.; Morris, D. E.

    2004-01-01

    The electronic structures of complexes of the form [(C{sub 5}Me{sub 5}){sub 2}Yb(L)]{sup +/0} (L = bipyridine, phenanthroline, terpyridine) have been probed using cyclic voltammetry and electronic spectroscopy. Remarkably, the voltammetric data reveal that the imine-based LUMO is stabilized and the redox-active metal f orbital is destabilized by ca. 1 V each upon formation of the ytterbocene-imine adduct, which is presumably responsible for the [(f){sup 13}({pi}*(L)){sup 1}] charge-transfer ground state characteristic of these complexes. The ca. 0.8 V separation between ligand-based oxidation and metal-based reduction waves for each ytterbocene adduct correlates with the energy of its optically promoted {pi}*(L)-f(Yb) charge transfer (LMCT) transition (ca. 5000 cm{sup -1}). The coupling between this LMCT excited state and the {sup 2}F{sub 7/2} ground and {sup 2}F{sub 5/2} excited states of Yb(III) leads to unusually large intensities ({var_epsilon} {approx} 1000) for the metal-localized f-f bands, which will be discussed in the context of an intensity borrowing mechanism that invokes exchange between the ligand-based {sup 2}S and metal-based {sup 2}F spin states.

  10. Electron Liquids in Semiconductor Quantum Structures

    SciTech Connect

    Aron Pinczuk

    2009-05-25

    The groups led by Stormer and Pinczuk have focused this project on goals that seek the elucidation of novel many-particle effects that emerge in two-dimensional electron systems (2DES) as the result from fundamental quantum interactions. This experimental research is conducted under extreme conditions of temperature and magnetic field. From the materials point of view, the ultra-high mobility systems in GaAs/AlGaAs quantum structures continue to be at the forefront of this research. The newcomer materials are based on graphene, a single atomic layer of graphite. The graphene research is attracting enormous attention from many communities involved in condensed matter research. The investigated many-particle phenomena include the integer and fractional quantum Hall effect, composite fermions, and Dirac fermions, and a diverse group of electron solid and liquid crystal phases. The Stormer group performed magneto-transport experiments and far-infrared spectroscopy, while the Pinczuk group explores manifestations of such phases in optical spectra.

  11. Electronic structures of reconstructed zigzag silicene nanoribbons

    SciTech Connect

    Ding, Yi E-mail: wangyanli-04@tsinghua.org.cn; Wang, Yanli E-mail: wangyanli-04@tsinghua.org.cn

    2014-02-24

    Edge states and magnetism are crucial for spintronic applications of nanoribbons. Here, using first-principles calculations, we explore structural stabilities and electronic properties of zigzag silicene nanoribbons (ZSiNRs) with Klein and pentagon-heptagon reconstructions. Comparing to unreconstructed zigzag edges, deformed bare pentagon-heptagon ones are favored under H-poor conditions, while H-rich surroundings stabilize di-hydrogenated Klein edges. These Klein edges have analogous magnetism to zigzag ones, which also possess the electric-field-induced half-metallicity of nanoribbons. Moreover, diverse magnetic states can be achieved by asymmetric Klein and zigzag edges into ZSiNRs, which could be transformed from antiferromagnetic-semiconductors to bipolar spin-gapless-semiconductors and ferromagnetic-metals depending on edge hydrogenations.

  12. Multilevel domain decomposition for electronic structure calculations

    SciTech Connect

    Barrault, M. . E-mail: maxime.barrault@edf.fr; Cances, E. . E-mail: cances@cermics.enpc.fr; Hager, W.W. . E-mail: hager@math.ufl.edu; Le Bris, C. . E-mail: lebris@cermics.enpc.fr

    2007-03-01

    We introduce a new multilevel domain decomposition method (MDD) for electronic structure calculations within semi-empirical and density functional theory (DFT) frameworks. This method iterates between local fine solvers and global coarse solvers, in the spirit of domain decomposition methods. Using this approach, calculations have been successfully performed on several linear polymer chains containing up to 40,000 atoms and 200,000 atomic orbitals. Both the computational cost and the memory requirement scale linearly with the number of atoms. Additional speed-up can easily be obtained by parallelization. We show that this domain decomposition method outperforms the density matrix minimization (DMM) method for poor initial guesses. Our method provides an efficient preconditioner for DMM and other linear scaling methods, variational in nature, such as the orbital minimization (OM) procedure.

  13. Structure, Stability and Electronic Properties of Nanodiamonds

    NASA Astrophysics Data System (ADS)

    Galli, Giulia

    Diamond nanoparticles, or nanodiamonds, have the most disparate origins. They are found in crude oil at concentrations up to thousands of parts per million, in meteorites, interstellar dust, and protoplanetary nebulae, as well as in certain sediment layers on Earth. They can also be produced in the laboratory by chemical vapor deposition or by detonating high explosive materials. Here we summarize what is known about nanodiamond sources; we then describe the atomic and electronic structure, and stability of diamond nanoparticles, highlighting the role of theory and computations in understanding and predicting their properties. Possible technological applications of thin films composed of nanodiamonds, ranging from micro-resonators to substrates for drug delivery, are briefly discussed.

  14. Relativistic effects on the thermal expansion of the actinide elements

    SciTech Connect

    Soederlind, P.; Nordstroem, L.; Lou Yongming; Johansson, B. )

    1990-09-01

    The room-temperature linear thermal-expansion coefficient is calculated for the light actinides thorium, protactinium, uranium, neptunium, and plutonium for the fcc crystal structure. The relativistic spin-orbit interaction is included in these calculations. We show that the spin-orbit splitting of the 5{ital f} band gives rise to a considerable increase of the thermal expansion and to a large extent explains the observed anomalously large thermal expansion for the neptunium and plutonium metals.

  15. Probing the population of the spin-orbit split levels in the actinide 5f states.

    PubMed

    Moore, K T; van der Laan, G; Tobin, J G; Chung, B W; Wall, M A; Schwartz, A J

    2006-03-01

    Spin-orbit interaction in the 5f states is believed to strongly influence exotic behaviors observed in actinide metals and compounds. Understanding these interactions and how they relate to the actinide series is of considerable importance. To address this issue, the branching ratio of the white-line peaks of the N4,5 edge for the light actinide metals, alpha-Th, alpha-U, and alpha-Pu were recorded using electron energy-loss spectroscopy (EELS) in a transmission electron microscope (TEM) and synchrotron-radiation-based X-ray absorption spectroscopy (XAS). Using the spin-orbit sum rule and the branching ratios from both experimental spectra and many-electron atomic spectral calculations, accurate values of the spin-orbit interaction, and thus the relative occupation of the j = 5/2 and 7/2 levels, are determined for the actinide 5f states. Results show that the spin-orbit sum rule works very well with both EELS and XAS spectra, needing little or no correction. This is important, since the high spatial resolution of a TEM can be used to overcome the problems of single-crystal growth often encountered with actinide metals, allowing acquisition of EELS spectra, and subsequent spin-orbit analysis, from nm-sized regions. The relative occupation numbers obtained by our method have been compared with recent theoretical results and they show a good agreement in their trend.

  16. Experimental and theoretical electronic structure of quinacridone

    NASA Astrophysics Data System (ADS)

    Lüftner, Daniel; Refaely-Abramson, Sivan; Pachler, Michael; Resel, Roland; Ramsey, Michael G.; Kronik, Leeor; Puschnig, Peter

    2014-08-01

    The energy positions of frontier orbitals in organic electronic materials are often studied experimentally by (inverse) photoemission spectroscopy and theoretically within density functional theory. However, standard exchange-correlation functionals often result in too small fundamental gaps, may lead to wrong orbital energy ordering, and do not capture polarization-induced gap renormalization. Here we examine these issues and a strategy for overcoming them by studying the gas phase and bulk electronic structure of the organic molecule quinacridone (5Q), a promising material with many interesting properties for organic devices. Experimentally we perform angle-resolved photoemission spectroscopy (ARUPS) on thin films of the crystalline β phase of 5Q. Theoretically we employ an optimally tuned range-separated hybrid functional (OT-RSH) within density functional theory. For the gas phase molecule, our OT-RSH result for the ionization potential (IP) represents a substantial improvement over the semilocal PBE and the PBE0 hybrid functional results, producing an IP in quantitative agreement with experiment. For the bulk crystal we take into account the correct screening in the bulk, using the recently developed optimally tuned screened range-separated hybrid (OT-SRSH) approach, while retaining the optimally tuned parameters for the range separation and the short-range Fock exchange. This leads to a band gap narrowing due to polarization effects and results in a valence band spectrum in excellent agreement with experimental ARUPS data, with respect to both peak positions and heights. Finally, full-frequency G0W0 results based on a hybrid functional starting point are shown to agree with the OT-SRSH approach, improving substantially on the PBE-starting point.

  17. Nonlinearity in structural and electronic materials

    SciTech Connect

    Bishop, A.R.; Beardmore, K.M.; Ben-Naim, E.

    1997-11-01

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The project strengthens a nonlinear technology base relevant to a variety of problems arising in condensed matter and materials science, and applies this technology to those problems. In this way the controlled synthesis of, and experiments on, novel electronic and structural materials provide an important focus for nonlinear science, while nonlinear techniques help advance the understanding of the scientific principles underlying the control of microstructure and dynamics in complex materials. This research is primarily focused on four topics: (1) materials microstructure: growth and evolution, and porous media; (2) textures in elastic/martensitic materials; (3) electro- and photo-active polymers; and (4) ultrafast photophysics in complex electronic materials. Accomplishments included the following: organization of a ``Nonlinear Materials`` seminar series and international conferences including ``Fracture, Friction and Deformation,`` ``Nonequilibrium Phase Transitions,`` and ``Landscape Paradigms in Physics and Biology``; invited talks at international conference on ``Synthetic Metals,`` ``Quantum Phase Transitions,`` ``1996 CECAM Euroconference,`` and the 1995 Fall Meeting of the Materials Research Society; large-scale simulations and microscopic modeling of nonlinear coherent energy storage at crack tips and sliding interfaces; large-scale simulation and microscopic elasticity theory for precursor microstructure and dynamics at solid-solid diffusionless phase transformations; large-scale simulation of self-assembling organic thin films on inorganic substrates; analysis and simulation of smoothing of rough atomic surfaces; and modeling and analysis of flux pattern formation in equilibrium and nonequilibrium Josephson junction arrays and layered superconductors.

  18. RESCU: A real space electronic structure method

    NASA Astrophysics Data System (ADS)

    Michaud-Rioux, Vincent; Zhang, Lei; Guo, Hong

    2016-02-01

    In this work we present RESCU, a powerful MATLAB-based Kohn-Sham density functional theory (KS-DFT) solver. We demonstrate that RESCU can compute the electronic structure properties of systems comprising many thousands of atoms using modest computer resources, e.g. 16 to 256 cores. Its computational efficiency is achieved from exploiting four routes. First, we use numerical atomic orbital (NAO) techniques to efficiently generate a good quality initial subspace which is crucially required by Chebyshev filtering methods. Second, we exploit the fact that only a subspace spanning the occupied Kohn-Sham states is required, and solving accurately the KS equation using eigensolvers can generally be avoided. Third, by judiciously analyzing and optimizing various parts of the procedure in RESCU, we delay the O (N3) scaling to large N, and our tests show that RESCU scales consistently as O (N2.3) from a few hundred atoms to more than 5000 atoms when using a real space grid discretization. The scaling is better or comparable in a NAO basis up to the 14,000 atoms level. Fourth, we exploit various numerical algorithms and, in particular, we introduce a partial Rayleigh-Ritz algorithm to achieve efficiency gains for systems comprising more than 10,000 electrons. We demonstrate the power of RESCU in solving KS-DFT problems using many examples running on 16, 64 and/or 256 cores: a 5832 Si atoms supercell; a 8788 Al atoms supercell; a 5324 Cu atoms supercell and a small DNA molecule submerged in 1713 water molecules for a total 5399 atoms. The KS-DFT is entirely converged in a few hours in all cases. Our results suggest that the RESCU method has reached a milestone of solving thousands of atoms by KS-DFT on a modest computer cluster.

  19. Investigating Actinide Molecular Adducts From Absorption Edge Spectroscopy

    SciTech Connect

    Den Auwer, C.; Conradson, S.D.; Guilbaud, P.; Moisy, P.; Mustre de Leon, J.; Simoni, E.; /SLAC, SSRL

    2006-10-27

    Although Absorption Edge Spectroscopy has been widely applied to the speciation of actinide elements, specifically at the L{sub III} edge, understanding and interpretation of actinide edge spectra are not complete. In that sense, semi-quantitative analysis is scarce. In this paper, different aspects of edge simulation are presented, including semi-quantitative approaches. Comparison is made between various actinyl (U, Np) aquo or hydroxy compounds. An excursion into transition metal osmium chemistry allows us to compare the structurally related osmyl and uranyl hydroxides. The edge shape and characteristic features are discussed within the multiple scattering picture and the role of the first coordination sphere as well as contributions from the water solvent are described.

  20. International Workshop on Orbital and Spin Magnetism of Actinides (IWOSMA-3)

    SciTech Connect

    Temmerman, W; Tobin, J; der Laan, G v

    2006-11-08

    This International Workshop on Orbital and Spin Magnetism of Actinides (IWOSMA) is the third in a series. The first workshop took place in Daresbury in 1999 and the second in Berkeley, CA, USA in 2002. These workshops are informal gatherings of theoreticians and experimentalists addressing the latest issues in the electronic and magnetic properties of actinides. The magnetism of transition metal systems and lanthanide systems is now fairly well understood, where d and f electrons can be described in a delocalized and localized model, respectively. On the other hand, actinide systems do not fit in such a description. The localization of the 5f is in between that of the 3d and 4f and the strong spin-orbit interaction necessitates a relativistic approach. Furthermore, electron correlation effects play a major role in these compounds. Recently, it has become possible to determine element-specific magnetic moments using neutron diffraction and x-ray scattering and absorption. The latter technique makes it even possible to separate the orbital and spin contribution to the total magnetic moment. The results are very interesting but difficult to reproduce with present state-of-art calculations. Not only a very large orbital polarization but also a large magnetic dipole term has been measured in cubic compounds, such as US. This allows for severe testing of the extra terms included in band theory to account for orbital polarization. It is also clear that deeper insight in magnetism can be obtained by studying the unusual behavior of the actinides. The recent development and application of such techniques as DMFT could contribute to the understanding of magnetism in actinides. Despite the fact that actinides for health reasons will find less application in technological market products, the understanding of their magnetic and electronic properties will no doubt provide key elements for a general description of electron correlation and relativistic effects.

  1. Synthesis of yttria-stabilised zirconia matrices for immobilisation of actinides by internal gelation method

    SciTech Connect

    Benay, G.; Modolo, G.; Odoj, R.

    2007-07-01

    In the scope of the co-conversion of actinides solutions obtained from partitioning spent nuclear fuel, the internal gelation of ceria-doped yttria-stabilized zirconia was investigated. This dust-free method to fabricate kernels, which can be used as fuel or pressed into pellets, is technically easy to implement and compatible with remote handling. The effects of the quantity of reactants used on the properties of the material were studied. Gels, kernels and pellets were analyzed by thermal analysis, electron microscopy and X-ray diffraction. It was found that the initial broth composition played an important role in the structure of kernels and the formation of cracks during thermal treatment. Pellets obtained with a repressing method were found to present densities up to 86% TD. (authors)

  2. Experimental studies of actinides in molten salts

    SciTech Connect

    Reavis, J.G.

    1985-06-01

    This review stresses techniques used in studies of molten salts containing multigram amounts of actinides exhibiting intense alpha activity but little or no penetrating gamma radiation. The preponderance of studies have used halides because oxygen-containing actinide compounds (other than oxides) are generally unstable at high temperatures. Topics discussed here include special enclosures, materials problems, preparation and purification of actinide elements and compounds, and measurements of various properties of the molten volts. Property measurements discussed are phase relationships, vapor pressure, density, viscosity, absorption spectra, electromotive force, and conductance. 188 refs., 17 figs., 6 tabs.

  3. Final Project Report for ER15351 “A Study of New Actinide Zintl Ion Materials”

    SciTech Connect

    Peter K. Dorhout

    2007-11-12

    The structural chemistry of actinide main-group metal materials provides the fundamental basis for the understanding of structural coordination chemistry and the formation of materials with desired or predicted structural features. The main-group metal building blocks, comprising sulfur-group, phosphorous-group, or silicon-group elements, have shown versatility in oxidation state, coordination, and bonding preferences. These building blocks have allowed us to elucidate a series of structures that are unique to the actinide elements, although we can find structural relationships to transition metal and 4f-element materials. In the past year, we investigated controlled metathesis and self-propagating reactions between actinide metal halides and alkali metal salts of main-group metal chalcogenides such as K-P-S salts. Ternary plutonium thiophosphates have resulted from these reactions at low temperature in sealed ampules. we have also focused efforts to examine reactions of Th, U, and Pu halide salts with other alkali metal salts such as Na-Ge-S and Na-Si-Se and copper chloride to identify if self-propagating reactions may be used as a viable reaction to prepare new actinide materials and we prepared a series of U and Th copper chalcogenide materials. Magnetic measurements continued to be a focus of actinide materials prepared in our laboratory. We also contributed to the XANES work at Los Alamos by preparing materials for study and for comparison with environmental samples.

  4. Subsurface interactions of actinide species and microorganisms : implications for the bioremediation of actinide-organic mixtures.

    SciTech Connect

    Banaszak, J.E.; Reed, D.T.; Rittmann, B.E.

    1999-02-12

    By reviewing how microorganisms interact with actinides in subsurface environments, we assess how bioremediation controls the fate of actinides. Actinides often are co-contaminants with strong organic chelators, chlorinated solvents, and fuel hydrocarbons. Bioremediation can immobilize the actinides, biodegrade the co-contaminants, or both. Actinides at the IV oxidation state are the least soluble, and microorganisms accelerate precipitation by altering the actinide's oxidation state or its speciation. We describe how microorganisms directly oxidize or reduce actinides and how microbiological reactions that biodegrade strong organic chelators, alter the pH, and consume or produce precipitating anions strongly affect actinide speciation and, therefore, mobility. We explain why inhibition caused by chemical or radiolytic toxicities uniquely affects microbial reactions. Due to the complex interactions of the microbiological and chemical phenomena, mathematical modeling is an essential tool for research on and application of bioremediation involving co-contamination with actinides. We describe the development of mathematical models that link microbiological and geochemical reactions. Throughout, we identify the key research needs.

  5. Electronic structure of cyclohexane on Ni(111)

    NASA Astrophysics Data System (ADS)

    Huber, W.; Zebisch, P.; Bornemann, T.; Steinrück, H.-P.

    1990-12-01

    Mono- and multilayers of cyclohexane adsorbed on a Ni(111) surface have been studied by angle resolved UV photoelectron spectroscopy (ARUPS) using linearly polarized synchrotron radiation, temperature programmed desorption (TPD) and low energy electron diffraction (LEED). Cyclohexane is molecularly adsorbed on Ni(111) at temperatures below 200 K and desorbs without dehydrogenation. Desorption from the first layer exhibits zeroth-order desorption behavior indicative of desorption from two-dimensional islands. The first layer exhibits a well ordered ( 7 × 7)R19.1° LEED structure starting at coverages of 0.04 ML up to the saturation coverage of 0.143 ML, also indicative of island formation. For cyclohexane in the first layer the binding energies of the various molecular levels are, apart from an overall shift to smaller values by 0.7 eV, within ± 0.1 eV identical to those of condensed cyclohexane. This absence of chemical shifts indicates that there is only very weak (if any) chemical interaction between cyclohexane and the Ni(111) surface. From the normal emission ARUPS spectra and symmetry selection rules we conclude that the symmetry of cyclohexane adsorbed on Ni(111) is lower than C 3v. This is attributed to a slightly inclined adsorption geometry with intramolecular C 3v symmetry of the adsorbed molecules.

  6. Actinide removal from spent salts

    DOEpatents

    Hsu, Peter C.; von Holtz, Erica H.; Hipple, David L.; Summers, Leslie J.; Adamson, Martyn G.

    2002-01-01

    A method for removing actinide contaminants (uranium and thorium) from the spent salt of a molten salt oxidation (MSO) reactor is described. Spent salt is removed from the reactor and analyzed to determine the contaminants present and the carbonate concentration. The salt is dissolved in water, and one or more reagents are added to precipitate the thorium as thorium oxide and/or the uranium as either uranium oxide or as a diuranate salt. The precipitated materials are filtered, dried and packaged for disposal as radioactive waste. About 90% of the thorium and/or uranium present is removed by filtration. After filtration, salt solutions having a carbonate concentration >20% can be dried and returned to the reactor for re-use. Salt solutions containing a carbonate concentration <20% require further clean-up using an ion exchange column, which yields salt solutions that contain less than 0.1 ppm of thorium or uranium.

  7. PF-4 actinide disposition strategy

    SciTech Connect

    Margevicius, Robert W

    2010-05-28

    The dwindling amount of Security Category I processing and storage space across the DOE Complex has driven the need for more effective storage of nuclear materials at LANL's Plutonium Facility's (PF-4's) vault. An effort was begun in 2009 to create a strategy, a roadmap, to identify all accountable nuclear material and determine their disposition paths, the PF-4 Actinide Disposition Strategy (PADS). Approximately seventy bins of nuclear materials with similar characteristics - in terms of isotope, chemical form, impurities, disposition location, etc. - were established in a database. The ultimate disposition paths include the material to remain at LANL, disposition to other DOE sites, and disposition to waste. If all the actions described in the document were taken, over half of the containers currently in the PF-4 vault would been eliminated. The actual amount of projected vault space will depend on budget and competing mission requirements, however, clearly a significant portion of the current LANL inventory can be either dispositioned or consolidated.

  8. Electronic Structure and Dynamics of Nitrosyl Porphyrins

    PubMed Central

    Scheidt, W. Robert; Barabanschikov, Alexander; Pavlik, Jeffrey W.; Silvernail, Nathan J.; Sage, J. Timothy

    2010-01-01

    fully successful at capturing the interaction between the axial NO and imidazole ligands. This supports previous conclusions that hemeNO complexes exhibit an unusual degree of variability with respect to computational method, and we speculate that this variability hints at a genuine electronic instability that a protein can exploit to tune reactivity. We anticipate that ongoing characterization of heme-NO complexes will deepen our understanding of their structure, dynamics, and reactivity. PMID:20666384

  9. Graph-based linear scaling electronic structure theory

    NASA Astrophysics Data System (ADS)

    Niklasson, Anders M. N.; Mniszewski, Susan M.; Negre, Christian F. A.; Cawkwell, Marc J.; Swart, Pieter J.; Mohd-Yusof, Jamal; Germann, Timothy C.; Wall, Michael E.; Bock, Nicolas; Rubensson, Emanuel H.; Djidjev, Hristo

    2016-06-01

    We show how graph theory can be combined with quantum theory to calculate the electronic structure of large complex systems. The graph formalism is general and applicable to a broad range of electronic structure methods and materials, including challenging systems such as biomolecules. The methodology combines well-controlled accuracy, low computational cost, and natural low-communication parallelism. This combination addresses substantial shortcomings of linear scaling electronic structure theory, in particular with respect to quantum-based molecular dynamics simulations.

  10. Graph-based linear scaling electronic structure theory.

    PubMed

    Niklasson, Anders M N; Mniszewski, Susan M; Negre, Christian F A; Cawkwell, Marc J; Swart, Pieter J; Mohd-Yusof, Jamal; Germann, Timothy C; Wall, Michael E; Bock, Nicolas; Rubensson, Emanuel H; Djidjev, Hristo

    2016-06-21

    We show how graph theory can be combined with quantum theory to calculate the electronic structure of large complex systems. The graph formalism is general and applicable to a broad range of electronic structure methods and materials, including challenging systems such as biomolecules. The methodology combines well-controlled accuracy, low computational cost, and natural low-communication parallelism. This combination addresses substantial shortcomings of linear scaling electronic structure theory, in particular with respect to quantum-based molecular dynamics simulations.

  11. Advanced Aqueous Separation Systems for Actinide Partitioning

    SciTech Connect

    Nash, Kenneth L.; Clark, Sue; Meier, G Patrick; Alexandratos, Spiro; Paine, Robert; Hancock, Robert; Ensor, Dale

    2012-03-21

    One of the most challenging aspects of advanced processing of spent nuclear fuel is the need to isolate transuranium elements from fission product lanthanides. This project expanded the scope of earlier investigations of americium (Am) partitioning from the lanthanides with the synthesis of new separations materials and a centralized focus on radiochemical characterization of the separation systems that could be developed based on these new materials. The primary objective of this program was to explore alternative materials for actinide separations and to link the design of new reagents for actinide separations to characterizations based on actinide chemistry. In the predominant trivalent oxidation state, the chemistry of lanthanides overlaps substantially with that of the trivalent actinides and their mutual separation is quite challenging.

  12. BWR Assembly Optimization for Minor Actinide Recycling

    SciTech Connect

    G. Ivan Maldonado; John M. Christenson; J.P. Renier; T.F. Marcille; J. Casal

    2010-03-22

    The Primary objective of the proposed project is to apply and extend the latest advancements in LWR fuel management optimization to the design of advanced boiling water reactor (BWR) fuel assemblies specifically for the recycling of minor actinides (MAs).

  13. Overview of actinide chemistry in the WIPP

    SciTech Connect

    Borkowski, Marian; Lucchini, Jean - Francois; Richmann, Michael K; Reed, Donald T; Khaing, Hnin; Swanson, Juliet

    2009-01-01

    The year 2009 celebrates 10 years of safe operations at the Waste Isolation Pilot Plant (WIPP), the only nuclear waste repository designated to dispose defense-related transuranic (TRU) waste in the United States. Many elements contributed to the success of this one-of-the-kind facility. One of the most important of these is the chemistry of the actinides under WIPP repository conditions. A reliable understanding of the potential release of actinides from the site to the accessible environment is important to the WIPP performance assessment (PA). The environmental chemistry of the major actinides disposed at the WIPP continues to be investigated as part of the ongoing recertification efforts of the WIPP project. This presentation provides an overview of the actinide chemistry for the WIPP repository conditions. The WIPP is a salt-based repository; therefore, the inflow of brine into the repository is minimized, due to the natural tendency of excavated salt to re-seal. Reducing anoxic conditions are expected in WIPP because of microbial activity and metal corrosion processes that consume the oxygen initially present. Should brine be introduced through an intrusion scenario, these same processes will re-establish reducing conditions. In the case of an intrusion scenario involving brine, the solubilization of actinides in brine is considered as a potential source of release to the accessible environment. The following key factors establish the concentrations of dissolved actinides under subsurface conditions: (1) Redox chemistry - The solubility of reduced actinides (III and IV oxidation states) is known to be significantly lower than the oxidized forms (V and/or VI oxidation states). In this context, the reducing conditions in the WIPP and the strong coupling of the chemistry for reduced metals and microbiological processes with actinides are important. (2) Complexation - For the anoxic, reducing and mildly basic brine systems in the WIPP, the most important

  14. Joint Actinide Shock Physics Experimental Research - JASPER

    ScienceCinema

    None

    2016-07-12

    Commonly known as JASPER the Joint Actinide Shock Physics Experimental Research facility is a two stage light gas gun used to study the behavior of plutonium and other materials under high pressures, temperatures, and strain rates.

  15. Joint Actinide Shock Physics Experimental Research - JASPER

    SciTech Connect

    2014-10-31

    Commonly known as JASPER the Joint Actinide Shock Physics Experimental Research facility is a two stage light gas gun used to study the behavior of plutonium and other materials under high pressures, temperatures, and strain rates.

  16. Crystalline matrices for the immobilization of plutonium and actinides

    SciTech Connect

    Anderson, E.B.; Burakov, E.E.; Galkin, Ya.B.; Starchenko, V.A.; Vasiliev, V.G.

    1996-05-01

    The management of weapon plutonium, disengaged as a result of conversion, is considered together with the problem of the actinide fraction of long-lived high level radioactive wastes. It is proposed to use polymineral ceramics based on crystalline host-phases: zircon ZrSiO{sub 4} and zirconium dioxide ZrO{sub 2}, for various variants of the management of plutonium and actinides (including the purposes of long-term safe storage or final disposal from the human activity sphere). It is shown that plutonium and actinides are able to form with these phases on ZrSiO{sub 4} and ZrO{sub 2} was done on laboratory level by the hot pressing method, using the plasmochemical calcination technology. To incorporate simulators of plutonium into the structure of ZrSiO{sub 4} and ZrO{sub 2} in the course of synthesis, an original method developed by the authors as a result of studying the high-uranium zircon (Zr,U) SiO{sub 4} form Chernobyl {open_quotes}lavas{close_quotes} was used.

  17. Redox response of actinide materials to highly ionizing radiation

    NASA Astrophysics Data System (ADS)

    Tracy, Cameron L.; Lang, Maik; Pray, John M.; Zhang, Fuxiang; Popov, Dmitry; Park, Changyong; Trautmann, Christina; Bender, Markus; Severin, Daniel; Skuratov, Vladimir A.; Ewing, Rodney C.

    2015-01-01

    Energetic radiation can cause dramatic changes in the physical and chemical properties of actinide materials, degrading their performance in fission-based energy systems. As advanced nuclear fuels and wasteforms are developed, fundamental understanding of the processes controlling radiation damage accumulation is necessary. Here we report oxidation state reduction of actinide and analogue elements caused by high-energy, heavy ion irradiation and demonstrate coupling of this redox behaviour with structural modifications. ThO2, in which thorium is stable only in a tetravalent state, exhibits damage accumulation processes distinct from those of multivalent cation compounds CeO2 (Ce3+ and Ce4+) and UO3 (U4+, U5+ and U6+). The radiation tolerance of these materials depends on the efficiency of this redox reaction, such that damage can be inhibited by altering grain size and cation valence variability. Thus, the redox behaviour of actinide materials is important for the design of nuclear fuels and the prediction of their performance.

  18. Redox response of actinide materials to highly ionizing radiation.

    PubMed

    Tracy, Cameron L; Lang, Maik; Pray, John M; Zhang, Fuxiang; Popov, Dmitry; Park, Changyong; Trautmann, Christina; Bender, Markus; Severin, Daniel; Skuratov, Vladimir A; Ewing, Rodney C

    2015-01-27

    Energetic radiation can cause dramatic changes in the physical and chemical properties of actinide materials, degrading their performance in fission-based energy systems. As advanced nuclear fuels and wasteforms are developed, fundamental understanding of the processes controlling radiation damage accumulation is necessary. Here we report oxidation state reduction of actinide and analogue elements caused by high-energy, heavy ion irradiation and demonstrate coupling of this redox behaviour with structural modifications. ThO2, in which thorium is stable only in a tetravalent state, exhibits damage accumulation processes distinct from those of multivalent cation compounds CeO2 (Ce(3+) and Ce(4+)) and UO3 (U(4+), U(5+) and U(6+)). The radiation tolerance of these materials depends on the efficiency of this redox reaction, such that damage can be inhibited by altering grain size and cation valence variability. Thus, the redox behaviour of actinide materials is important for the design of nuclear fuels and the prediction of their performance.

  19. Transmutation of actinides in power reactors.

    PubMed

    Bergelson, B R; Gerasimov, A S; Tikhomirov, G V

    2005-01-01

    Power reactors can be used for partial short-term transmutation of radwaste. This transmutation is beneficial in terms of subsequent storage conditions for spent fuel in long-term storage facilities. CANDU-type reactors can transmute the main minor actinides from two or three reactors of the VVER-1000 type. A VVER-1000-type reactor can operate in a self-service mode with transmutation of its own actinides.

  20. PREPARATION OF ACTINIDE-ALUMINUM ALLOYS

    DOEpatents

    Moore, R.H.

    1962-09-01

    BS>A process is given for preparing alloys of aluminum with plutonium, uranium, and/or thorium by chlorinating actinide oxide dissolved in molten alkali metal chloride with hydrochloric acid, chlorine, and/or phosgene, adding aluminum metal, and passing air and/or water vapor through the mass. Actinide metal is formed and alloyed with the aluminum. After cooling to solidification, the alloy is separated from the salt. (AEC)

  1. Dramatic changes in electronic structure revealed by fractionally charged nuclei

    NASA Astrophysics Data System (ADS)

    Cohen, Aron J.; Mori-Sánchez, Paula

    2014-01-01

    Discontinuous changes in the electronic structure upon infinitesimal changes to the Hamiltonian are demonstrated. These are revealed in one and two electron molecular systems by full configuration interaction (FCI) calculations when the realm of the nuclear charge is extended to be fractional. FCI electron densities in these systems show dramatic changes in real space and illustrate the transfer, hopping, and removal of electrons. This is due to the particle nature of electrons seen in stretched systems and is a manifestation of an energy derivative discontinuity at constant number of electrons. Dramatic errors of density functional theory densities are seen in real space as this physics is missing from currently used approximations. The movements of electrons in these simple systems encapsulate those in real physical processes, from chemical reactions to electron transport and pose a great challenge for the development of new electronic structure methods.

  2. Actinide recovery method -- Large soil samples

    SciTech Connect

    Maxwell , S.L. III

    2000-04-25

    There is a need to measure actinides in environmental samples with lower and lower detection limits, requiring larger sample sizes. This analysis is adversely affected by sample-matrix interferences, which make analyzing soil samples above five-grams very difficult. A new Actinide-Recovery Method has been developed by the Savannah River Site Central Laboratory to preconcentrate actinides from large-soil samples. Diphonix Resin (Eichrom Industries), a 1994 R and D 100 winner, is used to preconcentrate the actinides from large soil samples, which are bound powerfully to the resin's diphosphonic acid groups. A rapid microwave-digestion technique is used to remove the actinides from the Diphonix Resin, which effectively eliminates interfering matrix components from the soil matrix. The microwave-digestion technique is more effective and less tedious than catalyzed hydrogen peroxide digestions of the resin or digestion of diphosphonic stripping agents such as HEDPA. After resin digestion, the actinides are recovered in a small volume of nitric acid which can be loaded onto small extraction chromatography columns, such as TEVA Resin, U-TEVA Resin or TRU Resin (Eichrom Industries). Small, selective extraction columns do not generate large volumes of liquid waste and provide consistent tracer recoveries after soil matrix elimination.

  3. Rapid determination of actinides in seawater samples

    DOE PAGES

    Maxwell, Sherrod L.; Culligan, Brian K.; Hutchison, Jay B.; ...

    2014-03-09

    A new rapid method for the determination of actinides in seawater samples has been developed at the Savannah River National Laboratory. The actinides can be measured by alpha spectrometry or inductively-coupled plasma mass spectrometry. The new method employs novel pre-concentration steps to collect the actinide isotopes quickly from 80 L or more of seawater. Actinides are co-precipitated using an iron hydroxide co-precipitation step enhanced with Ti+3 reductant, followed by lanthanum fluoride co-precipitation. Stacked TEVA Resin and TRU Resin cartridges are used to rapidly separate Pu, U, and Np isotopes from seawater samples. TEVA Resin and DGA Resin were used tomore » separate and measure Pu, Am and Cm isotopes in seawater volumes up to 80 L. This robust method is ideal for emergency seawater samples following a radiological incident. It can also be used, however, for the routine analysis of seawater samples for oceanographic studies to enhance efficiency and productivity. In contrast, many current methods to determine actinides in seawater can take 1–2 weeks and provide chemical yields of ~30–60 %. This new sample preparation method can be performed in 4–8 h with tracer yields of ~85–95 %. By employing a rapid, robust sample preparation method with high chemical yields, less seawater is needed to achieve lower or comparable detection limits for actinide isotopes with less time and effort.« less

  4. Actinide speciation in relation to biological processes.

    PubMed

    Ansoborlo, Eric; Prat, Odette; Moisy, Philippe; Den Auwer, Christophe; Guilbaud, Philippe; Carriere, M; Gouget, Barbara; Duffield, John; Doizi, Denis; Vercouter, Thomas; Moulin, Christophe; Moulin, Valérie

    2006-11-01

    In case of accidental release of radionuclides into the environment, actinides represent a severe health risk to human beings following internal contamination (inhalation, ingestion or wound). For a better understanding of the actinide behaviour in man (in term of metabolism, retention, excretion) and in specific biological systems (organs, cells or biochemical pathways), it is of prime importance to have a good knowledge of the relevant actinide solution chemistry and biochemistry, in particular of the thermodynamic constants needed for computing actinide speciation. To a large extent, speciation governs bioavailability and toxicity of elements and has a significant impact on the mechanisms by which toxics accumulate in cell compartments and organs and by which elements are transferred and transported from cell to cell. From another viewpoint, speciation is the prerequisite for the design and success of potential decorporation therapies. The purpose of this review is to present the state of the art of actinide knowledge within biological media. It is also to discuss how actinide speciation can be determined or predicted and to highlight the areas where information is lacking with the aim to encourage new research efforts.

  5. Actinide sulfides in the gas phase: experimental and theoretical studies of the thermochemistry of AnS (An = Ac, Th, Pa, U, Np, Pu, Am and Cm).

    PubMed

    Pereira, Cláudia C L; Marsden, Colin J; Marçalo, Joaquim; Gibson, John K

    2011-07-28

    The gas-phase thermochemistry of actinide monosulfides, AnS, was investigated experimentally and theoretically. Fourier transform ion cyclotron resonance mass spectrometry was employed to study the reactivity of An(+) and AnO(+) (An = Th, Pa, U, Np, Pu, Am and Cm) with CS(2) and COS, as well as the reactivity of the produced AnS(+) with oxidants (COS, CO(2), CH(2)O and NO). From these experiments, An(+)-S bond dissociation energies could be bracketed. Density functional theory studies of the energetics of neutral and monocationic AnS (An = Ac, Th, Pa, U, Np, Pu, Am and Cm) provided values for bond dissociation energies and ionization energies; the computed energetics of neutral and monocationic AnO were also obtained for comparison. The theoretical data, together with comparisons with known An(+)-O bond dissociation energies and M(+)-S and M(+)-O dissociation energies for the early transition metals, allowed for the refining of the An(+)-S bond dissociation energy ranges obtained from experiment. Examination of the reactivity of AnS(+) with dienes, coupled to comparisons with reactivities of the AnO(+) analogues, systematic considerations and the theoretical results, allowed for the estimation of the ionization energies of the AnS; the bond dissociation energies of neutral AnS were consequently derived. Estimates for the case of AcS were also made, based on correlations of the data for the other An and the electronic energetics of neutral and ionic An. The nature of the bonding in the elementary molecular actinide chalcogenides (oxides and sulfides) is discussed, based on both the experimental data and the computed electronic structures. DFT calculations of ionization energies for the actinide atoms and the diatomic sulfides and oxides are relatively reliable, but the calculation of bond dissociation energies is not uniformly satisfactory, either with DFT or CCSD(T). A key conclusion from both the experimental and theoretical results is that the 5f electrons do not

  6. Affordable, Lightweight, Highly Conductive Polymer Composite Electronic Packaging Structures

    DTIC Science & Technology

    1996-06-01

    matrix composite materials and how various material designs can be utilized in various structural/thermal configurations to produce electronic housings and...conductive polymer composite electronic packaging (i.e., electronic housings and heat sinks). The research will center on predominately polymer

  7. Synthesis of crystalline ceramics for actinide immobilisation

    SciTech Connect

    Burakov, B.; Gribova, V.; Kitsay, A.; Ojovan, M.; Hyatt, N.C.; Stennett, M.C.

    2007-07-01

    Methods for the synthesis of ceramic wasteforms for the immobilization of actinides are common to those for non-radioactive ceramics: hot uniaxial pressing (HUP); hot isostatic pressing (HIP); cold pressing followed by sintering; melting (for some specific ceramics, such as garnet/perovskite composites). Synthesis of ceramics doped with radionuclides is characterized with some important considerations: all the radionuclides should be incorporated into crystalline structure of durable host-phases in the form of solid solutions and no separate phases of radionuclides should be present in the matrix of final ceramic wasteform; all procedures of starting precursor preparation and ceramic synthesis should follow safety requirements of nuclear industry. Synthesis methods that avoid the use of very high temperatures and pressures and are easily accomplished within the environment of a glove-box or hot cell are preferable. Knowledge transfer between the V. G. Khlopin Radium Institute (KRI, Russia) and Immobilisation Science Laboratory (ISL, UK) was facilitated in the framework of a joint project supported by UK Royal Society. In order to introduce methods of precursor preparation and ceramic synthesis we selected well-known procedures readily deployable in radiochemical processing plants. We accounted that training should include main types of ceramic wasteforms which are currently discussed for industrial applications. (authors)

  8. Velocity-space structure of runaway electrons

    SciTech Connect

    Fuchs, V.; Cairns, R.A.; Lashmore-Davies, C.N.; Shoucri, M.M.

    1986-09-01

    The region of velocity space is determined in which electron runaway occurs because of a dc electric field. Phase-space analysis of the relaxation equations describing test electrons, corroborated by two-dimensional (2-D) numerical integration of the Fokker--Planck equation, reveals that the Dreicer condition for runaway v-italic/sup 2//sub parallel/> or =(2+Z-italic/sub i-italic/)E-italic/sub c-italic//E-italic is only sufficient. A weaker condition v-italic/sup 2//sub parallel/> or =(2+Z-italic/sub i-italic/)/sup 1//sup ///sup 2/E-italic/sub c-italic//E-italic is established, and it is shown, in general, that runaway in velocity space only occurs for those electrons that are outside one of the separatrices of the relaxation equations. The scaling with v-italic/sub parallel/ of the parallel distribution function and of the perpendicular temperature is also derived.

  9. Experimentally characterizing the electronic structures of f-electron systems using advanced high resolution Fourier transform microwave spectroscopies

    SciTech Connect

    Cooke, Stephen, A

    2013-02-03

    We aim to (i) provide data that directly addresses the fundamental roles of actinide valence electrons in chemical bonding, and (ii) serve to provide prototypical data for the heavy element computational chemistry community. These goals will be achieved through the first pure rotational spectroscopic measurements on prototypical systems at ultra-high resolution. These systems encompass low oxidation state uranium and thorium compounds including, but not limited to, UX and ThX, X = F, Cl, Br, I, and UY and ThY, Y = O, S, and other simple U and Th-containing compounds. Our primary experimental tools involve time-domain rotational spectroscopy achieving line widths and resolutions of a few kHz.

  10. Nonaqueous method for dissolving lanthanide and actinide metals

    DOEpatents

    Crisler, L.R.

    1975-11-11

    Lanthanide and actinide beta-diketonate complex molecular compounds are produced by reacting a beta-diketone compound with a lanthanide or actinide element in the elemental metallic state in a mixture of carbon tetrachloride and methanol.

  11. TUCS/phosphate mineralization of actinides

    SciTech Connect

    Nash, K.L.

    1997-10-01

    This program has as its objective the development of a new technology that combines cation exchange and mineralization to reduce the concentration of heavy metals (in particular actinides) in groundwaters. The treatment regimen must be compatible with the groundwater and soil, potentially using groundwater/soil components to aid in the immobilization process. The delivery system (probably a water-soluble chelating agent) should first concentrate the radionuclides then release the precipitating anion, which forms thermodynamically stable mineral phases, either with the target metal ions alone or in combination with matrix cations. This approach should generate thermodynamically stable mineral phases resistant to weathering. The chelating agent should decompose spontaneously with time, release the mineralizing agent, and leave a residue that does not interfere with mineral formation. For the actinides, the ideal compound probably will release phosphate, as actinide phosphate mineral phases are among the least soluble species for these metals. The most promising means of delivering the precipitant would be to use a water-soluble, hydrolytically unstable complexant that functions in the initial stages as a cation exchanger to concentrate the metal ions. As it decomposes, the chelating agent releases phosphate to foster formation of crystalline mineral phases. Because it involves only the application of inexpensive reagents, the method of phosphate mineralization promises to be an economical alternative for in situ immobilization of radionuclides (actinides in particular). The method relies on the inherent (thermodynamic) stability of actinide mineral phases.

  12. Overview of the crystal chemistry of the actinide chalcogenides: incorporation of the alkaline-earth elements.

    PubMed

    Mesbah, Adel; Prakash, Jai; Ibers, James A

    2016-10-18

    This review focuses on the results of exploratory syntheses of alkaline-earth-metal actinide chalcogenides Ak-An-Q (Ak = Ba, Sr; An = Th, U; Q = S, Se, and Te). About thirty new compounds are described. Although the basic building blocks of their structures are usually AnQ6 octahedra and AkQ8 bicapped trigonal prisms, these are combined in diverse ways to afford eleven new structure types. The structures reconfirm the prevailing presence of An(4+) in chalcogenides, although some of the compounds discovered are mixed An(4+)/An(5+) systems, and a few contain only An(5+). The tendency of the chalcogens to form Q-Q bonds is again evident from the presence of S-S single bonds and infinite Te-Te-Te linear chains. The latter possess interatomic distances of lengths greater than that of a Te-Te single bond but less than that of a Te-Te van der Waals interaction. Assignment of formal oxidation states in compounds containing these chains is arbitrary at best. Addition of metal atoms (M) affords quaternary structures, some of which show remarkable flexibility in the positions of the An and M atoms, and in such compounds the nature of the M elements influences directly the dimensionality of the resultant structure. The presence of adventitious oxygen, often from etching of the fused-silica tubes by oxyphilic An elements, results in new quintary compounds that show remarkable structural variations with change of M. The compounds discussed have shown transport and electronic structures that range from metallic-like to semiconducting. We find, with the exception of BaUSe3, when comparisons can be made that the values of the calculated band gaps are reasonably close but usually lower than the experimentally derived values. Thus the method used, in particular the HSE functional, has been generally successful on these 5f actinides. This is an important result because in the absence of suitable crystals, and hence experimental measurements, it still may be possible to offer credible

  13. Syntheses and electronic structures of decamethylmetallocenes

    SciTech Connect

    Robbins, J.L.

    1981-04-01

    The synthesis of decamethylmanganocene ((eta-C/sub 5/(CH/sub 3/)/sub 5/)/sub 2/Mn or (Me/sub 5/Cp)/sub 2/Mn)) is described. Magnetic susceptibility and electron paramagnetic resonance (EPR) studies show that (Me/sub 5/Cp)/sub 2/Mn is a low-spin, 17-electron compound with an orbitally degenerate, /sup 2/E/sub 2g/ (e/sub 2g//sup 3/ a/sub 1g//sup 2/) ground state. An x-ray crystallographic study of (Me/sub 5/Cp)/sub 2/Mn shows that it is a monomeric, D/sub 5d/ decamethylmetallocene with metal to ring carbon distances that are about 0.3 A shorter than those determined for high-spin manganocenes. The syntheses of new (Me/sub 5/Cp)/sub 2/M (M = Mg,V,Cr,Co, and Ni) and ((Me/sub 5/Cp)/sub 2/M)PF/sub 6/ (M = Cr,Co, and Ni) compounds are described. In addition, a preparative route to a novel, dicationic decamethylmetallocene, ((Me/sub 5/Cp)/sub 2/Ni)(PF/sub 6/)/sub 2/ is reported. Infrared, nuclear magnetic resonance, magnetic susceptibility, and/or x-ray crystallographic studies indicate that all the above compounds are D/sub 5d/ or D/sub 5h/ decamethylmetallocenes with low-spin electronic configurations. Cyclic voltammetry studies verify the reversibility and the one-electron nature of the (Me/sub 5/Cp)/sub 2/M ..-->.. ((Me/sub 5/Cp)/sub 2/M)/sup +/ (M = Cr,Mn,Fe,Co,Ni), ((Me/sub 5/Cp)/sub 2/Mn)/sup -/ ..-->.. (Me/sub 5/Cp)/sub 2/Mn and ((Me/sub 5/Cp)/sub 2/Ni)/sup +/ ..-->.. (Me/sub 5/Cp)/sub 2/Ni)/sup 2 +/ redox reactions. These studies reveal that the neutral decamethylmetallocenes are much more easily oxidized than their metallocene counterparts. This result attests to the electron-donating properties of the ten substituent methyl groups. Proton and carbon-13 NMR data are reported for the diamagnetic Mg(II), Mn(I), Fe(II), Co(III), and Ni(IV) decamethylmetallocenes and for ((Me/sub 5/Cp)/sub 2/V(CO)/sub 2/)/sup +/. The uv-visible absorption spectra of the 15-, 18- and 20- electron decamethylmetallocenes are also reported.

  14. Electronic structure and optical properties of solid C 60

    NASA Astrophysics Data System (ADS)

    Mattesini, M.; Ahuja, R.; Sa, L.; Hugosson, H. W.; Johansson, B.; Eriksson, O.

    2009-06-01

    The electronic structure and the optical properties of face-centered-cubic C 60 have been investigated by using an all-electron full-potential method. Our ab initio results show that the imaginary dielectric function for high-energy values looks very similar to that of graphite, revealing close electronic structure similarities between the two systems. We have also identified the origin of different peaks in the dielectric function of fullerene by means of the calculated electronic density of states. The computed optical spectrum compares fairly well with the available experimental data for the Vis-UV absorption spectrum of solid C 60.

  15. Ultratrace analysis of transuranic actinides by laser-induced fluorescence

    DOEpatents

    Miller, Steven M.

    1988-01-01

    Ultratrace quantities of transuranic actinides are detected indirectly by their effect on the fluorescent emissions of a preselected fluorescent species. Transuranic actinides in a sample are coprecipitated with a host lattice material containing at least one preselected fluorescent species. The actinide either quenches or enhances the laser-induced fluorescence of the preselected fluorescent species. The degree of enhancement or quenching is quantitatively related to the concentration of actinide in the sample.

  16. Ultratrace analysis of transuranic actinides by laser-induced fluorescence

    DOEpatents

    Miller, S.M.

    1983-10-31

    Ultratrace quantities of transuranic actinides are detected indirectly by their effect on the fluorescent emissions of a preselected fluorescent species. Transuranic actinides in a sample are coprecipitated with a host lattice material containing at least one preselected fluorescent species. The actinide either quenches or enhances the laser-induced fluorescence of the preselected fluorescent species. The degree of enhancement or quenching is quantitatively related to the concentration of actinide in the sample.

  17. VUV and soft x-ray spectroscopy of actinides

    SciTech Connect

    Olson, C. G.; Joyce, J. J.; Durakiewicz, T.; Guziewicz, E.

    2004-01-01

    Optical and photoelectron spectroscopies using VUV and Soft X-ray photons are powerful tools for studies of elemental and compound actinides. Large changes in the relative atomic cross sections of the 5f, 6d and sp electrons allow decomposition of the character of the valence bands using photoemission. Resonant enhancement of photoelectrons and Auger electrons at the 5d core threshold further aids the decomposition and gives a measure of elemental specificity. Angle-resolved photoemission can be used to map the momentum dependence of the electronic states. The large changes in relative cross section with photon energy yields further details when the mapping is done at equivalent points in multiple zones. Spectra for well understood rare earth materials will be presented to establish spectral characteristics for known atomic character initial states. These signatures will be applied to the case of USb to investigate f-d hybridization near the Fermi level.

  18. Advanced Extraction Methods for Actinide/Lanthanide Separations

    SciTech Connect

    Scott, M.J.

    2005-12-01

    high level liquid wastes and a general actinide clean-up procedure. The selectivity of the standard extractant for tetravalent actinides, (N,N-diisobutylcarbamoylmethyl) octylphenylphosphineoxide (CMPO), was markedly improved by the attachment of three CMPO-like functions onto a triphenoxymethane platform, and a ligand that is both highly selective and effective for An(IV) ions was isolated. A 10 fold excess of ligand will remove virtually all of the 4+ actinides from the acidic layer without extracting appreciable quantities of An(III) and Ln(III) unlike simple CMPO ligands. Inspired by the success of the DIAMEX industrial process for extractions, three new tripodal chelates bearing three diglycolamide and thiodiglycolamide units precisely arranged on a triphenoxymethane platform have been synthesized for an highly efficient extraction of trivalent f-element cations from nitric acid media. A single equivalent of ligand will remove 80% of the Ln(III) ion from the acidic layer since the ligand is perfectly suited to accommodate the tricapped trigonal prismatic geometry preferred by the metal center. The ligand is perhaps the most efficient binder available for the heavier lanthanides and due to this unique attribute, the extraction event can be easily followed by 1H NMR spectroscopy confirming the formation of a TPP complex. The most lipophilic di-n-butyl tris-diglycolamide was found to be a significantly weaker extractant in comparison to the di-isopropyl analogs. The tris-thiodiglycolamide derivative proved to be an ineffective chelate for f-elements and demonstrated the importance of the etheric oxygens in the metal binding. The results presented herein clearly demonstrate a cooperative action of these three ligating groups within a single molecule, confirmed by composition and structure of the extracted complexes, and since actinides prefer to have high coordination numbers, the ligands should be particularly adept at binding with three arms. The use of such an

  19. Energy-filtered Electron Transport Structures for Low-power Low-noise 2-D Electronics

    PubMed Central

    Pan, Xuan; Qiu, Wanzhi; Skafidas, Efstratios

    2016-01-01

    In addition to cryogenic techniques, energy filtering has the potential to achieve high-performance low-noise 2-D electronic systems. Assemblies based on graphene quantum dots (GQDs) have been demonstrated to exhibit interesting transport properties, including resonant tunnelling. In this paper, we investigate GQDs based structures with the goal of producing energy filters for next generation lower-power lower-noise 2-D electronic systems. We evaluate the electron transport properties of the proposed GQD device structures to demonstrate electron energy filtering and the ability to control the position and magnitude of the energy passband by appropriate device dimensioning. We also show that the signal-to-thermal noise ratio performance of the proposed nanoscale device can be modified according to device geometry. The tunability of two-dimensional GQD structures indicates a promising route for the design of electron energy filters to produce low-power and low-noise electronics. PMID:27796343

  20. Energy-filtered Electron Transport Structures for Low-power Low-noise 2-D Electronics.

    PubMed

    Pan, Xuan; Qiu, Wanzhi; Skafidas, Efstratios

    2016-10-31

    In addition to cryogenic techniques, energy filtering has the potential to achieve high-performance low-noise 2-D electronic systems. Assemblies based on graphene quantum dots (GQDs) have been demonstrated to exhibit interesting transport properties, including resonant tunnelling. In this paper, we investigate GQDs based structures with the goal of producing energy filters for next generation lower-power lower-noise 2-D electronic systems. We evaluate the electron transport properties of the proposed GQD device structures to demonstrate electron energy filtering and the ability to control the position and magnitude of the energy passband by appropriate device dimensioning. We also show that the signal-to-thermal noise ratio performance of the proposed nanoscale device can be modified according to device geometry. The tunability of two-dimensional GQD structures indicates a promising route for the design of electron energy filters to produce low-power and low-noise electronics.

  1. Energy-filtered Electron Transport Structures for Low-power Low-noise 2-D Electronics

    NASA Astrophysics Data System (ADS)

    Pan, Xuan; Qiu, Wanzhi; Skafidas, Efstratios

    2016-10-01

    In addition to cryogenic techniques, energy filtering has the potential to achieve high-performance low-noise 2-D electronic systems. Assemblies based on graphene quantum dots (GQDs) have been demonstrated to exhibit interesting transport properties, including resonant tunnelling. In this paper, we investigate GQDs based structures with the goal of producing energy filters for next generation lower-power lower-noise 2-D electronic systems. We evaluate the electron transport properties of the proposed GQD device structures to demonstrate electron energy filtering and the ability to control the position and magnitude of the energy passband by appropriate device dimensioning. We also show that the signal-to-thermal noise ratio performance of the proposed nanoscale device can be modified according to device geometry. The tunability of two-dimensional GQD structures indicates a promising route for the design of electron energy filters to produce low-power and low-noise electronics.

  2. Electron Precipitation Associated with Small-Scale Auroral Structures

    NASA Astrophysics Data System (ADS)

    Michell, R.; Samara, M.; Grubbs, G. A., II; Hampton, D. L.; Bonnell, J. W.; Ogasawara, K.

    2014-12-01

    We present results from the Ground-to-Rocket Electrons Electrodynamics Correlative Experiment (GREECE) sounding rocket mission, where we combined high-resolution ground-based auroral imaging with high time-resolution precipitating electron measurements. The GREECE payload successfully launched from Poker Flat, Alaska on 03 March 2014 and reached an apogee of approximately 335 km. The narrow field-of-view auroral imaging was taken from Venetie, AK, which is directly under apogee. This enabled the small-scale auroral features at the magnetic footpoint of the rocket payload to be imaged in detail. The electron precipitation was measured with the Acute Precipitating Electron Spectrometer (APES) onboard the payload. Features in the electron data are matched up with their corresponding auroral structures and boundaries, enabling measurement of the exact electron distributions responsible for the specific small-scale auroral features. These electron distributions will then be used to infer what the potential electron acceleration processes were.

  3. Structural phase transition and electronic properties of NdBi

    SciTech Connect

    Sahu, Ashvini K.; Patiya, Jagdish; Sanyal, Sankar P.

    2015-06-24

    The structural and electronic properties of NdBi from an electronic structure calculation have been presented. The calculation is performed using self-consistent tight binding linear muffin tin orbital (TB-LMTO) method within the local density approximation (LDA). The calculated equilibrium structural parameters are in good agreement with the available experimental results. It is found that this compound shows metallic behavior under ambient condition and undergoes a structural phase transition from the NaCl structure to the CsCl structure at the pressure 20.1 GPa. The electronic structures of NdBi under pressure are investigated. It is found that NdBi have metallization and the hybridizations of atoms in NdBi under pressure become stronger.

  4. Evidence for the involvement of 5f orbitals in the bonding and reactivity of organometallic actinide compounds: thorium(IV) and uranium(IV) bis(hydrazonato) complexes.

    PubMed

    Cantat, Thibault; Graves, Christopher R; Jantunen, Kimberly C; Burns, Carol J; Scott, Brian L; Schelter, Eric J; Morris, David E; Hay, P Jeffrey; Kiplinger, Jaqueline L

    2008-12-24

    Migratory insertion of diphenyldiazomethane into both metal-carbon bonds of the bis(alkyl) and bis(aryl) complexes (C(5)Me(5))(2)AnR(2) yields the first f-element bis(hydrazonato) complexes (C(5)Me(5))(2)An[eta(2)-(N,N')-R-N-N=CPh(2)](2) [An = Th, R = CH(3) (18), PhCH(2) (15), Ph (16); An = U, R = CH(3) (17), PhCH(2) (14)], which have been characterized by a combination of spectroscopy, electrochemistry, and X-ray crystallography. The two hydrazonato ligands adopt an eta(2)-coordination mode leading to 20-electron (for Th) and 22-electron (for U) complexes that have no transition-metal analogues. In fact, reaction of (C(5)H(5))(2)Zr(CH(3))(2) or (C(5)Me(5))(2)Hf(CH(3))(2) with diphenyldiazomethane is limited to the formation of the corresponding mono(hydrazonato) complex (C(5)R(5))(2)M[eta(2)-(N,N')-CH(3)-N-N=CPh(2)](CH(3)) (M = Zr, R = H or M = Hf, R = CH(3)). The difference in the reactivities of the group 4 metal complexes and the actinides was used as a unique platform for investigating in depth the role of 5f orbitals on the reactivity and bonding in actinide organometallic complexes. The electronic structure of the (C(5)H(5))(2)M[eta(2)-(N,N')-CH(3)-N-N=CH(2)](2) (M = Zr, Th, U) model complexes was studied using density functional theory (DFT) calculations and compared to experimental structural, electrochemical, and spectroscopic results. Whereas transition-metal bis(cyclopentadienyl) complexes are known to stabilize three ligands in the metallocene girdle to form saturated (C(5)H(5))(2)ML(3) species, in a bis(hydrazonato) system, a fourth ligand is coordinated to the metal center to give (C(5)H(5))(2)ML(4). DFT calculations have shown that 5f orbitals in the actinide complexes play a crucial role in stabilizing this fourth ligand by stabilizing both the sigma and pi electrons of the two eta(2)-coordinated hydrazonato ligands. In contrast, the stabilization of the hydrazonato ligands was found to be significantly less effective for the putative bis

  5. Quest for Environmentally-Benign Ligands for Actinide Separations: Thermodynamic, Spectroscopic, and Structural Characterization of U(VI) Complexes with Oxa-Diamide and Related Ligands

    SciTech Connect

    Advanced Light Source; Tian, Guoxin; Rao, Linfeng; Teat, Simon J.; Liu, Guokui

    2009-01-05

    Complexation of U(VI) with N,N,N{prime},N{prime}-tetramethyl-3-oxa-glutaramide (TMOGA) and N,N-dimethyl-3-oxa-glutaramic acid (DMOGA) was studied in comparison with their dicarboxylate analog, oxydiacetic acid (ODA). Thermodynamic parameters, including stability constants, enthalpy and entropy of complexation, were determined by spectrophotometry, potentiometry and calorimetry. Single-crystal X-ray diffractometry, EXAFS spectroscopy, FT-IR absorption and laser-induced luminescence spectroscopy were used to obtain structural information on the U(VI) complexes. Like ODA, TMOGA and DMOGA form tridentate U(VI) complexes, with three oxygen atoms (the amide, ether and/or carboxylate oxygen) coordinating to the linear UO{sub 2}{sup 2+} cation via the equatorial plane. The stability constants, enthalpy and entropy of complexation all decrease in the order ODA > DMOGA > TMOGA, showing that the complexation is entropy driven and the substitution of a carboxylate group with an amide group reduces the strength of complexation with U(VI) due to the decrease in the entropy of complexation. The trend in the thermodynamic stability of the complexes correlates very well with the structural and spectroscopic data obtained by single crystal XRD, FT-IR and laser-induced luminescence spectroscopy.

  6. SiC Schottky Diode Detectors for Measurement of Actinide Concentrations from Alpha Activities in Molten Salt Electrolyte

    SciTech Connect

    Windl, Wolfgang; Blue, Thomas

    2013-01-28

    In this project, we have designed a 4H-SiC Schottky diode detector device in order to monitor actinide concentrations in extreme environments, such as present in pyroprocessing of spent fuel. For the first time, we have demonstrated high temperature operation of such a device up to 500 °C in successfully detecting alpha particles. We have used Am-241 as an alpha source for our laboratory experiments. Along with the experiments, we have developed a multiscale model to study the phenomena controlling the device behavior and to be able to predict the device performance. Our multiscale model consists of ab initio modeling to understand defect energetics and their effect on electronic structure and carrier mobility in the material. Further, we have developed the basis for a damage evolution model incorporating the outputs from ab initio model in order to predict respective defect concentrations in the device material. Finally, a fully equipped TCAD-based device model has been developed to study the phenomena controlling the device behavior. Using this model, we have proven our concept that the detector is capable of performing alpha detection in a salt bath with the mixtures of actinides present in a pyroprocessing environment.

  7. The Actinide-Lanthanide Separation Process

    SciTech Connect

    Lumetta, Gregg J.; Gelis, Artem V.; Carter, Jennifer C.; Niver, Cynthia M.; Smoot, Margaret R.

    2014-02-21

    The Actinide-Lanthanide SEParation (ALSEP) process is described. The process uses an extractant phase consisting of either N,N,N',N'-tetraoctyldiglycolamide (TODGA) or N,N,N',N'-tetra(2 ethylhexyl)diglycolamide (T2EHDGA) combined with 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]). The neutral TODGA or T2EHDGA serves to co-extract the trivalent actinide and lanthanide ions from nitric acid media. Switching the aqueous phase chemistry to a citrate buffered diethylenetriaminepentaacetic acid (DTPA) solution at pH 2.5 to 4 results in selective transfer of the actinides to the aqueous phase, thus resulting in separation of these two groups of elements.

  8. Actinide Lanthanide Separation Process – ALSEP

    SciTech Connect

    Gelis, Artem V.; Lumetta, Gregg J.

    2014-01-29

    Separation of the minor actinides (Am, Cm) from the lanthanides at an industrial scale remains a significant technical challenge for closing the nuclear fuel cycle. To increase the safety of used nuclear fuel (UNF) reprocessing, as well as reduce associated costs, a novel solvent extraction process has been developed. The process allows for partitioning minor actinides, lanthanides and fission products following uranium/plutonium/neptunium removal; minimizing the number of separation steps, flowsheets, chemical consumption, and waste. This new process, Actinide Lanthanide SEParation (ALSEP), uses an organic solvent consisting of a neutral diglycolamide extractant, either N,N,N',N'-tetra(2 ethylhexyl)diglycolamide (T2EHDGA) or N,N,N',N'-tetraoctyldiglycolamide (TODGA), and an acidic extractant 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]), dissolved in an aliphatic diluent (e.g. n-dodecane). The An/Ln co-extraction is conducted from moderate-to-strong nitric acid, while the selective stripping of the minor actinides from the lanthanides is carried out using a polyaminocarboxylic acid/citrate buffered solution at pH anywhere between 3 and 4.5. The extraction and separation of the actinides from the fission products is very effective in a wide range of HNO3 concentrations and the minimum separation factors for lanthanide/Am exceed 30 for Nd/Am, reaching > 60 for Eu/Am under some conditions. The experimental results presented here demonstrate the great potential for a combined system, consisting of a neutral extractant such as T2EHDGA or TODGA, and an acidic extractant such as HEH[EHP], for separating the minor actinides from the lanthanides.

  9. Writing silica structures in liquid with scanning transmission electron microscopy.

    PubMed

    van de Put, Marcel W P; Carcouët, Camille C M C; Bomans, Paul H H; Friedrich, Heiner; de Jonge, Niels; Sommerdijk, Nico A J M

    2015-02-04

    Silica nanoparticles are imaged in solution with scanning transmission electron microscopy (STEM) using a liquid cell with silicon nitride (SiN) membrane windows. The STEM images reveal that silica structures are deposited in well-defined patches on the upper SiN membranes upon electron beam irradiation. The thickness of the deposits is linear with the applied electron dose. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) demonstrate that the deposited patches are a result of the merging of the original 20 nm-diameter nanoparticles, and that the related surface roughness depends on the electron dose rate used. Using this approach, sub-micrometer scale structures are written on the SiN in liquid by controlling the electron exposure as function of the lateral position.

  10. Electronic Structure of PbSe Nanowires

    NASA Astrophysics Data System (ADS)

    Avdeev, I. D.; Nestoklon, M. O.

    2016-11-01

    We present the tight binding calculations of the lead selenide nanowires: energy spectra of quantum confined states as a function of nanowire radius, dispersion in the full Brillouin zone, and the radial part of local electronic state density, which helps us to recognise valley splitting in the spectra. Also, we compare our results to KP perturbation theory predictions. We show that the value of the valley splitting is comparable with the distance between two levels of size quantization and that it strongly depends on the arrangement of the atoms in the wire.

  11. Electronic-structure calculation for metals by local optimization

    NASA Astrophysics Data System (ADS)

    Woodward, C.; Min, B. I.; Benedek, R.; Garner, J.

    1989-03-01

    Recent work by Car and Parrinello has generated considerable interest in the calculation of electronic structure by nonlinear optimization. The technique introduced by these authors, dynamical simulated annealing, is designed for problems that involve energy barriers. When local optimization suffices to determine the energy minimum, more direct methods are available. In this paper we apply the algorithm suggested by Williams and Soler to calculate the electronic structure of metals, using a plane-wave expansion for the electronic orbitals and an electron-ion pseudopotential of the Kleinman-Bylander form. Radial pseudopotentials were taken from the compilation of Bachelet, Hamann, and Schlüter. Calculations are performed to optimize the electronic structure (i) with fixed atomic configuration, or (ii) with the atomic volume being optimized simultaneously. It is found that the dual optimization (ii) converges in essentially the same number of steps as the static lattice optimization (i). Numerical results are presented for Li, K, Al, and simple-cubic P.

  12. Basis functions for electronic structure calculations on spheres

    SciTech Connect

    Gill, Peter M. W. Loos, Pierre-François Agboola, Davids

    2014-12-28

    We introduce a new basis function (the spherical Gaussian) for electronic structure calculations on spheres of any dimension D. We find general expressions for the one- and two-electron integrals and propose an efficient computational algorithm incorporating the Cauchy-Schwarz bound. Using numerical calculations for the D = 2 case, we show that spherical Gaussians are more efficient than spherical harmonics when the electrons are strongly localized.

  13. Elevated concentrations of actinides in Mono Lake

    SciTech Connect

    Anderson, R.F.; Bacon, M.P.; Brewer, P.G.

    1982-04-30

    Tetravalent thorium, pentavalent protactinium, hexavalent uranium, and plutonium (oxidation state uncertain) are present in much higher concentrations in Mono Lake, a saline, alkaline lake in eastern central California, than in seawater. Low ratios of actinium to protactinium and of americium to plutonium indicate that the concentrations of trivalent actinides are not similarly enhanced. The elevated concentrations of the ordinarily very insoluble actinides are maintained in solution by natural ligands, which inhibit their chemical removal from the water column, rather than by an unusually large rate of supply.

  14. Elevated concentrations of actinides in mono lake.

    PubMed

    Anderson, R F; Bacon, M P; Brewer, P G

    1982-04-30

    Tetravalent thorium, pentavalent protactinium, hexavalent uranium, and plutonium (oxidation state uncertain) are present in much higher concentrations in Mono Lake, a saline, alkaline lake in eastern central California, than in seawater. Low ratios of actinium to protactinium and of americium to plutonium indicate that the concentrations of trivalent actinides are not similarly enhanced. The elevated concentrations of the ordinarily very insoluble actinides are maintained in solution by natural ligands, which inhibit their chemical removal from the water column, rather than by an unusually large rate of supply.

  15. The gastrointestinal absorption of the actinide elements.

    PubMed

    Harrison, J D

    1991-03-01

    The greatest uncertainty in dose estimates for the ingestion of long-lived, alpha-emitting isotopes of the actinide elements is in the values used for their fractional absorption from the gastrointestinal tract (f1 values). Recent years have seen a large increase in the available data on actinide absorption. Human data are reviewed here, together with animal data, to illustrate the effect on absorption of chemical form, incorporation into food materials, fasting and other dietary factors, and age at ingestion. The f1 values recommended by the International Commission on Radiological Protection, by an Expert Group of the Nuclear Energy Agency and by the National Radiological Protection Board are discussed.

  16. Systematization of actinides using cluster analysis

    SciTech Connect

    Kopyrin, A.A.; Terent`eva, T.N.; Khramov, N.N.

    1994-11-01

    A representation of the actinides in multidimensional property space is proposed for systematization of these elements using cluster analysis. Literature data for their atomic properties are used. Owing to the wide variation of published ionization potentials, medians are used to estimate them. Vertical dendograms are used for classification on the basis of distances between the actinides in atomic-property space. The properties of actinium and lawrencium are furthest removed from the main group. Thorium and mendelevium exhibit individualized properties. A cluster based on the einsteinium-fermium pair is joined by californium.

  17. Secondary electron emission from surfaces with small structure

    NASA Astrophysics Data System (ADS)

    Dzhanoev, A. R.; Spahn, F.; Yaroshenko, V.; Lühr, H.; Schmidt, J.

    2015-09-01

    It is found that for objects possessing small surface structures with differing radii of curvature the secondary electron emission (SEE) yield may be significantly higher than for objects with smooth surfaces of the same material. The effect is highly pronounced for surface structures of nanometer scale, often providing a more than 100 % increase of the SEE yield. The results also show that the SEE yield from surfaces with structure does not show a universal dependence on the energy of the primary, incident electrons as it is found for flat surfaces in experiments. We derive conditions for the applicability of the conventional formulation of SEE using the simplifying assumption of universal dependence. Our analysis provides a basis for studying low-energy electron emission from nanometer structured surfaces under a penetrating electron beam important in many technological applications.

  18. Linear Scaling Electronic Structure Methods with Periodic Boundary Conditions

    SciTech Connect

    Gustavo E. Scuseria

    2008-02-08

    The methodological development and computational implementation of linear scaling quantum chemistry methods for the accurate calculation of electronic structure and properties of periodic systems (solids, surfaces, and polymers) and their application to chemical problems of DOE relevance.

  19. Stacking dependent electronic structures of transition metal dichalcogenides heterobilayer

    NASA Astrophysics Data System (ADS)

    Lee, Yea-Lee; Park, Cheol-Hwan; Ihm, Jisoon

    The systematic study of the electronic structures and optical properties of the transition metal dichalcogenides (TMD) heterobilayers can significantly improve the designing of new electronic and optoelectronic devices. Here, we theoretically study the electronic structures and optical properties of TMD heterobilayers using the first-principles methods. The band structures of TMD heterobilayer are shown to be determined by the band alignments of the each layer, the weak interlayer interactions, and angle dependent stacking patterns. The photoluminescence spectra are investigated using the calculated band structures, and the optical absorption spectra are examined by the GW approximations including the electron-hole interaction through the solution of the Bethe-Salpeter equation. It is expected that the weak interlayer interaction gives rise to the substantial interlayer optical transition which will be corresponding to the interlayer exciton.

  20. Electron Diffraction Determination of Nanoscale Structures

    SciTech Connect

    Parks, Joel H

    2013-03-01

    Dominant research results on adsorption on gold clusters are reviewed, including adsorption of H{sub 2}O and O{sub 2} on gold cluster cations and anions, kinetics of CO adsorption to middle sized gold cluster cations, adsorption of CO on Au{sub n}{sup +} with induced changes in structure, and H{sub 2}O enhancement of CO adsorption.

  1. Direct investigation of subsurface interface electronic structure by ballistic-electron-emission microscopy

    NASA Technical Reports Server (NTRS)

    Kaiser, W. J.; Bell, L. D.

    1988-01-01

    A new technique for spectroscopic investigation of subsurface interface electronic structure has been developed. The method, ballistic-electron-emission microscopy (BEEM), is based on scanning tunneling microscopy. BEEM makes possible, for the first time, direct imaging of subsurface interface properties with nanometer spatial resolution. The first application of BEEM to subsurface Schottky-barrier interfaces is reported.

  2. Electronic structure calculations of ESR parameters of melanin units.

    PubMed

    Batagin-Neto, Augusto; Bronze-Uhle, Erika Soares; Graeff, Carlos Frederico de Oliveira

    2015-03-21

    Melanins represent an important class of natural pigments present in plants and animals that are currently considered to be promising materials for applications in optic and electronic devices. Despite their interesting properties, some of the basic features of melanins are not satisfactorily understood, including the origin of their intrinsic paramagnetism. A number of experiments have been performed to investigate the electron spin resonance (ESR) response of melanin derivatives, but until now, there has been no consensus regarding the real structure of the paramagnetic centers involved. In this work, we have employed electronic structure calculations to evaluate the ESR parameters of distinct melanin monomers and dimers in order to identify the possible structures associated with unpaired spins in this biopolymer. The g-factors and hyperfine constants of the cationic, anionic and radicalar structures were investigated. The results confirm the existence of at least two distinct paramagnetic centers in melanin structure, identifying the chemical species associated with them and their roles in electrical conductivity.

  3. Structural properties of amorphous silicon produced by electron irradiation

    SciTech Connect

    Yamasaki, J.; Takeda, S.

    1999-07-01

    The structural properties of the amorphous Si (a-Si), which was created from crystalline silicon by 2 MeV electron irradiation at low temperatures about 25 K, are examined in detail by means of transmission electron microscopy and transmission electron diffraction. The peak positions in the radial distribution function (RDF) of the a-Si correspond well to those of a-Si fabricated by other techniques. The electron-irradiation-induced a-Si returns to crystalline Si after annealing at 550 C.

  4. Distinct electronic structure for the extreme magnetoresistance in YSb

    SciTech Connect

    He, Junfeng; Zhang, Chaofan; Ghimire, Nirmal J.; Liang, Tian; Jia, Chunjing; Jiang, Juan; Tang, Shujie; Chen, Sudi; He, Yu; Mo, S. -K.; Hwang, C. C.; Hashimoto, M.; Lu, D. H.; Moritz, B.; Devereaux, T. P.; Chen, Y. L.; Mitchell, J. F.; Shen, Z. -X.

    2016-12-23

    An extreme magnetoresistance (XMR) has recently been observed in several nonmagnetic semimetals. Increasing experimental and theoretical evidence indicates that the XMR can be driven by either topological protection or electron-hole compensation. Moreover, by investigating the electronic structure of a XMR material, YSb, we present spectroscopic evidence for a special case which lacks topological protection and perfect electron-hole compensation. Further investigations reveal that a cooperative action of a substantial difference between electron and hole mobility and a moderate carrier compensation might contribute to the XMR in YSb.

  5. Electronic structure modulation of graphene edges by chemical functionalization

    NASA Astrophysics Data System (ADS)

    Taira, Remi; Yamanaka, Ayaka; Okada, Susumu

    2016-11-01

    Using the density functional theory with the effective screening medium method, we study the electronic properties of graphene nanoribbons with zigzag edges that are terminated by hydrogen and ketone, hydroxyl, carbonyl, and carboxyl functional groups. Our calculations showed that the work function and electronic structures of the edges of the nanoribbons are sensitive to the functional groups attached to the edges. The nearly free electron state emerges in the vacuum region outside the hydroxylated edges and crosses the Fermi level, indicating the possibility of negative electron affinity at the edges.

  6. Electron beam enhanced surface modification for making highly resolved structures

    DOEpatents

    Pitts, John R.

    1986-01-01

    A method for forming high resolution submicron structures on a substrate is provided by direct writing with a submicron electron beam in a partial pressure of a selected gas phase characterized by the ability to dissociate under the beam into a stable gaseous leaving group and a reactant fragment that combines with the substrate material under beam energy to form at least a surface compound. Variations of the method provide semiconductor device regions on doped silicon substrates, interconnect lines between active sites, three dimensional electronic chip structures, electron beam and optical read mass storage devices that may include color differentiated data areas, and resist areas for use with selective etching techniques.

  7. Electron beam enhanced surface modification for making highly resolved structures

    DOEpatents

    Pitts, J.R.

    1984-10-10

    A method for forming high resolution submicron structures on a substrate is provided by direct writing with a submicron electron beam in a partial pressure of a selected gas phase characterized by the ability to dissociate under the beam into a stable gaseous leaving group and a reactant fragment that combines with the substrate material under beam energy to form at least a surface compound. Variations of the method provide semiconductor device regions on doped silicon substrates, interconnect lines between active sites, three dimensional electronic chip structures, electron beam and optical read mass storage devices that may include color differentiated data areas, and resist areas for use with selective etching techniques.

  8. Solitary structures with ion and electron thermal anisotropy

    NASA Astrophysics Data System (ADS)

    Khusroo, Murchana; Bora, Madhurjya P.

    2015-11-01

    The formation of electrostatic solitary structures is analysed for a magnetised plasma with ion and electron thermal anisotropies. The ion thermal anisotropy is modelled with the help of the Chew-Goldberger-Low (CGL) double adiabatic equations of state while the electrons are treated as inertia-less species with an anisotropic bi-Maxwellian velocity distribution function. A negative electron thermal anisotropy ≤ft({{T}e\\bot}/{{T}e\\parallel}>1\\right) is found to help form large amplitude solitary structures which are in agreement with observational data.

  9. Electron-interface phonon interaction in multiple quantum well structures

    NASA Astrophysics Data System (ADS)

    Sun, J. P.; Teng, H. B.; Haddad, G. I.; Stroscio, M. A.

    1998-08-01

    Intersubband relaxation rates due to electron interactions with the interface phonons are evaluated for multiple quantum well structures designed for step quantum well lasers operating at mid-infrared to submillimetre wavelengths. The interface phonon modes and electron-phonon interaction Hamiltonians for the structures are derived using the transfer matrix method, based on the macroscopic dielectric continuum model, whereas the electron wavefunctions are obtained by solving the Schrödinger equation. Fermi's golden rule is employed to calculate the electron relaxation rates between the subbands in these structures. The relaxation rates for two different structures are examined and compared with those calculated using the bulk phonon modes and the Fröhlich interaction Hamiltonian. The sum rule for the relationship between the form factors of the various localized phonon modes and the bulk phonon modes is verified. The results obtained in this work illustrate that the transfer matrix method provides a convenient way for deriving the properties of the interface phonon modes in different structures of current interest and that, for preferential electron relaxation in intersubband laser structures, the effects of the interface phonon modes are significant and should be considered for optimal design of these laser structures.

  10. Nano-structured electron transporting materials for perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Liu, Hefei; Huang, Ziru; Wei, Shiyuan; Zheng, Lingling; Xiao, Lixin; Gong, Qihuang

    2016-03-01

    Organic-inorganic hybrid perovskite solar cells have been developing rapidly in the past several years, and their power conversion efficiency has reached over 20%, nearing that of polycrystalline silicon solar cells. Because the diffusion length of the hole in perovskites is longer than that of the electron, the performance of the device can be improved by using an electron transporting layer, e.g., TiO2, ZnO and TiO2/Al2O3. Nano-structured electron transporting materials facilitate not only electron collection but also morphology control of the perovskites. The properties, morphology and preparation methods of perovskites are reviewed in the present article. A comprehensive understanding of the relationship between the structure and property will benefit the precise control of the electron transporting process and thus further improve the performance of perovskite solar cells.

  11. Nano-structured electron transporting materials for perovskite solar cells.

    PubMed

    Liu, Hefei; Huang, Ziru; Wei, Shiyuan; Zheng, Lingling; Xiao, Lixin; Gong, Qihuang

    2016-03-28

    Organic-inorganic hybrid perovskite solar cells have been developing rapidly in the past several years, and their power conversion efficiency has reached over 20%, nearing that of polycrystalline silicon solar cells. Because the diffusion length of the hole in perovskites is longer than that of the electron, the performance of the device can be improved by using an electron transporting layer, e.g., TiO2, ZnO and TiO2/Al2O3. Nano-structured electron transporting materials facilitate not only electron collection but also morphology control of the perovskites. The properties, morphology and preparation methods of perovskites are reviewed in the present article. A comprehensive understanding of the relationship between the structure and property will benefit the precise control of the electron transporting process and thus further improve the performance of perovskite solar cells.

  12. Structural complexities in the active layers of organic electronics.

    PubMed

    Lee, Stephanie S; Loo, Yueh-Lin

    2010-01-01

    The field of organic electronics has progressed rapidly in recent years. However, understanding the direct structure-function relationships between the morphology in electrically active layers and the performance of devices composed of these materials has proven difficult. The morphology of active layers in organic electronics is inherently complex, with heterogeneities existing across multiple length scales, from subnanometer to micron and millimeter range. A major challenge still facing the organic electronics community is understanding how the morphology across all of the length scales in active layers collectively determines the device performance of organic electronics. In this review we highlight experiments that have contributed to the elucidation of structure-function relationships in organic electronics and also point to areas in which knowledge of such relationships is still lacking. Such knowledge will lead to the ability to select active materials on the basis of their inherent properties for the fabrication of devices with prespecified characteristics.

  13. MINOR ACTINIDE SEPARATIONS USING ION EXCHANGERS OR IONIC LIQUIDS

    SciTech Connect

    Hobbs, D.; Visser, A.; Bridges, N.

    2011-09-20

    This project seeks to determine if (1) inorganic-based ion exchange materials or (2) electrochemical methods in ionic liquids can be exploited to provide effective Am and Cm separations. Specifically, we seek to understand the fundamental structural and chemical factors responsible for the selectivity of inorganic-based ion-exchange materials for actinide and lanthanide ions. Furthermore, we seek to determine whether ionic liquids can serve as the electrolyte that would enable formation of higher oxidation states of Am and other actinides. Experiments indicated that pH, presence of complexants and Am oxidation state exhibit significant influence on the uptake of actinides and lanthanides by layered sodium titanate and hybrid zirconium and tin phosphonate ion exchangers. The affinity of the ion exchangers increased with increasing pH. Greater selectivity among Ln(III) ions with sodium titanate materials occurs at a pH close to the isoelectric potential of the ion exchanger. The addition of DTPA decreased uptake of Am and Ln, whereas the addition of TPEN generally increases uptake of Am and Ln ions by sodium titanate. Testing confirmed two different methods for producing Am(IV) by oxidation of Am(III) in ionic liquids (ILs). Experimental results suggest that the unique coordination environment of ionic liquids inhibits the direct electrochemical oxidation of Am(III). The non-coordinating environment increases the oxidation potential to a higher value, while making it difficult to remove the inner coordination of water. Both confirmed cases of Am(IV) were from the in-situ formation of strong chemical oxidizers.

  14. Electronic band structure of surface-doped black phosphorus

    NASA Astrophysics Data System (ADS)

    Kim, Jimin; Ryu, Sae Hee; Sohn, Yeongsup; Kim, Keun Su

    2015-03-01

    There are rapidly growing interests in the study of few-layer black phosphorus owing to its promising device characteristics that may impact our future electronics technology. The low-energy band structure of black phosphorus has been widely predicted to be controllable by external perturbations, such as strain and doping. In this work, we attempt to control the electronic band structure of black phosphorous by in-situ surface deposition of alkali-metal atoms. We found that surface doping induces steep band bending towards the bulk, leading to the emergence of new 2D electronic states that are confined within only few phosphorene layers of black phosphorus. Using angle-resolved photoemission spectroscopy, we directly measured the electronic band structure and its evolution as a function of dopant density. Supported by IBS.

  15. Electronic structure of a graphene superlattice with massive Dirac fermions

    SciTech Connect

    Lima, Jonas R. F.

    2015-02-28

    We study the electronic and transport properties of a graphene-based superlattice theoretically by using an effective Dirac equation. The superlattice consists of a periodic potential applied on a single-layer graphene deposited on a substrate that opens an energy gap of 2Δ in its electronic structure. We find that extra Dirac points appear in the electronic band structure under certain conditions, so it is possible to close the gap between the conduction and valence minibands. We show that the energy gap E{sub g} can be tuned in the range 0 ≤ E{sub g} ≤ 2Δ by changing the periodic potential. We analyze the low energy electronic structure around the contact points and find that the effective Fermi velocity in very anisotropic and depends on the energy gap. We show that the extra Dirac points obtained here behave differently compared to previously studied systems.

  16. Trends in actinide processing at Hanford

    SciTech Connect

    Harmon, H.D.

    1993-09-01

    In 1989, the mission at the Hanford Site began a dramatic and sometimes painful transition. The days of production--as we used to know it--are over. Our mission officially has become waste management and environmental cleanup. This mission change didn`t eliminate many jobs--in fact, budgets have grown dramatically to support the new mission. Most all of the same skilled crafts, engineers, and scientists are still required for the new mission. This change has not eliminated the need for actinide processing, but it has certainly changed the focus that our actinide chemists and process engineers have. The focus used to be on such things as increasing capacity, improving separations efficiency, and product purity. Minimizing waste had become a more important theme in recent years and it is still a very important concept in the waste management and environmental cleanup arena. However, at Hanford, a new set of words dominates the actinide process scene as we work to deal with actinides that still reside in a variety of forms at the Hanford Site. These words are repackage, stabilize, remove, store and dispose. Some key activities in each of these areas are described in this report.

  17. Actinide measurements by AMS using fluoride matrices

    NASA Astrophysics Data System (ADS)

    Cornett, R. J.; Kazi, Z. H.; Zhao, X.-L.; Chartrand, M. G.; Charles, R. J.; Kieser, W. E.

    2015-10-01

    Actinides can be measured by alpha spectroscopy (AS), mass spectroscopy or accelerator mass spectrometry (AMS). We tested a simple method to separate Pu and Am isotopes from the sample matrix using a single extraction chromatography column. The actinides in the column eluent were then measured by AS or AMS using a fluoride target matrix. Pu and Am were coprecipitated with NdF3. The strongest AMS beams of Pu and Am were produced when there was a large excess of fluoride donor atoms in the target and the NdF3 precipitates were diluted about 6-8 fold with PbF2. The measured concentrations of 239,240Pu and 241Am agreed with the concentrations in standards of known activity and with two IAEA certified reference materials. Measurements of 239,240Pu and 241Am made at A.E. Lalonde AMS Laboratory agree, within their statistical uncertainty, with independent measurements made using the IsoTrace AMS system. This work demonstrated that fluoride targets can produce reliable beams of actinide anions and that the measurement of actinides using fluorides agree with published values in certified reference materials.

  18. Rapid determination of actinides in asphalt samples

    SciTech Connect

    Maxwell, Sherrod L.; Culligan, Brian K.; Hutchison, Jay B.

    2014-01-12

    A new rapid method for the determination of actinides in asphalt samples has been developed that can be used in emergency response situations or for routine analysis If a radiological dispersive device (RDD), Improvised Nuclear Device (IND) or a nuclear accident such as the accident at the Fukushima Nuclear Power Plant in March, 2011 occurs, there will be an urgent need for rapid analyses of many different environmental matrices, including asphalt materials, to support dose mitigation and environmental clean up. The new method for the determination of actinides in asphalt utilizes a rapid furnace step to destroy bitumen and organics present in the asphalt and sodium hydroxide fusion to digest the remaining sample. Sample preconcentration steps are used to collect the actinides and a new stacked TRU Resin + DGA Resin column method is employed to separate the actinide isotopes in the asphalt samples. The TRU Resin plus DGA Resin separation approach, which allows sequential separation of plutonium, uranium, americium and curium isotopes in asphalt samples, can be applied to soil samples as well.

  19. Rapid determination of actinides in asphalt samples

    DOE PAGES

    Maxwell, Sherrod L.; Culligan, Brian K.; Hutchison, Jay B.

    2014-01-12

    A new rapid method for the determination of actinides in asphalt samples has been developed that can be used in emergency response situations or for routine analysis If a radiological dispersive device (RDD), Improvised Nuclear Device (IND) or a nuclear accident such as the accident at the Fukushima Nuclear Power Plant in March, 2011 occurs, there will be an urgent need for rapid analyses of many different environmental matrices, including asphalt materials, to support dose mitigation and environmental clean up. The new method for the determination of actinides in asphalt utilizes a rapid furnace step to destroy bitumen and organicsmore » present in the asphalt and sodium hydroxide fusion to digest the remaining sample. Sample preconcentration steps are used to collect the actinides and a new stacked TRU Resin + DGA Resin column method is employed to separate the actinide isotopes in the asphalt samples. The TRU Resin plus DGA Resin separation approach, which allows sequential separation of plutonium, uranium, americium and curium isotopes in asphalt samples, can be applied to soil samples as well.« less

  20. Positron Spectroscopy of Hydrothermally Grown Actinide Oxides

    DTIC Science & Technology

    2014-03-27

    In this method, the powdered material is placed in a solution which contains extremely powerful mineralizers, such as cesium fluoride for actinide...the isotope that acts as a positron source is sodium -22, which has a relatively short half-life (2.6 y) and emits a characteristic gamma photon (at

  1. Topological Insulators: Electronic Band Structure and Spectroscopy

    NASA Astrophysics Data System (ADS)

    Palaz, S.; Koc, H.; Mamedov, A. M.; Ozbay, E.

    2017-02-01

    In this study, we present the results of our ab initio calculation of the elastic constants, density of states, charge density, and Born effective charge tensors for ferroelectric (rhombohedral) and paraelectric phases (cubic) of the narrow band ferroelectrics (GeTe, SnTe) pseudopotentials. The related quantities such as bulk modulus and shear modulus using obtained elastic constants have also been estimated in the present work. The total and partial densities of states corresponding to the band structure of Sn(Ge)Te(S,Se) were calculated. We also calculated the Born effective charge tensor of an atom (for instance, Ge, Sn, Te, etc.), which is defined as the induced polarization of the solid along the main direction by a unit displacement in the perpendicular direction of the sublattice of an atom at the vanishing electric field.

  2. Electronic Structure and Transport in Magnetic Multilayers

    SciTech Connect

    2008-02-18

    ORNL assisted Seagate Recording Heads Operations in the development of CIPS pin Valves for application as read sensors in hard disk drives. Personnel at ORNL were W. H. Butler and Xiaoguang Zhang. Dr. Olle Heinonen from Seagate RHO also participated. ORNL provided codes and materials parameters that were used by Seagate to model CIP GMR in their heads. The objectives were to: (1) develop a linearized Boltzmann transport code for describing CIP GMR based on realistic models of the band structure and interfaces in materials in CIP spin valves in disk drive heads; (2) calculate the materials parameters needed as inputs to the Boltzmann code; and (3) transfer the technology to Seagate Recording Heads.

  3. Electronic correlation in magnetic contributions to structural energies

    NASA Astrophysics Data System (ADS)

    Haydock, Roger

    For interacting electrons the density of transitions [see http://arxiv.org/abs/1405.2288] replaces the density of states in calculations of structural energies. Extending previous work on paramagnetic metals, this approach is applied to correlation effects on the structural stability of magnetic transition metals. Supported by the H. V. Snyder Gift to the University of Oregon.

  4. Electron vortex magnetic holes: A nonlinear coherent plasma structure

    SciTech Connect

    Haynes, Christopher T. Burgess, David; Sundberg, Torbjorn; Camporeale, Enrico

    2015-01-15

    We report the properties of a novel type of sub-proton scale magnetic hole found in two dimensional particle-in-cell simulations of decaying turbulence with a guide field. The simulations were performed with a realistic value for ion to electron mass ratio. These structures, electron vortex magnetic holes (EVMHs), have circular cross-section. The magnetic field depression is associated with a diamagnetic azimuthal current provided by a population of trapped electrons in petal-like orbits. The trapped electron population provides a mean azimuthal velocity and since trapping preferentially selects high pitch angles, a perpendicular temperature anisotropy. The structures arise out of initial perturbations in the course of the turbulent evolution of the plasma, and are stable over at least 100 electron gyroperiods. We have verified the model for the EVMH by carrying out test particle and PIC simulations of isolated structures in a uniform plasma. It is found that (quasi-)stable structures can be formed provided that there is some initial perpendicular temperature anisotropy at the structure location. The properties of these structures (scale size, trapped population, etc.) are able to explain the observed properties of magnetic holes in the terrestrial plasma sheet. EVMHs may also contribute to turbulence properties, such as intermittency, at short scale lengths in other astrophysical plasmas.

  5. Electron vortex magnetic holes: A nonlinear coherent plasma structure

    NASA Astrophysics Data System (ADS)

    Haynes, Christopher T.; Burgess, David; Camporeale, Enrico; Sundberg, Torbjorn

    2015-01-01

    We report the properties of a novel type of sub-proton scale magnetic hole found in two dimensional particle-in-cell simulations of decaying turbulence with a guide field. The simulations were performed with a realistic value for ion to electron mass ratio. These structures, electron vortex magnetic holes (EVMHs), have circular cross-section. The magnetic field depression is associated with a diamagnetic azimuthal current provided by a population of trapped electrons in petal-like orbits. The trapped electron population provides a mean azimuthal velocity and since trapping preferentially selects high pitch angles, a perpendicular temperature anisotropy. The structures arise out of initial perturbations in the course of the turbulent evolution of the plasma, and are stable over at least 100 electron gyroperiods. We have verified the model for the EVMH by carrying out test particle and PIC simulations of isolated structures in a uniform plasma. It is found that (quasi-)stable structures can be formed provided that there is some initial perpendicular temperature anisotropy at the structure location. The properties of these structures (scale size, trapped population, etc.) are able to explain the observed properties of magnetic holes in the terrestrial plasma sheet. EVMHs may also contribute to turbulence properties, such as intermittency, at short scale lengths in other astrophysical plasmas.

  6. Actinide nuclear data for reactor physics calculations

    SciTech Connect

    Brady, M.C.; Wright, R.Q. ); England, T.R. )

    1991-07-01

    Calculational methodologies and data sources used to predict and recommend fission-product yields and delayed neutron and prompt neutron data for a number of actinide nuclides are presented and discussed. This compilation of nuclear data is the result of a nearly three-year effort under the Japan/US Actinide Program (JUSAP) at Oak Ridge National Laboratory to provide nuclear data supporting the preliminary design of an actinide burner reactor. In this type of reactor, minor actinides are the major components of the fuel. Nuclear data for these minor actinides are, therefore, essential in the design of such reactors. Fission yield, delayed neutron, and prompt neutron data are presented in the report for the following nuclides: Neptumium-237, Plutonium-238, -240, and -242, Americium-241 and -243, and Curium-242, -243, -244, -246, and -248. Additionally, prompt neutron data are also presented for these nuclides (except Plutonium-240, -242 and Curium-242) and for Curium-245 and -247. As in all compilations of nuclear data, the information in this report is subject to change as newer data become available. Most of the data presented here are based on calculational methodologies and should be revised as experimental data become available. The release of Version 6 of the Evaluated Nuclear Data Files (ENDF/B-6) is expected to be completed in 1991 and should replace this evaluation in areas of overlap although no serious discrepancies are expected between this compilation and ENDF/B-6. Because of the large amount of data comprising this compilation and limitations in publishing such a voluminous report, a complete listing of the explicit data is not included in this report. The data are, however, available from the authors on 5 {1/2}-in. high-density (1.2-Mbyte) diskettes. The file contents and formats are described in the text, and examples are given in the appendices. 34 refs., 18 tabs.

  7. Decoupling of structural and electronic phase transitions in VO2.

    PubMed

    Tao, Zhensheng; Han, Tzong-Ru T; Mahanti, Subhendra D; Duxbury, Phillip M; Yuan, Fei; Ruan, Chong-Yu; Wang, Kevin; Wu, Junqiao

    2012-10-19

    Using optical, TEM, and ultrafast electron diffraction experiments we find that single crystal VO(2) microbeams gently placed on insulating substrates or metal grids exhibit different behaviors, with structural and metal-insulator transitions occurring at the same temperature for insulating substrates, while for metal substrates a new monoclinic metal phase lies between the insulating monoclinic phase and the metallic rutile phase. The structural and electronic phase transitions in these experiments are strongly first order and we discuss their origins in the context of current understanding of multiorbital splitting, strong correlation effects, and structural distortions that act cooperatively in this system.

  8. Electronic states in hybrid boron nitride and graphene structures

    NASA Astrophysics Data System (ADS)

    Zhao, M.; Huang, Y. H.; Ma, F.; Hu, T. W.; Xu, K. W.; Chu, Paul K.

    2013-08-01

    The energy bands and electronic states of hybrid boron nitride (BN) and graphene structures are studied by first principle calculations. The electronic states change from semi-metallic to insulating depending on the number of B and N atoms as well as domain symmetry. When there are unequal numbers of B and N atoms, mid-gap states usually appear around the Fermi level and the corresponding hybrid structure possesses magnetic and semi-metallic properties. However, when the numbers of B and N atoms are equal, a band gap exists indicative of a semiconducting or insulating nature which depends on the structural symmetry.

  9. Engineering the Electronic Band Structure for Multiband Solar Cells

    SciTech Connect

    Lopez, N.; Reichertz, L.A.; Yu, K.M.; Campman, K.; Walukiewicz, W.

    2010-07-12

    Using the unique features of the electronic band structure of GaNxAs1-x alloys, we have designed, fabricated and tested a multiband photovoltaic device. The device demonstrates an optical activity of three energy bands that absorb, and convert into electrical current, the crucial part of the solar spectrum. The performance of the device and measurements of electroluminescence, quantum efficiency and photomodulated reflectivity are analyzed in terms of the Band Anticrossing model of the electronic structure of highly mismatched alloys. The results demonstrate the feasibility of using highly mismatched alloys to engineer the semiconductor energy band structure for specific device applications.

  10. Engineering the electronic band structure for multiband solar cells.

    PubMed

    López, N; Reichertz, L A; Yu, K M; Campman, K; Walukiewicz, W

    2011-01-14

    Using the unique features of the electronic band structure of GaN(x)As(1-x) alloys, we have designed, fabricated and tested a multiband photovoltaic device. The device demonstrates an optical activity of three energy bands that absorb, and convert into electrical current, the crucial part of the solar spectrum. The performance of the device and measurements of electroluminescence, quantum efficiency and photomodulated reflectivity are analyzed in terms of the band anticrossing model of the electronic structure of highly mismatched alloys. The results demonstrate the feasibility of using highly mismatched alloys to engineer the semiconductor energy band structure for specific device applications.

  11. Electronic structure and bonding in skutterudite-type phosphides

    NASA Astrophysics Data System (ADS)

    Llunell, Miquel; Alemany, Pere; Alvarez, Santiago; Zhukov, Vladlen P.; Vernes, Andreas

    1996-04-01

    The electronic structures of the skutterudite-type phosphides CoP3 and NiP3 have been investigated by means of first-principles linear muffin-tin orbital-atomic sphere approximation band-structure calculations. The presence of P4 rings in the skutterudite structure is of great importance in determining the nature of the electronic bands around the Fermi level, composed mainly of π-type molecular orbitals of these units. The metallic character found for NiP3 should be ascribed to the phosphorus framework rather than to the metal atoms.

  12. Goeppert-Mayer Award Recipient: Electron Scattering and Nucleon Structure

    NASA Astrophysics Data System (ADS)

    Beise, Elizabeth

    1998-04-01

    Electron scattering from hydrogen and light nuclear targets has long been recognized as one of the best tools for understanding the electromagnetic structure of protons, neutrons and few-nucleon systems. In the last decade, considerable progress has been made in the field through advances in polarized beams and polarized targets. Improvements in polarized electron sources has made it feasible to also study the structure of the nucleon through parity-violating electron scattering, where the nucleon's neutral weak structure is probed. In this talk, a summary of the present experimental status of the nucleon's electroweak structure will be presented, with an emphasis on recent results from the MIT-Bates and Jefferson Laboratories.

  13. Advanced accelerating structures and their interaction with electron beams.

    SciTech Connect

    Gai, W.; High Energy Physics

    2008-01-01

    In this paper, we give a brief description of several advanced accelerating structures, such as dielectric loaded waveguides, photonic band gap, metamaterials and improved iris-loaded cavities. We describe wakefields generated by passing high current electron beams through these structures, and applications of wakefields to advanced accelerator schemes. One of the keys to success for high gradient wakefield acceleration is to develop high current drive beam sources. As an example, the high current RF photo injector at the Argonne Wakefield Accelerator, passed a {approx}80 nC electron beam through a high gradient dielectric loaded structure to achieve a 100 MV/m gradient. We will summarize recent related experiments on beam-structure interactions and also discuss high current electron beam generation and propagation and their applications to wakefield acceleration.

  14. Advanced Accelerating Structures and Their Interaction with Electron Beams

    SciTech Connect

    Gai Wei

    2009-01-22

    In this paper, we give a brief description of several advanced accelerating structures, such as dielectric loaded waveguides, photonic band gap, metamaterials and improved iris-loaded cavities. We describe wakefields generated by passing high current electron beams through these structures, and applications of wakefields to advanced accelerator schemes. One of the keys to success for high gradient wakefield acceleration is to develop high current drive beam sources. As an example, the high current RF photo injector at the Argonne Wakefield Accelerator, passed a {approx}80 nC electron beam through a high gradient dielectric loaded structure to achieve a 100 MV/m gradient. We will summarize recent related experiments on beam-structure interactions and also discuss high current electron beam generation and propagation and their applications to wakefield acceleration.

  15. Sorption speciation of lanthanides/actinides on minerals by TRLFS, EXAFS and DFT studies: a review.

    PubMed

    Tan, Xiaoli; Fang, Ming; Wang, Xiangke

    2010-11-17

    Lanthanides/actinides sorption speciation on minerals and oxides by means of time resolved laser fluorescence spectroscopy (TRLFS), extended X-ray absorption fine structure spectroscopy (EXAFS) and density functional theory (DFT) is reviewed in the field of nuclear disposal safety research. The theoretical aspects of the methods are concisely presented. Examples of recent research results of lanthanide/actinide speciation and local atomic structures using TRLFS, EXAFS and DFT are discussed. The interaction of lanthanides/actinides with oxides and minerals as well as their uptake are also of common interest in radionuclide chemistry. Especially the sorption and inclusion of radionuclides into several minerals lead to an improvement in knowledge of minor components in solids. In the solid-liquid interface, the speciation and local atomic structures of Eu(III), Cm(III), U(VI), and Np(IV/VI) in several natural and synthetic minerals and oxides are also reviewed and discussed. The review is important to understand the physicochemical behavior of lanthanides/actinides at a molecular level in the natural environment.

  16. Structure of a Bacterial Cell Surface Decaheme Electron Conduit

    SciTech Connect

    Clarke, Thomas A.; Edwards, Marcus; Gates, Andrew J.; Hall, Andrea; White, Gaye; Bradley, Justin; Reardon, Catherine L.; Shi, Liang; Beliaev, Alex S.; Marshall, Matthew J.; Wang, Zheming; Watmough, Nicholas; Fredrickson, Jim K.; Zachara, John M.; Butt, Julea N.; Richardson, David J.

    2011-05-23

    Some bacterial species are able to utilize extracellular mineral forms of iron and manganese as respiratory electron acceptors. In Shewanella oneidensis this involves deca-heme cytochromes that are located on the bacterial cell surface at the termini of trans-outermembrane (OM) electron transfer conduits. The cell surface cytochromes can potentially play multiple roles in mediating electron transfer directly to insoluble electron sinks, catalyzing electron exchange with flavin electron shuttles or participating in extracellular inter-cytochrome electron exchange along ‘nanowire’ appendages. We present a 3.2 Å crystal structure of one of these deca-heme cytochromes, MtrF, that allows the spatial organization of the ten hemes to be visualized for the first time. The hemes are organized across four domains in a unique crossed conformation, in which a staggered 65 Å octa-heme chain transects the length of the protein and is bisected by a planar 45 Å tetra-heme chain that connects two extended Greek key split β-barrel domains. The structure provides molecular insight into how reduction of insoluble substrate (e.g. minerals), soluble substrates (e.g. flavins) and cytochrome redox partners might be possible in tandem at different termini of a trifurcated electron transport chain on the cell surface.

  17. Structure of a bacterial cell surface decaheme electron conduit.

    PubMed

    Clarke, Thomas A; Edwards, Marcus J; Gates, Andrew J; Hall, Andrea; White, Gaye F; Bradley, Justin; Reardon, Catherine L; Shi, Liang; Beliaev, Alexander S; Marshall, Matthew J; Wang, Zheming; Watmough, Nicholas J; Fredrickson, James K; Zachara, John M; Butt, Julea N; Richardson, David J

    2011-06-07

    Some bacterial species are able to utilize extracellular mineral forms of iron and manganese as respiratory electron acceptors. In Shewanella oneidensis this involves decaheme cytochromes that are located on the bacterial cell surface at the termini of trans-outer-membrane electron transfer conduits. The cell surface cytochromes can potentially play multiple roles in mediating electron transfer directly to insoluble electron sinks, catalyzing electron exchange with flavin electron shuttles or participating in extracellular intercytochrome electron exchange along "nanowire" appendages. We present a 3.2-Å crystal structure of one of these decaheme cytochromes, MtrF, that allows the spatial organization of the 10 hemes to be visualized for the first time. The hemes are organized across four domains in a unique crossed conformation, in which a staggered 65-Å octaheme chain transects the length of the protein and is bisected by a planar 45-Å tetraheme chain that connects two extended Greek key split β-barrel domains. The structure provides molecular insight into how reduction of insoluble substrate (e.g., minerals), soluble substrates (e.g., flavins), and cytochrome redox partners might be possible in tandem at different termini of a trifurcated electron transport chain on the cell surface.

  18. Electronic Structure and Phase Stability of PdPt Nanoparticles.

    PubMed

    Ishimoto, Takayoshi; Koyama, Michihisa

    2016-03-03

    To understand the origin of the physicochemical nature of bimetallic PdPt nanoparticles, we theoretically investigated the phase stability and electronic structure employing the PdPt nanoparticles models consisting of 711 atoms (ca. 3 nm). For the Pd-Pt core-shell nanoparticle, the PdPt solid-solution phase was found to be a thermodynamically stable phase in the nanoparticle as the result of difference in surface energy of Pd and Pt nanoparticles and configurational entropy effect, while it is well known that the Pd and Pt are the immiscible combination in the bulk phase. The electronic structure of nanoparticles is conducted to find that the electron transfer occurs locally within surface and subsurface layers. In addition, the electron transfer from Pd to Pt at the interfacial layers in core-shell nanoparticles is observed, which leads to unique geometrical and electronic structure changes. Our results show a clue for the tunability of the electronic structure of nanoparticles by controlling the arrangement in the nanoparticles.

  19. Structure and electronic properties of lead-selenide nanocrystal solids

    NASA Astrophysics Data System (ADS)

    Whitham, Kevin

    Recent advances in the controlled formation of nanocrystal superlattices have potential for creating materials with properties by design. The ability to tune nanocrystal size, shape and composition as well as symmetry of the superlattice opens routes to new materials. Calculations of such materials predict interesting electronic phenomena including topological states and Dirac cones, however experimental support is lacking. We have investigated electron localization in nanocrystal superlattices using a combination of advanced structural characterization techniques and charge transport measurements. Recent experimental efforts to improve the electronic properties of nanocrystal solids have focused on increasing inter-dot coupling. However, this approach only leads to electronic bands if the coupling energy can overcome energetic and translational disorder. We have investigated oriented-attachment as a method to create nanocrystal superlattices with increased coupling and translational order. We show that epitaxially connected superlattices form by a coherent phase transformation that is sensitive to structural defects and ligand length. In order to measure intrinsic electronic properties we demonstrate control over electronic defects by tailoring surface chemistry and device architecture. To probe charge transport in these structures we performed variable temperature field-effect measurements. By integrating structure analysis, surface chemistry, and transport measurements we find that carriers are localized to a few superlattice constants due to disorder. Importantly, our analysis shows that greater delocalization is possible by optimizing dot-to-dot bonding, thus providing a path forward to create quantum dot solids in which theoretically predicted properties can be realized.

  20. Parallel adaptive mesh refinement for electronic structure calculations

    SciTech Connect

    Kohn, S.; Weare, J.; Ong, E.; Baden, S.

    1996-12-01

    We have applied structured adaptive mesh refinement techniques to the solution of the LDA equations for electronic structure calculations. Local spatial refinement concentrates memory resources and numerical effort where it is most needed, near the atomic centers and in regions of rapidly varying charge density. The structured grid representation enables us to employ efficient iterative solver techniques such as conjugate gradients with multigrid preconditioning. We have parallelized our solver using an object-oriented adaptive mesh refinement framework.

  1. Plutonium Futures -- The Science. Topical Conference on Plutonium and Actinides. AIP Conference Proceedings, No. 532 [APCPCS

    SciTech Connect

    Pillay, K.K.S.; Kim, K.C.

    2000-12-31

    Presentations at this conference covered the topics of materials science/nuclear fuels, condensed matter physics, actinides in the environment/separation and analysis, actinides/processing, actinides/TRU wastes, materials science, TRU waste forms, nuclear fuels/isotopes, separations and process chemistry, actinides in the environment, detection and analysis, Pu and Pu compounds, actinide compounds and complexes.

  2. Variability of Protein Structure Models from Electron Microscopy.

    PubMed

    Monroe, Lyman; Terashi, Genki; Kihara, Daisuke

    2017-03-02

    An increasing number of biomolecular structures are solved by electron microscopy (EM). However, the quality of structure models determined from EM maps vary substantially. To understand to what extent structure models are supported by information embedded in EM maps, we used two computational structure refinement methods to examine how much structures can be refined using a dataset of 49 maps with accompanying structure models. The extent of structure modification as well as the disagreement between refinement models produced by the two computational methods scaled inversely with the global and the local map resolutions. A general quantitative estimation of deviations of structures for particular map resolutions are provided. Our results indicate that the observed discrepancy between the deposited map and the refined models is due to the lack of structural information present in EM maps and thus these annotations must be used with caution for further applications.

  3. Electronic structure of tetraphenylporphyrin layers on Ag(100)

    NASA Astrophysics Data System (ADS)

    Classen, Andrej; Pöschel, Rebecca; Di Filippo, Gianluca; Fauster, Thomas; Malcıoǧlu, Osman Barış; Bockstedte, Michel

    2017-03-01

    The electronic structure of Mg and free-base tetraphenylporphyrin films on Ag(100) is investigated by one- and two-photon photoemission in combination with electronic structure calculations using density functional theory and the self-consistent G W0 method. We determine the two highest occupied and the nearly degenerate lowest unoccupied molecular orbitals. Higher unoccupied states are seen in an enhanced emission as a final-state effect. For photon energies close to the prominent absorption of the Soret band we observe a strong electron emission attributed to the break up of the bound electron-hole pairs in the S2 excited state. The experimental results on the occupied and unoccupied energy levels for the molecular films on Ag(100) nicely agree with calculated quasiparticle energies and experiments of the molecules in the gas phase.

  4. Enhancement of electron mobility in asymmetric coupled quantum well structures

    SciTech Connect

    Das, S.; Nayak, R. K.; Sahu, T. Panda, A. K.

    2014-02-21

    We study the low temperature multisubband electron mobility in a structurally asymmetric GaAs/Al{sub x}Ga{sub 1-x}As delta doped double quantum well. We calculate the subband energy levels and wave functions through selfconsistent solution of the coupled Schrodinger equation and Poisson's equation. We consider ionized impurity scattering, interface roughness scattering, and alloy disorder scattering to calculate the electron mobility. The screening of the scattering potentials is obtained by using static dielectric response function formalism within the random phase approximation. We analyze, for the first time, the effect of asymmetric structure parameters on the enhancement of multisubband electron mobility through intersubband interactions. We show that the asymmetric variation of well width, doping concentration, and spacer width considerably influences the interplay of scattering mechanisms on mobility. Our results of asymmetry induced enhancement of electron mobility can be utilized for low temperature device applications.

  5. Synthesis of actinide nitrides, phosphides, sulfides and oxides

    DOEpatents

    Van Der Sluys, William G.; Burns, Carol J.; Smith, David C.

    1992-01-01

    A process of preparing an actinide compound of the formula An.sub.x Z.sub.y wherein An is an actinide metal atom selected from the group consisting of thorium, uranium, plutonium, neptunium, and americium, x is selected from the group consisting of one, two or three, Z is a main group element atom selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur and y is selected from the group consisting of one, two, three or four, by admixing an actinide organometallic precursor wherein said actinide is selected from the group consisting of thorium, uranium, plutonium, neptunium, and americium, a suitable solvent and a protic Lewis base selected from the group consisting of ammonia, phosphine, hydrogen sulfide and water, at temperatures and for time sufficient to form an intermediate actinide complex, heating said intermediate actinide complex at temperatures and for time sufficient to form the actinide compound, and a process of depositing a thin film of such an actinide compound, e.g., uranium mononitride, by subliming an actinide organometallic precursor, e.g., a uranium amide precursor, in the presence of an effectgive amount of a protic Lewis base, e.g., ammonia, within a reactor at temperatures and for time sufficient to form a thin film of the actinide compound, are disclosed.

  6. High Pressure X-ray Absorption Studies on Correlated-Electron Systems

    SciTech Connect

    Cornelius, Andrew L.

    2016-08-26

    This project used high pressure to alter the electron-electron and electron-lattice interactions in rare earth and actinide compounds. Knowledge of these properties is the starting points for a first-principles understanding of electronic and electronically related macroscopic properties. The research focused on a systematic study of x-ray absorption measurements on rare earth and actinide compounds.

  7. Theory in Evaluation of Actinide Fission and Capture Cross Sections

    SciTech Connect

    Lynn, J. Eric

    2005-05-24

    We discuss the possibilities and limitations of the use of theory as a tool in the evaluation of actinide fission and capture cross sections. We consider especially the target 235U as an example. We emphasize the roles of intermediate structure in the fission cross section and of level width fluctuations in both intermediate structure and fine structure, noting that these lead to a breakdown of Hauser-Feshbach theory at sub-barrier and near-barrier energies. At higher energies (where fluctuation-averaged Hauser-Feshbach theory is applicable) semi-quantitative and intuitive representations of transition state spectra and barrier level density functions have to be tested against experimental data wherever these are available. Adjustment of the fission cross section against inelastic scattering to the much better known levels of the residual nucleus should then lead to a fairly sound estimate of the capture cross section. We compare such estimates with evaluated and experimental data for 235U.

  8. Vibrational stability and electronic structure of a B80 fullerene

    NASA Astrophysics Data System (ADS)

    Baruah, Tunna; Pederson, Mark R.; Zope, Rajendra R.

    2008-07-01

    We investigate the vibrational stability and the electronic structure of the proposed icosahedral fullerenelike cage structure of B80 [N. G. Szwacki, A. Sadrzadeh, and B. I. Yakobson, Phys. Rev. Lett. 98, 166804 (2007)], by an all electron density-functional theory using polarized Gaussian basis functions containing 41 basis functions per atom. The vibrational analysis of B80 indicates that the icosahedral structure is vibrationally unstable with seven imaginary frequencies. The equilibrium structure has Th symmetry and a smaller gap of 0.96 eV between the highest occupied and the lowest unoccupied molecular orbital energy levels compared to the icosahedral structure. The static dipole polarizability of a B80 cage is 149Å3 , and the first ionization energy is 6.4 eV. The B80 cage has rather large electron affinity of 3 eV making it a useful candidate as electron acceptor if it is synthesized. The infrared and Raman spectra of the highly symmetric structure are characterized by a few absorption peaks.

  9. Human enamel structure studied by high resolution electron microscopy

    SciTech Connect

    Wen, S.L. )

    1989-01-01

    Human enamel structural features are characterized by high resolution electron microscopy. The human enamel consists of polycrystals with a structure similar to Ca10(PO4)6(OH)2. This article describes the structural features of human enamel crystal at atomic and nanometer level. Besides the structural description, a great number of high resolution images are included. Research into the carious process in human enamel is very important for human beings. This article firstly describes the initiation of caries in enamel crystal at atomic and unit-cell level and secondly describes the further steps of caries with structural and chemical demineralization. The demineralization in fact, is the origin of caries in human enamel. The remineralization of carious areas in human enamel has drawn more and more attention as its potential application is realized. This process has been revealed by high resolution electron microscopy in detail in this article. On the other hand, the radiation effects on the structure of human enamel are also characterized by high resolution electron microscopy. In order to reveal this phenomenon clearly, a great number of electron micrographs have been shown, and a physical mechanism is proposed. 26 references.

  10. Electronic and optical properties of novel carbon structures

    NASA Astrophysics Data System (ADS)

    Matthews, Manyalibo Joseph

    Novel carbon structures in the form of fullerenes and disordered carbon clusters offer a wide variety of physical systems, possessing both long or short range order, which can generally be tuned through non- combustive heat-treatment at various elevated temperatures, THT. Due to the sheer complexity and diversity of the possible nanoscale arrangements, the optical and electronic properties of carbon structures with finite dimensions and crystallinity are still not fully understood. In this study, we focus mainly on the structures produced from carbonization of the hydrocarbon polymer polyparaphenylene (PPP), but we also present experimental results from carbons based on other precursors (e.g. mesophase pitch) which yield quite different structures with both comparable and contrasting physical properties. In terms of electronic properties, we show that in the low-THT PPP-based structures, which exemplify extreme disorder, the electronic states are strongly localized, giving rise to a Mott T1/4 hopping conductivity and self-trapped spin defects AS evidenced by low-temperature transport and electron spin resonance experiments. Electronic transitions which give rise to ~2-3 eV photoluminescent emissions in PPP-based structures are found to be influenced most strongly by residual semi-localized polymeric states which weakly couple to low-frequency PPP phonon modes. However, at intermediate heat-treatment temperatures (THT~ 1500[-]2500oC), all sp2-bonded carbon compounds in this study exhibit a characteristic phonon spectrum (as evidenced by Raman spectroscopy) in which disorder may be characterized by non-zone-center phonon scattering arising from finite crystallite sizes. Because of its intimate connection to carrier confinement and structural disorder, the anomalous 'disorder-induced' graphite D-band is thoroughly investigated by use of Raman spectroscopy, showing that strong dispersion effects are due to a photon-phonon coupling mediated by electronic transitions

  11. Comparison of covalency in the complexes of trivalent actinide and lanthanide cations.

    PubMed

    Jensen, Mark P; Bond, Andrew H

    2002-08-21

    The complexes of trivalent actinide (Am(III) and Cm(III)) and lanthanide (Nd(III) and Sm(III)) cations with bis(2,4,4-trimethylpentyl)phosphinic acid, bis(2,4,4-trimethylpentyl)monothiophosphinic acid, and bis(2,4,4-trimethylpentyl)dithiophosphinic acid in n-dodecane have been studied by visible absorption spectroscopy and X-ray absorption fine structure (XAFS) measurements in order to understand the chemical interactions responsible for the great selectivity the dithiophosphinate ligand exhibits for trivalent actinide cations in liquid-liquid extraction. Under the conditions studied, each type of ligand displays a different coordination mode with trivalent f-element cations. The phosphinate ligand coordinates as hydrogen-bonded dimers, forming M(HL2)3. Both the oxygen and the sulfur donor of the monothiophosphinate ligand can bind the cations, affording both bidentate and monodentate ligands. The dithiophosphinate ligand forms neutral bidentate complexes, ML3, with no discernible nitrate or water molecules in the inner coordination sphere. Comparison of the Cm(III), Nd(III), and Sm(III) XAFS shows that the structure and metal-donor atom bond distances are indistinguishable within experimental error for similarly sized trivalent lanthanide and actinide cations, despite the selectivity of bis(2,4,4-trimethylpentyl)dithiophosphinic acid for trivalent actinide cations over trivalent lanthanide cations.

  12. Local Symmetry Effects in Actinide 4f X-ray Absorption in Oxides.

    PubMed

    Butorin, Sergei M; Modin, Anders; Vegelius, Johan R; Suzuki, Michi-To; Oppeneer, Peter M; Andersson, David A; Shuh, David K

    2016-04-19

    A systematic X-ray absorption study at actinide N6,7 (4f → 6d transitions) edges was performed for light-actinide oxides including data obtained for the first time for NpO2, PuO2, and UO3. The measurements were supported by ab initio calculations based on local-density-approximation with added 5f-5f Coulomb interaction (LDA+U). Improved energy resolution compared to common experiments at actinide L(2,3) (2p → 6d transitions) edges allowed us to resolve the major structures of the unoccupied 6d density of states (DOS) and estimate the crystal-field splittings in the 6d shell directly from the spectra of light-actinide dioxides. The measurements demonstrated an enhanced sensitivity of the N(6,7) spectral shape to changes in the compound crystal structure. For nonstoichiometric NpO(2-x), the filling of the entire band gap with Np 6d states was observed thus supporting a phase coexistence of Np metal and stoichiometric NpO2 which is in agreement with the tentative Np-O phase diagram.

  13. Atomic and electronic structure of exfoliated black phosphorus

    SciTech Connect

    Wu, Ryan J.; Topsakal, Mehmet; Jeong, Jong Seok; Wentzcovitch, Renata M.; Mkhoyan, K. Andre; Low, Tony; Robbins, Matthew C.; Haratipour, Nazila; Koester, Steven J.

    2015-11-15

    Black phosphorus, a layered two-dimensional crystal with tunable electronic properties and high hole mobility, is quickly emerging as a promising candidate for future electronic and photonic devices. Although theoretical studies using ab initio calculations have tried to predict its atomic and electronic structure, uncertainty in its fundamental properties due to a lack of clear experimental evidence continues to stymie our full understanding and application of this novel material. In this work, aberration-corrected scanning transmission electron microscopy and ab initio calculations are used to study the crystal structure of few-layer black phosphorus. Directly interpretable annular dark-field images provide a three-dimensional atomic-resolution view of this layered material in which its stacking order and all three lattice parameters can be unambiguously identified. In addition, electron energy-loss spectroscopy (EELS) is used to measure the conduction band density of states of black phosphorus, which agrees well with the results of density functional theory calculations performed for the experimentally determined crystal. Furthermore, experimental EELS measurements of interband transitions and surface plasmon excitations are also consistent with simulated results. Finally, the effects of oxidation on both the atomic and electronic structure of black phosphorus are analyzed to explain observed device degradation. The transformation of black phosphorus into amorphous PO{sub 3} or H{sub 3}PO{sub 3} during oxidation may ultimately be responsible for the degradation of devices exposed to atmosphere over time.

  14. Momentum space analysis of the electronic structure of biphenyl

    NASA Astrophysics Data System (ADS)

    Morini, F.; Shojaei, S. H. Reza; Deleuze, M. S.

    2014-11-01

    The results of a yet to come experimental study of the electronic structure of biphenyl employing electron momentum spectroscopy (EMS) have been theoretically predicted, taking into account complications such as structural mobility in the electronic ground state, electronic correlation and relaxation, and a dispersion of the inner-valence ionization intensity to electronically excited (shake-up) configurations in the cation. The main purpose of this work is to explore the current limits of EMS in unraveling details of the molecular structure, namely the torsional characteristics of large and floppy aromatic molecules. At the benchmark ADC(3)/cc-pVDZ level of theory, the influence of the twist angle between the two phenyl rings is found to be extremely limited, except for individual orbital momentum profiles corresponding to ionization lines at electron binding energies ranging from 15 to 18 eV. When taking band overlap effects into account, this influence is deceptively far too limited to allow for any experimental determination of the torsional characteristics of biphenyl by means of EMS.

  15. Theoretical studies of the electronic structure of small metal clusters

    NASA Technical Reports Server (NTRS)

    Jordan, K. D.

    1982-01-01

    Theoretical studies of the electronic structure of metal clusters, in particular clusters of Group IIA and IIB atoms were conducted. Early in the project it became clear that electron correlation involving d orbitals plays a more important role in the binding of these clusters than had been previously anticipated. This necessitated that computer codes for calculating two electron integrals and for constructing the resulting CI Hamiltonions be replaced with newer, more efficient procedures. Program modification, interfacing and testing were performed. Results of both plans are reported.

  16. Structural and electronic properties of dense liquid and amorphous nitrogen

    SciTech Connect

    Boates, B; Bonev, S A

    2011-02-11

    We present first-principles calculations of the structural and electronic properties of liquid nitrogen in the pressure-temperature range of 0-200 GPa and 2000-6000 K. The molecular-polymerization and molecular-atomic liquid phase boundaries have been mapped over this region. We find the polymeric liquid to be metallic, similar to what has been reported for the higher-temperature atomic fluid. An explanation of the electronic properties is given based on the structure and bonding character of the transformed liquids. We discuss the structural and bonding differences between the polymeric liquid and insulating solid cubic-gauche nitrogen to explain the differences in their electronic properties. Furthermore, we discuss the mechanism responsible for charge transport in polymeric nitrogen systems to explain the conductivity of the polymeric fluid and the semi-conducting nature of low-temperature amorphous nitrogen.

  17. Electronic structure and enthalpy of hydrogen and helium mixtures

    NASA Astrophysics Data System (ADS)

    Ross, M.; Klepeis, J. E.; Schafer, K. J.; Barbee, T. W., III

    1992-11-01

    The first local density approximation (LDA) calculations of the electronic structure, equation of state, and enthalpy of mixing were carried out for a number of different compositions of hydrogen and helium in bcc and fcc lattices. These are fully quantum mechanical, self-consistent calculations utilizing state-of-the-art methods of electron band theory, which make no assumptions regarding pressure ionization. The major approximation in the LDA method is that the exchange and correlation energy is given by a free electron functional in terms of the local electron density. The majority of previous mixture calculations start with the assumption that both hydrogen and helium are pressure-ionized so that the electronic structure is approximately that of free or weakly screened electrons in the presence of positive ions. Stevenson used a hard-sphere mixture model for the ions with an ion-ion pseudopotential to account for electron screening and predicted that a mixture containing 7% helium by number, the composition believed to be present in Jupiter and Saturn, would phase separate at a temperature of about 7000 K at 8 Mbar. Subsequent calculations carried out for the fully ionized mixture and for a mixture of screened ions (linear response theory) have all arrived at predictions similar to those of Stevenson. MacFarlane and Hubbard performed Thomas-Fermi-Dirac calculations for mixing enthalpies of hydrogen and helium in bcc and fcc lattices and predicted that phase separation would not occur at any temperature.

  18. Electronic Structure Analysis for Proteins on the FMO Method

    NASA Astrophysics Data System (ADS)

    Kobori, Tomoki; Tsuneyuki, Shinji; Sodeyama, Keitaro; Akagi, Kazuto; Terakura, Kiyoyuki; Fukuyama, Hidetoshi

    2009-03-01

    The enormity and complexity of proteins have rendered their electronic structure calculation very costly. Although recently established Fragment Molecular Orbital (FMO) method enables us to calculate total energy of a huge protein precisely based on quantum mechanics, the method does not refer to one-electron orbitals and one-electron energy spectrum. In this paper we propose a method of analyzing electronic structure of a protein based on first principles calculation with reasonable accuracy and CPU cost. We construct one- electron Hamiltonian of proteins by assembling the output of the FMO method: fragment orbitals are determined by fragment monomer calculation, while interaction and overlap between fragment orbitals in different fragments are obtained from dimer calculation. After one-electron Hamiltonian matrix of the whole system is fabricated with the fragment orbital basis, one- electron energy spectrum is obtained by its diagonalization. If the matrix dimension is too large, unimportant orbitals are eliminated from the matrix so that the diagonalization of the Hamiltonian becomes feasible. The method is applicable to both the Hartree-Fock method and the density functional theory. In this paper, validity of the method is verified by some test calculations of small peptides.

  19. Electronic Structure and Effectively Unpaired Electron Density Topology in closo-Boranes: Nonclassical Three-Center Two-Electron Bonding.

    PubMed

    Lobayan, Rosana M; Bochicchio, Roberto C; Torre, Alicia; Lain, Luis

    2011-04-12

    This article provides a detailed study of the structure and bonding in closo-borane cluster compounds X2B3H3 (X = BH(-), P, SiH, CH, N), with particular emphasis on the description of the electron distribution using the topology of the quantum many-body effectively unpaired density. The close relationship observed between the critical points of this quantity and the localization of the electron cloud allows us to characterize the nonclassical bonding patterns of these systems. The obtained results confirm the suitability of the local rule to detect three-center two-electron bonds, which was conjectured in our previous study on boron hydrides.

  20. Banded Electron Structure Formation in the Inner Magnetosphere

    NASA Technical Reports Server (NTRS)

    Liemohn, M. W.; Khazanov, G. V.

    1997-01-01

    Banded electron structures in energy-time spectrograms have been observed in the inner magnetosphere concurrent with a sudden relaxation of geomagnetic activity. In this study, the formation of these banded structures is considered with a global, bounce-averaged model of electron transport, and it is concluded that this structure is a natural occurrence when plasma sheet electrons are captured on closed drift paths near the Earth. These bands do not appear unless there is capture of plasma sheet electrons; convection along open drift paths making open pass around the Earth do not have time to develop this feature. The separation of high-energy bands from the injection population due to the preferential advection of the gradient-curvature drift creates spikes in the energy distribution, which overlap to form a series of bands in the energy spectrograms. The lowest band is the bulk of the injected population in the sub-key energy range. Using the Kp history for an observed banded structure event, a cloud of plasma sheet electrons is captured and the development of their distribution function is examined and discussed.

  1. The electronic structure and chemical bonding of vitamin B12

    NASA Astrophysics Data System (ADS)

    Kurmaev, E. Z.; Moewes, A.; Ouyang, L.; Randaccio, L.; Rulis, P.; Ching, W. Y.; Bach, M.; Neumann, M.

    2003-05-01

    The electronic structure and chemical bonding of vitamin B12 (cyanocobalamin) and B12-derivative (methylcobalamin) are studied by means of X-ray emission (XES) and photoelectron (XPS) spectroscopy. The obtained results are compared with ab initio electronic structure calculations using the orthogonalized linear combination of the atomic orbital method (OLCAO). We show that the chemical bonding in vitamin B12 is characterized by the strong Co-C bond and relatively weak axial Co-N bond. It is further confirmed that the Co-C bond in cyanocobalamin is stronger than that of methylcobalamin resulting in their different biological activity.

  2. Structural and luminescent properties of electron-irradiated silicon

    SciTech Connect

    Sobolev, N. A.; Loshachenko, A. S.; Aruev, P. N.; Kalyadin, A. E.; Shek, E. I.; Zabrodskiy, V. V.; Shtel'makh, K. F.; Vdovin, V. I.; Xiang, Luelue; Yang, Deren

    2014-02-21

    Structural defects induced by electron irradiation of p-Cz-Si wafers were identified. The influence of the annealing conditions in a chlorine-containing atmosphere on the structural and luminescent properties of the samples was examined. Light-emitting diodes based on electron-irradiated and high-temperature-annealed wafers were fabricated by a vapour-phase epitaxy technique and their luminescence properties were studied. A high-intensity dislocation-related D1 line was observed at 1.6 μm in the room-temperature electroluminescence spectrum.

  3. Electronic structure of Sn/Cu(100)-[Formula: see text].

    PubMed

    Martínez-Blanco, J; Joco, V; Fujii, J; Segovia, P; Michel, E G

    2009-02-04

    We present measurements of the Fermi surface and underlying band structure of Sn/Cu(100)-[Formula: see text]. This phase is observed for a coverage of 0.60-0.65 monolayers. Its electronic structure is characterized by a free-electron-like surface band folded with the reconstruction periodicity. At variance with other surface phases of Sn on Cu(100), no temperature-induced phase transition is observed for this phase from 100 K up to the desorption of Sn.

  4. Electronic Structure of Lanthanum Hydrides with Switchable Optical Properties

    SciTech Connect

    Ng, K.; Zhang, F.; Ng, K.; Zhang, F.; Anisimov, V.; Rice, T.; Anisimov, V.

    1997-02-01

    Recent dramatic changes in the optical properties of LaH{sub 2+x} and YH{sub 2+x} films discovered by Huiberts {ital et al.}[Nature (London) {bold 380}, 231 (1996)] suggest their electronic structure is described best by a local model. Electron correlation is important in H{sup -} centers and in explaining the transparent insulating behavior of LaH{sub 3}. The metal-insulator transition at x{approximately}0.8 takes place in a band of highly localized states centered on the H vacancies in the LaH{sub 3} structure. {copyright} {ital 1997} {ital The American Physical Society}

  5. Comparison of electronic structure between monolayer silicenes on Ag (111)

    NASA Astrophysics Data System (ADS)

    Chun-Liang, Lin; Ryuichi, Arafune; Maki, Kawai; Noriaki, Takagi

    2015-08-01

    The electronic structures of monolayer silicenes (4 × 4 and ) grown on Ag (111) surface are studied by scanning tunneling spectroscopy (STS) and density functional theory (DFT) calculations. While both phases have similar electronic structures around the Fermi level, significant differences are observed in the higher energy unoccupied states. The DFT calculations show that the contributions of Si 3pz orbitals to the unoccupied states are different because of their different buckled configurations. Project supported by the Ministry of Education, Culture, Sports, Science and Technology (MEXT) through Grants-in-Aid for Scientific Research (Grant Nos. 24241040 and 25110008) and the World Premier International Research Center Initiative (WPI), MEXT, Japan.

  6. Free electron laser-driven ultrafast rearrangement of the electronic structure in Ti

    PubMed Central

    Principi, E.; Giangrisostomi, E.; Cucini, R.; Bencivenga, F.; Battistoni, A.; Gessini, A.; Mincigrucci, R.; Saito, M.; Di Fonzo, S.; D'Amico, F.; Di Cicco, A.; Gunnella, R.; Filipponi, A.; Giglia, A.; Nannarone, S.; Masciovecchio, C.

    2015-01-01

    High-energy density extreme ultraviolet radiation delivered by the FERMI seeded free-electron laser has been used to create an exotic nonequilibrium state of matter in a titanium sample characterized by a highly excited electron subsystem at temperatures in excess of 10 eV and a cold solid-density ion lattice. The obtained transient state has been investigated through ultrafast absorption spectroscopy across the Ti M2,3-edge revealing a drastic rearrangement of the sample electronic structure around the Fermi level occurring on a time scale of about 100 fs. PMID:26798835

  7. Structural and electronic properties of monolayer group III monochalcogenides

    NASA Astrophysics Data System (ADS)

    Demirci, S.; Avazlı, N.; Durgun, E.; Cahangirov, S.

    2017-03-01

    We investigate the structural, mechanical, and electronic properties of the two-dimensional hexagonal structure of group III-VI binary monolayers, M X (M =B , Al, Ga, In and X =O , S, Se, Te) using first-principles calculations based on the density functional theory. The structural optimization calculations and phonon spectrum analysis indicate that all of the 16 possible binary compounds are thermally stable. In-plane stiffness values cover a range depending on the element types and can be as high as that of graphene, while the calculated bending rigidity is found to be an order of magnitude higher than that of graphene. The obtained electronic band structures show that M X monolayers are indirect band-gap semiconductors. The calculated band gaps span a wide optical spectrum from deep ultraviolet to near infrared. The electronic structure of oxides (M O ) is different from the rest because of the high electronegativity of oxygen atoms. The dispersions of the electronic band edges and the nature of bonding between atoms can also be correlated with electronegativities of constituent elements. The unique characteristics of group III-VI binary monolayers can be suitable for high-performance device applications in nanoelectronics and optics.

  8. First ionization potential of the heaviest actinide lawrencium, element 103

    NASA Astrophysics Data System (ADS)

    Sato, Tetsuya K.; Asai, Masato; Borschevsky, Anastasia; Stora, Thierry; Sato, Nozomi; Kaneya, Yusuke; Tsukada, Kazuaki; Düllmann, Christoph E.; Eberhardt, Klaus; Eliav, Ephraim; Ichikawa, Shinichi; Kaldor, Uzi; Kratz, Jens V.; Miyashita, Sunao; Nagame, Yuichiro; Ooe, Kazuhiro; Osa, Akihiko; Renisch, Dennis; Runke, Jörg; Schädel, Matthias; Thörle-Pospiech, Petra; Toyoshima, Atsushi; Trautmann, Norbert

    2016-12-01

    The first ionization potential (IP1) of element 103, lawrencium (Lr), has been successfully determined for the first time by using a newly developed method based on a surface ionization process. The measured IP1 value is 4.963 eV. This value is the smallest among those of actinide elements and is in excellent agreement with the value of 4.963(15) eV predicted by state-of-the-art relativistic calculations also performed in this work. Our results strongly support that the Lr atom has an electronic configuration of [Rn]7s25f147p, which is influenced by strong relativistic effects. The present work provides a reliable benchmark for theoretical calculations and also opens the way for studies on atomic properties of heavy elements with atomic number Z > 100. Moreover, the present achievement has triggered a controversy on the position of lutetium (Lu) and Lr in the Periodic Table of Elements.

  9. Electron-Phonon Renormalization of Electronic Band Structures of C Allotropes and BN Polymorphs

    NASA Astrophysics Data System (ADS)

    Tutchton, Roxanne M.; Marchbanks, Christopher; Wu, Zhigang

    The effect of lattice vibration on electronic band structures has been mostly neglected in first-principles calculations because the electron-phonon (e-ph) renormalization of quasi-particle energies is often small (< 100 meV). However, in certain materials, such as diamond, the electron-phonon coupling reduces the band gap by nearly 0.5 eV, which is comparable to the many-body corrections of the electronic band structures calculated using the density functional theory (DFT). In this work, we compared two implementations of the Allen-Heine-Cardona theory in the EPW code and the ABINIT package respectively. Our computations of Si and diamond demonstrate that the ABINIT implementation converges much faster. Using this method, the e-ph renormalizations of electronic structures of three C allotropes (diamond, graphite, graphene) and four BN polymorphs (zincblend, wurtzite, mono-layer, and layered-hexagonal) were calculated. Our results suggest that (1) all of the zero-point renormalizations of band gaps in these materials, except for graphene, are larger than 100 meV, and (2) there are large variations in e-ph renormalization of band gaps due to differences in crystal structure. This work was supported by a U.S. DOE Early Career Award (Grant No. DE-SC0006433). Computations were carried out at the Golden Energy Computing Organization at CSM and the National Energy Research Scientific Computing Center (NERSC).

  10. Electrodeposition of actinide compounds from an aqueous ammonium acetate matrix. Experimental development and optimization

    DOE PAGES

    Boll, Rose Ann; Matos, Milan; Torrico, Matthew N.

    2015-03-27

    Electrodeposition is a technique that is routinely employed in nuclear research for the preparation of thin solid films of actinide materials which can be used in accelerator beam bombardments, irradiation studies, or as radioactive sources. The present study investigates the deposition of both lanthanides and actinides from an aqueous ammonium acetate electrolyte matrix. Electrodepositions were performed primarily on stainless steel disks; with yield analysis evaluated using -spectroscopy. Experimental parameters were studied and modified in order to optimize the uniformity and adherence of the deposition while maximizing the yield. The initial development utilized samarium as the plating material, with and withoutmore » a radioactive tracer. As a result, surface characterization studies were performed by scanning electron microscopy, electron microprobe analysis, radiographic imaging, and x-ray diffraction.« less

  11. Electrodeposition of actinide compounds from an aqueous ammonium acetate matrix. Experimental development and optimization

    SciTech Connect

    Boll, Rose Ann; Matos, Milan; Torrico, Matthew N.

    2015-03-27

    Electrodeposition is a technique that is routinely employed in nuclear research for the preparation of thin solid films of actinide materials which can be used in accelerator beam bombardments, irradiation studies, or as radioactive sources. The present study investigates the deposition of both lanthanides and actinides from an aqueous ammonium acetate electrolyte matrix. Electrodepositions were performed primarily on stainless steel disks; with yield analysis evaluated using -spectroscopy. Experimental parameters were studied and modified in order to optimize the uniformity and adherence of the deposition while maximizing the yield. The initial development utilized samarium as the plating material, with and without a radioactive tracer. As a result, surface characterization studies were performed by scanning electron microscopy, electron microprobe analysis, radiographic imaging, and x-ray diffraction.

  12. Relativistic correlating basis sets for actinide atoms from 90Th to 103Lr.

    PubMed

    Noro, Takeshi; Sekiya, Masahiro; Osanai, You; Koga, Toshikatsu; Matsuyama, Hisashi

    2007-12-01

    For 14 actinide atoms from (90)Th to (103)Lr, contracted Gaussian-type function sets are developed for the description of correlations of the 5f, 6d, and 7s electrons. Basis sets for the 6d orbitals are also prepared, since the orbitals are important in molecular environments despite their vacancy in the ground state of some actinides. A segmented contraction scheme is employed for the compactness and efficiency. Contraction coefficients and exponents are so determined as to minimize the deviation from accurate natural orbitals of the lowest term arising from the 5f(n-1)6d(1)7s(2) configuration. The spin-free relativistic effects are considered through the third-order Douglas-Kroll approximation. To test the present correlating sets, all-electron calculations are performed on the ground state of (90)ThO molecule. The calculated spectroscopic constants are in excellent agreement with experimental values.

  13. Actinide Isotopes for the Synthesis of Superheavy Nuclei

    NASA Astrophysics Data System (ADS)

    Roberto, J. B.; Alexander, C. W.; Boll, R. A.; Dean, D. J.; Ezold, J. G.; Felker, L. K.; Rykaczewski, K. P.

    2014-09-01

    Recent research resulting in the synthesis of isotopes of new elements 113-118 has demonstrated the importance of actinide targets in superheavy element research. Oak Ridge National Laboratory (ORNL) has unique facilities for the production and processing of actinide target materials, including the High Flux Isotope Reactor (HFIR) and the Radiochemical Engineering Development Center (REDC). These facilities have provided actinide target materials that have been used for the synthesis of all superheavy (SHE) elements above Copernicium (element 112). In this paper, the use of actinide targets for SHE research and discovery is described, including recent results for element 117 using 249Bk target material from ORNL. ORNL actinide capabilities are reviewed, including production and separation/purification, availabilities of actinide materials, and future opportunities including novel target materials such as 251Cf.

  14. Actinide phosphonate complexes in aqueous solutions

    SciTech Connect

    Nash, K.L.

    1993-10-01

    Complexes formed by actinides with carboxylic acids, polycarboxylic acids, and aminopolycarboxylic acids play a central role in both the basic and process chemistry of the actinides. Recent studies of f-element complexes with phosphonic acid ligands indicate that new ligands incorporating doubly ionizable phosphonate groups (-PO{sub 3}H{sub 2}) have many properties which are unique chemically, and promise more efficient separation processes for waste cleanup and environmental restoration. Simple diphosphonate ligands form much stronger complexes than isostructural carboxylates, often exhibiting higher solubility as well. In this manuscript recent studies of the thermodynamics and kinetics of f-element complexation by 1,1 and 1,2 diphosphonic acid ligands are described.

  15. Effects of inverse degree on electronic structure and electron energy-loss spectrum in zinc ferrites

    NASA Astrophysics Data System (ADS)

    Sun, D.; Wang, M. X.; Zhang, Z. H.; Tao, H. L.; He, M.; Song, B.; Li, Q.

    2015-12-01

    First-principles calculations were performed to study the effects of inverse degree in zinc ferrite on electronic structure and properties. The electron energy-loss near-edge fine structure (ELNES) were simulated, and the splitting of peak and intensities of the oxygen K-edges can be used to identify the inversion of zinc ferrite. More Fe3+ transferring from the octahedral sites to the tetrahedral sites lead to the changing of the ligand shells surrounding the absorbing atom, accounting for the observed changing in ELNES. The standard criterion for determining the reversal extent of the cations in zinc ferrite by ELNES was given.

  16. Electronic structure of nitrides PuN and UN

    NASA Astrophysics Data System (ADS)

    Lukoyanov, A. V.; Anisimov, V. I.

    2016-11-01

    The electronic structure of uranium and plutonium nitrides in ambient conditions and under pressure is investigated using the LDA + U + SO band method taking into account the spin-orbit coupling and the strong correlations of 5 f electrons of actinoid ions. The parameters of these interactions for the equilibrium cubic structure are calculated additionally. The application of pressure reduces the magnetic moment in PuN due to predominance of the f 6 configuration and the jj-type coupling. An increase in the occupancy of the 5 f state in UN leads to a decrease in the magnetic moment, which is also detected in the trigonal structure of the UN x β phase (La2O3-type structure). The theoretical results are in good agreement with the available experimental data.

  17. Chiral phosphorus nanotubes: structure, bonding, and electronic properties.

    PubMed

    Fernández-Escamilla, H N; Quijano-Briones, J J; Tlahuice-Flores, A

    2016-05-14

    The study of black phosphorus nanotubes (PNTs) had been devoted to zigzag and armchair structures, with no consideration of chiral structures to date. In this communication, we studied the structural and electronic (band structure) properties of chiral nanotubes using a periodic plane wave-pseudopotential approach. We found that some chiral nanotubes display similar bandgaps and binding energies per atom (BEA) as armchair PNTs and Born-Oppenheimer molecular dynamics (BOMD) calculations attest their thermal stability. Interestingly, we determined that the bandgap is tuned by varying the PNTs chirality and it is not related to their diameters. This feature can be exploited in optical and electronic applications wherein a direct and sizable bandgap is required.

  18. Structural and electronic properties of small silicon clusters

    NASA Astrophysics Data System (ADS)

    Baturin, V. S.; Lepeshkin, S. V.; Magnitskaya, M. V.; Matsko, N. L.; Uspenskii, Yu A.

    2014-05-01

    The atomic structure and electronic spectrum of silicon nanoclusters (Si-ncs) Si7, Si10,Si10H16 and Si10H20 are calculated using the evolutionary algorithm with total energy computed within density functional theory and generalized gradient approximation (DFT-GGA). When analysing the low-energy structures, we pay significant attention to their symmetry and interatomic bond geometry. The candidate structures arising in the process of evolutionary algorithm convergence are also considered and classified by their topology and grouping near local energy minima. Possible ways to improve the convergence of evolutionary computation are discussed. Addressing qualitative criteria for the ground-state atomic structure of Si-ncs, we consider correlations between the density of electronic states and the total energetics of clusters in the ground state and low-energy-isomer configurations.

  19. Structural investigation of californium under pressure

    NASA Astrophysics Data System (ADS)

    Heathman, S.; Le Bihan, T.; Yagoubi, S.; Johansson, B.; Ahuja, R.

    2013-06-01

    The high-pressure structural behavior of californium has been studied experimentally and theoretically up to 100 GPa. A valence change from divalent to trivalent forms was observed under modest pressure revealing californium to be the only actinide to exhibit more than one metallic valence at near to ambient conditions as is the case for cerium in the lanthanide series. Three metallic valencies and four different crystallographic phases were observed in californium as a function of pressure. High-pressure techniques, synchrotron radiation, and ab initio electronic structure calculations of total energies were used to investigate the material and to determine the role which californium's 5f electrons play in influencing these transitions. The crystallographic structures observed are similar to those found in the preceding actinide elements, curium and americium, with the initially localized 5f states becoming completely delocalized under the influence of high pressure.

  20. Layer-stacking effect on electronic structures of bilayer arsenene

    NASA Astrophysics Data System (ADS)

    Mi, Kui; Xie, Jiafeng; Si, M. S.; Gao, C. X.

    2017-01-01

    A monolayer of orthorhombic arsenic (arsenene) is a promising candidate for nano-electronic devices due to the uniquely electronic properties. To further extend its practical applications, an additional layer is introduced to tune the electronic structures. Four layer-stacking manners, namely AA-, AB-, AB‧-, and AC-stacking, are constructed and studied through using first-principles calculations. Compared with monolayer, an indirect-direct gap transition is realized in AB-stacking. More importantly, a semimetal feature appears in the AC- and AB‧-stacked bilayers, leaving the electronic structure of AA-stacking trivial. In addition, the energy dispersion around Γ is largely tuned from the layer-stacking effect. To understand the underlying physics, the \\textbf{k}\\cdot\\textbf{p} approximation is taken to address this issue. Our results show that the level repulsion from the additional layer domaintes the anisotropy of energy dispersion around Γ. The works like ours would shed new light on the tunability of the electronic structure in layered arsenene.

  1. Molecular and electronic structure of electroactive self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Méndez De Leo, Lucila P.; de la Llave, Ezequiel; Scherlis, Damián; Williams, Federico J.

    2013-03-01

    Self-assembled monolayers (SAMs) containing electroactive functional groups are excellent model systems for the formation of electronic devices by self-assembly. In particular ferrocene-terminated alkanethiol SAMs have been extensively studied in the past. However, there are still open questions related with their electronic structure including the influence of the ferrocene group in the SAM-induced work function changes of the underlying metal. We have thus carried out a thorough experimental and theoretical investigation in order to determine the molecular and electronic structure of ferrocene-terminated alkanethiol SAMs on Au surfaces. In agreement with previous studies we found that the Fc-containing alkanethiol molecules adsorb forming a thiolate bond with the Au surface with a molecular geometry 30° tilted with respect to the surface normal. Measured surface coverages indicate the formation of a compact monolayer. We found for the first time that the ferrocene group has little influence on the observed work function decrease which is largely determined by the alkanethiol. Furthermore, the ferrocene moiety lies 14 Å above the metal surface covalently bonded to the alkanethiol SAM and its HOMO is located at -1.6 eV below the Fermi level. Our results provide new valuable insight into the molecular and electronic structure of electroactive SAMs which are of fundamental importance in the field of molecular electronics.

  2. Molecular and electronic structure of electroactive self-assembled monolayers.

    PubMed

    Méndez De Leo, Lucila P; de la Llave, Ezequiel; Scherlis, Damián; Williams, Federico J

    2013-03-21

    Self-assembled monolayers (SAMs) containing electroactive functional groups are excellent model systems for the formation of electronic devices by self-assembly. In particular ferrocene-terminated alkanethiol SAMs have been extensively studied in the past. However, there are still open questions related with their electronic structure including the influence of the ferrocene group in the SAM-induced work function changes of the underlying metal. We have thus carried out a thorough experimental and theoretical investigation in order to determine the molecular and electronic structure of ferrocene-terminated alkanethiol SAMs on Au surfaces. In agreement with previous studies we found that the Fc-containing alkanethiol molecules adsorb forming a thiolate bond with the Au surface with a molecular geometry 30° tilted with respect to the surface normal. Measured surface coverages indicate the formation of a compact monolayer. We found for the first time that the ferrocene group has little influence on the observed work function decrease which is largely determined by the alkanethiol. Furthermore, the ferrocene moiety lies 14 Å above the metal surface covalently bonded to the alkanethiol SAM and its HOMO is located at -1.6 eV below the Fermi level. Our results provide new valuable insight into the molecular and electronic structure of electroactive SAMs which are of fundamental importance in the field of molecular electronics.

  3. Surrogate Reactions in the Actinide Region

    SciTech Connect

    Burke, J T; Bernstein, L A; Scielzo, N D; Bleuel, D L; Lesher, S R; Escher, J; Ahle, L; Dietrich, F S; Hoffman, R D; Norman, E B; Sheets, S A; Phair, L; Fallon, P; Clark, R M; Gibelin, J; Jewett, C; Lee, I Y; Macchiavelli, A O; McMahan, M A; Moretto, L G; Rodriguez-Vieitez, E; Wiedeking, M; Lyles, B F; Beausang, C W; Allmond, J M; Ai, H; Cizewski, J A; Hatarik, R; O'Malley, P D; Swan, T

    2008-01-30

    Over the past three years we have studied various surrogate reactions (d,p), ({sup 3}He,t), ({alpha},{alpha}{prime}) on several uranium isotopes {sup 234}U, {sup 235}U, {sup 236}U, and {sup 238}U. An overview of the STARS/LIBERACE surrogate research program as it pertains to the actinides is discussed. A summary of results to date will be presented along with a discussion of experimental difficulties encountered in surrogate experiments and future research directions.

  4. Separation of Californium from other Actinides

    DOEpatents

    Mailen, J C; Ferris, L M

    1973-09-25

    A method is provided for separating californium from a fused fluoride composition containing californium and at least one element selected from the group consisting of plutonium, americium, curium, uranium, thorium, and protactinium which comprises contacting said fluoride composition with a liquid bismuth phase containing sufficient lithium or thorium to effect transfer of said actinides to the bismuth phase and then contacting the liquid bismuth phase with molten LiCl to effect selective transfer of californium to the chloride phase.

  5. Electron Diffraction and High-Resolution Electron Microscopy of Mineral Structures

    NASA Astrophysics Data System (ADS)

    Nord, Gordon L., Jr.

    This book is a well-written English translation of the original 1981 Russian edition, Strukturnoye issledovaniye mineralov metodami mikrodifraktsii i elechtronnoi mikroskopii vysokogo razresheniya. The 1987 English version has been extensively updated and includes references up to 1986. The book is essentially a text on the theoretical and experimental aspects of transmission electron microscopy and has chapters on the reciprocal lattice, electron diffraction (both kinematic and dynamic), and high-resolution electron microscopy.Electron diffraction is emphasized, especially its use for structure analysis of poorly crystalline and fine-grained phases not readily determined by the more exact X ray diffraction method. Two methods of electron diffraction are discussed: selected area electron diffraction (SAED) and oblique-texture electron diffraction (OTED); the latter technique is rarely used in the west and is never discussed in western electron microscopy texts. A SAED pattern is formed by isolating a small micrometer-size area with an aperture and obtaining single-crystal patterns from the diffracted beams. By tilting the sample and obtaining many patterns, a complete picture of the reciprocal lattice can be taken. An OTED pattern is formed when the incident electron beam passes through an inclined preparation consisting of a great number of thin platy crystals lying normal to the texture axis (axis normal to the support grid). To form an OTED pattern, the plates must all lie on a common face, such as a basal plane in phyllosilicates. Upon tilting the plates, an elliptical powder diffraction pattern is formed. Intensities measured from these patterns are used for a structural analysis of the platy minerals.

  6. Actinide behavior in a freshwater pond

    SciTech Connect

    Trabalka, J.R.; Bogle, M.A.; Scott, T.G.

    1983-01-01

    Long-term investigations of solution chemistry in an alkaline freshwater pond have revealed that actinide oxidation state behavior, particularly that of plutonium, is complex. The Pu(V,VI) fraction was predominant in solution, but it varied over the entire range reported from other natural aquatic environments, in this case, as a result of intrinsic biological and chemical cycles (redox and pH-dependent phenomena). A strong positive correlation between plutonium (Pu), but not uranium (U), and hydroxyl ion over the observation period, especially when both were known to be in higher oxidation states, was particularly notable. Coupled with other examples of divergent U and Pu behavior, this result suggests that Pu(V), or perhaps a mixture of Pu(V,VI), was the prevalent oxidation state in solution. Observations of trivalent actinide sorption behavior during an algal bloom, coupled with the association with a high-molecular weight (nominally 6000 to 10,000 mol wt) organic fraction in solution, indicate that solution-detritus cycling of organic carbon, in turn, may be the primary mechanism in amercium-curium (Am-Cm) cycling. Sorption by sedimentary materials appears to predominate over other factors controlling effective actinide solubility and may explain, at least partially, the absence of an expected strong positive correlation between carbonate and dissolved U. 49 references, 6 figures, 12 tables.

  7. Actinide and lanthanide separation process (ALSEP)

    DOEpatents

    Guelis, Artem V.

    2013-01-15

    The process of the invention is the separation of minor actinides from lanthanides in a fluid mixture comprising, fission products, lanthanides, minor actinides, rare earth elements, nitric acid and water by addition of an organic chelating aid to the fluid; extracting the fluid with a solvent comprising a first extractant, a second extractant and an organic diluent to form an organic extractant stream and an aqueous raffinate. Scrubbing the organic stream with a dicarboxylic acid and a chelating agent to form a scrubber discharge. The scrubber discharge is stripped with a simple buffering agent and a second chelating agent in the pH range of 2.5 to 6.1 to produce actinide and lanthanide streams and spent organic diluents. The first extractant is selected from bis(2-ethylhexyl)hydrogen phosphate (HDEHP) and mono(2-ethylhexyl)2-ethylhexyl phosphonate (HEH(EHP)) and the second extractant is selected from N,N,N,N-tetra-2-ethylhexyl diglycol amide (TEHDGA) and N,N,N',N'-tetraoctyl-3-oxapentanediamide (TODGA).

  8. Electronic Structure of Crystalline 4He at High Pressures

    SciTech Connect

    Mao, Ho Kwang; Shirley, Eric L.; Ding, Yang; Eng, Peter; Cai, Yong Q.; Chow, Paul; Xiao, Yuming; Jinfu Shu, A=Kao, Chi-Chang; Hemley, Russell J.; Kao, Chichang; Mao, Wendy L.; /Stanford U., Geo. Environ. Sci. /SLAC

    2011-01-10

    Using inelastic X-ray scattering techniques, we have succeeded in probing the high-pressure electronic structure of helium crystal at 300 K which has the widest known electronic energy bandgap of all materials, that was previously inaccessible to measurements due to the extreme energy and pressure range. We observed rich electron excitation spectrum, including a cut-off edge above 23 eV, a sharp exciton peak showing linear volume dependence, and a series of excitations and continuum at 26 to 45 eV. We determined electronic dispersion along the {Gamma}-M direction over two Brillouin zones, and provided a quantitative picture of the helium exciton beyond the simplified Wannier-Frenkel description.

  9. Modulated structures in calcian dolomite: A study by electron microscopy

    NASA Astrophysics Data System (ADS)

    van Tendeloo, G.; Wenk, H. R.; Gronsky, R.

    1985-11-01

    Calcian dolomite from the Devonian Lost Burro formation has been investigated with electron microscopy techniques. Electron diffraction shows evidence for “c” and “d” type reflections which may occur independently and are indicative of ordered superstructures. High resolution electron microscopy combined with selected area optical diffraction is the basis for models to explain the superstructures in calcian dolomite. It is proposed that “c” reflections are due to ordered substitution of Mg by Ca in basal cation layers. “d” reflections result when the rhombohedral stacking of basal layers is interrupted by intercalation of additional Ca layers. During electron irradiation at 1 MeV the Mg-Ca distribution becomes disordered and the crystal structure attains calcite symmetry. The arrangement of CO3 groups remains ordered.

  10. Electronic structure and isomer shifts of neptunium compounds

    NASA Astrophysics Data System (ADS)

    Svane, A.; Petit, L.; Temmerman, W. M.; Szotek, Z.

    2002-08-01

    The electronic structures of αNp metal and 28 Np compounds are calculated with the generalized gradient approximation to density-functional theory, implemented with the full-potential linear-muffin-tin-orbital method. The calculations are compared to experimental isomer shifts providing a calibration of the 237Np isomeric transition with a value of Δ=(-40.1+/-1.3)×10- 3 fm2 for the difference in nuclear radius between the excited isomeric level and the ground state. The isomer shift is primarily determined by the chemical environment. Decreasing the volume, either by external or chemical pressure, causes an f-->s+d charge transfer on Np, which leads to a higher electron contact density. The possible f-electron localization in Np compounds is discussed using self-interaction corrections, and it is concluded that f-electron localization has only a minor influence on the isomer shift.

  11. Superconducting properties and electronic structure of NaBi.

    PubMed

    Kushwaha, S K; Krizan, J W; Xiong, J; Klimczuk, T; Gibson, Q D; Liang, T; Ong, N P; Cava, R J

    2014-05-28

    Resistivity, dc magnetization, and heat capacity measurements are reported for superconducting NaBi. T(c), the electronic contribution to the specific heat γ, the ΔC(p)/γT(c) ratio, and the Debye temperature are found to be 2.15 K, 3.4 mJ mol(-1) K(-2), 0.78, and 140 K respectively. The calculated electron-phonon coupling constant (λ(ep) = 0.62) implies that NaBi is a moderately coupled superconductor. The upper critical field and coherence length are found to be 250 Oe and 115 nm, respectively. Electronic structure calculations show NaBi to be a good metal, in agreement with the experiments; the p(x) and p(y) orbitals of Bi dominate the electronic states at the Fermi Energy.

  12. Correlative Light Electron Microscopy: Connecting Synaptic Structure and Function

    PubMed Central

    Begemann, Isabell; Galic, Milos

    2016-01-01

    Many core paradigms of contemporary neuroscience are based on information obtained by electron or light microscopy. Intriguingly, these two imaging techniques are often viewed as complementary, yet separate entities. Recent technological advancements in microscopy techniques, labeling tools, and fixation or preparation procedures have fueled the development of a series of hybrid approaches that allow correlating functional fluorescence microscopy data and ultrastructural information from electron micrographs from a singular biological event. As correlative light electron microscopy (CLEM) approaches become increasingly accessible, long-standing neurobiological questions regarding structure-function relation are being revisited. In this review, we will survey what developments in electron and light microscopy have spurred the advent of correlative approaches, highlight the most relevant CLEM techniques that are currently available, and discuss its potential and limitations with respect to neuronal and synapse-specific applications. PMID:27601992

  13. Surface crystallography and electronic structure of potassium yttrium tungstate

    SciTech Connect

    Atuchin, V. V.; Pokrovsky, L. D.; Khyzhun, O. Yu.; Sinelnichenko, A. K.; Ramana, C. V.

    2008-08-01

    Structural and electronic characteristics of KY(WO{sub 4}){sub 2} (KYW) (010) crystal surfaces have been studied using reflection high-energy electron diffraction (RHEED) and x-ray photoelectron spectroscopy (XPS). The results indicate that the crystal structure and chemical composition of the mechanically polished pristine surface is stoichiometrically well maintained as expected for KYW crystals. Combined measurements of RHEED and XPS as a function of 1.5 keV Ar{sup +} ion irradiation of the KYW (010) surfaces indicate amorphization, partial loss of potassium atoms, and partial transformation of chemical valence state of tungsten from W{sup 6+} to a lower valence state, W{sup 0} state predominantly, which induces electronic states at the top of valence band.

  14. Structural and electronic properties of a tetrahedral amorphous carbon surface

    NASA Astrophysics Data System (ADS)

    Dong, Jianjun; Drabold, D. A.

    1997-03-01

    We present ab initio studies of a model of tetrahedral amorphous carbon (ta-C) surface. Our methodology is LDA (with Harris functional and local basis) molecular dynamics simulations. The surface is modeled by a 216 atom slab supercell. Several candidate slabs are constructed by starting with the DTW model (B.R. Djordjevic, M.F. Thorpe and F. Wooten, Phys. Rev. B 52) 5685 (1995) and applying various simulated heating/quenching cycles. We analyze the structural and electronic properties of the surface , with special attention forcused on the electronic signatures of surface structural defects. Preliminary results indicate that the surface layer significantly graphitizes, and many surface gap states are present in the electronic density of states.

  15. Electronic, magnetic, and geometric structure of metallo-carbohedrenes

    SciTech Connect

    Reddy, B.V.; Khanna, S.N.; Jena, P. )

    1992-12-04

    The energetics and the electronic, magnetic, and geometric structure of the metallocarbohedrene Ti[sub 8]C[sub 12] have been calculated self-consistently in the density functional formulation. The structure of Ti[sub 8]C[sub 12] is a distorted dodecahedron with a binding energy of 6.1 electron volts per atom. The unusual stability is derived from covalent-like bonding between carbon atoms and between titanium and carbon atoms with no appreciable interaction between titanium atoms. The density of states at the Fermi energy is high and is derived from a strong hybridization between titanium 3d and carbon sp electrons. Titanium sites carry a small magnetic moment of 0.35 Bohr magneton per atom and the cluster is only weakly magnetic. 13 refs., 3 figs., 1 tab.

  16. Electronic origin of structural transition in 122 Fe based superconductors

    NASA Astrophysics Data System (ADS)

    Ghosh, Haranath; Sen, Smritijit; Ghosh, Abyay

    2017-03-01

    Direct quantitative correlations between the orbital order and orthorhombicity is achieved in a number of Fe-based superconductors of 122 family. The former (orbital order) is calculated from first principles simulations using experimentally determined doping and temperature dependent structural parameters while the latter (the orthorhombicity) is taken from already established experimental studies; when normalized, both the above quantities quantitatively corresponds to each other in terms of their doping as well as temperature variations. This proves that the structural transition in Fe-based materials is electronic in nature due to orbital ordering. An universal correlations among various structural parameters and electronic structure are also obtained. Most remarkable among them is the mapping of two Fe-Fe distances in the low temperature orthorhombic phase, with the band energies Edxz, Edyz of Fe at the high symmetry points of the Brillouin zone. The fractional co-ordinate zAs of As which essentially determines anion height is inversely (directly) proportional to Fe-As bond distances (with exceptions of K doped BaFe2As2) for hole (electron) doped materials as a function of doping. On the other hand, Fe-As bond-distance is found to be inversely (directly) proportional to the density of states at the Fermi level for hole (electron) doped systems. Implications of these results to current issues of Fe based superconductivity are discussed.

  17. Highlighting material structure with transmission electron diffraction correlation coefficient maps.

    PubMed

    Kiss, Ákos K; Rauch, Edgar F; Lábár, János L

    2016-04-01

    Correlation coefficient maps are constructed by computing the differences between neighboring diffraction patterns collected in a transmission electron microscope in scanning mode. The maps are shown to highlight material structural features like grain boundaries, second phase particles or dislocations. The inclination of the inner crystal interfaces are directly deduced from the resulting contrast.

  18. Electron Heat Flux in Pressure Balance Structures at Ulysses

    NASA Technical Reports Server (NTRS)

    Yamauchi, Yohei; Suess, Steven T.; Sakurai, Takashi; Whitaker, Ann F. (Technical Monitor)

    2001-01-01

    Pressure balance structures (PBSs) are a common feature in the high-latitude solar wind near solar minimum. Rom previous studies, PBSs are believed to be remnants of coronal plumes and be related to network activity such as magnetic reconnection in the photosphere. We investigated the magnetic structures of the PBSs, applying a minimum variance analysis to Ulysses/Magnetometer data. At 2001 AGU Spring meeting, we reported that PBSs have structures like current sheets or plasmoids, and suggested that they are associated with network activity at the base of polar plumes. In this paper, we have analyzed high-energy electron data at Ulysses/SWOOPS to see whether bi-directional electron flow exists and confirm the conclusions more precisely. As a result, although most events show a typical flux directed away from the Sun, we have obtained evidence that some PBSs show bi-directional electron flux and others show an isotropic distribution of electron pitch angles. The evidence shows that plasmoids are flowing away from the Sun, changing their flow direction dynamically in a way not caused by Alfven waves. From this, we have concluded that PBSs are generated due to network activity at the base of polar plumes and their magnetic structures axe current sheets or plasmoids.

  19. Structural and electronic properties of perylene from first principles calculations.

    PubMed

    Fedorov, I A; Zhuravlev, Y N; Berveno, V P

    2013-03-07

    The electronic structure of crystalline perylene has been investigated within the framework of density functional theory including van der Waals interactions. The computations of the lattice parameters and cohesive energy have good agreement with experimental values. We have also calculated the binding distance and energy of perylene dimers, using different schemes, which include van der Waals interactions.

  20. Synchrotron-Radiation-based Investigationsof the Electronic Structure of Pu

    SciTech Connect

    Tobin, J; Chung, B; Terry, J; Schulze, R; Farr, J; Heinzelman, K; Rotenberg, E; Shuh, D

    2004-09-27

    Synchrotron radiation from the Advanced Light Source has been used to investigate the electronic structure of {alpha}-Pu and {delta}-Pu. Measurements include core level and valence band photoelectron spectroscopy, Resonant Photoelectron Spectroscopy (REPES), and X-ray Absorption Spectroscopy (XAS).

  1. Geometric and electronic structures of potassium-adsorbed rubrene complexes

    SciTech Connect

    Li, Tsung-Lung; Lu, Wen-Cai

    2015-06-28

    The geometric and electronic structures of potassium-adsorbed rubrene complexes are studied in this article. It is found that the potassium-rubrene (K{sub 1}RUB) complexes inherit the main symmetry characteristics from their pristine counterparts and are thus classified into D{sub 2}- and C{sub 2h}-like complexes according to the relative orientations of the four phenyl side groups. The geometric structures of K{sub 1}RUB are governed by two general effects on the total energy: Deformation of the carbon frame of the pristine rubrene increases the total energy, while proximity of the potassium ion to the phenyl ligands decreases the energy. Under these general rules, the structures of D{sub 2}- and C{sub 2h}-like K{sub 1}RUB, however, exhibit their respective peculiarities. These peculiarities can be illustrated by their energy profiles of equilibrium structures. For the potassium adsorption-sites, the D{sub 2}-like complexes show minimum-energy basins, whereas the C{sub 2h}-like ones have single-point minimum-energies. If the potassium atom ever has the energy to diffuse from the minimum-energy site, the potassium diffusion path on the D{sub 2}-like complexes is most likely along the backbone in contrast to the C{sub 2h}-like ones. Although the electronic structures of the minimum-energy structures of D{sub 2}- and C{sub 2h}-like K{sub 1}RUB are very alike, decompositions of their total spectra reveal insights into the electronic structures. First, the spectral shapes are mainly determined by the facts that, in comparison with the backbone carbons, the phenyl carbons have more uniform chemical environments and far less contributions to the electronic structures around the valence-band edge. Second, the electron dissociated from the potassium atom mainly remains on the backbone and has little effects on the electronic structures of the phenyl groups. Third, the two phenyls on the same side of the backbone as the potassium atom have more similar chemical environments

  2. Bidentate organophosphorus solvent extraction process for actinide recovery and partition

    DOEpatents

    Schulz, Wallace W.

    1976-01-01

    A liquid-liquid extraction process for the recovery and partitioning of actinide values from acidic nuclear waste aqueous solutions, the actinide values including trivalent, tetravalent and hexavalent oxidation states is provided and includes the steps of contacting the aqueous solution with a bidentate organophosphorous extractant to extract essentially all of the actinide values into the organic phase. Thereafter the respective actinide fractions are selectively partitioned into separate aqueous solutions by contact with dilute nitric or nitric-hydrofluoric acid solutions. The hexavalent uranium is finally removed from the organic phase by contact with a dilute sodium carbonate solution.

  3. Development of the Actinide-Lanthanide Separation (ALSEP) Process

    SciTech Connect

    Lumetta, Gregg J.; Carter, Jennifer C.; Niver, Cynthia M.; Gelis, Artem V.

    2014-09-30

    Separating the minor actinide elements (Am and Cm) from acidic high-level raffinates arising from the reprocessing of irradiated nuclear fuel is an important step in closing the nuclear fuel cycle. Most proposed approaches to this problem involve two solvent extraction steps: 1) co-extraction of the trivalent lanthanides and actinides, followed by 2) separation of the actinides from the lanthanides. The objective of our work is to develop a single solvent-extraction process for isolating the minor actinide elements. We report here a solvent containing N,N,N',N'-tetra(2 ethylhexyl)diglycolamide (T2EHDGA) combined with 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) that can be used to separate the minor actinides in a single solvent-extraction process. T2EHDGA serves to co-extract the trivalent actinide and lanthanide ions from nitric acid solution. Switching the aqueous phase chemistry to a citrate buffered solution of N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid at pH 2.5 to 4 results in selective transfer of the actinides to the aqueous phase, thus affecting separation of the actinides from the lanthanides. Separation factors between the lanthanides and actinides are approximately 20 in the pH range of 3 to 4, and the distribution ratios are not highly dependent on the pH in this system.

  4. Writing Electron Dot Structures: Abstract of Issue 9905M

    NASA Astrophysics Data System (ADS)

    Magnell, Kenneth R.

    1999-10-01

    Writing Electron Dot Structures is a computer program for Mac OS that provides drill with feedback for students learning to write electron dot structures. While designed for students in the first year of college general chemistry it may also be used by high school chemistry students. A systematic method similar to that found in many general chemistry texts is employed:

    1. determine the number of valence shell electrons,
    2. select the central atom,
    3. construct a skeleton,
    4. add electrons to complete octets,
    5. examine the structure for resonance forms.
    During the construction of a structure, the student has the option of quitting, selecting another formula, or returning to a previous step. If an incorrect number of electrons is entered the student may not proceed until the correct number is entered. The symbol entered for the central atom must follow accepted upper/lower case practice, and entry of the correct symbol must be accomplished before proceeding to the next step. A periodic table is accessible and feedback provides assistance for these steps. Construction of the skeleton begins with the placement of the central atom. Atoms can be added, moved, or removed. Prompts and feedback keep the student informed of progress and problems. A correct skeleton is required before proceeding to the next step. Completion of the structure begins with the addition of electron pairs to form the required bonds. Remaining electrons are added to complete the formation of multiple bonds, assure compliance with the octet rule, and form expanded octets. Resonance forms are made by moving or removing and replacing electron pairs in the existing skeleton. Prompts and feedback guide the student through this process. A running tally of bond pairs, unshared pairs, octets, electrons used, and electrons remaining is provided during this step. Structural and Electronic Investigations of Complex Intermetallic Compounds

    SciTech Connect

    Ko, Hyunjin

    2008-01-01

    In solid state chemistry, numerous investigations have been attempted to address the relationships between chemical structure and physical properties. Such questions include: (1) How can we understand the driving forces of the atomic arrangements in complex solids that exhibit interesting chemical and physical properties? (2) How do different elements distribute themselves in a solid-state structure? (3) Can we develop a chemical understanding to predict the effects of valence electron concentration on the structures and magnetic ordering of systems by both experimental and theoretical means? Although these issues are relevant to various compound classes, intermetallic compounds are especially interesting and well suited for a joint experimental and theoretical effort. For intermetallic compounds, the questions listed above are difficult to answer since many of the constituent atoms simply do not crystallize in the same manner as in their separate, elemental structures. Also, theoretical studies suggest that the energy differences between various structural alternatives are small. For example, Al and Ga both belong in the same group on the Periodic Table of Elements and share many similar chemical properties. Al crystallizes in the fcc lattice with 4 atoms per unit cell and Ga crystallizes in an orthorhombic unit cell lattice with 8 atoms per unit cell, which are both fairly simple structures (Figure 1). However, when combined with Mn, which itself has a very complex cubic crystal structure with 58 atoms per unit cell, the resulting intermetallic compounds crystallize in a completely different fashion. At the 1:1 stoichiometry, MnAl forms a very simple tetragonal lattice with two atoms per primitive unit cell, while MnGa crystallizes in a complicated rhombohedral unit cell with 26 atoms within the primitive unit cell. The mechanisms influencing the arrangements of atoms in numerous crystal structures have been studied theoretically by calculating electronic

  5. Structural and electronic properties of UnOm (n=1-3,m=1-3n) clusters: A theoretical study using screened hybrid density functional theory.

    PubMed

    Yang, Yu; Liu, Haitao; Zhang, Ping

    2016-05-14

    The structural and electronic properties of small uranium oxide clusters UnOm (n=1-3, m=1-3n) are systematically studied within the screened hybrid density functional theory. It is found that the formation of U-O-U bondings and isolated U-O bonds are energetically more stable than U-U bondings. As a result, no uranium cores are observed. Through fragmentation studies, we find that the UnOm clusters with the m/n ratio between 2 and 2.5 are very stable, hinting that UO2+x hyperoxides are energetically stable. Electronically, we find that the O-2p states always distribute in the deep energy range, and the U-5f states always distribute at the two sides of the Fermi level. The U-6d states mainly hybridize with the U-5f states in U-rich clusters, while hybridizing with O-2p states in O-rich clusters. Our work is the first one on the screened hybrid density functional theory level studying the atomic and electronic properties of the actinide oxide clusters.

  6. Shigella flexneri Spa15 Crystal Structure Verified in Solution by Double Electron Electron Resonance

    PubMed Central

    Lillington, James E.D.; Lovett, Janet E.; Johnson, Steven; Roversi, Pietro; Timmel, Christiane R.; Lea, Susan M.

    2011-01-01

    Shigella flexneri Spa15 is a chaperone of the type 3 secretion system, which binds a number of effectors to ensure their stabilization prior to secretion. One of these effectors is IpgB1, a mimic of the human Ras-like Rho guanosine triphosphatase RhoG. In this study, Spa15 alone and in complex with IpgB1 has been studied by double electron electron resonance, an experiment that gives distance information showing the spacial separation of attached spin labels. This distance is explained by determining the crystal structure of the spin-labeled Spa15 where labels are seen to be buried in hydrophobic pockets. The double electron electron resonance experiment on the Spa15 complex with IpgB1 shows that IpgB1 does not bind Spa15 in the same way as is seen in the homologous Salmonella sp. chaperone:effector complex InvB:SipA. PMID:21075116

  7. Thermoelectric power as a probe of density of states in correlated actinide materials: The case of PuCoGa5 superconductor

    NASA Astrophysics Data System (ADS)

    Gofryk, K.; Griveau, J.-C.; Riseborough, P. S.; Durakiewicz, T.

    2016-11-01

    We present measurements of the thermoelectric power of the plutonium-based unconventional superconductor PuCoGa5. The data is interpreted within a phenomenological model for the quasiparticle density of states of intermediate valence systems, and the results are compared with results obtained from photoemission spectroscopy. The results are consistent with the intermediate valence nature of 5 f electrons; furthermore, we propose that measurements of the Seebeck coefficient can be used as a probe of density of states in this material, thereby providing a link between transport measurements and photoemission in strongly correlated materials. We discuss these results and their implications for the electronic structure determination of other strongly correlated systems, especially actinide materials.

  8. Electronic structure tuning via surface modification in semimetallic nanowires

    NASA Astrophysics Data System (ADS)

    Sanchez-Soares, Alfonso; O'Donnell, Conor; Greer, James C.

    2016-12-01

    Electronic structure properties of nanowires (NWs) with diameters of 1.5 and 3 nm based on semimetallic α -Sn are investigated by employing density functional theory and perturbative GW methods. We explore the dependence of electron affinity, band structure, and band-gap values with crystallographic orientation, NW cross-sectional size, and surface passivants of varying electronegativity. We consider four chemical terminations in our study: methyl (CH3), hydrogen (H ), hydroxyl (OH ), and fluorine (F ). Results suggest a high degree of elasticity of Sn-Sn bonds within the Sn NWs' cores with no significant structural variations for nanowires with different surface passivants. Direct band gaps at Brillouin-zone centers are found for most studied structures with quasiparticle corrected band-gap magnitudes ranging from 0.25 to 3.54 eV in 1.5-nm-diameter structures, indicating an exceptional range of properties for semimetal NWs below the semimetal-to-semiconductor transition. Band-gap variations induced by changes in surface passivants indicate the possibility of realizing semimetal-semiconductor interfaces in NWs with constant cross-section and crystallographic orientation, allowing the design of novel dopant-free NW-based electronic devices.

  9. Solid-state actinide acid phosphites from phosphorous acid melts

    SciTech Connect

    Oh, George N.; Burns, Peter C.

    2014-07-01

    The reaction of UO{sub 3} and H{sub 3}PO{sub 3} at 100 °C and subsequent reaction with dimethylformamide (DMF) produces crystals of the compound (NH{sub 2}(CH{sub 3}){sub 2})[UO{sub 2}(HPO{sub 2}OH)(HPO{sub 3})]. This compound crystallizes in space group P2{sub 1}/n and consists of layers of uranyl pentagonal bipyramids that share equatorial vertices with phosphite units, separated by dimethylammonium. In contrast, the reaction of phosphorous acid and actinide oxides at 210 °C produces a viscous syrup. Subsequent dilution in solvents and use of standard solution-state methods results in the crystallization of two polymorphs of the actinide acid phosphites An(HPO{sub 2}OH){sub 4} (An=U, Th) and of the mixed acid phosphite–phosphite U(HPO{sub 3})(HPO{sub 2}OH){sub 2}(H{sub 2}O)·2(H{sub 2}O). α- and β-An(HPO{sub 2}OH){sub 4} crystallize in space groups C2/c and P2{sub 1}/n, respectively, and comprise a three-dimensional network of An{sup 4+} cations in square antiprismatic coordination corner-sharing with protonated phosphite units, whereas U(HPO{sub 3})(HPO{sub 2}OH){sub 2}(H{sub 2}O){sub 2}·(H{sub 2}O) crystallizes in a layered structure in space group Pbca that is composed of An{sup 4+} cations in square antiprismatic coordination corner-sharing with protonated phosphites and water ligands. We discuss our findings in using solid inorganic reagents to produce a solution-workable precursor from which solid-state compounds can be crystallized. - Graphical abstract: Reaction of UO{sub 3} and H{sub 3}PO{sub 3} at 100 °C and subsequent reaction with DMF produces crystals of (NH{sub 2}(CH{sub 3}){sub 2})[UO{sub 2}(HPO{sub 2}OH)(HPO{sub 3})] with a layered structure. Reaction of phosphorous acid and actinide oxides at 210 °C produces a viscous syrup and further solution-state reactions result in the crystallization of the actinide acid phosphites An(HPO{sub 2}OH){sub 4} (An=U, Th), with a three-dimensional network structure, and the mixed acid phosphite

  10. Molecular and electronic structures of cerium and cerium suboxide clusters

    NASA Astrophysics Data System (ADS)

    Kafader, Jared O.; Topolski, Josey E.; Jarrold, Caroline Chick

    2016-10-01

    The anion photoelectron (PE) spectra of Ce2Oy- (y = 1, 2), Ce3Oy- (y = 0-4), Ce4Oy- (y = 0-2), and Ce5Oy- (y = 1, 2) are reported and analyzed with supporting results from density functional theory calculations. The PE spectra all exhibit an intense electronic transition to the neutral ground state, all falling in the range of 0.7 to 1.1 eV electron binding energy, with polarization dependence consistent with detachment from diffuse Ce 6s-based molecular orbitals. There is no monotonic increase in electron affinity with increasing oxidation. A qualitative picture of how electronic structure evolves with an oxidation state emerges from comparison between the spectra and the computational results. The electronic structure of the smallest metallic cluster observed in this study, Ce3, is similar to the bulk structure in terms of atomic orbital occupancy (4f 5d2 6s). Initial cerium cluster oxidation involves largely ionic bond formation via Ce 5d and O 2p orbital overlap (i.e., larger O 2p contribution), with Ce—O—Ce bridge bonding favored over Ce=O terminal bond formation. With subsequent oxidation, the Ce 5d-based molecular orbitals are depleted of electrons, with the highest occupied orbitals described as diffuse Ce 6s based molecular orbitals. In the y ≤ (x + 1) range of oxidation states, each Ce center has a singly occupied non-bonding 4f orbital. The PE spectrum of Ce3O4- is unique in that it exhibits a single nearly vertical transition. The highly symmetric structure predicted computationally is the same structure determined from Ce3O4+ IR predissociation spectra [A. M. Burow et al., Phys. Chem. Chem. Phys. 13, 19393 (2011)], indicating that this structure is stable in -1, 0, and +1 charge states. Spectra of clusters with x ≥ 3 exhibit considerable continuum signal above the ground state transition; the intensity of the continuum signal decreases with increasing oxidation. This feature is likely the result of numerous quasi-bound anion states or two-electron

  11. Defective graphene and nanoribbons: electronic, magnetic and structural properties

    NASA Astrophysics Data System (ADS)

    Guerra, Thiago; Azevedo, Sérgio; Machado, Marcelo

    2016-03-01

    We make use of first-principles calculations, based on the density functional theory (DFT), to investigate the alterations at the structural, energetic, electronic and magnetic properties of graphene and zigzag graphene nanoribbons (ZGNRs) due to the inclusion of different types of line and punctual defects. For the graphene it is found that the inclusion of defects breaks the translational symmetry of the crystal with drastic changes at its electronic structure, going from semimetallic to semiconductor and metallic. Regarding the magnetic properties, no magnetization is observed for the defective graphene. We also show that the inclusion of defects at ZGNRs is a good way to create and control pronounced peaks at the Fermi level. Furthermore, defective ZGNRs structures show magnetic moment by supercell up to 2.0 μ B . For the non defective ZGNRs is observed a switch of the magnetic coupling between opposite ribbon edges from the antiferromagnetic to the ferrimagnetic and ferromagnetic configurations.

  12. Biomechanics of DNA structures visualized by 4D electron microscopy

    PubMed Central

    Lorenz, Ulrich J.; Zewail, Ahmed H.

    2013-01-01

    We present a technique for in situ visualization of the biomechanics of DNA structural networks using 4D electron microscopy. Vibrational oscillations of the DNA structure are excited mechanically through a short burst of substrate vibrations triggered by a laser pulse. Subsequently, the motion is probed with electron pulses to observe the impulse response of the specimen in space and time. From the frequency and amplitude of the observed oscillations, we determine the normal modes and eigenfrequencies of the structures involved. Moreover, by selective “nano-cutting” at a given point in the network, it was possible to obtain Young’s modulus, and hence the stiffness, of the DNA filament at that position. This experimental approach enables nanoscale mechanics studies of macromolecules and should find applications in other domains of biological networks such as origamis. PMID:23382239

  13. Characterization of electronic structure of periodically strained graphene

    SciTech Connect

    Aslani, Marjan; Garner, C. Michael Nishi, Yoshio; Kumar, Suhas; Nordlund, Dennis; Pianetta, Piero

    2015-11-02

    We induced periodic biaxial tensile strain in polycrystalline graphene by wrapping it over a substrate with repeating pillar-like structures with a periodicity of 600 nm. Using Raman spectroscopy, we determined to have introduced biaxial strains in graphene in the range of 0.4% to 0.7%. Its band structure was characterized using photoemission from valance bands, shifts in the secondary electron emission, and x-ray absorption from the carbon 1s levels to the unoccupied graphene conduction bands. It was observed that relative to unstrained graphene, strained graphene had a higher work function and higher density of states in the valence and conduction bands. We measured the conductivity of the strained and unstrained graphene in response to a gate voltage and correlated the changes in their behavior to the changes in the electronic structure. From these sets of data, we propose a simple band diagram representing graphene with periodic biaxial strain.

  14. Characterization of electronic structure of periodically strained graphene

    SciTech Connect

    Aslani, Marjan; Garner, C. Michael; Kumar, Suhas; Nordlund, Dennis; Pianetta, Piero; Nishi, Yoshio

    2015-11-03

    We induced periodic biaxial tensile strain in polycrystalline graphene by wrapping it over a substrate with repeating pillar-like structures with a periodicity of 600 nm. Using Raman spectroscopy, we determined to have introduced biaxial strains in graphene in the range of 0.4% to 0.7%. Its band structure was characterized using photoemission from valance bands, shifts in the secondary electron emission, and x-ray absorption from the carbon 1s levels to the unoccupied graphene conduction bands. It was observed that relative to unstrained graphene, strained graphene had a higher work function and higher density of states in the valence and conduction bands. Furthermore, we measured the conductivity of the strained and unstrained graphene in response to a gate voltage and correlated the changes in their behavior to the changes in the electronic structure. From these sets of data, we propose a simple band diagram representing graphene with periodic biaxial strain.

  15. Local atomic order, electronic structure and electron transport properties of Cu-Zr metallic glasses

    NASA Astrophysics Data System (ADS)

    Antonowicz, J.; Pietnoczka, A.; Pekała, K.; Latuch, J.; Evangelakis, G. A.

    2014-05-01

    We studied atomic and electronic structures of binary Cu-Zr metallic glasses (MGs) using combined experimental and computational methods including X-ray absorption fine structure spectroscopy, electrical resistivity, thermoelectric power (TEP) measurements, molecular dynamics (MD) simulations, and ab-initio calculations. The results of MD simulations and extended X-ray absorption fine structure analysis indicate that atomic order of Cu-Zr MGs and can be described in terms of interpenetrating icosahedral-like clusters involving five-fold symmetry. MD configurations were used as an input for calculations of theoretical electronic density of states (DOS) functions which exhibits good agreement with the experimental X-ray absorption near-edge spectra. We found no indication of minimum of DOS at Fermi energy predicted by Mott's nearly free electron (NFE) model for glass-forming alloys. The theoretical DOS was subsequently used to test Mott's model describing the temperature variation of electrical resistivity and thermoelectric power of transition metal-based MGs. We demonstrate that the measured temperature variations of electrical resistivity and TEP remain in a contradiction with this model. On the other hand, the experimental temperature dependence of electrical resistivity can be explained by incipient localization of conduction electrons. It is shown that weak localization model works up to relatively high temperatures when localization is destroyed by phonons. Our results indicate that electron transport properties of Cu-Zr MGs are dominated by localization effects rather than by electronic structure. We suggest that NFE model fails to explain a relatively high glass-forming ability of binary Cu-Zr alloys.

  16. Local atomic order, electronic structure and electron transport properties of Cu-Zr metallic glasses

    SciTech Connect

    Antonowicz, J. Pietnoczka, A.; Pękała, K.; Latuch, J.; Evangelakis, G. A.

    2014-05-28

    We studied atomic and electronic structures of binary Cu-Zr metallic glasses (MGs) using combined experimental and computational methods including X-ray absorption fine structure spectroscopy, electrical resistivity, thermoelectric power (TEP) measurements, molecular dynamics (MD) simulations, and ab-initio calculations. The results of MD simulations and extended X-ray absorption fine structure analysis indicate that atomic order of Cu-Zr MGs and can be described in terms of interpenetrating icosahedral-like clusters involving five-fold symmetry. MD configurations were used as an input for calculations of theoretical electronic density of states (DOS) functions which exhibits good agreement with the experimental X-ray absorption near-edge spectra. We found no indication of minimum of DOS at Fermi energy predicted by Mott's nearly free electron (NFE) model for glass-forming alloys. The theoretical DOS was subsequently used to test Mott's model describing the temperature variation of electrical resistivity and thermoelectric power of transition metal-based MGs. We demonstrate that the measured temperature variations of electrical resistivity and TEP remain in a contradiction with this model. On the other hand, the experimental temperature dependence of electrical resistivity can be explained by incipient localization of conduction electrons. It is shown that weak localization model works up to relatively high temperatures when localization is destroyed by phonons. Our results indicate that electron transport properties of Cu-Zr MGs are dominated by localization effects rather than by electronic structure. We suggest that NFE model fails to explain a relatively high glass-forming ability of binary Cu-Zr alloys.

  17. Advanced Aqueous Separation Systems for Actinide Partitioning

    SciTech Connect

    Nash, Ken; Martin, Leigh; Lumetta, Gregg

    2015-04-02

    One of the most challenging aspects of advanced processing of used nuclear fuel is the separation of transplutonium actinides from fission product lanthanides. This separation is essential if actinide transmutation options are to be pursued in advanced fuel cycles, as lanthanides compete with actinides for neutrons in both thermal and fast reactors, thus limiting efficiency. The separation is difficult because the chemistry of Am3+ and Cm3+ is nearly identical to that of the trivalent lanthanides (Ln3+). The prior literature teaches that two approaches offer the greatest probability of devising a successful group separation process based on aqueous processes: 1) the application of complexing agents containing ligand donor atoms that are softer than oxygen (N, S, Cl-) or 2) changing the oxidation state of Am to the IV, V, or VI state to increase the essential differences between Am and lanthanide chemistry (an approach utilized in the PUREX process to selectively remove Pu4+ and UO22+ from fission products). The latter approach offers the additional benefit of enabling a separation of Am from Cm, as Cm(III) is resistant to oxidation and so can easily be made to follow the lanthanides. The fundamental limitations of these approaches are that 1) the soft(er) donor atoms that interact more strongly with actinide cations than lanthanides form substantially weaker bonds than oxygen atoms, thus necessitating modification of extraction conditions for adequate phase transfer efficiency, 2) soft donor reagents have been seen to suffer slow phase transfer kinetics and hydro-/radiolytic stability limitations and 3) the upper oxidation states of Am are all moderately strong oxidants, hence of only transient stability in media representative of conventional aqueous separations systems. There are examples in the literature of both approaches having been described. However, it is not clear at present that any extant process is sufficiently robust for application at the scale

  18. Electronic structure of multi-walled carbon fullerenes

    NASA Astrophysics Data System (ADS)

    Doore, Keith; Cook, Matthew; Clausen, Eric; Lukashev, Pavel V.; Kidd, Tim E.; Stollenwerk, Andrew J.

    2017-02-01

    Despite an enormous amount of research on carbon based nanostructures, relatively little is known about the electronic structure of multi-walled carbon fullerenes, also known as carbon onions. In part, this is due to the very high computational expense involved in estimating electronic structure of large molecules. At the same time, experimentally, the exact crystal structure of the carbon onion is usually unknown, and therefore one relies on qualitative arguments only. In this work we present the results of a computational study on a series of multi-walled fullerenes and compare their electronic structures to experimental data. Experimentally, the carbon onions were fabricated using ultrasonic agitation of isopropanol alcohol and deposited onto the surface of highly ordered pyrolytic graphite using a drop cast method. Scanning tunneling microscopy images indicate that the carbon onions produced using this technique are ellipsoidal with dimensions on the order of 10 nm. The majority of differential tunneling spectra acquired on individual carbon onions are similar to that of graphite with the addition of molecular-like peaks, indicating that these particles span the transition between molecules and bulk crystals. A smaller, yet sizable number exhibited a semiconducting gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) levels. These results are compared with the electronic structure of different carbon onion configurations calculated using first-principles. Similar to the experimental results, the majority of these configurations are metallic with a minority behaving as semiconductors. Analysis of the configurations investigated here reveals that each carbon onion exhibiting an energy band gap consisted only of non-metallic fullerene layers, indicating that the interlayer interaction is not significant enough to affect the total density of states in these structures.

  19. Electronic structure and crystal phase stability of palladium hydrides

    SciTech Connect

    Houari, Abdesalem; Matar, Samir F.; Eyert, Volker

    2014-11-07

    The results of electronic structure calculations for a variety of palladium hydrides are presented. The calculations are based on density functional theory and used different local and semilocal approximations. The thermodynamic stability of all structures as well as the electronic and chemical bonding properties are addressed. For the monohydride, taking into account the zero-point energy is important to identify the octahedral Pd-H arrangement with its larger voids and, hence, softer hydrogen vibrational modes as favorable over the tetrahedral arrangement as found in the zincblende and wurtzite structures. Stabilization of the rocksalt structure is due to strong bonding of the 4d and 1s orbitals, which form a characteristic split-off band separated from the main d-band group. Increased filling of the formerly pure d states of the metal causes strong reduction of the density of states at the Fermi energy, which undermines possible long-range ferromagnetic order otherwise favored by strong magnetovolume effects. For the dihydride, octahedral Pd-H arrangement as realized, e.g., in the pyrite structure turns out to be unstable against tetrahedral arrangement as found in the fluorite structure. Yet, from both heat of formation and chemical bonding considerations, the dihydride turns out to be less favorable than the monohydride. Finally, the vacancy ordered defect phase Pd{sub 3}H{sub 4} follows the general trend of favoring the octahedral arrangement of the rocksalt structure for Pd:H ratios less or equal to one.

  1. Electronic structures of Ascaris trypsin inhibitor in solution

    NASA Astrophysics Data System (ADS)

    Zheng, Haoping

    2003-11-01

    The electronic structures of Ascaris trypsin inhibitor in solution are obtained by the first-principles, all-electron, ab initio calculation using the self-consistent cluster-embedding (SCCE) method. The inhibitor, made up of 62 amino acid residues with 912 atoms, has two three-dimensional solution structures: 1ata and 1atb. The calculated ground-state energy of structure 1atb is lower than that of structure 1ata by 6.12 eV. The active sites are determined and explained: only structure 1atb has a N terminal at residue ARG+31. This shows that the structure 1atb is the stable and active form of the inhibitor, which is in agreement with the experimental results. The calculation reveals that some parts of the inhibitor can be easily changed while the inhibitor’s biological activity may be kept. This kind of information may be helpful in fighting viruses such as AIDS, SARS, and flu, since these viruses have higher variability. The calculation offers an independent theoretical estimate of the precision of structure determination.

  2. Electronic structure and crystal phase stability of palladium hydrides

    NASA Astrophysics Data System (ADS)

    Houari, Abdesalem; Matar, Samir F.; Eyert, Volker

    2014-11-01

    The results of electronic structure calculations for a variety of palladium hydrides are presented. The calculations are based on density functional theory and used different local and semilocal approximations. The thermodynamic stability of all structures as well as the electronic and chemical bonding properties are addressed. For the monohydride, taking into account the zero-point energy is important to identify the octahedral Pd-H arrangement with its larger voids and, hence, softer hydrogen vibrational modes as favorable over the tetrahedral arrangement as found in the zincblende and wurtzite structures. Stabilization of the rocksalt structure is due to strong bonding of the 4d and 1s orbitals, which form a characteristic split-off band separated from the main d-band group. Increased filling of the formerly pure d states of the metal causes strong reduction of the density of states at the Fermi energy, which undermines possible long-range ferromagnetic order otherwise favored by strong magnetovolume effects. For the dihydride, octahedral Pd-H arrangement as realized, e.g., in the pyrite structure turns out to be unstable against tetrahedral arrangement as found in the fluorite structure. Yet, from both heat of formation and chemical bonding considerations, the dihydride turns out to be less favorable than the monohydride. Finally, the vacancy ordered defect phase Pd3H4 follows the general trend of favoring the octahedral arrangement of the rocksalt structure for Pd:H ratios less or equal to one.

  3. Electronic and structural reconstruction in titanate heterostructures from first principles

    NASA Astrophysics Data System (ADS)

    Mulder, Andrew T.; Fennie, Craig J.

    2014-03-01

    Recent advances in transition metal oxide heterostructures have opened new routes to create materials with novel functionalities and properties. One direction has been to combine a Mott insulating perovskite with an electronic d1 configuration, such as LaTiO3, with a band insulating d0 perovskite, such as SrTiO3. An exciting recent development is the demonstration of interfacial conductivity in GdTiO3/SrTiO3 heterostructures that display a complex structural motif of octahedral rotations and ferromagnetic properties similar to bulk GdTiO3. In this talk we present our first principles investigation of the interplay of structural, electronic, magnetic, and orbital degrees of freedom for a wide range of d1/d0 titanate heterostructures. We find evidence for both rotation driven ferroelectricity and a symmetry breaking electronic reconstruction with a concomitant structural distortion at the interface. We argue that these materials represent an ideal platform to realize novel functionalities such as the electric field control of electronic and magnetic properties.

  4. Toward the origin of exciton electronic structure in phycobiliproteins

    NASA Astrophysics Data System (ADS)

    Womick, Jordan M.; Miller, Stephen A.; Moran, Andrew M.

    2010-07-01

    Femtosecond laser spectroscopies are used to examine the electronic structures of two proteins found in the phycobilisome antenna of cyanobacteria, allophycocyanin (APC) and C-phycocyanin (CPC). The wave function composition involving the pairs of phycocyanobilin pigments (i.e., dimers) found in both proteins is the primary focus of this investigation. Despite their similar geometries, earlier experimental studies conducted in our laboratory and elsewhere observe clear signatures of exciton electronic structure in APC but not CPC. This issue is further investigated here using new experiments. Transient grating (TG) experiments employing broadband quasicontinuum probe pulses find a redshift in the signal spectrum of APC, which is almost twice that of CPC. Dynamics in the TG signal spectra suggest that the sub-100 fs dynamics in APC and CPC are respectively dominated by internal conversion and nuclear relaxation. A specialized technique, intraband electronic coherence spectroscopy (IECS), photoexcites electronic and nuclear coherences with nearly full suppression of signals corresponding to electronic populations. The main conclusion drawn by IECS is that dephasing of intraband electronic coherences in APC occurs in less than 25 fs. This result rules out correlated pigment fluctuations as the mechanism enabling exciton formation in APC and leads us to propose that the large Franck-Condon factors of APC promote wave function delocalization in the vibronic basis. For illustration, we compute the Hamiltonian matrix elements involving the electronic origin of the α84 pigment and the first excited vibronic level of the β84 pigment associated with a hydrogen out-of-plane wagging mode at 800 cm-1. For this pair of vibronic states, the -51 cm-1 coupling is larger than the 40 cm-1 energy gap, thereby making wave function delocalization a feasible prospect. By contrast, CPC possesses no pair of vibronic levels for which the intermolecular coupling is larger than the energy

  5. Grid-based electronic structure calculations: The tensor decomposition approach

    SciTech Connect

    Rakhuba, M.V.; Oseledets, I.V.

    2016-05-01

    We present a fully grid-based approach for solving Hartree–Fock and all-electron Kohn–Sham equations based on low-rank approximation of three-dimensional electron orbitals. Due to the low-rank structure the total complexity of the algorithm depends linearly with respect to the one-dimensional grid size. Linear complexity allows for the usage of fine grids, e.g. 8192{sup 3} and, thus, cheap extrapolation procedure. We test the proposed approach on closed-shell atoms up to the argon, several molecules and clusters of hydrogen atoms. All tests show systematical convergence with the required accuracy.

  6. Multi-million atom electronic structure calculations for quantum dots

    NASA Astrophysics Data System (ADS)

    Usman, Muhammad

    Quantum dots grown by self-assembly process are typically constructed by 50,000 to 5,000,000 structural atoms which confine a small, countable number of extra electrons or holes in a space that is comparable in size to the electron wavelength. Under such conditions quantum dots can be interpreted as artificial atoms with the potential to be custom tailored to new functionality. In the past decade or so, these nanostructures have attracted significant experimental and theoretical attention in the field of nanoscience. The new and tunable optical and electrical properties of these artificial atoms have been proposed in a variety of different fields, for example in communication and computing systems, medical and quantum computing applications. Predictive and quantitative modeling and simulation of these structures can help to narrow down the vast design space to a range that is experimentally affordable and move this part of nanoscience to nano-Technology. Modeling of such quantum dots pose a formidable challenge to theoretical physicists because: (1) Strain originating from the lattice mismatch of the materials penetrates deep inside the buffer surrounding the quantum dots and require large scale (multi-million atom) simulations to correctly capture its effect on the electronic structure, (2) The interface roughness, the alloy randomness, and the atomistic granularity require the calculation of electronic structure at the atomistic scale. Most of the current or past theoretical calculations are based on continuum approach such as effective mass approximation or k.p modeling capturing either no or one of the above mentioned effects, thus missing some of the essential physics. The Objectives of this thesis are: (1) to model and simulate the experimental quantum dot topologies at the atomistic scale; (2) to theoretically explore the essential physics i.e. long range strain, linear and quadratic piezoelectricity, interband optical transition strengths, quantum confined

  7. FY2011 Annual Report for the Actinide Isomer Detection Project

    SciTech Connect

    Warren, Glen A.; Francy, Christopher J.; Ressler, Jennifer J.; Erikson, Luke E.; Tatishvili, Gocha; Hatarik, R.

    2011-10-01

    This project seeks to identify a new signature for actinide element detection in active interrogation. This technique works by exciting and identifying long-lived nuclear excited states (isomers) in the actinide isotopes and/or primary fission products. Observation of isomers in the fission products will provide a signature for fissile material. For the actinide isomers, the decay time and energy of the isomeric state is unique to a particular isotope, providing an unambiguous signature for SNM. This project entails isomer identification and characterization and neutron population studies. This document summarizes activities from its third year - completion of the isomer identification characterization experiments and initialization of the neutron population experiments. The population and decay of the isomeric state in 235U remain elusive, although a number of candidate gamma rays have been identified. In the course of the experiments, a number of fission fragment isomers were populated and measured [Ressler 2010]. The decays from these isomers may also provide a suitable signature for the presence of fissile material. Several measurements were conducted throughout this project. This report focuses on the results of an experiment conducted collaboratively by PNNL, LLNL and LBNL in December 2010 at LBNL. The measurement involved measuring the gamma-rays emitted from an HEU target when bombarded with 11 MeV neutrons. This report discussed the analysis and resulting conclusions from those measurements. There was one strong candidate, at 1204 keV, of an isomeric signature of 235U. The half-life of the state is estimated to be 9.3 {mu}s. The measured time dependence fits the decay time structure very well. Other possible explanations for the 1204-keV state were investigated, but they could not explain the gamma ray. Unfortunately, the relatively limited statistics of the measurement limit, and the lack of understanding of some of the systematic of the experiment, limit

  8. Electronic structures of solids made of C20 clusters

    NASA Astrophysics Data System (ADS)

    Hussain, M. B.; Xu, L. H.; Wu, S. Q.; Zhu, Z. Z.

    2017-02-01

    By performing first-principles calculations based on the density functional theory, we have investigated the optimized structures, cohesive energies and electronic properties of crystalline solids made of C20 clusters. A very interesting result is found from the optimized diamond structure made of C20's, where the dimered C20 clusters, i.e., (C20)2 dimmers, are formed. Such (C20)2 dimers are then condensed by weak van der Waals interaction between them, leading to the formation of a molecular solid. We also found that one-dimensional molecular solid could be formed when C20 clusters are head to head. Results on C20 clusters arranged in the two-dimensional graphene structure and in fcc structure both show that there are significant coalescences of neighboring C20 fullerenes, leading to metallic characters for both the graphene and fcc structures.

  9. Antistiction technique using elastomer contact structure in woven electronic textiles

    NASA Astrophysics Data System (ADS)

    Yamashita, Takahiro; Takamatsu, Seiichi; Miyake, Koji; Itoh, Toshihiro

    2014-01-01

    In this paper, we present an antistiction technique using an elastomer contact structure in woven electronic textiles (e-textiles). A coating of poly(3,4-ethylenedioxythiophene):poly(4-styrene sulfonate) (PEDOT:PSS) in the form of a solid conductive film on a hemispherical silicone elastomer structure is employed in creating an electrical circuit embedded into the fabric of a woven e-textile, where the contact structure reduces the contact area and capillary force generated by the moisture in air between weft and warp ribbons. Stiction occurs between a weft and a warp without the contact structure under an RH of 80%, and the detachment of the stuck ribbon requires a delamination load of about 0.2 N. On the other hand, in the case of contact between the contact structure and the ribbon coated with plain PEDOT:PSS, stiction does not occur as the relative humidity increases from 20 to 80%.

  10. Fluctuation electron microscopy studies of complex structured materials

    NASA Astrophysics Data System (ADS)

    Zhao, Gongpu; Rougée, Annick; Buseck, Peter; Treacy, Michael

    2008-03-01

    Fluctuation electron microscopy (FEM) is a hybrid imaging-diffraction technique. This technique is particularly sensitive to paracrystalline structures of dimension 0.5-2 nm, which are difficult to detect by either imaging or diffraction techniques alone. It has been successfully deployed to study paracrystalline structures in amorphous silicon, germanium thin film. This technique has also been used to study metallic glasses and oxide glasses. Until now, FEM has not been used to study disordered geological materials. In this talk we present our FEM studies of shungite, a naturally occurring disordered carbonaceous material, reveal that trace quantities of tightly curved graphene structures such as C60, or fragments of C60, is present in shungite. We also present results from our study of metamict zircon, whose crystal structure is destroyed by self-radiation during naturally occurring α decay events. Work is in progress to study the structural evolution during the metamictization process.

  11. Electronic and Thermal Properties of Graphene and Carbon Structures

    NASA Astrophysics Data System (ADS)

    Anthony, Gilmore; Khatun, Mahfuza

    2011-10-01

    We will present the general properties of carbon structures. The research involves the study of carbon structures: Graphene, Graphene nanoribbons (GNRs), and Carbon Nanotubes (CNTs). A review of electrical and thermal conduction phenomena of the structures will be discussed. Particularly carbon nanoribbons and CNTs have many interesting physical properties, and have the potential for device applications. Our research interests include the study of electronic structures, electrical and thermal transport properties of the carbon structures. Results are produced analytically as well as by simulation. The numerical simulations are conducted using various tools such as Visual Molecular Dynamics (VMD), Large Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS), NanoHub at Purdue University and the Beowulf Cluster at Ball State University.

  12. Compressed Sensing Electron Tomography for Determining Biological Structure

    NASA Astrophysics Data System (ADS)

    Guay, Matthew D.; Czaja, Wojciech; Aronova, Maria A.; Leapman, Richard D.

    2016-06-01

    There has been growing interest in applying compressed sensing (CS) theory and practice to reconstruct 3D volumes at the nanoscale from electron tomography datasets of inorganic materials, based on known sparsity in the structure of interest. Here we explore the application of CS for visualizing the 3D structure of biological specimens from tomographic tilt series acquired in the scanning transmission electron microscope (STEM). CS-ET reconstructions match or outperform commonly used alternative methods in full and undersampled tomogram recovery, but with less significant performance gains than observed for the imaging of inorganic materials. We propose that this disparity stems from the increased structural complexity of biological systems, as supported by theoretical CS sampling considerations and numerical results in simulated phantom datasets. A detailed analysis of the efficacy of CS-ET for undersampled recovery is therefore complicated by the structure of the object being imaged. The numerical nonlinear decoding process of CS shares strong connections with popular regularized least-squares methods, and the use of such numerical recovery techniques for mitigating artifacts and denoising in reconstructions of fully sampled datasets remains advantageous. This article provides a link to the software that has been developed for CS-ET reconstruction of electron tomographic data sets.

  13. Oligothiophene wires: impact of torsional conformation on the electronic structure.

    PubMed

    Kislitsyn, D A; Taber, B N; Gervasi, C F; Zhang, L; Mannsfeld, S C B; Prell, J S; Briseno, A L; Nazin, G V

    2016-02-14

    Charge transport in polymer- and oligomer-based semiconductor materials depends strongly on the structural ordering of the constituent molecules. Variations in molecular conformations influence the electronic structures of polymers and oligomers, and thus impact their charge-transport properties. In this study, we used Scanning Tunneling Microscopy and Spectroscopy (STM/STS) to investigate the electronic structures of different alkyl-substituted oligothiophenes displaying varied torsional conformations on the Au(111) surface. STM imaging showed that on Au(111), oligothiophenes self-assemble into chain-like structures, binding to each other via interdigitated alkyl ligands. The molecules adopted distinct planar conformations with alkyl ligands forming cis- or trans- mutual orientations. For each molecule, by using STS mapping, we identify a progression of particle-in-a-box-like states corresponding to the LUMO, LUMO+1 and LUMO+2 orbitals. Analysis of STS data revealed very similar unoccupied molecular orbital energies for different possible molecular conformations. By using density functional theory calculations, we show that the lack of variation in molecular orbital energies among the different oligothiophene conformers implies that the effect of the Au-oligothiophene interaction on molecular orbital energies is nearly identical for all studied torsional conformations. Our results suggest that cis-trans torsional disorder may not be a significant source of electronic disorder and charge carrier trapping in organic semiconductor devices based on oligothiophenes.

  14. Electronic structural investigations of ruthenium compounds and anticancer prodrugs.

    PubMed

    Harris, Travis V; Szilagyi, Robert K; McFarlane Holman, Karen L

    2009-08-01

    Several Ru(III) compounds are propitious anticancer agents although the precise mechanisms of action remain unknown. With this paper we start to establish an experimental library of X-ray absorption spectroscopy (XAS) data for ten Ru compounds wherein the ligands [Cl(-), dimethyl sulfoxide, imidazole, and indazole] were varied systematically to provide electronic structural information for future use in correlating spectroscopic signatures with chemical properties. Despite the considerable difference in the coordination environments of the complexes studied, the overall differences in spectral features and electronic structures calculated using density functional theory are unexpectedly small. However, the differences in the electronic structure of the Ru(III) prodrugs KP1019 ([IndH][trans-RuCl(4)(Ind)(2)], Ind is indazole) and ICR ([ImH][trans-RuCl(4)(Im)(2)], Im is imidazole) observed in the XAS data show correlation with known chemical and biological activities in addition to the donor abilities of imidazole compared with indazole and reduction potentials of the complexes. These semiquantitative results lay the groundwork for future biochemical studies into the structure-function relationships of Ru-based anticancer drugs.

  15. Compressed Sensing Electron Tomography for Determining Biological Structure

    PubMed Central

    Guay, Matthew D.; Czaja, Wojciech; Aronova, Maria A.; Leapman, Richard D.

    2016-01-01

    There has been growing interest in applying compressed sensing (CS) theory and practice to reconstruct 3D volumes at the nanoscale from electron tomography datasets of inorganic materials, based on known sparsity in the structure of interest. Here we explore the application of CS for visualizing the 3D structure of biological specimens from tomographic tilt series acquired in the scanning transmission electron microscope (STEM). CS-ET reconstructions match or outperform commonly used alternative methods in full and undersampled tomogram recovery, but with less significant performance gains than observed for the imaging of inorganic materials. We propose that this disparity stems from the increased structural complexity of biological systems, as supported by theoretical CS sampling considerations and numerical results in simulated phantom datasets. A detailed analysis of the efficacy of CS-ET for undersampled recovery is therefore complicated by the structure of the object being imaged. The numerical nonlinear decoding process of CS shares strong connections with popular regularized least-squares methods, and the use of such numerical recovery techniques for mitigating artifacts and denoising in reconstructions of fully sampled datasets remains advantageous. This article provides a link to the software that has been developed for CS-ET reconstruction of electron tomographic data sets. PMID:27291259

  16. Real-time feedback from iterative electronic structure calculations.

    PubMed

    Vaucher, Alain C; Haag, Moritz P; Reiher, Markus

    2016-04-05

    Real-time feedback from iterative electronic structure calculations requires to mediate between the inherently unpredictable execution times of the iterative algorithm used and the necessity to provide data in fixed and short time intervals for real-time rendering. We introduce the concept of a mediator as a component able to deal with infrequent and unpredictable reference data to generate reliable feedback. In the context of real-time quantum chemistry, the mediator takes the form of a surrogate potential that has the same local shape as the first-principles potential and can be evaluated efficiently to deliver atomic forces as real-time feedback. The surrogate potential is updated continuously by electronic structure calculations and guarantees to provide a reliable response to the operator for any molecular structure. To demonstrate the application of iterative electronic structure methods in real-time reactivity exploration, we implement self-consistent semiempirical methods as the data source and apply the surrogate-potential mediator to deliver reliable real-time feedback.

  17. Specific sequestering agents for iron and the actinides

    SciTech Connect

    Raymond, K.N.

    1983-06-01

    The transuranium actinide ions represent one unique environmental hazard associated with the waste of the nuclear power industry. A major component associated with that waste and a potential hazard is plutonium. The synthesis of metal-ion-specific complexing agents for ions such as Pu(IV) potentially represents a powerful new approach to many of the problems posed by waste treatment. This document is a progress report of a rational approach to the synthesis of such chelating agents based on the similarities of Pu(IV) and Fe(III), the structures of naturally-occurring complexing agents which are highly specific for Fe(III), and the incorporation of the same kinds of ligating groups present in the iron complexes to make octadentate complexes highly specific for plutonium. Both thermodynamic and animal test results indicate that a relatively high degree of success has already been achieved in this aim.

  18. Structural, optical and electronic structure studies of Al doped ZnO thin films

    NASA Astrophysics Data System (ADS)

    Devi, Vanita; Kumar, Manish; Shukla, D. K.; Choudhary, R. J.; Phase, D. M.; Kumar, Ravindra; Joshi, B. C.

    2015-07-01

    Structural, optical and electronic structure of Al doped ZnO thin films grown using pulsed laser deposition on glass substrate are investigated. X-ray diffraction measurements reveal that all the films are textured along the c-axis and have wurtzite structure. Al doping in ZnO films leads to increase in grain size due to relaxation in compressive stress. Enhancement in band gap of ZnO films with the Al doping is also noticed which can be ascribed to the Brustein-Moss shift. The changes in the electronic structure caused by Al in the doped thin film samples are understood through X-ray absorption measurements.

  19. Electronic Structure of Crystalline 4He at High Pressure

    SciTech Connect

    Mao, H.K.; Cai, Y.; Shirley, E.L.; Ding, Y.; Eng, P.; Chow, P.; Xiao, Y.; Shu, J.; Hemley, R.J.; Kao, C.C.; Mao, W.L.

    2010-10-29

    Using inelastic x-ray scattering techniques, we have succeeded in probing the high-pressure electronic structure of helium at 300 K. Helium has the widest known valence-conduction band gap of all materials a property whose high-pressure response has been inaccessible to direct measurements. We observed a rich electron excitation spectrum, including a cutoff edge above 23 eV, a sharp exciton peak showing linear volume dependence, and a series of excitations and continuum at 26 to 45 eV. We determined the electronic dispersion along the {Gamma}-M direction over two Brillouin zones, and provided a quantitative picture of the helium exciton beyond the simplified Wannier-Frenkel description.

  20. Approximate ab initio calculations of electronic structure of amorphous silicon

    NASA Astrophysics Data System (ADS)

    Durandurdu, M.; Drabold, D. A.; Mousseau, N.

    2000-12-01

    We report on ab initio calculations of electronic states of two large and realistic models of amorphous silicon generated using a modified version of the Wooten-Winer-Weaire algorithm and relaxed, in both cases, with a Keating and a modified Stillinger-Weber potentials. The models have no coordination defects and a very narrow bond-angle distribution. We compute the electronic density-of-states and pay particular attention to the nature of the band-tail states around the electronic gap. All models show a large and perfectly clean optical gap and realistic Urbach tails. Based on these results and the extended quasi-one-dimensional stringlike structures observed for certain eigenvalues in the band tails, we postulate that the generation of model a-Si without localized states might be achievable under certain circumstances.

  1. DFT investigation on the electronic structure of Faujasite

    NASA Astrophysics Data System (ADS)

    Popeneciu, Horea; Calborean, Adrian; Tudoran, Cristian; Buimaga-Iarinca, Luiza

    2013-11-01

    We report here first-principle pseudopotential DFT calculations to investigate relevant aspects of the electronic structure of zeolites based FAU. Fundamental molecular issues of the band-gap and electronic population analysis were reviewed under GGA/RPBE level of theory, corroborated with a DZP basis set and Troullier-Martins norm conserving pseudo-potentials. The atom-projected density of states and the analysis of HOMO-LUMO frontier orbitals at Gamma point were performed. Their electronic transfers are discussed through the alignment and relative positions of orbitals in order to determine the way that the molecule interacts with adsorbed molecules and other practical applications. Mulliken population analysis was employed for describing atomic charge distribution in the chosen systems.

  2. Sorting carbon nanotubes by electronic structure using density differentiation.

    PubMed

    Arnold, Michael S; Green, Alexander A; Hulvat, James F; Stupp, Samuel I; Hersam, Mark C

    2006-10-01

    The heterogeneity of as-synthesized single-walled carbon nanotubes (SWNTs) precludes their widespread application in electronics, optics and sensing. We report on the sorting of carbon nanotubes by diameter, bandgap and electronic type using structure-discriminating surfactants to engineer subtle differences in their buoyant densities. Using the scalable technique of density-gradient ultracentrifugation, we have isolated narrow distributions of SWNTs in which >97% are within a 0.02-nm-diameter range. Furthermore, using competing mixtures of surfactants, we have produced bulk quantities of SWNTs of predominantly a single electronic type. These materials were used to fabricate thin-film electrical devices of networked SWNTs characterized by either metallic or semiconducting behaviour.

  3. Electronic structure and energetics of graphene antidot lattice

    NASA Astrophysics Data System (ADS)

    Sakurai, Masahiro; Saito, Susumu; Takada, Yasutami

    2012-02-01

    We have made a systematic study of the electronic structure and the energetics of graphene with periodic array of vacancy clusters (graphene antidot lattice) in the framework of the density-functional theory (DFT). We find that the electronic property of the system is well controlled by its lattice periodicity. More specifically, this system can be either metallic or semiconducting, depending on its lattice geometry. Interestingly, some of them are predicted to be direct-gap semiconductors. For example, graphene sheet with high-symmetry arrangements of periodic circle-shape vacancies always has a direct fundamental gap [1]. The DFT total-energy calculations indicate that the geometry of hole edges plays an important role in determining its stability. [1] ``Electronic properties of graphene and boron-nitride based nanostructured materials'' M. Sakurai, Y. Sakai, and S. Saito, J. Phys.: Conf. Ser. 302 (2011) 012018.

  4. Spatially Resolved Electronic Structures of Atomically Precise Armchair Graphene Nanoribbons

    PubMed Central

    Huang, Han; Wei, Dacheng; Sun, Jiatao; Wong, Swee Liang; Feng, Yuan Ping; Neto, A. H. Castro; Wee, Andrew Thye Shen

    2012-01-01

    Graphene has attracted much interest in both academia and industry. The challenge of making it semiconducting is crucial for applications in electronic devices. A promising approach is to reduce its physical size down to the nanometer scale. Here, we present the surface-assisted bottom-up fabrication of atomically precise armchair graphene nanoribbons (AGNRs) with predefined widths, namely 7-, 14- and 21-AGNRs, on Ag(111) as well as their spatially resolved width-dependent electronic structures. STM/STS measurements reveal their associated electron scattering patterns and the energy gaps over 1 eV. The mechanism to form such AGNRs is addressed based on the observed intermediate products. Our results provide new insights into the local properties of AGNRs, and have implications for the understanding of their electrical properties and potential applications. PMID:23248746

  5. Anomalous electronic structure and magnetoresistance in TaAs2

    PubMed Central

    Luo, Yongkang; McDonald, R. D.; Rosa, P. F. S.; Scott, B.; Wakeham, N.; Ghimire, N. J.; Bauer, E. D.; Thompson, J. D.; Ronning, F.

    2016-01-01

    The change in resistance of a material in a magnetic field reflects its electronic state. In metals with weakly- or non-interacting electrons, the resistance typically increases upon the application of a magnetic field. In contrast, negative magnetoresistance may appear under some circumstances, e.g., in metals with anisotropic Fermi surfaces or with spin-disorder scattering and semimetals with Dirac or Weyl electronic structures. Here we show that the non-magnetic semimetal TaAs2 possesses a very large negative magnetoresistance, with an unknown scattering mechanism. Density functional calculations find that TaAs2 is a new topological semimetal [ℤ2 invariant (0;111)] without Dirac dispersion, demonstrating that a negative magnetoresistance in non-magnetic semimetals cannot be attributed uniquely to the Adler-Bell-Jackiw chiral anomaly of bulk Dirac/Weyl fermions. PMID:27271852

  6. Anomalous electronic structure and magnetoresistance in TaAs2

    DOE PAGES

    Luo, Yongkang; McDonald, R. D.; Rosa, P. F. S.; ...

    2016-01-01

    We report that the change in resistance of a material in a magnetic field reflects its electronic state. In metals with weakly- or non-interacting electrons, the resistance typically increases upon the application of a magnetic field. In contrast, negative magnetoresistance may appear under some circumstances, e.g., in metals with anisotropic Fermi surfaces or with spin-disorder scattering and semimetals with Dirac or Weyl electronic structures. Here we show that the non-magnetic semimetal TaAs2 possesses a very large negative magnetoresistance, with an unknown scattering mechanism. In conclusion, density functional calculations find that TaAs2 is a new topological semimetal [Z2 invariant (0;111)] withoutmore » Dirac dispersion, demonstrating that a negative magnetoresistance in non-magnetic semimetals cannot be attributed uniquely to the Adler-Bell-Jackiw chiral anomaly of bulk Dirac/Weyl fermions.« less

  7. {ELECTRONIC Structure and Spectroscopy of O_2 and O_2^+}

    NASA Astrophysics Data System (ADS)

    Vazquez, Gabriel J.; Lefebvre-Brion, H.; Liebermann, Hans P.

    2014-06-01

    We carried out a comprehensive SCF MRD--CI ab initio study of the electronic structure of O_2 and O_2^+. Potential energy curves (PECs) of about 150 electronic states of O_2 and about 100 of O_2^+, as well as a number of states of O_2++ were computed. The cc--pVQZ basis set augmented with diffuse functions was employed. Spectroscopic parameters (T_e, T_v, ω_e, ω_ex_e, B_e, D_e, D_0, μ, IP, etc.) are reported. A preliminary sample of the results will be presented. The electronic absorption spectrum of O_2 has proved difficult to analyze/interpret due to the unusually large number of electronic states which arise from the peculiar open--shell structure of both the oxygen atomic fragments and the O_2 molecule. For instance, there are 62 valence molecular electronic states which correlate to the six lowest dissociation limits resulting from the three valence O atom fragment states (^3P, ^1D, ^1S). In addition, there are several nlλ Rydberg series converging to the X^2Π_g ground ionic state and to the lowest two excited states of the cation, a^4Π_u_i and A^2Π_u. Furthermore, a number of interactions of various types among several electronic states result in rovibronic perturbations which manifest themselves, e.g., as irregular vibronic structure, hence severely complicating the assignment of the absorption features and the analysis and interpretation of the spectrum. An overview of the electronic states and spectroscopy of O_2 will be presented. A chief motivation of this study of O_2 was to try to provide a theoretical insight on the nature, energetic position, shape, and dissociation asymptotes, of electronic states located in the 4 eV energy region encompassed between the O_2^+ ground state X^2Π_g (IP=12.07 eV) and the first excited state of the cation a^4Π_u_i (IP=16.10 eV). This in order to aid in the interpretation of experimental data related to the mechanism(s) of the neutral dissociation of the O_2** (Rydberg) superexcited states, which competes with

  8. Quantum mirages formed by coherent projection of electronic structure

    PubMed

    Manoharan; Lutz; Eigler

    2000-02-03

    Image projection relies on classical wave mechanics and the use of natural or engineered structures such as lenses or resonant cavities. Well-known examples include the bending of light to create mirages in the atmosphere, and the focusing of sound by whispering galleries. However, the observation of analogous phenomena in condensed matter systems is a more recent development, facilitated by advances in nanofabrication. Here we report the projection of the electronic structure surrounding a magnetic Co atom to a remote location on the surface of a Cu crystal; electron partial waves scattered from the real Co atom are coherently refocused to form a spectral image or 'quantum mirage'. The focusing device is an elliptical quantum corral, assembled on the Cu surface. The corral acts as a quantum mechanical resonator, while the two-dimensional Cu surface-state electrons form the projection medium. When placed on the surface, Co atoms display a distinctive spectroscopic signature, known as the many-particle Kondo resonance, which arises from their magnetic moment. By positioning a Co atom at one focus of the ellipse, we detect a strong Kondo signature not only at the atom, but also at the empty focus. This behaviour contrasts with the usual spatially-decreasing response of an electron gas to a localized perturbation.

  9. Perspective: Explicitly correlated electronic structure theory for complex systems

    NASA Astrophysics Data System (ADS)

    Grüneis, Andreas; Hirata, So; Ohnishi, Yu-ya; Ten-no, Seiichiro

    2017-02-01

    The explicitly correlated approach is one of the most important breakthroughs in ab initio electronic structure theory, providing arguably the most compact, accurate, and efficient ansatz for describing the correlated motion of electrons. Since Hylleraas first used an explicitly correlated wave function for the He atom in 1929, numerous attempts have been made to tackle the significant challenges involved in constructing practical explicitly correlated methods that are applicable to larger systems. These include identifying suitable mathematical forms of a correlated wave function and an efficient evaluation of many-electron integrals. R12 theory, which employs the resolution of the identity approximation, emerged in 1985, followed by the introduction of novel correlation factors and wave function ansätze, leading to the establishment of F12 theory in the 2000s. Rapid progress in recent years has significantly extended the application range of explicitly correlated theory, offering the potential of an accurate wave-function treatment of complex systems such as photosystems and semiconductors. This perspective surveys explicitly correlated electronic structure theory, with an emphasis on recent stochastic and deterministic approaches that hold significant promise for applications to large and complex systems including solids.

  10. Electronic absorption and ground state structure of carotenoid molecules.

    PubMed

    Mendes-Pinto, Maria M; Sansiaume, Elodie; Hashimoto, Hideki; Pascal, Andrew A; Gall, Andrew; Robert, Bruno

    2013-09-26

    Predicting the complete electronic structure of carotenoid molecules remains an extremely complex problem, particularly in anisotropic media such as proteins. In this paper, we address the electronic properties of nine relatively simple carotenoids by the combined use of electronic absorption and resonance Raman spectroscopies. Linear carotenoids exhibit an excellent correlation between (i) the inverse of their conjugation chain length N, (ii) the energy of their S0 → S2 electronic transition, and (iii) the position of their ν1 Raman band (corresponding to the stretching mode of their conjugated C═C bonds). For cyclic carotenoids such as β-carotene, this correlation is also observed between the latter two parameters (S0 → S2 energy and ν1 frequency), whereas their "nominal" conjugation length N does not follow the same relationship. We conclude that β-carotene and cyclic carotenoids in general exhibit a shorter effective conjugation length than that expected from their chemical structure. In addition, the effect of solvent polarizability on these molecular parameters was investigated for four of the carotenoids used in this study. We demonstrate that resonance Raman spectroscopy can discriminate between the different effects underlying shifts in the S0 → S2 transition of carotenoid molecules.

  11. Electronic Structure of Silicon Nanowires Matrix from Ab Initio Calculations

    NASA Astrophysics Data System (ADS)

    Monastyrskii, Liubomyr S.; Boyko, Yaroslav V.; Sokolovskii, Bogdan S.; Potashnyk, Vasylyna Ya.

    2016-01-01

    An investigation of the model of porous silicon in the form of periodic set of silicon nanowires has been carried out. The electronic energy structure was studied using a first-principle band method—the method of pseudopotentials (ultrasoft potentials in the basis of plane waves) and linearized mode of the method of combined pseudopotentials. Due to the use of hybrid exchange-correlation potentials (B3LYP), the quantitative agreement of the calculated value of band gap in the bulk material with experimental data is achieved. The obtained results show that passivation of dangling bonds with hydrogen atoms leads to substantial transformation of electronic energy structure. At complete passivation of the dangling silicon bonds by hydrogen atoms, the band gap value takes the magnitude which substantially exceeds that for bulk silicon. The incomplete passivation gives rise to opposite effect when the band gap value decreases down the semimetallic range.

  12. Strongly correlated electron materials. I. Theory of the quasiparticle structure

    SciTech Connect

    Lopez-Aguilar, F.; Costa-Quintana, J.; Puig-Puig, L. )

    1993-07-01

    In this paper we give a method for analyzing the renormalized electronic structure of the Hubbard systems. The first step is the determination of effective interactions from the random-phase approximation (RPA) and from an extended RPA (ERPA) that introduces vertex effects within the bubble polarization. The second step is the determination of the density of states deduced from the spectral functions. Its analysis leads us to conclude that these systems can exhibit three types of resonances in their electronic structures: the lower-, middle-, and upper-energy resonances. Furthermore, we analyze the conditions for which there is only one type of resonance and the causes that lead to the disappearance of the heavy-fermion state. We finally introduce the RPA and ERPA effective interactions within the strong-coupling theory and we give the conditions for obtaining coupling and superconductivity.

  13. Electronic structure of Gd-doped MgO

    NASA Astrophysics Data System (ADS)

    Lukoyanov, A. V.; Anisimov, V. I.

    2016-02-01

    The electronic structure of Gd-doped MgO is investigated using the LSDA+U (local spin density approximation with U-correction) method and compared with the MgO structure. The total density of states obtained accounting for the correlation effects in the 4 f shell of gadolinium is found to be formed by the oxygen 2 p states at the valence band and the 4 f gadolinium occupied states, while the conduction band is represented by a mixture of empty electronic states. Magnetic properties of the calculated Gd-doped MgO are found to be formed solely by the Gd-4 f-magnetic moment of about 7μB, in good agreement with recent experimental results suggesting a ferromagnetic coupling of the local magnetic moments induced by Gd.

  14. Atomic and electronic structure of Ni-Nb metallic glasses

    SciTech Connect

    Yuan, C. C.; Yang, Y.-F. Xi, X. K.

    2013-12-07

    Solid state {sup 93}Nb nuclear magnetic resonance spectroscopy has been employed to investigate the atomic and electronic structures in Ni-Nb based metallic glass (MG) model system. {sup 93}Nb nuclear magnetic resonance (NMR) isotropic metallic shift of Ni{sub 60}Nb{sub 35}Sn{sub 5} has been found to be ∼100 ppm lower than that of Ni{sub 60}Nb{sub 35}Zr{sub 5} MG, which is correlated with their intrinsic fracture toughness. The evolution of {sup 93}Nb NMR isotropic metallic shifts upon alloying is clearly an electronic origin, as revealed by both local hyperfine fields analysis and first-principle computations. This preliminary result indicates that, in addition to geometrical considerations, atomic form factors should be taken into a description of atomic structures for better understanding the mechanical behaviors of MGs.

  15. Structural and electronic properties of arsenic nitrogen monolayer

    NASA Astrophysics Data System (ADS)

    Liu, Pei; Nie, Yao-zhuang; Xia, Qing-lin; Guo, Guang-hua

    2017-03-01

    We present our first-principles calculations of a new two-dimensional material, arsenic nitrogen monolayer. The structural, electronic, and mechanical properties are investigated in detail by means of density functional theory computations. The calculated binding energy and the phonon spectra demonstrate that the AsN can form stable monolayer in puckered honeycomb structure. It is a semiconductor with indirect band gap of 0.73 eV, and displays highly anisotropic mechanical properties. Strain has obvious influence on the electronic properties of AsN monolayer. It is found that in the armchair direction, a moderate compression strain (-12%) can trigger an indirect to direct band gap transition and a tensile strain of 18% can make the AsN becoming a stable metal. In the zigzag direction, a rather smaller strain than armchair direction (12% for compression and 8% for stretch) can induce the indirect band gap to metal transition.

  16. Electronic structure of polyimide and related monomers: Theory and experiment

    NASA Astrophysics Data System (ADS)

    Kowalczyk, Steven P.; Stafström, Sven; Brédas, J. L.; Salaneck, William R.; Jordan-Sweet, Jean L.

    1990-01-01

    The electronic structure of polymide and several related compounds was investigated theoretically and experimentally. The compounds include pyromellitic dianhydride, oxydianiline, and polyamic acid. Experimental electronic-structure determinations for poly(methyl phenylene oxide) and poly(vinyl methyl ketone) are also reported. The theoretical approach employed valence-effective-Hamiltonian calculations. Photoelectron spectroscopy (x-ray photoelectron spectroscopy, soft-x-ray photoelectron spectroscopy, and ultraviolet photoelectron spectroscopy) was used to experimentally measure the total valence-band density of states (VBDOS) from thin films of the above compounds. The theoretical VBDOS's were cross-section modulated to facilitate comparison with experiment. Very good agreement is found between the theoretical results and the experimental VBDOS's.

  17. Electronic structure of spontaneously strained graphene on hexagonal boron nitride

    NASA Astrophysics Data System (ADS)

    San-Jose, Pablo; Gutiérrez-Rubio, A.; Sturla, Mauricio; Guinea, Francisco

    2014-09-01

    Hexagonal boron nitride substrates have been shown to dramatically improve the electric properties of graphene. Recently, it has been observed that when the two honeycomb crystals are close to perfect alignment, strong lattice distortions develop in graphene due to the moiré adhesion landscape. Simultaneously, a gap opens at the Dirac point. Here, we derive a simple low-energy electronic model for graphene aligned with the substrate, taking into account spontaneous strains at equilibrium and pseudogauge fields. We carry out a detailed characterization of the modified band structure, gap, local and global density of states, and band topology in terms of physical parameters. We show that the overall electronic structure is strongly modified by the spontaneous strains.

  18. Electronic Structure Rearrangements in Hybrid Ribozyme/Protein Catalysis

    NASA Astrophysics Data System (ADS)

    Kang, Jiyoung; Kino, Hiori; Field, Martin J.; Tateno, Masaru

    2017-04-01

    We analyzed the electronic structural changes that occur in the reaction cycle of a biological catalyst composed of RNA and protein, and elucidated the dynamical rearrangements of the electronic structure that was obtained from our previous study in which ab initio quantum mechanics/molecular mechanics molecular dynamics simulations were performed. Notable results that we obtained include the generation of a reactive HOMO that is responsible for bond formation in the initial stages of the reaction, and the appearance of a reactive LUMO that is involved in the bond rupture that leads to products. We denote these changes as dynamical induction of the reactive HOMO (DIRH) and LUMO (DIRL), respectively. Interestingly, we also find that the induction of the reactive HOMO is enhanced by the formation of a low-barrier hydrogen bond (LBHB), which, to the best of our knowledge, represents a novel role for LBHBs in enzymatic systems.

  19. Electronic Structure of Silicon Nanowires Matrix from Ab Initio Calculations.

    PubMed

    Monastyrskii, Liubomyr S; Boyko, Yaroslav V; Sokolovskii, Bogdan S; Potashnyk, Vasylyna Ya

    2016-12-01

    An investigation of the model of porous silicon in the form of periodic set of silicon nanowires has been carried out. The electronic energy structure was studied using a first-principle band method-the method of pseudopotentials (ultrasoft potentials in the basis of plane waves) and linearized mode of the method of combined pseudopotentials. Due to the use of hybrid exchange-correlation potentials (B3LYP), the quantitative agreement of the calculated value of band gap in the bulk material with experimental data is achieved. The obtained results show that passivation of dangling bonds with hydrogen atoms leads to substantial transformation of electronic energy structure. At complete passivation of the dangling silicon bonds by hydrogen atoms, the band gap value takes the magnitude which substantially exceeds that for bulk silicon. The incomplete passivation gives rise to opposite effect when the band gap value decreases down the semimetallic range.

  20. On the Electronic Structure of Cocaine and its Metabolites

    NASA Astrophysics Data System (ADS)

    Rincón, David A.; Dias Soeiro Cordeiro, Maria Natália; Mosquera, Ricardo A.

    2009-11-01

    This work aims at describing the electronic features of cocaine and how they are modified by the different substituents present in its metabolites. The QTAIM analysis of B3LYP and MP2 electron densities obtained with the 6-311++G** 6d basis set for cocaine and its principal metabolites indicates: (i) its positive charge is shared among the amino hydrogen, those of the methylamino group, and all of the hydrogens attached to the bicycle structure; (ii) the zwitterionic structure of benzoylecgonine can be described as two partial charges of 0.63 au, the negative one shared by the oxygens of the carboxylate group, whereas the positive charge is distributed among all the hydrogens that bear the positive charge in cocaine; (iii) its hydrogen bond is strengthened in the derivatives without benzoyloxy group and is also slightly strengthened as the size of the alkyl ester group at position 2 increases.