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Sample records for valence bond vb

  1. Atoms in Valence Bond - AiVB. Synopsis and test results

    NASA Astrophysics Data System (ADS)

    Zielinski, Marcin; van Lenthe, Joop H.

    2010-11-01

    The Atoms in Valence Bond (AiVB) method, a new approach in the Valence Bond, is introduced. This approach combines the ideas behind the early Atoms in Molecules (AIM) developments, e.g. by Moffit [21], to understand a molecular wave function in terms of proper atomic wave functions, with the available framework of the VBSCF [17,18] as implemented in TURTLE[19]. The fundamental theoretical tools, to explain the AiVB concept, are shown and the initial test results are presented.

  2. Valence-Bond Theory and Chemical Structure.

    ERIC Educational Resources Information Center

    Klein, Douglas J.; Trinajstic, Nenad

    1990-01-01

    Discussed is the importance of valence bond theory on the quantum-mechanical theory of chemical structure and the nature of the chemical bond. Described briefly are early VB theory, development of VB theory, modern versions, solid-state applications, models, treatment in textbooks, and flaws in criticisms of valence bond theory. (KR)

  3. The Valence Bond Interpretation of Molecular Geometry.

    ERIC Educational Resources Information Center

    Smith, Derek W.

    1980-01-01

    Presents ways in which the valence bond (VB) theory describes the bonding and geometry of molecules, following directly from earlier principles laid down by Pauling and others. Two other theories (molecular orbital approach and valence shell electron pair repulsion) are discussed and compared to VB. (CS)

  4. Measurement of the low energy spectral contribution in coincidence with valence band (VB) energy levels of Ag(100) using VB-VB coincidence spectroscopy

    NASA Astrophysics Data System (ADS)

    Joglekar, P. V.; Gladen, R.; Lim, Z. H.; Shastry, K.; Hulbert, S. L.; Weiss, A. H.

    2015-03-01

    A set of coincidence measurements were obtained for the study and measurement of the electron contribution arising from the inter-valence band (VB) transitions along with the inelastically scattered VB electron contribution. These Auger-unrelated contributions arise in the Auger spectrum (Ag 4p NVV) obtained using Auger Photoelectron Coincidence Spectroscopy (APECS). The measured Auger-unrelated contribution can be eliminated from Auger spectrum to obtain the spectrum related to Auger. In our VB-VB coincidence measurement, a photon beam of energy 180eV was used to probe the Ag(100) sample. The coincidence spectrum was obtained using two Cylindrical Mirror Analyzers (CMA's). The scan CMA measured the low energy electron contribution in the energy range 0-70eV in coincidence with VB electrons measured by the fixed CMA. In this talk, we present the data obtained for VB-VB coincidence at the valence band energy of 171eV along with the coincidence measurements in the energy range of 4p core and valence band. NSF DMR 0907679, NSF Award Number: 1213727. Use of the National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U.S. DOE, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886.

  5. Chemical Bonding: The Orthogonal Valence-Bond View

    PubMed Central

    Sax, Alexander F.

    2015-01-01

    Chemical bonding is the stabilization of a molecular system by charge- and spin-reorganization processes in chemical reactions. These processes are said to be local, because the number of atoms involved is very small. With multi-configurational self-consistent field (MCSCF) wave functions, these processes can be calculated, but the local information is hidden by the delocalized molecular orbitals (MO) used to construct the wave functions. The transformation of such wave functions into valence bond (VB) wave functions, which are based on localized orbitals, reveals the hidden information; this transformation is called a VB reading of MCSCF wave functions. The two-electron VB wave functions describing the Lewis electron pair that connects two atoms are frequently called covalent or neutral, suggesting that these wave functions describe an electronic situation where two electrons are never located at the same atom; such electronic situations and the wave functions describing them are called ionic. When the distance between two atoms decreases, however, every covalent VB wave function composed of non-orthogonal atomic orbitals changes its character from neutral to ionic. However, this change in the character of conventional VB wave functions is hidden by its mathematical form. Orthogonal VB wave functions composed of orthonormalized orbitals never change their character. When localized fragment orbitals are used instead of atomic orbitals, one can decide which local information is revealed and which remains hidden. In this paper, we analyze four chemical reactions by transforming the MCSCF wave functions into orthogonal VB wave functions; we show how the reactions are influenced by changing the atoms involved or by changing their local symmetry. Using orthogonal instead of non-orthogonal orbitals is not just a technical issue; it also changes the interpretation, revealing the properties of wave functions that remain otherwise undetected. PMID:25906476

  6. On the Relative Merits of Non-Orthogonal and Orthogonal Valence Bond Methods Illustrated on the Hydrogen Molecule

    ERIC Educational Resources Information Center

    Angeli, Celestino; Cimiraglia, Renzo; Malrieu, Jean-Paul

    2008-01-01

    Valence bond (VB) is one of the cornerstone theories of quantum chemistry. Even if in practical applications the molecular orbital (MO) approach has obtained more attention, some basic chemical concepts (such as the nature of the chemical bond and the failure of the single determinant-based MO methods in describing the bond cleavage) are normally…

  7. Resonance and aromaticity: an ab initio valence bond approach.

    PubMed

    Rashid, Zahid; van Lenthe, Joop H; Havenith, Remco W A

    2012-05-17

    Resonance energy is one of the criteria to measure aromaticity. The effect of the use of different orbital models is investigated in the calculated resonance energies of cyclic conjugated hydrocarbons within the framework of the ab initio Valence Bond Self-Consistent Field (VBSCF) method. The VB wave function for each system was constructed using a linear combination of the VB structures (spin functions), which closely resemble the Kekulé valence structures, and two types of orbitals, that is, strictly atomic (local) and delocalized atomic (delocal) p-orbitals, were used to describe the ?-system. It is found that the Pauling-Wheland's resonance energy with nonorthogonal structures decreases, while the same with orthogonalized structures and the total mean resonance energy (the sum of the weighted off-diagonal contributions in the Hamiltonian matrix of orthogonalized structures) increase when delocal orbitals are used as compared to local p-orbitals. Analysis of the interactions between the different structures of a system shows that the resonance in the 6? electrons conjugated circuits have the largest contributions to the resonance energy. The VBSCF calculations also show that the extra stability of phenanthrene, a kinked benzenoid, as compared to its linear counterpart, anthracene, is a consequence of the resonance in the ?-system rather than the H-H interaction in the bay region as suggested previously. Finally, the empirical parameters for the resonance interactions between different 4n+2 or 4n ? electrons conjugated circuits, used in Randi?'s conjugated circuits theory or Herdon's semi-emprical VB approach, are quantified. These parameters have to be scaled by the structure coefficients (weights) of the contributing structures. PMID:22559175

  8. A tutorial for understanding chemical reactivity through the valence bond approach.

    PubMed

    Usharani, Dandamudi; Lai, Wenzhen; Li, Chunsen; Chen, Hui; Danovich, David; Shaik, Sason

    2014-07-21

    This is a tutorial on the usage of valence bond (VB) diagrams for understanding chemical reactivity in general, and hydrogen atom transfer (HAT) reactivity in particular. The tutorial instructs the reader how to construct the VB diagrams and how to estimate HAT barriers from raw data, starting with the simplest reaction H + H2 and going all the way to HAT in the enzyme cytochrome P450. Other reactions are treated as well, and some unifying principles are outlined. The tutorial projects the unity of reactivity treatments, following Coulson's dictum "give me insight, not numbers", albeit with its modern twist: giving numbers and insight. PMID:24710199

  9. Exploring the Nature of the H[subscript 2] Bond. 1. Using Spreadsheet Calculations to Examine the Valence Bond and Molecular Orbital Methods

    ERIC Educational Resources Information Center

    Halpern, Arthur M.; Glendening, Eric D.

    2013-01-01

    A three-part project for students in physical chemistry, computational chemistry, or independent study is described in which they explore applications of valence bond (VB) and molecular orbital-configuration interaction (MO-CI) treatments of H[subscript 2]. Using a scientific spreadsheet, students construct potential-energy (PE) curves for several…

  10. Nonorthogonal orbital based N-body reduced density matrices and their applications to valence bond theory. I. Hamiltonian matrix elements between internally contracted excited valence bond wave functions.

    PubMed

    Chen, Zhenhua; Chen, Xun; Wu, Wei

    2013-04-28

    In this series, the n-body reduced density matrix (n-RDM) approach for nonorthogonal orbitals and their applications to ab initio valence bond (VB) methods are presented. As the first paper of this series, Hamiltonian matrix elements between internally contracted VB wave functions are explicitly provided by means of nonorthogonal orbital based RDM approach. To this end, a more generalized Wick's theorem, called enhanced Wick's theorem, is presented both in arithmetical and in graphical forms, by which the deduction of expressions for the matrix elements between internally contracted VB wave functions is dramatically simplified, and the matrix elements are finally expressed in terms of tensor contractions of electronic integrals and n-RDMs of the reference VB self-consistent field wave function. A string-based algorithm is developed for the purpose of evaluating n-RDMs in an efficient way. Using the techniques presented in this paper, one is able to develop new methods and efficient algorithms for nonorthogonal orbital based many-electron theory much easier than by use of the first quantized formulism. PMID:23635123

  11. The variational subspace valence bond method

    NASA Astrophysics Data System (ADS)

    Fletcher, Graham D.

    2015-04-01

    The variational subspace valence bond (VSVB) method based on overlapping orbitals is introduced. VSVB provides variational support against collapse for the optimization of overlapping linear combinations of atomic orbitals (OLCAOs) using modified orbital expansions, without recourse to orthogonalization. OLCAO have the advantage of being naturally localized, chemically intuitive (to individually model bonds and lone pairs, for example), and transferrable between different molecular systems. Such features are exploited to avoid key computational bottlenecks. Since the OLCAO can be doubly occupied, VSVB can access very large problems, and calculations on systems with several hundred atoms are presented.

  12. Charge-Shift Bonding Emerges as a Distinct Electron-Pair Bonding Family from Both Valence Bond and Molecular Orbital Theories.

    PubMed

    Zhang, Huaiyu; Danovich, David; Wu, Wei; Braïda, Benoît; Hiberty, Philippe C; Shaik, Sason

    2014-06-10

    The charge-shift bonding (CSB) concept was originally discovered through valence bond (VB) calculations. Later, CSB was found to have signatures in atoms-in-molecules and electron-localization-function and in experimental electron density measurements. However, the CSB concept has never been derived from a molecular orbital (MO)-based theory. We now provide a proof of principle that an MO-based approach enables one to derive the CSB family alongside the distinctly different classical family of covalent bonds. In this bridging energy decomposition analysis, the covalent-ionic resonance energy, RECS, of a bond is extracted by cloning an MO-based purely covalent reference state, which is a constrained two-configuration wave function. The energy gap between this reference state and the variational TCSCF ground state yields numerical values for RECS, which correlate with the values obtained at the VBSCF level. This simple MO-based method, which only takes care of static electron correlation, is already sufficient for distinguishing the classical covalent or polar-covalent bonds from charge-shift bonds. The equivalence of the VB and MO-based methods is further demonstrated when both methods are augmented by dynamic correlation. Thus, it is shown from both MO and VB perspectives that the bonding in the CSB family does not arise from electron correlation. Considering that the existence of the CSB family is associated also with quite a few experimental observations that we already reviewed ( Shaik , S. , Danovich , D. , Wu , W. , and Hiberty , P. C. Nat. Chem. , 2009 , 1 , 443 - 449 ), the new bonding concept has passed by now two stringent tests. This derivation, on the one hand, supports the new concept and on the other, it creates bridges between the two main theories of electronic structure. PMID:26580761

  13. Valence-Bond Concepts in Coordination Chemistry and the Nature of Metal-Metal Bonds.

    ERIC Educational Resources Information Center

    Pauling, Linus; Herman, Zelek S.

    1984-01-01

    Discusses the valence-bond method, applying it to some coordination compounds of metals, especially those involving metal-metal bonds. Suggests that transition metals can form as many as nine covalent bonds, permitting valence-theory to be extended to transition metal compounds in a more effective way than has been possible before. (JN)

  14. Orbital Exponent Optimization in Elementary VB Calculations of the Chemical Bond in the Ground State of Simple Molecular Systems

    ERIC Educational Resources Information Center

    Magnasco, Valerio

    2008-01-01

    Orbital exponent optimization in the elementary ab-initio VB calculation of the ground states of H[subscript 2][superscript +], H[subscript 2], He[subscript 2][superscript +], He[subscript 2] gives a fair description of the exchange-overlap component of the interatomic interaction that is important in the bond region. Correct bond lengths and…

  15. Bond-valence methods for pKa prediction. II. Bond-valence, electrostatic, molecular geometry, and solvation effects

    SciTech Connect

    Bickmore, Barry R.; Rosso, Kevin M.; Tadanier, Christopher J.; Bylaska, Eric J.; Doud, Darrin

    2006-08-15

    In a previous contribution, we outlined a method for predicting (hydr)oxy-acid and oxide surface acidity constants based on three main factors: bond valence, Me?O bond ionicity, and molecular shape. Here electrostatics calculations and ab initio molecular dynamics simulations are used to qualitatively show that Me?O bond ionicity controls the extent to which the electrostatic work of proton removal departs from ideality, bond valence controls the extent of solvation of individual functional groups, and bond valence and molecular shape controls local dielectric response. These results are consistent with our model of acidity, but completely at odds with other methods of predicting acidity constants for use in multisite complexation models. In particular, our ab initio molecular dynamics simulations of solvated monomers clearly indicate that hydrogen bonding between (hydr)oxo-groups and water molecules adjusts to obey the valence sum rule, rather than maintaining a fixed valence based on the coordination of the oxygen atom as predicted by the standard MUSIC model.

  16. Valence-bond quantum Monte Carlo algorithms defined on trees.

    PubMed

    Deschner, Andreas; Sørensen, Erik S

    2014-09-01

    We present a class of algorithms for performing valence-bond quantum Monte Carlo of quantum spin models. Valence-bond quantum Monte Carlo is a projective T=0 Monte Carlo method based on sampling of a set of operator strings that can be viewed as forming a treelike structure. The algorithms presented here utilize the notion of a worm that moves up and down this tree and changes the associated operator string. In quite general terms, we derive a set of equations whose solutions correspond to a whole class of algorithms. As specific examples of this class of algorithms, we focus on two cases. The bouncing worm algorithm, for which updates are always accepted by allowing the worm to bounce up and down the tree, and the driven worm algorithm, where a single parameter controls how far up the tree the worm reaches before turning around. The latter algorithm involves only a single bounce where the worm turns from going up the tree to going down. The presence of the control parameter necessitates the introduction of an acceptance probability for the update. PMID:25314561

  17. Nonorthogonal orbital based N-body reduced density matrices and their applications to valence bond theory. IV. The automatic implementation of the Hessian based VBSCF method

    NASA Astrophysics Data System (ADS)

    Chen, Xun; Chen, Zhenhua; Wu, Wei

    2014-11-01

    In this paper, the Hessian matrix of valence bond (VB) self-consistent field (VBSCF) energy with respect to orbitals are evaluated by applying the nonorthogonal orbital based N-body reduced density matrices, which was presented in Paper I. To this end, an automatic formula/code generator (AFCG) is developed; with which the matrix elements between internally contracted excited configurations of VB wave function and the corresponding codes are generated automatically. Compared to the tedious manual formula deducing and implementing, AFCG is much more convenient and efficient, and enables us to avoid troublesome debugging. With the help of AFCG, the Hessian-based Newton-Raphson algorithm is implemented for the VBSCF orbital optimization. Test calculations indicate that the Newton-Raphson algorithm converges quadratically and has much better convergence behavior than the gradient-based LBFGS algorithms. Furthermore, a combined approach with LBFGS and Newton-Raphson algorithms is applied to reduce the total CPU time of the calculation.

  18. PHYSICAL REVIEW B 88, 104102 (2013) Reinterpretation of the bond-valence model with bond-order formalism: An improved

    E-print Network

    Rappe, Andrew M.

    2013-01-01

    of the relationships between composition, structure, and properties.3­5 Despite the success of first-principles methods the bond valences Vij , which can be calculated from an empirical inverse power-law relationship23 when the constant volume constraint is lifted. In this paper, we show how the bond-valence energy can

  19. Hybrid valence-bond states for universal quantum computation

    NASA Astrophysics Data System (ADS)

    Wei, Tzu-Chieh; Haghnegahdar, Poya; Raussendorf, Robert

    2014-10-01

    The spin-3/2 Affleck-Kennedy-Lieb-Tasaki (AKLT) valence-bond state on a hexagonal lattice was shown to be a universal resource state for measurement-based quantum computation (MBQC). Can AKLT states of higher spin magnitude support universal MBQC? We demonstrate that several hybrid two-dimensional AKLT states involving a mixture of spin-2 and other lower-spin entities, such as spin-3/2 and spin-1, are also universal for MBQC. This significantly expands universal resource states in the AKLT family. Even though frustration may be a hindrance to quantum computational universality, lattices can be modified to yield AKLT states that are universal. The family of AKLT states thus provides a versatile playground for quantum computation.

  20. On the Possibility of Mixed Rydberg-Valence Bonds Alexander I. Boldyrev and Jack Simons*

    E-print Network

    Simons, Jack

    , via their 2s, 3s, or 4s valence orbitals, is examined using flexible atomic orbital basis sets frequencies, and plots of the Rydberg-valence bonding orbitals are given. The activation barriers separating- cal bond via the overlap of their Rydberg orbitals. The NH4 molecule consists of an underlying closed

  1. Valence bond supersolid in a bilayer extended Bose-Hubbard model

    NASA Astrophysics Data System (ADS)

    Ng, Kwai-Kong

    2015-02-01

    The hardcore extended Bose Hubbard model on a bilayer square lattice with attractive (repulsive) interplane (intraplane) interactions has been investigated numerically. Focusing on the strong interplane hopping parameter regime, triplet valence bonds of dimers are stabilized to form valence bond checkerboard solid at quarter filling. Increasing the particle number we confirm the presence of the exotic valence bond supersolid phase, where the valence bond solid ordering and the boson superfluidity coexist. Rising further the particle number will lead to a checkerboard solid of dimer pair at half filling for strong intraplane repulsion, or a valence bond Mott insulator for weak repulsive interactions. We analyze the rich ground state phase diagrams of this model, which can be experimentally realized in optical lattices of cold atoms.

  2. Valence bond phases in S = 1/2 Kane-Mele-Heisenberg model

    NASA Astrophysics Data System (ADS)

    Zare, Mohammad H.; Mosadeq, Hamid; Shahbazi, Farhad; Jafari, S. A.

    2014-11-01

    The phase diagram of the Kane-Mele-Heisenberg model in a classical limit [47] contains disordered regions in the coupling space, as the result of competition between different terms in the Hamiltonian, leading to frustration in finding a unique ground state. In this work we explore the nature of these phases in the quantum limit, for a S = 1/2. Employing exact diagonalization in Sz and nearest neighbour valence bond bases, and bond and plaquette valence bond mean field theories, we show that the disordered regions are divided into ordered quantum states in the form of plaquette valence bond crystals and staggered dimerized phases.

  3. Valence bond solid (AKLT) state from t2 g electrons

    NASA Astrophysics Data System (ADS)

    Koch-Janusz, Maciej; Khomskii, Daniel; Sela, Eran

    2015-03-01

    The models constructed by Affleck, Kennedy, Lieb, and Tasaki (AKLT) describe gapped quantum spin liquids with fractionalized boundary spin excitations. The AKLT spin-spin interactions consist of projection operators onto the maximal possible spin formed between nearest neighbours, which involves a linear combination of powers of the Heisenberg coupling (S-->i .S-->j) n, making these states difficult to realize. Indeed, except for the one dimensional spin-1 case, simple antiferromagnetic Heisenberg interactions which are typically found in magnetic insulators, do not stabilize these spin liquid states, but rather generate conventional antiferromagnetically ordered states. We show that this type of interactions can be generated by orbital physics in multiorbital Mott insulators. Motivated by microscopic modeling of spin-orbit entangled Mott insulators such as the layered hexagonal Iridates, we focus on t2 g electrons on the honeycomb lattice and propose a physical realization of the spin- 3 / 2 AKLT state. Interestingly enough, the valence bond solid (AKLT) state found for the noninteracting electrons survives the increase of the on-site (Hubbard) repulsion, but it changes to the antiferromagnetic Neel state with increase of the Hund's rule coupling.

  4. Configuration interaction studies using biorthogonal approach to VB basis

    SciTech Connect

    Kadolkar, C.; Sarma, C.R.; Rettrup, S.

    1995-01-15

    In the present article, we have attempted a systematic procedure for use of biorthogonal techniques to the configuration interaction studies in molecules using nonorthogonal valence bond (VB) orbitals. The procedure developed is integral-driven and a program based on this has been developed. Test runs of the program have been carried out in case of full and truncated configuration spaces. 29 refs., 3 tabs.

  5. Accounting for the differences in the structures and relative energies of the highly homoatomic np pi-np pi (n > or = 3)-bonded S2I4 2+, the Se-I pi-bonded Se2I4 2+, and their higher-energy isomers by AIM, MO, NBO, and VB methodologies.

    PubMed

    Brownridge, Scott; Crawford, Margaret-Jane; Du, Hongbin; Harcourt, Richard D; Knapp, Carsten; Laitinen, Risto S; Passmore, Jack; Rautiainen, J Mikko; Suontamo, Reijo J; Valkonen, Jussi

    2007-02-01

    The bonding in the highly homoatomic np pi-np pi (n > or = 3)-bonded S2I42+ (three sigma + two pi bonds), the Se-I pi-bonded Se2I42+ (four sigma + one pi bonds), and their higher-energy isomers have been studied using modern DFT and ab initio calculations and theoretical analysis methods: atoms in molecules (AIM), molecular orbital (MO), natural bond orbital (NBO), and valence bond (VB) analyses, giving their relative energies, theoretical bond orders, and atomic charges. The aim of this work was to seek theory-based answers to four main questions: (1) Are the previously proposed simple pi*-pi* bonding models valid for S2I42+ and Se2I42+? (2) What accounts for the difference in the structures of S2I42+ and Se2I42+? (3) Why are the classically bonded isolobal P2I4 and As2I4 structures not adopted? (4) Is the high experimentally observed S-S bond order supported by theoretical bond orders, and how does it relate to high bond orders between other heavier main group elements? The AIM analysis confirmed the high bond orders and established that the weak bonds observed in S2I42+ and Se2I42+ are real and the bonding in these cations is covalent in nature. The full MO analysis confirmed that S2I42+ contains three sigma and two pi bonds, that the positive charge is essentially equally distributed over all atoms, that the bonding between S2 and two I2+ units in S2I42+ is best described by two mutually perpendicular 4c2e pi*-pi* bonds, and that in Se2I42+, two SeI2+ moieties are joined by a 6c2e pi*-pi* bond, both in agreement with previously suggested models. The VB treatment provided a complementary approach to MO analysis and provided insight how the formation of the weak bonds affects the other bonds. The NBO analysis and the calculated AIM charges showed that the minimization of the electrostatic repulsion between EI2+ units (E = S, Se) and the delocalization of the positive charge are the main factors that explain why the nonclassical structures are favored for S2I42+ and Se2I42+. The difference in the structures of S2I42+ and Se2I42+ is related to the high strength of the S-S pi bond compared to the weak S-I sigma bond and the additional stabilization from increased delocalization of positive charge in the structure of S2I42+ compared to the structure of Se2I42+. The investigation of the E2X42+ series (E = S, Se, Te; X = Cl, Br, I) revealed that only S2I42+ adopts the highly np pi-np pi (n > or = 3)-bonded structure, while all other dications favor the pi-bonded Se2I42+ structure. Theoretical bond order calculations for S2I42+ confirm the previously presented experimentally based bond orders for S-S (2.1-2.3) and I-I (1.3-1.5) bonds. The S-S bond is determined to have the highest reported S-S bond order in an isolated compound and has a bond order that is either similar to or slightly less than the Si-Si bond order in the proposed triply bonded [(Me3Si)2CH]2(iPr)SiSi triple bond SiSi(iPr)[CH(SiMe3)2]2 depending on the definition of bond orders used. PMID:17257010

  6. Comprehensive derivation of bond-valence parameters for ion pairs involving oxygen

    PubMed Central

    Gagné, Olivier Charles; Hawthorne, Frank Christopher

    2015-01-01

    Published two-body bond-valence parameters for cation–oxygen bonds have been evaluated via the root mean-square deviation (RMSD) from the valence-sum rule for 128 cations, using 180?194 filtered bond lengths from 31?489 coordination polyhedra. Values of the RMSD range from 0.033–2.451?v.u. (1.1–40.9% per unit of charge) with a weighted mean of 0.174?v.u. (7.34% per unit of charge). The set of best published parameters has been determined for 128 ions and used as a benchmark for the determination of new bond-valence parameters in this paper. Two common methods for the derivation of bond-valence parameters have been evaluated: (1) fixing B and solving for R o; (2) the graphical method. On a subset of 90 ions observed in more than one coordination, fixing B at 0.37?Å leads to a mean weighted-RMSD of 0.139?v.u. (6.7% per unit of charge), while graphical derivation gives 0.161?v.u. (8.0% per unit of charge). The advantages and disadvantages of these (and other) methods of derivation have been considered, leading to the conclusion that current methods of derivation of bond-valence parameters are not satisfactory. A new method of derivation is introduced, the GRG (generalized reduced gradient) method, which leads to a mean weighted-RMSD of 0.128?v.u. (6.1% per unit of charge) over the same sample of 90 multiple-coordination ions. The evaluation of 19 two-parameter equations and 7 three-parameter equations to model the bond-valence–bond-length relation indicates that: (1) many equations can adequately describe the relation; (2) a plateau has been reached in the fit for two-parameter equations; (3) the equation of Brown & Altermatt (1985 ?) is sufficiently good that use of any of the other equations tested is not warranted. Improved bond-valence parameters have been derived for 135 ions for the equation of Brown & Altermatt (1985 ?) in terms of both the cation and anion bond-valence sums using the GRG method and our complete data set. PMID:26428406

  7. Comprehensive derivation of bond-valence parameters for ion pairs involving oxygen.

    PubMed

    Gagné, Olivier Charles; Hawthorne, Frank Christopher

    2015-10-01

    Published two-body bond-valence parameters for cation-oxygen bonds have been evaluated via the root mean-square deviation (RMSD) from the valence-sum rule for 128 cations, using 180,194 filtered bond lengths from 31,489 coordination polyhedra. Values of the RMSD range from 0.033-2.451?v.u. (1.1-40.9% per unit of charge) with a weighted mean of 0.174?v.u. (7.34% per unit of charge). The set of best published parameters has been determined for 128 ions and used as a benchmark for the determination of new bond-valence parameters in this paper. Two common methods for the derivation of bond-valence parameters have been evaluated: (1) fixing B and solving for R(o); (2) the graphical method. On a subset of 90 ions observed in more than one coordination, fixing B at 0.37?Å leads to a mean weighted-RMSD of 0.139?v.u. (6.7% per unit of charge), while graphical derivation gives 0.161?v.u. (8.0% per unit of charge). The advantages and disadvantages of these (and other) methods of derivation have been considered, leading to the conclusion that current methods of derivation of bond-valence parameters are not satisfactory. A new method of derivation is introduced, the GRG (generalized reduced gradient) method, which leads to a mean weighted-RMSD of 0.128?v.u. (6.1% per unit of charge) over the same sample of 90 multiple-coordination ions. The evaluation of 19 two-parameter equations and 7 three-parameter equations to model the bond-valence-bond-length relation indicates that: (1) many equations can adequately describe the relation; (2) a plateau has been reached in the fit for two-parameter equations; (3) the equation of Brown & Altermatt (1985) is sufficiently good that use of any of the other equations tested is not warranted. Improved bond-valence parameters have been derived for 135 ions for the equation of Brown & Altermatt (1985) in terms of both the cation and anion bond-valence sums using the GRG method and our complete data set. PMID:26428406

  8. Stoichiometric Valence and Structural Valence--Two Different Sides of the Same Coin: "Bonding Power"

    E-print Network

    Wang, Xiqu

    that chemical compounds contain elements in certain weight or atom ratios. For exam- ple, in NH3, PH3, AsH3 and SbH3, one pnictide atom is equivalent to three hydrogen atoms and one mole of a pnic- tide is equivalent to three moles of hydrogen. The property of an atom to compensate the bonding power of an equiva

  9. Geometry of the n. pi. * states of p-benzoquinone. A comparison of valence-bond and configuration-interaction descriptions

    SciTech Connect

    Martin, R.L.; Wadt, W.R.

    1982-06-24

    The description of the n..pi..* excited states of p-benzoquinone by a configuration-interaction (CI) expansion based on symmetry-restricted molecular orbitals is compared to a valence-bond (VB) model based on a nonorthogonal two-configuration wave function utilizing broken-symmetry, self-consistent-field solutions. The former approximation is found to converge only very slowly to the latter. The valence-bond model was used to examine the potential energy surface for motion involving the symmetric and antisymmetric combinations of the two carbonyl stretches. The minimum in the symmetric stretch coordinate for both the /sup 3/B/sub 1g/ and /sup 3/A/sub u/ states is substantially longer than the ground-state distance. The surface along the antisymmetric stretch coordinate is very flat, but the calculations find no overwhelming evidence for a global C/sub 2nu/ minimum in the /sup 3/B/sub 1g/ state. 3 figures, 6 tables.

  10. Valence-Bond Crystal and Anisotropic Excitation Spectrum on 3-Dimensionally Frustrated Pyrochlore

    NASA Astrophysics Data System (ADS)

    Isoda, Makoto; Mori, Shigeyoshi

    1998-12-01

    The valence-bond crystal is proposed as a ground state of spin-1/2Heisenberg antiferromagnet on 3-dimensional fully frustrated pyrochlore bythe bond-operator theory. This crystal, formed as a set of RVB-liketetrahedral singlet states, has lower energy than the state consisting oftwo dimers in a tetrahedron. The spectra of triplet excitation have afinite gap and a symmetry lower than that of the lattice. The comparisonwith Y(Sc)Mn2 is discussed.

  11. A generalized direct inversion in the iterative subspace approach for generalized valence bond wave functions

    E-print Network

    Goddard III, William A.

    a greatly improved method for converging generalized valence bond (GVB) self-consistent wave functions-shell HF, or a single pair GVB wave function. Here we extend this method to general wave functions GVB wave functions with up to ten pairs) and comparing with other standard methods. 1. INTRODUCTION

  12. Resonating-Valence-Bond Physics Is Not Always Governed by the Shortest Tunneling Loops.

    PubMed

    Ralko, Arnaud; Rousochatzakis, Ioannis

    2015-10-16

    It is well known that the low-energy sector of quantum spin liquids and other magnetically disordered systems is governed by short-ranged resonating-valence bonds. Here we show that the standard minimal truncation to the nearest-neighbor valence-bond basis fails completely even for systems where it should work the most, according to received wisdom. This paradigm shift is demonstrated for the quantum spin-1/2 square kagome, where strong geometric frustration, similar to the kagome, prevents magnetic ordering down to zero temperature. The shortest tunneling events bear the strongest longer-range singlet fluctuations, leading to amplitudes that do not drop exponentially with the length of the loop L, and to an unexpected loop-six valence-bond crystal, which is otherwise very high in energy at the minimal truncation level. The low-energy effective description gives in addition a clear example of correlated loop processes that depend not only on the type of the loop but also on its lattice embedding, a direct manifestation of the long-range nature of the virtual singlets. PMID:26550898

  13. Resonating-Valence-Bond Physics Is Not Always Governed by the Shortest Tunneling Loops

    NASA Astrophysics Data System (ADS)

    Ralko, Arnaud; Rousochatzakis, Ioannis

    2015-10-01

    It is well known that the low-energy sector of quantum spin liquids and other magnetically disordered systems is governed by short-ranged resonating-valence bonds. Here we show that the standard minimal truncation to the nearest-neighbor valence-bond basis fails completely even for systems where it should work the most, according to received wisdom. This paradigm shift is demonstrated for the quantum spin-1 /2 square kagome, where strong geometric frustration, similar to the kagome, prevents magnetic ordering down to zero temperature. The shortest tunneling events bear the strongest longer-range singlet fluctuations, leading to amplitudes that do not drop exponentially with the length of the loop L , and to an unexpected loop-six valence-bond crystal, which is otherwise very high in energy at the minimal truncation level. The low-energy effective description gives in addition a clear example of correlated loop processes that depend not only on the type of the loop but also on its lattice embedding, a direct manifestation of the long-range nature of the virtual singlets.

  14. The Breathing Orbital Valence Bond Method in Diffusion Monte Carlo: C-H Bond Dissociation ofAcetylene

    SciTech Connect

    Domin, D.; Braida, Benoit; Lester Jr., William A.

    2008-05-30

    This study explores the use of breathing orbital valence bond (BOVB) trial wave functions for diffusion Monte Carlo (DMC). The approach is applied to the computation of the carbon-hydrogen (C-H) bond dissociation energy (BDE) of acetylene. DMC with BOVB trial wave functions yields a C-H BDE of 132.4 {+-} 0.9 kcal/mol, which is in excellent accord with the recommended experimental value of 132.8 {+-} 0.7 kcal/mol. These values are to be compared with DMC results obtained with single determinant trial wave functions, using Hartree-Fock orbitals (137.5 {+-} 0.5 kcal/mol) and local spin density (LDA) Kohn-Sham orbitals (135.6 {+-} 0.5 kcal/mol).

  15. Quantum melting of valence-bond crystal insulators and novel supersolid phase at commensurate density.

    PubMed

    Ralko, Arnaud; Trousselet, Fabien; Poilblanc, Didier

    2010-03-26

    Bosonic and fermionic Hubbard models on the checkerboard lattice are studied numerically for infinite on-site repulsion. At particle density n=1/4 and strong nearest-neighbor repulsion, insulating Valence-Bond crystals (VBC) of resonating particle pairs are stabilized. Their melting into superfluid or metallic phases under increasing hopping is investigated at T=0 K. We identify a novel and unconventional commensurate VBC supersolid region, precursor to the melting of the bosonic crystal. Hardcore bosons (spins) are compared to fermions (electrons), as well as positive to negative (frustrating) hoppings. PMID:20366561

  16. Quantum Melting of Valence-Bond Crystal Insulators and Novel Supersolid Phase at Commensurate Density

    NASA Astrophysics Data System (ADS)

    Ralko, Arnaud; Trousselet, Fabien; Poilblanc, Didier

    2010-03-01

    Bosonic and fermionic Hubbard models on the checkerboard lattice are studied numerically for infinite on-site repulsion. At particle density n=1/4 and strong nearest-neighbor repulsion, insulating Valence-Bond crystals (VBC) of resonating particle pairs are stabilized. Their melting into superfluid or metallic phases under increasing hopping is investigated at T=0K. We identify a novel and unconventional commensurate VBC supersolid region, precursor to the melting of the bosonic crystal. Hardcore bosons (spins) are compared to fermions (electrons), as well as positive to negative (frustrating) hoppings.

  17. Complementary method to locate atomic coordinates by combined searching method of structure-sensitive indexes based on bond valence method

    NASA Astrophysics Data System (ADS)

    Song, Zhen; Liu, Xiao-Lang; He, Li-Zhu; Xia, Zhi-Guo; Liu, Quan-Lin

    2015-10-01

    Bond valence method illustrates the relation between valence and length of a particular bond type. This theory has been used to predict structure information, but the effect is very limited. In this paper, two indexes, i.e., global instability index (GII) and bond strain index (BSI), are adopted as a judgment of a search-match program for prediction. The results show that with GII and BSI combined as judgment, the predicted atom positions are very close to real ones. The mechanism and validity of this searching program are also discussed. The GII & BSI distribution contour map reveals that the predicted function is a reflection of exponential feature of bond valence formula. This combined searching method may be integrated with other structure-determination method, and may be helpful in refining and testifying light atom positions. Project supported by the National Natural Science Foundation of China (Grant No. 51272027).

  18. Emergent $SO(5)$ Symmetry at the Néel to Valence-Bond-Solid Transition

    E-print Network

    Adam Nahum; P. Serna; J. T. Chalker; M. Ortuño; A. M. Somoza

    2015-08-26

    We show numerically that the `deconfined' quantum critical point between the N\\'eel antiferromagnet and the columnar valence-bond-solid, for a square lattice of spin-1/2s, has an emergent $SO(5)$ symmetry. This symmetry allows the N\\'eel vector and the valence-bond-solid order parameter to be rotated into each other. It is a remarkable 2+1-dimensional analogue of the $SO(4)= [SU(2)\\times SU(2)]/Z_2$ symmetry that appears in the scaling limit for the spin-1/2 Heisenberg chain. The emergent $SO(5)$ is strong evidence that the phase transition in the 2+1D system is truly continuous, despite the violations of finite-size scaling observed previously in this problem. It also implies surprising relations between correlation functions at the transition. The symmetry enhancement is expected to apply generally to the critical two-component Abelian Higgs model (non-compact $CP^1$ model). The result indicates that in three dimensions there is an $SO(5)$-symmetric conformal field theory which has no relevant singlet operators, so is radically different to conventional Wilson-Fisher-type conformal field theories.

  19. The electronic structure of Ullman's biradicals: an orthogonal valence bond interpretation.

    PubMed

    Angeli, Celestino; Calzado, Carmen J; de Graaf, Coen; Caballol, Rosa

    2011-08-28

    This paper addresses the electronic structure of Ullman's organic biradical, bis(nitronyl) nitroxide, in the frame of ab initio wave function based methods, both using standard (delocalized) molecular orbital methods and a valence bond strategy based on orthogonal localized orbitals. The aim of this study is to clarify the origin of the magnetic coupling of this molecule and to understand the recently observed unexpected behavior of the computed magnetic coupling constant with respect to the use of different theoretical methods. A detailed analysis of the physical effects that govern the correct description of the main characteristics of the electronic structure, in particular the spin density, reveals that the wave functions of the radical fragments are better seen as arising from the interaction of three unpaired electrons and that the intuitive picture of one unpaired electron per fragment is oversimplified and can lead to incorrect results. Furthermore, we establish that both the triplet and the singlet wave functions are well represented by the antisymmetrized product of the two fragment wavefunctions, thus corroborating previous observations concerning the low weight of the ionic structures (hopping of one electron from one fragment to the other) in the biradical singlet wavefunction. The use of the orthogonal valence bond formalism has also allowed us to extract a set of parameters for the fragment (direct exchange, hopping integral, on-site repulsion) which can be used for larger magnetic systems in studies based on model Hamiltonians. PMID:21743922

  20. Z2 gauge theory for valence bond solids on the kagome lattice

    NASA Astrophysics Data System (ADS)

    Hwang, Kyusung; Huh, Yejin; Kim, Yong Baek

    2015-11-01

    We present an effective Z2 gauge theory that captures various competing phases in spin-1/2 kagome lattice antiferromagnets: the topological Z2 spin liquid (SL) phase, and the 12-site and 36-site valence bond solid (VBS) phases. Our effective theory is a generalization of the recent Z2 gauge theory proposed for SL phases by Wan and Tchernyshyov. In particular, we investigate possible VBS phases that arise from vison condensations in the SL. In addition to the 12-site and 36-site VBS phases, there exists 6-site VBS that is closely related to the symmetry-breaking valence bond modulation patterns observed in the recent density matrix renormalization group simulations. We find that our results have remarkable consistency with a previous study using a different Z2 gauge theory. Motivated by the lattice geometry in the recently reported vanadium oxyfluoride kagome antiferromagnet, our gauge theory is extended to incorporate lowered symmetry by inequivalent up and down triangles. We investigate effects of this anisotropy on the 12-site, 36-site, and 6-site VBS phases. The 12-site VBS is stable to anisotropy while the 36-site VBS undergoes severe dimer melting. Interestingly, any analog of the 6-site VBS is not found in this approach. We discuss the implications of these findings and also compare the results with a different type of Z2 gauge theory used in previous studies.

  1. Exact valence bond entanglement entropy and probability distribution in the XXX spin chain and the Potts model

    E-print Network

    Jesper Lykke Jacobsen; Hubert Saleur

    2007-11-21

    By relating the ground state of Temperley-Lieb hamiltonians to partition functions of 2D statistical mechanics systems on a half plane, and using a boundary Coulomb gas formalism, we obtain in closed form the valence bond entanglement entropy as well as the valence bond probability distribution in these ground states. We find in particular that for the XXX spin chain, the number N_c of valence bonds connecting a subsystem of size L to the outside goes, in the thermodynamic limit, as = (4/pi^2) ln L, disproving a recent conjecture that this should be related with the von Neumann entropy, and thus equal to 1/(3 ln 2) ln L. Our results generalize to the Q-state Potts model.

  2. Transport pathways for mobile ions in disordered solids from the analysis of energy-scaled bond-valence mismatch landscapes.

    PubMed

    Adams, Stefan; Rao, R Prasada

    2009-05-01

    Structure-property relationships provide valuable guidelines for a systematic development of functional materials. Here an augmented bond-valence approach is worked out that is linked directly to the energy scale. This energy-scaled bond-valence approach is then used to identify ion-conduction pathways and to establish structure-property relationships in complex disordered solids using lithium silicate glasses as model systems. Representative local structure models of glassy solid electrolytes as a basis for the pathway analysis are derived from molecular dynamics simulations. Predictions of the bond-valence model from a static structure model are compared to a complete trajectory analysis, showing a high degree of agreement. The method yields consistent results when changing the simulation force field and is applicable to a wide range of glasses. PMID:19370216

  3. Symmetry breaking in benzene and larger aromatic molecules within generalized valence bond coupled cluster methods

    NASA Astrophysics Data System (ADS)

    Lawler, Keith V.; Beran, Gregory J. O.; Head-Gordon, Martin

    2008-01-01

    The origin of symmetry breaking (SB) in benzene in generalized valence bond methods is investigated within a coupled cluster formalism that correlates all valence electrons. Retention of a limited number of pair correlation amplitudes (as in the perfect- and imperfect-pairing models) that incompletely describes interpair correlations leads to symmetry breaking as the orbitals and amplitudes are optimized. Local correlation models that are exact for one, two, and three interacting pairs at the doubles excitation level are compared against the exact pair correlation treatment, which correlates four interacting pairs at once in the connected double substitution operator. For simplicity, this comparison is performed with a second-order model of electron correlation, which is reasonably faithful to the infinite-order result. The significant SB known for the one-pair model (perfect pairing) is not eliminated at the two-pair level, but is virtually eliminated at the three-pair level. Therefore, a tractable hybrid model is proposed, which combines three-pair correlations at the second-order level and infinite-order treatment for the strong imperfect-pairing correlations involving one and two-pair correlations. This model greatly reduces SB in benzene and larger delocalized ? systems such as naphthalene and the phenalenyl cation and anion. The resulting optimized orbitals are localized in the ? space but exhibit significant delocalization in the ? space. This means that correlation effects associated with different resonance structures are treated in a more balanced way than if the ? orbitals localize, leading to reduced SB.

  4. The resonating valence bond state in La2CuO4 and superconductivity

    NASA Astrophysics Data System (ADS)

    Anderson, P. W.

    1987-03-01

    The oxide superconductors, particularly those recently discovered that are based on La2CuO4, have a set of peculiarities that suggest a common, unique mechanism: they tend in every case to occur near a metal-insulator transition into an odd-electron insulator with peculiar magnetic properties. This insulating phase is proposed to be the long-sought 'resonating-valence-bond' state or 'quantum spin liquid' hypothesized in 1973. This insulating magnetic phase is favored by low spin, low dimensionality, and magnetic frustration. The preexisting magnetic singlet pairs of the insulating state become charged superconducting pairs when the insulator is doped sufficiently strongly. The mechanism for superconductivity is hence predominantly electronic and magnetic, although weak phonon interactions may favor the state. Many unusual properties are predicted, especially of the insulating state.

  5. Resonating Valence Bond Quantum Monte Carlo: Application to the ozone molecule

    E-print Network

    Sam Azadi; Ranber Singh; Thomas D. Kühne

    2015-02-24

    We study the potential energy surface of the ozone molecule by means of Quantum Monte Carlo simulations based on the resonating valence bond concept. The trial wave function consists of an antisymmetrized geminal power arranged in a single-determinant that is multiplied by a Jastrow correlation factor. Whereas the determinantal part incorporates static correlation effects, the augmented real-space correlation factor accounts for the dynamics electron correlation. The accuracy of this approach is demonstrated by computing the potential energy surface for the ozone molecule in three vibrational states: symmetric, asymmetric and scissoring. We find that the employed wave function provides a detailed description of rather strongly-correlated multi-reference systems, which is in quantitative agreement with experiment.

  6. Resonating Valence Bond Quantum Monte Carlo: Application to the ozone molecule

    E-print Network

    Azadi, Sam; Kühne, Thomas D

    2015-01-01

    We study the potential energy surface of the ozone molecule by means of Quantum Monte Carlo simulations based on the resonating valence bond concept. The trial wave function consists of an antisymmetrized geminal power arranged in a single-determinant that is multiplied by a Jastrow correlation factor. Whereas the determinantal part incorporates static correlation effects, the augmented real-space correlation factor accounts for the dynamics electron correlation. The accuracy of this approach is demonstrated by computing the potential energy surface for the ozone molecule in three vibrational states: symmetric, asymmetric and scissoring. We find that the employed wave function provides a detailed description of rather strongly-correlated multi-reference systems, which is in quantitative agreement with experiment.

  7. Frustrated resonating valence bond states in two dimensions: classification and short-range correlations.

    PubMed

    Yang, Fan; Yao, Hong

    2012-10-01

    Resonating valence bond (RVB) states are of crucial importance in our intuitive understanding of quantum spin liquids in 2D. We systematically classify short-range bosonic RVB states into symmetric or nematic spin liquids by examining their flux patterns. We further map short-range bosonic RVB states into projected BCS wave functions, on which we perform large-scale Monte Carlo simulations without the minus sign problem. Our results clearly show that both spin and dimer correlations decay exponentially in all the short-range frustrated (nonbipartite or Z2) bosonic RVB states we studied, indicating that they are gapped Z2 quantum spin liquids. Generically, we conjecture that all short-range frustrated bosonic RVB states in 2D have only short-range correlations. PMID:23083281

  8. Simulating a two-dimensional frustrated spin system with fermionic resonating-valence-bond states

    NASA Astrophysics Data System (ADS)

    Chou, Chung-Pin; Chen, Hong-Yi

    2014-07-01

    The frustrated Heisenberg J1-J2 model on a square lattice is numerically investigated by variational Monte Carlo simulations. We propose an antiferromagnetic fermion resonating-valence-bond (AF-fRVB) state that has the ability to examine the entire phase diagram in the J1-J2 model. Two phase transition points, the second order around J2/J1=0.45 and the first order around J2/J1=0.6, can be extracted more clearly than the conventional bosonic RVB state. At the maximally frustrated point (J2/J1=0.5), the AF-fRVB state shows the variational ground-state energy in the thermodynamic limit very close to the one estimated by the projected entangled pair state at the largest bond dimension available. On the other hand, in the frustrated regime 0.4?J2/J1?0.5, AF-fRVB states with exts2 (using the terminology in the field of iron-based superconductors) and dxy pairing symmetries are degenerate in the thermodynamic limit, implying the existence of gapless Dirac excitations in the spinon spectrum.

  9. Resonating Valence Bonds and Mean-Field d-Wave Superconductivity in Graphite

    SciTech Connect

    Black-Schaffer, Annica M.

    2010-04-27

    We investigate the possibility of inducing superconductivity in a graphite layer by electronic correlation effects. We use a phenomenological microscopic Hamiltonian which includes nearest neighbor hopping and an interaction term which explicitly favors nearest neighbor spin-singlets through the well-known resonance valence bond (RVB) character of planar organic molecules. Treating this Hamiltonian in mean-field theory, allowing for bond-dependent variation of the RVB order parameter, we show that both s- and d-wave superconducting states are possible. The d-wave solution belongs to a two-dimensional representation and breaks time reversal symmetry. At zero doping there exists a quantum critical point at the dimensionless coupling J/t = 1.91 and the s- and d-wave solutions are degenerate for low temperatures. At finite doping the d-wave solution has a significantly higher T{sub c} than the s-wave solution. By using density functional theory we show that the doping induced from sulfur absorption on a graphite layer is enough to cause an electronically driven d-wave superconductivity at graphite-sulfur interfaces. We also discuss applying our results to the case of the intercalated graphites as well as the validity of a mean-field approach.

  10. Mixed valency in quadruple hydrogen-bonded dimers of bis(biimidazolate)dirhodium complexes.

    PubMed

    Jin-Long; Matsuda, Yuki; Uemura, Kazuhiro; Ebihara, Masahiro

    2015-03-01

    Dirhodium complexes with biimidazole (H2bim) ligands [Rh2(O2CR)2(H2bim)2Cl2] (R = Bu ([1Cl2]), Pr ([2Cl2])), [Rh2(O2CBu)2(H2bim)2](PF6)2 ([1](PF6)2), [Rh2(O2CBu)2(H2bim)2(PPh3)2](PF6)2 ([1(PPh3)2](PF6)2), and [Rh2(O2CPr)2(H2bim)2(PPh3)2]Cl2 ([2(PPh3)2]Cl2) have been synthesized. Deprotonation of the biimidazole complexes afforded the quadruply hydrogen-bonded dimers of the biimidazolate complexes [Rh2(O2CR)2(Hbim)2(PPh3)2]2 (R = Bu ([1'(PPh3)2]2) and Pr ([2'(PPh3)2]2)). Complementary hydrogen bonds between the Hbim(-) ligands are not coplanar because the Hbim(-) ions in one dirhodium complex are not parallel (the dihedral angle between them is ca. 15°). A cyclic voltammogram of [1'(PPh3)2]2 shows two sets of two consecutive oxidation waves in CH2Cl2. The one-electron-oxidized species of [1'(PPh3)2]2 showed no intervalence charge-transfer band in the electronic spectrum and an axially symmetrical ESR spectrum with hyperfine structure because of two phosphorus atoms. These observations show that the odd electron is localized in a ?(Rh-Rh) orbital on one dirhodium unit. Theoretical calculations indicate that an oxidized complex [Rh2(O2CMe)2(bim)2(PMe3)2](-) hydrogen bonded with a biimidazole complex [Rh2(O2CMe)2(H2bim)2(PMe3)2](2+) was a stable mixed-valence complex. PMID:25692759

  11. Nonorthogonal orbital based n-body reduced density matrices and their applications to valence bond theory. III. Second-order perturbation theory using valence bond self-consistent field function as reference

    NASA Astrophysics Data System (ADS)

    Chen, Zhenhua; Chen, Xun; Ying, Fuming; Gu, Junjing; Zhang, Huaiyu; Wu, Wei

    2014-10-01

    Using the formulas and techniques developed in Papers I and II of this series, the recently developed second-order perturbation theory based on a valence bond self-consistent field reference function (VBPT2) has been extended by using the internally contracted correction wave function. This ansatz strongly reduces the size of the interaction space compared to the uncontracted wave function and thus improves the capability of the VBPT2 method dramatically. Test calculations show that internally contracted VBPT2 using only a small number of reference valence bond functions, can give results as accuracy as the VBPT2 method and other more sophisticated methods such as full configuration interaction and multireference configuration interaction.

  12. Valence bond and enzyme catalysis: a time to break down and a time to build up.

    PubMed

    Sharir-Ivry, Avital; Varatharaj, Rajapandian; Shurki, Avital

    2015-05-01

    Understanding enzyme catalysis and developing ability to control of it are two great challenges in biochemistry. A few successful examples of computational-based enzyme design have proved the fantastic potential of computational approaches in this field, however, relatively modest rate enhancements have been reported and the further development of complementary methods is still required. Herein we propose a conceptually simple scheme to identify the specific role that each residue plays in catalysis. The scheme is based on a breakdown of the total catalytic effect into contributions of individual protein residues, which are further decomposed into chemically interpretable components by using valence bond theory. The scheme is shown to shed light on the origin of catalysis in wild-type haloalkane dehalogenase (wt-DhlA) and its mutants. Furthermore, the understanding gained through our scheme is shown to have great potential in facilitating the selection of non-optimal sites for catalysis and suggesting effective mutations to enhance the enzymatic rate. PMID:25808731

  13. Q: a molecular dynamics program for free energy calculations and empirical valence bond simulations in biomolecular systems.

    PubMed

    Marelius, J; Kolmodin, K; Feierberg, I; Aqvist, J

    1998-01-01

    A new molecular dynamics program for free energy calculations in biomolecular systems is presented. It is principally designed for free energy perturbation simulations, empirical valence bond calculations, and binding affinity estimation by linear interaction energy methods. Evaluation of ligand-binding selectivity and free energy profiles for nucleophile activation in two protein tyrosine phosphatases as well as absolute binding affinity estimation for a lysine-binding protein are given as examples. PMID:10522241

  14. Chemical bonding, elasticity, and valence force field models: A case study for -Pt2Si and PtSi J. E. Klepeis,1

    E-print Network

    Hart, Gus

    Chemical bonding, elasticity, and valence force field models: A case study for -Pt2Si and PtSi J. E 26 September 2001 We have carried out a detailed study of the chemical bonding for two room yields quantitative information about the nature of the chemical bonding that is not easily discernible

  15. Insights into the Electronic Structure of Ozone and Sulfur Dioxide from Generalized Valence Bond Theory: Bonding in O3 and SO2.

    PubMed

    Takeshita, Tyler Y; Lindquist, Beth A; Dunning, Thom H

    2015-07-16

    There are many well-known differences in the physical and chemical properties of ozone (O3) and sulfur dioxide (SO2). O3 has longer and weaker bonds than O2, whereas SO2 has shorter and stronger bonds than SO. The O-O2 bond is dramatically weaker than the O-SO bond, and the singlet-triplet gap in SO2 is more than double that in O3. In addition, O3 is a very reactive species, while SO2 is far less so. These disparities have been attributed to variations in the amount of diradical character in the two molecules. In this work, we use generalized valence bond (GVB) theory to characterize the electronic structure of ozone and sulfur dioxide, showing O3 does indeed possess significant diradical character, whereas SO2 is effectively a closed shell molecule. The GVB results provide critical insights into the genesis of the observed difference in these two isoelectronic species. SO2 possesses a recoupled pair bond dyad in the a"(?) system, resulting in SO double bonds. The ? system of O3, on the other hand, has a lone pair on the central oxygen atom plus a pair of electrons in orbitals on the terminal oxygen atoms that give rise to a relatively weak ? interaction. PMID:26068052

  16. Valence-bond crystal in the extended kagome spin-(1)/(2) quantum Heisenberg antiferromagnet: A variational Monte Carlo approach

    NASA Astrophysics Data System (ADS)

    Iqbal, Yasir; Becca, Federico; Poilblanc, Didier

    2011-03-01

    The highly frustrated spin-(1)/(2) quantum Heisenberg model with both nearest (J1) and next-nearest (J2) neighbor exchange interactions is revisited by using an extended variational space of projected wave functions that are optimized with state-of-the-art methods. Competition between modulated valence-bond crystals (VBCs) proposed in the literature and the Dirac spin liquid (DSL) is investigated. We find that the addition of a small ferromagnetic next-nearest-neighbor exchange coupling |J2|>0.09J1 leads to stabilization of a 36-site unit cell VBC, although the DSL remains a local minimum of the variational parameter landscape. This implies that the VBC is not trivially connected to the DSL; instead it possesses a nontrivial flux pattern and large dimerization.

  17. Valence-bond crystal in the extended Kagomé spin- 1 / 2 quantum Heisenberg antiferromagnet: A variational Monte Carlo approach

    NASA Astrophysics Data System (ADS)

    Becca, Federico; Iqbal, Yasir; Poilblanc, Didier

    2011-03-01

    The highly-frustrated spin- 1 / 2 quantum Heisenberg model with both nearest (J1) and next-nearest (J2) neighbor exchange interactions is revisited by using an extended variational space of projected wave functions that are optimized with state-of-the-art methods. Competition between modulated valence-bond crystals (VBC) proposed in the literature and the Dirac spin liquid (DSL) is investigated. We find that the addition of a small ferromagnetic next-nearest-neighbor exchange coupling |J2 | > 0.09J1 leads to stabilization of a 36-site unit cell VBC, although the DSL remains a local minimum of the variational parameter landscape. This implies that the VBC is not trivially connected to the DSL: instead it possesses a non-trivial flux pattern and large dimerization.

  18. Efficient automatic screening for Li ion conductive inorganic oxides with bond valence pathway models and percolation algorithm

    NASA Astrophysics Data System (ADS)

    Nakayama, Masanobu; Kimura, Mayumi; Jalem, Randy; Kasuga, Toshihiro

    2016-01-01

    Fast ion conductive solid oxide electrolytes are urgently needed because of the development of batteries, fuel cells, and sensors. Ab initio density functional theory can predict ionic conductivities with high accuracy, although it often requires large computational resources and time. In this paper, we use empirical bond valence relations [Adams et al., Phys. Status Solidi A 208, 1746 (2011)] and a percolation algorithm for fast, efficient, fully automated evaluation of migration energies for Li ion conduction in 14 olivine-type LiMXO4 compounds. The results showed a high correlation coefficient with the ab initio density functional theory (DFT) approach, indicating that our method could be attractive for identifying fast ion conductors in databases of numerous candidates.

  19. High-Order Coupled Cluster Method (CCM) Calculations for Quantum Magnets with Valence-Bond Ground States

    NASA Astrophysics Data System (ADS)

    Farnell, D. J. J.; Richter, J.; Zinke, R.; Bishop, R. F.

    2009-04-01

    In this article, we prove that exact representations of dimer and plaquette valence-bond ket ground states for quantum Heisenberg antiferromagnets may be formed via the usual coupled cluster method (CCM) from independent-spin product (e.g. Néel) model states. We show that we are able to provide good results for both the ground-state energy and the sublattice magnetization for dimer and plaquette valence-bond phases within the CCM. As a first example, we investigate the spin-half J 1- J 2 model for the linear chain, and we show that we are able to reproduce exactly the dimerized ground (ket) state at J 2/ J 1=0.5. The dimerized phase is stable over a range of values for J 2/ J 1 around 0.5, and results for the ground-state energies are in good agreement with the results of exact diagonalizations of finite-length chains in this regime. We present evidence of symmetry breaking by considering the ket- and bra-state correlation coefficients as a function of J 2/ J 1. A radical change is also observed in the behavior of the CCM sublattice magnetization as we enter the dimerized phase. We then consider the Shastry-Sutherland model and demonstrate that the CCM can span the correct ground states in both the Néel and the dimerized phases. Once again, very good results for the ground-state energies are obtained. We find CCM critical points of the bra-state equations that are in agreement with the known phase transition point for this model. The results for the sublattice magnetization remain near to the "true" value of zero over much of the dimerized regime, although they diverge exactly at the critical point. Finally, we consider a spin-half system with nearest-neighbor bonds for an underlying lattice corresponding to the magnetic material CaV4O9 (CAVO). We show that we are able to provide excellent results for the ground-state energy in each of the plaquette-ordered, Néel-ordered, and dimerized regimes of this model. The exact plaquette and dimer ground states are reproduced by the CCM ket state in their relevant limits. Furthermore, we estimate the range over which the Néel order is stable, and we find the CCM result is in reasonable agreement with the results obtained by other methods. Our new approach has the dual advantages that it is simple to implement and that existing CCM codes for independent-spin product model states may be used from the outset. Furthermore, it also greatly extends the range of applicability to which the CCM may be applied. We believe that the CCM now provides an excellent choice of method for the study of systems with valence-bond quantum ground states.

  20. On The Nature of the Halogen Bond.

    PubMed

    Wang, Changwei; Danovich, David; Mo, Yirong; Shaik, Sason

    2014-09-01

    The wide-ranging applications of the halogen bond (X-bond), notably in self-assembling materials and medicinal chemistry, have placed this weak intermolecular interaction in a center of great deal of attention. There is a need to elucidate the physical nature of the halogen bond for better understanding of its similarity and differences vis-à-vis other weak intermolecular interactions, for example, hydrogen bond, as well as for developing improved force-fields to simulate nano- and biomaterials involving X-bonds. This understanding is the focus of the present study that combines the insights of a bottom-up approach based on ab initio valence bond (VB) theory and the block-localized wave function (BLW) theory that uses monomers to reconstruct the wave function of a complex. To this end and with an aim of unification, we studied the nature of X-bonds in 55 complexes using the combination of VB and BLW theories. Our conclusion is clear-cut; most of the X-bonds are held by charge transfer interactions (i.e., intermolecular hyperconjugation) as envisioned more than 60 years ago by Mulliken. This is consistent with the experimental and computational findings that X-bonds are more directional than H-bonds. Furthermore, the good linear correlation between charge transfer energies and total interaction energies partially accounts for the success of simple force fields in the simulation of large systems involving X-bonds. PMID:26588518

  1. Analysis of Bonding Patterns in the Valence Isoelectronic series O-3, S-3, SO2 and OS2 in Terms of Oriented Quasi-Atomic Molecular Orbitals

    SciTech Connect

    Glezakou, Vassiliki Alexandra; Elbert, Stephen T.; Xantheas, Sotiris S.; Ruedenberg, Klaus

    2010-08-26

    A novel analysis of the chemical bonding pattern in the valence isoelectronic series of triatomic molecules O3, S3, SO2 and OS2 is reported. The analysis is based on examining the bond order matrix elements between the Oriented Localized Molecular Orbitals (OLMOs) that are localized on the three individual left (L), center (C) and right (R) atoms. The analysis indicates that there is a (L-C) and (C-R) ?-bonding interaction and a (L-R) ??antibonding interaction. This finding supports the previously proposed "partial biradical" interpretation of these triatomic systems, which had recently been challenged.

  2. Charge Order Instability in Doped Resonating Valence Bond State and Magnetic Orbits from Reconstructed Fermi Surface in Underdoped Cuprates

    NASA Astrophysics Data System (ADS)

    Zhang, Long; Mei, Jia-Wei

    2015-03-01

    Recent experiments reveal incommensurate charge density wave (CDW) and quantum oscillations (QO) in the pseudogap phase of underdoped cuprates. In this work, we take a phenomenological synthesis of the resonating valence bond (RVB) state and the CDW order. Starting from the Yang-Rice-Zhang (YRZ) ansatz for the Green's function of the RVB state, we show that the CDW instability at wavevectors connecting the tips of the Fermi arcs can induce Fermi surface reconstruction. We find three primary magnetic orbits in the QO spectrum, the CDW-induced electron-like ? and hole-like ? orbits and the ? orbit enclosing the initial nodal YRZ hole pockets due to magnetic breakdown. Their combinations naturally explain the multi-component QO pattern observed in experiments. The ? orbit encloses an area satisfying the generalized Luttinger theorem. The cyclotron mass of the ? orbit increases monotonically with doping in agreement with the optical Hall angle measurements , while that of the ? orbit is enhanced as the CDW order vanishes on approaching two critical dopings. However, we find that the enhancement of mHα is overestimated in QO experiments due to the ignorance of the impact of the CDW order suppression with increasing temperature. Work supported by the NBRPC Grant No. 2010CB923003, by the Government of Canada through Industry Canada and by the Province of Ontario through the Ministry of Research.

  3. Test of the Bardeen-Cooper-Schrieffer and the resonant-valence-bond wave functions as solutions of the Hubbard model: A small-cluster calculation

    SciTech Connect

    Falicov, L.M.; Proetto, C.R. )

    1993-06-01

    With the purpose of assessing the validity of commonly used approximations, best variational solutions are calculated for a four-site (tetrahedral-cluster) Hubbard model with periodic boundary conditions and compared with exact results. In particular, the optimum number-conserving Bardeen-Cooper-Schrieffer-type variational solution is obtained for two, four, and six electrons, and the optimal resonanting-valence-bond state for four electrons. For an attractive interaction [ital U], the exact ground state of the system is obtained in all four cases. If the interaction [ital U] is repulsive, the exact ground state is obtained only when the cluster contains two and six electrons. For four electrons the BCS approximation is only satisfactory for relatively small [ital U]. For any positive [ital U] the resonating-valence-bond state on the other hand, gives very good (albeit not exact) energies for the ground state.

  4. Chemical bonding and charge redistribution - Valence band and core level correlations for the Ni/Si, Pd/Si, and Pt/Si systems

    NASA Technical Reports Server (NTRS)

    Grunthaner, P. J.; Grunthaner, F. J.; Madhukar, A.

    1982-01-01

    Via a systematic study of the correlation between the core and valence level X-ray photoemission spectra, the nature of the chemical bonding and charge redistribution for bulk transition metal silicides has been examined. Particular emphasis is placed on Pt2Si and PtSi. It is observed that the strength of the metal (d)-silicon (p) interaction increases in the order Ni2Si, Pd2Si, Pt2Si. It is also observed that both the metal and silicon core lines shift to higher binding energy as the silicides are formed. The notion of charge redistribution for metallic bonds is invoked to explain these data.

  5. On the transferability of electron density in binary vanadium borides VB, V3B4 and VB2.

    PubMed

    Terlan, Bürgehan; Akselrud, Lev; Baranov, Alexey I; Borrmann, Horst; Grin, Yuri

    2015-12-01

    Binary vanadium borides are suitable model systems for a systematic analysis of the transferability concept in intermetallic compounds due to chemical intergrowth in their crystal structures. In order to underline this structural relationship, topological properties of the electron density in VB, V3B4 and VB2 reconstructed from high-resolution single-crystal X-ray diffraction data as well as derived from quantum chemical calculations, are analysed in terms of Bader's Quantum Theory of Atoms in Molecules [Bader (1990). Atoms in Molecules: A Quantum Theory, 1st ed. Oxford: Clarendon Press]. The compounds VB, V3B4 and VB2 are characterized by a charge transfer from the metal to boron together with two predominant atomic interactions, the shared covalent B-B interactions and the polar covalent B-M interactions. The resembling features of the crystal structures are well reflected by the respective B-B interatomic distances as well as by ?(r) values at the B-B bond critical points. The latter decrease with an increase in the corresponding interatomic distances. The B-B bonds show transferable electron density properties at bond critical points depending on the respective bond distances. PMID:26634735

  6. Metal-Metal Bonding in Trinuclear, Mixed-Valence [Ti3X12](4-) (X = F, Cl, Br, I) Face-Shared Complexes.

    PubMed

    Hewage, Jinasena W; Cavigliasso, Germán; Stranger, Robert

    2015-11-16

    Metal-metal bonding in structurally characterized In4Ti3Br12, comprising linear, mixed-valence d(1)d(2)d(1) face-shared [Ti3Br12](4-) units with a Ti-Ti separation of 3.087 Å and strong antiferromagnetic coupling (? = -1216 K), has been investigated using density functional theory. The antiferromagnetic configuration, in which the single d electron on each terminal Ti(III) (d(1)) metal center is aligned antiparallel to the two electrons occupying the central Ti(II) (d(2)) metal site, is shown to best agree with the reported structural and magnetic data and is consistent with an S = 0 ground state in which two of the four metal-based electrons are involved in a two-electron, three-center ? bond between the Ti atoms (formal Ti-Ti bond order of ?0.5). However, the unpaired spin densities on the Ti sites indicate that while the metal-metal ? interaction is strong, the electrons are not fully paired off and consequently dominate the ground state antiferromagnetic coupling. The same overall partially delocalized bonding regime is predicted for the other three halide [Ti3X12](4-) (X = F, Cl, I) systems with the metal-metal bonding becoming weaker as the halide group is descended. The possibility of bond-stretch isomerism was also examined where one isomer has a symmetric structure with identical Ti-Ti bonds while the other is unsymmetric with one short and one long Ti-Ti bond. Although calculations indicate that the latter form is more stable, the barrier to interconversion between equivalent unsymmetric forms, where the short Ti-Ti bond is on one side of the trinuclear unit or the other, is relatively small such that at room temperature only the averaged (symmetric) structure is likely to be observed. PMID:26523831

  7. Electronic structure and chemical bonding of {alpha}- and {beta}-CeIr{sub 2}Si{sub 2} intermediate valence compounds

    SciTech Connect

    Matar, Samir F.; Poettgen, Rainer; Chevalier, Bernard

    2012-02-15

    The dimorphism of the intermediate valence ternary cerium silicide CeIr{sub 2}Si{sub 2} in the ThCr{sub 2}Si{sub 2} ({alpha}) and CaBe{sub 2}Ge{sub 2} ({beta}) modifications is addressed in the framework of the density functional theory. The geometry optimization is in good agreement with the experiment and the subsequent establishment of the energy-volume equation of state (EOS) indicates a stabilization of the {beta}-type relative to the {alpha}-type concomitant with the trend of the cerium valence, changing to tetravalent in {beta}-CeIr{sub 2}Si{sub 2}. This is equally shown from the site projected DOS and from the large increase of the electronic contribution to the specific heat. The chemical bonding indicates the strongest bonding interactions within the Ir-Si substructure in both varieties. Stabilization of {beta}-CeIr{sub 2}Si{sub 2} with almost tetravalent cerium is in good agreement with Th{sup IV}Ir{sub 2}Si{sub 2} which exclusively crystallizes in the CaBe{sub 2}Ge{sub 2} type. The EOS behavior of different RIr{sub 2}Si{sub 2} (R=Th, Ce, La) is comparatively discussed. - Graphical abstract: The crystal structures of {alpha}- and {beta}-CeIr{sub 2}Si{sub 2}. Relevant interatomic distances (A), the three-dimensional [Ir{sub 2}Si{sub 2}] networks and the crystallographically independent iridium and silicon sites are indicated. Highlights: Black-Right-Pointing-Pointer Energy stabilization of (HT) {beta}-CeIr{sub 2}Si{sub 2} versus (LT) {alpha}-CeIr{sub 2}Si{sub 2} from DFT methods. Black-Right-Pointing-Pointer Concomitant with the change of Ce valence to tetravalent (HT)-enhanced specific heat. Black-Right-Pointing-Pointer Equations of states for La, Ce and Th members with CeIr{sub 2}Si{sub 2} resembling tetravalent-Th. Black-Right-Pointing-Pointer Chemical bonding shows changes on the {l_brace}Ir{sub 2}Si{sub 2}{r_brace} intralayer and Ce{sup IV}-Ir bonds.

  8. Chemical-shift tensors of heavy nuclei in network solids: a DFT/ZORA investigation of (207)Pb chemical-shift tensors using the bond-valence method.

    PubMed

    Alkan, Fahri; Dybowski, C

    2015-10-14

    Cluster models are used in calculation of (207)Pb NMR magnetic-shielding parameters of ?-PbO, ?-PbO, Pb3O4, Pb2SnO4, PbF2, PbCl2, PbBr2, PbClOH, PbBrOH, PbIOH, PbSiO3, and Pb3(PO4)2. We examine the effects of cluster size, method of termination of the cluster, charge on the cluster, introduction of exact exchange, and relativistic effects on calculation of magnetic-shielding tensors with density functional theory. Proper termination of the cluster for a network solid, including approximations such as compensation of charge by the bond-valence (BV) method, is essential to provide results that agree with experiment. The inclusion of relativistic effects at the spin-orbit level for such heavy nuclei is an essential factor in achieving agreement with experiment. PMID:26345261

  9. Hydrogen-bonded assemblies of two-electron reduced mixed-valence [XMo12O40] (X = P and Si) with p-phenylenediamines.

    PubMed

    Akutagawa, Tomoyuki; Kudo, Fumito; Tsunashima, Ryo; Noro, Shin-ichiro; Cronin, Leroy; Nakamura, Takayoshi

    2011-07-18

    Hydrogen-bonded assemblies of the two-electron reduced mixed-valence Keggin clusters [PMo(12)O(40)](5-) and [SiMo(12)O(40)](6-) were obtained by the one-pot electron-transfer reactions between p-phenylenediamine (PPD) or 2,3,5,6-tetramethyl-PPD (TMPPD) (donors) and H(+)(3)[PMo(12)O(40)](3-) or H(+)(4)[SiMo(12)O(40)](4-) (acceptors) in CH(3)CN. The redox states of the [PMo(12)O(40)](5-) and [SiMo(12)O(40)](6-) clusters were confirmed by the redox titrations and electronic absorption measurements. In (HPPD(+))(3)(H(+))(2)[PMo(12)O(40)](5-)(CH(3)CN)(3-6) (1), the N-H ~ O hydrogen-bonded interactions between the monoprotonated HPPD(+) (or diprotonated H2PPD(2+)) and the [PMo(12)O(40)](5-) resulted in a windmill-like assembly and hydrophilic one-dimensional channels are formed with a cross-sectional area of 0.065 nm(2), and these are filled by the CH(3)CN molecules. Also, the CH(3)CN molecules in salt 1 were removed by immersing the single crystals of 1 into H(2)O, CH(3)OH, and C(2)H(5)OH solvents. In the compound, (HTMPPD(+))(6)[SiMo(12)O(40)](6-)(CH(3)CN)(6) (2), the N-H ~ O hydrogen-bonded interactions between the monoprotonated HTMPPD(+) molecules and the [SiMo(12)O(40)](6-) formed a "Saturn-ring"-like assembly. Each Saturn-ring was arranged into an hexagonally packed array via hydrogen-bonded and ?-stacking interactions of HTMPPD(+), while the CH(3)CN solvent present in salt 2 are only found in the zero-dimensional isolated cavities. PMID:21671561

  10. Valence State Driven Site Preference in the Quaternary Compound Ca5MgAgGe5: An Electron-Deficient Phase with Optimized Bonding

    SciTech Connect

    Ponou, Simeon; Lidin, Sven; Zhang, Yuemei; Miller, Gordon J.

    2014-04-18

    The quaternary phase Ca5Mg0.95Ag1.05(1)Ge5 (3) was synthesized by high-temperature solid-state techniques, and its crystal structure was determined by single-crystal diffraction methods in the orthorhombic space group Pnma – Wyckoff sequence c12 with a = 23.1481(4) Å, b = 4.4736(1) Å, c = 11.0128(2) Å, V = 1140.43(4) Å3, Z = 4. The crystal structure can be described as linear intergrowths of slabs cut from the CaGe (CrB-type) and the CaMGe (TiNiSi-type; M = Mg, Ag) structures. Hence, 3 is a hettotype of the hitherto missing n = 3 member of the structure series with the general formula R2+nT2X2+n, previously described with n = 1, 2, and 4. The member with n = 3 was predicted in the space group Cmcm – Wyckoff sequence f5c2. The experimental space group Pnma (in the nonstandard setting Pmcn) corresponds to a klassengleiche symmetry reduction of index two of the predicted space group Cmcm. This transition originates from the switching of one Ge and one Ag position in the TiNiSi-related slab, a process that triggers an uncoupling of each of the five 8f sites in Cmcm into two 4c sites in Pnma. The Mg/Ag site preference was investigated using VASP calculations and revealed a remarkable example of an intermetallic compound for which the electrostatic valency principle is a critical structure-directing force. The compound is deficient by one valence electron according to the Zintl concept, but LMTO electronic structure calculations indicate electronic stabilization and overall bonding optimization in the polyanionic network. Other stability factors beyond the Zintl concept that may account for the electronic stabilization are discussed.

  11. Relation between the structure of black phosphorus and the structure of its photoelectron spectrum, due to the electrons of the inner valence bands, and their role in the chemical bond

    SciTech Connect

    Gagarin, S.G.; Teterin, Yu.A.

    1986-01-01

    On the basis of calculations by the extended Hueckel method it was shown that there is a relation between the structure of the photoelectron spectrum of black phosphorus, arising from the electrons of the valence bands, and its structure in the solid phase. The bonding (or antibonding) character of these bands and the preferred contribution from the electrons of the inner valence bands to the chemical bonding of the phosphorus atoms were established. It was noted the main conclusions about the nature of the bond in the atomic crystal can be reached on the basis of the cluster approximation, whereas the band structure has to be taken into account for the interpretation of the individual details of the spectrum.

  12. The Haldane State in CsNiCl 3 Detected by Magnetization Measurements —Observation of Quantum-Classical Crossover and the Valence Bond Solid State—

    NASA Astrophysics Data System (ADS)

    Asano, Takayuki; Ajiro, Yoshitami; Mekata, Mamoru; Kamishima, Kenji; Koui, Katsuhiko; Goto, Tsuneaki; Furusawa, Masahiro; Hori, Hidenobu

    1997-02-01

    We have confirmed from susceptibility and magnetization measurements that the Haldane state really exists in 1D phase of CsNiCl3 which undergoes 3D ordering at T N=4.8 K. The observed susceptibility at low fields follows the predicted curve for the S=1 quantum chain with energy gap (?/k B˜10 K) down to near T N. A more definite evidence for the Haldane state is given by studying the effect of the nonmagnetic impurities. We have revealed a real existence of S=1/2 edge states characteristic of the Haldane state and further revealed a crossover from the quantum to classical regimes as a function of both temperature and field. The result is consistent with the model that at low temperatures (TValence-Bond-Solid while at high temperatures (T>|J|/k B) and high fields (H>H G) the system is not in the Haldane state any more.

  13. High-throughput design and optimization of fast lithium ion conductors by the combination of bond-valence method and density functional theory

    NASA Astrophysics Data System (ADS)

    Xiao, Ruijuan; Li, Hong; Chen, Liquan

    2015-09-01

    Looking for solid state electrolytes with fast lithium ion conduction is an important prerequisite for developing all-solid-state lithium secondary batteries. By combining the simulation techniques in different levels of accuracy, e.g. the bond-valence (BV) method and the density functional theory (DFT), a high-throughput design and optimization scheme is proposed for searching fast lithium ion conductors as candidate solid state electrolytes for lithium rechargeable batteries. The screening from more than 1000 compounds is performed through BV-based method, and the ability to predict reliable tendency of the Li+ migration energy barriers is confirmed by comparing with the results from DFT calculations. ?-Li3PS4 is taken as a model system to demonstrate the application of this combination method in optimizing properties of solid electrolytes. By employing the high-throughput DFT simulations to more than 200 structures of the doping derivatives of ?-Li3PS4, the effects of doping on the ionic conductivities in this material are predicted by the BV calculations. The O-doping scheme is proposed as a promising way to improve the kinetic properties of this materials, and the validity of the optimization is proved by the first-principles molecular dynamics (FPMD) simulations.

  14. High-throughput design and optimization of fast lithium ion conductors by the combination of bond-valence method and density functional theory

    PubMed Central

    Xiao, Ruijuan; Li, Hong; Chen, Liquan

    2015-01-01

    Looking for solid state electrolytes with fast lithium ion conduction is an important prerequisite for developing all-solid-state lithium secondary batteries. By combining the simulation techniques in different levels of accuracy, e.g. the bond-valence (BV) method and the density functional theory (DFT), a high-throughput design and optimization scheme is proposed for searching fast lithium ion conductors as candidate solid state electrolytes for lithium rechargeable batteries. The screening from more than 1000 compounds is performed through BV-based method, and the ability to predict reliable tendency of the Li+ migration energy barriers is confirmed by comparing with the results from DFT calculations. ?-Li3PS4 is taken as a model system to demonstrate the application of this combination method in optimizing properties of solid electrolytes. By employing the high-throughput DFT simulations to more than 200 structures of the doping derivatives of ?-Li3PS4, the effects of doping on the ionic conductivities in this material are predicted by the BV calculations. The O-doping scheme is proposed as a promising way to improve the kinetic properties of this materials, and the validity of the optimization is proved by the first-principles molecular dynamics (FPMD) simulations. PMID:26387639

  15. High-throughput design and optimization of fast lithium ion conductors by the combination of bond-valence method and density functional theory.

    PubMed

    Xiao, Ruijuan; Li, Hong; Chen, Liquan

    2015-01-01

    Looking for solid state electrolytes with fast lithium ion conduction is an important prerequisite for developing all-solid-state lithium secondary batteries. By combining the simulation techniques in different levels of accuracy, e.g. the bond-valence (BV) method and the density functional theory (DFT), a high-throughput design and optimization scheme is proposed for searching fast lithium ion conductors as candidate solid state electrolytes for lithium rechargeable batteries. The screening from more than 1000 compounds is performed through BV-based method, and the ability to predict reliable tendency of the Li(+) migration energy barriers is confirmed by comparing with the results from DFT calculations. ?-Li3PS4 is taken as a model system to demonstrate the application of this combination method in optimizing properties of solid electrolytes. By employing the high-throughput DFT simulations to more than 200 structures of the doping derivatives of ?-Li3PS4, the effects of doping on the ionic conductivities in this material are predicted by the BV calculations. The O-doping scheme is proposed as a promising way to improve the kinetic properties of this materials, and the validity of the optimization is proved by the first-principles molecular dynamics (FPMD) simulations. PMID:26387639

  16. Valence band spectra of 4d and 5d silicides

    NASA Astrophysics Data System (ADS)

    Yarmoshenko, Yu M.; Shamin, S. N.; Elokhina, L. V.; Dolgih, V. E.; Kurmaev, E. Z.; Bartkowski, S.; Neumann, M.; Ederer, D. L.; Göransson, K.; Noläng, B.; Engström, I.

    1997-10-01

    A full study of the electronic structure of 4d and 5d silicides (RuSi, RhSi, PdSi, OsSi, IrSi, 0953-8984/9/43/023/img14, PtSi) is undertaken including XPS VB and XES (0953-8984/9/43/023/img15 and 0953-8984/9/43/023/img16) measurements and LMTO band structure calculations. It is found that d bands which dominate the density of states are more localized with increasing atomic number Z of the transition metal. A strong hybridization between silicon 3p and transition metal d states occurs over the entire valence band. Si 3s states are found to be not mixed with Si 3p and nd states but Si 3d states participate in bonding and hybridize with transition metal d states. The non-bonding character of the majority of nd states is not confirmed for 4d and 5d silicides.

  17. Bond electron pair: its relevance and analysis from the quantum chemistry point of view.

    PubMed

    Malrieu, Jean-Paul; Guihéry, Nathalie; Calzado, Carmen Jiménez; Angeli, Celestino

    2007-01-15

    This paper first comments on the surprisingly poor status that Quantum Chemistry has offered to the fantastic intuition of Lewis concerning the distribution of the electrons in the molecule. Then, it advocates in favor of a hierarchical description of the molecular wave-function, distinguishing the physics taking place in the valence space (in the bond and between the bonds), and the dynamical correlation effects. It is argued that the clearest pictures of the valence electronic population combine two localized views, namely the bond (and lone pair) Molecular Orbitals and the Valence Bond decomposition of the wave-function, preferably in the orthogonal version directly accessible from the complete active space self consistent field method. Such a reading of the wave function enables one to understand the work of the nondynamical correlation as an enhancement of the weight of the low-energy VB components, i.e. as a better compromise between the electronic delocalization and the energetic preferences of the atoms. It is suggested that regarding the bond building, the leading dynamical correlation effect may be the dynamical polarization phenomenon. It is shown that most correlation effects do not destroy the bond electron pairs and remain compatible with Lewis' vision. A certain number of free epistemological considerations have been introduced in the development of the argument. PMID:17109436

  18. Titanium Target Module V.B. Graves

    E-print Network

    McDonald, Kirk

    Titanium Target Module Changes V.B. Graves P.T. Spampinato T.A. Gabriel MERIT VRVS Meeting February, reducer also Titanium #12;7 OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY MERIT VRVS Mtg 1 Feb

  19. Unprecedented structural variations in trinuclear mixed valence Co(II/III) complexes: theoretical studies, pnicogen bonding interactions and catecholase-like activities.

    PubMed

    Hazari, Alokesh; Kanta Das, Lakshmi; Kadam, Ramakant M; Bauzá, Antonio; Frontera, Antonio; Ghosh, Ashutosh

    2015-02-28

    Three new mixed valence trinuclear Co(II/III) compounds cis-[Co3L2(MeOH)2(N3)2(?1,1-N3)2] (1), trans-[Co3L2(H2O)2(N3)2(?1,1-N3)2]·(H2O)2 (2) and [Co3L(R)2(N3)3(?1,3-N3)] (3) have been synthesized by reacting a di-Schiff base ligand (H2L) or its reduced form [H2LR] (where H2L= N,N'-bis(salicylidene)-1,3-propanediamine and H2LR= N,N'-bis(2-hydroxybenzyl)-1,3-propanediamine) with cobalt perchlorate hexahydrate and sodium azide. All three products have been characterized by IR, UV-Vis and EPR spectroscopies, ESI-MS, elemental, powder and single crystal X-ray diffraction analyses. Complex 2 is an angular trinuclear species in which two terminal octahedral Co(III)N2O4 centers coordinate to the central octahedral cobalt(II) ion through ?2-phenoxido oxygen and ?1,1-azido nitrogen atoms along with two mutually cis-oxygen atoms of methanol molecules. On the other hand, in linear trinuclear complex , in addition to the ?2-phenoxido and ?1,1-azido bridges with terminal octahedral Co(III) centres, the central Co(II) is bonded with two mutually trans-oxygen atoms of water molecules. Thus the cis-trans configuration of the central Co(II) is solvent dependent. In complex 3, the two terminal octahedral Co(III)N2O4 centers coordinate to the central penta-coordinated Co(II) ion through double phenoxido bridges along with the nitrogen atom of a terminal azido ligand. In addition, the two terminal Co(III) are connected through a ?1,3-azido bridge that participates in pnicogen bonding interactions (intermolecular N-N interaction) as an acceptor. Both the cis and trans isomeric forms of 1 and 2 have been optimized using density functional theory (DFT) calculations and it is found that the cis configuration is energetically more favorable than the trans one. However, the trans configuration of 2 is stabilized by the hydrogen bonding network involving a water dimer. The pnicogen bonding interactions have been demonstrated using MEP surfaces and CSD search which support the counter intuitive electron acceptor ability of the ?1,3-azido ligand. Complexes 1-3 exhibit catecholase-like activities in the aerial oxidation of 3,5-di-tert-butylcatechol to the corresponding o-quinone. Kinetic data analyses of this oxidation reaction in acetonitrile reveal that the catecholase-like activity follows the order: 1 (kcat = 142 h(-1)) > 3 (kcat = 99 h(-1)) > 2 (kcat = 85 h(-1)). Mechanistic investigations of the catalytic behaviors by X-band EPR spectroscopy and estimation of hydrogen peroxide formation indicate that the oxidation reaction proceeds through the reduction of Co(III) to Co(II). PMID:25611163

  20. Effect of the valence electron concentration on the bulk modulus and chemical bonding in Ta{sub 2}AC and Zr{sub 2}AC (A=Al, Si, and P)

    SciTech Connect

    Schneider, Jochen M.; Music, Denis; Sun Zhimei

    2005-03-15

    We have studied the effect of the valence electron concentration, on the bulk modulus and the chemical bonding in Ta{sub 2}AC and Zr{sub 2}AC (A=Al, Si, and P) by means of ab initio calculations. Our equilibrium volume and the hexagonal ratio (c/a) agree well (within 2.7% and 1.2%, respectively) with previously published experimental data for Ta{sub 2}AlC. The bulk moduli of both Ta{sub 2}AC and Zr{sub 2}AC increase as Al is substituted with Si and P by 13.1% and 20.1%, respectively. This can be understood since the substitution is associated with an increased valence electron concentration, resulting in band filling and an extensive increase in cohesion.

  1. DERIVATION AND SIGNIFICANCE OF VALENCE MOLECULAR CONNECTIVITY

    EPA Science Inventory

    The physical basis for valence molecular connectivity was studied. The sigma sup upsilon and sigma values are cardinal numbers describing the electronic structure of atoms in their valence states. The value (sigma sup upsilon) + (sigma) describes the volume of a bonding atom whil...

  2. The valence band structure of Ag{sub x}Rh{sub 1–x} alloy nanoparticles

    SciTech Connect

    Yang, Anli; Sakata, Osami; Kusada, Kohei; Kobayashi, Hirokazu; Yayama, Tomoe; Ishimoto, Takayoshi; Yoshikawa, Hideki; Koyama, Michihisa; and others

    2014-10-13

    The valence band (VB) structures of face-centered-cubic Ag-Rh alloy nanoparticles (NPs), which are known to have excellent hydrogen-storage properties, were investigated using bulk-sensitive hard x-ray photoelectron spectroscopy. The observed VB spectra profiles of the Ag-Rh alloy NPs do not resemble simple linear combinations of the VB spectra of Ag and Rh NPs. The observed VB hybridization was qualitatively reproduced via a first-principles calculation. The electronic structure of the Ag{sub 0.5}Rh{sub 0.5} alloy NPs near the Fermi edge was strikingly similar to that of Pd NPs, whose superior hydrogen-storage properties are well known.

  3. Levels of Valence

    PubMed Central

    Shuman, Vera; Sander, David; Scherer, Klaus R.

    2013-01-01

    The distinction between the positive and the negative is fundamental in our emotional life. In appraisal theories, in particular in the component process model of emotion (Scherer, 1984, 2010), qualitatively different types of valence are proposed based on appraisals of (un)pleasantness, goal obstructiveness/conduciveness, low or high power, self-(in)congruence, and moral badness/goodness. This multifaceted conceptualization of valence is highly compatible with the frequent observation of mixed feelings in real life. However, it seems to contradict the one-dimensional conceptualization of valence often encountered in psychological theories, and the notion of valence as a common currency used to explain choice behavior. Here, we propose a framework to integrate the seemingly disparate conceptualizations of multifaceted valence and one-dimensional valence by suggesting that valence should be conceived at different levels, micro and macro. Micro-valences correspond to qualitatively different types of evaluations, potentially resulting in mixed feelings, whereas one-dimensional macro-valence corresponds to an integrative “common currency” to compare alternatives for choices. We propose that conceptualizing levels of valence may focus research attention on the mechanisms that relate valence at one level (micro) to valence at another level (macro), leading to new hypotheses, and addressing various concerns that have been raised about the valence concept, such as the valence-emotion relation. PMID:23717292

  4. Angle-resolved photoemission studies of the valence-band structure of stepped crystal surfaces: Cu(S)-(3(111) x (100))

    SciTech Connect

    Davis, R.F.; Williams, R.S.; Kevan, S.D.; Wehner, P.S.; Shirley, D.A.

    1985-02-15

    Angle-resolved photoemission spectra are reported for the stepped Cu(211) face in the photon-energy range 9< or =h..nu..< or =34 eV. The valence-band (VB) spectra are interpreted in terms of a direct-transition model for bulk photoemission. Determination of VB dispersion relations and assignment of the bands are aided by use of selection rules involving the transmitted-radiation vector potential and several different experimental geometries. The major results are (1) it is possible to determine experimental VB dispersion relations for a lower-symmetry direction such as Cu(211), and (2) VB dispersion relations for stepped Cu(211) show excellent agreement with bulk valence bands interpolated along the (211) direction, uninterrupted by band-gap photoemission, the effects of which are not observed. It is concluded that the unusual structure of the stepped surface does not significantly perturb the bulk electronic structure near the surface in this case.

  5. How resonance assists hydrogen bonding interactions: an energy decomposition analysis.

    PubMed

    Beck, John Frederick; Mo, Yirong

    2007-01-15

    Block-localized wave function (BLW) method, which is a variant of the ab initio valence bond (VB) theory, was employed to explore the nature of resonance-assisted hydrogen bonds (RAHBs) and to investigate the mechanism of synergistic interplay between pi delocalization and hydrogen-bonding interactions. We examined the dimers of formic acid, formamide, 4-pyrimidinone, 2-pyridinone, 2-hydroxpyridine, and 2-hydroxycyclopenta-2,4-dien-1-one. In addition, we studied the interactions in beta-diketone enols with a simplified model, namely the hydrogen bonds of 3-hydroxypropenal with both ethenol and formaldehyde. The intermolecular interaction energies, either with or without the involvement of pi resonance, were decomposed into the Hitler-London energy (DeltaEHL), polarization energy (DeltaEpol), charge transfer energy (DeltaECT), and electron correlation energy (DeltaEcor) terms. This allows for the examination of the character of hydrogen bonds and the impact of pi conjugation on hydrogen bonding interactions. Although it has been proposed that resonance-assisted hydrogen bonds are accompanied with an increasing of covalency character, our analyses showed that the enhanced interactions mostly originate from the classical dipole-dipole (i.e., electrostatic) attraction, as resonance redistributes the electron density and increases the dipole moments in monomers. The covalency of hydrogen bonds, however, changes very little. This disputes the belief that RAHB is primarily covalent in nature. Accordingly, we recommend the term "resonance-assisted binding (RAB)" instead of "resonance-assisted hydrogen bonding (RHAB)" to highlight the electrostatic, which is a long-range effect, rather than the electron transfer nature of the enhanced stabilization in RAHBs. PMID:17143867

  6. Fabrication of VB2/Air Cells for Electrochemical Testing

    PubMed Central

    Stuart, Jessica; Lopez, Ruben; Lau, Jason; Li, Xuguang; Waje, Mahesh; Mullings, Matthew; Rhodes, Christopher; Licht, Stuart

    2013-01-01

    A technique to investigate the properties and performance of new multi-electron metal/air battery systems is proposed and presented. A method for synthesizing nanoscopic VB2 is presented as well as step-by-step procedure for applying a zirconium oxide coating to the VB2 particles for stabilization upon discharge. The process for disassembling existing zinc/air cells is shown, in addition construction of the new working electrode to replace the conventional zinc/air cell anode with a the nanoscopic VB2 anode. Finally, discharge of the completed VB2/air battery is reported. We show that using the zinc/air cell as a test bed is useful to provide a consistent configuration to study the performance of the high-energy high capacity nanoscopic VB2 anode. PMID:23962835

  7. Different symmetry of the magnetization-direction dependence between the impurity band and valence band in GaMnAs

    NASA Astrophysics Data System (ADS)

    Muneta, Iriya; Kanaki, Toshiki; Ohya, Shinobu; Tanaka, Masaaki

    2015-03-01

    In semiconductors with heavily doped with nonmagnetic shallow acceptors, an impurity band (IB) is formed around the valence band (VB) top and merged with VB. As a result, the parabolic VB top is strongly deformed in a non-parabolic dispersion. In GaMnAs, however, the VB top keeps the parabolic dispersion though there is energy overlap between VB and IB, which is completely different from the conventional nonmagnetic semiconductors. Here, we measure tunneling anisotropic magnetoresistance on GaMnAs tunnel devices in a spectroscopic way, analyze the magnetization-direction and energy dependence of the density of states (DOS), and investigate the different symmetry between VB and IB to clarify the mysterious overlap between the two bands. We find that the magnetization-direction dependence of VB DOS is mainly four-fold symmetry along [100] which is the same as the crystal symmetry, while that of IB DOS is mainly two-fold symmetry along [110] unlike the crystal symmetry. These results reveal the unique band structures of Mn-doped III-V ferromagnetic semiconductors. This work was partly supported by Grant-in-Aids for Scientific Research including Specially Promoted Research, I.M. thanks the JSPS research Fellowship Program for Young Scientists.

  8. Dynamics of dipole- and valence bound anions in iodide-adenine binary complexes: A time-resolved photoelectron imaging and quantum mechanical investigation

    NASA Astrophysics Data System (ADS)

    Stephansen, Anne B.; King, Sarah B.; Yokoi, Yuki; Minoshima, Yusuke; Li, Wei-Li; Kunin, Alice; Takayanagi, Toshiyuki; Neumark, Daniel M.

    2015-09-01

    Dipole bound (DB) and valence bound (VB) anions of binary iodide-adenine complexes have been studied using one-color and time-resolved photoelectron imaging at excitation energies near the vertical detachment energy. The experiments are complemented by quantum chemical calculations. One-color spectra show evidence for two adenine tautomers, the canonical, biologically relevant A9 tautomer and the A3 tautomer. In the UV-pump/IR-probe time-resolved experiments, transient adenine anions can be formed by electron transfer from the iodide. These experiments show signals from both DB and VB states of adenine anions formed on femto- and picosecond time scales, respectively. Analysis of the spectra and comparison with calculations suggest that while both the A9 and A3 tautomers contribute to the DB signal, only the DB state of the A3 tautomer undergoes a transition to the VB anion. The VB anion of A9 is higher in energy than both the DB anion and the neutral, and the VB anion is therefore not accessible through the DB state. Experimental evidence of the metastable A9 VB anion is instead observed as a shape resonance in the one-color photoelectron spectra, as a result of UV absorption by A9 and subsequent electron transfer from iodide into the empty ?-orbital. In contrast, the iodide-A3 complex constitutes an excellent example of how DB states can act as doorway state for VB anion formation when the VB state is energetically available.

  9. An ab initio study of core-valence correlation. [in atoms

    NASA Technical Reports Server (NTRS)

    Partridge, H.; Bauschlicher, C. W., Jr.; Walch, S. P.; Liu, B.

    1983-01-01

    Especially in the cases of the first two columns of the periodic table, the inclusion of core-valence correlation in ab initio CI calculations yields a contraction of the atomic valence shell and improves both calculated atomic ionization potentials and atomic energy separations. For the alkali dimers Na2, K2, and Rb2, the presently calculated bond lengths are in excellent agreement with experiments when core-valence is included. In addition, the valence dissociation energies are accurate.

  10. Valence, Covalence, Hypervalence, Oxidation State, and Coordination Number

    ERIC Educational Resources Information Center

    Smith, Derek W.

    2005-01-01

    Valence as a numerical measure of an atom's combining power, expressed by the number of bonds it forms in a molecular formulation of the compound in question, was unable to cope with coordination compounds. The covalence of an atom is the nearest model equivalent, but is subject to ambiguity since it often depends on which bonding model is being…

  11. Draft Genome Sequence of Tolypothrix boutellei Strain VB521301

    PubMed Central

    Chandrababunaidu, Mathu Malar; Singh, Deeksha; Sen, Diya; Bhan, Sushma; Das, Subhadeep; Gupta, Akash

    2015-01-01

    We report here the draft genome sequence of the filamentous nitrogen-fixing cyanobacterium Tolypothrix boutellei strain VB521301. The organism is lipid rich and hydrophobic and produces polyunsaturated fatty acids which can be harnessed for industrial purpose. The draft genome sequence assembled into 11,572,263 bp with 70 scaffolds and 7,777 protein coding genes. PMID:25700407

  12. Hg System Operation Review V.B. Graves

    E-print Network

    McDonald, Kirk

    in cleanup · Control system functions as expected - Tested emergency stop conditions · Hg vapor detection disassembly, no vapors detected inside bellows · Small Hg leak discovered in nozzle supply threaded jointHg System Operation Review V.B. Graves Muon Collaboration Friday Meeting April 13, 2007 #12;2 OAK

  13. Magnet/Syringe Separation Issues V.B. Graves

    E-print Network

    McDonald, Kirk

    1 Magnet/Syringe Separation Issues V.B. Graves 8/12/05 This document is an initial response or separate the cylinders from the magnet. Since the cost of stainless cylinders is prohibitively high indicated that 1m would be a sufficient separation distance, in our subsequent phone conversation we thought

  14. PREDICTING METAL BIOSORPTION PERFORMANCE , Diniz V.b

    E-print Network

    Volesky, Bohumil

    PREDICTING METAL BIOSORPTION PERFORMANCE Naja G.a , Diniz V.b , Volesky B.b a Department 2B2. ABSTRACT Heavy metals can be removed from solutions and recovered using physico seaweed biomass is well known for its outstanding metal biosorption performance. Biosorption of Cu2+ , Zn2

  15. Direct determination of the band offset in atomic layer deposited ZnO/hydrogenated amorphous silicon heterojunctions from X-ray photoelectron spectroscopy valence band spectra

    SciTech Connect

    Korte, L. Rößler, R.; Pettenkofer, C.

    2014-05-28

    The chemical composition and band alignment at the heterointerface between atomic layer deposition-grown zinc oxide (ZnO) and hydrogenated amorphous silicon (a-Si:H) is investigated using monochromatized X-ray photoelectron spectroscopy. A new approach for obtaining the valence band offset ?E{sub V} is developed, which consists in fitting the valence band (VB) spectrum obtained for a-Si:H with a thin ZnO overlayer as the sum of experimentally obtained VB spectra of a bulk a-Si:H film and a thick ZnO film. This approach allows obtaining ?E{sub V}?=?2.71?±?0.15?eV with a minimum of assumptions, and also yields information on the change in band bending of both substrate and ZnO film. The band offset results are compared to values obtained using the usual approach of comparing valence band edge-to-core level energy differences, ?E{sub B,CL} ???E{sub B,VB}. Furthermore, a theoretical value for the VB offset is calculated from the concept of charge neutrality level line-up, using literature data for the charge neutrality levels and the experimentally determined ZnO/a-Si:H interface dipole. The thus obtained value of ?E{sub V}{sup CNL}?=?2.65?±?0.3?eV agrees well with the experimental ?E{sub V}.

  16. Direct determination of the band offset in atomic layer deposited ZnO/hydrogenated amorphous silicon heterojunctions from X-ray photoelectron spectroscopy valence band spectra

    NASA Astrophysics Data System (ADS)

    Korte, L.; Rößler, R.; Pettenkofer, C.

    2014-05-01

    The chemical composition and band alignment at the heterointerface between atomic layer deposition-grown zinc oxide (ZnO) and hydrogenated amorphous silicon (a-Si:H) is investigated using monochromatized X-ray photoelectron spectroscopy. A new approach for obtaining the valence band offset ?EV is developed, which consists in fitting the valence band (VB) spectrum obtained for a-Si:H with a thin ZnO overlayer as the sum of experimentally obtained VB spectra of a bulk a-Si:H film and a thick ZnO film. This approach allows obtaining ?EV = 2.71 ± 0.15 eV with a minimum of assumptions, and also yields information on the change in band bending of both substrate and ZnO film. The band offset results are compared to values obtained using the usual approach of comparing valence band edge-to-core level energy differences, ?EB,CL - ?EB,VB. Furthermore, a theoretical value for the VB offset is calculated from the concept of charge neutrality level line-up, using literature data for the charge neutrality levels and the experimentally determined ZnO/a-Si:H interface dipole. The thus obtained value of ?EVCNL = 2.65 ± 0.3 eV agrees well with the experimental ?EV.

  17. Climatology of Vb cyclones, physical mechanisms and their impact on extreme precipitation over Central Europe

    NASA Astrophysics Data System (ADS)

    Messmer, M.; Gómez-Navarro, J. J.; Raible, C. C.

    2015-09-01

    Cyclones, which develop over the western Mediterranean and move northeastward are a major source of extreme weather and known to be responsible for heavy precipitation over the northern side of the Alpine range and Central Europe. As the relevant processes triggering these so-called Vb events and their impact on extreme precipitation are not yet fully understood, this study focuses on gaining insight into the dynamics of past events. For this, a cyclone detection and tracking tool is applied to the ERA-Interim reanalysis (1979-2013) to identify prominent Vb situations. Precipitation in the ERA-Interim and the E-OBS data sets is used to evaluate case-to-case precipitation amounts and to assess consistency between the two data sets. Both data sets exhibit high variability in precipitation amounts among different Vb events. While only 23 % of all Vb events are associated with extreme precipitation, around 15 % of all extreme precipitation days (99 percentile) over the northern Alpine region and Central Europe are induced by Vb events, although Vb cyclones are rare events (2.3 per year). To obtain a better understanding of the variability within Vb events, the analysis of the 10 heaviest and lowest precipitation Vb events reveals noticeable differences in the state of the atmosphere. These differences are most pronounced in the geopotential height and potential vorticity field, indicating a much stronger cyclone for heavy precipitation events. The related differences in wind direction are responsible for the moisture transport around the Alps and the orographical lifting along the northern slopes of the Alps. These effects are the main reasons for a disastrous outcome of Vb events, and consequently are absent in the Vb events associated with low precipitation. Hence, our results point out that heavy precipitation related to Vb events is mainly related to large-scale dynamics rather than to thermodynamic processes.

  18. THE PROPOSED GIANT PLANET ORBITING VB 10 DOES NOT EXIST

    SciTech Connect

    Bean, Jacob L.; Seifahrt, Andreas; Reiners, Ansgar; Dreizler, Stefan; Hartman, Henrik; Nilsson, Hampus; Henry, Todd J.; Wiedemann, Guenter

    2010-03-01

    We present high-precision relative radial velocities of the very low mass star VB 10 that were obtained over a time span of 0.61 years as part of an ongoing search for planets around stars at the end of the main sequence. The radial velocities were measured from high-resolution near-infrared spectra obtained using the CRIRES instrument on the Very Large Telescope with an ammonia gas cell. The typical internal precision of the measurements is 10 m s{sup -1}. These data do not exhibit significant variability and are essentially constant at a level consistent with the measurement uncertainties. Therefore, we do not detect the radial velocity variations of VB 10 expected due to the presence of an orbiting giant planet similar to that recently proposed by Pravdo and Shaklan based on apparent astrometric perturbations. In addition, we do not confirm the {approx}1 km s{sup -1} radial velocity variability of the star tentatively detected by Zapatero Osorio and colleagues with lower precision measurements. Our measurements rule out planets with M {sub p} > 3 M {sub Jup} and the orbital period and inclination suggested by Pravdo and Shaklan at better than 5{sigma} confidence. We conclude that the planet detection claimed by Pravdo and Shaklan is spurious on the basis of this result. Although the outcome of this work is a non-detection, it illustrates the potential of using ammonia cell radial velocities to detect planets around very low mass stars.

  19. Valence photoelectron spectroscopy of Gd silicides

    SciTech Connect

    Braicovich, L. ); Puppin, E.; Lindau, I. ); Iandelli, A.; Olcese, G.L.; Palenzona, A. )

    1990-02-15

    Gd{sub 3}Si{sub 5}, GdSi, and Gd{sub 5}Si{sub 3} were investigated with photoemission spectroscopy in the photon-energy range 40.8--149 eV by exploiting the energy dependence of the photoemission cross sections and the valence resonance at the crossing of the Gd 4{ital d}-4{ital f} threshold. The modification of the spectra versus photon energy, along with their stoichiometry dependence, show the relevance of covalent mixed Gd 5{ital d}--Si 3{ital sp} states in the formation of the chemical bond. In the region close to the Fermi level an increase of the {ital d} contribution is observed. These points are discussed in connection with the existing models of the silicide bond.

  20. Sodium-sulfur battery development. Phase VB, October 1, 1981-February 28, 1985. Final report

    SciTech Connect

    Not Available

    1985-10-04

    The program addressed the development of Na/S batteries for stationary energy storage (SES) and electric vehicle (EV) applications, although during Phase VB the EV application was emphasized. Phase VB technical achievements are summarized as follows: Cell Development, Electrolyte Development and Production, and Battery Development.

  1. Deciphering the Genome Sequences of the Hydrophobic Cyanobacterium Scytonema tolypothrichoides VB-61278

    PubMed Central

    Das, Abhishek; Panda, Arijit; Singh, Deeksha; Chandrababunaidu, Mathu Malar; Mishra, Gyan Prakash; Bhan, Sushma

    2015-01-01

    Scytonema tolypothrichoides VB-61278, a terrestrial cyanobacterium, can be exploited to produce commercially important products. Here, we report for the first time a 10-Mb draft genome assembly of S. tolypothrichoides VB-61278, with 214 scaffolds and 7,148 putative protein-coding genes. PMID:25838486

  2. VB12-coated Gel-Core-SLN containing insulin: Another way to improve oral absorption.

    PubMed

    He, Haibing; Wang, Puxiu; Cai, Cuifang; Yang, Rui; Tang, Xing

    2015-09-30

    To improve the oral absorption of insulin, a novel carrier of Vitamin B12 (VB12) gel core solid lipid nanopaticles (Gel-Core-SLN, GCSLN) was designed with a gel core, lipid matrix and VB12-coated surface. VB12-stearate was synthesized and characterized by infrared spectroscopy (IR), nuclear magnetic resonance spectroscopy (NMR) and mass spectrometry (MS). Sol-gel conversion following ultrasonic heating and double emulsion technology were combined to implant the insulin-containing gel into solid lipid nanoparticles (SLN). The influence of the mode of administration, food, the amount of VB12-stearate and the particle size on the oral absorption of insulin incorporated in the VB12-GCSLN was investigated. The determined partition coefficient (LogP) of VB12-stearate in a dichloromethane (DCM)-water system was 3.4. This new structure of VB12-GCSLN had higher insulin encapsulation efficiency (EE) of 55.9%, a lower burst release of less than 10% in the first 2h. In vivo studies demonstrated that stronger absorption of insulin with a relative pharmacological availability (PA) of 9.31% compared with the normal insulin-loaded SLN and GCSLN and fairly stable blood glucose levels up to 12h were maintained without any sharp fluctuations. This study suggests that VB12-GCSLN containing insulin appears to be a promising nano carrier for oral delivery of biomacromolecules with relatively high pharmacological availability. PMID:26253378

  3. Micro-Valences: Perceiving Affective Valence in Everyday Objects

    PubMed Central

    Lebrecht, Sophie; Bar, Moshe; Barrett, Lisa Feldman; Tarr, Michael J.

    2012-01-01

    Perceiving the affective valence of objects influences how we think about and react to the world around us. Conversely, the speed and quality with which we visually recognize objects in a visual scene can vary dramatically depending on that scene’s affective content. Although typical visual scenes contain mostly “everyday” objects, the affect perception in visual objects has been studied using somewhat atypical stimuli with strong affective valences (e.g., guns or roses). Here we explore whether affective valence must be strong or overt to exert an effect on our visual perception. We conclude that everyday objects carry subtle affective valences – “micro-valences” – which are intrinsic to their perceptual representation. PMID:22529828

  4. Theoretical description of hydrogen bonding in oxalic acid dimer and trimer based on the combined extended-transition-state energy decomposition analysis and natural orbitals for chemical valence (ETS-NOCV)

    PubMed Central

    Mitoraj, Mariusz P.; Kurczab, Rafa?; Boczar, Marek

    2010-01-01

    In the present study we have analyzed hydrogen bonding in dimer and trimer of oxalic acid, based on a recently proposed charge and energy decomposition scheme (ETS-NOCV). In the case of a dimer, two conformations, ? and ?, were considered. The deformation density contributions originating from NOCV’s revealed that the formation of hydrogen bonding is associated with the electronic charge deformation in both the ?—(???) and ?-networks (???). It was demonstrated that ?-donation is realized by electron transfer from the lone pair of oxygen on one monomer into the empty \\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$ \\rho_{H - O}^* $$\\end{document} orbital of the second oxalic acid fragment. In addition, a covalent contribution is observed by the density transfer from hydrogen of H-O group in one oxalic acid monomer to the oxygen atom of the second fragment. The resonance assisted component (???), is based on the transfer of electron density from the ?—orbital localized on the oxygen of OH on one oxalic acid monomer to the oxygen atom of the other fragment. ETS-NOCV allowed to conclude that the ?(O---HO) component is roughly eight times as important as ? (RAHB) contribution in terms of energetic estimation. The electrostatic factor (?Eelstat) is equally as important as orbital interaction term (?Eorb). Finally, comparing ?-dimer of oxalic acid with trimer we found practically no difference concerning each of the O---HO bonds, neither qualitative nor quantitative. Figure The contours of deformation density ?- and ?-contributions describing the hydrogen bonding between the monomers in the oxalic acid dimer, together with the corresponding ETS-NOCV-based orbital-interaction energies (in kcal/mol). PMID:20505966

  5. Bonding with parallel spins: high-spin clusters of monovalent metal atoms.

    PubMed

    Danovich, David; Shaik, Sason

    2014-02-18

    Bonding is a glue of chemical matter and is also a useful concept for designing new molecules. Despite the fact that electron pairing remains the bonding mechanism in the great majority of molecules, in the past few decades scientists have had a growing interest in discovering novel bonding motifs. As this Account shows, monovalent metallic atoms having exclusively parallel spins, such as (11)Li10, (11)Au10, and (11)Cu10, can nevertheless form strongly bound clusters, without having even one traditional bond due to electron pairing. These clusters, which also can be made chiral, have high magnetic moments. We refer to this type as no-pair ferromagnetic (NPFM) bonding, which characterizes the (n+1)Mn clusters, which were all predicted by theoretical computations. The small NPFM alkali clusters that have been "synthesized" to date, using cold-atom techniques, support the computational predictions. In this Account, we describe the origins of NPFM bonding using a valence bond (VB) analysis, which shows that this bonding motif arises from bound triplet electron pairs that spread over all the close neighbors of a given atom in the cluster. The bound triplet pair owes its stabilization to the resonance energy provided by the mixing of the local ionic configurations, [(3)M(??)(-)]M(+) and M(+)[(3)M(??)(-)], and the various excited covalent configurations (involving pz and dz(2) atomic orbitals) into the repulsive covalent structure (3)(M??M) with the s(1)s(1) electronic configuration. The NPFM bond of the bound triplet is described by a resonating wave function with "in-out" and "out-in" pointing hybrids. The VB model accounts for the tendency of NPFM clusters to assume polyhedral shapes with rather high symmetry. In addition, this model explains the very steep rise of the bonding energy per atom (De/n), which starts out small in the (3)M2 dimer (<1 kcal/mol) and reaches 12-19 kcal/mol for clusters with 10 atoms. The model further predicts that usage of heteroatomic clusters should increase the bonding energy of an NPFM cluster. These NPFM clusters are excited state species. We suggest here stabilizing these states and making them accessible, for example, by using magnetic fields, or a combination of magnetic and electric fields. The advent of NPFM clusters offers new horizons in chemistry and enriches the scope of chemical bonding. These prospects form a strong incentive to investigate the origins of the bound triplet pairs and further chart the territory of NPFM clusters, for example, in clusters of Be, Mg, or Zn, possibly in clusters of their monosubstituted species, and the group III metalloids, such as B, Al, as well as in transition metals such as Sc. PMID:23941238

  6. Reactive Force Fields via Explicit Valency

    NASA Astrophysics Data System (ADS)

    Kale, Seyit

    Computational simulations are invaluable in elucidating the dynamics of biological macromolecules. Unfortunately, reactions present a fundamental challenge. Calculations based on quantum mechanics can predict bond formation and rupture; however they suffer from severe length- and time-limitations. At the other extreme, classical approaches provide orders of magnitude faster simulations; however they regard chemical bonds as immutable entities. A few exceptions exist, but these are not always trivial to adopt for routine use. We bridge this gap by providing a novel, pseudo-classical approach, based on explicit valency. We unpack molecules into valence electron pairs and atomic cores. Particles bear ionic charges and interact via pairwise-only potentials. The potentials are informed of quantum effects in the short-range and obey dissociation limits in the long-range. They are trained against a small set of isolated species, including geometries and thermodynamics of small hydrides and of dimers formed by them. The resulting force field captures the essentials of reactivity, polarizability and flexibility in a simple, seamless setting. We call this model LEWIS, after the chemical theory that inspired the use of valence pairs. Following the introduction in Chapter 1, we initially focus on the properties of water. Chapter 2 considers gas phase clusters. To transition to the liquid phase, Chapter 3 describes a novel pairwise long-range compensation that performs comparably to infinite lattice summations. The approach is suited to ionic solutions in general. In Chapters 4 and 5, LEWIS is shown to correctly predict the dipolar and quadrupolar response in bulk liquid, and can accommodate proton transfers in both acid and base. Efficiency permits the study of proton defects at dilutions not accessible to experiment or quantum mechanics. Chapter 6 discusses explicit valency approaches in other hydrides, forming the basis of a reactive organic force field. Examples of simple proton transfer and more complex reactions are discussed. Chapter 7 provides a framework for variable electron spread. This addition resolves some of the inherent limitations of the former model which implicitly assumed that electron spread was not affected by the environment. A brief summary is provided in Chapter 8.

  7. Valence-Dependent Metal-Metal Bonding and Optical Spectra in Confacial Bioctahedral [Re(2)Cl(9)](z)()(-) (z = 1, 2, 3). Crystallographic and Computational Characterization of [Re(2)Cl(9)](-) and [Re(2)Cl(9)](2)(-).

    PubMed

    Heath, Graham A.; McGrady, John E.; Raptis, Raphael G.; Willis, Anthony C.

    1996-11-01

    The geometric structure of the confacial bioctahedral [Re(2)Cl(9)](z)()(-) anion has been determined by single-crystal X-ray diffraction in two distinct oxidation states, Re(IV)(2) and Re(III)Re(IV). [Bu(4)N][Re(2)Cl(9)] crystallizes in the monoclinic space group P2(1)/m [a/Å = 10.6363(3), b/Å = 11.420(1), c/Å = 13.612(1), beta/deg = 111.18(1), Z = 2], while [Et(4)N](2)[Re(2)Cl(9)] crystallizes in the orthorhombic space group Pnma [a/Å = 15.82(1), b/Å = 8.55(2), c/Å = 22.52(3), Z = 4]. The Re-Re separation contracts from 2.704(1) Å in [Bu(4)N][Re(2)Cl(9)] to 2.473(4) Å in [Et(4)N](2)[Re(2)Cl(9)] (or, equivalently, from 2.725 to 2.481 Å after standard corrections for thermal motions), while the formal metal-metal bond order falls from 3.0 to 2.5. SCF-Xalpha-SW molecular orbital calculations show that, despite the {d(3)d(3)} configuration, the single sigma bond in [Re(2)Cl(9)](-) dominates the observed structural properties. For [Re(2)Cl(9)](2)(-), the 0.23 Å contraction in Re-Re is attributed jointly to radial expansion of the Re 5d orbitals and to diminished metal-metal electrostatic repulsion, which act in concert to make both sigma and delta(pi) bonding more important in the reduced species. Computed transition energies and oscillator strengths for the two structurally defined anions permit rational analysis of their ultraviolet spectra, which involve both sigma --> sigma and halide-to-metal change-transfer absorptions. The intense sigma --> sigma band progresses from 31 000 cm(-)(1) in [Re(2)Cl(9)](-) to 36 400 cm(-)(1) in [Re(2)Cl(9)](2)(-), according to the present assignments. For electrogenerated, highly reactive [Re(2)Cl(9)](3)(-) (where conventional X-ray structural information is unlikely to become available), the dominant absorption band advances to 40 000 cm(-)(1), suggesting further strengthening of the metal-metal sigma bond in the Re(III)(2) species. PMID:11666851

  8. Hydrogen multicentre bonds

    NASA Astrophysics Data System (ADS)

    Janotti, Anderson; van de Walle, Chris G.

    2007-01-01

    The concept of a chemical bond stands out as a major development in the process of understanding how atoms are held together in molecules and solids. Lewis' classical picture of chemical bonds as shared-electron pairs evolved to the quantum-mechanical valence-bond and molecular-orbital theories, and the classification of molecules and solids in terms of their bonding type: covalent, ionic, van der Waals and metallic. Along with the more complex hydrogen bonds and three-centre bonds, they form a paradigm within which the structure of almost all molecules and solids can be understood. Here, we present evidence for hydrogen multicentre bonds-a generalization of three-centre bonds-in which a hydrogen atom equally bonds to four or more other atoms. When substituting for oxygen in metal oxides, hydrogen bonds equally to all the surrounding metal atoms, becoming fourfold coordinated in ZnO, and sixfold coordinated in MgO. These multicentre bonds are remarkably strong despite their large hydrogen-metal distances. The calculated local vibration mode frequency in MgO agrees with infrared spectroscopy measurements. Multicoordinated hydrogen also explains the dependence of electrical conductivity on oxygen partial pressure, resolving a long-standing controversy on the role of point defects in unintentional n-type conductivity of ZnO (refs 8-10).

  9. The Realization of Drilling Fault Diagnosis Based on Hybrid Programming with Matlab and VB

    NASA Astrophysics Data System (ADS)

    Wang, Jiangping; Hu, Yingcai

    This paper presents a method using hybrid programming with Matlab and VB based on ActiveX to design the system of drilling accident prediction and diagnosis. So that the powerful calculating function and graphical display function of Matlab and visual development interface of VB are combined fully. The main interface of the diagnosis system is compiled in VB,and the analysis and fault diagnosis are implemented by neural network tool boxes in Matlab.The system has favorable interactive interface,and the fault example validation shows that the diagnosis result is feasible and can meet the demands of drilling accident prediction and diagnosis.

  10. Modeling planar 3-valence meshes 

    E-print Network

    Gonen, Ozgur

    2009-05-15

    modeling approach to design constructible shapes is introduced. This method guarantees that the resulting shapes are planar meshes with 3-valence vertices, which can always be physically constructed using planar or developable materials such as glass, sheet...

  11. A Multidimensional Measure of Work Valences

    ERIC Educational Resources Information Center

    Porfeli, Erik J.; Lee, Bora; Weigold, Ingrid K.

    2012-01-01

    Work valence is derived from expectancy-valence theory and the literature on children's vocational development and is presumed to be a general appraisal of work that emerges during the childhood period. Work valence serves to promote and inhibit the motivation and tasks associated with vocational development. A measure of work valence, composed of…

  12. Myosin Vb Mobilizes Recycling Endosomes and AMPA Receptors for Postsynaptic Plasticity

    PubMed Central

    Wang, Zhiping; Edwards, Jeffrey G.; Riley, Nathan; Provance, D. William; Karcher, Ryan; Li, Xiang-dong; Davison, Ian G.; Ikebe, Mitsuo; Mercer, John A.; Kauer, Julie A.; Ehlers, Michael D.

    2008-01-01

    Summary Learning-related plasticity at excitatory synapses in the mammalian brain requires the trafficking of AMPA receptors and the growth of dendritic spines. However, the mechanisms that couple plasticity stimuli to the trafficking of postsynaptic cargo are poorly understood. Here we demonstrate that myosin Vb (MyoVb), a Ca2+-sensitive motor, conducts spine trafficking during long-term potentiation (LTP) of synaptic strength. Upon activation of NMDA receptors and corresponding Ca2+ influx, MyoVb associates with recycling endosomes (REs), triggering rapid spine recruitment of endosomes and local exocytosis in spines. Disruption of MyoVb or its interaction with the RE adaptor Rab11-FIP2 abolishes LTP-induced exocytosis from REs and prevents both AMPA receptor insertion and spine growth. Furthermore, induction of tight binding of MyoVb to actin using an acute chemical genetic strategy eradicates LTP in hippocampal slices. Thus, Ca2+-activated MyoVb captures and mobilizes of REs for AMPA receptor insertion and spine growth, providing a mechanistic link between the induction and expression of postsynaptic plasticity. PMID:18984164

  13. Fundamental aspects of recoupled pair bonds. I. Recoupled pair bonds in carbon and sulfur monofluoride

    SciTech Connect

    Dunning, Thom H. Xu, Lu T.; Takeshita, Tyler Y.

    2015-01-21

    The number of singly occupied orbitals in the ground-state atomic configuration of an element defines its nominal valence. For carbon and sulfur, with two singly occupied orbitals in their {sup 3}P ground states, the nominal valence is two. However, in both cases, it is possible to form more bonds than indicated by the nominal valence—up to four bonds for carbon and six bonds for sulfur. In carbon, the electrons in the 2s lone pair can participate in bonding, and in sulfur the electrons in both the 3p and 3s lone pairs can participate. Carbon 2s and sulfur 3p recoupled pair bonds are the basis for the tetravalence of carbon and sulfur, and 3s recoupled pair bonds enable sulfur to be hexavalent. In this paper, we report generalized valence bond as well as more accurate calculations on the a{sup 4}?{sup ?} states of CF and SF, which are archetypal examples of molecules that possess recoupled pair bonds. These calculations provide insights into the fundamental nature of recoupled pair bonds and illustrate the key differences between recoupled pair bonds formed with the 2s lone pair of carbon, as a representative of the early p-block elements, and recoupled pair bonds formed with the 3p lone pair of sulfur, as a representative of the late p-block elements.

  14. Forming Beliefs: Why Valence Matters.

    PubMed

    Sharot, Tali; Garrett, Neil

    2016-01-01

    One of the most salient attributes of information is valence: whether a piece of news is good or bad. Contrary to classic learning theories, which implicitly assume beliefs are adjusted similarly regardless of valence, we review evidence suggesting that different rules and mechanisms underlie learning from desirable and undesirable information. For self-relevant beliefs this asymmetry generates a positive bias, with significant implications for individuals and society. We discuss the boundaries of this asymmetry, characterize the neural system supporting it, and describe how changes in this circuit are related to individual differences in behavior. PMID:26704856

  15. Electronegativity and the Bond Triangle

    ERIC Educational Resources Information Center

    Meek, Terry L.; Garner, Leah D.

    2005-01-01

    The usefulness of the bond triangle for categorizing compounds of the main-group elements may be extended by the use of weighted average electronegativities to allow distinction between compounds of the same elements with different stoichiometries. In such cases a higher valency for the central atom leads to greater covalent character and the…

  16. Functional characterization of mutations in the myosin Vb gene associated with microvillus inclusion disease

    PubMed Central

    Szperl, Agata M.; Golachowska, Magdalena R.; Bruinenberg, Marcel; Prekeris, Rytis; Thunnissen, Andy-Mark W. H.; Karrenbeld, Arend; Dijkstra, Gerard; Hoekstra, Dick; Mercer, David; Ksiazyk, Janusz; Wijmenga, Cisca; Wapenaar, Martin C.; Rings, Edmond H. H. M.; van IJzendoorn, Sven C. D.

    2010-01-01

    Objectives Microvillus inclusion disease (MVID) is a rare autosomal recessive enteropathy characterized by intractable diarrhea and malabsorption. Recently, various MYO5B gene mutations have been identified in MVID patients. Interestingly, several MVID patients showed only a MYO5B mutation in one allele (heterozygous) or no mutations in the MYO5B gene, illustrating the need to further functionally characterize the cell biological effects of the MYO5B mutations. Methods The genomic DNA of nine patients diagnosed with microvillus inclusion disease was screened for MYO5B mutations, and qPCR and immunohistochemistry on the material of two patients was performed to investigate resultant cellular consequences. Results We demonstrate for the first time that MYO5B mutations can be correlated with altered myosin Vb mRNA expression and with an aberrant subcellular distribution of the myosin Vb protein. Moreover, we demonstrate that the typical and myosin Vb–controlled accumulation of rab11a-and FIP5-positive recycling endosomes in the apical cytoplasm of the cells is abolished in MVID enterocytes, which is indicative for altered myosin Vb function. Also, we report 8 novel MYO5B mutations in 9 MVID patients of various etnic backgrounds, including compound heterozygous mutations. Conclusions Our functional analysis indicate that MYO5B mutations can be correlated with an aberrant subcellular distribution of the myosin Vb protein and apical recycling endosomes which, together with the additional compound heterozygous mutations, significantly strengthen the link between MYO5B and MVID. PMID:21206382

  17. Valence-bound and diffuse-bound anions of 5-azauracil.

    PubMed

    Corzo, H H; Dolgounitcheva, O; Zakrzewski, V G; Ortiz, J V

    2014-08-28

    Structures, isomerization energies, and electron binding energies of 5-azauracil and its anions have been calculated ab initio with perturbative, coupled-cluster, and electron-propagator methods. Tautomeric structures, including those produced by proton transfer to a CH group, have been considered. Dyson orbitals and pole strengths from electron-propagator calculations validated a simple, molecular-orbital picture of anion formation. In one case, an electron may enter a delocalized ? orbital, yielding a valence-bound (VB) anion with a puckered ring structure. The corresponding electron affinity is 0.27 eV; the vertical electron detachment energy (VEDE) of this anion 1.05 eV. An electron also may enter a molecular orbital that lies outside the nuclear framework, resulting in a diffuse-bound (DB) anion. In the latter case, the electron affinity is 0.06 eV and the VEDE of the DB anion is 0.09 eV. Another VB isomer that is only 0.02 eV more stable than the neutral molecule has a VEDE of 2.0 eV. PMID:25102270

  18. Implementation of RS-485 Communication between PLC and PC of Distributed Control System Based on VB

    NASA Astrophysics Data System (ADS)

    Lian Zhang, Chuan; Da Huang, Zhi; Qing Zhou, Gui; Chong, Kil To

    2015-05-01

    This paper focuses on achieving RS-485 communication between programmable logical controller (PLC) and PC based on visual basic 6.0 (VB6.0) on an experimental automatic production line. Mitsubishi FX2N PLCs and a PC are chosen as slave stations and main station, respectively. Monitoring software is developed using VB6.0 for data input/output, flow control and online parameters setting. As a result, all functions are fulfilled with robust performance. It is concluded from results that one PC can monitor several PLCs using RS-485 communication.

  19. Pauling bond strength, bond length and electron density distribution

    SciTech Connect

    Gibbs, Gerald V.; Ross, Nancy L.; Cox, David F.; Rosso, Kevin M.; Iversen, Bo B.; Spackman, M. A.

    2014-01-18

    A power law regression equation, = 1.46(/r)-0.19, connecting the average experimental bond lengths, , with the average accumulation of the electron density at the bond critical point, , between bonded metal M and oxygen atoms, determined at ambient conditions for oxide crystals, where r is the row number of the M atom, is similar to the regression equation R(M-O) = 1.39(?(rc)/r)-0.21 determined for three perovskite crystals for pressures as high as 80 GPa. The two equations are also comparable with those, = 1.43(/r)-0.21, determined for a large number of oxide crystals at ambient conditions and = 1.39(/r)-0.22, determined for geometry optimized hydroxyacid molecules, that connect the bond lengths to the average Pauling electrostatic bond strength, , for the M-O bonded interactions. On the basis of the correspondence between the two sets of equations connecting ?(rc) and the Pauling bond strength s with bond length, it appears that Pauling’s simple definition of bond strength closely mimics the accumulation of the electron density between bonded pairs of atoms. The similarity of the expressions for the crystals and molecules is compelling evidence that the M-O bonded interactions for the crystals and molecules 2 containing the same bonded interactions are comparable. Similar expressions, connecting bond lengths and bond strength, have also been found to hold for fluoride, nitride and sulfide molecules and crystals. The Brown-Shannon bond valence, ?, power law expression ? = [R1/(R(M-O)]N that has found wide use in crystal chemistry, is shown to be connected to a more universal expression determined for oxides and the perovskites, = r[(1.41)/]4.76, demonstrating that the bond valence for a bonded interaction is likewise closely connected to the accumulation of the electron density between the bonded atoms. Unlike the Brown-Shannon expression, it is universal in that it holds for the M-O bonded interactions for a relatively wide range of M atoms of the periodic table. The power law equation determined for the oxide crystals at ambient conditions is similar to the power law expression = r[1.46/]5.26 determined for the perovskites at pressures as high as 80 GPa, indicating that the intrinsic connection between R(M-O) and ?(rc) that holds at ambient conditions also holds, to a first approximation, at high pressures.

  20. Valence band structure of binary chalcogenide vitreous semiconductors by high-resolution XPS

    SciTech Connect

    Kozyukhin, S.; Golovchak, R.; Kovalskiy, A.; Shpotyuk, O.; Jain, H.

    2011-04-15

    High-resolution X-ray photoelectron spectroscopy (XPS) is used to study regularities in the formation of valence band electronic structure in binary As{sub x}Se{sub 100-x}, As{sub x}S{sub 100-x}, Ge{sub x}Se{sub 100-x} and Ge{sub x}S{sub 100-x} chalcogenide vitreous semiconductors. It is shown that the highest occupied energetic states in the valence band of these materials are formed by lone pair electrons of chalcogen atoms, which play dominant role in the formation of valence band electronic structure of chalcogen-rich glasses. A well-expressed contribution from chalcogen bonding p electrons and more deep s orbitals are also recorded in the experimental valence band XPS spectra. Compositional dependences of the observed bands are qualitatively analyzed from structural and compositional points of view.

  1. X-ray imaging of chemically active valence electrons during a pericyclic reaction.

    PubMed

    Bredtmann, Timm; Ivanov, Misha; Dixit, Gopal

    2014-01-01

    Time-resolved imaging of chemically active valence electron densities is a long-sought goal, as these electrons dictate the course of chemical reactions. However, X-ray scattering is always dominated by the core and inert valence electrons, making time-resolved X-ray imaging of chemically active valence electron densities extremely challenging. Here we demonstrate an effective and robust method, which emphasizes the information encoded in weakly scattered photons, to image chemically active valence electron densities. The degenerate Cope rearrangement of semibullvalene, a pericyclic reaction, is used as an example to visually illustrate our approach. Our work also provides experimental access to the long-standing problem of synchronous versus asynchronous bond formation and breaking during pericyclic reactions. PMID:25424639

  2. X-ray imaging of chemically active valence electrons during a pericyclic reaction

    PubMed Central

    Bredtmann, Timm; Ivanov, Misha; Dixit, Gopal

    2014-01-01

    Time-resolved imaging of chemically active valence electron densities is a long-sought goal, as these electrons dictate the course of chemical reactions. However, X-ray scattering is always dominated by the core and inert valence electrons, making time-resolved X-ray imaging of chemically active valence electron densities extremely challenging. Here we demonstrate an effective and robust method, which emphasizes the information encoded in weakly scattered photons, to image chemically active valence electron densities. The degenerate Cope rearrangement of semibullvalene, a pericyclic reaction, is used as an example to visually illustrate our approach. Our work also provides experimental access to the long-standing problem of synchronous versus asynchronous bond formation and breaking during pericyclic reactions. PMID:25424639

  3. Syllabus CHEM 8833 1. Structure and Models of Bonding

    E-print Network

    Sherrill, David

    Syllabus CHEM 8833 1. Structure and Models of Bonding · Atomic structure · Quantum numbers and atomic orbitals · Lewis structures · Valence-shell electron pair repulsion rules · Hybridization structure theory · Larger molecules: Qualitative molecular orbital theory (QMOT) First Exam 2. Strain

  4. Cluster molecular orbital description of the electronic structures of mixed-valence iron oxides and silicates

    USGS Publications Warehouse

    Sherman, David M.

    1986-01-01

    A molecular orbital description, based on spin-unrestricted X??-scattered wave calculations, is given for the electronic structures of mixed valence iron oxides and silicates. The cluster calculations show that electron hopping and optical intervalence charge-transger result from weak FeFe bonding across shared edges of FeO6 coordination polyhedra. In agreement with Zener's double exchange model, FeFe bonding is found to stabilize ferromagnetic coupling between Fe2+ and Fe3+ cations. ?? 1986.

  5. Analysis of the linear response function relating AL to VB{sub s} for individual substorms

    SciTech Connect

    Blanchard, G.T.; McPherron, R.L.

    1995-10-01

    Time series of the AL index and rectified solar wind electric field are used to study solar wind coupling to auroral ionospheric currents during individual substorms. Calculation of the individual filters is accompanied by representing them as the product of two simple filters: a low-pass filter that accounts for the response of the ionospheric electric field to the reconnection electric field, and a filter composed of delta function. The delta functions each have the effect of delaying and scaling the response of AL relative to VB{sub s} without distorting the waveform of VB{sub s}. Nearly all significant correlation between AL and VB{sub s} can be accounted for when the second filter contains only two components. This result suggests that the westward electrojet indexed by AL is controlled by two distinct processes, both proportional to VB{sub s}. For an ensemble of 117 isolated substorms the average prediction efficiency of a filter with two delays is 71%. If one were able to determine the exact values of the two delays and the two gain factors prior to an event, then one would be able to estimate the instantaneous magnetospheric response function. The authors examined season, universal time, and prior activity as possible factors controlling the magnitude of the parameters but found no apparent relationships. Until such relations are found the average parameters provide the best estimate but account for only 47% of the variance in the AL index. 20 refs., 10 figs.

  6. Draft Genome Sequence of Cyanobacterium Hassallia byssoidea Strain VB512170, Isolated from Monuments in India

    PubMed Central

    Singh, Deeksha; Chandrababunaidu, Mathu Malar; Panda, Arijit; Sen, Diya; Bhattacharyya, Sourav

    2015-01-01

    The draft genome assembly of Hassallia byssoidea strain VB512170 with a genome size of ~13 Mb and 10,183 protein-coding genes in 62 scaffolds is reported here for the first time. This is a terrestrial hydrophobic cyanobacterium isolated from monuments in India. We report several copies of luciferase and antibiotic genes in this organism. PMID:25745001

  7. Microhardness of Czochralski-grown single crystals of VB{sub 2}

    SciTech Connect

    Bulfon, C.; Sassik, H.; Leithe-Jasper, A.; Rogl, P.

    1997-10-01

    Single crystals of congruent melting hexagonal VB{sub 2} were grown used a triarc furnace applying the Czochralski technique. Orientation dependent microhardness measurements on a single crystal reveal quasi similar hardness in the crystallographic directions <00.1> and <10.0>, whereas the <10.1> shows slightly lower values.

  8. P/VB/CB/LCD-09-11't-Paris, Ie 10 septembre 2009

    E-print Network

    Hélein, Frédéric - Institut de Mathématiques de Jussieu, Université Paris 7

    P/VB/CB/LCD-09- 11't- Paris, Ie 10 septembre 2009 FEDERATION DE MATHEMATIQUES DE PARIS CENTRE INSTITUT DE MATHEMA TIQUES DE JUSSIEU 175 rue du Chevaleret 75013 PARIS Mesdames, Messieurs les membres du conseil de la Federation de Mathematiques de Paris Centre, chers collegues, J'ai pris connaissance du

  9. PHILOSOPHICAL MAGAZINE, 2003, VOL. 83, NO. 2, 165178 Synthesis and characterization of mixed-valence barium

    E-print Network

    Wang, Xiqu

    -valence barium titanates Thomas Ho« chey, Paula Olhe, Ralf Keding, Christian Ru« sselz Otto October 2001 and accepted in revised form 9 August 2002] Abstract A single-crystal barium oxotitanate and bonding in related compounds. } 1. Introduction Barium titanate (BaTiO3) is an important electroceramic

  10. Bent Bonds and Multiple Bonds.

    ERIC Educational Resources Information Center

    Robinson, Edward A.; Gillespie, Ronald J.

    1980-01-01

    Considers carbon-carbon multiple bonds in terms of Pauling's bent bond model, which allows direct calculation of double and triple bonds from the length of a CC single bond. Lengths of these multiple bonds are estimated from direct measurements on "bent-bond" models constructed of plastic tubing and standard kits. (CS)

  11. Adsorption mechanism and valency of catechol-functionalized hyperbranched polyglycerols

    PubMed Central

    Krysiak, Stefanie; Wei, Qiang; Rischka, Klaus; Hartwig, Andreas; Haag, Rainer

    2015-01-01

    Summary Nature often serves as a model system for developing new adhesives. In aqueous environments, mussel-inspired adhesives are promising candidates. Understanding the mechanism of the extraordinarily strong adhesive bonds of the catechol group will likely aid in the development of adhesives. With this aim, we study the adhesion of catechol-based adhesives to metal oxides on the molecular level using atomic force microscopy (AFM). The comparison of single catechols (dopamine) with multiple catechols on hyperbranched polyglycerols (hPG) at various pH and dwell times allowed us to further increase our understanding. In particular, we were able to elucidate how to achieve strong bonds of different valency. It was concluded that hyperbranched polyglycerols with added catechol end groups are promising candidates for durable surface coatings. PMID:26150898

  12. Valence atom with bohmian quantum potential: the golden ratio approach

    PubMed Central

    2012-01-01

    Background The alternative quantum mechanical description of total energy given by Bohmian theory was merged with the concept of the golden ratio and its appearance as the Heisenberg imbalance to provide a new density-based description of the valence atomic state and reactivity charge with the aim of clarifying their features with respect to the so-called DFT ground state and critical charge, respectively. Results The results, based on the so-called double variational algorithm for chemical spaces of reactivity, are fundamental and, among other issues regarding chemical bonding, solve the existing paradox of using a cubic parabola to describe a quadratic charge dependency. Conclusions Overall, the paper provides a qualitative-quantitative explanation of chemical reactivity based on more than half of an electronic pair in bonding, and provide new, more realistic values for the so-called “universal” electronegativity and chemical hardness of atomic systems engaged in reactivity (analogous to the atoms-in-molecules framework). PMID:23146157

  13. A Corpuscular Picture of Electrons in Chemical Bond

    E-print Network

    Ando, Koji

    2015-01-01

    We introduce a theory of chemical bond with a corpuscular picture of electrons. It employs a minimal set of localized electron wave packets with 'floating and breathing' degrees of freedom and the spin-coupling of non-orthogonal valence-bond theory. It accurately describes chemical bonds in ground and excited states of spin singlet and triplet, in a distinct manner from conventional theories, indicating potential for establishing a dynamical theory of electrons in chemical bonds.

  14. The flavin reductase ActVB from Streptomyces coelicolor: characterization of the electron transferase activity of the flavoprotein form

    E-print Network

    Laurent Filisetti; Julien Valton; Marc Fontecave; Vincent Nivière

    2015-01-07

    The flavin reductase ActVB is involved in the last step of actinorhodin biosynthesis in Streptomyces coelicolor. Although ActVB can be isolated with some FMN bound, this form was not involved in the flavin reductase activity. By studying the ferric reductase activity of ActVB, we show that its FMN-bound form exhibits a proper enzymatic activity of reduction of iron complexes by NADH. This shows that ActVB active site exhibits a dual property with regard to the FMN. It can use it as a substrate that goes in and off the active site or as a cofactor to provide an electron transferase activity to the polypeptide.

  15. Draft Genome Sequence of Bioactive-Compound-Producing Cyanobacterium Tolypothrix campylonemoides Strain VB511288

    PubMed Central

    Das, Subhadeep; Singh, Deeksha; Madduluri, Madhavi; Chandrababunaidu, Mathu Malar; Gupta, Akash

    2015-01-01

    We report here the draft genome sequence of Tolypothrix campylonemoides VB511288, isolated from building facades in Santiniketan, India. The members of this genus produce several compounds of commercial importance. The draft assembly is 10,627,177 bases in 135 scaffolds, and it contains 7,886 protein-coding genes, 994 pseudogenes, 18 rRNA genes, and 76 tRNA genes. PMID:25838485

  16. Evolution of substellar 'brown' dwarfs and the evolutionary status of VB8B

    NASA Technical Reports Server (NTRS)

    Stringfellow, Guy S.

    1986-01-01

    Detailed evolutionary calculations for stars near and below the minimum main sequence (MS) mass are presented, and the results are compared to VB8B. The standard set of stellar equations are solved, and the influence of both high and low grain opacities is assessed. All masses less than 0.08 solar are found to evolve to 0.0001 solar luminosities in a billion years or less. Both 0.08 solar mass and 0.075 solar mass stars become MS stars after five billion years, but with luminosities substantially below 0.0001 solar. The best fit to VB8B is 0.06 + or - 0.02 solar mass, but less than 0.8 solar mass. Depending upon its very precise mass, VB8B can be either a substellar brown dwarf with an age of 0.3-3 billion years, or an MS star with an age anywhere from two billion years to a Hubble time.

  17. Avoided valence transition in a plutonium superconductor

    PubMed Central

    Ramshaw, B. J.; Shekhter, Arkady; McDonald, Ross D.; Betts, Jon B.; Mitchell, J. N.; Tobash, P. H.; Mielke, C. H.; Bauer, E. D.; Migliori, Albert

    2015-01-01

    The d and f electrons in correlated metals are often neither fully localized around their host nuclei nor fully itinerant. This localized/itinerant duality underlies the correlated electronic states of the high-Tc cuprate superconductors and the heavy-fermion intermetallics and is nowhere more apparent than in the 5f valence electrons of plutonium. Here, we report the full set of symmetry-resolved elastic moduli of PuCoGa5—the highest Tc superconductor of the heavy fermions (Tc = 18.5 K)—and find that the bulk modulus softens anomalously over a wide range in temperature above Tc. The elastic symmetry channel in which this softening occurs is characteristic of a valence instability—therefore, we identify the elastic softening with fluctuations of the plutonium 5f mixed-valence state. These valence fluctuations disappear when the superconducting gap opens at Tc, suggesting that electrons near the Fermi surface play an essential role in the mixed-valence physics of this system and that PuCoGa5 avoids a valence transition by entering the superconducting state. The lack of magnetism in PuCoGa5 has made it difficult to reconcile with most other heavy-fermion superconductors, where superconductivity is generally believed to be mediated by magnetic fluctuations. Our observations suggest that valence fluctuations play a critical role in the unusually high Tc of PuCoGa5. PMID:25737548

  18. Avoided valence transition in a plutonium superconductor.

    PubMed

    Ramshaw, B J; Shekhter, Arkady; McDonald, Ross D; Betts, Jon B; Mitchell, J N; Tobash, P H; Mielke, C H; Bauer, E D; Migliori, Albert

    2015-03-17

    The d and f electrons in correlated metals are often neither fully localized around their host nuclei nor fully itinerant. This localized/itinerant duality underlies the correlated electronic states of the high-Tc cuprate superconductors and the heavy-fermion intermetallics and is nowhere more apparent than in the 5f valence electrons of plutonium. Here, we report the full set of symmetry-resolved elastic moduli of PuCoGa5--the highest Tc superconductor of the heavy fermions (Tc = 18.5 K)--and find that the bulk modulus softens anomalously over a wide range in temperature above Tc. The elastic symmetry channel in which this softening occurs is characteristic of a valence instability--therefore, we identify the elastic softening with fluctuations of the plutonium 5f mixed-valence state. These valence fluctuations disappear when the superconducting gap opens at Tc, suggesting that electrons near the Fermi surface play an essential role in the mixed-valence physics of this system and that PuCoGa5 avoids a valence transition by entering the superconducting state. The lack of magnetism in PuCoGa5 has made it difficult to reconcile with most other heavy-fermion superconductors, where superconductivity is generally believed to be mediated by magnetic fluctuations. Our observations suggest that valence fluctuations play a critical role in the unusually high Tc of PuCoGa5. PMID:25737548

  19. Lecture Notes Chapter 1 Structure and Bonding

    E-print Network

    White, Douglas R.

    of compounds that contain carbon >95% of all chemical compounds are organic. Natural Synthetic enzymes rubber. In nature elements are usually found as mixtures of isotopes. Three isotopes of elemental carbon are carbon the octet rule: Atom Valence Electrons To Complete Shell Number of Bonds in Neutral Compounds Carbon (C) 4 4

  20. The influence of spectral nudging in simulating Vb-events with COSMO-CLM

    NASA Astrophysics Data System (ADS)

    Paumann, Manuela; Anders, Ivonne; Hofstätter, Michael; Chimani, Barbara

    2015-04-01

    In previous studies certain European cyclones have been investigated in terms of related extreme precipitation events in Austria. Those systems passing the Mediterranean are of special interest as the atmospheric moisture content is increased. It has been shown in recent investigations that state-of-the-art RCMs can approximately reproduce observed heavy precipitation characteristics. This provides a basic confidence in the models ability to capture future changes of such events under increased greenhouse gas conditions as well. In this contribution we focus on high spatial and temporal scales and assess the currently achievable accuracy in the simulation of Vb-events. The state-of-the-art regional climate model CCLM is applied in a hindcast-mode to the case of individual Vb-events in August 2002 and Mai/June 2013. Besides the conventional forcing of the regional climate model at its lateral boundaries a spectral nudging technique is applied. This means that inside the model area the regional model is forced to accept the analysis for large scales whereas it has no effect on the small scales. The simulations for the Vb-events mentioned above covering the European domain have been varied systematically by changing nudging factor, number of nudged waves, nudged variables, and other parameters. The resulting precipitation amounts have been compared to E-OBS gridded European precipitation data set and a recent high spatially resolved precipitation data set for Austria (GPARD-6). Varying the spectral nudging setup in the short-term Vb-cases helps us on one hand learn something about 3D-processes during Vb-events e.g. vorticity and formation but on the other hand identify the model deficiencies. The results show, that increasing the number of nudged waves from 1 to 7 as well as the choice of the variables used in the nudging process have a large influence on the development of the low pressure system and the related precipitation patterns. On the contrary, the nudging factor or the definition of the uppermost pressure level for the nudging are of low impact on the results.

  1. Crossover from impurity to valence band in diluted magnetic semiconductors: Role of Coulomb attraction by acceptors

    SciTech Connect

    Popescu, Florentin; Sen, Cengiz; Dagotto, Elbio R; Moreo, Adriana

    2007-01-01

    The crossover between an impurity band (IB) and a valence band (VB) regime as a function of the magnetic impurity concentration in a model for diluted magnetic semiconductors (DMSs) is studied systematically by taking into consideration the Coulomb attraction between the carriers and the magnetic impurities. The density of states and the ferromagnetic transition temperature of a spin-fermion model applied to DMSs are evaluated using dynamical mean-field theory and Monte Carlo (MC) calculations. It is shown that the addition of a square-well-like attractive potential can generate an IB at small enough Mn doping x for values of the p-d exchange J that are not strong enough to generate one by themselves. We observe that the IB merges with the VB when x>=xc where xc is a function of J and the Coulomb strength V. Using MC simulations, we demonstrate that the range of the Coulomb attraction plays an important role. While the on-site attraction, which has been used in previous numerical simulations, effectively renormalizes J for all values of x, an unphysical result, a nearest-neighbor range attraction renormalizes J only at very low dopings, i.e., until the bound holes wave functions start to overlap. Thus, our results indicate that the Coulomb attraction can be neglected to study Mn-doped GaSb, GaAs, and GaP in the relevant doping regimes, but it should be included in the case of Mn-doped GaN, which is expected to be in the IB regime.

  2. M{sub 1-x}[W{sub 2}O{sub 2}X{sub 6}] with M=K{sup +}, Tl{sup +}, Ag{sup +}, Hg{sup 2+}, Pb{sup 2+}; X=Cl, Br-A class of mixed valence tungsten (IV,V) compounds with layered structures, W-W bonds and high conductivity

    SciTech Connect

    Beck, Johannes . E-mail: j.beck@uni-bonn.de; Kusterer, Christian; Hoffmann, Rolf-Dieter; Poettgen, Rainer

    2006-08-15

    The crystal structure of WOCl{sub 3}, determined on the basis of powder diffraction data (tetragonal, P4{sub 2}/mnm, a=10.6856(6), c=3.8537(2)), is isotypic to WOI{sub 3} and contains one-dimensional strands of edge-sharing double-octahedral W{sub 2}O{sub 4/2}Cl{sub 6} groups connected via common corners in trans position. A W-W bond of 2.99A is present within the planar W{sub 2}Cl{sub 6} groups. A series of non-stochiometric, mixed valence W(IV,V) compounds M{sub 1-x}[W{sub 2}O{sub 2}Cl{sub 6}] can be obtained from WOCl{sub 3} by reaction with metal halides (TlCl, KCl, PbCl{sub 2}) or by reaction of elemental Hg with WOCl{sub 4}. All were characterized by single crystal structure determinations and EDX measurements (Tl{sub 0.981(2)}[W{sub 2}O{sub 2}Cl{sub 6}]: monoclinic, C2/m, a=12.7050(4), b=3.7797(1), c=10.5651(3)A, {beta}=107.656(1){sup o}; K{sub 0.84(2)}[W{sub 2}O{sub 2}Cl{sub 6}]: monoclinic, C2/m, a=12.812(3), b=3.7779(6), c=10.196(3)A, {beta}=107.422(8){sup o}; Pb{sub 0.549(3)}[W{sub 2}O{sub 2}Cl{sub 6}]: orthorhombic, Immm,a=3.7659(1), b=9.8975(4), c=12.1332(6)A; Hg{sub 0.554(6)}[W{sub 2}O{sub 2}Cl{sub 6}]: monoclinic, C2/m, a=12.8361(8), b=3.7622(3), c=10.2581(9)A, {beta}=113.645(3){sup o}). Two representatives of this family of compounds have already been reported: Na[W{sub 2}O{sub 2}Br{sub 6}] [Y.-Q. Zhang, K. Peters, H.G. von Schnering, Z. Anorg. Allg. Chem. 624 (1998) 1415-1418] and Ag{sub 0.74}[W{sub 2}O{sub 2}Br{sub 6}] [S. Imhaine, C. Perrin, M. Sergent, Mat. Res. Bull. 33 (1998) 927-933]. The Ag containing compound can be obtained from elemental Ag and WOBr{sub 3}. The crystal structure, originally reported in the triclinic system, was redetermined and shown to be monoclinic with space group C2/m (a=13.7338(10), b=3.7769(3), c=10.7954(9)A, {beta}=112.401(3){sup o}). The crystal structures of these compounds are in close relationship to the structure of WOCl{sub 3} and all contain W{sub 2}O{sub 4/2}X{sub 6} (X=Cl, Br) double strands with the mono and divalent cations coordinated by the terminal halogen atoms of the W{sub 2}X{sub 6} groups and a short W-W bond (2.85A for X=Cl). A cube-shaped coordination environment is present for M=Tl, K and a trigonal-prismatic coordination for M=Ag, Hg. Hg{sub 0.55}[W{sub 2}O{sub 2}Cl{sub 6}] is a semiconductor with a non-Arrhenius behaviour, high specific conductivity of 0.05{omega}{sup -1}cm{sup -1} and a very small activation energy of 0.03eV. Hg{sub 0.55}[W{sub 2}O{sub 2}Cl{sub 6}] and Ag{sub 0.8}[W{sub 2}O{sub 2}Br{sub 6}] show a temperature independent paramagnetism with a magnetic moment around 300x10{sup -6}cm{sup 3}mol{sup -1}.

  3. Action versus valence in decision making

    PubMed Central

    Guitart-Masip, Marc; Duzel, Emrah; Dolan, Ray; Dayan, Peter

    2014-01-01

    The selection of actions, and the vigor with which they are executed, are influenced by the affective valence of predicted outcomes. This interaction between action and valence significantly influences appropriate and inappropriate choices and is implicated in the expression of psychiatric and neurological abnormalities, including impulsivity and addiction. We review a series of recent human behavioral, neuroimaging, and pharmacological studies whose key design feature is an orthogonal manipulation of action and valence. These studies find that the interaction between the two is subject to the critical influence of dopamine. They also challenge existing views that neural representations in the striatum focus on valence, showing instead a dominance of the anticipation of action. PMID:24581556

  4. The role of valence-band excitation in laser ablation of KCl

    NASA Technical Reports Server (NTRS)

    Haglund, Richard F., Jr.; Tang, Kai; Bunton, Patrick H.; Wang, Ling-Jun

    1991-01-01

    We present recent measurements of excited-atom and ion emission from KCl surfaces illuminated by vacuum-ultraviolet synchrotron radiation (h-nu = 8-28 eV) and ultraviolet laser light (h-nu = 4 eV). At low intensities characteristic of the synchrotron experiments, excited atoms are desorbed by simple valence-band excitation process involving the metallization of the KCl surface. At the higher intensities typical of laser desorption and ablation, we observe a strong decrease in K emission as a function of the number of laser shots, but an essentially constant yield of Cl. K(+) and Cl(-) emission at high intensities show similar behavior. The energetics of these desorption phenomena can be treated in a bond-orbital model which shows that creation of a single valence hole is sufficient to excite an ion to an anti-bonding state.

  5. Physical Nature of Hydrogen Bond

    E-print Network

    Zhyganiuk, I V

    2015-01-01

    The physical nature and the correct definition of hydrogen bond (H-bond) are considered.\\,\\,The influence of H-bonds on the thermodynamic, kinetic, and spectroscopic properties of water is analyzed.\\,\\,The conventional model of H-bonds as sharply directed and saturated bridges between water molecules is incompatible with the behavior of the specific volume, evaporation heat, and self-diffusion and kinematic shear viscosity coefficients of water. On the other hand, it is shown that the variation of the dipole moment of a water molecule and the frequency shift of valence vibrations of a hydroxyl group can be totally explained in the framework of the electrostatic model of H-bond.\\,\\,At the same time, the temperature dependences of the heat capacity of water in the liquid and vapor states clearly testify to the existence of weak H-bonds.\\,\\,The analysis of a water dimer shows that the contribution of weak H-bonds to its ground state energy is approximately 4--5 times lower in comparison with the energy of electr...

  6. Myosin Vb Mediated Plasma Membrane Homeostasis Regulates Peridermal Cell Size and Maintains Tissue Homeostasis in the Zebrafish Epidermis

    PubMed Central

    Phatak, Mandar; Banerjee, Shamik; Mulay, Aditya; Deshpande, Ojas; Bhide, Sourabh; Jacob, Tressa; Gehring, Ines; Nuesslein-Volhard, Christiane; Sonawane, Mahendra

    2014-01-01

    The epidermis is a stratified epithelium, which forms a barrier to maintain the internal milieu in metazoans. Being the outermost tissue, growth of the epidermis has to be strictly coordinated with the growth of the embryo. The key parameters that determine tissue growth are cell number and cell size. So far, it has remained unclear how the size of epidermal cells is maintained and whether it contributes towards epidermal homeostasis. We have used genetic analysis in combination with cellular imaging to show that zebrafish goosepimples/myosin Vb regulates plasma membrane homeostasis and is involved in maintenance of cell size in the periderm, the outermost epidermal layer. The decrease in peridermal cell size in Myosin Vb deficient embryos is compensated by an increase in cell number whereas decrease in cell number results in the expansion of peridermal cells, which requires myosin Vb (myoVb) function. Inhibition of cell proliferation as well as cell size expansion results in increased lethality in larval stages suggesting that this two-way compensatory mechanism is essential for growing larvae. Our analyses unravel the importance of Myosin Vb dependent cell size regulation in epidermal homeostasis and demonstrate that the epidermis has the ability to maintain a dynamic balance between cell size and cell number. PMID:25233349

  7. The valence-fluctuating ground state of plutonium

    PubMed Central

    Janoschek, Marc; Das, Pinaki; Chakrabarti, Bismayan; Abernathy, Douglas L.; Lumsden, Mark D.; Lawrence, John M.; Thompson, Joe D.; Lander, Gerard H.; Mitchell, Jeremy N.; Richmond, Scott; Ramos, Mike; Trouw, Frans; Zhu, Jian-Xin; Haule, Kristjan; Kotliar, Gabriel; Bauer, Eric D.

    2015-01-01

    A central issue in material science is to obtain understanding of the electronic correlations that control complex materials. Such electronic correlations frequently arise because of the competition of localized and itinerant electronic degrees of freedom. Although the respective limits of well-localized or entirely itinerant ground states are well understood, the intermediate regime that controls the functional properties of complex materials continues to challenge theoretical understanding. We have used neutron spectroscopy to investigate plutonium, which is a prototypical material at the brink between bonding and nonbonding configurations. Our study reveals that the ground state of plutonium is governed by valence fluctuations, that is, a quantum mechanical superposition of localized and itinerant electronic configurations as recently predicted by dynamical mean field theory. Our results not only resolve the long-standing controversy between experiment and theory on plutonium’s magnetism but also suggest an improved understanding of the effects of such electronic dichotomy in complex materials. PMID:26601219

  8. Sodium-sulfur battery development. Phase VB final report, October 1, 1981--February 28, 1985

    SciTech Connect

    1985-04-01

    This report describes the technical progress made under Contract No. DE-AM04-79CH10012 between the U.S. Department of Energy, Ford Aerospace & Communications Corporations and Ford Motor Company, for the period 1 October 1981 through 28 February 1985, which is designated as Phase VB of the Sodium-Sulfur Battery Development Program. During this period, Ford Aerospace held prime technical responsibility and Ford Motor Company carried out supporting research. Ceramatec, Inc., was a major subcontractor to Ford Aerospace for electrolyte development and production.

  9. Aluminum-Oxide Temperatures on the Mark VB, VE, VR, 15, and Mark 25 Assemblies

    SciTech Connect

    Aleman, S.E.

    2001-07-17

    The task was to compute the maximum aluminum-oxide and oxide-coolant temperatures of assemblies cladded in 99 plus percent aluminum. The assemblies considered were the Mark VB, VE, V5, 15 and 25. These assemblies consist of nested slug columns with individual uranium slugs cladded in aluminum cans. The CREDIT code was modified to calculate the oxide film thickness and the aluminum-oxide temperature at each axial increment. The information in this report will be used to evaluate the potential for cladding corrosion of the Mark 25 assembly.

  10. Aluminum-Oxide Temperatures on the Mark VB, VE, VR, 15, and Mark 25 Assemblies

    SciTech Connect

    Aleman, S.E.

    2001-07-17

    The task was to compute the maximum aluminum-oxide and oxide-coolant temperatures of assemblies cladded in 99+ percent aluminum. The assemblies considered were the Mark VB, VE, V5, 15 and 25. These assemblies consist of nested slug columns with individual uranium slugs cladded in aluminum cans. The CREDIT code was modified to calculate the oxide film thickness and the aluminum-oxide temperature at each axial increment. This information in this report will be used to evaluate the potential for cladding corrosion of the Mark 25 assembly.

  11. Size-consistent wave functions for nondynamical correlation energy: The valence active space optimized orbital coupled-cluster

    E-print Network

    Krylov, Anna I.

    optimized orbital coupled-cluster doubles model Anna I. Krylov,a) C. David Sherrill, Edward F. C. Byrd as the difference between full configuration interaction within the space of all valence orbitals and a single determinant of molecular orbitals Hartree­Fock theory . In order to describe bond breaking, diradicals

  12. The bondons: the quantum particles of the chemical bond.

    PubMed

    Putz, Mihai V

    2010-01-01

    By employing the combined Bohmian quantum formalism with the U(1) and SU(2) gauge transformations of the non-relativistic wave-function and the relativistic spinor, within the Schrödinger and Dirac quantum pictures of electron motions, the existence of the chemical field is revealed along the associate bondon particle B? characterized by its mass (m(B?)), velocity (v(B?)), charge (e(B?)), and life-time (t(B?)). This is quantized either in ground or excited states of the chemical bond in terms of reduced Planck constant ?, the bond energy E(bond) and length X(bond), respectively. The mass-velocity-charge-time quaternion properties of bondons' particles were used in discussing various paradigmatic types of chemical bond towards assessing their covalent, multiple bonding, metallic and ionic features. The bondonic picture was completed by discussing the relativistic charge and life-time (the actual zitterbewegung) problem, i.e., showing that the bondon equals the benchmark electronic charge through moving with almost light velocity. It carries negligible, although non-zero, mass in special bonding conditions and towards observable femtosecond life-time as the bonding length increases in the nanosystems and bonding energy decreases according with the bonding length-energy relationship Ebond[kcal/mol]×Xbond[A0]=182019, providing this way the predictive framework in which the B? particle may be observed. Finally, its role in establishing the virtual states in Raman scattering was also established. PMID:21151435

  13. Sticker Bonding.

    ERIC Educational Resources Information Center

    Frazier, Laura Corbin

    2000-01-01

    Introduces a science activity on the bonding of chemical compounds. Assigns students the role of either a cation or anion and asks them to write the ions they may bond with. Assesses students' understanding of charge, bonding, and other concepts. (YDS)

  14. Bond Issues.

    ERIC Educational Resources Information Center

    Pollack, Rachel H.

    2000-01-01

    Notes trends toward increased borrowing by colleges and universities and offers guidelines for institutions that are considering issuing bonds to raise money for capital projects. Discussion covers advantages of using bond financing, how use of bonds impacts on traditional fund raising, other cautions and concerns, and some troubling aspects of…

  15. Subliminal Affect Valence Words Change Conscious Mood Potency but Not Valence: Is This Evidence for Unconscious Valence Affect?

    PubMed Central

    Shevrin, Howard; Panksepp, Jaak; Brakel, Linda A. W.; Snodgrass, Michael

    2012-01-01

    Whether or not affect can be unconscious remains controversial. Research claiming to demonstrate unconscious affect fails to establish clearly unconscious stimulus conditions. The few investigations that have established unconscious conditions fail to rule out conscious affect changes. We report two studies in which unconscious stimulus conditions were met and conscious mood changes measured. The subliminal stimuli were positive and negative affect words presented at the objective detection threshold; conscious mood changes were measured with standard manikin valence, potency, and arousal scales. We found and replicated that unconscious emotional stimuli produced conscious mood changes on the potency scale but not on the valence scale. Were positive and negative affects aroused unconsciously, but reflected consciously in potency changes? Or were the valence words unconscious cognitive causes of conscious mood changes being activated without unconscious affect? A thought experiment is offered as a way to resolve this dilemma. PMID:24961258

  16. ALLOYING-DRIVEN PHASE STABILITY IN GROUP-VB TRANSITION METALS UNDER COMPRESSION

    SciTech Connect

    Landa, A; Soderlind, P

    2011-04-11

    The change in phase stability of Group-VB (V, Nb, and Ta) transition metals due to pressure and alloying is explored by means of first-principles electronic-structure calculations. It is shown that under compression stabilization or destabilization of the ground-state body-centered cubic (bcc) phase of the metal is mainly dictated by the band-structure energy that correlates well with the position of the Kohn anomaly in the transverse acoustic phonon mode. The predicted position of the Kohn anomaly in V, Nb, and Ta is found to be in a good agreement with data from the inelastic x-ray or neutron scattering measurements. In the case of alloying the change in phase stability is defined by the interplay between the band-structure and Madelung energies. We show that band-structure effects determine phase stability when a particular Group-VB metal is alloyed with its nearest neighbors within the same d-transition series: the neighbor with less and more d electrons destabilize and stabilize the bcc phase, respectively. When V is alloyed with neighbors of a higher (4d- or 5d-) transition series, both electrostatic Madelung and band-structure energies stabilize the body-centered-cubic phase. The opposite effect (destabilization) happens when Nb or Ta is alloyed with neighbors of the 3d-transition series.

  17. Myosin Vb and Rab11a regulate phosphorylation of ezrin in enterocytes.

    PubMed

    Dhekne, Herschel S; Hsiao, Nai-Hua; Roelofs, Pieter; Kumari, Meena; Slim, Christiaan L; Rings, Edmond H H M; van Ijzendoorn, Sven C D

    2014-03-01

    Microvilli at the apical surface of enterocytes allow the efficient absorption of nutrients in the intestine. Ezrin activation by its phosphorylation at T567 is important for microvilli development, but how such ezrin phosphorylation is controlled is not well understood. We demonstrate that a subset of kinases that phosphorylate ezrin closely co-distributes with apical recycling endosome marker Rab11a in the subapical domain. Expression of dominant-negative Rab11a mutant or depletion of the Rab11a-binding motor protein myosin Vb prevents the subapical enrichment of Rab11a and these kinases and inhibits ezrin phosphorylation and microvilli development, without affecting the polarized distribution of ezrin itself. We observe a similar loss of the subapical enrichment of Rab11a and the kinases and reduced phosphorylation of ezrin in microvillus inclusion disease, which is associated with MYO5B mutations, intestinal microvilli atrophy and malabsorption. Thus, part of the machinery for ezrin activation depends on recycling endosomes controlled by myosin Vb and Rab11a which, we propose, might act as subapical signaling platforms that enterocytes use to regulate development of microvilli and maintain human intestinal function. PMID:24413175

  18. VB-CHEP chemotherapy regimen for aggressive non-Hodgkin's lymphomas.

    PubMed

    Yalçin, S; Kars, A; Ozi?ik, Y; Tekuzman, G; Ozyilkan, O; Celik, I; Bari?ta, I; Güllü, I; Güler, N; Baltali, E; Firat, D

    1998-10-01

    Despite intensive search for the optimal combination chemotherapy for aggressive non-Hodgkin's lymphoma (NHL), the CHOP (cyclophosphamide, adriamycin, vincristine and prednisolone) regimen is still the standard therapy. We investigated the clinical efficacy of a new combination regimen consisting of vincristine, bleomycin-cyclophosphamide, adriamycin, etoposide and prednisolone (VB-CHEP) in patients with aggressive NHL. A total of 29 patients with aggressive NHL was enrolled into the protocol. Eight patients were consolidated with cisplatin and cytarabine and 5 patients received radiotherapy for bulky disease. Objective response was achieved in 82.8% of the patients. Complete remission (CR) and partial remission rates were 72.4%, and 10.3%, respectively. CR rate was significantly lower in patients with advanced stage, extranodal disease and bone marrow involvement. Median follow-up time is 34+ months; 17 patients are disease-free while 12 died and only 2 patients with CR have relapsed so far. Median response duration is 29+ months and the median survival is 48+ months. The survival rate is 69% in the first year and 66% in the second year. A total of 152 cycles were evaluated for toxicity. Major hematological toxicity was myelosuppression and neutropenia, detected in 50.65%, was mostly grades 1-2. Neutropenic fever occurred in only 11 cycles. The side effects of the consolidation therapy were also acceptable. We conclude that the VB-CHEP regimen with consolidation therapy for high-risk patients may be an effective treatment for advanced stage aggressive NHL. PMID:9820633

  19. Molybdenum Valence in Basaltic Silicate Melts

    NASA Technical Reports Server (NTRS)

    Danielson, L. R.; Righter, K.; Newville, M.; Sutton, S.; Pando, K.

    2010-01-01

    The moderately siderophile element molybdenum has been used as an indicator in planetary differentiation processes, and is particularly relevant to core formation [for example, 1-6]. However, models that apply experimental data to an equilibrium differentiation scenario infer the oxidation state of molybdenum from solubility data or from multivariable coefficients from metal-silicate partitioning data [1,3,7]. Partitioning behavior of molybdenum, a multivalent element with a transition near the J02 of interest for core formation (IW-2) will be sensitive to changes in JO2 of the system and silicate melt structure. In a silicate melt, Mo can occur in either 4+ or 6+ valence state, and Mo6+ can be either octahedrally or tetrahedrally coordinated. Here we present first XANES measurements of Mo valence in basaltic run products at a range of P, T, and JO2 and further quantify the valence transition of Mo.

  20. Arrays Test Problem-1: Understanding simple one dimensional arrays Problem Statement: Design a VB program to compute the areas of "n" number of squares and circles,

    E-print Network

    Clement, Prabhakar

    : Design a VB program to compute the areas of "n" number of squares and circles, given their characteristic a VB program to compute the areas of "n" number of squares and circles, given their characteristic() to first store the values internally and then we output the results after finishing all the computations

  1. Emotions and false memories: valence or arousal?

    PubMed

    Corson, Yves; Verrier, Nadège

    2007-03-01

    The effects of mood on false memories have not been studied systematically until recently. Some results seem to indicate that negative mood may reduce false recall and thus suggest an influence of emotional valence on false memory. The present research tested the effects of both valence and arousal on recall and recognition and indicates that the effect is actually due to arousal. In fact, whether participants' mood is positive, negative, or neutral, false memories are significantly more frequent under conditions of high arousal than under conditions of low arousal. PMID:17444912

  2. Fluctuating valence in a correlated solid and the anomalous properties of delta-plutonium.

    PubMed

    Shim, J H; Haule, K; Kotliar, G

    2007-03-29

    Although the nuclear properties of the late actinides (plutonium, americium and curium) are fully understood and widely applied to energy generation, their solid-state properties do not fit within standard models and are the subject of active research. Plutonium displays phases with enormous volume differences, and both its Pauli-like magnetic susceptibility and resistivity are an order of magnitude larger than those of simple metals. Curium is also highly resistive, but its susceptibility is Curie-like at high temperatures and orders antiferromagnetically at low temperatures. The anomalous properties of the late actinides stem from the competition between itinerancy and localization of their f-shell electrons, which makes these elements strongly correlated materials. A central problem in this field is to understand the mechanism by which these conflicting tendencies are resolved in such materials. Here we identify the electronic mechanisms responsible for the anomalous behaviour of late actinides, revisiting the concept of valence using a theoretical approach that treats magnetism, Kondo screening, atomic multiplet effects and crystal field splitting on the same footing. We find that the ground state in plutonium is a quantum superposition of two distinct atomic valences, whereas curium settles into a magnetically ordered single valence state at low temperatures. The f(7) configuration of curium is contrasted with the multiple valences of the plutonium ground state, which we characterize by a valence histogram. The balance between the Kondo screening and magnetism is controlled by the competition between spin-orbit coupling, the strength of atomic multiplets and the degree of itinerancy. Our approach highlights the electronic origin of the bonding anomalies in plutonium, and can be applied to predict generalized valences and the presence or absence of magnetism in other compounds starting from first principles. PMID:17392780

  3. Fluctuating valence in a correlated solid and the anomalous properties of ?-plutonium

    NASA Astrophysics Data System (ADS)

    Shim, J. H.; Haule, K.; Kotliar, G.

    2007-03-01

    Although the nuclear properties of the late actinides (plutonium, americium and curium) are fully understood and widely applied to energy generation, their solid-state properties do not fit within standard models and are the subject of active research. Plutonium displays phases with enormous volume differences, and both its Pauli-like magnetic susceptibility and resistivity are an order of magnitude larger than those of simple metals. Curium is also highly resistive, but its susceptibility is Curie-like at high temperatures and orders antiferromagnetically at low temperatures. The anomalous properties of the late actinides stem from the competition between itinerancy and localization of their f-shell electrons, which makes these elements strongly correlated materials. A central problem in this field is to understand the mechanism by which these conflicting tendencies are resolved in such materials. Here we identify the electronic mechanisms responsible for the anomalous behaviour of late actinides, revisiting the concept of valence using a theoretical approach that treats magnetism, Kondo screening, atomic multiplet effects and crystal field splitting on the same footing. We find that the ground state in plutonium is a quantum superposition of two distinct atomic valences, whereas curium settles into a magnetically ordered single valence state at low temperatures. The f7 configuration of curium is contrasted with the multiple valences of the plutonium ground state, which we characterize by a valence histogram. The balance between the Kondo screening and magnetism is controlled by the competition between spin-orbit coupling, the strength of atomic multiplets and the degree of itinerancy. Our approach highlights the electronic origin of the bonding anomalies in plutonium, and can be applied to predict generalized valences and the presence or absence of magnetism in other compounds starting from first principles.

  4. Spectroscopic studies, fluorescence quenching by molecular oxygen and amplified spontaneous emission of 1,4-bis [2-(2-pyridyl) vinyl] benzene (P2VB) diolefinic laser dye

    NASA Astrophysics Data System (ADS)

    El-Daly, Samy A.; Ebeid, E. M.

    2014-04-01

    The UV-visible electronic absorption spectra, molar absorptivity, fluorescence spectra, fluorescence quantum yield and excited state lifetime of 1,4-bis [2-(2-pyridyl) vinyl] benzene P2VB were measured in different solvents. The fluorescence quenching of P2VB by molecular oxygen was also studied using lifetime measurements. A 2 × 10-4 mol dm-3 solution of P2VB in dimethyl formamide (DMF) gave amplified spontaneous emission (ASE) in blue spectral region with emission maximum at 420 nm upon pumping by 337.1 nitrogen laser pulse. The photochemical quantum yields (?c) of trans-cis photoisomerization of P2VB were calculated in different organic solvents. The photoreactivity of P2VB are also studied PMMA matrix.

  5. Volume 34 | Issues 910 | 2013 Included in this print edition

    E-print Network

    Ponder, Jay

    on the cover). The AMOEBA Polarizable Force Field The image shows a snapshot taken from an AMOEBA molecular on valence bond (VB) theory and incorporated into the AMOEBA polarizable force field. Gas phase calculations of ion-aqua complexes show that the proposed AMOEBA-VB model improves the accuracy of MM model energetics

  6. Affective Priming with Associatively Acquired Valence

    ERIC Educational Resources Information Center

    Aguado, Luis; Pierna, Manuel; Saugar, Cristina

    2005-01-01

    Three experiments explored the effect of affectively congruent or incongruent primes on evaluation responses to positive or negative valenced targets (the "affective priming" effect). Experiment 1 replicated the basic affective priming effect with Spanish nouns: reaction time for evaluative responses (pleasant/unpleasant) were slower on…

  7. Draft Genome Sequence of Vibrio sp. Strain Vb278, an Antagonistic Bacterium Isolated from the Marine Sponge Sarcotragus spinosulus

    PubMed Central

    Gonçalves, Ana C. S.; Franco, Telma; Califano, Gianmaria; Dowd, Scot E.; Pohnert, Georg

    2015-01-01

    We report here the draft genome sequence of Vibrio sp. Vb278, a biofilm-producing strain isolated from the marine sponge Sarcotragus spinosulus, showing in vitro antibacterial activity. The annotated genome displays a range of symbiotic factors and the potential for the biosynthesis of several biologically active natural products. PMID:26021918

  8. 30 CFR 57.22218 - Seals and stoppings (III, V-A, and V-B mines).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-UNDERGROUND METAL AND NONMETAL MINES Safety Standards for Methane in Metal and Nonmetal Mines Ventilation § 57.22218 Seals and... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Seals and stoppings (III, V-A, and V-B...

  9. 30 CFR 57.22314 - Flow-control devices (V-A and V-B mines).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-UNDERGROUND METAL AND NONMETAL MINES Safety Standards for Methane in Metal and Nonmetal Mines Equipment § 57.22314 Flow-control devices... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Flow-control devices (V-A and V-B mines)....

  10. 30 CFR 57.22314 - Flow-control devices (V-A and V-B mines).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-UNDERGROUND METAL AND NONMETAL MINES Safety Standards for Methane in Metal and Nonmetal Mines Equipment § 57.22314 Flow-control devices... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Flow-control devices (V-A and V-B mines)....

  11. 30 CFR 57.22314 - Flow-control devices (V-A and V-B mines).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-UNDERGROUND METAL AND NONMETAL MINES Safety Standards for Methane in Metal and Nonmetal Mines Equipment § 57.22314 Flow-control devices... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Flow-control devices (V-A and V-B mines)....

  12. 30 CFR 57.22218 - Seals and stoppings (III, V-A, and V-B mines).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-UNDERGROUND METAL AND NONMETAL MINES Safety Standards for Methane in Metal and Nonmetal Mines Ventilation § 57.22218 Seals and... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Seals and stoppings (III, V-A, and V-B...

  13. 30 CFR 57.22218 - Seals and stoppings (III, V-A, and V-B mines).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-UNDERGROUND METAL AND NONMETAL MINES Safety Standards for Methane in Metal and Nonmetal Mines Ventilation § 57.22218 Seals and... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Seals and stoppings (III, V-A, and V-B...

  14. 30 CFR 57.22218 - Seals and stoppings (III, V-A, and V-B mines).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-UNDERGROUND METAL AND NONMETAL MINES Safety Standards for Methane in Metal and Nonmetal Mines Ventilation § 57.22218 Seals and... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Seals and stoppings (III, V-A, and V-B...

  15. 30 CFR 57.22314 - Flow-control devices (V-A and V-B mines).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-UNDERGROUND METAL AND NONMETAL MINES Safety Standards for Methane in Metal and Nonmetal Mines Equipment § 57.22314 Flow-control devices... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Flow-control devices (V-A and V-B mines)....

  16. 30 CFR 57.22314 - Flow-control devices (V-A and V-B mines).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-UNDERGROUND METAL AND NONMETAL MINES Safety Standards for Methane in Metal and Nonmetal Mines Equipment § 57.22314 Flow-control devices... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Flow-control devices (V-A and V-B mines)....

  17. 30 CFR 57.22218 - Seals and stoppings (III, V-A, and V-B mines).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-UNDERGROUND METAL AND NONMETAL MINES Safety Standards for Methane in Metal and Nonmetal Mines Ventilation § 57.22218 Seals and... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Seals and stoppings (III, V-A, and V-B...

  18. The nature of the fourth bond in the ground state of C2: the quadruple bond conundrum.

    PubMed

    Danovich, David; Hiberty, Philippe C; Wu, Wei; Rzepa, Henry S; Shaik, Sason

    2014-05-19

    Does, or doesn't C2 break the glass ceiling of triple bonding? This work provides an overview on the bonding conundrum in C2 and on the recent discussions regarding our proposal that it possesses a quadruple bond. As such, we focus herein on the main point of contention, the 4th?bond of C2, and discuss the main views. We present new data and an overview of the nature of the 4th?bond--its proposed antiferromagnetically coupled nature, its strength, and a derivation of its bond energy from experimentally based thermochemical data. We address the bond-order conundrum of C2 arising from generalized VB (GVB) calculations by comparing it to HC?CH, and showing that the two molecules behave very similarly, and C2 is in no way an exception. We analyse the root cause of the deviation of C2 from the Badger Rule, and demonstrate that the reason for the smaller force constant (FC) of C2 relative to HC?CH has nothing to do with the bond energies, or with the number of bonds in the two molecules. The FC is determined primarily by the bond length, which is set by the balance between the bond length preferences of the ?- versus ?-bonds in the two molecules. This interplay in the case of C2 clearly shows the fingerprints of the 4th?bond. Our discussion resolves the points of contention and shows that the arguments used to dismiss the quadruple bond nature of C2 are not well founded. PMID:24782210

  19. Diffusion bonding

    NASA Astrophysics Data System (ADS)

    Brown, L. E.

    1993-03-01

    A temperature between 400 and 500 and a pressure between 40 MPa and 160 MPa were indicated by a two-factor, three-level factorial experiment for diffusion bonding of molybdenum sheet substrates. These substrates were sputter ion plated with palladium (0.5 microns) and silver (10 microns) films on the mating surfaces, with the silver used as a bonding interlayer. The palladium acted as an adhesive layer between the silver film and molybdenum substrate. The silver diffusion bonds that resulted were qualitatively characterized at the interfacial regions, and bonds with no visible interface were obtained at 7500X magnification. Correlations were obtained for voids found optically at the silver/silver bonding interface and colored image maps, illustrating bond quality, produced by nondestructive ultrasonic imaging. Above 160 MPa, the bonding process produces samples with a nonuniform load distribution. These samples contained regions with gaps and well-bonded regions at the silver/silver interface, and all had macroscopic deformation of the silver films.

  20. The Bondons: The Quantum Particles of the Chemical Bond

    PubMed Central

    Putz, Mihai V.

    2010-01-01

    By employing the combined Bohmian quantum formalism with the U(1) and SU(2) gauge transformations of the non-relativistic wave-function and the relativistic spinor, within the Schrödinger and Dirac quantum pictures of electron motions, the existence of the chemical field is revealed along the associate bondon particle B? characterized by its mass (mB?), velocity (vB?), charge (eB?), and life-time (tB?). This is quantized either in ground or excited states of the chemical bond in terms of reduced Planck constant ?, the bond energy Ebond and length Xbond, respectively. The mass-velocity-charge-time quaternion properties of bondons’ particles were used in discussing various paradigmatic types of chemical bond towards assessing their covalent, multiple bonding, metallic and ionic features. The bondonic picture was completed by discussing the relativistic charge and life-time (the actual zitterbewegung) problem, i.e., showing that the bondon equals the benchmark electronic charge through moving with almost light velocity. It carries negligible, although non-zero, mass in special bonding conditions and towards observable femtosecond life-time as the bonding length increases in the nanosystems and bonding energy decreases according with the bonding length-energy relationship Ebond[kcal/mol]×Xbond[A0]=182019, providing this way the predictive framework in which the B? particle may be observed. Finally, its role in establishing the virtual states in Raman scattering was also established. PMID:21151435

  1. Core-Level And Valence-Band Study Using Angle-Integrated Photoemission on LaFeAsO(0.9)F(0.1)

    SciTech Connect

    Garcia, D.R.; Jozwiak, C.; Hwang, C.G.; Fedorov, A.; Hanrahan, S.M.; Wilson, S.D.; Rotundu, C.R.; Freelon, B.K.; Birgeneau, R.J.; Bourret-Courchesne, E.; Lanzara, A.

    2009-05-18

    Using angle-integrated photoemission spectroscopy we have probed the novel LaFeAsO{sub 0.9}F{sub 0.1} superconductor over a wide range of photon energies and temperatures. We have provided a full characterization of the orbital character of the valence-band (VB) density of states (DOS) and of the magnitude of the d-p hybridization energy. Finally, we have identified two characteristic temperatures: 90 K where a pseudogap-like feature appears to close and 120 K where a sudden change in the DOS near E{sub F} occurs. We associate these phenomena with the spin density wave magnetic ordering and the structural transition seen in the parent compound, respectively. These results suggest the important role of electron correlation, spin physics, and structural distortion in the physics of Fe-based superconductors.

  2. Pion valence-quark parton distribution function

    NASA Astrophysics Data System (ADS)

    Chang, Lei; Thomas, Anthony W.

    2015-10-01

    Within the Dyson-Schwinger equation formulation of QCD, a rainbow ladder truncation is used to calculate the pion valence-quark distribution function (PDF). The gap equation is renormalized at a typical hadronic scale, of order 0.5 GeV, which is also set as the default initial scale for the pion PDF. We implement a corrected leading-order expression for the PDF which ensures that the valence-quarks carry all of the pion's light-front momentum at the initial scale. The scaling behavior of the pion PDF at a typical partonic scale of order 5.2 GeV is found to be (1 - x) ?, with ? ? 1.6, as x approaches one.

  3. Strong electron correlations in cobalt valence tautomers

    NASA Astrophysics Data System (ADS)

    LaBute, M. X.; Kulkarni, R. V.; Endres, R. G.; Cox, D. L.

    2002-03-01

    We have examined cobalt based valence tautomer molecules such as Co(SQ)2(phen) using density functional theory (DFT) and variational configuration interaction (VCI) approaches based upon a model Hamiltonian. Our DFT results extend earlier work by finding a reduced total energy gap (order 0.6 eV) between high-temperature and low-temperature states when we fully relax the coordinates (relative to experimental ones). Furthermore, we demonstrate that a charge transfer picture based upon formal valence arguments succeeds qualitatively while failing quantitatively due to strong covalency between the Co 3d orbitals and ligand p orbitals. With the VCI approach, we argue that the high-temperature, high spin phase is strongly mixed valent, with about 30% admixture of Co (III) into the predominantly Co(II) ground state. We confirm this mixed valence through a fit to the XANES spectra. Moreover, the strong electron correlations of the mixed valent phase provide an energy lowering of about 0.2-0.3 eV of the high-temperature phase relative to the low-temperature one. Finally, we use the domain model to account for the extraordinarily large entropy and enthalpy values associated with the transition.

  4. The DIET from semiconductor surfaces by excitation of valence electrons

    NASA Astrophysics Data System (ADS)

    Kanasaki, Jun'ichi; Okano, Akiko; Ishikawa, Ken'ichi; Nakai, Yasuo; Itoh, Noriaki

    1995-06-01

    We discuss the desorption induced by electronic transitions (DIET) of constituent atoms from several types of non-metallic solids, particularly the DIET from semiconductors by valence electron excitations. We first classify the non-metallic solids into type A, in which no self-trapping of excitons occurs, and type B, in which self-trapping occurs. We argue that in type B solids the localization of electron-hole pairs or excitons through the self-trapping on the surfaces induces the Menzel-Gomer-Redhead-type anti-bonding state resulting in DIET. For the DIET from type A non-metals, typically semiconductors, in which the self-trapping is not induced, we derive two important characteristics: (1) the emission is related to defects on the surfaces and (2) single electronic excitation cannot induce the emissions. The recent experimental observations of laser-induced emissions satisfying these characteristics for the DIET from semiconductors are surveyed. Furthermore we present experimental evidence demonstrating that the observed emissions are of the electronic origin: the emission occurs dominantly when the excitation is localized on the surface. Finally, surface phenomena, such as laser ablation and dry etching, related to the DIET from semiconductors, and the applications of the DIET from semiconductors are discussed.

  5. Electron transfer mediated decay of outer-valence ionised states

    NASA Astrophysics Data System (ADS)

    Gokhberg, Kirill; Stumpf, Vasili; Cederbaum, Lorenz S.

    2014-05-01

    Electronically excited states of atoms and molecules embedded in an environment may efficiently decay by ionising neighbouring species in the energy or charge transfer mediated processes. The energy transfer driven interatomic Coulombic decay (ICD) has been shown to proceed on a fs time scale in weakly bonded systems upon the production of a localised electronic excitation. Related electron transfer mediated decay (ETMD) is usually a slower process and becomes an important relaxation pathway whenever ICD channel is unavailable. In this talk we show that this situation is realised for singly and multiply outer-valence ionised atoms in a medium leading to unexpected physical effects. In particular, we demonstrate that ETMD provides an efficient and general neutralisation pathway for multiply charged ions produced via Auger decay in an environment. As an example we show the results of an ab initio study of the NeKr2 cluster following the Auger decay of 1s vacancy of Ne. We also discuss how the single photon double ionisation efficiency can be dramatically enhanced in a medium due to ETMD. As an example we show that the double ionization cross section of Mg in MgHe cluster becomes three orders of magnitude larger than the respective cross section of the isolated Mg atom.

  6. Influence of valence, electronegativity, atomic radii, and crest-trough interaction with phonons on the high-temperature copper oxide superconductors

    SciTech Connect

    Pauling, L.

    1987-07-13

    Several structural features, including electron transfer between atoms of different electronegativity, oxygen deficiency, and unsynchronized resonance of valence bonds, as well as tight binding of atoms and the presence of both hypoelectronic and hyperelectronic elements, cooperatre to confer metallic properties and high-temperature superconductivity on compounds such as (Sr,Ba,Y,La)/sub 2/CuO/sub 4-//sub y/. .AE

  7. Evidence for valence quark-hadron duality

    SciTech Connect

    Niculescu, I.; Armstrong, C.S.; Arrington, J.

    1999-04-01

    A newly obtained data sample of inclusive electron-nucleon scattering from both hydrogen and deuterium targets is analyzed. These JLab data are in the nucleon resonance region in the four-momentum transfer range between 0.3 and 5 (GeV/c){sup 2}. The data are in agreement with SLAC data at similar kinematics, and are found to follow an average scaling curve. The inclusion of low-momentum transfer data yields a scaling curve resembling deep inelastic neutrino-nucleus scattering data, suggesting a sensitivity to the valence quarks only.

  8. Valence quark distributions of the proton from maximum entropy approach

    E-print Network

    Rong Wang; Xurong Chen

    2015-03-30

    We present an attempt of maximum entropy principle to determine valence quark distributions in the proton at very low resolution scale $Q_0^2$. The initial three valence quark distributions are obtained with limited dynamical information from quark model and QCD theory. Valence quark distributions from this method are compared to the lepton deep inelastic scattering data, and the widely used CT10 and MSTW08 data sets. The obtained valence quark distributions are consistent with experimental observations and the latest global fits of PDFs. Maximum entropy method is expected to be particularly useful in the case where relatively little information from QCD calculation is given.

  9. Generalized valence-force-field model of (Ga,In)(N,P) ternary alloys

    NASA Astrophysics Data System (ADS)

    Biswas, Koushik; Franceschetti, Alberto; Lany, Stephan

    2008-08-01

    We present a generalized valence-force-field (VFF) model for the ternary III V alloys ( III=Ga , In and V=N , P) to predict the formation energies and atomic structures of ordered and disordered alloy configurations. For each alloy (GaInN, GaInP, GaNP, and InNP) the VFF parameters, which include bond-angle/bond-length interactions, are fitted to the first-principles calculated formation energies of 30 ternary structures. Compared to standard approaches where the VFF parameters are transferred from the individual binary III V compounds, our generalized VFF approach predicts alloy formation energies and atomic structures with considerably improved accuracy. Using this generalized approach and random realizations in large supercells (4096 atoms), we determine the temperature-composition phase diagram, i.e., the binodal and spinodal decomposition curves, of the (Ga, In) (N, P) ternary alloys.

  10. Generalized Valence-Force-Field Model of (Ga,In)(N,P) Ternary Alloys

    SciTech Connect

    Biswas, K.; Franceschetti, A.; Lany, S.

    2008-01-01

    We present a generalized valence-force-field (VFF) model for the ternary III-V alloys (III=Ga, In and V=N, P) to predict the formation energies and atomic structures of ordered and disordered alloy configurations. For each alloy (GaInN, GaInP, GaNP, and InNP) the VFF parameters, which include bond-angle/bond-length interactions, are fitted to the first-principles calculated formation energies of 30 ternary structures. Compared to standard approaches where the VFF parameters are transferred from the individual binary III-V compounds, our generalized VFF approach predicts alloy formation energies and atomic structures with considerably improved accuracy. Using this generalized approach and random realizations in large supercells (4096 atoms), we determine the temperature-composition phase diagram, i.e., the binodal and spinodal decomposition curves, of the (Ga, In) (N, P) ternary alloys.

  11. Extreme floods in central Europe over the past 500 years: Role of cyclone pathway ``Zugstrasse Vb''

    NASA Astrophysics Data System (ADS)

    Mudelsee, M.; BöRngen, M.; Tetzlaff, G.; Grünewald, U.

    2004-12-01

    Anthropogenically induced climate change has been hypothesized to add to the risk of extreme river floods because a warmer atmosphere can carry more water. In the case of the central European rivers Elbe and Oder, another possibility that has been considered is a more frequent occurrence of a weather situation of the type "Zugstrasse Vb," where a low-pressure system travels from the Adriatic region northeastward, carrying moist air and bringing orographic rainfall in the mountainous catchment areas (Erzgebirge, Sudeten, and Beskids). Analysis of long, homogeneous records of past floods allows us to test such ideas. M. Mudelsee and co-workers recently presented flood records for the middle parts of the Elbe and Oder, which go continuously back to A.D. 1021 and A.D. 1269, respectively. Here we review the reconstruction and assess the data quality of the records, which are based on combining documentary data from the interval up to 1850 and measurements thereafter, finding both the Elbe and Oder records to provide reliable information on heavy floods at least since A.D. 1500. We explain that the statistical method of kernel occurrence rate estimation can overcome deficiencies of techniques previously used to investigate trends in the occurrence of climatic extremes, because it (1) allows nonmonotonic trends, (2) imposes no parametric restrictions, and (3) provides confidence bands, which are essential for evaluating whether observed trends are real or came by chance into the data. We further give a hypothesis test that can be used to evaluate monotonic trends. On the basis of these data and methods, we find for both the Elbe and Oder rivers (1) significant downward trends in winter flood risk during the twentieth century, (2) no significant trends in summer flood risk in the twentieth century, and (3) significant variations in flood risk during past centuries, with notable differences between the Elbe and Oder. The observed trends are shown to be both robust against data uncertainties and only slightly sensitive to land use changes or river engineering, lending support for climatic influences on flood occurrence rate. In the case of winter floods, regional warming during the twentieth century has likely reduced winter flood risk via a reduced rate of strong river freezing (breaking ice at the end of winter may function as a water barrier and enhance a high water stage severely). In the case of summer floods, correlation analysis shows a significant, but weak, relation between flood occurrence and meridional airflow, compatible with a "Zugstrasse Vb" weather situation. The weakness of this relation, together with the uncertainty about whether this weather situation became more frequent, explains the absence of trends in summer flood risk for the Elbe and Oder in the twentieth century. We finally draw conclusions about flood disaster management and modeling of flood occurrence under a changed climate.

  12. STRONG CONSTRAINTS TO THE PUTATIVE PLANET CANDIDATE AROUND VB 10 USING DOPPLER SPECTROSCOPY

    SciTech Connect

    Anglada-Escude, Guillem; Shkolnik, Evgenya L.; Weinberger, Alycia J.; Thompson, Ian B.; Osip, David J.; Debes, John H. E-mail: shkolnik@dtm.ciw.edu E-mail: ian@obs.carnegiescience.edu E-mail: john.H.debes@nasa.gov

    2010-03-01

    We present new radial velocity (RV) measurements of the ultra-cool dwarf VB 10, which was recently announced to host a giant planet detected with astrometry. The new observations were obtained using optical spectrographs (MIKE/Magellan and ESPaDOnS/CFHT) and cover 65% of the reported period of 270 days. The nominal precision of the new Doppler measurements is about 150 m s{sup -1} while their standard deviation is 250 m s{sup -1}. However, there are indications that such a larger variation is due to uncontrolled systematic errors. We apply least-squares periodograms to identify the most significant signals and evaluate their false alarm probabilities (FAPs). We show that this method is the proper generalization to astrometric data because (1) it mitigates the coupling of the orbital parameters with the parallax and proper motion, and (2) it permits a direct generalization to include nonlinear Keplerian parameters in a combined fit to astrometry and RV data. Our analysis of the astrometry alone uncovers the reported 270 day period and an even stronger signal at {approx}50 days. We estimate the uncertainties in the parameters using a Markov chain Monte Carlo approach. Although the new data alone cannot rule out the presence of a candidate, when combined with published RV measurements, the FAPs of the best solutions grow to unacceptable levels strongly suggesting that the observed astrometric wobble is not due to an unseen companion. The new measurements put an upper limit of m sin i {approx} 2.5 m {sub jup} for a companion with a period shorter than one year and moderate eccentricities.

  13. Pi Bond Orders and Bond Lengths

    ERIC Educational Resources Information Center

    Herndon, William C.; Parkanyi, Cyril

    1976-01-01

    Discusses three methods of correlating bond orders and bond lengths in unsaturated hydrocarbons: the Pauling theory, the Huckel molecular orbital technique, and self-consistent-field techniques. (MLH)

  14. Teaching Valence Shell Electron Pair Repulsion (VSEPR) Theory

    ERIC Educational Resources Information Center

    Talbot, Christopher; Neo, Choo Tong

    2013-01-01

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

  15. EMOTIONAL VALENCE CATEGORIZATION USING HOLISTIC IMAGE FEATURES V. Yanulevskaya,

    E-print Network

    Sebe, Nicu

    . 2.1. Emotional valences ground truth IAPS consists of 716 natural colored photographs. They depictEMOTIONAL VALENCE CATEGORIZATION USING HOLISTIC IMAGE FEATURES V. Yanulevskaya, J.C. van Gemert, A learn to perceive emotions as evoked by an artwork? Here we propose an emotion categorization system

  16. Intermediate valence in Yb Intermetallic compounds Jon Lawrence

    E-print Network

    Lawrence, Jon

    1 Intermediate valence in Yb Intermetallic compounds Jon Lawrence University of California, Irvine-based intermetallics. The ground state is that of a heavy mass Fermi liquid. The d.c. and optical conductivity reflect. Talk at LBL, 12 April 2006 #12;2 Intermediate Valence Compounds CeSn3 Fermi liquid (FL) YbAgCu4, Yb

  17. Aggregating Entries of Semantic Valence Dictionary of Polish Verbs

    E-print Network

    Aggregating Entries of Semantic Valence Dictionary of Polish Verbs Elzbieta Hajnicz Institute of Computer Science, Polish Academy of Sciences ul. Ordona 21, 01-237 Warsaw, Poland hajnicz@ipipan.waw.pl Abstract In this paper the phase of semantic valence dictionary of Polish verbs consisting in ag- gregating

  18. Core Polarization with Variable Length Parameters for Valence Particles

    E-print Network

    Larry Zamick

    2011-03-30

    We study quadrupole and monopole core polarization using harmonic oscillator wave funtions but with different length parameters for the valence particle as compared to the core. We use perturbation theory with a delta interaction. The results also hold for a density dependent delta interaction [1]. We study how the amount of core polarization varies with the distance of the valence particle from the core.

  19. Investing in Bonds 

    E-print Network

    Johnson, Jason; Polk, Wade

    2002-08-12

    Bonds, which are issued by governments and corporations, can be an important part of one's investment portfolio. U.S. government bonds, municipal bonds, zero-coupon bonds and other types are described. Also learn strategies for coping with inflation...

  20. Stellar Activity at the End of the Main Sequence: GHRS Observations of the M8 Ve Star VB 10

    NASA Technical Reports Server (NTRS)

    Linsky, Jeffrey L.; Wood, Brian E.; Brown, Alexander; Giampapa, Mark S.; Ambruster, Carol

    1995-01-01

    We present Goddard High Resolution Spectrograph observations of the M8 Ve star VB 10 (equal to G1 752B), located very near the end of the stellar main sequence, and its dM3.5 binary companion G1 752A. These coeval stars provide a test bed for studying whether the outer atmospheres of stars respond to changes in internal structure as stars become fully convective near mass 0.3 solar mass (about spectral type M5), where the nature of the stellar magnetic dynamo presumably changes, and near the transition from red to brown dwarfs near mass 0.08 solar mass (about spectral type M9), when hydrogen burning ceases at the end of the main sequence. We obtain upper limits for the quiescent emission of VB 10 but observe a transition region spectrum during a large flare, which indicates that some type of magnetic dynamo must be present. Two indirect lines of evidence-scaling from the observed X-ray emission and scaling from a time-resolved flare on AD Leo suggest that the fraction of the stellar bolometric luminosity that heats the transition region of VB 10 outside of obvious flares is comparable to, or larger than, that for G1 752A. This suggests an increase in the magnetic heating rates, as measured by L(sub line)/L(sub bol) ratios, across the radiative/convective core boundary and as stars approach the red/brown dwarf boundary. These results provide new constraints for dynamo models and models of coronal and transition-region heating in late-type stars.

  1. ON THE DETECTABILITY OF A PREDICTED MESOLENSING EVENT ASSOCIATED WITH THE HIGH PROPER MOTION STAR VB 10

    SciTech Connect

    Lepine, Sebastien; DiStefano, Rosanne E-mail: rd@cfa.harvard.edu

    2012-04-10

    Extrapolation of the astrometric motion of the nearby low-mass star VB 10 indicates that sometime in late 2011 December or during the first 2-3 months of 2012, the star will make a close approach to a background point source. Based on astrometric uncertainties, we estimate a 1 in 2 chance that the distance of closest approach {rho}{sub min} will be less than 100 mas, a 1 in 5 chance that {rho}{sub min} < 50 mas, and a 1 in 10 chance that {rho}{sub min} < 20 mas. The last would result in a microlensing event with a 6% magnification in the light from the background source and an astrometric shift of 3.3 mas. The lensing signal will however be significantly diluted by the light from VB 10, which is 1.5 mag brighter than the background source in B band, 5 mag brighter in I band, and 10 mag brighter in K band, making the event undetectable in all but the bluer optical bands. However, we show that if VB 10 happens to harbor a {approx}1 M{sub J} planet on a moderately wide ( Almost-Equal-To 0.18 AU-0.84 AU) orbit, there is a chance (1% to more than 10%, depending on the distance of closest approach and orbital period and inclination) that a passage of the planet closer to the background source will result in a secondary event of higher magnification. The detection of secondary events could be made possible with a several-times-per-night multi-site monitoring campaign.

  2. Study of Iron Dimers Reveals Angular Dependence of Valence-to-Core X-ray Emission Spectra

    PubMed Central

    2015-01-01

    Transition-metal K? X-ray emission spectroscopy (XES) is a developing technique that probes the occupied molecular orbitals of a metal complex. As an element-specific probe of metal centers, K? XES is finding increasing applications in catalytic and, in particular, bioinorganic systems. For the continued development of XES as a probe of these complex systems, however, the full range of factors which contribute to XES spectral modulations must be explored. In this report, an investigation of a series of oxo-bridged iron dimers reveals that the intensity of valence-to-core features is sensitive to the Fe–O–Fe bond angle. The intensity of these features has a well-known dependence on metal–ligand bond distance, but a dependence upon bond angle has not previously been documented. Herein, we explore the angular dependence of valence-to-core XES features both experimentally and computationally. Taken together, these results show that, as the Fe–O–Fe angle decreases, the intensity of the K?? feature increases and that this effect is modulated by increasing amounts of Fe np mixing into the O 2s orbital at smaller bond angles. The relevance of these findings to the identification of oxygenated intermediates in bioinorganic systems is highlighted, with special emphasis given to the case of soluble methane monooxygenase. PMID:25211540

  3. Basics of Fidelity Bonding.

    ERIC Educational Resources Information Center

    Kahn, Steven P.

    Fidelity bonds are important for an agency to hold to protect itself against any financial loss that can result from dishonest acts by its employees. Three types of fidelity bonds are available to an agency: (1) public official bonds; (2) dishonesty bonds; and (3) faithful performance bonds. Public official bonds are required by state law to be…

  4. Partial Ionic Bonding in Homogeneous Sodium Clusters

    E-print Network

    Kaware, Vaibhav

    2015-01-01

    In this work, we report an interesting observation of partial ionic bonding due to charge transfer in homogeneous sodium clusters. The charge transfer causes the electronic charge to accumulate on the surface, and the resulting charges on atoms range between +0.4 to -1.0 |e^-|. We also demonstrate that this disparity among effective charges on atoms is geometry dependent, such that atoms experiencing similar surrounding, have equal effective charge. It is speculated that this phenomenon will occur among other homogeneous clusters as well, and its extent will be defined by the valence electron delocalization.

  5. The Valence of Titanium in Refractory Forsterite

    SciTech Connect

    Simon, S.B.; Sutton, S.; Newville, M.; Grossman, L.

    2007-03-06

    Models of melts in equilibrium with refractory forsterite (RF) suggest that RF contains trivalent Ti (Pack et al., 2005), with major implications for the origin of RF. We tested this prediction, measuring Ti valence by XANES in RF from Tagish Lake. One of the more intriguing components of unequilibrated chondrites is the population of relatively Ca-, Al-rich, Fe-poor isolated olivine grains known as 'refractory forsterite'. Some workers have concluded that these grains formed in and were released from chondrules. Other workers, noting that these grains occur in all major types of unequilibrated chondrites yet have many features in common, favor a single, pre-chondrule source from which the grains were distributed into their present hosts. Thought by some to be condensates, refractory forsterite (RF) grains have been found in chondrules, but their high CaO contents and trends of decreasing CaO contents from core to rim are inconsistent with closed-system fractional crystallization, so those grains must be relict. Previous workers calculated the compositions of melts parental to RF from the minor and trace element contents of RF grains and known olivine/liquid partition coefficients. Results indicated that melts in equilibrium with RF would have been uniformly enriched in refractory lithophile elements by {approx}20 x CI, as is observed in many refractory inclusions. Two exceptions are V, for which enrichments <20 x CI were derived, and Ti, for which enrichments of 50-65 x CI were obtained. For V, the depletion was attributed to its enhanced volatility under reducing conditions. The inferred Ti content is higher than observed in refractory inclusions. This rather unreasonable result was obtained using the olivine/liquid partition coefficient for Ti{sup 4+} (D{sub Ti{sup 4+}}). A higher D for Ti would allow lower Ti contents in parental melts, and noted that the larger ionic radius of Ti{sup 3+} relative to that of Ti{sup 4+} could yield a D{sub Ti{sup 3+}} that is a factor of {approx}50 greater than D{sub Ti{sup 4+}}. The presence of significant proportions of Ti{sup 3+} in RF would provide important evidence of reducing conditions where the grains formed, support the model of [8] and rule out formation in typical, FeO-bearing chondrules. To test the prediction of [8], we have used X-ray absorption near-edge structure (XANES) analysis to determine the valence of Ti in two RF grains from the Tagish Lake carbonaceous chondrite.

  6. Inelastic neutron scattering in valence fluctuation compounds

    SciTech Connect

    Jon M Lawrence

    2011-02-15

    The valence fluctuation compounds are rare earth intermetallics where hybridization of the nearly-localized 4f electrons with the conduction electrons leads to incorporation of the 4f's into the itinerant states. This hybridization slows down the conduction electrons and hence gives them a heavy effective mass, justifying application of the term 'heavy Fermion' (HF) to these materials. During the project period, we grew large single crystals of several such compounds and measured their properties using both standard thermodynamic probes and state-of-the-art inelastic neutron scattering. We obtained three main results. For the intermediate valence compounds CePd{sub 3} and YbAl{sub 3}, we showed that the scattering of neutrons by the fluctuations of the 4f magnetic moment does not have the momentum dependence expected for the itinerant heavy mass state; rather, the scattering is more typical of a localized spin fluctuation. We believe that incoherent scattering localizes the excitation. For the heavy Fermion compound Ce(Ni{sub 0.935}Pd{sub 0.065}){sub 2}Ge{sub 2}, which sits at a T = 0 critical point for transformation into an antiferromagnetic (AF) phase, we showed that the scattering from the AF fluctuations does not exhibit any of the divergences that are expected at a phase transition. We speculate that alloy disorder profoundly suppresses the growth of the fluctuating AF regions, leading to short range clusters rather than regions of infinite size. Finally, we explored the applicability of key concepts used to describe the behavior of rare earth heavy Fermions to uranium based HF compounds where the 5f electrons are itinerant as opposed to localized. We found that scaling laws relating the spin fluctuation energy measured in neutron scattering to the low temperature specific heat and susceptibility are valid for the uranium compounds, once corrections are made for AF fluctuations; however, the degeneracy of the high temperature moment is smaller than expected for rare-earth-like Hund's rule behavior, essentially because the orbital moment is suppressed for itinerant 5f electrons. We also found that the standard local-moment-based theory of the temperature dependence of the specific heat, susceptibility and neutron scattering fails badly for URu{sub 2}Zn{sub 20} and UCo{sub 2}Zn{sub 20}, even though the theory is phenomenally successful for the closely related rare earth compound YbFe{sub 2}Zn{sub 20}. Both these results highlight the distinction between the itineracy of the 5f's and the localization of the 4f's. It is our hope that these results are sufficiently significant as to stimulate deeper investigation of these compounds.

  7. A density explanation of valence asymmetries in recognition memory.

    PubMed

    Alves, Hans; Unkelbach, Christian; Burghardt, Juliane; Koch, Alex S; Krüger, Tobias; Becker, Vaughn D

    2015-08-01

    The density hypothesis states that positive information is more similar than negative information, resulting in higher density of positive information in mental representations. The present research applies the density hypothesis to recognition memory to explain apparent valence asymmetries in recognition memory, namely, a recognition advantage for negative information. Previous research explained this negativity advantage on the basis of valence-induced affect. We predicted that positive information's higher density impairs recognition performance. Two old-new word recognition experiments tested whether differential density between positive and negative stimuli creates a negativity advantage in recognition memory, over and above valence-induced affect. In Experiment 1, participants better discriminated negative word stimuli (i.e., less false alarms) and showed a response bias towards positive words. Regression analyses showed the asymmetry to be function of density and not of valence. Experiment 2 varied stimulus density orthogonal to valence. Again, discriminability and response bias were a function of density and not of valence. We conclude that the higher density of positive information causes an apparent valence asymmetry in recognition memory. PMID:25772462

  8. Emotion and language: valence and arousal affect word recognition.

    PubMed

    Kuperman, Victor; Estes, Zachary; Brysbaert, Marc; Warriner, Amy Beth

    2014-06-01

    Emotion influences most aspects of cognition and behavior, but emotional factors are conspicuously absent from current models of word recognition. The influence of emotion on word recognition has mostly been reported in prior studies on the automatic vigilance for negative stimuli, but the precise nature of this relationship is unclear. Various models of automatic vigilance have claimed that the effect of valence on response times is categorical, an inverted U, or interactive with arousal. In the present study, we used a sample of 12,658 words and included many lexical and semantic control factors to determine the precise nature of the effects of arousal and valence on word recognition. Converging empirical patterns observed in word-level and trial-level data from lexical decision and naming indicate that valence and arousal exert independent monotonic effects: Negative words are recognized more slowly than positive words, and arousing words are recognized more slowly than calming words. Valence explained about 2% of the variance in word recognition latencies, whereas the effect of arousal was smaller. Valence and arousal do not interact, but both interact with word frequency, such that valence and arousal exert larger effects among low-frequency words than among high-frequency words. These results necessitate a new model of affective word processing whereby the degree of negativity monotonically and independently predicts the speed of responding. This research also demonstrates that incorporating emotional factors, especially valence, improves the performance of models of word recognition. PMID:24490848

  9. Emotion and language: Valence and arousal affect word recognition

    PubMed Central

    Brysbaert, Marc; Warriner, Amy Beth

    2014-01-01

    Emotion influences most aspects of cognition and behavior, but emotional factors are conspicuously absent from current models of word recognition. The influence of emotion on word recognition has mostly been reported in prior studies on the automatic vigilance for negative stimuli, but the precise nature of this relationship is unclear. Various models of automatic vigilance have claimed that the effect of valence on response times is categorical, an inverted-U, or interactive with arousal. The present study used a sample of 12,658 words, and included many lexical and semantic control factors, to determine the precise nature of the effects of arousal and valence on word recognition. Converging empirical patterns observed in word-level and trial-level data from lexical decision and naming indicate that valence and arousal exert independent monotonic effects: Negative words are recognized more slowly than positive words, and arousing words are recognized more slowly than calming words. Valence explained about 2% of the variance in word recognition latencies, whereas the effect of arousal was smaller. Valence and arousal do not interact, but both interact with word frequency, such that valence and arousal exert larger effects among low-frequency words than among high-frequency words. These results necessitate a new model of affective word processing whereby the degree of negativity monotonically and independently predicts the speed of responding. This research also demonstrates that incorporating emotional factors, especially valence, improves the performance of models of word recognition. PMID:24490848

  10. Positron annihilation with core and valence electrons

    E-print Network

    Green, D G

    2015-01-01

    $\\gamma$-ray spectra for positron annihilation with the core and valence electrons of the noble gas atoms Ar, Kr and Xe is calculated within the framework of diagrammatic many-body theory. The effect of positron-atom and short-range positron-electron correlations on the annihilation process is examined in detail. Short-range correlations, which are described through non-local corrections to the vertex of the annihilation amplitude, are found to significantly enhance the spectra for annihilation on the core orbitals. For Ar, Kr and Xe, the core contributions to the annihilation rate are found to be 0.55\\%, 1.5\\% and 2.2\\% respectively, their small values reflecting the difficulty for the positron to probe distances close to the nucleus. Importantly however, the core subshells have a broad momentum distribution and markedly contribute to the annihilation spectra at Doppler energy shifts $\\gtrsim3$\\,keV, and even dominate the spectra of Kr and Xe at shifts $\\gtrsim5$\\,keV. Their inclusion brings the theoretical ...

  11. Equalized Electronegativity Based on the Valence Electrons and Its Application

    NASA Astrophysics Data System (ADS)

    Wu, Ya-xin; Cao, Chen-zhong; Yuan, Hua

    2011-02-01

    We take the contribution of all valence electrons into consideration and propose a new valence electrons equilibration method to calculate the equalized electronegativity including molecular electronegativity, group electronegativity, and atomic charge. The ionization potential of alkanes and mono-substituted alkanes, the chemical shift of 1H NMR, and the gas phase proton affinity of aliphatic amines, alcohols, and ethers were estimated. All the expressions have good correlations. Moreover, the Sanderson method and Bratsch method were modified on the basis of the valence electrons equilibration theory. The modified Sanderson method and modified Bratsch method are more effective than their original methods to estimate these properties.

  12. Valence band anticrossing in GaBixAs1-x

    SciTech Connect

    Alberi, K.; Dubon, O. D.; Walukiewicz, W.; Yu, K. M.; Bertulis, K.; Krotkus, A.

    2007-07-11

    The optical properties of GaBixAs1-x (0.04< x< 0.08) grown by molecular beam epitaxy have been studied by photomodulated reflectance spectroscopy. The alloys exhibit a strong reduction in the bandgap as well as an increase in the spin-orbit splitting energy with increasing Bi concentration. These observations are explained by a valence band anticrossing model, which shows that a restructuring of the valence band occurs as the result of an anticrossing interaction between the extended states of the GaAs valence band and the resonant T2 states of the Bi atoms.

  13. On Lexicalized Valency and the Valency of (New) Complex Verbal Formations in Slovenian

    E-print Network

    Žele, Andreja

    2013-01-01

    - ate], deti [to put], vzeti [to take], igrati (se) [to play]; spreminjati (se) [to change]; iti [to go], hoditi [to walk]. These verbs retain the type of state/action/process (s/d/p) due to their wide semantic field, and are therefore also considered... to be the main representatives of separate verbal valency groups. A special subgroup of basic verbs consists of elementary verbs of basic life processes/actions, and natural phenomena. Basic and elementary verbs function as lexical semantic features, whereas...

  14. A Valence Isomer Trapping Procedure for Introductory Organic Laboratory.

    ERIC Educational Resources Information Center

    Kurtz, David W.; Johnson, Richard P.

    1989-01-01

    Described is an experiment which illustrates valence isomerization, the trapping of a reactive intermediate and retrosynthetic analysis applied to the Diels-Alder reaction. Included is a background discussion, experimental procedures, and a discussion of the analysis. (CW)

  15. Towards the Automatic Acquisition of a Valence Dictionary for Polish

    E-print Network

    Institute of Computer Science, Polish Academy of Sciences, ul. Ordona 21, 01-237 Warszawa, Poland, adamp-097 Warszawa, Poland Abstract. This article presents the evaluation of a valence dictionary for Polish produced

  16. Inelastic collisions of positrons with one-valence-electron targets

    NASA Technical Reports Server (NTRS)

    Abdel-Raouf, Mohamed Assad

    1990-01-01

    The total elastic and positronium formation cross sections of the inelastic collisions between positrons and various one-valence-electron atoms, (namely hydrogen, lithium, sodium, potassium and rubidium), and one-valence-electron ions, (namely hydrogen-like, lithium-like and alkaline-earth positive ions) are determined using an elaborate modified coupled-static approximation. Special attention is devoted to the behavior of the Ps cross sections at the energy regions lying above the Ps formation thresholds.

  17. XPS valence bands of Ti, Zr, Nb, Mo and Hf

    NASA Astrophysics Data System (ADS)

    Höchst, H.; Steiner, P.; Reiter, G.; Hüfner, S.

    1981-09-01

    The XPS valence band spectra of polycrystalline Ti, Zr, Nb, Mo and Hf have been measured with a resolution of 0.6 eV. The spectra were compared with theoretical densities of states. Good agreement is achieved if the partial densities of states are considered and a many body line shape function and life time broadening are taken into account. The sigularity index ? determined at various core lines as well as the experimentally determined relative valence band cross sections are reported.

  18. On the bond distance in methane

    NASA Technical Reports Server (NTRS)

    Bowen-Jenkins, Philippa; Pettersson, Lars G. M.; Siegbahn, Per; Almloef, Jan; Taylor, Peter R.

    1987-01-01

    The equilibrium bond distance in methane was optimized using coupled-pair functional and contracted CI wave functions, and a Gaussian basis that includes g-type functions on carbon and d-type functions on hydrogen. The resulting bond distance, when corrected for core-valence correlation effects, agrees with the experimental value of 2.052 a(0) to within the experimental uncertainty of 0.002 a(0). The main source of error in the best previous studies, which showed discrepancies with experiment of 0.007 a(0) is shown to be basis set incompleteness. In particular, it is important that the basis set be close to saturation, at least for the lower angular quantum numbers.

  19. Reservoir impact assessment in sub-Saharan Africa: The Volta Basin Water Allocation System (VB-WAS)

    NASA Astrophysics Data System (ADS)

    Leemhuis, C.; Jung, G.; Kasei, R.; Liebe, J.

    2009-04-01

    In the Volta River Basin, infrastructure watershed development with respect to the impact of climate conditions is hotly debated due to the lack of adequate tools to model the consequences of such development. The Volta basin drains an area of approx. 400 000 km² of the subhumid to semiarid West-African savannah zone and is shared by six riparian countries. The region is characterized by erratic rainfall patterns, and domestic and agricultural water users in the upper regions of the Basin complete with hydropower generation in the south for increasingly scarce water resources. There is an ongoing debate on the impact of further development of small, medium and large reservoirs on the water level of Lake Volta. The GLOWA Volta Project (GVP) has developed a Volta Basin Water Allocation System (VB-WAS), a decision support tool that allows assessing the impact of infrastructure development in the basin on the availability of current and future water resources, given the current or future climate conditions. The simulated historic and future discharge time series of the coupled climate-hydrological model (MM5/WaSiM) serve as input data for a river basin management model (MIKE BASIN). MIKE BASIN uses a network approach, and allows fast simulations of water allocation and of the consequences of different development scenarios on the available water resources. Furthermore it is possible to up set up climate scenario time series scenarios for an assessment of the consequences of extreme climate conditions. Within a case study analysis the impact of small and medium scale reservoir development on the water resources of the Volta basin has been evaluated under different climatic conditions. For the evaluation of the impact of large reservoir development in particular the impact of Bui dam, which is under construction on the Black Volta River in Ghana, on the water level of Lake Volta has been simulated with the VB-WAS model. The VB-WAS model allows a quantified impact assessment of small, medium and large scale reservoir development within the Volta basin and can be used as an objective communication basis for water management issues.

  20. Chemical Bonds II

    ERIC Educational Resources Information Center

    Sanderson, R. T.

    1972-01-01

    The continuation of a paper discussing chemical bonding from a bond energy viewpoint, with a number of examples of single and multiple bonds. (Part I appeared in volume 1 number 3, pages 16-23, February 1972.) (AL)

  1. Character Disposition and Behavior Type: Influences of Valence on Preschool Children's Social Judgments

    ERIC Educational Resources Information Center

    Jones, Elaine F.; Tobias, Marvin; Pauley, Danielle; Thomson, Nicole Renick; Johnson, Shawana Lewis

    2009-01-01

    The authors studied the influences of valence information on preschool children's (n = 47) moral (good or bad), liking (liked or disliked by a friend), and consequence-of-behavior (reward or punishment) judgments. The authors presented 8 scenarios describing the behavior valence, positive valence (help, share), negative valence (verbal insult,…

  2. Sequential and Prosodic Design of English and Greek Non-Valenced News Receipts

    ERIC Educational Resources Information Center

    Kaimaki, Marianna

    2012-01-01

    Results arising from a prosodic and interactional study of the organization of everyday talk in English suggest that news receipts can be grouped into two categories: valenced (e.g., "oh good") and non-valenced (e.g., "oh really"). In-depth investigation of both valenced and non-valenced news receipts shows that differences in their prosodic…

  3. 29 CFR 2580.412-20 - Use of existing bonds, separate bonds and additional bonding.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...bonds, separate bonds and additional bonding. 2580.412-20 Section 2580...DEPARTMENT OF LABOR TEMPORARY BONDING RULES UNDER THE EMPLOYEE RETIREMENT INCOME SECURITY ACT OF 1974 TEMPORARY BONDING RULES General Bond Rules §...

  4. 29 CFR 2580.412-20 - Use of existing bonds, separate bonds and additional bonding.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...bonds, separate bonds and additional bonding. 2580.412-20 Section 2580...DEPARTMENT OF LABOR TEMPORARY BONDING RULES UNDER THE EMPLOYEE RETIREMENT INCOME SECURITY ACT OF 1974 TEMPORARY BONDING RULES General Bond Rules §...

  5. Final report from VFL Technologies for the pilot-scale thermal treatment of Lower East Fork Poplar Creek floodplain soils. LEFPC Appendices, Volume 3, Appendix V-B

    SciTech Connect

    1994-09-01

    This report consists of appendix V-B which contains the final verification run data package. Validation of analytical data is presented for Ecotek LSI. Analytical results are included of both soil and creek bed samples for the following contaminants: metals; metals (TCLP); uranium; gross alpha/beta; and polychlorinated biphenyls.

  6. An Alaska fur seal family on St. Paul Island, Pribilof Group, Alaska . (Photo: V.B . Scheffe SEC. STANS REPORTS FAVORABLY ON

    E-print Network

    IV An Alaska fur seal family on St. Paul Island, Pribilof Group, Alaska . (Photo: V.B . Scheffe #12;SEC. STANS REPORTS FAVORABLY ON SEAL HARVESTING IN PRIBILOF ISLANDS Secretary of Commerce Maurice H. Stans 1 eported, July 14, 1971, his conclusions on ethods used to harvest seals after a visit to he

  7. Muon Collider / Neutrino Factory Targetry R&D 2009-2012 V.B. Graves, H.G. Kirk, K.T. McDonald

    E-print Network

    McDonald, Kirk

    System and Support Facility, Neutrino Factory Study 1 (April 1, 2000), http://www.fnal.gov/projects/muon_collider/nu/study/report/machine1 Muon Collider / Neutrino Factory Targetry R&D 2009-2012 V.B. Graves, H.G. Kirk, K.T. Mc for muons colliders and neutrino factories has been centered around the MERIT experiment which took data

  8. VB-201, an oxidized phospholipid small molecule, inhibits CD14- and Toll-like receptor-2-dependent innate cell activation and constrains atherosclerosis

    PubMed Central

    Mendel, I; Feige, E; Yacov, N; Salem, Y; Levi, I; Propheta-Meiran, O; Shoham, A; Ishai, E; George, J; Harats, D; Breitbart, E

    2014-01-01

    Atherosclerosis is an inflammatory disease of the vascular wall. Activated monocytes and dendritic cells (DC) in the intima layer of the vasculature promote atherogenesis. Toll-like receptor (TLR)-2 and TLR-4, which are predominantly expressed on these cells and mediate their activation, are essential for atherosclerosis development. In this study we demonstrate that VB-201, an oxidized phospholipid (Ox-PL) small molecule, inhibits TLR signalling restricted to TLR-2 and TLR-4 in human and mouse monocytes and DC. Mechanistically, we show that VB-201 binds directly to TLR-2 and CD14, the TLR-4 co-receptor, to impair downstream cues and cytokine production. In a rabbit model, oral administration of VB-201 constrained atherosclerosis progression. This effect was not due to reduced cholesterol abundance, as hyperlipidaemia was sustained. We suggest that VB-201 may counter inflammation where TLR-2 and/or CD14 complicity is essential, and is therefore beneficial for the treatment of atherosclerosis. PMID:24116867

  9. 2D multipartite valence bond states in quantum anti-ferromagnets

    SciTech Connect

    Rico, E. Briegel, H.J.

    2008-09-15

    A quantum anti-ferromagnetic spin-1 model is characterised on a 2D lattice with the following requirements: (i) The Hamiltonian is made out of nearest neighbour interactions. (ii) It is homogeneous, translational and rotational invariant. (iii) The ground state is a real singlet state of SU(2) (non-chiral). (iv) It has a local spin-1 representation. Along the way to characterise the system, connections with classical statistical mechanics and integrable models are explored. Finally, the relevance of the model in the physics of low dimensional anti-ferromagnetic Mott-Hubbard insulators is discussed.

  10. Crystal structure, physical properties and bond valence analysis of NaLuP2O7

    NASA Astrophysics Data System (ADS)

    Béjaoui, Anis; Horchani-Naifer, Karima; Hajji, Mounir; Férid, Mokhtar

    2014-05-01

    Single crystals of a diphosphate NaLuP2O7 have been synthesized by the flux method and characterized by single-crystal X-Ray diffraction. NaLuP2O7 crystallizes in the monoclinic system with P21/n space group with cell parameters: a = 8.9985(8) Å, b = 5.3473(5) Å, c = 12.756(1) Å, ? = 103.174° (1), V = 597.67 (9) Å3, Z = 4. Its structure consists of a three-dimensional framework of P2O7 units that are corner-shared by LuO6 octahedra, forming tunnels running parallel to [010] which are occupied by Na atoms. NaLuP2O7 powder was characterized by XRD, SEM, FTIR and Raman spectroscopy. The activation energy of (1.49 eV) obtained by electrical measurements suggests the charge carriers to be the sodium cations. The activation energies obtained from impedance and loss spectra were analyzed in order to explain the mechanism of conduction. The correlation between ionic conductivity of NaLuP2O7 and its crystallographic structure was investigated and the most probable transport pathway model was determined.

  11. Unusual structure, bonding and properties in a californium borate

    NASA Astrophysics Data System (ADS)

    Polinski, Matthew J.; Garner, Edward B.; Maurice, Rémi; Planas, Nora; Stritzinger, Jared T.; Parker, T. Gannon; Cross, Justin N.; Green, Thomas D.; Alekseev, Evgeny V.; van Cleve, Shelley M.; Depmeier, Wulf; Gagliardi, Laura; Shatruk, Michael; Knappenberger, Kenneth L.; Liu, Guokui; Skanthakumar, S.; Soderholm, Lynda; Dixon, David A.; Albrecht-Schmitt, Thomas E.

    2014-05-01

    The participation of the valence orbitals of actinides in bonding has been debated for decades. Recent experimental and computational investigations demonstrated the involvement of 6p, 6d and/or 5f orbitals in bonding. However, structural and spectroscopic data, as well as theory, indicate a decrease in covalency across the actinide series, and the evidence points to highly ionic, lanthanide-like bonding for late actinides. Here we show that chemical differentiation between californium and lanthanides can be achieved by using ligands that are both highly polarizable and substantially rearrange on complexation. A ligand that suits both of these desired properties is polyborate. We demonstrate that the 5f, 6d and 7p orbitals are all involved in bonding in a Cf(III) borate, and that large crystal-field effects are present. Synthetic, structural and spectroscopic data are complemented by quantum mechanical calculations to support these observations.

  12. Unusual structure, bonding and properties in a californium borate.

    PubMed

    Polinski, Matthew J; Garner, Edward B; Maurice, Rémi; Planas, Nora; Stritzinger, Jared T; Parker, T Gannon; Cross, Justin N; Green, Thomas D; Alekseev, Evgeny V; Van Cleve, Shelley M; Depmeier, Wulf; Gagliardi, Laura; Shatruk, Michael; Knappenberger, Kenneth L; Liu, Guokui; Skanthakumar, S; Soderholm, Lynda; Dixon, David A; Albrecht-Schmitt, Thomas E

    2014-05-01

    The participation of the valence orbitals of actinides in bonding has been debated for decades. Recent experimental and computational investigations demonstrated the involvement of 6p, 6d and/or 5f orbitals in bonding. However, structural and spectroscopic data, as well as theory, indicate a decrease in covalency across the actinide series, and the evidence points to highly ionic, lanthanide-like bonding for late actinides. Here we show that chemical differentiation between californium and lanthanides can be achieved by using ligands that are both highly polarizable and substantially rearrange on complexation. A ligand that suits both of these desired properties is polyborate. We demonstrate that the 5f, 6d and 7p orbitals are all involved in bonding in a Cf(III) borate, and that large crystal-field effects are present. Synthetic, structural and spectroscopic data are complemented by quantum mechanical calculations to support these observations. PMID:24755589

  13. Fractional bond orders in E 2H 4 molecules (E?Si, Ge, and Sn)

    NASA Astrophysics Data System (ADS)

    Lendvay, G.

    1991-06-01

    The Si, Ge and Sn analogues of ethene have a special bond between the E atoms. As we found in ab initio calculations, the polarized banana bond (called papaw bond) in the trans—bent equilibrium geometry of these compounds have a bond order smaller than two but larger than one: BSiSi?1.76, BGeGe?1.61 and BSnSn?1.46. The d orbitals of the E atoms do not participate in the E?E bond. The bond order is smaller than that characteristics for a ? + ? double bonds as the p z orbital of one E atom interacts with the s orbital of the other one and only to a lesser extent with its p z orbitals. The trans—bent equilibrium structure corresponds to a valence state between sp 3 and sp 2 and to valences VSi?3.78, VGe?3.59 and VSn ?3.40. The ab initio bond orders are in reasonable agreement with the bond numbers calculated from the formula of Pauling supporting the applicability of the latter relation.

  14. Space-valence priming with subliminal and supraliminal words.

    PubMed

    Ansorge, Ulrich; Khalid, Shah; König, Peter

    2013-01-01

    To date it is unclear whether (1) awareness-independent non-evaluative semantic processes influence affective semantics and whether (2) awareness-independent affective semantics influence non-evaluative semantic processing. In the current study, we investigated these questions with the help of subliminal (masked) primes and visible targets in a space-valence across-category congruence effect. In line with (1), we found that subliminal space prime words influenced valence classification of supraliminal target words (Experiment 1): classifications were faster with a congruent prime (e.g., the prime "up" before the target "happy") than with an incongruent prime (e.g., the prime "up" before the target "sad"). In contrast to (2), no influence of subliminal valence primes on the classification of supraliminal space targets into up- and down-words was found (Experiment 2). Control conditions showed that standard masked response priming effects were found with both subliminal prime types, and that an across-category congruence effect was also found with supraliminal valence primes and spatial target words. The final Experiment 3 confirmed that the across-category congruence effect indeed reflected priming of target categorization of a relevant meaning category. Together, the data jointly confirmed prediction (1) that awareness-independent non-evaluative semantic priming influences valence judgments. PMID:23439863

  15. Highly Active Supported Pt Nanocatalysts Synthesized by Alcohol Reduction towards Hydrogenation of Cinnamaldehyde: Synergy of Metal Valence and Hydroxyl Groups.

    PubMed

    Wang, Yanyan; He, Wanhong; Wang, Liren; Yang, Junjiao; Xiang, Xu; Zhang, Bing; Li, Feng

    2015-07-01

    The hydrogenation of ?,?-unsaturated aldehydes to allylic alcohols or saturated aldehydes provides a typical example to study the catalytic effect on structure-sensitive reactions. In this work, supported platinum nanocatalysts over hydrotalcite were synthesized by an alcohol reduction method. The Pt catalyst prepared by the reduction with a polyol (ethylene glycol) outperforms those prepared with ethanol and methanol in the hydrogenation of cinnamaldehyde. The selectivity towards the C=O bond is the highest over the former, although its mean size of Pt particles is the smallest. The hydroxyl groups on hydrotalcite could act as an internally accessible promoter to enhance the selectivity towards the C=O bond. The optimal Pt catalyst showed a high activity with an initial turnover frequency (TOF) of 2.314?s(-1). This work unveils the synergic effect of metal valence and in situ promoter on the chemoselective hydrogenation, which could open up a new direction in designing hydrogenation catalysts. PMID:25882904

  16. Hydroxide-catalyzed bonding

    NASA Technical Reports Server (NTRS)

    Gwo, Dz-Hung (Inventor)

    2003-01-01

    A method of bonding substrates by hydroxide-catalyzed hydration/dehydration involves applying a bonding material to at least one surface to be bonded, and placing the at least one surface sufficiently close to another surface such that a bonding interface is formed between them. A bonding material of the invention comprises a source of hydroxide ions, and may optionally include a silicate component, a particulate filling material, and a property-modifying component. Bonding methods of the invention reliably and reproducibly provide bonds which are strong and precise, and which may be tailored according to a wide range of possible applications. Possible applications for bonding materials of the invention include: forming composite materials, coating substrates, forming laminate structures, assembly of precision optical components, and preparing objects of defined geometry and composition. Bonding materials and methods of preparing the same are also disclosed.

  17. Paradigms and Plastic Facts in the History of Valence.

    ERIC Educational Resources Information Center

    Zavaleta, David

    1988-01-01

    Traces the development of bonding theory and notes the influence of preconceived theory upon this development. Considers ideas of alchemy, Newton, Dalton, Lewis, and quantum mechanics. Suggests a move away from conservative descriptive approaches of bonding theory. (ML)

  18. Ultrafast Charge Transfer of a Valence Double Hole in Glycine Driven Exclusively by Nuclear Motion

    NASA Astrophysics Data System (ADS)

    Li, Zheng; Vendrell, Oriol; Santra, Robin

    2015-10-01

    We explore theoretically the ultrafast transfer of a double electron hole between the functional groups of glycine after K -shell ionization and subsequent Auger decay. Although a large energy gap of about 15 eV initially exists between the two electronic states involved and coherent electronic dynamics play no role in the hole transfer, we find that the double hole is transferred within 3 to 4 fs between both functional ends of the glycine molecule driven solely by specific nuclear displacements and non-Born-Oppenheimer effects. The nuclear displacements along specific vibrational modes are of the order of 15% of a typical chemical bond between carbon, oxygen, and nitrogen atoms and about 30% for bonds involving hydrogen atoms. The time required for the hole transfer corresponds to less than half a vibrational period of the involved nuclear modes. This finding challenges the common wisdom that nuclear dynamics of the molecular skeleton are unimportant for charge transfer processes at the few-femtosecond time scale and shows that they can even play a prominent role. It also indicates that in x-ray imaging experiments, in which ionization is unavoidable, valence electron redistribution caused by nuclear dynamics might be much faster than previously anticipated. Thus, non-Born-Oppenheimer effects may affect the apparent electron densities extracted from such measurements.

  19. Ultrafast Charge Transfer of a Valence Double Hole in Glycine Driven Exclusively by Nuclear Motion.

    PubMed

    Li, Zheng; Vendrell, Oriol; Santra, Robin

    2015-10-01

    We explore theoretically the ultrafast transfer of a double electron hole between the functional groups of glycine after K-shell ionization and subsequent Auger decay. Although a large energy gap of about 15 eV initially exists between the two electronic states involved and coherent electronic dynamics play no role in the hole transfer, we find that the double hole is transferred within 3 to 4 fs between both functional ends of the glycine molecule driven solely by specific nuclear displacements and non-Born-Oppenheimer effects. The nuclear displacements along specific vibrational modes are of the order of 15% of a typical chemical bond between carbon, oxygen, and nitrogen atoms and about 30% for bonds involving hydrogen atoms. The time required for the hole transfer corresponds to less than half a vibrational period of the involved nuclear modes. This finding challenges the common wisdom that nuclear dynamics of the molecular skeleton are unimportant for charge transfer processes at the few-femtosecond time scale and shows that they can even play a prominent role. It also indicates that in x-ray imaging experiments, in which ionization is unavoidable, valence electron redistribution caused by nuclear dynamics might be much faster than previously anticipated. Thus, non-Born-Oppenheimer effects may affect the apparent electron densities extracted from such measurements. PMID:26551809

  20. Charge-displacement analysis via natural orbitals for chemical valence: Charge transfer effects in coordination chemistry

    NASA Astrophysics Data System (ADS)

    Bistoni, Giovanni; Rampino, Sergio; Tarantelli, Francesco; Belpassi, Leonardo

    2015-02-01

    We recently devised a simple scheme for analyzing on quantitative grounds the Dewar-Chatt-Duncanson donation and back-donation in symmetric coordination complexes. Our approach is based on a symmetry decomposition of the so called Charge-Displacement (CD) function quantifying the charge flow, upon formation of a metal (M)-substrate (S) bond, along the M-S interaction axis and provides clear-cut measures of donation and back-donation charges in correlation with experimental observables [G. Bistoni et al., Angew. Chem., Int. Ed. 52, 11599 (2013)]. The symmetry constraints exclude of course from the analysis most systems of interest in coordination chemistry. In this paper, we show how to entirely overcome this limitation by taking advantage of the properties of the natural orbitals for chemical valence [M. Mitoraj and A. Michalak, J. Mol. Model. 13, 347 (2007)]. A general scheme for disentangling donation and back-donation in the CD function of both symmetric and non-symmetric systems is presented and illustrated through applications to M-ethyne (M = Au, Ni and W) coordination bonds, including an explicative study on substrate activation in a model reaction mechanism.

  1. Radiation thermal processes in Cr13Mo2NbVB steel - the material of the fuel assembly shell in reactor BN-350 under mechanical tests

    NASA Astrophysics Data System (ADS)

    Larionov, A. S.; Dikov, A. S.; Poltavtseva, V. P.; Kislitsin, S. B.; Kuimova, M. V.; Chernyavskii, A. V.

    2015-04-01

    Regularities of changes of structural-phase state and mechanical properties of steel 13Mo2NbVB - the material of the fuel assembly shell in reactor BN-350 after various mechanical tests at 350°C are experimentally studied. The formation of microprecipitations FeMo, enriched or depleted with molybdenum was found in the short-time mechanical tests, which is the cause of thermal hardening of irradiated Cr13Mo2NbVB steel and its destruction by the ductile-brittle mechanism. On the basis of long-time creep tests it was shown that the material of the spent fuel assembly shell has sufficient resource for long-time storage in the temperature and force conditions simulating long-time storage of spent nuclear fuel.

  2. Behavioral/Systems/Cognitive Action Dominates Valence in Anticipatory Representations

    E-print Network

    Dayan, Peter

    Behavioral/Systems/Cognitive Action Dominates Valence in Anticipatory Representations in the Human. M. Huys,2,3 Peter Dayan,3 Raymond J. Dolan,2 and Emrah Duzel1,4 1Institute of Cognitive Neuroscience, Institute of Neurology, University College London, London WC1N 3BG, United Kingdom, 3Gatsby Computational

  3. Vection Modulates Emotional Valence of Autobiographical Episodic Memories

    ERIC Educational Resources Information Center

    Seno, Takeharu; Kawabe, Takahiro; Ito, Hiroyuki; Sunaga, Shoji

    2013-01-01

    We examined whether illusory self-motion perception ("vection") induced by viewing upward and downward grating motion stimuli can alter the emotional valence of recollected autobiographical episodic memories. We found that participants recollected positive episodes more often while perceiving upward vection. However, when we tested a small moving…

  4. Racah materials: role of atomic multiplets in intermediate valence systems.

    PubMed

    Shick, A B; Havela, L; Lichtenstein, A I; Katsnelson, M I

    2015-01-01

    We address the long-standing mystery of the nonmagnetic insulating state of the intermediate valence compound SmB6. Within a combination of the local density approximation (LDA) and an exact diagonalization (ED) of an effective discrete Anderson impurity model, the intermediate valence ground state with the f-shell occupation ?n4f??=?5.6 is found for the Sm atom in SmB6. This ground state is a singlet, and the first excited triplet state ~3?meV higher in the energy. SmB6 is a narrow band insulator already in LDA, with the direct band gap of ~10?meV. The electron correlations increase the band gap which now becomes indirect. Thus, the many-body effects are relevant to form the indirect band gap, crucial for the idea of "topological Kondo insulator" in SmB6. Also, an actinide analog PuB6 is considered, and the intermediate valence singlet ground state is found for the Pu atom. We propose that [Sm, Pu]B6 belong to a new class of the intermediate valence materials with the multi-orbital "Kondo-like" singlet ground-state. Crucial role of complex spin-orbital f(??n)-f?(?n+1) multiplet structure differently hybridized with ligand states in such Racah materials is discussed. PMID:26490021

  5. Real-time observation of valence electron motion.

    SciTech Connect

    Goulielmakis, E.; Loh, Z.-H.; Wirth, A.; Santra, R.; Rohringer, N.; Yakovlev, V. S.; Zherebtsov, S.; Pfeifer, T.; Azzeer, A. M.; Kling, M. F.; Leone, S. R.; Krausz, F.; Chemical Sciences and Engineering Division; Max-Planck-Insti. fur Quantenoptik; Univ. of California at Berkeley; LBNL; Univ. of Chicago; LLNL; Ludwig-Maximilians-Univ.; King Saud Univ.

    2010-08-05

    The superposition of quantum states drives motion on the atomic and subatomic scales, with the energy spacing of the states dictating the speed of the motion. In the case of electrons residing in the outer (valence) shells of atoms and molecules which are separated by electronvolt energies, this means that valence electron motion occurs on a subfemtosecond to few-femtosecond timescale (1 fs = 10{sup -15} s). In the absence of complete measurements, the motion can be characterized in terms of a complex quantity, the density matrix. Here we report an attosecond pump-probe measurement of the density matrix of valence electrons in atomic krypton ions. We generate the ions with a controlled few-cycle laser field and then probe them through the spectrally resolved absorption of an attosecond extreme-ultraviolet pulse, which allows us to observe in real time the subfemtosecond motion of valence electrons over a multifemtosecond time span. We are able to completely characterize the quantum mechanical electron motion and determine its degree of coherence in the specimen of the ensemble. Although the present study uses a simple, prototypical open system, attosecond transient absorption spectroscopy should be applicable to molecules and solid-state materials to reveal the elementary electron motions that control physical, chemical and biological properties and processes.

  6. "Plug-and-go" strategy to manipulate streptavidin valencies.

    PubMed

    Sun, Xun; Montiel, Daniel; Li, Hao; Yang, Haw

    2014-08-20

    The streptavidin-biotin set is one of the most widely utilized conjugation pairs in biotechnological applications. The tetravalent nature of streptavidin and its homologues, however, tends to result in such undesirable complications as cross-linking or ill-defined stoichiometry. Here, we describe a mutagenesis-free strategy to manipulate the valencies of wild-type streptavidin that only requires commercially available reagents. The basic idea is simple: one obtains the desired streptavidin valency by blocking off unwanted binding sites using ancillary biotin ("plug"); this way, the extraordinary fM-biotin-binding affinity is fully retained for the remaining sites in streptavidin. In the present implementation, the ancillary biotin is attached to an auxiliary separation handle, negatively charged DNA or His-tagged protein, via a photochemically or enzymatically cleavable linker. Mixing streptavidin with the ancillary biotin construct produces a distribution of streptavidin valencies. The subsequent chromatographic separation readily isolates the construct of desired streptavidin valency, and the auxiliary handles are easily removed afterward ("go"). We demonstrate how this "plug-and-go" strategy allows a precise control for the compositions of streptavidin-biotin conjugates at the single-molecule level. This low-entry-barrier protocol could further expand the application scope of the streptavidin technology. PMID:25082796

  7. Social Learning Modulates the Lateralization of Emotional Valence

    ERIC Educational Resources Information Center

    Shamay-Tsoory, Simone G.; Lavidor, Michal; Aharon-Peretz, Judith

    2008-01-01

    Although neuropsychological studies of lateralization of emotion have emphasized valence (positive vs. negative) or type (basic vs. complex) dimensions, the interaction between the two dimensions has yet to be elucidated. The purpose of the current study was to test the hypothesis that recognition of basic emotions is processed preferentially by…

  8. THEORY OF VALENCE TRANSITIONS IN YTTERBIUM-BASED COMPOUNDS

    E-print Network

    Freericks, Jim

    . INTRODUCTION The intermetallic compounds of the YbInCu§ family exhibit an isostructural transition from highChapter 1 THEORY OF VALENCE TRANSITIONS IN YTTERBIUM-BASED COMPOUNDS V. Zlati´c ¢¡ £ , and J. K of YbInCu¦ and similar compounds is modeled by the exact solution of the spin one-half Falicov

  9. Racah materials: role of atomic multiplets in intermediate valence systems

    PubMed Central

    Shick, A. B.; Havela, L.; Lichtenstein, A. I.; Katsnelson, M. I.

    2015-01-01

    We address the long-standing mystery of the nonmagnetic insulating state of the intermediate valence compound SmB6. Within a combination of the local density approximation (LDA) and an exact diagonalization (ED) of an effective discrete Anderson impurity model, the intermediate valence ground state with the f-shell occupation ?n4f??=?5.6 is found for the Sm atom in SmB6. This ground state is a singlet, and the first excited triplet state ~3?meV higher in the energy. SmB6 is a narrow band insulator already in LDA, with the direct band gap of ~10?meV. The electron correlations increase the band gap which now becomes indirect. Thus, the many-body effects are relevant to form the indirect band gap, crucial for the idea of “topological Kondo insulator" in SmB6. Also, an actinide analog PuB6 is considered, and the intermediate valence singlet ground state is found for the Pu atom. We propose that [Sm, Pu]B6 belong to a new class of the intermediate valence materials with the multi-orbital “Kondo-like" singlet ground-state. Crucial role of complex spin-orbital f??n–f??n+1 multiplet structure differently hybridized with ligand states in such Racah materials is discussed. PMID:26490021

  10. A resource-light approach to learning verb valencies

    E-print Network

    Wintner, Shuly

    in a very restricted resource situation. - For Quechua, all we have is some text and a morphological; generation has been done too. - We've got a version in Python #12;Synchronous XDG - Mike Gasser's talk last's unweighted... #12;valency vs. subcat I shouldn't use them interchangeably: I really just mean subcategory

  11. Racah materials: role of atomic multiplets in intermediate valence systems

    NASA Astrophysics Data System (ADS)

    Shick, A. B.; Havela, L.; Lichtenstein, A. I.; Katsnelson, M. I.

    2015-10-01

    We address the long-standing mystery of the nonmagnetic insulating state of the intermediate valence compound SmB6. Within a combination of the local density approximation (LDA) and an exact diagonalization (ED) of an effective discrete Anderson impurity model, the intermediate valence ground state with the f-shell occupation ?=?5.6 is found for the Sm atom in SmB6. This ground state is a singlet, and the first excited triplet state ~3?meV higher in the energy. SmB6 is a narrow band insulator already in LDA, with the direct band gap of ~10?meV. The electron correlations increase the band gap which now becomes indirect. Thus, the many-body effects are relevant to form the indirect band gap, crucial for the idea of “topological Kondo insulator" in SmB6. Also, an actinide analog PuB6 is considered, and the intermediate valence singlet ground state is found for the Pu atom. We propose that [Sm, Pu]B6 belong to a new class of the intermediate valence materials with the multi-orbital “Kondo-like" singlet ground-state. Crucial role of complex spin-orbital f??n–f??n+1 multiplet structure differently hybridized with ligand states in such Racah materials is discussed.

  12. Emotional Valence and Arousal Effects on Memory and Hemispheric Asymmetries

    ERIC Educational Resources Information Center

    Mneimne, Malek; Powers, Alice S.; Walton, Kate E.; Kosson, David S.; Fonda, Samantha; Simonetti, Jessica

    2010-01-01

    This study examined predictions based upon the right hemisphere (RH) model, the valence-arousal model, and a recently proposed integrated model (Killgore & Yurgelun-Todd, 2007) of emotion processing by testing immediate recall and recognition memory for positive, negative, and neutral verbal stimuli among 35 right-handed women. Building upon…

  13. Recognizing the Emotional Valence of Names: An ERP Study

    ERIC Educational Resources Information Center

    Wang, Lin; Zhu, Zude; Bastiaansen, Marcel; Hagoort, Peter; Yang, Yufang

    2013-01-01

    Unlike common nouns, person names refer to unique entities and generally have a referring function. We used event-related potentials to investigate the time course of identifying the emotional meaning of nouns and names. The emotional valence of names and nouns were manipulated separately. The results show early N1 effects in response to emotional…

  14. Bonding effects on the slip differences in the B1 monocarbides.

    PubMed

    De Leon, Nicholas; Yu, Xiao-Xiang; Yu, Hang; Weinberger, Christopher R; Thompson, Gregory B

    2015-04-24

    Differences in plasticity are usually attributed to significant changes in crystalline symmetry or the strength of the interatomic bonds. In the B1 monocarbides, differences in slip planes exist at low temperatures despite having the same structure and very similar bonding characteristics. Our experimental results demonstrate concretely that HfC slips on {110} planes while TaC slips on {111} planes. Density functional theory calculations rationalize this difference through the formation of an intrinsic stacking fault on the {111} planes, formation of Shockley partials, and enhanced metallic bonding because of the valence filling of electrons between these transitional metal carbides. PMID:25955056

  15. Simulations of hydrogen bonds in crystals and their comparison with neutron diffraction results

    SciTech Connect

    Grabowski, Slawomir J.

    1999-06-15

    The influence of the hydrogen bond formation on O-H, N-H and C-H groups have been studied by crystal structure correlation methods on neutron diffraction data taken from Cambridge Structural Database. The correlations between the lengths of the donor groups and the proton...acceptor distances may be supported using the valence sum rule. Hydrogen bonds play a major role in determining molecular packing and conformations of molecules in crystals. Even the weak C-H..X hydrogen bonds which do not influence the donor groups may play a role for the arrangement of molecules in crystals.

  16. Superconductivity and mixed valency in thallium-doped lead telluride

    NASA Astrophysics Data System (ADS)

    Matsushita, Yana

    Tl-doped PbTe (Pb1-xTl xTe) is a degenerate semiconductor exhibiting superconductivity at a remarkably high Tc given its relatively low carrier concentration of ˜1020 cm-3. For Tl concentrations x beyond a critical value x c˜0.3%, it is observed to superconduct with T c rapidly increasing with x up to a maximum Tc of 1.5 K for the highest Tl doping of 1.5%. In comparison, other similar superconducting semiconductors can achieve comparable Tc values with much higher carrier concentrations. Since thallium is the only impurity known to cause superconductivity in PbTe, there has been considerable discussion as to the role of the Tl impurities in this material. In particular, it has been suggested that the superconductivity can be linked to the presence of a mixed Tl valence fluctuating between Tl + and Tl3+ states. We investigate the superconducting and normal state properties of single crystal Tl-doped PbTe samples for a range of Tl concentrations up to the solubility limit of approximately 1.5%. Estimates of superconducting parameters from heat capacity and upper critical field measurements show that the material is a Type-II, weak-coupled BCS superconductor in the dirty limit. Evidence for the mixed valence state appears as a carrier concentration saturation in the Hall effect measurements, indicating a self-compensating mixture of Tl+ (acceptors) and Tl3+ (donors) beyond a characteristic Tl concentration near xc. Furthermore, we show evidence that an anomalous low-temperature resistivity upturn may be associated with a charge Kondo effect arising; from the quantum valence fluctuations between the degenerate valence states of the Tl impurities. The resistivity anomaly was observed only in superconducting samples where x > xc These observations would support the notion of an alternate pairing mechanism for superconductivity in this material which is linked to the presence of the mixed valence state.

  17. Selective extraction based on poly(MAA-VB-EGMDA) monolith followed by HPLC for determination of hordenine in plasma and urine samples.

    PubMed

    Chen, Yonggang; Meng, Junhua; Zou, Jili; An, Jing

    2015-06-01

    Hordenine is an active compound found in several foods, herbs and beer. In this work, a novel sorbent was fabricated for selective solid-phase extraction (SPE) of hordenine in biological samples. The organic polymer sorbent was synthesized in one step in the plastic barrel of a syringe by a pre-polymerization solution consisting of methacrylic acid (MAA), 4-vinylphenylboronic acid (VB) and ethylene glycol dimethacrylate (EGDMA). The conditions for preparation were optimized to generate a poly(MAA-VB-EGMDA) monolith with good permeability. The monolith exhibited good enrichment efficiency towards hordenine. By using tyramine as the internal standard, a poly(MAA-VB-EGMDA)-based SPE-HPLC method was established for analysis of hordenine. Conditions for SPE, including volume of eluting solvent, pH of sample solution, sampling rate and sample volume, were optimized. The proposed SPE-HPLC method presented good linearity (R(2) ?=?0.9992) within 10-2000?ng/mL and the detection limits was 3?ng/mL, which is significantly more sensitive than reported methods. The method was also applied in plasma and urine samples; good capability of removing matrices was observed, while hordenine in low content was well extracted and enriched. The recoveries were from 90.6 to 94.7% and from 89.3 to 91.5% for the spiked plasma and urine samples, respectively, with the relative standard deviations <4.7%. PMID:25355709

  18. Two-electron bond-orbital model, 2

    NASA Technical Reports Server (NTRS)

    Huang, C.; Moriarty, J. A.; Sher, A.

    1976-01-01

    The two-electron bond-orbital model of tetrahedrally-coordinated solids is generalized and its application extended. All intrabond matrix elements entering the formalism are explicitly retained, including the direct overlap S between the anion and cation sp3 hybrid wavefunctions. Complete analytic results are obtained for the six two-electron eigenvalues and eigenstates of the anion-cation bond in terms of S, one-electron parameters V2 and V3, and two-electron correlation parameters V4, V5 and V6. Refined formulas for the dielectric constant and the nuclear exchange and pseudodipolar coefficients, as well as new expressions for the valence electron density, polarity of the bond and the cohesive energy, are then derived. The theory gives a good account of the experimentally observed trends in all properties considered and approximate quantitative agreement is achieved for the pseudodipolar coefficient.

  19. Essays on corporate bonds

    E-print Network

    Bao, Jack (Jack C.)

    2009-01-01

    This thesis consists of three empirical essays on corporate bonds, examining the role of both credit risk and liquidity. In the first chapter, I test the ability of structural models of default to price corporate bonds in ...

  20. A phase I clinical study of VB4-845: Weekly intratumoral administration of an anti-EpCAM recombinant fusion protein in patients with squamous cell carcinoma of the head and neck

    PubMed Central

    MacDonald, Glen C; Rasamoelisolo, Michèle; Entwistle, Joycelyn; Cizeau, Jeannick; Bosc, Denis; Cuthbert, Wendy; Kowalski, Mark; Spearman, Maureen; Glover, Nick

    2008-01-01

    VB4-845 is a scFv-Pseudomonas exotoxin A fusion construct that targets epithelial cell adhesion molecule (EpCAM). A phase I trial was conducted to determine the maximum tolerated dose (MTD) of VB4-845 when administered as weekly intratumoral (IT) injections to patients with squamous cell carcinoma of the head and neck (SCCHN). Secondary objectives included the evaluation of the safety, tolerability, pharmacokinetic profile, and immunogenicity, and a preliminary assessment of tumor response. Twenty patients with advanced, recurrent SCCHN were treated weekly for four weeks in ascending dose cohorts of 100, 200, 330, 500, 700, and 930 ?g. The MTD was established as 930 ?g with a dose limiting toxicity of elevated liver enzymes in two of five patients. VB4-845 therapy was well tolerated with common treatment-related adverse events of injection site reactions, fever, gastrointestinal disorders, and elevated liver enzyme levels. All patients developed antibodies to VB4-845 by the end of the study, but only seven patients had neutralizing antibodies. Preliminary efficacy data found 87.5% of EpCAM-positive patients had a positive response to VB4-845 therapy. Noninjected dermal metastases were also resolved in one patient. VB4-845 IT therapy is safe and feasible and warrants further clinical evaluation for the treatment of SCCHN. PMID:19920898

  1. Embrittlement by liquid U in some group VB and VIB metals and alloys during tensile loading at 1473 K

    NASA Astrophysics Data System (ADS)

    Huang, J. S.; Gallegos, G. F.

    1990-07-01

    An investigation was conducted to determine the effect on tensile behavior of Ta, W, V, Nb, and a Ta-2.5 wt pct W alloy when they were exposed to liquid U. Tantalum, wolfram, and the Ta-2.5 wt pct W alloy were embrittled with a negligible reduction of cross section at failure, whereas V and Nb showed ductile behavior, with the samples necking down to a point. Tensile deformation of Ta in liquid U was also investigated at different displacement rates. It was found that ductility and strength increased with increasing displacement rate. The embrittlement in Ta, W, and the Ta-2.5 wt pct W alloy was associated with intergranular penetration of U, and the fracture surfaces showed evidence of grain boundary dissolution. At higher displacement rates, however, this evidence was less obvious. These results indicate that intergranular penetration of liquid U and tensile embrittlement in some of the Group VB and VIB metals correlate with low mutual solubility between the solid and liquid elements. It was also found that the thermo-dynamic criterion for intergranular penetration of liquid into a solid (grain boundary energy > 2 × liquid/solid interfacial energy) only applies to these systems.

  2. Borderline Class II/III Ligand-Centered Mixed Valency in a Porphyrinic Molecular Rectangle

    E-print Network

    Dinolfo, Peter H.

    Borderline Class II/III Ligand-Centered Mixed Valency in a Porphyrinic Molecular Rectangle Peter H reduced rectangle is assigned as a borderline class II/class III mixed-valence species. Introduction Among

  3. Chemical Bonding Forces and Metallization of Hydrogen

    NASA Astrophysics Data System (ADS)

    Naumov, Ivan; Hemley, Russell; Carnegie Inst of Washington Collaboration

    2015-03-01

    Recent theoretical and experimental studies reveal that compressed molecular hydrogen at 200-350 GPa transforms to layered structures consisting of distorted graphene sheets. The new phases of dense solid hydrogen contrast with the long-held view that symmetric close-packed, ambient alkali-metal-like structures form at these high pressures -this raises the question about the nature and fate of molecular bonding in hydrogen on compression. The realization of such unexpected structures can be explained by consideration of simple low-dimensional model systems- H6 rings and graphene-like monolayers. Both molecular quantum chemistry and well-tested solid state approaches show that these model systems like aromatic hydrocarbons exhibit a special stability, associated with the completely filled set of bonding orbitals or valence bands. This close-shell effect persists in progressing to the real layered structures where it prevents the dielectric energy gap from closing, thus delaying the pressure-induced metallization. The latter nevertheless can occur upon further compression via destroying the closed shell electronic structure which is mainly determined by the 1s electrons. The most likely scenario is the lowering of the bonding bands (their bottoms) stemming from the unoccupied atomic 2s and 2p orbitals. This research was supported by EFree, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award DESC0001057.

  4. Diffusion bonding aeroengine components

    NASA Astrophysics Data System (ADS)

    Fitzpatrick, G. A.; Broughton, T.

    1988-10-01

    The use of diffusion bonding processes at Rolls-Royce for the manufacture of titanium-alloy aircraft engine components and structures is described. A liquid-phase diffusion bonding process called activated diffusion bonding has been developed for the manufacture of the hollow titanium wide chord fan blade. In addition, solid-state diffusion bonding is being used in the manufacture of hollow vane/blade airfoil constructions mainly in conjunction with superplastic forming and hot forming techniques.

  5. Introduction Valence dictionaries vs. corpora What to acquire from corpora Data sparseness References What to acquire in automatic valence acquisition

    E-print Network

    -dat] najlepszej [best-gen z of naszych our lodzi. boats] `We have not given those seven sailors the best of our boats.' #12;Introduction Valence dictionaries vs. corpora What to acquire from corpora Data sparseness lodzi. boats] `We have not given those seven sailors the best of our boats.' Implicit: NPs are actually

  6. Acrylic mechanical bond tests

    SciTech Connect

    Wouters, J.M.; Doe, P.J.

    1991-02-01

    The tensile strength of bonded acrylic is tested as a function of bond joint thickness. 0.125 in. thick bond joints were found to posses the maximum strength while the acceptable range of joints varied from 0.063 in. to almost 0.25 in. Such joints are used in the Sudbury Neutrino Observatory.

  7. Creating ?-holes through the formation of beryllium bonds.

    PubMed

    Brea, Oriana; Mó, Otilia; Yáñez, Manuel; Alkorta, Ibon; Elguero, José

    2015-09-01

    Through the use of ab initio theoretical models based on MP2/aug-cc-pVDZ-optimized geometries and CCSD(T)/aug-cc-pVTZ and CCSD(T)/aug-c-pVDZ total energies, it has been shown that the significant electron density rearrangements that follow the formation of a beryllium bond may lead to the appearance of a ?-hole in systems that previously do not exhibit this feature, such as CH3 OF, NO2 F, NO3 F, and other fluorine-containing systems. The creation of the ?-hole is another manifestation of the bond activation-reinforcement (BAR) rule. The appearance of a ?-hole on the F atoms of CH3 OF is due to the enhancement of the electronegativity of the O atom that participates in the beryllium bond. This atom recovers part of the charge transferred to Be by polarizing the valence density of the F into the bonding region. An analysis of the electron density shows that indeed this bond becomes reinforced, but the F atom becomes more electron deficient with the appearance of the ?-hole. Importantly, similar effects are also observed even when the atom participating in the beryllium bond is not directly attached to the F atom, as in NO2 F, NO3 F, or NCF. Hence, whereas the isolated CH3 OF, NO2 F, and NO3 F are unable to yield F???Base halogen bonds, their complexes with BeX2 derivatives are able to yield such bonds. Significant cooperative effects between the new halogen bond and the beryllium bond reinforce the strength of both noncovalent interactions. PMID:26212472

  8. X-ray Emission Spectroscopy to Study Ligand Valence Orbitals in Mn Coordination Complexes

    SciTech Connect

    Smolentsev, Grigory; Soldatov, Alexander V; Messinger, Johannes; Merz, Kathrin; Weyhermuller, Thomas; Bergmann, Uwe; Pushkar, Yulia; Yano, Junko; Yachandra, Vittal K.; Glatzel, Pieter

    2009-03-02

    We discuss a spectroscopic method to determine the character of chemical bonding and for the identification of metal ligands in coordination and bioinorganic chemistry. It is based on the analysis of satellite lines in X-ray emission spectra that arise from transitions between valence orbitals and the metal ion 1s level (valence-to-core XES). The spectra, in connection with calculations based on density functional theory (DFT), provide information that is complementary to other spectroscopic techniques, in particular X-ray absorption (XANES and EXAFS). The spectral shape is sensitive to protonation of ligands and allows ligands, which differ only slightly in atomic number (e.g., C, N, O...), to be distinguished. A theoretical discussion of the main spectral features is presented in terms of molecular orbitals for a series of Mn model systems: [Mn(H2O)6]2+, [Mn(H2O)5OH]+, [Mn(H2O)5NH2]+, and [Mn(H2O)5NH3]2+. An application of the method, with comparison between theory and experiment, is presented for the solvated Mn2+ ion in water and three Mn coordination complexes, namely [LMn(acac)N3]BPh4, [LMn(B2O3Ph2)(ClO4)], and [LMn(acac)N]BPh4, where L represents 1,4,7-trimethyl-1,4,7-triazacyclononane, acac stands for the 2,4-pentanedionate anion, and B2O3Ph2 represents the 1,3-diphenyl-1,3-dibora-2-oxapropane-1,3-diolato dianion.

  9. Valence-Specific Laterality Effects in Vocal Emotion: Interactions with Stimulus Type, Blocking and Sex

    ERIC Educational Resources Information Center

    Schepman, Astrid; Rodway, Paul; Geddes, Pauline

    2012-01-01

    Valence-specific laterality effects have been frequently obtained in facial emotion perception but not in vocal emotion perception. We report a dichotic listening study further examining whether valence-specific laterality effects generalise to vocal emotions. Based on previous literature, we tested whether valence-specific laterality effects were…

  10. ION SIZE AND VALENCE EFFECTS ON IONIC FLOWS VIA POISSON-NERNST-PLANCK MODELS

    E-print Network

    Liu, Weishi

    ION SIZE AND VALENCE EFFECTS ON IONIC FLOWS VIA POISSON-NERNST-PLANCK MODELS PETER W. BATES, WEISHI oppositely charged ion species through an ion channel, focusing on effects of ion sizes and ion valences) and diffusion coefficients, in addition to ion sizes and ion valences. For the relatively simple setting

  11. Entangled Valence Electron-Hole Dynamics Revealed by Stimulated Attosecond Xray Raman Scattering

    E-print Network

    Mukamel, Shaul

    Entangled Valence Electron-Hole Dynamics Revealed by Stimulated Attosecond Xray Raman Scattering. Attosecond resonant X-ray pulses, however, can be used to prepare valence excitations by a second), attosecond pulses can be similarly used to create and control wavepackets of valence electrons impulsively

  12. Work Valence as a Predictor of Academic Achievement in the Family Context

    ERIC Educational Resources Information Center

    Porfeli, Erik; Ferrari, Lea; Nota, Laura

    2013-01-01

    This study asserts a theoretical model of academic and work socialization within the family setting. The presumed associations between parents' work valences, children's work valences and valence perceptions, and children's academic interest and achievement are tested. The results suggest that children's perceptions of parents…

  13. Modulation of motor-meaning congruity effects for valenced words Geoffrey Broookshire1

    E-print Network

    Jacobs, Lucia

    , but eliminated with orientation to color. When people read words with emotional valence, vertical spatio, and Behavior, Nijmegen, NL Abstract We investigated the extent to which emotionally valenced words upward or downward while viewing words with positive or negative valence. Only the color of the words

  14. A mixed-valence copper coordination polymer generated by hydrothermal metal/ligand redox reactions

    E-print Network

    Li, Jing

    hydro- thermal conditions and wish to extend this to mixed-valence copper complexes. Copper(I) compounds-valence copper compounds, with hydroxylated bipyridyl ligands,3g have been recently reportedA mixed-valence copper coordination polymer generated by hydrothermal metal/ligand redox reactions

  15. Developmental Reversals in False Memory: Effects of Emotional Valence and Arousal

    ERIC Educational Resources Information Center

    Brainerd, C. J.; Holliday, R. E.; Reyna, V. F.; Yang, Y.; Toglia, M. P.

    2010-01-01

    Do the emotional valence and arousal of events distort children's memories? Do valence and arousal modulate counterintuitive age increases in false memory? We investigated those questions in children, adolescents, and adults using the Cornell/Cortland Emotion Lists, a word list pool that induces false memories and in which valence and arousal can…

  16. Prospective bonding applications

    NASA Astrophysics Data System (ADS)

    Ancenay, H.; Benazet, D.

    1981-07-01

    Adhesive bonding in industry and in the laboratory is surveyed and prospects for its wider utilization are assessed. The economic impact of bonding technology on industry is discussed. Research is reviewed, centering on the development of nondestructive testing and inspection techniques. Traditional (wood) as well as new materials susceptible to bonding are considered. Applications in construction and civil engineering, in aeronautics, and in the automobile industry are covered. The use of glues in mechanical constructions, in assembling cylindrical parts, and in metal-metal bonding are examined. Hybrid assembling and bonding of composite materials are included.

  17. Bonding thermoplastic polymers

    DOEpatents

    Wallow, Thomas I. (Fremont, CA); Hunter, Marion C. (Livermore, CA); Krafcik, Karen Lee (Livermore, CA); Morales, Alfredo M. (Livermore, CA); Simmons, Blake A. (San Francisco, CA); Domeier, Linda A. (Danville, CA)

    2008-06-24

    We demonstrate a new method for joining patterned thermoplastic parts into layered structures. The method takes advantage of case-II permeant diffusion to generate dimensionally controlled, activated bonding layers at the surfaces being joined. It is capable of producing bonds characterized by cohesive failure while preserving the fidelity of patterned features in the bonding surfaces. This approach is uniquely suited to production of microfluidic multilayer structures, as it allows the bond-forming interface between plastic parts to be precisely manipulated at micrometer length scales. The bond enhancing procedure is easily integrated in standard process flows and requires no specialized equipment.

  18. Lattice vibrations and the bonding nature of boron carbide

    NASA Astrophysics Data System (ADS)

    Shirai, Koun; Emura, Shuichi

    1996-12-01

    The vibrations of boron carbide 0953-8984/8/50/018/img1 have been studied by the valence force model. There have been so far several ambiguities in the interpretation of experimental spectra, which made theoretical study difficult. This paper solves the main difficulties, that is, characterization of the highest 0953-8984/8/50/018/img2 band and most of the Raman bands, providing reasonable interpretations for low-frequency modes. The 0953-8984/8/50/018/img2 band is ascribed to the anti-symmetric stretching of the linear chain. The necessity of large angle-bending forces of carbon atom arose for better fitting, which fact can be regarded as evidence for formation of strong covalent bonds around this atom. The present analysis also throws a new light on the Longuet-Higgins interpretation of the role of carbon incorporation. The coexistence of the strong covalent bonds of carbon atoms and the relatively weak icosahedral bonds results in such a balance of bonding that the intra-icosahedral and rhombohedral bonds are further weakened, and the covalent bonds of the carbon chain are instead reinforced.

  19. Conduction and Valence Band Offsets in WSe2 -Graphene Heterostructures

    NASA Astrophysics Data System (ADS)

    Kim, Kyounghwan; Larentis, Stefano; Fallahazad, Babak; Lee, Kayoung; Xue, Jiamin; Dillen, David; Corbet, Chris; Tutuc, Emanuel

    2015-03-01

    We investigate the electron transport in graphene-WSe2 heterostructures realized using a layer-by-layer transfer. Lateral electron transport shows ambipolar behavior characteristic of graphene, with a marked saturation at high positive (negative) gate bias, associated with the population of the conduction (valence) band in WSe2. The graphene carrier density dependence on gate bias was extracted from magneto-transport measurements. Using WSe2 as a top dielectric in dual-gate graphene field-effect transistors, we determine the WSe2 dielectric constant along the c-axis. By combining the graphene density dependence on gate bias in back-gated graphene-WSe2 heterostructures with the WSe2 dielectric constant, we determine the offset between the graphene charge neutrality point and the WSe2 conduction and valence bands. This work was supported by NRI, NSF and Intel.

  20. Quantum valence criticality as an origin of unconventional critical phenomena.

    PubMed

    Watanabe, Shinji; Miyake, Kazumasa

    2010-10-29

    It is shown that unconventional critical phenomena commonly observed in paramagnetic metals YbRh2Si2, YbRh2(Si0.95Ge0.05)2, and ?-YbAlB4 are naturally explained by the quantum criticality of Yb-valence fluctuations. We construct the mode-coupling theory taking account of local correlation effects of f electrons and find that unconventional criticality is caused by the locality of the valence fluctuation mode. We show that measured low-temperature anomalies such as divergence of uniform spin susceptibility ??T(-?) with ??0.6 giving rise to a huge enhancement of the Wilson ratio and the emergence of T-linear resistivity are explained in a unified way. PMID:21231120

  1. Zener Double Exchange from Local Valence Fluctuations in Magnetite

    SciTech Connect

    McQueeney, Robert John; Yethiraj, M.; Chang, S.; Montfrooij, W.; Perring, T. G.; Honig, J. M.; Metcalf, P.

    2007-01-01

    Magnetite (Fe3O4) is a mixed valent system where electronic conductivity occurs on the B site (octahedral) iron sublattice of the spinel structure. Below Tv = 123 K, a metal-insulator transition occurs which is argued to arise from the charge ordering of 2+ and 3+ iron valences on the B sites (Verwey transition). Inelastic neutron scattering measurements show that optical spin waves propagating on the B site sublattice (~80 meV) are shifted upwards in energy above TV due to the occurrence of B-B ferromagnetic double exchange in the mixed valent phase. The double exchange interaction affects only spin waves of 5 symmetry, not all modes, indicating that valence fluctuations are slow and the double exchange is constrained by short-range electron correlations above Tv.

  2. Comparison of the proton-transfer paths in hydrogen bonds from theoretical potential-energy surfaces and the concept of conservation of bond order III. O-H-O hydrogen bonds.

    PubMed

    Majerz, Irena; Olovsson, Ivar

    2010-01-01

    The quantum-mechanically derived reaction coordinates (QMRC) for the proton transfer in O-H-O hydrogen bonds have been derived from ab initio calculations of potential-energy surfaces. A comparison is made between the QMRC and the corresponding bond-order reaction coordinates (BORC) derived by applying the Pauling bond order concept together with the principle of conservation of bond order. In agreement with earlier results for N-H-N(+) hydrogen bonds there is virtually perfect agreement between the QMRC and BORC curves for intermolecular O-H-O hydrogen bonds. For intramolecular O-H-O hydrogen bonds, the donor and acceptor parts of the molecule impose strong constraints on the O···O distance and the QMRC does not follow the BORC relation in the whole range. The neutron-determined proton positions are located close to the theoretically calculated potential-energy minima, and where the QMRC and the BORC curves coincide with each other. The results confirm the universal character of intermolecular hydrogen bonds: BORC is identical with QMRC and the proton can be moved from donor to acceptor keeping its valency equal to 1. The shape of PES for intramolecular hydrogen bonds is more complex as it is sensitive to the geometry of the molecule as well as of the hydrogen bridge. PMID:20379578

  3. The computation of C-C and N-N bond dissociation energies for singly, doubly, and triply bonded systems

    NASA Technical Reports Server (NTRS)

    Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.; Taylor, Peter R.

    1989-01-01

    The bond dissociation energies (D sub e) of C2H2, C2H4, C2H6, N2, N2H2, and N2H4 are studied at various levels of correlation treatment. The convergence of D sub e with respect to the one particle basis is studied at the single reference modified coupled-pair functional (MCPF) level. At all levels of correlation treatment, the errors in the bond dissociation energies increase with the degree of multiple bond character. The multireference configuration interaction (MRCI) D sub e values, corrected for an estimate of higher excitations, are in excellent agreement with those determined using the size extensive averaged coupled pair functional (ACPF) method. It was found that the full valence complete active space self consistent field (CASSCF)/MRCI calculations are reproduced very well by MRCI calculations based on a CASSCF calculation that includes in the active space only those electrons involved in the C-C or N-N bonds. To achieve chemical accuracy (1 kcal/mole) for the D sub e values of the doubly bonded species C2H4 and N2H2 requires one particle basis sets including up through h angular momentum functions (l = 5) and a multireference treatment of electron correlation: still higher levels of calculation are required to achieve chemical accuracy for the triply bonded species C2H2 and N2.

  4. Sketching the pion's valence-quark generalised parton distribution

    DOE PAGESBeta

    Mezrag, C.; Chang, L.; Moutarde, H.; Roberts, C. D.; Rodríguez-Quintero, J.; Sabatié, F.; Schmidt, S. M.

    2015-02-01

    In order to learn effectively from measurements of generalised parton distributions (GPDs), it is desirable to compute them using a framework that can potentially connect empirical information with basic features of the Standard Model. We sketch an approach to such computations, based upon a rainbow-ladder (RL) truncation of QCD’s Dyson–Schwinger equations and exemplified via the pion’s valence dressed-quark GPD, Hv?(x, ?, t). Our analysis focuses primarily on ?=0, although we also capitalise on the symmetry-preserving nature of the RL truncation by connecting Hv?(x, ?=±1, t)with the pion’s valence-quark parton distribution amplitude. We explain that the impulse-approximation used hitherto to definemore »the pion’s valence dressed-quark GPD is generally invalid owing to omission of contributions from the gluons which bind dressed-quarks into the pion. A simple correction enables us to identify a practicable improvement to the approximation for Hv?(x, 0, t), expressed as the Radon transform of a single amplitude. Therewith we obtain results for Hv?(x, 0, t) and the associated impact-parameter dependent distribution, qv?(x, |b?|), which provide a qualitatively sound picture of the pion’s dressed-quark structure at a hadronic scale. We evolve the distributions to a scale ? = 2 GeV, so as to facilitate comparisons in future with results from experiment or other nonperturbative methods.« less

  5. Predicting the Valence of a Scene from Observers' Eye Movements.

    PubMed

    R-Tavakoli, Hamed; Atyabi, Adham; Rantanen, Antti; Laukka, Seppo J; Nefti-Meziani, Samia; Heikkilä, Janne

    2015-01-01

    Multimedia analysis benefits from understanding the emotional content of a scene in a variety of tasks such as video genre classification and content-based image retrieval. Recently, there has been an increasing interest in applying human bio-signals, particularly eye movements, to recognize the emotional gist of a scene such as its valence. In order to determine the emotional category of images using eye movements, the existing methods often learn a classifier using several features that are extracted from eye movements. Although it has been shown that eye movement is potentially useful for recognition of scene valence, the contribution of each feature is not well-studied. To address the issue, we study the contribution of features extracted from eye movements in the classification of images into pleasant, neutral, and unpleasant categories. We assess ten features and their fusion. The features are histogram of saccade orientation, histogram of saccade slope, histogram of saccade length, histogram of saccade duration, histogram of saccade velocity, histogram of fixation duration, fixation histogram, top-ten salient coordinates, and saliency map. We utilize machine learning approach to analyze the performance of features by learning a support vector machine and exploiting various feature fusion schemes. The experiments reveal that 'saliency map', 'fixation histogram', 'histogram of fixation duration', and 'histogram of saccade slope' are the most contributing features. The selected features signify the influence of fixation information and angular behavior of eye movements in the recognition of the valence of images. PMID:26407322

  6. Shell structure, emerging collectivity, and valence p-n interactions

    NASA Astrophysics Data System (ADS)

    Cakirli, R. B.

    2014-03-01

    The structure of atomic nuclei depends on the interactions of its constituents, protons and neutrons. These interactions play a key role in the development of configuration mixing and in the onset of collectivity and deformation, in changes to the single particle energies and magic numbers, and in the microscopic origins of phase transitional behavior. Particularly important are the valence proton-neutron interactions which can be studied experimentally using double differences of binding energies extracted from high-precision mass measurements. The resulting quantities, called ?Vpn, are average interaction strengths between the last two protons and the last two neutrons. Focusing on the Z=50-82, N=82-126 shells, we have considered a number of aspects of these interactions, ranging from their relation to the underlying orbits, their behaviour near close shells and throughout major shells, their relation to the onset of collectivity and deformation, and the appearance of unexpected spikes in ?Vpn values for a special set of heavy nuclei with nearly equal numbers of valence protons and neutrons. We have calculated spatial overlaps between proton and neutron Nilsson orbits and compared these with the experimental results. Finally we also address the relation between masses (separation energies), changes in structure and valence nucleon number.

  7. Measurement of valence band structure in arbitrary dielectric films

    SciTech Connect

    Uhm, Han S.; Choi, Eun H.

    2012-10-15

    A new way of measuring the band structure of various dielectric materials using the secondary electron emission from Auger neutralization of ions is introduced. The first example of this measurement scheme is the magnesium oxide (MgO) films with respect to the application of the films in the display industries. The density of state in the valence bands of MgO film and MgO film with a functional layer (FL) deposited over a dielectric surface reveals that the density peak of film with a FL is considerably less than that of film, thereby indicating a better performance of MgO film with functional layer in display devices. The second example of the measurement is the boron-zinc oxide (BZO) films with respect to the application of the films to the development of solar cells. The measurement of density of state in BZO film suggests that a high concentration of boron impurity in BZO films may enhance the transition of electrons and holes through the band gap from the valence to the conduction band in zinc oxide crystals; thereby improving the conductivity of the film. Secondary electron emission by the Auger neutralization of ions is highly instrumental for the determination of the density of states in the valence band of dielectric materials.

  8. Chromium valences in ureilite olivine and implications for ureilite petrogenesis

    NASA Astrophysics Data System (ADS)

    Goodrich, C. A.; Sutton, S. R.; Wirick, S.; Jercinovic, M. J.

    2013-12-01

    Ureilites are a group of ultramafic achondrites commonly thought to be residues of partial melting on a carbon-rich asteroid. They show a large variation in FeO content (olivine Fo values ranging from ?74 to 95) that cannot be due to igneous fractionation and suggests instead variation in oxidation state. The presence of chromite in only a few of the most ferroan (Fo 75-76) samples appears to support such a model. MicroXANES analyses were used in this study to determine the valence states of Cr (previously unknown) in olivine cores of 11 main group ureilites. The goal of this work was to use a method that is independent of Fo to determine the oxidation conditions under which ureilites formed, in order to evaluate whether the ureilite FeO-variation is correlated with oxidation state, and whether it is nebular or planetary in origin. Two of the analyzed samples, LEW 88774 (Fo 74.2) and NWA 766 (Fo 76.7) contain primary chromite; two others, LAP 03587 (Fo 74.4) and CMS 04048 (Fo 76.2) contain sub-micrometer-sized exsolutions of chromite + Ca-rich pyroxene in olivine; and one, EET 96328 (Fo 85.2) contains an unusual chromite grain of uncertain origin. No chromite has been observed in the remaining six samples (Fo 77.4-92.3). Chromium in olivine in all eleven samples was found to be dominated by the divalent species, with valences ranging from 2.10 ± 0.02 (1?) to 2.46 ± 0.04. The non-chromite-bearing ureilites have the most reduced Cr, with a weighted mean valence of 2.12 ± 0.01, i.e., Cr2+/Cr3+ = 7.33. All low-Fo chromite-bearing ureilites have more oxidized Cr, with valences ranging from 2.22 ± 0.03 to 2.46 ± 0.04. EET 96328, whose chromite grain we interpret as a late-crystallizing phase, yielded a reduced Cr valence of 2.15 ± 0.07, similar to the non-chromite-bearing samples. Based on the measured Cr valences, magmatic (1200-1300 °C) oxygen fugacities (fO2) of the non-chromite-bearing samples were estimated to be in the range IW-1.9 to IW-2.8 (assuming basaltic melt composition), consistent with fO2 values obtained by assuming olivine-silica-iron metal (OSI) equilibrium. For the primary chromite-bearing-ureilites, the corresponding fO2 were estimated (again, assuming basaltic melt composition) to be ?IW to IW+1.0, i.e., several orders of magnitude more oxidizing than the conditions estimated for the chromite-free ureilites. In terms of Fo and Cr valence properties, ureilites appear to form two groups rather than a single “Cr-valence (or fO2) vs. Fo” trend. The chromite-bearing ureilites show little variation in Fo (?74-76) but significant variation in Cr valence, while the non-chromite-bearing ureilites show significant variation in Fo (?77-95) and little variation in Cr valence. These groups are unrelated to petrologic type (i.e., olivine-pigeonite, olivine-orthopyroxene, or augite-bearing). The chromite-bearing ureilites also have lower contents of Cr in olivine than most non-chromite-bearing ureilites, consistent with predictions based on Cr olivine/melt partitioning in spinel saturated vs. non-spinel-saturated systems. Under the assumption that at magmatic temperatures graphite-gas equilibria controlled fO2 at all depths on the ureilite parent body, we conclude: (1) that ureilite precursor materials having the Fo and Cr valence properties now observed in ureilites are unlikely to have been preserved during planetary processing; and (2) that the Fo and Cr valence properties now observed in ureilites are consistent with having been established by high-temperature carbon redox control over a range of depths on a plausible-sized ureilite parent body. The apparent limit on ureilite Fo values around 74-76 suggests that the precursor material(s) had bulk mg# ? that of LL chondrites.

  9. Core-core and core-valence correlation

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Taylor, Peter R.

    1988-01-01

    The effect of (1s) core correlation on properties and energy separations was analyzed using full configuration-interaction (FCI) calculations. The Be 1 S - 1 P, the C 3 P - 5 S and CH+ 1 Sigma + or - 1 Pi separations, and CH+ spectroscopic constants, dipole moment and 1 Sigma + - 1 Pi transition dipole moment were studied. The results of the FCI calculations are compared to those obtained using approximate methods. In addition, the generation of atomic natural orbital (ANO) basis sets, as a method for contracting a primitive basis set for both valence and core correlation, is discussed. When both core-core and core-valence correlation are included in the calculation, no suitable truncated CI approach consistently reproduces the FCI, and contraction of the basis set is very difficult. If the (nearly constant) core-core correlation is eliminated, and only the core-valence correlation is included, CASSCF/MRCI approached reproduce the FCI results and basis set contraction is significantly easier.

  10. Basic features of the pion valence-quark distribution function

    SciTech Connect

    Chang, Lei; Mezrag, Cédric; Rodríguez-Quintero, Jose; Tandy, Peter C.

    2014-10-07

    The impulse-approximation expression used hitherto to define the pion's valence-quark distribution function is flawed because it omits contributions from the gluons which bind quarks into the pion. A corrected leading-order expression produces the model-independent result that quarks dressed via the rainbow–ladder truncation, or any practical analogue, carry all the pion's light-front momentum at a characteristic hadronic scale. Corrections to the leading contribution may be divided into two classes, responsible for shifting dressed-quark momentum into glue and sea-quarks. Working with available empirical information, we use an algebraic model to express the principal impact of both classes of corrections. This enables a realistic comparison with experiment that allows us to highlight the basic features of the pion's measurable valence-quark distribution, q?(x); namely, at a characteristic hadronic scale, q?(x)~(1-x)2 for x?0.85; and the valence-quarks carry approximately two-thirds of the pion's light-front momentum.

  11. Valency configuration of transition metal impurities in ZnO

    SciTech Connect

    Petit, Leon; Schulthess, Thomas C; Svane, Axel; Temmerman, Walter M; Szotek, Zdzislawa; Janotti, Anderson

    2006-01-01

    We use the self-interaction corrected local spin-density approximation to investigate the ground state valency configuration of transition metal (TM=Mn, Co) impurities in n- and p-type ZnO. We find that in pure Zn{sub 1-x}TM{sub x}O, the localized TM{sup 2+} configuration is energetically favored over the itinerant d-electron configuration of the local spin density (LSD) picture. Our calculations indicate furthermore that the (+/0) donor level is situated in the ZnO gap. Consequently, for n-type conditions, with the Fermi energy {epsilon}F close to the conduction band minimum, TM remains in the 2+ charge state, while for p-type conditions, with {epsilon}F close to the valence band maximum, the 3+ charge state is energetically preferred. In the latter scenario, modeled here by co-doping with N, the additional delocalized d-electron charge transfers into the entire states at the top of the valence band, and hole carriers will only exist, if the N concentration exceeds the TM impurity concentration.

  12. Basic features of the pion valence-quark distribution function

    DOE PAGESBeta

    Chang, Lei; Mezrag, Cédric; Moutarde, Hervé; Roberts, Craig D.; Rodríguez-Quintero, Jose; Tandy, Peter C.

    2014-10-07

    The impulse-approximation expression used hitherto to define the pion's valence-quark distribution function is flawed because it omits contributions from the gluons which bind quarks into the pion. A corrected leading-order expression produces the model-independent result that quarks dressed via the rainbow–ladder truncation, or any practical analogue, carry all the pion's light-front momentum at a characteristic hadronic scale. Corrections to the leading contribution may be divided into two classes, responsible for shifting dressed-quark momentum into glue and sea-quarks. Working with available empirical information, we use an algebraic model to express the principal impact of both classes of corrections. This enables amore »realistic comparison with experiment that allows us to highlight the basic features of the pion's measurable valence-quark distribution, q?(x); namely, at a characteristic hadronic scale, q?(x)~(1-x)2 for x?0.85; and the valence-quarks carry approximately two-thirds of the pion's light-front momentum.« less

  13. Predicting the Valence of a Scene from Observers’ Eye Movements

    PubMed Central

    R.-Tavakoli, Hamed; Atyabi, Adham; Rantanen, Antti; Laukka, Seppo J.; Nefti-Meziani, Samia; Heikkilä, Janne

    2015-01-01

    Multimedia analysis benefits from understanding the emotional content of a scene in a variety of tasks such as video genre classification and content-based image retrieval. Recently, there has been an increasing interest in applying human bio-signals, particularly eye movements, to recognize the emotional gist of a scene such as its valence. In order to determine the emotional category of images using eye movements, the existing methods often learn a classifier using several features that are extracted from eye movements. Although it has been shown that eye movement is potentially useful for recognition of scene valence, the contribution of each feature is not well-studied. To address the issue, we study the contribution of features extracted from eye movements in the classification of images into pleasant, neutral, and unpleasant categories. We assess ten features and their fusion. The features are histogram of saccade orientation, histogram of saccade slope, histogram of saccade length, histogram of saccade duration, histogram of saccade velocity, histogram of fixation duration, fixation histogram, top-ten salient coordinates, and saliency map. We utilize machine learning approach to analyze the performance of features by learning a support vector machine and exploiting various feature fusion schemes. The experiments reveal that ‘saliency map’, ‘fixation histogram’, ‘histogram of fixation duration’, and ‘histogram of saccade slope’ are the most contributing features. The selected features signify the influence of fixation information and angular behavior of eye movements in the recognition of the valence of images. PMID:26407322

  14. Prediction of the bond lengths, vibrational frequencies, and bond dissociation energy of octahedral seaborgium hexacarbonyl, Sg(CO){sub 6}

    SciTech Connect

    Nash, C.S.; Bursten, B.E.

    1999-11-24

    The recent syntheses of several new elements (including the recent reports of elements 116 and 118), coupled with the controversy surrounding the naming of elements 104--109, have stimulated a great interest in the chemistry of the transactinide elements. This contribution addresses hypothetical hexacarbonyl complex of seaborgium (Sg, element 106), which is predicted to be a 6d-block transition element with six valence electrons, analogous to Cr, Mo, and W. The authors have previously predicted that, if it were to exist, Sg(CO){sub 6} would exhibit metal-carbonyl bonding that is very similar to that in Cr(CO){sub 6}, Mo(CO){sub 6}, and W(CO){sub 6}, and quite unlike that of the unknown valence isoelectronic actinide complex U(CO){sub 6}. This finding is in accord with the scant experimental data available for Sg. The relativistic DV-X{alpha} method used in the earlier paper facilitated the analysis of the molecular orbitals of Sg(CO){sub 6}, but did not allow for the calculation of total-energy properties, such as bond lengths and vibrational frequencies. Here the authors will use the superior methodology they have applied to other transactinide molecules to compare the bond lengths, vibrational frequencies, and CO dissociation energy of hypothetical Sg(CO){sub 6} to those of Mo(CO){sub 6} and W(CO){sub 6}.

  15. Valenced Cues and Contexts Have Different Effects on Event-Based Prospective Memory

    PubMed Central

    Graf, Peter; Yu, Martin

    2015-01-01

    This study examined the separate influence and joint influences on event-based prospective memory task performance due to the valence of cues and the valence of contexts. We manipulated the valence of cues and contexts with pictures from the International Affective Picture System. The participants, undergraduate students, showed higher performance when neutral compared to valenced pictures were used for cueing prospective memory. In addition, neutral pictures were more effective as cues when they occurred in a valenced context than in the context of neutral pictures, but the effectiveness of valenced cues did not vary across contexts that differed in valence. The finding of an interaction between cue and context valence indicates that their respective influence on event-based prospective memory task performance cannot be understood in isolation from each other. Our findings are not consistent with by the prevailing view which holds that the scope of attention is broadened and narrowed, respectively, by positively and negatively valenced stimuli. Instead, our findings are more supportive of the recent proposal that the scope of attention is determined by the motivational intensity associated with valenced stimuli. Consistent with this proposal, we speculate that the motivational intensity associated with different retrieval cues determines the scope of attention, that contexts with different valence values determine participants’ task engagement, and that prospective memory task performance is determined jointly by attention scope and task engagement. PMID:25647484

  16. Excitations of one-valence-proton, one-valence-neutron nucleus 210Bi from cold-neutron capture

    NASA Astrophysics Data System (ADS)

    Cieplicka-Ory?czak, N.; Fornal, B.; Leoni, S.; Bazzacco, D.; Blanc, A.; Bocchi, G.; Bottoni, S.; de France, G.; Jentschel, M.; Köster, U.; Mutti, P.; Simpson, G.; Soldner, T.; Szpak, B.; Ur, C.; Urban, W.

    2015-10-01

    The low-spin structure of one-proton, one-neutron 210Bi nucleus was investigated in cold-neutron capture reaction on 209Bi. The ?-coincidence measurements were performed with use of EXILL array consisted of 16 HPGe detectors. The experimental results were compared to shell-model calculations involving valence particles excitations. The 210Bi nucleus offers the potential to test the effective proton-neutron interactions because most of the states should arise from the proton-neutron excitations. Additionally, it was discovered that a few states should come from the couplings of valence particles to the 3- octupole vibration in 208Pb which provides also the possibility of testing the calculations involving the core excitations.

  17. A local view of bonding and diffusion at metal surfaces

    SciTech Connect

    Feibelman, P.J.

    1996-09-01

    First-principles density functional calculations and corresponding experimental results underline the importance of basic chemical concepts, such as coordination, valence saturation and promotion-hybridization energetics, in understanding bonding and diffusion of atoms at and on metal surfaces. Several examples are reviewed, including outer-layer relaxations of clean hcp(0001) surfaces, liquid-metal-embrittlement energetics, separation energies of metal-adatom dimers, concerted substitutional self-diffusion on fcc(001) surfaces, and adsorption and diffusion barrier sites for adatoms near steps.

  18. Bonded semiconductor substrate

    DOEpatents

    Atwater, Jr.; Harry A. (South Pasadena, CA), Zahler; James M. (Pasadena, CA)

    2010-07-13

    Ge/Si and other nonsilicon film heterostructures are formed by hydrogen-induced exfoliation of the Ge film which is wafer bonded to a cheaper substrate, such as Si. A thin, single-crystal layer of Ge is transferred to Si substrate. The bond at the interface of the Ge/Si heterostructures is covalent to ensure good thermal contact, mechanical strength, and to enable the formation of an ohmic contact between the Si substrate and Ge layers. To accomplish this type of bond, hydrophobic wafer bonding is used, because as the invention demonstrates the hydrogen-surface-terminating species that facilitate van der Waals bonding evolves at temperatures above 600.degree. C. into covalent bonding in hydrophobically bound Ge/Si layer transferred systems.

  19. Chemical bonding technology

    NASA Technical Reports Server (NTRS)

    Plueddemann, E.

    1986-01-01

    Primers employed in bonding together the various material interfaces in a photovoltaic module are being developed. The approach develops interfacial adhesion by generating actual chemical bonds between the various materials bonded together. The current status of the program is described along with the progress toward developing two general purpose primers for ethylene vinyl acetate (EVA), one for glass and metals, and another for plastic films.

  20. Chemical Bonding, again ionic bonding (in salts): transfer of e-

    E-print Network

    Zakarian, Armen

    Chemical Bonding, again · ionic bonding (in salts): transfer of e- · covalent bonding (organic molecules, non-metals): sharing e- · metallic bonding: electron pooling (delocalization) Lewis electron 3A 4A 5A 6A 7A 8A 2 3 (exceptions) #12;Ionic Bonding Model See sample problem 9.1 4Na + O2 ! 2Na2O

  1. Theory and experiment on laser-enabled inner-valence Auger decay of rare-gas atoms

    SciTech Connect

    Tong, X. M.; Ranitovic, P.; Hogle, C. W.; Murnane, M. M.; Kapteyn, H. C.; Toshima, N.

    2011-07-15

    In rare-gas atoms, an inner-valence shell ns hole cannot be filled by Auger decay because of an energy deficiency. We show theoretically and experimentally that by adding a moderately intense infrared laser, Auger decay is possible with decay rates increasing dramatically for laser intensities {>=}10{sup 13} W/cm{sup 2}. For Xe atoms, the simulated laser-enabled Auger decay yields are comparable with the experimental one, while for Ar atoms, the simulated ones are much smaller. We attribute the discrepancies to screening effects of the photoelectron. Laser-enabled Auger decay is of fundamental importance for understanding attosecond science, and is also important for experimental applications in ultrafast atomic, molecular, and materials dynamics using x rays. More importantly it may provide a way to control the Auger decay time and selectively break chemical bonds of molecules using a control infrared laser field.

  2. The dissociative bond.

    PubMed

    Gordon, Nirit

    2013-01-01

    Dissociation leaves a psychic void and a lingering sense of psychic absence. How do 2 people bond while they are both suffering from dissociation? The author explores the notion of a dissociative bond that occurs in the aftermath of trauma--a bond that holds at its core an understanding and shared detachment from the self. Such a bond is confined to unspoken terms that are established in the relational unconscious. The author proposes understanding the dissociative bond as a transitional space that may not lead to full integration of dissociated knowledge yet offers some healing. This is exemplified by R. Prince's (2009) clinical case study. A relational perspective is adopted, focusing on the intersubjective aspects of a dyadic relationship. In the dissociative bond, recognition of the need to experience mutual dissociation can accommodate a psychic state that yearns for relationship when the psyche cannot fully confront past wounds. Such a bond speaks to the need to reestablish a sense of human relatedness and connection when both parties in the relationship suffer from disconnection. This bond is bound to a silence that becomes both a means of protection against the horror of traumatic memory and a way to convey unspoken gestures toward the other. PMID:23282044

  3. Chemical Bonds I

    ERIC Educational Resources Information Center

    Sanderson, R. T.

    1972-01-01

    Chemical bonding is discussed from a bond energy, rather than a wave mechanics, viewpoint. This approach is considered to be more suitable for the average student. (The second part of the article will appear in a later issue of the journal.) (AL)

  4. Mother-Child Bonding.

    ERIC Educational Resources Information Center

    Pearce, Joseph Chilton

    1994-01-01

    Examines the nature of mother-child bonding from the prenatal stage through early infancy, discussing how the mother's actions, even before birth, stimulate her child's senses. Explains the crucial role that physical contact, breastfeeding, and visual stimuli have on mother-child bonding in human and animal newborns. (MDM)

  5. Neural correlates of valence generalization in an affective conditioning paradigm.

    PubMed

    Schick, Anita; Adam, Ruth; Vollmayr, Barbara; Kuehner, Christine; Kanske, Philipp; Wessa, Michèle

    2015-10-01

    In case of uncertainty, predictions that are based on prior, similar experiences guide our decision by processes of generalization. Over-generalization of negative information has been identified as an important feature of several psychopathologies, including anxiety disorders and depression, and might underlie biased interpretation of ambiguous information. Here, we investigated the neural correlates of valence generalization to ambiguous stimuli using a translational affective conditioning task during fMRI. Twenty-five healthy individuals participated in a conditioning procedure with (1) an initial acquisition phase, where participants learned the positive and negative valence of two different tones (reference tones) through their responses and subsequent feedback and (2) a test phase, where participants were presented with the previously learned reference tones and three additional tones with intermediate frequency to the learned reference tones. By recording the responses to these intermediate stimuli we were able to assess the participantsí interpretation of ambiguous tones as either positive or negative. Behavioral results revealed a graded response pattern to the three intermediate tones, which was mirrored on the neural level. More specifically, parametric analyses OF BOLD responses to all five tones revealed a linear effect in bilateral anterior insula and SMA with lowest activation to the negative reference tone and highest activation to the positive negative tone. In addition, a cluster in the SMA showed a reverse-quadratic response, i.e., the strongest response for the most ambiguous tone. These findings suggest overlapping regions in the salience network that mediate valence generalization and decision-making under ambiguity, potentially underlying biased ambiguous cue interpretation. PMID:26057359

  6. Ultrasonically bonded value assembly

    NASA Technical Reports Server (NTRS)

    Salvinski, R. J. (inventor)

    1975-01-01

    A valve apparatus capable of maintaining a fluid-tight seal over a relatively long period of time by releasably bonding a valve member to its seat is described. The valve member is bonded or welded to the seat and then released by the application of the same energy to the bond joint. The valve member is held in place during the bonding by a clamping device. An appropriate force device can activate the opening and closing of the valve member. Various combinations of material for the valve member and valve seat can be utilized to provide an adequate sealing bond. Aluminum oxide, stainless steel, inconel, tungsten carbide as hard materials and copper, aluminum, titanium, silver, and gold as soft materials are suggested.

  7. Shape Bonding method

    NASA Technical Reports Server (NTRS)

    Pontius, James T. (Inventor)

    2010-01-01

    The present invention is directed to a method of bonding at least two surfaces together. The methods step of the present invention include applying a strip of adhesive to a first surface along a predefined outer boundary of a bond area and thereby defining a remaining open area there within. A second surface, or gusset plate, is affixed onto the adhesive before the adhesive cures. The strip of adhesive is allowed to cure and then a second amount of adhesive is applied to cover the remaining open area and substantially fill a void between said first and second surfaces about said bond area. A stencil may be used to precisely apply the strip of adhesive. When the strip cures, it acts as a dam to prevent overflow of the subsequent application of adhesive to undesired areas. The method results in a precise bond area free of undesired shapes and of a preferred profile which eliminate the drawbacks of the prior art bonds.

  8. Wood Bond Testing

    NASA Technical Reports Server (NTRS)

    1989-01-01

    A joint development program between Hartford Steam Boiler Inspection Technologies and The Weyerhaeuser Company resulted in an internal bond analyzer (IBA), a device which combines ultrasonics with acoustic emission testing techniques. It is actually a spinoff from a spinoff, stemming from a NASA Lewis invented acousto-ultrasonic technique that became a system for testing bond strength of composite materials. Hartford's parent company, Acoustic Emission Technology Corporation (AET) refined and commercialized the technology. The IBA builds on the original system and incorporates on-line process control systems. The IBA determines bond strength by measuring changes in pulsar ultrasonic waves injected into a board. Analysis of the wave determines the average internal bond strength for the panel. Results are displayed immediately. Using the system, a mill operator can adjust resin/wood proportion, reduce setup time and waste, produce internal bonds of a consistent quality and automatically mark deficient products.

  9. Magnetic-field Manipulation of Chemical Bonding in Artificial Molecules

    E-print Network

    Constantine Yannouleas; Uzi Landman

    2001-09-10

    The effect of orbital magnetism on the chemical bonding of lateral, two-dimensional artificial molecules is studied in the case of a 2e double quantum dot (artificial molecular hydrogen). It is found that a perpendicular magnetic field reduces the coupling (tunneling) between the individual dots and, for sufficiently high values, it leads to complete dissociation of the artificial molecule. The method used is building on Lowdin's work on Projection Operators in Quantum Chemistry; it is a spin-and-space unrestricted Hartree-Fock method in conjunction with the companion step of the restoration of spin and space symmetries via Projection Techniques (when such symmetries are broken). This method is able to describe the full range of couplings in two-dimensional double quantum dots, from the strong-coupling regime exhibiting delocalized molecular orbitals to the weak-coupling and dissociation regimes associated with a Generalized Valence Bond combination of atomic-type orbitals localized on the individual dots.

  10. The law of constant rejection. [chemical bonding in crystals

    NASA Technical Reports Server (NTRS)

    Philpotts, J. A.

    1978-01-01

    Improvements in analytical technique, study of multielement partitioning in natural systems, and improvements in ionic radius values have permitted construction of Onuma diagrams, in which the logarithm of partition coefficient is plotted versus ionic radius. The optimum radii, corresponding to crystallographic sites, do change in response to changes in major element composition for any particular mineral-type. In natural systems elements compete for sites rather than substituting for another element. It is proposed on empirical grounds, for equilibrium ionic bonding, that Onuma diagram curves for a particular lattice site are parabolic near optimum radius, linear elsewhere, parallel for different valences, and mirror images on opposite sides of optimum. Deviations may be due to overlapping peaks, liquid structure, polyvalence, bonding differences, contamination, kinetics, alteration, etc. However, dominant crystal-chemical control is indicated.

  11. A Time-Based Account of the Perception of Odor Objects and Valences

    PubMed Central

    Olofsson, Jonas K.; Bowman, Nicholas E.; Khatibi, Katherine; Gottfried, Jay A.

    2013-01-01

    Is human odor perception guided by memory or emotion? Object-centered accounts predict that recognition of unique odor qualities precedes valence decoding. Valence-centered accounts predict the opposite: that stimulus-driven valence responses precede and guide identification. In a speeded response time study, participants smelled paired odors, presented sequentially, and indicated whether the second odor in each pair belonged to the same category as the first (object evaluation task) or whether the second odor was more pleasant than the first (valence evaluation task). Object evaluation was faster and more accurate than valence evaluation. In a complementary experiment, participants performed an identification task, in which they indicated whether an odor matched the previously presented word label. Responses were quicker for odors preceded by semantically matching, rather than nonmatching, word labels, but results showed no evidence of interference from valence on nonmatching trials. These results are in accordance with object-centered accounts of odor perception. PMID:22961773

  12. Wafer-Level Thermocompression Bonds

    E-print Network

    Tsau, Christine H.

    Thermocompression bonding of gold is a promising technique for achieving low temperature, wafer-level bonding without the application of an electric field or complicated pre-bond cleaning procedure. The presence of a ductile ...

  13. An ecological valence theory of human color preference

    PubMed Central

    Palmer, Stephen E.; Schloss, Karen B.

    2010-01-01

    Color preference is an important aspect of visual experience, but little is known about why people in general like some colors more than others. Previous research suggested explanations based on biological adaptations [Hurlbert AC, Ling YL (2007) Curr Biol 17:623–625] and color-emotions [Ou L-C, Luo MR, Woodcock A, Wright A (2004) Color Res Appl 29:381–389]. In this article we articulate an ecological valence theory in which color preferences arise from people’s average affective responses to color-associated objects. An empirical test provides strong support for this theory: People like colors strongly associated with objects they like (e.g., blues with clear skies and clean water) and dislike colors strongly associated with objects they dislike (e.g., browns with feces and rotten food). Relative to alternative theories, the ecological valence theory both fits the data better (even with fewer free parameters) and provides a more plausible, comprehensive causal explanation of color preferences. PMID:20421475

  14. Intracranial markers of emotional valence processing and judgments in music.

    PubMed

    Omigie, Diana; Dellacherie, Delphine; Hasboun, Dominique; Clément, Sylvain; Baulac, Michel; Adam, Claude; Samson, Séverine

    2015-01-01

    The involvement of the amygdala and orbitofrontal cortex in the processing of valenced stimuli is well established. However, less is known about the extent to which activity in these regions reflects a stimulus' physical properties, the individual subjective experience it evokes, or both. We recorded cortical electrical activity from five epileptic patients implanted with depth electrodes for presurgical evaluation while they rated "consonant" and "dissonant" musical chords using a "pleasantness" scale. We compared the pattern of responses in the amygdala and orbitofrontal cortex when trials were sorted by pleasantness judgments relative to when they were sorted by the acoustic properties known to influence emotional reactions to musical chords. This revealed earlier differential activity in the amygdala in the physical properties-based, relative to in the judgment-based, analyses. Thus, our results demonstrate that the amygdala has, first and foremost, a high initial sensitivity to the physical properties of valenced stimuli. The finding that differentiations in the amygdala based on pleasantness ratings had a longer latency suggests that in this structure, mediation of emotional judgment follows accumulation of sensory information. This is in contrast to the orbitofrontal cortex where sensitivity to sensory information did not precede differentiation based on affective judgments. PMID:25496511

  15. +2 Valence Metal Concentrations in Lion Creek, Oakland, California

    NASA Astrophysics Data System (ADS)

    Vazquez, P.; Zedd, T.; Chagolla, R.; Dutton-Starbuck, M.; Negrete, A.; Jinham, M.; Lapota, M.

    2012-12-01

    Seven major creeks exist within the City of Oakland, California. These creeks all flow in the southwest direction from forested hills down through densely populated streets where they become susceptible to urban runoff. Lion Creek has been diverted to engineered channels and underground culverts and runs directly under our school (Roots International) before flowing into the San Leandro Bay. One branch of the creek begins near an abandoned sulfur mine. Previous studies have shown that extremely high levels of lead, arsenic and iron exist in this portion of the creek due to acid mine drainage. In this study +2 valence heavy metals concentration data was obtained from samples collected from a segment of the creek located approximately 2.8 miles downstream from the mine. Concentrations in samples collected at three different sites along this segment ranged between 50 ppb and 100 ppb. We hypothesize that these levels are related to the high concentration of +2 valence heavy metals at the mining site. To test this hypothesis, we have obtained samples from various locations along the roughly 3.75 miles of Lion Creek that are used to assess changes in heavy metals concentration levels from the mining site to the San Leandro Bay.

  16. Ligand-hole localization in oxides with unusual valence Fe

    PubMed Central

    Chen, Wei-Tin; Saito, Takashi; Hayashi, Naoaki; Takano, Mikio; Shimakawa, Yuichi

    2012-01-01

    Unusual high-valence states of iron are stabilized in a few oxides. A-site-ordered perovskite-structure oxides contain such iron cations and exhibit distinct electronic behaviors at low temperatures, e.g. charge disproportionation (4Fe4+ ? 2Fe3+ + 2Fe5+) in CaCu3Fe4O12 and intersite charge transfer (3Cu2+ + 4Fe3.75+ ? 3Cu3+ + 4Fe3+) in LaCu3Fe4O12. Here we report the synthesis of solid solutions of CaCu3Fe4O12 and LaCu3Fe4O12 and explain how the instabilities of their unusual valence states of iron are relieved. Although these behaviors look completely different from each other in simple ionic models, they can both be explained by the localization of ligand holes, which are produced by the strong hybridization of iron d and oxygen p orbitals in oxides. The localization behavior in the charge disproportionation of CaCu3Fe4O12 is regarded as charge ordering of the ligand holes, and that in the intersite charge transfer of LaCu3Fe4O12 is regarded as a Mott transition of the ligand holes. PMID:22690318

  17. Structure and bonding of [(SIPr)AgX] (X = Cl, Br, I and OTf).

    PubMed

    Wong, Valerie H L; White, Andrew J P; Hor, T S Andy; Hii, King Kuok Mimi

    2015-12-01

    A series of iso-structural complexes [(SIPr)AgX] (X = Cl, Br, I, OTf; SIPr = 1,3-bis(2,6-diisopropylphenyl)imidazolidene) were synthesised, including the first example of a N-heterocyclic carbene silver(i) complex containing an O-bound triflate. Bond Energy Dissociation and Natural Orbitals for Chemical Valence bond analyses (BEDA & ETS-NOCV) revealing a significant NHC ? M ?-back-donation, which influences the stability and sigma-donicity of these complexes. PMID:26489888

  18. The essential role of charge-shift bonding in hypervalent prototype XeF2

    NASA Astrophysics Data System (ADS)

    Braïda, Benoît; Hiberty, Philippe C.

    2013-05-01

    Hypervalency in XeF2 and isoelectronic complexes is generally understood in terms of the Rundle-Pimentel model (which invokes a three-centre/four-electron molecular system) or its valence bond version as proposed by Coulson, which replaced the old expanded octet model of Pauling. However, the Rundle-Pimentel model is not always successful in describing such complexes and has been shown to be oversimplified. Here using ab initio valence bond theory coupled to quantum Monte Carlo methods, we show that the Rundle-Pimentel model is insufficient by itself in accounting for the great stability of XeF2, and that charge-shift bonding, wherein the large covalent-ionic interaction energy has the dominant role, is a major stabilizing factor. The energetic contribution of the old expanded octet model is also quantified and shown to be marginal. Generalizing to isoelectronic systems such as ClF3, SF4, PCl5 and others, it is suggested that charge-shift bonding is necessary, in association with the Rundle-Pimentel model, for hypervalent analogues of XeF2 to be strongly bonded.

  19. Optimized conditions for imaging the effects of bonding charge density in electron microscopy.

    PubMed

    Ciston, J; Kim, J S; Haigh, S J; Kirkland, A I; Marks, L D

    2011-06-01

    We report on the observability of valence bonding effects in aberration-corrected high resolution electron microscopy (HREM) images along the [010] projection of the mineral Forsterite (Mg?SiO?). We have also performed exit wave restorations using simulated noisy images and have determined that both the intensities of individual images and the modulus of the restored complex exit wave are most sensitive to bonding effects at a level of 25% for moderately thick samples of 20-25 nm. This relatively large thickness is due to dynamical amplification of bonding contrast arising from partial de-channeling of 1s states. Simulations also suggest that bonding contrast is similarly high for an un-corrected conventional electron microscope, implying an experimental limitation of signal to noise ratio rather than spatial resolution. PMID:21193268

  20. Detecting Defective Solder Bonds

    NASA Technical Reports Server (NTRS)

    Paulson, R.; Barney, J.; Decker, H. J.

    1984-01-01

    Method is noncontact and nondestructive. Technique detects solder bonds in solar array of other large circuit board, using thermal-imaging camera. Board placed between heat lamp and camera. Poor joints indiated by "cold" spots on the infrared image.

  1. Gold Thermocompression Wafer Bonding

    E-print Network

    Spearing, S. Mark

    Thermocompression bonding of gold is a promising technique for the fabrication and packaging microelectronic and MEMS devices. The use of a gold interlayer and moderate temperatures and pressures results in a hermetic, ...

  2. Characterization of anodic bonding

    E-print Network

    Tudryn, Carissa Debra, 1978-

    2004-01-01

    Anodic bonding is a common process used in MicroElectroMechanical Systems (MEMS) device fabrication and packaging. Polycrystalline chemical vapor deposited (CVD) silicon carbide (SiC) is emerging as a new MEMS device and ...

  3. Water's Hydrogen Bond Strength

    E-print Network

    Martin Chaplin

    2007-06-10

    Water is necessary both for the evolution of life and its continuance. It possesses particular properties that cannot be found in other materials and that are required for life-giving processes. These properties are brought about by the hydrogen bonded environment particularly evident in liquid water. Each liquid water molecule is involved in about four hydrogen bonds with strengths considerably less than covalent bonds but considerably greater than the natural thermal energy. These hydrogen bonds are roughly tetrahedrally arranged such that when strongly formed the local clustering expands, decreasing the density. Such low density structuring naturally occurs at low and supercooled temperatures and gives rise to many physical and chemical properties that evidence the particular uniqueness of liquid water. If aqueous hydrogen bonds were actually somewhat stronger then water would behave similar to a glass, whereas if they were weaker then water would be a gas and only exist as a liquid at sub-zero temperatures. The overall conclusion of this investigation is that water's hydrogen bond strength is poised centrally within a narrow window of its suitability for life.

  4. 30 CFR 281.33 - Bonds and bonding requirements.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...Resources 2 2011-07-01 2011-07-01 false Bonds and bonding requirements. 281.33 Section 281.33 Mineral Resources...CONTINENTAL SHELF Financial Considerations § 281.33 Bonds and bonding requirements. (a) When the leasing notice...

  5. 30 CFR 281.33 - Bonds and bonding requirements.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...Resources 2 2010-07-01 2010-07-01 false Bonds and bonding requirements. 281.33 Section 281.33 Mineral Resources...CONTINENTAL SHELF Financial Considerations § 281.33 Bonds and bonding requirements. (a) When the leasing notice...

  6. Valence fluctuations and electric reconstruction in the extended Anderson model on the two-dimensional Penrose lattice

    NASA Astrophysics Data System (ADS)

    Takemura, Shinichi; Takemori, Nayuta; Koga, Akihisa

    2015-04-01

    We study the extended Anderson model on the two-dimensional Penrose lattice, combining the real-space dynamical mean-field theory with the noncrossing approximation. It is found that the Coulomb repulsion between localized and conduction electrons does not induce a valence transition, but the crossover between the Kondo and mixed valence states is in contrast to the conventional periodic system. In the mixed-valence region close to the crossover, nontrivial valence distributions appear, characteristic of the Penrose lattice, demonstrating that the mixed-valence state coexists with local Kondo states in certain sites. The electric reconstruction in the mixed valence region is also addressed.

  7. Formation of unprecedented actinidecarbon triple bonds in uranium methylidyne molecules

    PubMed Central

    Lyon, Jonathan T.; Hu, Han-Shi; Andrews, Lester; Li, Jun

    2007-01-01

    Chemistry of the actinide elements represents a challenging yet vital scientific frontier. Development of actinide chemistry requires fundamental understanding of the relative roles of actinide valence-region orbitals and the nature of their chemical bonding. We report here an experimental and theoretical investigation of the uranium methylidyne molecules X3UCH (X = F, Cl, Br), F2ClUCH, and F3UCF formed through reactions of laser-ablated uranium atoms and trihalomethanes or carbon tetrafluoride in excess argon. By using matrix infrared spectroscopy and relativistic quantum chemistry calculations, we have shown that these actinide complexes possess relatively strong UC triple bonds between the U 6d-5f hybrid orbitals and carbon 2s-2p orbitals. Electron-withdrawing ligands are critical in stabilizing the U(VI) oxidation state and sustaining the formation of uranium multiple bonds. These unique UC-bearing molecules are examples of the long-sought actinide-alkylidynes. This discovery opens the door to the rational synthesis of triple-bonded actinidecarbon compounds. PMID:18024591

  8. Inter-Valence-Subband/Conduction-Band-Transport IR Detectors

    NASA Technical Reports Server (NTRS)

    Ting, David; Gunapala, Sarath; Bandara, Sumith

    2004-01-01

    Infrared (IR) detectors characterized by a combination of (1) high-quantum-efficiency photoexcitation of inter-valence-subband transitions of charge carriers and (2) high-mobility conduction- band transport of the thus-excited charge carriers have been proposed in an effort to develop focal-plane arrays of such devices for infrared imaging. Like many prior quantum-well infrared photodetectors (QWIPs), the proposed devices would be made from semiconductor heterostructures. In order to obtain the combination of characteristics mentioned above, the proposed devices would be designed and fabricated in novel InAs/GaSb superlattice configurations that would exploit a phenomenon known in the semiconductor art as type-II broken-gap band offset.

  9. Incautiously Optimistic: Positively-Valenced Cognitive Avoidance in Adult ADHD

    PubMed Central

    Knouse, Laura E.; Mitchell, John T.

    2015-01-01

    Clinicians who conduct cognitive-behavioral therapy (CBT) targeting attention-deficit/hyperactivity disorder (ADHD) in adulthood have noted that their patients sometimes verbalize overly positive automatic thoughts and set overly optimistic goals. These cognitions are frequently related to failure to engage in compensatory behavioral strategies emphasized in CBT. In this paper, we offer a functional analysis of this problematic pattern, positively-valenced cognitive avoidance, and suggest methods for addressing it within CBT for adult ADHD. We propose that maladaptive positive cognitions function to relieve aversive emotions in the short-term and are therefore negatively reinforced but that, in the long-term, they are associated with decreased likelihood of active coping and increased patterns of behavioral avoidance. Drawing on techniques from Behavioral Activation (BA), we offer a case example to illustrate these concepts and describe step-by-step methods for clinicians to help patients recognize avoidant patterns and engage in more active coping. PMID:25908901

  10. Ab initio effective interactions for s d -shell valence nucleons

    NASA Astrophysics Data System (ADS)

    Dikmen, E.; Lisetskiy, A. F.; Barrett, B. R.; Maris, P.; Shirokov, A. M.; Vary, J. P.

    2015-06-01

    We perform ab initio no-core shell-model calculations for A =18 and 19 nuclei in a 4 ? ? , or Nmax=4 , model space by using the effective JISP16 and chiral N3LO nucleon-nucleon potentials and transform the many-body effective Hamiltonians into the 0 ? ? model space to construct the A -body effective Hamiltonians in the s d shell. We separate the A -body effective Hamiltonians with A =18 and A =19 into inert core, one-, and two-body components. Then we use these core, one-, and two-body components to perform standard shell-model calculations for the A =18 and A =19 systems with valence nucleons restricted to the s d shell. Finally, we compare the standard shell-model results in the 0 ? ? model space with the exact no-core shell-model results in the 4 ? ? model space for the A =18 and A =19 systems and find good agreement.

  11. Valence-shell photoionization of chlorine-like Ar$^{+}$ ions

    E-print Network

    Covington, A M; Covington, I R; Hinojosa, G; Shirley, C A; Álvarez, I; Cisneros, C; Dominguez-Lopez, I; Sant'Anna, M M; Schlachter, A S; Ballance, C P; McLaughlin, B M

    2012-01-01

    Absolute cross-section measurements for valence-shell photoionization of Ar$^{+}$ ions are reported for photon energies ranging from 27.4 eV to 60.0 eV. The data, taken by merging beams of ions and synchrotron radiation at a photon energy resolution of 10 meV, indicate that the primary ion beam was a statistically weighted mixture of the $^2P^o_{3/2}$ ground state and the $^2P^o_{1/2}$ metastable state of Ar$^{+}$. Photoionization of this C$\\ell$-like ion is characterized by multiple Rydberg series of autoionizing resonances superimposed on a direct photoionization continuum. Observed resonance lineshapes indicate interference between indirect and direct photoionization channels. Resonance features are spectroscopically assigned and their energies and quantum defects are tabulated. The measurements are satisfactorily reproduced by theoretical calculations based on an intermediate coupling semi-relativistic Breit-Pauli approximation.

  12. Overlap Valence Quarks on a Twisted Mass Sea

    E-print Network

    Krzysztof Cichy; Vincent Drach; Elena Garcia-Ramos; Gregorio Herdoiza; Karl Jansen

    2010-11-02

    We present the results of an investigation of a mixed action approach of overlap valence and maximally twisted mass sea quarks. Employing a particular matching condition on the pion mass, we analyze the continuum limit scaling of the pion decay constant and the role of chiral zero modes of the overlap operator in this process. We employ gauge field configurations generated by the European Twisted Mass Collaboration with linear lattice size $L$ ranging from 1.3 to 1.9 fm. The continuum limit is taken at a fixed value of $L=1.3$ fm, employing three values of the lattice spacing and two values of the pion mass constructed from sea quarks only.

  13. Valence-to-Core X-Ray Emission Spectroscopy as a Tool for Investigation of Organometallic Systems

    NASA Astrophysics Data System (ADS)

    Smolentsev, Grigory; Soldatov, Alexander V.; Messinger, Johannes; Merz, Katrin; Weyhermuller, Thomas; Pushkar, Yulia; Yano, Junko; Yachandra, Vittal K.; Glatzel, Pieter

    2007-02-01

    The fine structure of X-ray emission satellite lines just below the Fermi level (K? satellite lines), which arise from transitions from valence bands to the core 1s level in 3d transition metals, is a developing technique and the full potential is not well known or understood. On the basis of DFT calculations for some theoretical model complexes that are relevant in bioinorganic chemistry we show that the method can be used to distinguish bonds of the metal atom with different light atoms O/N/C even if the coordination geometries are exactly the same, which is not possible using EXAFS or XANES spectroscopy. Moreover the method is sensitive to the bonding of H to the ligands, which allows to discriminate, for example, between OH- and water near the metal. Both these aspects clearly demonstrate that the K? satellite lines yield information that is complementary to traditional X-ray absorption spectroscopy. Good agreement between theoretical and experimental spectra for a complex Mn system was also achieved.

  14. Nanostructured high valence silver oxide produced by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Dellasega, D.; Facibeni, A.; Di Fonzo, F.; Russo, V.; Conti, C.; Ducati, C.; Casari, C. S.; Li Bassi, A.; Bottani, C. E.

    2009-03-01

    Among silver oxides, Ag 4O 4, i.e. high valence Ag(I)Ag(III) oxide, is interesting for applications in high energy batteries and for the development of antimicrobial coatings. We here show that ns UV pulsed laser deposition (PLD) in an oxygen containing atmosphere allows the synthesis of pure Ag 4O 4 nanocrystalline thin films, permitting at the same time to control the morphology of the material at the sub-micrometer scale. Ag 4O 4 films with a crystalline domain size of the order of tens of nm can be deposited provided the deposition pressure is above a threshold (roughly 4 Pa pure O 2 or 20 Pa synthetic air). The formation of this particular high valence silver oxide is explained in terms of the reactions occurring during the expansion of the ablated species in the reactive atmosphere. In particular, expansion of the PLD plasma plume is accompanied by formation of low stability Ag-O dimers and atomic oxygen, providing reactive species at the substrate where the film grows. Evidence of reactive collisions in the expanding ablation plume is obtained by analysis of the plume visible shape in inert and reactive atmospheres. In addition, we show how the dimensionless deposition parameter L, relating the target-to-substrate distance to the ablation plume maximum expansion length, can be used to classify different growth regimes. It is thus possible to vary the stoichiometry and the morphology of the films, from compact and columnar to foam-like, by controlling both the gas pressure and the target-to-substrate distance.

  15. A density functional for core-valence correlation energy.

    PubMed

    Ranasinghe, Duminda S; Frisch, Michael J; Petersson, George A

    2015-12-01

    A density functional, ?CV-DFT(?c, ?v), describing the core-valence correlation energy has been constructed as a linear combination of ?LY P (corr)(?c), ?V WN5 (corr)(?c, ?v), ?PBE (corr)(?c, ?v), ?Slater (ex)(?c, ?v), ?HCTH (ex)(?c, ?v), ?HF (ex)(?c, ?v), and FCV-DFTNi,Zi, a function of the nuclear charges. This functional, with 6 adjustable parameters, reproduces (±0.27 kcal/mol rms error) a benchmark set of 194 chemical energy changes including 9 electron affinities, 18 ionization potentials, and 167 total atomization energies covering the first- and second-rows of the periodic table. This is almost twice the rms error (±0.16 kcal/mol) obtained with CCSD(T)/MTsmall calculations, but less than half the rms error (±0.65 kcal/mol) obtained with MP2/GTlargeXP calculations, and somewhat smaller than the rms error (±0.39 kcal/mol) obtained with CCSD/MTsmall calculations. The largest positive and negative errors from ?CV-DFT(?c, ?v) were 0.88 and -0.75 kcal/mol with the set of 194 core-valence energy changes ranging from +3.76 kcal/mol for the total atomization energy of propyne to -9.05 kcal/mol for the double ionization of Mg. Evaluation of the ?CV-DFT(?c, ?v) functional requires less time than a single SCF iteration, and the accuracy is adequate for any model chemistry based on the CCSD(T) level of theory. PMID:26646873

  16. Effects of Emotional Valence and Arousal on Recollective and Nonrecollective Recall

    ERIC Educational Resources Information Center

    Gomes, Carlos F. A.; Brainerd, Charles J.; Stein, Lilian M.

    2013-01-01

    The authors investigated the effects of valence and arousal on memory using a dual-process model that quantifies recollective and nonrecollective components of recall without relying on metacognitive judgments to separate them. The results showed that valenced words increased reconstruction (a component of nonrecollective retrieval) relative to…

  17. Mapping the Valence States of Transition-Metal Elements Using Energy-Filtered Transmission Electron Microscopy

    E-print Network

    Wang, Zhong L.

    forming a compound. Transition- and rare-earth-metal elements with mixed valences are unique determination.2-5 In EELS, the L ionization edges of transition-metal, rare-earth, and actinide compounds of transition- and rare-earth-metal elements. EELS analysis of the valence state is carried out in reference

  18. Building the Valency Lexicon of Arabic Verbs Viktor Bielicky Otakar Smrz

    E-print Network

    Cerveny, Vlastislav

    verbs using a morphologically and syntactically annotated corpus, the Prague Arabic Dependency TreebankBuilding the Valency Lexicon of Arabic Verbs Viktor Bielick´y Otakar Smrz Institute of Formal Republic padt@ufal.mff.cuni.cz Abstract This paper describes the building of a valency lexicon of Arabic

  19. Frontal brain electrical activity (EEG) distinguishes valence and intensity of musical emotions

    E-print Network

    Trainor, Laurel J.

    Frontal brain electrical activity (EEG) distinguishes valence and intensity of musical emotions activity distinguished emotions induced by musical excerpts which were known to vary in affective valence circuits in the brain have for the most part ignored emotions arising from musical stimuli. Yet music

  20. Yb valence states in YbC2: a HERFD-XANES spectroscopic investigation.

    PubMed

    Link, Pascal; Glatzel, Pieter; Kvashnina, Kristina; Smith, Ronald I; Ruschewitz, Uwe

    2011-06-20

    The valence state of Yb in YbC(2) was analyzed using high-energy-resolution fluorescence detection (HERFD) X-ray absorption near-edge structure (XANES) spectroscopy and time-of-flight neutron powder diffraction to clarify a controversy in the literature. The unit cell volume of YbC(2) suggests a mixed Yb valence, which was formerly determined to be 2.8 by magnetization measurements and paramagnetic neutron scattering techniques. However, the nature of the intermediate valence was not clearly established. Both homogeneous and heterogeneous mixed valences were assumed in different publications. The temperature-dependent behavior of the valence state was only predicted, albeit not explicitly studied. In this work, the valence state of Yb in YbC(2) is, therefore, investigated thoroughly by HERFD-XANES spectroscopy at low and high temperatures. Our measurements result in an average Yb valence of 2.81 that is temperature-independent from 15 to 1123 K. These findings are confirmed by neutron powder diffraction experiments, which reveal a constant C-C distance of 128.7(9) pm in a temperature range from 5 to 100 K. A significant temperature dependence of the Yb valence state in YbC(2) can, therefore, be excluded by our experimental results. PMID:21612187

  1. EELS analysis of cation valence states and oxygen vacancies in magnetic oxides

    E-print Network

    Wang, Zhong L.

    EELS analysis of cation valence states and oxygen vacancies in magnetic oxides Z.L. Wang*, J.S. Yin with mixed valences of transition elements. Electron energy- loss spectroscopy (EELS) in the transmission of practical importance. This paper reports our current progress in applying EELS for quantitative

  2. Walenty: Towards a comprehensive valence dictionary of Polish Adam Przepirkowski, Elzbieta Hajnicz, Agnieszka Patejuk,

    E-print Network

    , a comprehensive valence dictionary of Polish devel- oped at the Institute of Computer Science, Polish Academy of Sciences (ICS PAS).1 The dictionary is meant to be both human- and machine-readable; in particularWalenty: Towards a comprehensive valence dictionary of Polish Adam Przepiórkowski, Elzbieta Hajnicz

  3. Excited states theory for optimized orbitals and valence optimized orbitals coupled-cluster doubles models

    E-print Network

    Krylov, Anna I.

    Excited states theory for optimized orbitals and valence optimized orbitals coupled-cluster doubles May 2000; accepted 31 July 2000 We introduce an excited state theory for the optimized orbital coupled cluster doubles OO-CCD and valence optimized orbital coupled cluster doubles VOO-CCD models. The equations

  4. Valence Focus and Self-Esteem Lability: Reacting to Hedonic Cues in the Social Environment

    E-print Network

    Barrett, Lisa Feldman

    Valence Focus and Self-Esteem Lability: Reacting to Hedonic Cues in the Social Environment Paula R experience) demonstrated greater self-esteem lability (i.e., larger changes in self-esteem) to pleasant. Keywords: valence focus, emotion, self-esteem lability, experience sampling, social interactions Hedonic

  5. Identifying Facial Emotions: Valence Specific Effects and an Exploration of the Effects of Viewer Gender

    ERIC Educational Resources Information Center

    Jansari, Ashok; Rodway, Paul; Goncalves, Salvador

    2011-01-01

    The valence hypothesis suggests that the right hemisphere is specialised for negative emotions and the left hemisphere is specialised for positive emotions (Silberman & Weingartner, 1986). It is unclear to what extent valence-specific effects in facial emotion perception depend upon the gender of the perceiver. To explore this question 46…

  6. VALENCE STATES OF SULFUR IN POLLUTION SAMPLES BY X-RAY ANALYSIS

    EPA Science Inventory

    A flat single crystal spectrometer was configured to measure the valence band x-ray spectra of various forms of sulfur in air pollutants. While most different valence states showed differences in the structure of the K sub beta band, particular emphasis was placed on distinguishi...

  7. The computation of C-C and N-N bond dissociation energies for singly, doubly, and triply bonded systems

    NASA Technical Reports Server (NTRS)

    Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.; Taylor, Peter R.

    1991-01-01

    The bond dissociation energies (De) of C2H2, C2H4, C2H6, N2, N2H2, and N2H4 are studied at various levels of correlation treatment. The convergence of De with respect to the one-particle basis is studied at the single-reference modified coupled-pair-functional (MCPF)level. At all levels of correlation treatment, the errors in the bond dissociation energies increase with the degree of multiple bond character. The multireference configuration-interaction (MRCI) De values, corrected for an estimate of higher excitations, are in excellent agreement with those determined using the size-extensive averaged-coupled-pair-functional (ACPF) method. The full-valence complete-active-space self-consistent-field (CASSCF)/MRCI calculations are reproduced very well by MRCI calculations based on a CASSCF calculation that includes in the active space only those electrons involved in the C-C or N-N bonds.

  8. Comparative study of the Pros and Cons of Programming languages Java, Scala, C++, Haskell, VB .NET, AspectJ, Perl, Ruby, PHP & Scheme - a Team 11 COMP6411-S10 Term Report

    E-print Network

    Dwarampudi, Venkatreddy; Shah, Jivitesh; Sebastian, Nikhil Joseph; Kanigicharla, Nitin

    2010-01-01

    With the advent of numerous languages it is difficult to realize the edge of one language in a particular scope over another one. We are making an effort, realizing these few issues and comparing some main stream languages like Java, Scala, C++, Haskell, VB .NET, AspectJ, Perl, Ruby, PHP and Scheme keeping in mind some core issues in program development.

  9. PLEASE CITE AS: Sanders, V.B. 2013. Charophyte management in reservoir fisheries on a Texas military installation. Biodiversity Stewardship Report Series. No. BS13.02. Biodiversity Stewardship Lab, Texas

    E-print Network

    Packard, Jane M.

    PLEASE CITE AS: Sanders, V.B. 2013. Charophyte management in reservoir fisheries on a Texas/publications/BS13.02.pdf CHAROPHYTE MANAGEMENT IN RESERVOIR FISHERIES ON A TEXAS MILITARY INSTALLATION Written in the style of Lake and Reservoir Management #12;ii CHAROPHYTE MANAGEMENT IN RESERVOIR FISHERIES

  10. The following changes to the EIA in the Yucca Mountain Rule Docket (A-95-12, V-B-2) were made in this document to correct typographical and other minor errors in the text.

    E-print Network

    The following changes to the EIA in the Yucca Mountain Rule Docket (A-95-12, V-B-2) were made Radiation Protection Standards for Yucca Mountain, Nevada" Pg. ii Item 4.1 changed to read, "Performance Standards with Expected Values of TSPA-SR Calculations for a Repository at Yucca Mountain for Nominal

  11. Identifying words that emerge into consciousness: Effects of word valence and unconscious previewing.

    PubMed

    Prioli, Simone C; Kahan, Todd A

    2015-09-01

    Words with negative valence capture attention and this increase in attentional resources typically enhances perceptual processing. Recently, data using continuous flash suppression (CFS) appear to contradict this. In prior research when Chinese words were unconsciously presented in CFS and contrast was raised until the word was identified, RTs to identify words with negative valence were slower than RTs to words with neutral valence. This result might be limited to situations where a logographic writing system is used and could reflect a type of cognitive aftereffect where previewing the word causes habituation. Data (N=60) indicate that results generalize from a logographic (Chinese) to an orthographic writing system (English). In addition, when words were previewed in CFS RTs were slowed for words with negative valence relative to words with neutral valence and this was reversed when words were shown binocularly. Implications for theories of unconscious word processing and cognitive aftereffects are discussed. PMID:25982055

  12. Emotions and language about motion: Differentiating affective dominance with syntax from valence with semantics.

    PubMed

    Freddi, Sébastien; Esteban, José; Dru, Vincent

    2015-12-15

    Motion as encoded in linguistic cues is used to differentiate affective valence and dominance. Participants were invited to rate their affective responses to different words along valence and dominance scales. The words were nouns describing static cues and verbs describing motion, connected to DOWN/UP and Avoidance/Approach cues. The results of three studies showed that valence and dominance could be differentiated through syntax and semantics of motion. On one hand, dominance feelings, compared to valence ones, are particularly influenced by motion encoded in syntactic classes (verbs vs. nouns). On the other hand, valence feelings, compared to dominance ones, are influenced by a semantics of motion through DOWN/UP and Avoidance/Approach cues, considered as polarities. A polarity correspondence effect is proposed to explain these results. PMID:26497068

  13. Adhesive for composite bonding

    SciTech Connect

    Lyon, R.E.; Walkup, C.M.; Matthews, J.T.

    1989-11-27

    Adhesive bonding is a viable option for structural joining of carbon fiber reinforced epoxy composites. Recent examples from laboratory programs include a composite tube joined to a flared composite collar (skirt) to provide a means for mechanical attachment. Another application involves adhesive bonding of a close-tolerance composite ring to the inside of a tapered, cylindrical composite penetrator case in order to provide a load bearing surface for prestressing the internal package. The adhesive bond in both of these applications is the critical load bearing component and must sustain large shearing stresses in order to maintain the structural integrity and viability of the part. The ideal adhesive would be a low viscosity (<10 poise) liquid with a long pot life, good wetting characteristics and high ultimate shear strength when cured at moderate (<50{degree}C) temperature. An adhesive with these characteristics would allow for the production of defect-free bonds by capillary wetting or squeezing flow of the adhesive into the narrow (.005{double prime}) annular space between the concentric composite parts. Since adhesives possessing these characteristics were not known to be available commercially, candidate materials were evaluated for this application. In this paper we present bond shear strength data and selected physical properties for some epoxy adhesive formulations. 7 refs., 5 figs., 2 tabs.

  14. Strength of Chemical Bonds

    NASA Technical Reports Server (NTRS)

    Christian, Jerry D.

    1973-01-01

    Students are not generally made aware of the extraordinary magnitude of the strengths of chemical bonds in terms of the forces required to pull them apart. Molecular bonds are usually considered in terms of the energies required to break them, and we are not astonished at the values encountered. For example, the Cl2 bond energy, 57.00 kcal/mole, amounts to only 9.46 x 10(sup -20) cal/molecule, a very small amount of energy, indeed, and impossible to measure directly. However, the forces involved in realizing the energy when breaking the bond operate over a very small distance, only 2.94 A, and, thus, f(sub ave) approx. equals De/(r - r(sub e)) must be very large. The forces involved in dissociating the molecule are discussed in the following. In consideration of average forces, the molecule shall be assumed arbitrarily to be dissociated when the atoms are far enough separated so that the potential, relative to that of the infinitely separated atoms, is reduced by 99.5% from the potential of the molecule at the equilibrium bond length (r(sub e)) for Cl2 of 1.988 A this occurs at 4.928 A.

  15. ?-Hole aerogen bonding interactions.

    PubMed

    Bauzá, Antonio; Frontera, Antonio

    2015-09-23

    In this manuscript we combine high level ab initio calculations (RI-MP2/aug-cc-pVTZ) and the analysis of several crystal structures to demonstrate the existence of ?-hole aerogen bonding interactions in Xe(iv) compounds. The ability of XeF4 and Xe(OMe)4 to interact with electron rich molecules is rationalized using several computational tools, including molecular electrostatic potential surfaces, energetic and geometric features of the complexes and "atoms in molecules" (AIM) and Natural Bond Orbital (NBO) analyses. We have found support for the ?-hole interaction involving the xenon atom from the solid state architecture of several X-ray structures retrieved from the crystal structural depot. Particularly, ?-hole aerogen bonding interactions are quite common in the solid state of Xe(iv) compounds. PMID:26252726

  16. Factors affecting the relation between stretching frequencies and bond lengths. Diatomic and polyatomic species without adjustable fitting parameters.

    PubMed

    Zavitsas, Andreas A

    2015-12-01

    In 76 sets of similar type bonds in species A2, AB, AB2, AB3, and AB4 the stretching frequency, ?, is related to the bond length, r, by ?=a/(r?(1/2))-b, where ? is the reduced mass. The sets treated include all ground states for which spectroscopic date were found for stable molecules, free radicals, carbenes and other species with unsatisfied valences, both ionic and covalent. The linear correlation coefficients of each set are always greater than 0.998. The slopes a and intercepts b are defined by the data of each set and vary widely. They become congruent, but not exactly identical, when a is multiplied by the square root of the mean value of the number of electrons in the valence shell of the two bonded atoms, the electrons that become joined in the molecular orbitals formed upon bonding. No adjustable parameters are used. The number of bonds treated, over 300, is not as important as the fact that all species found were treated. The aim is not to add yet another parametric correlation to the many extant, but to better understand the relation between these two fundamental properties of chemical bonds. PMID:26162344

  17. Insurance and bonding

    SciTech Connect

    Katzman, M.T.

    1989-01-01

    Societal risk management in industrial democracies relies upon mechanisms of prior restraint rather than on responsibility for the consequence of accidents. The evolution of risk management from one based upon private, voluntary standard of risk management from one based upon private, voluntary standard setting to one based upon restraint is reviewed. While insurance and bonding historically have played a major role in private management of catastrophic risks, their role has been underutilized in the current, restraint-based mode. The conditions under the insurance and bonding that can serve as a tool for risk regulation are illustrated in the arena of toxic pollution risks. 45 refs., 1 fig.

  18. Qualifying Energy Conservation Bonds 

    E-print Network

    Briggs, J.

    2013-01-01

    ) of the interest cost associated with the transaction • Typical effective interest rates anywhere from 0%-2% depending on credit strength • Bond issuance or private placement is acceptable 2 What are QECB’s ESL-KT-13-12-39 CATEE 2013: Clean Air Through Energy... Bonds (QECB’s) CATEE Conference December 18, 2013 ESL-KT-13-12-39 CATEE 2013: Clean Air Through Energy Efficiency Conference, San Antonio, Texas Dec. 16-18 • Originally authorized by the Energy Improvement & Extension Act of 2008 • American Recovery...

  19. Bond dissociation energies and bond orders for some astrophysical molecules

    NASA Astrophysics Data System (ADS)

    Reddy, R. R.; Viswanath, R.

    1989-06-01

    The bond dissociation energies for various astrophysically important diatomic molecules have been determined using a formula in which bond dissociation energies are the sum of the geometric average of the component bond energies and 32.058 times the Pauling electronegativity difference. Bond orders are estimated according to the formula of Reddy et al. (1985, 1987). The results confirm the definition of bond order given by Politzer (1969). The estimated bond energies are found to agree well with previous values and to give an error of 8 percent, as compared to the error of 26.8 percent found using Pauling's (1960) equation.

  20. Dangling bonds and vacancies in germanium

    NASA Astrophysics Data System (ADS)

    Weber, J. R.; Janotti, A.; Van de Walle, C. G.

    2013-01-01

    The quest for metal-oxide-semiconductor field-effect transistors (MOSFETs) with higher carrier mobility has triggered great interest in germanium-based MOSFETs. Still, the performance of germanium-based devices lags significantly behind that of their silicon counterparts, possibly due to the presence of defects such as dangling bonds (DBs) and vacancies. Using screened hybrid functional calculations we investigate the role of DBs and vacancies in germanium. We find that the DB defect in germanium has no levels in the band gap; it acts as a negatively charged acceptor with the (0/-1) transition level below the valence-band maximum (VBM). This explains the absence of electron-spin-resonance observations of DBs in germanium. The vacancy in germanium has a much lower formation energy than the vacancy in silicon and is stable in a number of charge states, depending on the position of the Fermi level. We find the (0/-1) and (-1/-2) transition levels at 0.16 and 0.38 eV above the VBM; the spacing of these levels is explained based on the strength of intraorbital repulsion. We compare these results with calculations for silicon, as well as with available experimental data.

  1. Valence Scaling of Dynamic Facial Expressions Is Altered in High-Functioning Subjects with Autism Spectrum Disorders: An FMRI Study

    ERIC Educational Resources Information Center

    Rahko, Jukka S.; Paakki, Jyri-Johan; Starck, Tuomo H.; Nikkinen, Juha; Pauls, David L.; Katsyri, Jari V.; Jansson-Verkasalo, Eira M.; Carter, Alice S.; Hurtig, Tuula M.; Mattila, Marja-Leena; Jussila, Katja K.; Remes, Jukka J.; Kuusikko-Gauffin, Sanna A.; Sams, Mikko E.; Bolte, Sven; Ebeling, Hanna E.; Moilanen, Irma K.; Tervonen, Osmo; Kiviniemi, Vesa

    2012-01-01

    FMRI was performed with the dynamic facial expressions fear and happiness. This was done to detect differences in valence processing between 25 subjects with autism spectrum disorders (ASDs) and 27 typically developing controls. Valence scaling was abnormal in ASDs. Positive valence induces lower deactivation and abnormally strong activity in ASD…

  2. Photochemical tissue bonding

    DOEpatents

    Redmond, Robert W. (Brookline, MA); Kochevar, Irene E. (Charlestown, MA)

    2012-01-10

    Photochemical tissue bonding methods include the application of a photosensitizer to a tissue and/or tissue graft, followed by irradiation with electromagnetic energy to produce a tissue seal. The methods are useful for tissue adhesion, such as in wound closure, tissue grafting, skin grafting, musculoskeletal tissue repair, ligament or tendon repair and corneal repair.

  3. Dialogic Bonds and Boundaries.

    ERIC Educational Resources Information Center

    Khawaja, Mabel

    A study of literature cannot be divorced from cultural contexts, nor can it ignore the humanist vision in interpreting literary texts. To discover dialogic bonds and boundaries between the reader and the text, or the writer and the audience, English classes should have two objectives: (1) to explore the diversity of perspectives, and (2) to relate…

  4. Flax Fiber - Interfacial Bonding

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Measured flax fiber physical and chemical properties potentially impact bonding and thus stress transfer between the matrix and fiber within composites. These first attempts at correlating flax fiber quality and biofiber composites contain the initial steps towards identifying key flax fiber charac...

  5. Selective Permeability Jackie Bonds

    E-print Network

    Alford, Simon

    ;Selective Permeability ­ What · Selective permeability means that the cell membrane has some control overSelective Permeability Jackie Bonds January 23, 2012 Neus 586 Monday, January 30, 2012 #12 what can cross it, so that only certain molecules either enter or leave the cell. Monday, January 30

  6. Heavy-Fermion Valence-Bond Liquids in Ultracold Atoms: Cooperation of the Kondo Effect and Geometric Frustration

    NASA Astrophysics Data System (ADS)

    Isaev, L.; Rey, A. M.

    2015-10-01

    We analyze a microscopic mechanism behind the coexistence of a heavy Fermi liquid and geometric frustration in Kondo lattices. We consider a geometrically frustrated periodic Anderson model and demonstrate how orbital fluctuations lead to a Kondo-screened phase in the limit of extreme strong frustration when only local singlet states participate in the low-energy physics. We also propose a setup to realize and study this exotic state with S U (3 ) -symmetric alkaline-earth cold atoms.

  7. PHYSICAL REVIEW B 84, 174427 (2011) Properties of resonating-valence-bond spin liquids and critical dimer models

    E-print Network

    Henley, Christopher L.

    2011-01-01

    November 2011) We use Monte Carlo simulations to study properties of Anderson's resonating of frustrated magnetism, where they were first considered.4 In studies of specific Hamiltonians, RVB states can

  8. Nel and valence-bond crystal order on a distorted kagome lattice: Implications for Zn-paratacamite

    E-print Network

    Sørensen, Erik S.

    -paratacamite through the application of quantum Monte Carlo techniques. These numerical results support a recent doping, this material undergoes a structural distortion which relieves the frustration and introduces Recently, a number of spin-1/2 frustrated magnetic insu- lators have been discovered without any sign

  9. The electronic properties of mixed valence hydrated europium chloride thin film.

    PubMed

    Silly, M G; Charra, F; Lux, F; Lemercier, G; Sirotti, F

    2015-07-28

    We investigate the electronic properties of a model mixed-valence hydrated chloride europium salt by means of high resolution photoemission spectroscopy (HRPES) and resonant photoemission spectroscopy (RESPES) at the Eu 3d ? 4f and 4d ? 4f transitions. From the HRPES spectra, we have determined that the two europium oxidation states are homogeneously distributed in the bulk and that the hydrated salt film is exempt from surface mixed valence transition. From the RESPES spectra, the well separated resonant contributions characteristic of divalent and trivalent europium species (4f(6) and 4f(7) final states, respectively) are accurately extracted and quantitatively determined from the resonant features measured at the two edges. The partial absorption yield spectra, obtained by integrating the photoemission intensity in the valence-band region, can be well reproduced by atomic multiplet calculation at the M(4,5) (3d-4f) absorption edge and by an asymmetric Fano-like shape profile at the N(4,5) (4d-4f) absorption edge. The ratio of Eu(2+) and Eu(3+) species measured at the two absorption edges matches with the composition of the mixed valence europium salt as determined chemically. We have demonstrated that the observed spectroscopic features of the mixed valence salt are attributed to the mixed-valence ground state rather than surface valence transition. HRPES and RESPES spectra provide reference spectra for the study of europium salts and their derivatives. PMID:26105214

  10. Interfacial chemical bonding state and band alignment of CaF{sub 2}/hydrogen-terminated diamond heterojunction

    SciTech Connect

    Liu, J. W.; Liao, M. Y.; Cheng, S. H.; Imura, M.; Koide, Y.

    2013-03-28

    CaF{sub 2} films are deposited on hydrogen-terminated diamond (H-diamond) by a radio-frequency sputter-deposition technique at room temperature. Interfacial chemical bonding state and band alignment of CaF{sub 2}/H-diamond heterojunction are investigated by X-ray photoelectron spectroscopy. It is confirmed that there are only C-Ca bonds at the CaF{sub 2}/H-diamond heterointerface. Valence and conductance band offsets of the CaF{sub 2}/H-diamond heterojunciton are determined to be 3.7 {+-} 0.2 and 0.3 {+-} 0.2 eV, respectively. It shows a type I straddling band configuration. The large valence band offset suggests advantage of the CaF{sub 2}/H-diamond heterojunciton for the development of high power and high frequency field effect transistors.

  11. Effect of Pr Valence State on Interfacial Structure and Electrical Properties of Pr Oxide/PrON/Ge Gate Stack Structure

    NASA Astrophysics Data System (ADS)

    Kato, Kimihiko; Sakashita, Mitsuo; Takeuchi, Wakana; Kondo, Hiroki; Nakatsuka, Osamu; Zaima, Shigeaki

    2011-04-01

    In this study, we investigated the valence state and chemical bonding state of Pr in a Pr oxide/PrON/Ge structure. We clarified the relationship between the valence state of Pr and the Pr oxide/Ge interfacial reaction using Pr oxide/Ge and Pr oxide/PrON/Ge samples. We found the formation of three Pr oxide phases in Pr oxide films; hexagonal Pr2O3 (h-Pr2O3) (Pr3+), cubic Pr2O3 (c-Pr2O3) (Pr3+), and c-PrO2 (Pr4+). We also investigated the effect of a nitride interlayer on the interfacial reaction in Pr oxide/Ge gate stacks. In a sample with a nitride interlayer (Pr oxide/PrON/Ge), metallic Pr-Pr bonds are also formed in the c-Pr2O3 film. After annealing in H2 ambient, the diffusion of Ge into Pr oxide is not observed in this sample. Pr-Pr bonds probably prevent the interfacial reaction and Ge oxide formation, considering that the oxygen chemical potential of this film is lower than that of a GeO2/Ge system. On the other hand, the rapid thermal oxidation (RTO) treatment terminates the O vacancies and defects in c-Pr2O3. As a result, c-PrO2 with tetravalent Pr is formed in the Pr oxide/PrON/Ge sample with RTO. In this sample, the leakage current density is effectively decreased in comparison with the sample without RTO. Hydrogen termination works effectively in Pr oxide/PrON/Ge samples with and without RTO, and we can achieve an interface state density of as low as 4 ×1011 eV-1·cm-2.

  12. Correlation among electronegativity, cation polarizability, optical basicity and single bond strength of simple oxides

    SciTech Connect

    Dimitrov, Vesselin; Komatsu, Takayuki

    2012-12-15

    A suitable relationship between free-cation polarizability and electronegativity of elements in different valence states and with the most common coordination numbers has been searched on the basis of the similarity in physical nature of both quantities. In general, the cation polarizability increases with decreasing element electronegativity. A systematic periodic change in the polarizability against the electronegativity has been observed in the isoelectronic series. It has been found that generally the optical basicity increases and the single bond strength of simple oxides decreases with decreasing the electronegativity. The observed trends have been discussed on the basis of electron donation ability of the oxide ions and type of chemical bonding in simple oxides. - Graphical abstract: This figure shows the single bond strength of simple oxides as a function of element electronegativity. A remarkable correlation exists between these independently obtained quantities. High values of electronegativity correspond to high values of single bond strength and vice versa. It is obvious that the observed trend in this figure is closely related to the type of chemical bonding in corresponding oxide. Highlights: Black-Right-Pointing-Pointer A suitable relationship between free-cation polarizability and electronegativity of elements was searched. Black-Right-Pointing-Pointer The cation polarizability increases with decreasing element electronegativity. Black-Right-Pointing-Pointer The single bond strength of simple oxides decreases with decreasing the electronegativity. Black-Right-Pointing-Pointer The observed trends were discussed on the basis of type of chemical bonding in simple oxides.

  13. Chemical activation of molecules by metals: Experimental studies of electron distributions and bonding

    NASA Astrophysics Data System (ADS)

    Lichtenberger, D. L.

    1991-10-01

    The formal relationship between measured molecular ionization energies and thermodynamic bond dissociation energies has been developed into a single equation which unifies the treatment of covalent bonds, ionic bonds, and partially ionic bonds. This relationship has been used to clarify the fundamental thermodynamic information relating to metal-hydrogen, metal-alkyl, and metal-metal bond energies. We have been able to obtain a direct observation and measurement of the stabilization energy provided by the agostic interaction of the C-H bond with the metal. The ionization energies have also been used to correlate the rates of carbonyl substitution reactions of (eta sup 5-C5H4)Rh(CO)2 complexes, and to reveal the electronic factors that control the stability of the transition state. The extent that the electronic features of these bonding interactions transfer to other chemical systems is being investigated in terms of the principle of additivity of ligand electronic effects. Specific examples under study include metal- phosphines, metal-halides, and metallocenes. Especially interesting has been the recent application of these techniques to the characterization of the soccer-ball shaped C60 molecule, buckminsterfullerene, and its interaction with a metal surface. The high resolution valence ionizations in the gas phase reveal the high symmetry of the molecule, and studies of thin films of C60 reveal weak intermolecular interactions. Scanning tunneling and atomic force microscopy reveal the arrangement of spherical molecules on gold substrates, with significant delocalization of charge from the metal surface.

  14. Re-evaluation of the bond length-bond strength rule: The stronger bond is not always the shorter bond.

    PubMed

    Kraka, Elfi; Setiawan, Dani; Cremer, Dieter

    2016-01-01

    A set of 42 molecules with N-F, O-F, N-Cl, P-F, and As-F bonds has been investigated in the search for potential bond anomalies, which lead to reverse bond length-bond strength (BLBS) relationships. The intrinsic strength of each bond investigated has been determined by the local stretching force constant obtained at the CCSD(T)/aug-cc-pVTZ level of theory. N-F or O-F bond anomalies were found for fluoro amine radicals, fluoro amines, and fluoro oxides, respectively. A rationale for the deviation from the normal Badger-type inverse BLBS relation is given and it is shown that electron withdrawal accompanied by strong orbital contraction and bond shortening is one of the prerequisites for a bond anomaly. In the case of short electron-rich bonds such as N-F or O-F, anomeric delocalization of lone pair electrons in connection with lone pair repulsion are decisive whether a bond anomaly can be observed. This is quantitatively assessed with the help of the CCSD(T) local stretching force constants, CCSD(T) charge distributions, and G4 bond dissociation energies. Bond anomalies are not found for fluoro phosphines and fluoro arsines because the bond weakening effects are no longer decisive. © 2015 Wiley Periodicals, Inc. PMID:26515027

  15. Valence Auger decay following 3 s photoionization in potassium

    NASA Astrophysics Data System (ADS)

    Palaudoux, J.; Sheinerman, S.; Soronen, J.; Huttula, S.-M.; Huttula, M.; Jänkälä, K.; Andric, L.; Ito, K.; Lablanquie, P.; Penent, F.; Bizau, J.-M.; Guilbaud, S.; Cubaynes, D.

    2015-07-01

    We have studied photoionization in the inner valence 3 s subshell of K and the spectroscopic properties of the two 3 s-1(1S) and (3S) resulting states. Similar to the Rb and Cs cases, the lifetime widths of the (1S) and (3S) states are found to be markedly different, due to the electron correlation effects. The main part of the study deals with the subsequent Auger decay of the 3 s-1 states, which have the particularity to involve low energy (˜5 eV ) Auger electrons. A magnetic bottle spectrometer with a multicoincidence technique has been used to observe and filter the Auger spectra with respect to the K2 + final state. The evolution of these Auger spectra has been investigated near the ionization threshold. They show strong post-collision interaction (PCI) effects, which are well reproduced by semiclassical and eikonal models. They reveal the importance of the photoelectron-Auger-electron interaction associated with these low energy Auger electrons.

  16. Valence shell photoionization of SF6 and high harmonic generation

    NASA Astrophysics Data System (ADS)

    Jobin, Jobin; Fulfer, K.; Wilson, B.; Poliakoff, E.; Trallero, C.; Mondal, S.; Le, A.-T.; Lin, C.-D.; Lucchese, Robert

    2013-05-01

    When an atom or molecule is exposed to highly intense laser fields, the target can emit coherent radiation at photon energies which are multiples of incident laser energy. This process is known as High-order harmonic generation (HHG). There has been experimental and theoretical investigation of HHG for atoms and simple linear molecules. However, there have been few such studies for non-linear polyatomic molecules. In the current work, we investigate HHG for SF6 experimentally and theoretically. We employ quantitative rescattering theory (QRS) which makes use of the magnitude and phase of the dipole transition matrix elements for photoionization. For calculating dipole transition matrix elements we employ the ePolyscat static-exchange method. The features seen in the computed results will be compared to corresponding features in the measured HHG spectrum. The calculation is repeated for different polarization of incident laser and different intensities. The analysis allows us to reproduce then understand experimentally measured HHG spectra from SF6. Additionally, the valence shell photoionization parameters are also compared with several other theoretical and experimental results.

  17. Breakdown of ionic character of molecular alkali bromides in inner-valence photoionization

    SciTech Connect

    Karpenko, A. Iablonskyi, D.; Kettunen, J. A.; Cao, W.; Huttula, M.; Aksela, H.; Urpelainen, S.

    2014-05-28

    The inner-valence region of alkali bromide XBr (X=Li, Na, K, Rb) vapours has been studied experimentally by means of synchrotron radiation excited photoelectron spectroscopy. Experimental spectra were analyzed by comparing them with available theoretical results and previous experiments. Ionic character of alkali bromides is seen to change in the inner-valence region with increasing atomic number of the alkali atom. A mechanism involving mixing between Br 4s and Rb 4p orbitals has been suggested to account for the fine structure observed in inner-valence ionization region of RbBr.

  18. Terminology Bonds selling at par are called par bonds.

    E-print Network

    Lyuu, Yuh-Dauh

    payment date C(1 - ) coupon payment date -(1 - )% -% c 2014 Prof. Yuh-Dauh Lyuu, National Taiwan. · There are 60 days between July 1, 1993, and the next coupon date, September 1, 1993. c 2014 Prof. Yuh-Dauh Lyuu premium bonds. · Bonds selling at a discount are called discount bonds. c 2014 Prof. Yuh-Dauh Lyuu

  19. Bond properties of liquid adhesive

    SciTech Connect

    Bohnert, G.W.

    1982-10-01

    Studies were conducted on a liquid adhesive used to bond circuit laminates to rigid plastic components. Areas investigated include: adhesive formulation, factors influencing bond strength, laminate cleaning, and automated adhesive application.

  20. 46 CFR Sec. 10 - Bonds.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ...Shipping 8 2010-10-01 2010-10-01 false Bonds. Sec. 10 Section 10 Shipping MARITIME ADMINISTRATION, DEPARTMENT...AUTHORITY MASTER LUMP SUM REPAIR CONTRACT-NSA-LUMPSUMREP Sec. 10 Bonds. (a) All bids in response to an...

  1. 46 CFR Sec. 10 - Bonds.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... REPAIRS UNDER NATIONAL SHIPPING AUTHORITY MASTER LUMP SUM REPAIR CONTRACT-NSA-LUMPSUMREP Sec. 10 Bonds. (a... awarded work and the furnishing of the performance and payment bonds required by Article 14 of the NSA... of the NSA-LUMPSUMREP Contract, the standard form of individual performance bond (Standard Form...

  2. 46 CFR Sec. 10 - Bonds.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... REPAIRS UNDER NATIONAL SHIPPING AUTHORITY MASTER LUMP SUM REPAIR CONTRACT-NSA-LUMPSUMREP Sec. 10 Bonds. (a... awarded work and the furnishing of the performance and payment bonds required by Article 14 of the NSA... of the NSA-LUMPSUMREP Contract, the standard form of individual performance bond (Standard Form...

  3. 46 CFR Sec. 10 - Bonds.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... REPAIRS UNDER NATIONAL SHIPPING AUTHORITY MASTER LUMP SUM REPAIR CONTRACT-NSA-LUMPSUMREP Sec. 10 Bonds. (a... awarded work and the furnishing of the performance and payment bonds required by Article 14 of the NSA... of the NSA-LUMPSUMREP Contract, the standard form of individual performance bond (Standard Form...

  4. 46 CFR Sec. 10 - Bonds.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... REPAIRS UNDER NATIONAL SHIPPING AUTHORITY MASTER LUMP SUM REPAIR CONTRACT-NSA-LUMPSUMREP Sec. 10 Bonds. (a... awarded work and the furnishing of the performance and payment bonds required by Article 14 of the NSA... of the NSA-LUMPSUMREP Contract, the standard form of individual performance bond (Standard Form...

  5. 46 CFR Sec. 10 - Bonds.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... REPAIRS UNDER NATIONAL SHIPPING AUTHORITY MASTER LUMP SUM REPAIR CONTRACT-NSA-LUMPSUMREP Sec. 10 Bonds. (a... awarded work and the furnishing of the performance and payment bonds required by Article 14 of the NSA... of the NSA-LUMPSUMREP Contract, the standard form of individual performance bond (Standard Form...

  6. Pion form factor using domain wall valence and asqtad sea quarks

    E-print Network

    LHP Collaboration; George T. Fleming; Frederic D. R. Bonnet; Robert G. Edwards; Randy Lewis; David G. Richards

    2004-09-14

    We compute the pion electromagnetic form factor in a hybrid calculation with domain wall valence quarks and improved staggered (asqtad) sea quarks. This method can easily be extended to rho-to-gamma-pi transition form factors.

  7. Of Caucasians, Asians, and Giraffes: The Influence of Categorization and Target Valence on Social Projection.

    PubMed

    Machunsky, Maya; Walther, Eva

    2015-09-01

    Past research has indicated that social projection is moderated by categorization, with more projection onto ingroups than onto outgroups. However, a few studies have reported elevated levels of projection even onto outgroups. In line with recent evidence, we hypothesized that positive target valence is the key feature of conditions that elicit projection onto outgroups. The present research extends previous findings by testing whether the effect of valence occurs independent of categorization, with increased levels of projection onto positive ingroup and non-ingroup targets alike. We designed two experiments in which target valence was manipulated by means of evaluative conditioning. Category membership was varied by using faces of Caucasians, Asians, and giraffes. The results supported our valence hypothesis. Counter-intuitively, we also found higher levels of projection onto giraffes than onto humans. These findings suggest that current cognition-based models of projection are not sufficient to account for the whole range of projection phenomena. PMID:26160332

  8. An Intracranial EEG Study of the Neural Dynamics of Musical Valence Processing.

    PubMed

    Omigie, Diana; Dellacherie, Delphine; Hasboun, Dominique; George, Nathalie; Clement, Sylvain; Baulac, Michel; Adam, Claude; Samson, Severine

    2015-11-01

    The processing of valence is known to recruit the amygdala, orbitofrontal cortex, and relevant sensory areas. However, how these regions interact remains unclear. We recorded cortical electrical activity from 7 epileptic patients implanted with depth electrodes for presurgical evaluation while they listened to positively and negatively valenced musical chords. Time-frequency analysis suggested a specific role of the orbitofrontal cortex in the processing of positively valenced stimuli while, most importantly, Granger causality analysis revealed that the amygdala tends to drive both the orbitofrontal cortex and the auditory cortex in theta and alpha frequency bands, during the processing of valenced stimuli. Results from the current study show the amygdala to be a critical hub in the emotion processing network: specifically one that influences not only the higher order areas involved in the evaluation of a stimulus's emotional value but also the sensory cortical areas involved in the processing of its low-level acoustic features. PMID:24904066

  9. The American Flag and the Presidential Election of 1988: Reconsidering the Importance of Valence Issues

    E-print Network

    Dietrich, Bryce Jensen

    2008-08-18

    , adding to our understanding of the importance valence issues and the American flag. Additional studies are needed in order to elucidate these results, but this thesis serves as a guide for future research....

  10. Subjective Reality: The Influence of Perceived and Objective Conversational Valence on Binge Drinking Determinants.

    PubMed

    Hendriks, Hanneke; Putte, Bas van den; de Bruijn, Gert-Jan

    2015-01-01

    Previous studies have shown that interpersonal communication, and particularly perceived conversational valence (i.e., the perceived negativity or positivity of conversations) about health topics, influences health determinants. On the basis of 43 dyads (N = 86) discussing the topic of alcohol consumption, this study is the first to show that whereas perceived and objective conversational valence are positively related, only perceived conversational valence is a significant predictor of binge drinking attitudes and intentions. Thus, subjective reality matters more than objective reality. Furthermore, only the perceived valence of the participants' own contributions-and not of their conversation partners--influences binge drinking intentions, indicating that self-persuasion is more influential than persuasion by others. Thus, conversations in which discussants themselves express negative opinions about unhealthy behaviors can enhance public health. PMID:25848964

  11. Changing the conversation: the influence of emotions on conversational valence and alcohol consumption.

    PubMed

    Hendriks, Hanneke; van den Putte, Bas; de Bruijn, Gert-Jan

    2014-10-01

    Health campaign effects may be improved by taking interpersonal communication processes into account. The current study, which employed an experimental, pretest-posttest, randomized exposure design (N?=?208), investigated whether the emotions induced by anti-alcohol messages influence conversational valence about alcohol and subsequent persuasion outcomes. The study produced three main findings. First, an increase in the emotion fear induced a negative conversational valence about alcohol. Second, fear was most strongly induced by a disgusting message, whereas a humorous appeal induced the least fear. Third, a negative conversational valence elicited healthier binge drinking attitudes, subjective norms, perceived behavioral control, intentions, and behaviors. Thus, health campaign planners and health researchers should pay special attention to the emotional characteristics of health messages and should focus on inducing a healthy conversational valence. PMID:23812888

  12. THE VALENCE AND METHYLATION STATE OF ARSENIC DETERMINES ITS POTENCY IN INTERACTION WITH THE MITOTIC APPARATUS

    EPA Science Inventory

    We have previously shown that the cytotoxic and genotoxic potency of arsenicals is dependent upon their valence and methylation state. Trivalent methylated arsenicals are much more potent DNA damaging agents than are their inorganic and pentavalent counterparts. Furthermore, thei...

  13. Bidirectional switch of the valence associated with a hippocampal contextual memory engram

    E-print Network

    Redondo, Roger L.

    The valence of memories is malleable because of their intrinsic reconstructive property. This property of memory has been used clinically to treat maladaptive behaviours. However, the neuronal mechanisms and brain circuits ...

  14. Optogenetic dissection of neural circuits underlying emotional valence and motivated behaviors

    E-print Network

    Nieh, Horng-An Edward

    The neural circuits underlying emotional valence and motivated behaviors are several synapses away from both defined sensory inputs and quantifiable motor outputs. Electrophysiology has provided us with a suitable means ...

  15. Of two minds: forming and changing valence-inconsistent implicit and explicit attitudes.

    PubMed

    Rydell, Robert J; McConnell, Allen R; Mackie, Diane M; Strain, Laura M

    2006-11-01

    Because different processes underlie implicit and explicit attitudes, we hypothesized that they are differentially sensitive to different kinds of information. We measured implicit and explicit attitudes over time, as different types of attitude-relevant information about a single attitude object were presented. As expected, explicit attitudes formed and changed in response to the valence of consciously accessible, verbally presented behavioral information about the target. In contrast, implicit attitudes formed and changed in response to the valence of subliminally presented primes, reflecting the progressive accretion of attitude object-evaluation pairings. As a consequence, when subliminal primes and behavioral information were of opposite valence, people formed implicit and explicit attitudes of conflicting valence. PMID:17176426

  16. Evolution of the Impurity Band to Diamond-Like Valence Bands in Boron Doped Diamond

    NASA Astrophysics Data System (ADS)

    Inushima, Takashi; Ota, Yuichi; Shiomi, Hiromu

    2014-02-01

    We present the absorption coefficient and the refractive index of boron doped diamond having an impurity band at 0.07 eV above the valence band maximum and compare them with those obtained by first principles calculation using a C63B supercell model containing 1.57% boron. These optical constants are in good accordance with each other, indicating that the impurity band that forms at 2p excited states of impurity boron becomes top of the valence bands in metallic condition. Based on this result we present a model of the evolution of boron atoms from isolated impurity to constituent atoms in the boron doped diamond, where the valence electrons of boron become to have k dependence and form the top of the valence bands of the C63B supercell diamond.

  17. Metallic bond effects on mean excitation energies for stopping powers

    NASA Technical Reports Server (NTRS)

    Wilson, J. W.; Xu, Y. J.

    1982-01-01

    Mean excitation energies for first row metals are evaluated by means of the local plasma approximation. Particle corrections based on Pines' (1953) procedure and the Wigner Seitz (1934) model of the metallic state are included. The agreement with experimental values is remarkably good. In contrast to previous work, the calculations given here estimate shifts in the plasma frequency according to the theory for plane wave states in an extended plasma as calculated by Pines. It is demonstrated that the effects of the metallic bond in lithium and beryllium are quite large and that they appear mainly as a result of collective oscillations in the 'free' electron gas formed from the valence electrons. The usefulness of the plasma frequency shift derived for a degenerate electron gas in predicting the plasma frequency shift within the ion core is considered surprising.

  18. The determinants of bond angle variability in protein/peptide backbones: A comprehensive statistical/quantum mechanics analysis.

    PubMed

    Improta, Roberto; Vitagliano, Luigi; Esposito, Luciana

    2015-11-01

    The elucidation of the mutual influence between peptide bond geometry and local conformation has important implications for protein structure refinement, validation, and prediction. To gain insights into the structural determinants and the energetic contributions associated with protein/peptide backbone plasticity, we here report an extensive analysis of the variability of the peptide bond angles by combining statistical analyses of protein structures and quantum mechanics calculations on small model peptide systems. Our analyses demonstrate that all the backbone bond angles strongly depend on the peptide conformation and unveil the existence of regular trends as function of ? and/or ?. The excellent agreement of the quantum mechanics calculations with the statistical surveys of protein structures validates the computational scheme here employed and demonstrates that the valence geometry of protein/peptide backbone is primarily dictated by local interactions. Notably, for the first time we show that the position of the H(?) hydrogen atom, which is an important parameter in NMR structural studies, is also dependent on the local conformation. Most of the trends observed may be satisfactorily explained by invoking steric repulsive interactions; in some specific cases the valence bond variability is also influenced by hydrogen-bond like interactions. Moreover, we can provide a reliable estimate of the energies involved in the interplay between geometry and conformations. Proteins 2015; 83:1973-1986. © 2015 Wiley Periodicals, Inc. PMID:26264789

  19. Chiral perturbation theory for staggered sea quarks and Ginsparg-Wilson valence quarks

    SciTech Connect

    Baer, Oliver; Bernard, Claude; Rupak, Gautam; Shoresh, Noam

    2005-09-01

    We study lattice QCD with staggered sea and Ginsparg-Wilson valence quarks. The Symanzik effective action for this mixed lattice theory, including the lattice spacing contributions of O(a{sup 2}), is derived. Using this effective theory we construct the leading-order chiral Lagrangian. The masses and decay constants of pseudoscalars containing two Ginsparg-Wilson valence quarks are computed at one-loop order.

  20. Physica B 378380 (2006) 752753 Anisotropic intermediate valence in Yb2Rh3Ga9

    E-print Network

    Lawrence, Jon

    2006-01-01

    Physica B 378­380 (2006) 752­753 Anisotropic intermediate valence in Yb2Rh3Ga9 A.D. Christiansona for the anisotropic intermediate valence system Yb2Rh3Ga9. Calculations for the Anderson impurity model with crystal are important to the physics of Yb2Rh3Ga9. r 2006 Elsevier B.V. All rights reserved. Keywords: Intermediate

  1. 29 CFR 2580.412-19 - Term of the bond, discovery period, other bond clauses.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 9 2010-07-01 2010-07-01 false Term of the bond, discovery period, other bond clauses... SECURITY ACT OF 1974 TEMPORARY BONDING RULES General Bond Rules § 2580.412-19 Term of the bond, discovery period, other bond clauses. (a) Term of the bond. The amount of any required bond must in each...

  2. The power of emotional valence—from cognitive to affective processes in reading

    PubMed Central

    Altmann, Ulrike; Bohrn, Isabel C.; Lubrich, Oliver; Menninghaus, Winfried; Jacobs, Arthur M.

    2012-01-01

    The comprehension of stories requires the reader to imagine the cognitive and affective states of the characters. The content of many stories is unpleasant, as they often deal with conflict, disturbance or crisis. Nevertheless, unpleasant stories can be liked and enjoyed. In this fMRI study, we used a parametric approach to examine (1) the capacity of increasing negative valence of story contents to activate the mentalizing network (cognitive and affective theory of mind, ToM), and (2) the neural substrate of liking negatively valenced narratives. A set of 80 short narratives was compiled, ranging from neutral to negative emotional valence. For each story mean rating values on valence and liking were obtained from a group of 32 participants in a prestudy, and later included as parametric regressors in the fMRI analysis. Another group of 24 participants passively read the narratives in a three Tesla MRI scanner. Results revealed a stronger engagement of affective ToM-related brain areas with increasingly negative story valence. Stories that were unpleasant, but simultaneously liked, engaged the medial prefrontal cortex (mPFC), which might reflect the moral exploration of the story content. Further analysis showed that the more the mPFC becomes engaged during the reading of negatively valenced stories, the more coactivation can be observed in other brain areas related to the neural processing of affective ToM and empathy. PMID:22754519

  3. Determining the Oxygen Fugacity of Lunar Pyroclastic Glasses Using Vanadium Valence - An Update

    NASA Technical Reports Server (NTRS)

    Karner, J. M.; Sutton, S. R.; Papike, J. J.; Shearer, C. K.; Jones, J. H.; Newville, M.

    2004-01-01

    We have been developing an oxygen barometer based on the valence state of V (V(2+), V(3+), V(4+), and V(5+)) in solar system basaltic glasses. The V valence is determined by synchrotron micro x-ray absorption near edge structure (XANES), which uses x-ray absorption associated with core-electronic transitions (absorption edges) to reveal a pre-edge peak whose intensity is directly proportional to the valence state of an element. XANES has advantages over other techniques that determine elemental valence because measurements can be made non-destructively in air and in situ on conventional thin sections at a micrometer spatial resolution with elemental sensitivities of approx. 100 ppm. Recent results show that fO2 values derived from the V valence technique are consistent with fO2 estimates determined by other techniques for materials that crystallized above the IW buffer. The fO2's determined by V valence (IW-3.8 to IW-2) for the lunar pyroclastic glasses, however, are on the order of 1 to 2.8 log units below previous estimates. Furthermore, the calculated fO2's decrease with increasing TiO2 contents from the A17 VLT to the A17 Orange glasses. In order to investigate these results further, we have synthesized lunar green and orange glasses and examined them by XANES.

  4. 77 FR 32128 - Cancellation of Bond Subject to Enhanced Bonding Requirements Upon CBP's Acceptance of Qualified...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-05-31

    ...Cancellation of Bond Subject to Enhanced Bonding Requirements Upon CBP's Acceptance of...amount was calculated pursuant to enhanced bonding requirements (EBR bond) upon the agency's...INFORMATION: Background I. Enhanced Bonding Requirements In 2004, U.S....

  5. 27 CFR 19.162 - Operations bond for distilled spirits plant and adjacent bonded wine cellar.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... Operations bond for distilled spirits plant and adjacent bonded wine cellar. 19...TREASURY LIQUORS DISTILLED SPIRITS PLANTS Bonds and Consents of Surety Requirements... Operations bond for distilled spirits plant and adjacent bonded wine cellar....

  6. 27 CFR 19.162 - Operations bond for distilled spirits plant and adjacent bonded wine cellar.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... Operations bond for distilled spirits plant and adjacent bonded wine cellar. 19...TREASURY LIQUORS DISTILLED SPIRITS PLANTS Bonds and Consents of Surety Requirements... Operations bond for distilled spirits plant and adjacent bonded wine cellar....

  7. 27 CFR 19.162 - Operations bond for distilled spirits plant and adjacent bonded wine cellar.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... Operations bond for distilled spirits plant and adjacent bonded wine cellar. 19...TREASURY ALCOHOL DISTILLED SPIRITS PLANTS Bonds and Consents of Surety Requirements... Operations bond for distilled spirits plant and adjacent bonded wine cellar....

  8. 27 CFR 19.162 - Operations bond for distilled spirits plant and adjacent bonded wine cellar.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... Operations bond for distilled spirits plant and adjacent bonded wine cellar. 19...TREASURY ALCOHOL DISTILLED SPIRITS PLANTS Bonds and Consents of Surety Requirements... Operations bond for distilled spirits plant and adjacent bonded wine cellar....

  9. 27 CFR 19.241 - Operations bond-distilled spirits plant and adjacent bonded wine cellar.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...false Operations bond-distilled spirits plant and adjacent bonded wine cellar. 19...TREASURY LIQUORS DISTILLED SPIRITS PLANTS Bonds and Consents of Surety § 19.241 Operations bond—distilled spirits plant and adjacent bonded wine cellar....

  10. A comparison of the bonding in the second-row transition-metal oxides and carbenes

    NASA Astrophysics Data System (ADS)

    Siegbahn, Per E. M.

    1993-01-01

    Calculations including electron correlation of all valence electrons have been performed for the sequence of second-row transition-metal oxides and carbenes. For the atoms to the right the bond strengths of the carbenes and the oxides are similar while for the atoms to the left the oxide bond strengths are much larger. The origin of this difference is the interaction between the oxygen lone pairs and empty 4d orbitals on the metal. With the large donation of electrons from the oxygen lone pair to the metal for the atoms to the left, the bonding can almost be described as triple bond formation for YO, ZrO and NbO. For MoO, where a 4d ? orbital is singly occupied on the metal, the bond strength is much smaller than for the oxides to the left. For the metal carbenes two covalent bonds are formed. The ground state spin for the oxides to the right is higher than for the corresponding carbenes, which can be explained by the presence of the ? degeneracy for the oxides. The relevance of the present results for the epoxidation and the olefin metathesis reactions are discussed.

  11. 30 CFR 57.22227 - Approved testing devices (I-A, I-B, I-C, II-A, II-B, III, IV, V-A, and V-B mines).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Approved testing devices (I-A, I-B, I-C, II-A, II-B, III, IV, V-A, and V-B mines). 57.22227 Section 57.22227 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-UNDERGROUND METAL AND NONMETAL...

  12. 30 CFR 57.22227 - Approved testing devices (I-A, I-B, I-C, II-A, II-B, III, IV, V-A, and V-B mines).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Approved testing devices (I-A, I-B, I-C, II-A, II-B, III, IV, V-A, and V-B mines). 57.22227 Section 57.22227 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-UNDERGROUND METAL AND NONMETAL...

  13. Comparison of brain capillary endothelial cell-based and epithelial (MDCK-MDR1, Caco-2, and VB-Caco-2) cell-based surrogate blood-brain barrier penetration models.

    PubMed

    Hellinger, Eva; Veszelka, Szilvia; Tóth, Andrea E; Walter, Fruzsina; Kittel, Agnes; Bakk, Mónika Laura; Tihanyi, Károly; Háda, Viktor; Nakagawa, Shinsuke; Duy, Thuy Dinh Ha; Niwa, Masami; Deli, Mária A; Vastag, Monika

    2012-10-01

    An accurate means of predicting blood-brain barrier (BBB) penetration and blood-brain partitioning of NCEs (new chemical entities) would fulfill a major need in pharmaceutical research. Currently, an industry-standard BBB drug penetration model is not available. Primary brain capillary endothelial cells, optionally co-cultured with astrocytes and/or pericytes, are the most valued models of BBB. For routine use, establishing and maintaining a co-culture system is too costly and labor intensive. Alternatively, non-cerebral cell lines such as MDCK-MDR1 are used, and most recently, the suitability of native and modified Caco-2 for predicting brain penetration has also come under investigation. This study provides comparative data on the morphology and functionality of the high integrity brain capillary endothelial BBB model (EPA: triple culture of brain capillary endothelial cells with pericytes and astrocytes) and the epithelial cell-based (native Caco-2, high P-glycoprotein expressing vinblastine-treated VB-Caco-2 and MDCK-MDR1) surrogate BBB models. Using a panel of 10 compounds VB-Caco-2 and MDCK-MDR1 cell lines show restrictive paracellular pathway and BBB-like selective passive permeability that makes them comparable to the rat brain BBB model, which gave correlation with the highest r(2) value with in vivo permeability data. In bidirectional assay, the VB-Caco-2 and the MDCK-MDR1 models identified more P-glycoprotein drug substrates than the rat brain BBB model. While the complexity and predictive value of the BBB model is the highest, for the screening of NCEs to determine whether they are efflux substrates or not, the VB-Caco-2 and the MDCK-MDR1 models may provide a simple and inexpensive tool. PMID:22906709

  14. Correlating conduction properties with the molecular symmetry: segregation of Z and E isomers in the charge-assisted, halogen-bonded cocrystal [(Z,E)-Me2I2TTF]2Br.

    PubMed

    Jeannin, Olivier; Canadell, Enric; Auban-Senzier, Pascale; Fourmigué, Marc

    2016-01-01

    The Z and E isomers of the iodinated TTF derivative (Z,E)-Me2I2-TTF co-crystallize in a mixed-valence salt with Br(-) anions, and are segregated into Z and E stacks, each of them with a different charge localization pattern, which also revealed charge-assisted halogen bonding. PMID:26512923

  15. Interfacial chemistry and valence band offset between GaN and Al{sub 2}O{sub 3} studied by X-ray photoelectron spectroscopy

    SciTech Connect

    Duan, T. L.; Ang, D. S.; Pan, J. S.

    2013-05-20

    The interface region between Ga-face n-type GaN and Al{sub 2}O{sub 3} dielectric (achieved via atomic-layer deposition or ALD) is investigated by X-ray photoelectron spectroscopy (XPS). An increase in the Ga-O to Ga-N bond intensity ratio following Al{sub 2}O{sub 3} deposition implies that the growth of an interfacial gallium sub-oxide (GaO{sub x}) layer occurred during the ALD process. This finding may be ascribed to GaN oxidation, which may still happen following the reduction of a thin native GaO{sub x} by trimethylaluminum (TMA) in the initial TMA-only cycles. The valence band offset between GaN and Al{sub 2}O{sub 3}, obtained using both core-level and valence band spectra, is found to vary with the thickness of the deposited Al{sub 2}O{sub 3}. This observation may be explained by an upward energy band bending at the GaN surface (due to the spontaneous polarization induced negative bound charge on the Ga-face GaN) and the intrinsic limitation of the XPS method for band offset determination.

  16. Re-entrant phase behaviour of network fluids: a patchy particle model with temperature-dependent valence.

    PubMed

    Russo, J; Tavares, J M; Teixeira, P I C; Telo da Gama, M M; Sciortino, F

    2011-07-21

    We study a model consisting of particles with dissimilar bonding sites ("patches"), which exhibits self-assembly into chains connected by Y-junctions, and investigate its phase behaviour by both simulations and theory. We show that, as the energy cost ?(j) of forming Y-junctions increases, the extent of the liquid-vapour coexistence region at lower temperatures and densities is reduced. The phase diagram thus acquires a characteristic "pinched" shape in which the liquid branch density decreases as the temperature is lowered. To our knowledge, this is the first model in which the predicted topological phase transition between a fluid composed of short chains and a fluid rich in Y-junctions is actually observed. Above a certain threshold for ?(j), condensation ceases to exist because the entropy gain of forming Y-junctions can no longer offset their energy cost. We also show that the properties of these phase diagrams can be understood in terms of a temperature-dependent effective valence of the patchy particles. PMID:21787007

  17. Simulating Valence-to-Core X-ray Emission Spectroscopy of Transition Metal Complexes with Time-Dependent Density Functional Theory.

    PubMed

    Zhang, Yu; Mukamel, Shaul; Khalil, Munira; Govind, Niranjan

    2015-12-01

    Valence-to-core (VtC) X-ray emission spectroscopy (XES) has emerged as a powerful technique for the structural characterization of complex organometallic compounds in realistic environments. Since the spectrum represents electronic transitions from the ligand molecular orbitals to the core holes of the metal centers, the approach is more chemically sensitive to the metal-ligand bonding character compared with conventional X-ray absorption techniques. In this paper we study how linear-response time-dependent density functional theory (LR-TDDFT) can be harnessed to simulate K-edge VtC X-ray emission spectra reliably. LR-TDDFT allows one to go beyond the single-particle picture that has been extensively used to simulate VtC-XES. We consider seven low- and high-spin model complexes involving chromium, manganese, and iron transition metal centers. Our results are in good agreement with experiment. PMID:26588191

  18. C-H⋯Cl relevant discrepancy on structure, magnetic and electronic conductivity of two mixed-valence Cu ICu II coordination polymers

    NASA Astrophysics Data System (ADS)

    Shi, Ling; Yang, Ping; Huang, Guang; Li, Qian; Wang, Ning; Wu, Jian-Zhong; Yu, Ying

    2011-07-01

    Two mixed-valence Cu ICu II coordination polymers [Cu ICu II(qdiol)ClL] n (qdiol 2-=2,3-dioxyquinoxalinate, L=2,2'-bipyridine, 1; L=1,10-phenanthroline, 2) were obtained in basic ethanolic solution of CuCl 2, 1,4-dihydro-2,3-quinoxalinedione and L under the solvothermal condition. 1 and 2 are similar in composition, but differ remarkably in structure. The coordination modes of Cu II, qdiol 2- and L are identical in both complexes. But the Cu I ions are two- and three-coordinated, and the Cl - ions are terminal and bridging, in 1 and 2, respectively, which are relevant to the significantly different C-H⋯Cl hydrogen bonding pattern of bpy and phen. The temperature variable magnetic susceptibilities show that 1 is paramagnetic and 2 is weakly antiferromagnetic. The complex impedance spectroscopic studies indicate that both 1 and 2 are semiconductors and 2 is more conducting.

  19. Simulating Valence-to-Core X-ray Emission Spectroscopy of Transition Metal Complexes with Time-Dependent Density Functional Theory

    SciTech Connect

    Zhang, Yu; Mukamel, Shaul; Khalil, Munira; Govind, Niranjan

    2015-11-09

    Valence-to-core (VtC) X-ray emission spectroscopy (XES) has emerged as a power- ful technique for the structural characterization of complex organometallic compounds in realistic environments. Since the spectrum represents electronic transitions from the ligand molecular orbitals to the core holes of the metal centers, the approach is more chemically sensitive to the metal-ligand bonding character compared with con- ventional X-ray absorption techniques. In this paper we study how linear-response time-dependent density functional theory (LR-TDDFT) can be harnessed to simulate K-edge VtC X-ray emission spectra reliably. LR-TDDFT allows one to go beyond the single-particle picture that has been extensively used to simulate VtC-XES. We con- sider seven low- and high-spin model complexes involving chromium, manganese and iron transition metal centers. Our results are in good agreement with experiment.

  20. Covalent bonding and the nature of band gaps in some half-Heusler compounds

    NASA Astrophysics Data System (ADS)

    Kandpal, Hem Chandra; Felser, Claudia; Seshadri, Ram

    2006-03-01

    Half-Heusler compounds XYZ, also called semi-Heusler compounds, crystallize in the C1b MgAgAs structure, in the space group F\\bar{4}3m . We report a systematic examination of band gaps and the nature (covalent or ionic) of bonding in semiconducting 8- and 18-electron half-Heusler compounds through first-principles density functional calculations. We find that the most appropriate description of these compounds from the viewpoint of electronic structures is one of a YZ zinc blende lattice stuffed by the X ion. Simple valence rules are obeyed for bonding in the 8-electron compound. For example, LiMgN can be written Li+ + (MgN)- and (MgN)-, which is isoelectronic with (SiSi), forms a zinc blende lattice. The 18-electron compounds can similarly be considered as obeying valence rules. A semiconductor such as TiCoSb can be written Ti4+ + (CoSb)4-; the latter unit is isoelectronic and isostructural with zinc-blende GaSb. For both the 8- and the 18-electron compounds, when X is fixed as some electropositive cation, the computed band gap varies approximately as the difference in Pauling electronegativities of Y and Z. What is particularly exciting is that this simple idea of a covalently bonded YZ lattice can also be extended to the very important magnetic half-Heusler phases; we describe these as valence compounds, i.e. possessing a band gap at the Fermi energy albeit only in one spin direction. The local moment in these magnetic compounds resides on the X site.

  1. Solder extrusion pressure bonding process and bonded products produced thereby

    DOEpatents

    Beavis, L.C.; Karnowsky, M.M.; Yost, F.G.

    1992-06-16

    Disclosed is a process for production of soldered joints which are highly reliable and capable of surviving 10,000 thermal cycles between about [minus]40 C and 110 C. Process involves interposing a thin layer of a metal solder composition between the metal surfaces of members to be bonded and applying heat and up to about 1000 psi compression pressure to the superposed members, in the presence of a reducing atmosphere, to extrude the major amount of the solder composition, contaminants including fluxing gases and air, from between the members being bonded, to form a very thin, strong intermetallic bonding layer having a thermal expansion tolerant with that of the bonded members.

  2. Solder extrusion pressure bonding process and bonded products produced thereby

    DOEpatents

    Beavis, Leonard C. (Albuquerque, NM); Karnowsky, Maurice M. (Albuquerque, NM); Yost, Frederick G. (Ceder Crest, NM)

    1992-01-01

    Production of soldered joints which are highly reliable and capable of surviving 10,000 thermal cycles between about -40.degree. C. and 110.degree. C. Process involves interposing a thin layer of a metal solder composition between the metal surfaces of members to be bonded and applying heat and up to about 1000 psi compression pressure to the superposed members, in the presence of a reducing atmosphere, to extrude the major amount of the solder composition, contaminants including fluxing gases and air, from between the members being bonded, to form a very thin, strong intermetallic bonding layer having a thermal expansion tolerant with that of the bonded members.

  3. Light-scattering detection of quantum phases of ultracold atoms in optical lattices

    SciTech Connect

    Ye Jinwu; Zhang, J. M.; Liu, W. M.; Zhang Keye; Li Yan; Zhang Weiping

    2011-05-15

    Ultracold atoms loaded on optical lattices can provide unprecedented experimental systems for the quantum simulations and manipulations of many quantum phases. However, so far, how to detect these quantum phases effectively remains an outstanding challenge. Here, we show that the optical Bragg scattering of cold atoms loaded on optical lattices can be used to detect many quantum phases, which include not only the conventional superfluid and Mott insulating phases, but also other important phases, such as various kinds of charge density wave (CDW), valence bond solid (VBS), CDW supersolid (CDW-SS) and Valence bond supersolid (VB-SS).

  4. Bidirectional switch of the valence associated with a hippocampal contextual memory engram.

    PubMed

    Redondo, Roger L; Kim, Joshua; Arons, Autumn L; Ramirez, Steve; Liu, Xu; Tonegawa, Susumu

    2014-09-18

    The valence of memories is malleable because of their intrinsic reconstructive property. This property of memory has been used clinically to treat maladaptive behaviours. However, the neuronal mechanisms and brain circuits that enable the switching of the valence of memories remain largely unknown. Here we investigated these mechanisms by applying the recently developed memory engram cell- manipulation technique. We labelled with channelrhodopsin-2 (ChR2) a population of cells in either the dorsal dentate gyrus (DG) of the hippocampus or the basolateral complex of the amygdala (BLA) that were specifically activated during contextual fear or reward conditioning. Both groups of fear-conditioned mice displayed aversive light-dependent responses in an optogenetic place avoidance test, whereas both DG- and BLA-labelled mice that underwent reward conditioning exhibited an appetitive response in an optogenetic place preference test. Next, in an attempt to reverse the valence of memory within a subject, mice whose DG or BLA engram had initially been labelled by contextual fear or reward conditioning were subjected to a second conditioning of the opposite valence while their original DG or BLA engram was reactivated by blue light. Subsequent optogenetic place avoidance and preference tests revealed that although the DG-engram group displayed a response indicating a switch of the memory valence, the BLA-engram group did not. This switch was also evident at the cellular level by a change in functional connectivity between DG engram-bearing cells and BLA engram-bearing cells. Thus, we found that in the DG, the neurons carrying the memory engram of a given neutral context have plasticity such that the valence of a conditioned response evoked by their reactivation can be reversed by re-associating this contextual memory engram with a new unconditioned stimulus of an opposite valence. Our present work provides new insight into the functional neural circuits underlying the malleability of emotional memory. PMID:25162525

  5. Bidirectional switch of the valence associated with a hippocampal contextual memory engram

    PubMed Central

    Redondo, Roger L; Kim, Joshua; Arons, Autumn L; Ramirez, Steve; Liu, Xu; Tonegawa, Susumu

    2014-01-01

    The valence of memories is malleable because of their intrinsic reconstructive property1. This property of memory has been used clinically to treat maladaptive behaviours2. However, the neuronal mechanisms and brain circuits that enable the switching of the valence of memories remain largely unknown. Here, we investigated these mechanisms by applying the recently developed memory engram cell-labelling and -manipulation technique 3,4. We labelled, with Channelrhodopsin-2 (ChR2), a population of cells in either the dorsal dentate gyrus (DG) of the hippocampus or the basolateral complex of the amygdala (BLA) that were specifically activated during contextual fear or reward conditioning. Both groups of fear-conditioned mice displayed aversive light-dependent responses in an optogenetic place avoidance test, whereas both DG- and BLA-labelled mice that underwent reward conditioning exhibited an appetitive response in an optogenetic place preference test. Next, in an attempt to reverse the valence of memory within a subject, mice whose DG or BLA engram had initially been labelled by contextual fear or reward conditioning were subjected to a second conditioning of the opposite valence while their original DG or BLA engram was reactivated by blue light. Subsequent optogenetic place avoidance and preference tests revealed that while the DG-engram group displayed a response indicating a switch of the memory valence, the BLA-engram group did not. This switch was also evident at the cellular level by a change in functional connectivity between DG engram-bearing cells and BLA engram-bearing cells. Thus, we found that in the DG, the neurons carrying the memory engram of a given neutral context have plasticity such that the valence of a conditioned response evoked by their reactivation can be reversed by re-associating this contextual memory engram with a new US of an opposite valence. Our present work provides new insight into the functional neural circuit underlying the malleability of emotional memory. PMID:25162525

  6. Better Bonded Ethernet Load Balancing

    SciTech Connect

    Gabler, Jason

    2006-09-29

    When a High Performance Storage System's mover shuttles large amounts of data to storage over a single Ethernet device that single channel can rapidly become saturated. Using Linux Ethernet channel bonding to address this and similar situations was not, until now, a viable solution. The various modes in which channel bonding could be configured always offered some benefit but only under strict conditions or at a system resource cost that was greater than the benefit gained by using channel bonding. Newer bonding modes designed by various networking hardware companies, helpful in such networking scenarios, were already present in their own switches. However, Linux-based systems were unable to take advantage of those new modes as they had not yet been implemented in the Linux kernel bonding driver. So, except for basic fault tolerance, Linux channel bonding could not positively combine separate Ethernet devices to provide the necessary bandwidth.

  7. The first example of a mixed valence ternary compound of silver with random distribution of Ag(I) and Ag(II) cations.

    PubMed

    Mazej, Zoran; Micha?owski, Tomasz; Goreshnik, Evgeny A; Jagli?i?, Zvonko; Ar?on, Iztok; Szyd?owska, Jadwiga; Grochala, Wojciech

    2015-06-28

    The reaction between colourless AgSbF6 and sky-blue Ag(SbF6)2 (molar ratio 2?:?1) in gaseous HF at 323 K yields green Ag3(SbF6)4, a new mixed-valence ternary fluoride of silver. Unlike in all other Ag(I)/Ag(II) systems known to date, the Ag(+) and Ag(2+) cations are randomly distributed on a single 12b Wyckoff position at the 4? axis of the I4?3d cell. Each silver forms four short (4 × 2.316(7) Å) and four long (4 × 2.764(6) Å) contacts with the neighbouring fluorine atoms. The valence bond sum analysis suggests that such coordination would correspond to a severely overbonded Ag(I) and strongly underbonded Ag(II). Thorough inspection of thermal ellipsoids of the fluorine atoms closest to Ag centres reveals their unusual shape, indicating that silver atoms must in fact have different local coordination spheres; this is not immediately apparent from the crystal structure due to static disorder of fluorine atoms. The Ag K-edge XANES analysis confirmed that the average oxidation state of silver is indeed close to +1?. The optical absorption spectra lack features typical of a metal thus pointing out to the semiconducting nature of Ag3(SbF6)4. Ag3(SbF6)4 is magnetically diluted and paramagnetic (?(eff) = 1.9 ?(B)) down to 20 K with a very weak temperature independent paramagnetism. Below 20 K weak antiferromagnetism is observed (? = -4.1 K). Replacement of Ag(I) with potassium gives K(I)2Ag(II)(SbF6)4 which is isostructural to Ag(I)2Ag(II)(SbF6)4. Ag3(SbF6)4 is a genuine mixed-valence Ag(I)/Ag(II) compound, i.e. Robin and Day Class I system (localized valences), despite Ag(I) and Ag(II) adopting the same crystallographic position. PMID:25815902

  8. The valence of event-based prospective memory cues or the context in which they occur affects their detection.

    PubMed

    Clark-Foos, Arlo; Brewer, Gene A; Marsh, Richard L; Meeks, J Thadeus; Cook, Gabriel I

    2009-01-01

    Event-based prospective memory tasks entail detecting cues or reminders in our environment related to previously established intentions. If they are detected at an opportune time, then the intention can be fulfilled. In Experiments 1a-1c, we gave people 3 different nonfocal intentions (e.g., respond to words denoting animals) and discovered that negatively valenced cues delivered the intention to mind less frequently than positively valenced cues. In Experiment 2, this effect was extended to valenced and neutral sentential contexts with convergent results that cues embedded in negatively valenced sentences evoked remembering the intention less often than in positive contexts. In addition, both classes of valence caused the intention to be forgotten more often than a more neutral context. We propose that valence has the ability to usurp attentional resources that otherwise would have supported successful prospective memory performance. PMID:19353934

  9. Experimental Constraints on the Partitioning and Valence of V and Cr in Garnet and Coexisting Glass

    NASA Technical Reports Server (NTRS)

    Righter, K.; Sutton, S.; Berthet, S.; Newville, M.

    2008-01-01

    A series of experiments with garnet and coexisting melt have been carried out across a range of oxygen fugacities (near hematite-magnetite (HM) to below the iron-wustite (IW) buffers) at 1.7 GPa to study the partitioning and valence of Cr and V in both phases. Experiments were carried out in a non end loaded piston cylinder apparatus, and the run products were analyzed with electron microprobe and xray absorption near edge structure (XANES) analysis at beamline 13-ID at the Advanced Photon Source of Argonne National Lab. The valence of vanadium and chromium were determined using the position and intensity of the Ka pre-edge peaks, calibrated on a series of Cr and Vbearing standard glasses. This technique has been applied to V and Cr in glasses and V in spinels previously, and in these isotropic phases there are no orientational effects on the XANES spectra (Righter et al., 2006, Amer. Mineral. 91, 1643-1656). We also now demonstrate this to be true for V and Cr in garnet. Also, previous work has shown that V has a higher valence in the glass (or melt) than in the coexisting spinel. This is also true for V in garnet-glass pairs in this study. Vanadium valence in garnets varies from 2.7 below the IW buffer to 3.7 near HM, and for coexisting glass it varies from 3.2 to 4.3. Vanadium valence measured in some natural garnets from mantle localities indicates V in the more reduced range at 2.5. Comparisons will be made between fO2 estimated from V valence and other methods for garnet-bearing mantle samples. In contrast, Cr valence measured in garnet and coexisting glass for all experimental and natural samples is 2.9- 3.0, suggesting that the valence of Cr does not vary within either phase across a large fO2 range. These results demonstrate that while V varies from 2+ to 3+ to 4+ in garnet-melt systems, Cr does not, and this will ultimately affect the partitioning behavior of these two elements in natural systems. Garnet/melt D(Cr) are between 12 and 17 across this range of fO2, whereas D(V) has the highest partition coefficient approx.3, near the IW buffer where the valence of V is almost entirely 3+.

  10. Superplastic forming and diffusion bonding

    NASA Astrophysics Data System (ADS)

    Bolo, Claude

    Technology and applications of superplastic forming and diffusion bonding are surveyed. Cycle-calculation and equipment considerations are examined. Emphasis is placed on aeronautical applications of these processes.

  11. Segregation of information about emotional arousal and valence in horse whinnies

    PubMed Central

    Briefer, Elodie F.; Maigrot, Anne-Laure; Mandel, Roi; Freymond, Sabrina Briefer; Bachmann, Iris; Hillmann, Edna

    2015-01-01

    Studying vocal correlates of emotions is important to provide a better understanding of the evolution of emotion expression through cross-species comparisons. Emotions are composed of two main dimensions: emotional arousal (calm versus excited) and valence (negative versus positive). These two dimensions could be encoded in different vocal parameters (segregation of information) or in the same parameters, inducing a trade-off between cues indicating emotional arousal and valence. We investigated these two hypotheses in horses. We placed horses in five situations eliciting several arousal levels and positive as well as negative valence. Physiological and behavioral measures collected during the tests suggested the presence of different underlying emotions. First, using detailed vocal analyses, we discovered that all whinnies contained two fundamental frequencies (“F0” and “G0”), which were not harmonically related, suggesting biphonation. Second, we found that F0 and the energy spectrum encoded arousal, while G0 and whinny duration encoded valence. Our results show that cues to emotional arousal and valence are segregated in different, relatively independent parameters of horse whinnies. Most of the emotion-related changes to vocalizations that we observed are similar to those observed in humans and other species, suggesting that vocal expression of emotions has been conserved throughout evolution. PMID:25897781

  12. Emotional reactivity to valence-loaded stimuli are related to treatment response of neurocognitive therapy.

    PubMed

    Vanderhasselt, Marie-Anne; De Raedt, Rudi; Namur, Victoria; Valiengo, Leandro C L; Lotufo, Paulo A; Bensenor, Isabela M; Baeken, Chris; Boggio, Paulo S; Brunoni, Andre R

    2016-01-15

    Emotional Context Insensitivity (ECI) is a psychological feature observed in depressed patients characterized by a decreased emotional reactivity when presented to positive- and negative valence-loaded stimuli. Given that fronto-cingulate-limbic circuits are implicated in abnormal reactivity to valence-loaded stimuli, neurocognitive treatments engaging the prefrontal cortex may be able to modulate this emotional blunting observed in MDD. Therefore, our goal was to evaluate emotional reactivity in depressed patients before and after a combination of neurocognitive interventions that engage the prefrontal cortex (cognitive control training and/or transcranial direct current stimulation). In line with the premises of the ECI framework, before the start of the antidepressant intervention, patients showed blunted emotional reactivity after exposure to negative valence-loaded stimuli. This emotional reactivity pattern changed after 9 sessions of the intervention: positive affect decreased and negative affect increased after watching a series of negative valence-loaded stimuli (i.e. images). Interestingly, higher emotional reactivity (as indexed by a larger increase in negative affect after watching the valence-loaded stimuli) at baseline predicted reductions in depression symptoms after the intervention. On the other hand, higher emotional reactivity (as indexed by a decrease in positive affect) after the intervention was marginally associated with reductions in depression symptoms. To conclude, emotional reactivity increased after the neurocognitive antidepressant intervention and it was directly associated to the degree of depression improvement. PMID:26551403

  13. Music, emotion, and time perception: the influence of subjective emotional valence and arousal?

    PubMed Central

    Droit-Volet, Sylvie; Ramos, Danilo; Bueno, José L. O.; Bigand, Emmanuel

    2013-01-01

    The present study used a temporal bisection task with short (<2 s) and long (>2 s) stimulus durations to investigate the effect on time estimation of several musical parameters associated with emotional changes in affective valence and arousal. In order to manipulate the positive and negative valence of music, Experiments 1 and 2 contrasted the effect of musical structure with pieces played normally and backwards, which were judged to be pleasant and unpleasant, respectively. This effect of valence was combined with a subjective arousal effect by changing the tempo of the musical pieces (fast vs. slow) (Experiment 1) or their instrumentation (orchestral vs. piano pieces). The musical pieces were indeed judged more arousing with a fast than with a slow tempo and with an orchestral than with a piano timbre. In Experiment 3, affective valence was also tested by contrasting the effect of tonal (pleasant) vs. atonal (unpleasant) versions of the same musical pieces. The results showed that the effect of tempo in music, associated with a subjective arousal effect, was the major factor that produced time distortions with time being judged longer for fast than for slow tempi. When the tempo was held constant, no significant effect of timbre on the time judgment was found although the orchestral music was judged to be more arousing than the piano music. Nevertheless, emotional valence did modulate the tempo effect on time perception, the pleasant music being judged shorter than the unpleasant music. PMID:23882233

  14. Dissociation of a trait and a valence representation in the mPFC.

    PubMed

    Ma, Ning; Baetens, Kris; Vandekerckhove, Marie; Van der Cruyssen, Laurens; Van Overwalle, Frank

    2014-10-01

    A previous functional MRI adaptation study on trait inference indicated that a trait code is located in the ventral medial prefrontal cortex (vmPFC), but could not rule out that this adaptation effect is due to the trait's underlying valence. To address this issue, we presented sentences describing positive and negative valences of either a human trait or object characteristic, and manipulated whether the human trait or object characteristic was repeated or not, either with the same or opposite valance. In two trait conditions, a behavioral trait-implying sentence was preceded by a prime sentence that implied the same or the opposite trait. The results confirmed the earlier finding of robust trait adaptation from prime to target in the vmPFC, and also found adaptation in the precuneus and right mid-occipital cortex. In contrast, no valence adaptation was found in two novel object conditions, in which the target sentence again implied a positive or negative trait, but was preceded by a prime sentence that described an object with the same or the opposite valence. Together with the previous study, this indicates that a specific trait code, but not a generalized valence code, is represented in the vmPFC. PMID:23974949

  15. Representational Similarity of Social and Valence Information in the Medial Prefrontal Cortex

    PubMed Central

    Chavez, Robert S.; Heatherton, Todd F.

    2015-01-01

    The human brain is remarkably adept at integrating complex information to form unified psychological representations of agents, objects, and events in the environment. Two domains in which this ability is particularly salient are the processing of social and valence information and are supported by common cortical areas in the medial prefrontal cortex (MPFC). Because social information is often embedded within valenced emotional contexts, it is possible that activation patterns within the MPFC may represent both of these types of cognitive processes when presented simultaneously. The current study tested this possibility by employing a large-scale automated meta-analysis tool, together with multi-voxel pattern analysis to investigate the representational similarity of social and valence information in the MPFC during functional magnetic resonance imaging. Using a representational similarity analysis, we found a high degree of representational similarity both within social dimensions and within valence dimensions, but not across them (e.g., positive social information was highly dissimilar to negative non-social information), in a ventral portion of the MPFC. These results were significantly correlated with a behaviorally measured similarity structure of the same stimuli, suggesting that a psychologically meaningful representation of social and valence information is reflected by multi-voxel activation patterns in the ventral MPFC. PMID:25100218

  16. Making and breaking of chemisorption bonds

    NASA Astrophysics Data System (ADS)

    Lundqvist, Bengt I.

    1982-07-01

    A brief review of recent contributions from surface physics to the understanding of chemisorption and desorption is given. The first question that is addressed is: What happens to a molecule when itcomes close to a metal surface? On the basis of self-consistent calculations for atoms [1,2] and molecules [3] on simple metal surfaces general trends and concepts are described and a scenario for H 2 on Mg(0001) is presented [4]. Except for the physisorption occuring at distances ˜ 3 Å or larger outside the surface the molecule-surface interaction is characterized by substantial redistributions of the electrons. Molecular electron energy levels are shifted and broadened. In particular, the antibonding affinity level of H 2 is shifted to lower energies. The spatial redistribution of the electrons is beneficial for an increased electron-proton interaction, and thereby for the chemisorption energy of H, i.e. for the constituents of H 2. The intramolecular bond between the constituents, on the other hand, is weakened on the surface by at least one order of magnitude and at some instances even becomes repulsive. The reason for this breaking of the molecular bond is the downward shift at the antibonding molecular-orbital resonance allowing its partial filling with conduction electrons from the metal [5]. Also for the dynamic aspects of the chemisorption, the variation of electron structure upon the molecular approach to the surface is of key importance. For instance, there can be electronic mechanisms for the dissipation of the molecular translational energy, required for the trapping of the molecule [6]. For the emission of ions, occuring in, e.g., sputtering, the variation of the electron structure of the emitted particle is also very important [7]. The second question concerns the desorption of adsorbed species upon electron or photon impact. A brief review is given of proposed mechanisms for electron- and photon-stimulated desorption, ESD and PSD, respectively [8]. The Redhead-Gomer-Menzel mechanism for ESD [9] assumes the incoming electron to excite a valence electron contributing to the adsorbate-substrate bond into an antibonding orbital. This changes the attractive potential energy curve of the adsorbate into a repulsive one, and the adparticle finds it energetically favourable to leave the surface, i.e., to desorb. The mechanism of Knotek and Feibelman [10] originated from studies of O + desorption from TiO 2, where the O + ion yield was found to increase considerably at incident electron energies that coincide with ionization potentials of core electrons of the metal ion. Their mechanism is an Auger decay model, where after the creation of a core hole there is a deexcitation by an interatomic Auger process, where due to the suddenness of the process and the Coulomb repulsion between electrons the Auger electron is likely to be followed by a second emitted electron. The resulting O + ion ends up on a repulsive potential-energy curve and desorbs. The mechanism has later been extended to intraatomic Auger processes and PSD and successfully applied to selective breaking of bonds [8].

  17. Mixed valency and site-preference chemistry for cerium and its compounds: A predictive density-functional theory study

    SciTech Connect

    Alam, Aftab; Johnson, Duane D.

    2014-06-01

    Cerium and its technologically relevant compounds are examples of anomalous mixed valency, originating from two competing oxidation states—itinerant Ce4+ and localized Ce3+. Under applied stress, anomalous transitions are observed but not well understood. Here we treat mixed valency as an “alloy” problem involving two valences with competing and numerous site-occupancy configurations. We use density-functional theory with Hubbard U (i.e., DFT+U) to evaluate the effective valence and predict properties, including controlling the valence by pseudoternary alloying. For Ce and its compounds, such as (Ce,La)2(Fe,Co)14B permanent magnets, we find a stable mixed-valent ? state near the spectroscopic value of ?s=3.53. Ce valency in compounds depends on its steric volume and local chemistry. For La doping, Ce valency shifts towards ?-like Ce3+, as expected from steric volume; for Co doping, valency depends on local Ce-site chemistry and steric volume. Our approach captures the key origins of anomalous valency and site-preference chemistry in complex compounds.

  18. Core-core and core-valence correlation energy atomic and molecular benchmarks for Li through Ar.

    PubMed

    Ranasinghe, Duminda S; Frisch, Michael J; Petersson, George A

    2015-12-01

    We have established benchmark core-core, core-valence, and valence-valence absolute coupled-cluster single double (triple) correlation energies (±0.1%) for 210 species covering the first- and second-rows of the periodic table. These species provide 194 energy differences (±0.03 mEh) including ionization potentials, electron affinities, and total atomization energies. These results can be used for calibration of less expensive methodologies for practical routine determination of core-core and core-valence correlation energies. PMID:26646872

  19. Electron localization in a mixed-valence diniobium benzene complex

    DOE PAGESBeta

    Gianetti, Thomas L.; Nocton, Grégory; Minasian, Stefan G.; Kaltsoyannis, Nikolas; Kilcoyne, A. L. David; Kozimor, Stosh A.; Shuh, David K.; Tyliszczak, Tolek; Bergman, Robert G.; Arnold, John

    2014-11-11

    Reaction of the neutral diniobium benzene complex {[Nb(BDI)NtBu]2(?-C6H6)} (BDI = N,N'-diisopropylbenzene-?-diketiminate) with Ag[B(C6F5)4] results in a single electron oxidation to produce a cationic diniobium arene complex, {[Nb(BDI)NtBu]2(?-C6H6)}{B(C6F5)4}. Investigation of the solid state and solution phase structure using single-crystal X-ray diffraction, cyclic voltammetry, magnetic susceptibility, and multinuclear NMR spectroscopy indicates that the oxidation results in an asymmetric molecule with two chemically inequivalent Nb atoms. Further characterization using density functional theory (DFT) calculations, UV-visible, Nb L3,2-edge X-ray absorption near-edge structure (XANES), and EPR spectroscopies supports assignment of a diniobium complex, in which one Nb atom carries a single unpaired electron that ismore »not largely delocalized on the second Nb atom. During the oxidative transformation, one electron is removed from the ?-bonding HOMO, which causes a destabilization of the molecule and formation of an asymmetric product. Subsequent reactivity studies indicate that the oxidized product allows access to metal-based chemistry with substrates that did not exhibit reactivity with the starting neutral complex.« less

  20. Electron localization in a mixed-valence diniobium benzene complex

    SciTech Connect

    Gianetti, Thomas L.; Nocton, Grégory; Minasian, Stefan G.; Kaltsoyannis, Nikolas; Kilcoyne, A. L. David; Kozimor, Stosh A.; Shuh, David K.; Tyliszczak, Tolek; Bergman, Robert G.; Arnold, John

    2014-11-11

    Reaction of the neutral diniobium benzene complex {[Nb(BDI)NtBu]2(?-C6H6)} (BDI = N,N'-diisopropylbenzene-?-diketiminate) with Ag[B(C6F5)4] results in a single electron oxidation to produce a cationic diniobium arene complex, {[Nb(BDI)NtBu]2(?-C6H6)}{B(C6F5)4}. Investigation of the solid state and solution phase structure using single-crystal X-ray diffraction, cyclic voltammetry, magnetic susceptibility, and multinuclear NMR spectroscopy indicates that the oxidation results in an asymmetric molecule with two chemically inequivalent Nb atoms. Further characterization using density functional theory (DFT) calculations, UV-visible, Nb L3,2-edge X-ray absorption near-edge structure (XANES), and EPR spectroscopies supports assignment of a diniobium complex, in which one Nb atom carries a single unpaired electron that is not largely delocalized on the second Nb atom. During the oxidative transformation, one electron is removed from the ?-bonding HOMO, which causes a destabilization of the molecule and formation of an asymmetric product. Subsequent reactivity studies indicate that the oxidized product allows access to metal-based chemistry with substrates that did not exhibit reactivity with the starting neutral complex.

  1. Electronic structure of ?-RbSm(MoO?)? and chemical bonding in molybdates.

    PubMed

    Atuchin, V V; Aleksandrovsky, A S; Chimitova, O D; Diao, Cheng-Peng; Gavrilova, T A; Kesler, V G; Molokeev, M S; Krylov, A S; Bazarov, B G; Bazarova, J G; Lin, Zheshuai

    2015-01-28

    Microcrystals of orthorhombic rubidium samarium molybdate, ?-RbSm(MoO4)2, have been fabricated by solid state synthesis at T = 450 °C, 70 h, and at T = 600 °C, 150 h. The crystal structure has been refined by the Rietveld method in space group Pbcn with cell parameters a = 5.0984(2), b = 18.9742(6) and c = 8.0449(3) Å (R(B) = 1.72%). Thermal properties of ?-RbSm(MoO4)2 were traced by DSC over the temperature range of T = 20-965 °C, and the earlier reported ? ? ? phase transition at T ? 860-910 °C was not verified. The electronic structure of ?-RbSm(MoO4)2 was studied by employing theoretical calculations and X-ray photoelectron spectroscopy. It has been established that the O 2p-like states contribute mainly to the upper part of the valence band and occupy the valence band maximum, whereas the Mo 4d-like states contribute mainly to the lower part of the valence band. Chemical bonding effects have been analysed from the element core level binding energy data. In addition, it was found that the luminescence spectrum of ?-RbSm(MoO4)2 is rather peculiar among the Sm(3+) containing materials. The optical refractive index dispersion in ?-RbSm(MoO4)2 was also predicted by the first-principles calculations. PMID:25474328

  2. Feasibility of Valence-to-Core X-ray Emission Spectroscopy for Tracking Transient Species

    PubMed Central

    2015-01-01

    X-ray spectroscopies, when combined in laser-pump, X-ray-probe measurement schemes, can be powerful tools for tracking the electronic and geometric structural changes that occur during the course of a photoinitiated chemical reaction. X-ray absorption spectroscopy (XAS) is considered an established technique for such measurements, and X-ray emission spectroscopy (XES) of the strongest core-to-core emission lines (K? and K?) is now being utilized. Flux demanding valence-to-core XES promises to be an important addition to the time-resolved spectroscopic toolkit. In this paper we present measurements and density functional theory calculations on laser-excited, solution-phase ferrocyanide that demonstrate the feasibility of valence-to-core XES for time-resolved experiments. We discuss technical improvements that will make valence-to-core XES a practical pump–probe technique. PMID:26568779

  3. Reactivity of seventeen- and nineteen-valence electron complexes in organometallic chemistry

    NASA Technical Reports Server (NTRS)

    Stiegman, Albert E.; Tyler, David R.

    1986-01-01

    A guideline to the reactivity of 17- and 19-valence electron species in organometallic chemistry is proposed which the authors believe will supersede all others. The thesis holds that the reactions of 17-electron metal radicals are associatively activated with reactions proceeding through a 19-valence electron species. The disparate reaction chemistry of the 17-electron metal radicals are unified in terms of this associative reaction pathway, and the intermediacy of 19-valence electron complexes in producing the observed products is discussed. It is suggested that related associatively activated pathways need to be considered in some reactions that are thought to occur by more conventional routes involving 16- and 18-electron intermediates. The basic reaction chemistry and electronic structures of these species are briefly discussed.

  4. Reducibility of valence-3 Killing tensors in Weyl's class of stationary and axially symmetric spacetimes

    NASA Astrophysics Data System (ADS)

    Vollmer, Andreas

    2015-10-01

    Stationary and axially symmetric spacetimes play an important role in astrophysics, particularly in the theory of neutron stars and black holes. The static vacuum subclass of these spacetimes is known as Weyl's class, and contains the Schwarzschild spacetime as its most prominent example. This paper is going to study the space of Killing tensor fields of valence 3 for spacetimes of Weyl's class. Killing tensor fields play a crucial role in physics since they are in correspondence to invariants of the geodesic motion (i.e. constants of the motion). It will be proven that in static and axially symmetric vacuum spacetimes the space of Killing tensor fields of valence 3 is generated by Killing vector fields and quadratic Killing tensor fields. Using this result, it will be proven that for the family of Zipoy-Voorhees metrics, valence-3 Killing tensor fields are always generated by Killing vector fields and the metric.

  5. Emotional Valence, Arousal, and Threat Ratings of 160 Chinese Words among Adolescents

    PubMed Central

    Ho, Samuel M. Y.; Mak, Christine W. Y.; Yeung, Dannii; Duan, Wenjie; Tang, Sandy; Yeung, June C.; Ching, Rita

    2015-01-01

    This study was conducted to provide ratings of valence/pleasantness, arousal/excitement, and threat/potential harm for 160 Chinese words. The emotional valence classification (positive, negative, or neutral) of all of the words corresponded to that of the equivalent English language words. More than 90% of the participants, junior high school students aged between 12 and 17 years, understood the words. The participants were from both mainland China and Hong Kong, thus the words can be applied to adolescents familiar with either simplified (e.g. in mainland China) or traditional Chinese (e.g. in Hong Kong) with a junior secondary school education or higher. We also established eight words with negative valence, high threat, and high arousal ratings to facilitate future research, especially on attentional and memory biases among individuals prone to anxiety. Thus, the new emotional word list provides a useful source of information for affective research in the Chinese language. PMID:26226604

  6. Reversing Stimulus Timing in Visual Conditioning Leads to Memories with Opposite Valence in Drosophila

    PubMed Central

    Vogt, Katrin; Yarali, Ayse; Tanimoto, Hiromu

    2015-01-01

    Animals need to associate different environmental stimuli with each other regardless of whether they temporally overlap or not. Drosophila melanogaster displays olfactory trace conditioning, where an odor is followed by electric shock reinforcement after a temporal gap, leading to conditioned odor avoidance. Reversing the stimulus timing in olfactory conditioning results in the reversal of memory valence such that an odor that follows shock is later on approached (i.e. relief conditioning). Here, we explored the effects of stimulus timing on memory in another sensory modality, using a visual conditioning paradigm. We found that flies form visual memories of opposite valence depending on stimulus timing and can associate a visual stimulus with reinforcement despite being presented with a temporal gap. These results suggest that associative memories with non-overlapping stimuli and the effect of stimulus timing on memory valence are shared across sensory modalities. PMID:26430885

  7. Reference Valence Effects of Affective S–R Compatibility: Are Visual and Auditory Results Consistent?

    PubMed Central

    Xiaojun, Zhao; Xuqun, You; Changxiu, Shi; Shuoqiu, Gan; Chaoyi, Hu

    2014-01-01

    Humans may be faster to avoid negative words than to approach negative words, and faster to approach positive words than to avoid positive words. That is an example of affective stimulus–response (S–R) compatibility. The present study identified the reference valence effects of affective stimulus–response (S–R) compatibility when auditory stimulus materials are used. The researchers explored the reference valence effects of affective S–R compatibility using a mixed-design experiment based on visual words, visual pictures and audition. The study computed the average compatibility effect size. A t-test based on visual pictures showed that the compatibility effect size was significantly different from zero, t (22)?=?2.43, p<.05 (M?=?485 ms). Smaller compatibility effects existed when switching the presentation mode from visual stimuli to auditory stimuli. This study serves as an important reference for the auditory reference valence effects of affective S–R compatibility. PMID:24743797

  8. fK /f{pi} in Full QCD with Domain Wall Valence Quarks

    SciTech Connect

    Silas Beane; Paulo Bedaque; Konstantinos Orginos; Martin Savage

    2007-05-01

    We compute the ratio of pseudoscalar decay constants f{sub K}/f{sub {pi}} using domain-wall valence quarks and rooted improved Kogut-Susskind sea quarks. By employing continuum chiral perturbation theory, we extract the Gasser-Leutwyler low-energy constant L{sub 5}, and extrapolate f{sub K}/f{sub {pi}} to the physical point. We find: f{sub K}/f{sub {pi}} = 1.218 {+-} 0.002{sub -0.024}{sup +0.011} where the first error is statistical and the second error is an estimate of the systematic due to chiral extrapolation and fitting procedures. This value agrees within the uncertainties with the determination by the MILC collaboration, calculated using Kogut-Susskind valence quarks, indicating that systematic errors arising from the choice of lattice valence quark are small.

  9. Identification of Ectonucleotide Pyrophosphatase/Phosphodiesterase 3 (ENPP3) as a Regulator of N-Acetylglucosaminyltransferase GnT-IX (GnT-Vb)*

    PubMed Central

    Korekane, Hiroaki; Park, Jong Yi; Matsumoto, Akio; Nakajima, Kazuki; Takamatsu, Shinji; Ohtsubo, Kazuaki; Miyamoto, Yasuhide; Hanashima, Shinya; Kanekiyo, Kenji; Kitazume, Shinobu; Yamaguchi, Yoshiki; Matsuo, Ichiro; Taniguchi, Naoyuki

    2013-01-01

    Our previous studies on a ?1,6-N-acetylglucosaminyltransferase, GnT-IX (GnT-Vb), a homolog of GnT-V, indicated that the enzyme has a broad GlcNAc transfer activity toward N-linked and O-mannosyl glycan core structures and that its brain-specific gene expression is regulated by epigenetic histone modifications. In this study, we demonstrate the existence of an endogenous inhibitory factor for GnT-IX that functions as a key regulator for GnT-IX enzymatic activity in Neuro2a (N2a) cells. We purified this factor from N2a cells and found that it is identical to ectonucleotide pyrophosphatase/phosphodiesterase 3 (ENPP3), as evidenced by mass spectrometry and by the knockdown and overexpression of ENPP3 in cultured cells. Kinetic analyses revealed that the mechanism responsible for the inhibition of GnT-IX caused by ENPP3 is the ENPP3-mediated hydrolysis of the nucleotide sugar donor substrate, UDP-GlcNAc, with the resulting generation of UMP, a potent and competitive inhibitor of GnT-IX. Indeed, ENPP3 knockdown cells had significantly increased levels of intracellular nucleotide sugars and displayed changes in the total cellular glycosylation profile. In addition to chaperones or other known regulators of glycosyltransferases, the ENPP3-mediated hydrolysis of nucleotide sugars would have widespread and significant impacts on glycosyltransferase activities and would be responsible for altering the total cellular glycosylation profile and modulating cellular functions. PMID:23960081

  10. Microwave bonding of MEMS component

    NASA Technical Reports Server (NTRS)

    Barmatz, Martin B. (Inventor); Mai, John D. (Inventor); Jackson, Henry W. (Inventor); Budraa, Nasser K. (Inventor); Pike, William T. (Inventor)

    2005-01-01

    Bonding of MEMs materials is carried out using microwave. High microwave absorbing films are placed within a microwave cavity, and excited to cause selective heating in the skin of the material. This causes heating in one place more than another. Thereby minimizing the effects of the bonding microwave energy.

  11. Weld-bonded titanium structures

    NASA Technical Reports Server (NTRS)

    Vaughan, R. W.; Creedon, J. F. (inventors)

    1976-01-01

    Structurally stronger titanium articles are produced by a weld-bonding technique comprising fastening at least two plates of titanium together using spotwelding and curing an adhesive interspersed between the spot-weld nuggets. This weld-bonding may be employed to form lap joints or to stiffen titanium metal plates.

  12. Computational Chemistry of Adhesive Bonds

    NASA Technical Reports Server (NTRS)

    Phillips, Donald H.

    1999-01-01

    This investigation is intended to determine the electrical mechanical, and chemical properties of adhesive bonds at the molecular level. The initial determinations will be followed by investigations of the effects of environmental effects on the chemistry and properties of the bond layer.

  13. Perception of emotional valences and activity levels from vowel segments of continuous speech.

    PubMed

    Waaramaa, Teija; Laukkanen, Anne-Maria; Airas, Matti; Alku, Paavo

    2010-01-01

    This study aimed to investigate the role of voice source and formant frequencies in the perception of emotional valence and psychophysiological activity level from short vowel samples (approximately 150 milliseconds). Nine professional actors (five males and four females) read a prose passage simulating joy, tenderness, sadness, anger, and a neutral emotional state. The stress carrying vowel [a:] was extracted from continuous speech during the Finnish word [ta:k:ahan] and analyzed for duration, fundamental frequency (F0), equivalent sound level (L(eq)), alpha ratio, and formant frequencies F1-F4. Alpha ratio was calculated by subtracting the L(eq) (dB) in the range 50 Hz-1 kHz from the L(eq) in the range 1-5 kHz. The samples were inverse filtered by Iterative Adaptive Inverse Filtering and the estimates of the glottal flow obtained were parameterized with the normalized amplitude quotient (NAQ = f(AC)/(d(peak)T)). Fifty listeners (mean age 28.5 years) identified the emotional valences from the randomized samples. Multinomial Logistic Regression Analysis was used to study the interrelations of the parameters for perception. It appeared to be possible to identify valences from vowel samples of short duration ( approximately 150 milliseconds). NAQ tended to differentiate between the valences and activity levels perceived in both genders. Voice source may not only reflect variations of F0 and L(eq), but may also have an independent role in expression, reflecting phonation types. To some extent, formant frequencies appeared to be related to valence perception but no clear patterns could be identified. Coding of valence tends to be a complicated multiparameter phenomenon with wide individual variation. PMID:19111438

  14. Coordination-Resolved Spectrometrics of Local Bonding and Electronic Dynamics of Au Atomic Clusters, Solid Skins, and Oxidized Foils.

    PubMed

    Yu, Wang; Bo, Maolin; Huang, Yongli; Wang, Yan; Li, Can; Sun, Chang Q

    2015-07-20

    By using combination of bond-order-length-strength (BOLS) correlation, the tight-binding (TB) approach, and zone-selective photoelectron spectroscopy (ZPS), we were able to resolve local bond relaxation and the associated 4f7/2 core-level shift of Au atomic clusters, Au(100, 110, 111) skins, and Au foils exposed to ozone for different lengths of time. In addition to quantitative information, such as local bond length, bond energy, binding-energy density, and atomic cohesive energy, the results confirm our predictions that bond-order deficiency shortens and stiffens the bond between undercoordinated atoms, which results in local densification and quantum entrapment of bonding electrons. The entrapment perturbs the Hamiltonian, and hence, shifts the core-level energy accordingly. ZPS also confirms that oxidation enhances the effect of atomic undercoordination on the positive 4f7/2 energy shift, with the associated valence electron polarization contributing to the catalytic ability of undercoordinated Au atoms. PMID:25916877

  15. Social bonding: regulation by neuropeptides

    PubMed Central

    Lieberwirth, Claudia; Wang, Zuoxin

    2014-01-01

    Affiliative social relationships (e.g., among spouses, family members, and friends) play an essential role in human society. These relationships affect psychological, physiological, and behavioral functions. As positive and enduring bonds are critical for the overall well-being of humans, it is not surprising that considerable effort has been made to study the neurobiological mechanisms that underlie social bonding behaviors. The present review details the involvement of the nonapeptides, oxytocin (OT), and arginine vasopressin (AVP), in the regulation of social bonding in mammals including humans. In particular, we will discuss the role of OT and AVP in the formation of social bonds between partners of a mating pair as well as between parents and their offspring. Furthermore, the role of OT and AVP in the formation of interpersonal bonding involving trust is also discussed. PMID:25009457

  16. Lyman-series emission after valence and core excitation of water vapor

    NASA Astrophysics Data System (ADS)

    Hans, A.; Knie, A.; Schmidt, Ph.; Ben Ltaief, L.; Ozga, C.; Reiß, Ph.; Huckfeldt, H.; Förstel, M.; Hergenhahn, U.; Ehresmann, A.

    2015-09-01

    We report Lyman-series emission cross sections of neutral hydrogen dissociation fragments after valence (15-34 eV) and inner-shell (533-542 eV) excitation of water vapor with monochromatic synchrotron radiation as functions of the exciting-photon energy. In the valence excitation energy region, the thermodynamical limits of the production of the differently excited hydrogen fragments are directly observed and absolute emission cross sections are determined. For resonant inner-shell excitations, the fluorescing excited hydrogen state is found to be strongly dependent on the molecular or Rydberg-like character of the excitation.

  17. A New Synthetic Route for Mixed-Valence Compounds: Leaching Treatments of Hydrogen Molybdenum Bronze

    NASA Astrophysics Data System (ADS)

    Eda, Kazuo; Sukejima, Ai; Sotani, Noriyuki

    2001-06-01

    In order to explore the possibilities of a new synthetic route, based on selective extraction of the same atomic species with different valences, for mixed-valence compounds, leaching treatments of HxMoO3 with various x values with various kinds of solutions were investigated. Both oxidation-type (pseudooxidation) and reduction-type (pseudoreduction) products could be obtained by these simple treatments without oxidizing or reducing agents. Their formation mechanisms were elucidated from various investigations of solutions as well as solids. Moreover, novel hydrated hydrogen-alkali metal co-insertion compounds of layered molybdenum oxide with larger hydrogen contents were obtained by the treatments.

  18. Retrieving the dielectric function of diamond from valence electron energy-loss spectroscopy

    SciTech Connect

    Zhang, L.; Verbeeck, J.; Tendeloo, G. van; Erni, R.

    2008-05-15

    A data-acquisition and data-processing method is proposed that aims at minimizing the effect of retardation on the Kramers-Kronig analysis of valence electron energy-loss spectra. This method is applied to diamond, which, due to its high dielectric constant, is a material that shows strong retardation effects and thus is a challenging material to be studied by valence electron energy-loss spectroscopy. The results obtained show a significant improvement but still show small discrepancies with respect to optical data, which are most likely due to the residual retardation contributions and the fact that nonzero momentum transfers are measured.

  19. 27 CFR 25.95 - New bond.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2014-04-01 2014-04-01 false New bond. 25.95 Section 25... TREASURY ALCOHOL BEER Bonds and Consents of Surety § 25.95 New bond. The appropriate TTB officer may at any time, at his or her discretion, require a new bond. A new bond is required immediately in the case...

  20. 27 CFR 25.95 - New bond.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2011-04-01 2011-04-01 false New bond. 25.95 Section 25... TREASURY LIQUORS BEER Bonds and Consents of Surety § 25.95 New bond. The appropriate TTB officer may at any time, at his or her discretion, require a new bond. A new bond is required immediately in the case...

  1. 27 CFR 25.95 - New bond.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2012-04-01 2012-04-01 false New bond. 25.95 Section 25... TREASURY LIQUORS BEER Bonds and Consents of Surety § 25.95 New bond. The appropriate TTB officer may at any time, at his or her discretion, require a new bond. A new bond is required immediately in the case...

  2. 27 CFR 25.95 - New bond.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false New bond. 25.95 Section 25... TREASURY LIQUORS BEER Bonds and Consents of Surety § 25.95 New bond. The appropriate TTB officer may at any time, at his or her discretion, require a new bond. A new bond is required immediately in the case...

  3. 27 CFR 25.95 - New bond.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2013-04-01 2013-04-01 false New bond. 25.95 Section 25... TREASURY ALCOHOL BEER Bonds and Consents of Surety § 25.95 New bond. The appropriate TTB officer may at any time, at his or her discretion, require a new bond. A new bond is required immediately in the case...

  4. Trends and surprises in bonding in anionic clusters of coinage metals

    NASA Astrophysics Data System (ADS)

    Moseler, Michael; Häkkinen, Hannu; Landman, Uzi

    2002-03-01

    Energetics, electronic stucture, and bonding in anionic coinage metal clusters is investigated via a density-functional study of an extensive set of cluster isomers of anionic heptamers of copper, silver, and gold. While Cu_7^- and Ag_7^- clusters have 3D ground state structures similar to those of a simple metal cluster Na_7^-, the ground-state structure of Au_7^- is planar, separated from the energetically best 3D isomer by 0.5 eV. The simulated photodetachment and photoabsorption spectra for the planar ground state of Au_7^- agree well with the available experimental data. The propensity of gold clusters to favor planar structures is shown to be correlated with strong relativistic s-d hybridization of the atomic valence states, making bonding in gold clusters unique among coinage metals. Planar structures are favored also in larger gold cluster anions, of up to about 13 atoms.

  5. 29 CFR 2580.412-19 - Term of the bond, discovery period, other bond clauses.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...DEPARTMENT OF LABOR TEMPORARY BONDING RULES UNDER THE EMPLOYEE RETIREMENT INCOME SECURITY ACT OF 1974 TEMPORARY BONDING RULES General Bond Rules § 2580...section 13, if, with respect to bonding coverage required under section...

  6. 29 CFR 2580.412-19 - Term of the bond, discovery period, other bond clauses.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...DEPARTMENT OF LABOR TEMPORARY BONDING RULES UNDER THE EMPLOYEE RETIREMENT INCOME SECURITY ACT OF 1974 TEMPORARY BONDING RULES General Bond Rules § 2580...section 13, if, with respect to bonding coverage required under section...

  7. Coordination-resolved local bond contraction and electron binding-energy entrapment of Si atomic clusters and solid skins

    SciTech Connect

    Bo, Maolin; Huang, Yongli; Zhang, Ting; Wang, Yan E-mail: ecqsun@ntu.edu.sg; Zhang, Xi; Li, Can; Sun, Chang Q. E-mail: ecqsun@ntu.edu.sg

    2014-04-14

    Consistency between x-ray photoelectron spectroscopy measurements and density-function theory calculations confirms our bond order-length-strength notation-incorporated tight-binding theory predictions on the quantum entrapment of Si solid skin and atomic clusters. It has been revealed that bond-order deficiency shortens and strengthens the Si-Si bond, which results in the local densification and quantum entrapment of the core and valence electrons. Unifying Si clusters and Si(001) and (111) skins, this mechanism has led to quantification of the 2p binding energy of 96.089?eV for an isolated Si atom, and their bulk shifts of 2.461?eV. Findings evidence the significance of atomic undercoordination that is of great importance to device performance.

  8. Halogen Bonding Molecular Capsules.

    PubMed

    Dumele, Oliver; Trapp, Nils; Diederich, François

    2015-10-12

    Molecular capsules based solely on the interaction of halogen bonding (XB) are presented along with their host-guest binding properties in solution. The first example of a well-defined four-point XB supramolecular system is realized by decorating resorcin[4]arene cavitands with polarized halogen atoms for dimerization with tetra(4-pyridyl) resorcin[4]arene cavitands. NMR binding data for the F, Cl, Br, and I cavitands as the XB donor show association constants (Ka ) of up to 5370?M(-1) (?G283?K =-4.85?kcal?mol(-1) , for I), even in XB-competitive solvent, such as deuterated benzene/acetone/methanol (70:30:1) at 283?K, where comparable monodentate model systems show no association. The XB capsular geometry is evidenced by two-dimensional HOESY NMR, and the thermodynamic profile shows that capsule formation is enthalpically driven. Either 1,4-dioxane or 1,4-dithiane are encapsulated within each of the two separate cavities within the XB capsule, with of up to Ka =9.0 10(8) ?M(-2) (?G283?K =-11.6?kcal?mol(-1) ). PMID:26013544

  9. Correlated Tunneling in Hydrogen Bonds

    NASA Astrophysics Data System (ADS)

    Lin, Lin; Morrone, Joseph A.; Car, Roberto

    2011-10-01

    We study the quantum nature of the protons participating in hydrogen bonds in several ice structures by analyzing the one particle density matrix. We find that in all cases, including ice Ih, the most common form of ice, and the high pressure phases, ice VIII, VII, and X, the system is ground-state dominated. However, while the dynamics is uncorrelated in the structures with standard asymmetric hydrogen bonds, such as ice Ih and VIII, local correlations among the protons characterize ice VII and, to a lesser extent, ice X in the so-called low barrier hydrogen bond regime. The correlations appear along the path to hydrogen bond symmetrization, when quantum fluctuations delocalize the proton on the two bond sides. The correlations derive from a strong requirement for local charge neutrality that favors concerted motion along the bonds. The resulting behavior deviates substantially from mean field theory, which would predict in ice VII coherent tunneling of the proton between the two bond sides, thereby causing an ionization catastrophe. Due to the correlations, the quantum state of the proton is entangled.

  10. 75 FR 39730 - Tribal Economic Development Bonds

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-07-12

    ... Tribal Economic Development Bonds AGENCY: Department of the Treasury, Departmental Offices. ACTION... from Indian Tribal Governments regarding the Tribal Economic Development Bond provision in Section 7871... ``Tribal Economic Development Bonds,'' under Section 7871(f) of the Internal Revenue Code (``Code'')...

  11. 43 CFR 3904.10 - Bonding requirements.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ...Interior 2 2011-10-01 2011-10-01 false Bonding requirements. 3904.10 Section 3904.10 Public Lands...MANAGEMENT-GENERAL Bonds and Trust Funds § 3904.10 Bonding requirements. (a) Prior to issuing a lease...

  12. 46 CFR Sec. 4 - Posting of bond.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ...2010-10-01 2010-10-01 false Posting of bond. Sec. 4 Section 4 Shipping MARITIME ADMINISTRATION, DEPARTMENT...A-NATIONAL SHIPPING AUTHORITY BONDING OF SHIP'S PERSONNEL Sec. 4 Posting of bond. The General Agent shall...

  13. Explosive bonding of metal-matrix composites

    NASA Technical Reports Server (NTRS)

    Reece, O. Y.

    1969-01-01

    Explosive bonding process produces sheet composites of aluminum alloy reinforced by high-strength stainless steel wires. The bonds are excellent metallurgically, no external heat is required, various metals can be bonded, and the process is inexpensive.

  14. 75 FR 39730 - Tribal Economic Development Bonds

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-07-12

    ...DEPARTMENT OF THE TREASURY Tribal Economic Development Bonds AGENCY: Department...Governments regarding the Tribal Economic Development Bond provision in Section...governments, known as ``Tribal Economic Development Bonds,'' under...

  15. 19 CFR 125.32 - Merchandise delivered to a bonded store or bonded warehouse.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...delivered to a bonded store or bonded warehouse. 125.32 Section 125.32 Customs...delivered to a bonded store or bonded warehouse. When merchandise is carried, carted...and received in a bonded store or bonded warehouse, the proprietor or his...

  16. 19 CFR 125.32 - Merchandise delivered to a bonded store or bonded warehouse.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ...delivered to a bonded store or bonded warehouse. 125.32 Section 125.32 Customs...delivered to a bonded store or bonded warehouse. When merchandise is carried, carted...and received in a bonded store or bonded warehouse, the proprietor or his...

  17. Abstract. We present a general approach for describing chemical processes (bond breaking and bond formation)

    E-print Network

    Goddard III, William A.

    Abstract. We present a general approach for describing chemical processes (bond breaking and bond the dissoci- ation and formation of chemical bonds. Although high- quality quantum mechanical (QM®c bond orders into speci®c bonds and do not allow bond breaking [1, 2]. In contrast, a chemical reaction

  18. Effect of laser irradiation on the structure and valence states of copper in Cu-phosphate glass by XPS studies

    E-print Network

    Mekki, Abdelkarim

    Effect of laser irradiation on the structure and valence states of copper in Cu-phosphate glass 2010 Keywords: XPS Phosphate glasses TM oxide glasses Laser effect on glass A B S T R A C T The effect on the local glass structure as well as on the valence state of the copper ions in copper phosphate glass

  19. Determination of Mn valence states in mixed-valent manganates by XANES spectroscopy AlAin MAnceAu,1,

    E-print Network

    + valences in mixed-valent manganates and phase mixtures. The XANES derivatives of tectomanganates positions of the main features characteristics of a particular valence composition. For these compounds to as phyllo- manganates or as birnessite-type compounds and those with a tunnel framework structure

  20. Intergroup Discrimination in Positive and Negative Outcome Allocations: Impact of Stimulus Valence, Relative Group Status, and Relative Group Size.

    ERIC Educational Resources Information Center

    Otten, Sabine; And Others

    1996-01-01

    Three studies investigated the determination of social discrimination by the valence of stimuli that are allocated between groups. The studies were based on either the minimal group paradigm or a more reality-based laboratory intergroup setting, with stimulus valence, group status, and group size as factors and with pull scores on Tajfel matrices…

  1. Theory of chemical bonds in metalloenzymes II: Hybrid-DFT studies in iron-sulfur clusters

    NASA Astrophysics Data System (ADS)

    Shoji, M.; Koizumi, K.; Kitagawa, Y.; Yamanaka, S.; Kawakami, T.; Okumura, M.; Yamaguchi, K.

    Important chemical reactions for life often require multistep electron transfers (ET) and strong reducing forces. In these reactions, electron transfer proteins as ferredoxins (Fds) play a key role. For elucidation of the core electronic states in these electron transfer processes, an inorganic model compound [Fe2S2(S2-o-xyl)2] is used as our first study. It was experimentally characterized that the model compound is in a similar electronic state to the active site core in Fds. On the reduced form, the diiron core exists in a characteristic mixed-valence state that has mobile electron (spin). Hybrid density functional theory (HDFT) calculations are performed to investigate the chemical bond nature, electronic structures, and magnetic interactions. The spin states and energy levels are further discussed with spin Hamiltonians, which contain Heisenberg exchange term and double exchange term to describe the mixed-valence state. We have determined their effective exchange integrals (J) and resonance parameters (B) from (HDFT) calculations in several procedures. These magnetic interactions are in good agreement with experiments. To estimate B values, we propose a new procedure using molecular orbital energies. The B values are properly evaluated compared with other procedures, using total energies. The chemical bond natures and the ground electronic structures are elucidated in terms of chemical indices defined by the occupation number of natural orbitals. Finally, implications of the computational results are discussed in relation to rational design of biomolecular devices.

  2. Method for vacuum fusion bonding

    DOEpatents

    Ackler, Harold D. (Sunnyvale, CA); Swierkowski, Stefan P. (Livermore, CA); Tarte, Lisa A. (Livermore, CA); Hicks, Randall K. (Stockton, CA)

    2001-01-01

    An improved vacuum fusion bonding structure and process for aligned bonding of large area glass plates, patterned with microchannels and access holes and slots, for elevated glass fusion temperatures. Vacuum pumpout of all components is through the bottom platform which yields an untouched, defect free top surface which greatly improves optical access through this smooth surface. Also, a completely non-adherent interlayer, such as graphite, with alignment and location features is located between the main steel platform and the glass plate pair, which makes large improvements in quality, yield, and ease of use, and enables aligned bonding of very large glass structures.

  3. Fusion bonding and alignment fixture

    DOEpatents

    Ackler, Harold D. (Sunnyvale, CA); Swierkowski, Stefan P. (Livermore, CA); Tarte, Lisa A. (Livermore, CA); Hicks, Randall K. (Stockton, CA)

    2000-01-01

    An improved vacuum fusion bonding structure and process for aligned bonding of large area glass plates, patterned with microchannels and access holes and slots, for elevated glass fusion temperatures. Vacuum pumpout of all the components is through the bottom platform which yields an untouched, defect free top surface which greatly improves optical access through this smooth surface. Also, a completely non-adherent interlayer, such as graphite, with alignment and location features is located between the main steel platform and the glass plate pair, which makes large improvements in quality, yield, and ease of use, and enables aligned bonding of very large glass structures.

  4. Ultrasonic Imaging Of Bond Layers Through Bond Layers

    NASA Technical Reports Server (NTRS)

    Chern, E. James

    1992-01-01

    Combination of hardware and software helps ultrasonic C-scan inspection system create images of bond layer in laminated composite material, even when obscured by another bond layer. Produces image of both layers in single scan. Includes ultrasonic transducer, pulser/receiver, mechanical scanner, personal computer as controller, and electronic circuitry that gates first and second peak signals, detects peaks, and feeds resulting amplitude data to computer.

  5. Beyond holo/hemidirectionality in Pb(II) complexes: Can the valence lone pair be bisdirected?

    NASA Astrophysics Data System (ADS)

    Severen, M.-C. van; Piquemal, J.-P.; Parisel, O.

    2009-08-01

    In this contribution, we investigate, by means of Density Functional Theory computations coupled to the analysis of the Electron Localisation Function (ELF), a new possible topology of the Pb 2+ valence lone pair. The possibility of bisdirectionality is uncovered for the first time and reveals another character of lead complexes beyond holo/hemidirectionality.

  6. Mixed-valence correlations in charge-transferring atom-surface collisions

    NASA Astrophysics Data System (ADS)

    Pamperin, M.; Bronold, F. X.; Fehske, H.

    2015-10-01

    Motivated by experimental evidence (He and Yarmoff 2010 Phys. Rev. Lett. 105 176806) for a mixed-valence state to occur in the neutralization of strontium ions on gold surfaces we analyze this type of charge-transferring atom-surface collision from a many-body theoretical point of view using quantum-kinetic equations together with a pseudo-particle representation for the electronic configurations of the atomic projectile. Particular attention is paid to the temperature dependence of the neutralization probability which—experimentally—seems to signal mixed-valence-type correlations affecting the charge-transfer between the gold surface and the strontium projectile. We also investigate the neutralization of magnesium ions on a gold surface which shows no evidence for a mixed-valence state. Whereas for magnesium excellent agreement between theory and experiment could be obtained, for strontium we could not reproduce the experimental data. Our results indicate mixed-valence correlations to be in principle present, but for the model mimicking most closely the experimental situation they are not strong enough to affect the neutralization process quantitatively.

  7. Implicit and Explicit Evaluation: fMRI Correlates of Valence, Emotional Intensity, and Control

    E-print Network

    Scholl, Brian

    and appropriately weighed. Often, these more complex attitudes about concepts such as gun control, abortion, sexImplicit and Explicit Evaluation: fMRI Correlates of Valence, Emotional Intensity, and Control they tried to control their evaluation of the concept. Amygdala activation correlated with emotional

  8. Valence band hybridization in N-rich GaN1-xAsx alloys

    SciTech Connect

    Wu, J.; Walukiewicz, W.; Yu, K.M.; Denlinger, J.D.; Shan, W.; Ager III, J.W.; Kimura, A.; Tang, H.F.; Kuech, T.F.

    2004-05-04

    We have used photo-modulated transmission and optical absorption spectroscopies to measure the composition dependence of interband optical transitions in N-rich GaN{sub 1-x}As{sub x} alloys with x up to 0.06. The direct bandgap gradually decreases as x increases. In the dilute x limit, the observed band gap approaches 2.8 eV; this limiting value is attributed to a transition between the As localized level, which has been previously observed in As-doped GaN at 0.6 eV above the valence band maximum in As-doped GaN, and the conduction band minimum. The structure of the valence band of GaN{sub 1-x}As{sub x} is explained by the hybridization of the localized As states with the extended valence band states of GaN matrix. The hybridization is directly confirmed by soft x-ray emission experiments. To describe the electronic structure of the GaN{sub 1-x}As{sub x} alloys in the entire composition range a linear interpolation is used to combine the effects of valence band hybridization in N-rich alloys with conduction band anticrossing in As-rich alloys.

  9. ULTRASONIC NEBULIZATION AND ARSENIC VALENCE STATE CONSIDERATIONS PRIOR TO DETERMINATION VIA INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY

    EPA Science Inventory

    An ultrasonic nebulizer (USN) was utilized as a sample introduction device for an inductively coupled plasma mass spectrometer in an attempt to increase the sensitivity for As. The USN produced a valence state response difference for As. The As response was suppressed approximate...

  10. Distinct populations of neurons respond to emotional valence and arousal in the human subthalamic nucleus

    PubMed Central

    Sieger, Tomáš; Serranová, Tereza; R?ži?ka, Filip; Vostatek, Pavel; Wild, Ji?í; Š?astná, Daniela; Bonnet, Cecilia; Novák, Daniel; R?ži?ka, Evžen; Urgošík, Dušan; Jech, Robert

    2015-01-01

    Both animal studies and studies using deep brain stimulation in humans have demonstrated the involvement of the subthalamic nucleus (STN) in motivational and emotional processes; however, participation of this nucleus in processing human emotion has not been investigated directly at the single-neuron level. We analyzed the relationship between the neuronal firing from intraoperative microrecordings from the STN during affective picture presentation in patients with Parkinson’s disease (PD) and the affective ratings of emotional valence and arousal performed subsequently. We observed that 17% of neurons responded to emotional valence and arousal of visual stimuli according to individual ratings. The activity of some neurons was related to emotional valence, whereas different neurons responded to arousal. In addition, 14% of neurons responded to visual stimuli. Our results suggest the existence of neurons involved in processing or transmission of visual and emotional information in the human STN, and provide evidence of separate processing of the affective dimensions of valence and arousal at the level of single neurons as well. PMID:25713375

  11. Emotional valence contributes to music-induced analgesia Mathieu Roy a,c

    E-print Network

    of many primitive forms of medicine. Nowadays, music therapy is emerging as an evidence-based disciplineEmotional valence contributes to music-induced analgesia Mathieu Roy a,c , Isabelle Peretz a March 2007; accepted 9 April 2007 Abstract The capacity of music to soothe pain has been used in many

  12. Valence and salience contribute to nucleus accumbens activation Jeffrey C. Cooper and Brian Knutson

    E-print Network

    Knutson, Brian

    that predict fitness-increasing outcomes for an organism; a cue's positive valen activation correlated with both valence and salience. On trials with certain outcomes, NAcc activation increased for anticipated gains and decreased for anticipated losses. On trials with uncertain outcomes

  13. Valence Electron Ionization Dynamics of Chromium by a Photoelectron Imaging Technique: J+

    E-print Network

    Kim, Sang Kyu

    Valence Electron Ionization Dynamics of Chromium by a Photoelectron Imaging Technique: J+ Dependent. Benzene chromium carbonyl or bis(6 - benzene) chromium was used as a precursor for the generation momentum quantum number of the chromium ion (J+ ). Anisotropy parameters associated with departing

  14. Mixed Meson Mass for Domain-Wall Valence and Staggered Sea Fermions

    SciTech Connect

    Konstantinos Orginos; Andre Walker-Loud

    2007-05-01

    Mixed action lattice calculations allow for an additive lattice spacing dependent mass renormalization of mesons composed of one sea and one valence quark, regardless of the type of fermion discretization methods used in the valence and sea sectors. The value of the mass renormalization depends upon the lattice actions used. This mixed meson mass shift is the most important lattice artifact to determine for mixed action calculations: because it modifies the pion mass, it plays a central role in the low energy dynamics of all hadronic correlation functions. We determine the leading order and next to leading order additive mass renormalization of valence-sea mesons for a mixed lattice action with domain-wall valence fermions and staggered sea fermions. We find that on the asqtad improved coarse MILC lattices, the leading order additive mass renormalization for the mixed mesons is ?(am)^2 LO = 0.0409(11) which corresponds to a^2 ?_Mix = (319 MeV)^2± (53 MeV)^2 for a = 0.125 fm. We also find significant next to leading order contributions which reduce the mass renormalization by a significant amount, such that for 0 < am_? ? 0.22 the mixed meson mass renormalization is well approximated by ?(am)^2 = 0.0340 (23) or a^2?_Mix = (290 MeV)^2 ± (76 MeV)^2. The full next-to-leading order analysis is presented in the text.

  15. Type of gesture, valence, and gaze modulate the influence of gestures on observer's behaviors

    PubMed Central

    De Stefani, Elisa; Innocenti, Alessandro; Secchi, Claudio; Papa, Veronica; Gentilucci, Maurizio

    2013-01-01

    The present kinematic study aimed at determining whether the observation of arm/hand gestures performed by conspecifics affected an action apparently unrelated to the gesture (i.e., reaching-grasping). In 3 experiments we examined the influence of different gestures on action kinematics. We also analyzed the effects of words corresponding in meaning to the gestures, on the same action. In Experiment 1, the type of gesture, valence and actor's gaze were the investigated variables Participants executed the action of reaching-grasping after discriminating whether the gestures produced by a conspecific were meaningful or not. The meaningful gestures were request or symbolic and their valence was positive or negative. They were presented by the conspecific either blindfolded or not. In control Experiment 2 we searched for effects of the sole gaze, and, in Experiment 3, the effects of the same characteristics of words corresponding in meaning to the gestures and visually presented by the conspecific. Type of gesture, valence, and gaze influenced the actual action kinematics; these effects were similar, but not the same as those induced by words. We proposed that the signal activated a response which made the actual action faster for negative valence of gesture, whereas for request signals and available gaze, the response interfered with the actual action more than symbolic signals and not available gaze. Finally, we proposed the existence of a common circuit involved in the comprehension of gestures and words and in the activation of consequent responses to them. PMID:24046742

  16. Composition dependent valence band order in c-oriented wurtzite AlGaN layers

    NASA Astrophysics Data System (ADS)

    Neuschl, B.; Helbing, J.; Knab, M.; Lauer, H.; Madel, M.; Thonke, K.; Meisch, T.; Forghani, K.; Scholz, F.; Feneberg, M.

    2014-09-01

    The valence band order of polar wurtzite aluminum gallium nitride (AlGaN) layers is analyzed for a dense series of samples, grown heteroepitaxially on sapphire substrates, covering the complete composition range. The excitonic transition energies, found by temperature dependent photoluminescence (PL) spectroscopy, were corrected to the unstrained state using input from X-ray diffraction. k ?p theory yields a critical relative aluminum concentration xc=(0.09±0.05) for the crossing of the uppermost two valence bands for strain free material, shifting to higher values for compressively strained samples, as supported by polarization dependent PL. The analysis of the strain dependent valence band crossing reconciles the findings of other research groups, where sample strain was neglected. We found a bowing for the energy band gap to the valence band with ?9 symmetry of b?9=0.85eV, and propose a possible bowing for the crystal field energy of bcf=-0.12eV. A comparison of the light extraction efficiency perpendicular and parallel to the c axis of AlxGa1-xN/AlyGa1-yN quantum well structures is discussed for different compositions.

  17. The Generation of Low-Valence Sn Derivatives by Neutralization-Reionization Mass Spectrometry

    E-print Network

    Greenlief, C. Michael

    The Generation of Low-Valence Sn Derivatives by Neutralization-Reionization Mass Spectrometry was to generate and characterize neutral Sn(I) derivatives in the gas phase by using neutralization-selected using an electromagnet and transmitted to the field-free region. Neutralization of the ions

  18. The Effect of an Extinction Cue on ABA-Renewal: Does Valence Matter?

    ERIC Educational Resources Information Center

    Dibbets, Pauline; Maes, Joseph H. R.

    2011-01-01

    The present human fear conditioning study examined whether the valence of an extinction cue has a differential effect on attenuating renewal that is induced by removal of the extinction context. Additionally, the study aimed to assess whether such attenuating effect is based on a modulatory or safety-signal role of the cue. In acquisition,…

  19. Two-electron mixed-valence complexes small molecule activation and photocatalytic hydrogen production

    E-print Network

    Heyduk, Alan F. (Alan Frank), 1974-

    2001-01-01

    Two-electron mixed-valence complexes of rhodium may be supported by diphosphazane ligands (RN(PY2)2). Whereas diphosphazane ligands with strongly [pi]-acidic phosphine groups (Y = F, OCH2CF3) react with RhI starting materials ...

  20. Valence Focus and the Perception of Facial Affect Lisa Feldman Barrett

    E-print Network

    Barrett, Lisa Feldman

    Valence Focus and the Perception of Facial Affect Lisa Feldman Barrett Boston College Paula M was a Lisa Feldman Barrett, Department of Psychology, Boston College; Paula M. Niedenthal, National Center and BCS 0074688 and National Institute of Mental Health Grant K02 MH001981 awarded to Lisa Feldman Barrett