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Sample records for valence bond vb

  1. The valence-bond self-consistent field method (VB-SCF): Theory and test calculations

    NASA Astrophysics Data System (ADS)

    van Lenthe, J. H.; Balint-Kurti, G. G.

    1983-05-01

    A new and very general form of valence-bond theory is described. In this theory the molecular wave function is written as any desired linear combination of valence-bond structures, and the nonorthogonal orbitals used in the construction of the valence-bond structures are allowed to distort to their optimal shapes. The orbital optimization is achieved through successive transformations of an orbital basis. The theory of the method is based on an extension of the ``generalized Brillouin theorem'' which is presented in the text. The new VB-SCF method is a generalization of the molecular orbital MC-SCF method to permit the use of nonorthogonal orbitals. It, therefore, encompasses the MC-SCF method as a restricted subclass. Several different forms of restriction may be imposed on the orbitals and on the optimization procedures. One of these only allows orbitals centered on the same atom to mix during optimization and in this way generates optimal hybrid orbitals, which it is expected will prove to be of particular interest in providing simple qualitative descriptions of the chemical bond. Test calculations are presented for LiH, He+2, and for the ground-state potential energy curve of OH. The VB-SCF wave function and optimized orbitals may be used as a starting point for the construction of a larger multistructure valence-bond wave function which we term a VB-CI function. The VB-SCF and VB-CI results presented in the paper show that the method is capable of yielding very accurate molecular potential energy curves.

  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. Valence bond entanglement entropy.

    PubMed

    Alet, Fabien; Capponi, Sylvain; Laflorencie, Nicolas; Mambrini, Matthieu

    2007-09-14

    We introduce for SU(2) quantum spin systems the valence bond entanglement entropy as a counting of valence bond spin singlets shared by two subsystems. For a large class of antiferromagnetic systems, it can be calculated in all dimensions with quantum Monte Carlo simulations in the valence bond basis. We show numerically that this quantity displays all features of the von Neumann entanglement entropy for several one-dimensional systems. For two-dimensional Heisenberg models, we find a strict area law for a valence bond solid state and multiplicative logarithmic corrections for the Néel phase. PMID:17930468

  5. XMVB: a program for ab initio nonorthogonal valence bond computations.

    PubMed

    Song, Lingchun; Mo, Yirong; Zhang, Qianer; Wu, Wei

    2005-04-15

    An ab initio nonorthogonal valence bond program, called XMVB, is described in this article. The XMVB package uses Heitler-London-Slater-Pauling (HLSP) functions as state functions, and calculations can be performed with either all independent state functions for a molecule or preferably a few selected important state functions. Both our proposed paired-permanent-determinant approach and conventional Slater determinant expansion algorithm are implemented for the evaluation of the Hamiltonian and overlap matrix elements among VB functions. XMVB contains the capabilities of valence bond self-consistent field (VBSCF), breathing orbital valence bond (BOVB), and valence bond configuration interaction (VBCI) computations. The VB orbitals, used to construct VB functions, can be defined flexibly in the calculations depending on particular applications and focused problems, and they may be strictly localized, delocalized, or bonded-distorted (semidelocalized). The parallel version of XMVB based on MPI (Message Passing Interface) is also available. PMID:15704237

  6. 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)

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

    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. DEAC02-98CH10886.

  7. 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

  8. Valence-bond description of chemical reactions on Born-Oppenheimer molecular dynamics trajectories

    NASA Astrophysics Data System (ADS)

    Noguchi, Nao; Nakano, Haruyuki

    2009-04-01

    The nature of chemical bonds on dynamic paths was investigated using the complete active space valence-bond (CASVB) method and the Born-Oppenheimer dynamics. To extract the chemical bond picture during reactions, a scheme to collect contributions from several VB (resonance) structures into a small numbers of indices was introduced. In this scheme, a tree diagram for the VB structures is constructed with the numbers of the ionic bonds treated as generation. A pair of VB structures is related to each other if one VB structure is transferred into the other by changing a covalent bond to an ionic bond. The former and latter VB structures are named parent and child structures, respectively. The weights of the bond pictures are computed as the sum of the CASVB occupation numbers running from the top generation to the bottom along the descent of the VB structures. Thus, a number of CASVB occupation numbers are collected into a small number of indices, and a clear bond picture may be obtained from the CASVB wave function. The scheme was applied to the hydrogen exchange reaction H2+F→H+HF and the Diels-Alder reaction C5H6(cyclopentadiene)+CH2=CH2(ethylene)→C7H10(norbornene). In both the reactions, the scheme gave a clear picture for the Born-Oppenheimer dynamics trajectories. The reconstruction of the bonds during reactions was well described by following the temporal changes in weight.

  9. 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…

  10. How valence bond theory can help you understand your (bio)chemical reaction.

    PubMed

    Shurki, Avital; Derat, Etienne; Barrozo, Alexandre; Kamerlin, Shina Caroline Lynn

    2015-03-01

    Almost a century has passed since valence bond (VB) theory was originally introduced to explain covalent bonding in the H2 molecule within a quantum mechanical framework. The past century has seen constant improvements in this theory, with no less than two distinct Nobel prizes based on work that is essentially developments in VB theory. Additionally, ongoing advances in both methodology and computational power have greatly expanded the scope of problems that VB theory can address. In this Tutorial Review, we aim to give the reader a solid understanding of the foundations of modern VB theory, using a didactic example of a model SN2 reaction to illustrate its immediate applications. This will be complemented by examples of challenging problems that at present can only be efficiently addressed by VB-based approaches. Finally, the ongoing importance of VB theory is demonstrated. It is concluded that VB will continue to be a major driving force for chemistry in the century to come. PMID:25352378

  11. Red-Shifting versus Blue-Shifting Hydrogen Bonds: Perspective from Ab Initio Valence Bond Theory.

    PubMed

    Chang, Xin; Zhang, Yang; Weng, Xinzhen; Su, Peifeng; Wu, Wei; Mo, Yirong

    2016-05-01

    Both proper, red-shifting and improper, blue-shifting hydrogen bonds have been well-recognized with enormous experimental and computational studies. The current consensus is that there is no difference in nature between these two kinds of hydrogen bonds, where the electrostatic interaction dominates. Since most if not all the computational studies are based on molecular orbital theory, it would be interesting to gain insight into the hydrogen bonds with modern valence bond (VB) theory. In this work, we performed ab initio VBSCF computations on a series of hydrogen-bonding systems, where the sole hydrogen bond donor CF3H interacts with ten hydrogen bond acceptors Y (═NH2CH3, NH3, NH2Cl, OH(-), H2O, CH3OH, (CH3)2O, F(-), HF, or CH3F). This series includes four red-shifting and six blue-shifting hydrogen bonds. Consistent with existing findings in literature, VB-based energy decomposition analyses show that electrostatic interaction plays the dominating role and polarization plays the secondary role in all these hydrogen-bonding systems, and the charge transfer interaction, which denotes the hyperconjugation effect, contributes only slightly to the total interaction energy. As VB theory describes any real chemical bond in terms of pure covalent and ionic structures, our fragment interaction analysis reveals that with the approaching of a hydrogen bond acceptor Y, the covalent state of the F3C-H bond tends to blue-shift, due to the strong repulsion between the hydrogen atom and Y. In contrast, the ionic state F3C(-) H(+) leads to the red-shifting of the C-H vibrational frequency, owing to the attraction between the proton and Y. Thus, the relative weights of the covalent and ionic structures essentially determine the direction of frequency change. Indeed, we find the correlation between the structural weights and vibrational frequency changes. PMID:27074500

  12. Recasting wave functions into valence bond structures: A simple projection method to describe excited states.

    PubMed

    Racine, Julien; Hagebaum-Reignier, Denis; Carissan, Yannick; Humbel, Stéphane

    2016-03-30

    A method is proposed to obtain coefficients and weights of valence bond (VB) determinants from multi configurational wave functions. This reading of the wave functions can apply to ground states as well as excited states. The method is based on projection operators. Both energetic and overlap-based criteria are used to assess the quality of the resulting VB wave function. The approach gives a simple access to a VB rewriting for low-lying states, and it is applied to the allyl cation, to the allyl radical and to the ethene (notably to the V-state). For these states, large overlap between VB and multi reference wave functions are easily obtained. The approach proves to be useful to propose an interpretation of the nature of the V-state of ethene. PMID:26786547

  13. The application of cholesky decomposition in valence bond calculation.

    PubMed

    Gong, Xiping; Chen, Zhenhua; Wu, Wei

    2016-09-01

    The Cholesky decomposition (CD) technique, used to approximate the two-electron repulsion integrals (ERIs), is applied to the valence bond self-consistent field (VBSCF) method. Test calculations on ethylene, C2 n H2 n +2 , and C2 n H4 n -2 molecules (n = 1-7) show that the performance of the VBSCF method is much improved using the CD technique, and thus, the integral transformation from basis functions to VB orbitals is no longer the bottleneck in VBSCF calculations. The errors of the CD-based ERIs and of the total energy are controlled by the CD threshold, for which a value of 10(-6) ensures to control the total energy error within 10(-6) Hartree. © 2016 Wiley Periodicals, Inc. PMID:27377531

  14. An efficient algorithm for energy gradients and orbital optimization in valence bond theory.

    PubMed

    Song, Lingchun; Song, Jinshuai; Mo, Yirong; Wu, Wei

    2009-02-01

    An efficient algorithm for energy gradients in valence bond theory with nonorthogonal orbitals is presented. A general Hartree-Fock-like expression for the Hamiltonian matrix element between valence bond (VB) determinants is derived by introducing a transition density matrix. Analytical expressions for the energy gradients with respect to the orbital coefficients are obtained explicitly, whose scaling for computational cost is m(4), where m is the number of basis functions, and is thus approximately the same as in HF method. Compared with other existing approaches, the present algorithm has lower scaling, and thus is much more efficient. Furthermore, the expression for the energy gradient with respect to the nuclear coordinates is also presented, and it provides an effective algorithm for the geometry optimization and the evaluation of various molecular properties in VB theory. Test applications show that our new algorithm runs faster than other methods. PMID:18629879

  15. 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…

  16. 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

  17. 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

    NASA Astrophysics Data System (ADS)

    Chen, Zhenhua; Chen, Xun; Wu, Wei

    2013-04-01

    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.

  18. The variational subspace valence bond method

    SciTech Connect

    Fletcher, Graham D.

    2015-04-07

    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.

  19. Exact valence bond entanglement entropy and probability distribution in the XXX spin chain and the potts model.

    PubMed

    Jacobsen, J L; Saleur, H

    2008-02-29

    We determine exactly the probability distribution of the number N_(c) of valence bonds connecting a subsystem of length L>1 to the rest of the system in the ground state of the XXX antiferromagnetic spin chain. This provides, in particular, the asymptotic behavior of the valence-bond entanglement entropy S_(VB)=N_(c)ln2=4ln2/pi(2)lnL disproving a recent conjecture that this should be related with the von Neumann entropy, and thus equal to 1/3lnL. Our results generalize to the Q-state Potts model. PMID:18352661

  20. Reentrant valence transition in EuO at high pressures : beyond the bond-valence model

    SciTech Connect

    Souza-Neto, N.M.; Zhao, J.; Alp, E.; Shen, G.; Sinogeikin, S. V.; Lapertot, G.; Haskel, D.

    2012-07-12

    The pressure-dependent relation between Eu valence and lattice structure in model compound EuO is studied with synchrotron-based x-ray spectroscopic and diffraction techniques. Contrary to expectation, a 7% volume collapse at {approx}45 GPa is accompanied by a reentrant Eu valence transition into a lower valence state. In addition to highlighting the need for probing both structure and electronic states directly when valence information is sought in mixed-valent systems, the results also show that widely used bond-valence methods fail to quantitatively describe the complex electronic valence behavior of EuO under pressure.

  1. The valence bond way: reactivity patterns of cytochrome P450 enzymes and synthetic analogs.

    PubMed

    Shaik, Sason; Lai, Wenzhen; Chen, Hui; Wang, Yong

    2010-08-17

    The preceding decade has witnessed an immense surge of activity in the bioinorganic chemistry of transition metal enzymes and synthetic analogs that model their operation. The wide range of research covers both experimental and theoretical investigations of structure and reactivity patterns. Theory, and especially density functional theory (DFT), has become a very useful tool, an important partner of experiment in resolving structural and mechanistic issues. This flare of activity has generated a great deal of knowledge on intermediates, transition states, barriers, rate constants, rate-equilibrium relationships, stereoselectivity, and so forth. This abundance of acquired knowledge has created the need for establishing order, namely, the outlining of broad generalizations, as well as the creation of a more-intuitive interface between experimental and theoretical data. The valence bond (VB) diagram model, originally developed for organic reactions, is such a theoretical framework that has the potential to guide the requisite generalizations in the field of bioinorganic chemical reactivity. In this Account, we briefly describe the principles of construction of VB diagrams for bioinorganic reactions, detailing applications in the booming research area of heme enzyme (specifically cytochrome P450) reactivity, and particularly two archetypal reactions of these enzymes, alkane hydroxylation and thioether sulfoxidation. For congruence with the lingua franca of bioinorganic chemistry, the VB model is formulated to create bridges to (i) the molecular orbital (MO) description, (ii) the oxidation state formulation of transition metal complexes, and (iii) widely used concepts such as the Bell-Evans-Polanyi (BEP) principle. The VB diagram model reveals the origins of the barrier, describes the formation of transition states and reaction intermediates, and allows the prediction of barrier heights and structure-reactivity relationships. Thus, from the VB diagram model, we can

  2. Valence bond and von Neumann entanglement entropy in Heisenberg ladders.

    PubMed

    Kallin, Ann B; González, Iván; Hastings, Matthew B; Melko, Roger G

    2009-09-11

    We present a direct comparison of the recently proposed valence bond entanglement entropy and the von Neumann entanglement entropy on spin-1/2 Heisenberg systems using quantum Monte Carlo and density-matrix renormalization group simulations. For one-dimensional chains we show that the valence bond entropy can be either less or greater than the von Neumann entropy; hence, it cannot provide a bound on the latter. On ladder geometries, simulations with up to seven legs are sufficient to indicate that the von Neumann entropy in two dimensions obeys an area law, even though the valence bond entanglement entropy has a multiplicative logarithmic correction. PMID:19792398

  3. 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…

  4. Reinterpretation of the bond-valence model with bond-order formalism: An improved bond-valence-based interatomic potential for PbTiO3

    NASA Astrophysics Data System (ADS)

    Liu, Shi; Grinberg, Ilya; Takenaka, Hiroyuki; Rappe, Andrew M.

    2013-09-01

    We present a modified bond-valence model of PbTiO3 based on the principles of bond-valence and bond-valence vector conservation. The relationship between the bond-valence model and the bond-order potential is derived analytically in the framework of a tight-binding model. An energy term, bond-valence vector energy, is introduced into the atomistic model and the potential parameters are reoptimized. This model potential can be applied both to canonical-ensemble (NVT) and isobaric-isothermal ensemble (NPT) molecular dynamics (MD) simulations. This model reproduces the experimental phase transition in NVT MD simulations and also exhibits the experimental sequence of temperature-driven and pressure-driven phase transitions in NPT simulations. We expect that this improved bond-valence model can be applied to a broad range of inorganic materials.

  5. 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)

  6. 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.

  7. Valence Bond Theory of Correlated-Electron Superconductivity

    NASA Astrophysics Data System (ADS)

    Dutta, Tirthankar; Mazumdar, Sumit; Clay, Torsten

    Whether or not the weakly doped Mott-Hubbard semiconductor is superconducting remains controversial. We present a new valence bond theory of correlated-electron superconductivity, that has overlap with the original RVB approach, and yet is substantively different. Superconductivity within the theory emerges from a correlated-electron state in which there is a strong tendency to spin-singlet formation, and where the bandwidth due to pair-tunneling is very large. We show that such a situation occurs far away from the 1/2-filled band, at or near banfilling of 1/4. In the presence of electron-phonon interactions the 1/4-filled band can form a spin-paired CDW state that we have called a paired-electron crystal, and that is a Wigner crystal of pairs. In the presence of frustration the spin-paired bonds become mobile to give a paired-electron liquid, which is a precursor to superconductivity. The superconducting state here is reached from a co-operative effect between electron-electron and electron-phonon interactions, and the theory thus has overlap also with the bipolaron theory of superconductivity. We will present exact numerical calculations on a 4x4 lattice using the valence bond basis to substantiate our conjectures. Supported by DOE Grant DE-FG02-06ER46315 and NSF-CHE-151475.

  8. 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

  9. On the Construction of Diabatic and Adiabatic Potential Energy Surfaces Based on Ab Initio Valence Bond Theory‡

    PubMed Central

    Song, Lingchun; Gao, Jiali

    2009-01-01

    A theoretical model is presented for deriving effective diabatic states based on ab initio self-consistent field valence bond (VBSCF) theory by reducing the multi-configurational VB Hamiltonian into an effective two-state model. We describe two computational approaches for the optimization of the effective diabatic configurations, resulting in two ways of interpreting such effective diabatic states. In the variational diabatic configuration (VDC) method, the energies of the individual diabatic states are variationally minimized. In the consistent diabatic configuration (CDC) method, both the configuration coefficients and orbital coefficients are simultaneously optimized to minimize the adiabatic ground-state energy in VBSCF calculations. In addition, we describe a mixed molecular orbital and valence bond (MOVB) approach to construct the CDC diabatic and adiabatic states for a chemical reaction, whereas the VDC-MOVB method has been described previously. Employing the symmetric SN2 reaction between NH3 and CH3NH3+ as a test system, we found that the results from ab initio VBSCF and from MOVB calculations are in good agreement, suggesting that the computationally efficient MOVB method is a reasonable model for VB simulations of condensed phase reactions. The results indicate that CDC and VDC diabatic states converge, respectively, to covalent and ionic states as the molecular geometries are distorted from the minimum of the respective diabatic state along the reaction coordinate. Furthermore, the resonance energy that stabilizes the energy of crossing between the two diabatic states, resulting in the transition state of the adiabatic ground-state reaction, has a strong dependence on the overlap integral between the two diabatic states and is a function of both the exchange integral and the total diabatic ground-state energy. PMID:18828577

  10. Quantum phase transitions around the staggered valence-bond solid

    SciTech Connect

    Xu Cenke; Balents, Leon

    2011-07-01

    Motivated by recent numerical results, we study the quantum phase transitions between Z{sub 2} spin-liquid, Neel-ordered, and various valence-bond solid (VBS) states on the honeycomb and square lattices, with emphasis on the staggered VBS. In contrast to the well-understood columnar VBS order, the staggered VBS is not described by an XY-order parameter with Z{sub N} anisotropy close to these quantum phase transitions. Instead, we demonstrate that on the honeycomb lattice, the staggered VBS is more appropriately described as an O(3)- or CP(2)-order parameter with cubic anisotropy, while on the square lattice it is described by an O(4)- or CP(3)-order parameter.

  11. Resonating Valence Bond states for low dimensional S=1 antiferromagnets

    NASA Astrophysics Data System (ADS)

    Liu, Zheng-Xin; Zhou, Yi; Ng, Tai-Kai

    2014-03-01

    We study S = 1 spin liquid states in low dimensions. We show that the resonating-valence-bond (RVB) picture of S = 1 / 2 spin liquid state can be generalized to S = 1 case. For S = 1 system, a many-body singlet (with even site number) can be decomposed into superposition of products of two-body singlets. In other words, the product states of two-body singlets, called the singlet pair states (SPSs), are over complete to span the Hilbert space of many-body singlets. Furthermore, we generalized fermionic representation and the corresponding mean field theory and Gutzwiller projected stats to S = 1 models. We applied our theory to study 1D anti-ferromagnetic bilinear-biquadratic model and show that both the ground states (including the phase transition point) and the excited states can be understood excellently well within the framework. Our method can be applied to 2D S = 1 antiferromagnets.

  12. Overlap populations, bond orders and valences for 'fuzzy' atoms

    NASA Astrophysics Data System (ADS)

    Mayer, I.; Salvador, P.

    2004-01-01

    Proper definitions are proposed to calculate interatomic overlap populations, bond order (multiplicity) indices and actual atomic valences from the results of ab initio quantum chemical calculations, in terms of 'fuzzy' atoms, i.e., such divisions of the three-dimensional physical space into atomic regions in which the regions assigned to the individual atoms have no sharp boundaries but exhibit a continuous transition from one to another. The results of test calculations are in agreement with the classical chemical notions, exhibit unexpectedly small basis sensitivity and do not depend too much on the selection of the weight function defining the actual division of the space into 'fuzzy' atomic regions. The scheme is applicable on both SCF and correlated levels of theory. A free program is available.

  13. Mesoscopic resonating valence bond system on a triple dot.

    PubMed

    Le Hur, Karyn; Recher, Patrik; Dupont, Emilie; Loss, Daniel

    2006-03-17

    We theoretically introduce a mesoscopic pendulum from a triple dot. The pendulum is fastened through a singly occupied dot (spin qubit). Two other strongly capacitively coupled islands form a double-dot charge qubit with one electron in excess oscillating between the two low-energy charge states (1,0) and (0,1). The triple dot is placed between two superconducting leads. Under realistic conditions, the main proximity effect stems from the injection of resonating singlet (valence) bonds on the triple dot. This gives rise to a Josephson current that is charge- and spin-dependent and, as a consequence, exhibits a distinct resonance as a function of the superconducting phase difference. PMID:16605773

  14. Resonating valence bond wave functions and classical interacting dimer models.

    PubMed

    Damle, Kedar; Dhar, Deepak; Ramola, Kabir

    2012-06-15

    We relate properties of nearest-neighbor resonating valence-bond (NNRVB) wave functions for SU(g) spin systems on two-dimensional bipartite lattices to those of fully packed interacting classical dimer models on the same lattice. The interaction energy can be expressed as a sum of n-body potentials V(n), which are recursively determined from the NNRVB wave function on finite subgraphs of the original lattice. The magnitude of the n-body interaction V(n) (n>1) is of order O(g(-(n-1))) for small g(-1). The leading term is a two-body nearest-neighbor interaction V2(g) favoring two parallel dimers on elementary plaquettes. For SU(2) spins, using our calculated value of V2(g=2), we find that the long-distance behavior of the bond-energy correlation function is dominated by an oscillatory term that decays as 1/|r|α with α≈1.22. This result is in remarkable quantitative agreement with earlier direct numerical studies of the corresponding wave function, which give α≈1.20. PMID:23004328

  15. Topologically distinct classes of valence-bond solid states with their parent Hamiltonians

    SciTech Connect

    Tu Honghao; Zhang Guangming; Xiang Tao; Liu Zhengxin; Ng Taikai

    2009-07-01

    We present a general method to construct one-dimensional translationally invariant valence-bond solid states with a built-in Lie group G and derive their matrix product representations. The general strategies to find their parent Hamiltonians are provided so that the valence-bond solid states are their unique ground states. For quantum integer-spin-S chains, we discuss two topologically distinct classes of valence-bond solid states: one consists of two virtual SU(2) spin-J variables in each site and another is formed by using two SO(2S+1) spinors. Among them, a spin-1 fermionic valence-bond solid state, its parent Hamiltonian, and its properties are discussed in detail. Moreover, two types of valence-bond solid states with SO(5) symmetries are further generalized and their respective properties are analyzed as well.

  16. Modern ab initio valence bond theory calculations reveal charge shift bonding in protic ionic liquids.

    PubMed

    Patil, Amol Baliram; Bhanage, Bhalchandra Mahadeo

    2016-06-21

    The nature of bonding interactions between the cation and the anion of an ionic liquid is at the heart of understanding ionic liquid properties. A particularly interesting case is a special class of ionic liquids known as protic ionic liquids. The extent of proton transfer in protic ionic liquids has been observed to vary according to the interacting species. Back proton transfer renders protic ionic liquids volatile and to be considered as inferior ionic liquids. We try to address this issue by employing modern ab initio valence bond theory calculations. The results indicate that the bonding in the cation and the anion of a prototypical ionic liquid, ethylammonium nitrate, is fundamentally different. It is neither characteristic of covalent/polar covalent bonding nor ionic bonding but rather charge shift bonding as a resonance hybrid of two competing ionic molecular electronic structure configurations. An investigation of other analogous protic ionic liquids reveals that this charge shift bonding seems to be a typical characteristic of protic ionic liquids while the ionic solid analogue compound ammonium nitrate has less charge shift bonding character as compared to protic ionic liquids. Further the extent of charge shift bonding character has been found to be congruent with the trends in many physicochemical properties such as melting point, conductivity, viscosity, and ionicity of the studied ionic liquids indicating that percentage charge shift character may serve as a key descriptor for large scale computational screening of ionic liquids with desired properties. PMID:27229870

  17. Magnetization jumps in 1D valence bond solids

    NASA Astrophysics Data System (ADS)

    Iaizzi, Adam; Sandvik, Anders

    2015-03-01

    A valence bond solid (VBS) is a long-range nonmagnetic state with broken lattice symmetries that can appear in certain quantum spin systems with competing interactions. Recent innovations in models and simulation techniques have enabled large scale numerical studies of these states and associated quantum phase transitions from the standard magnetic (Néel, for two or more dimensions) or power-law critical states (in one dimension). These studies have found evidence for the fractionalization of triplons into deconfined or nearly deconfined spinons (spin-1/2 bosons) in the VBS phase and at critical points. We here study the VBS and magnetization as a function of an external magnetic field in an extended Heisenberg model, known as the J-Q model, in one dimension. Using the stochastic series expansion (SSE) quantum monte carlo method with directed loop updates, we find discontinuities in the induced magnetization from a partially magnetized to a fully polarized state. We characterize the phases and the first-order quantum phase transition.

  18. 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.

  19. Experimental Realization of Plaquette Resonating Valence-Bond States with Ultracold Atoms in Optical Superlattices

    NASA Astrophysics Data System (ADS)

    Nascimbène, S.; Chen, Y.-A.; Atala, M.; Aidelsburger, M.; Trotzky, S.; Paredes, B.; Bloch, I.

    2012-05-01

    The concept of valence-bond resonance plays a fundamental role in the theory of the chemical bond and is believed to lie at the heart of many-body quantum physical phenomena. Here we show direct experimental evidence of a time-resolved valence-bond quantum resonance with ultracold bosonic atoms in an optical lattice. By means of a superlattice structure we create a three-dimensional array of independent four-site plaquettes, which we can fully control and manipulate in parallel. Moreover, we show how small-scale plaquette resonating valence-bond (RVB) states with s- and d-wave symmetry can be created and characterized. We anticipate our findings to open the path towards the creation and analysis of many-body RVB states in ultracold atomic gases.

  20. 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

  1. Block-Localized Density Functional Theory (BLDFT), Diabatic Coupling, and Their Use in Valence Bond Theory for Representing Reactive Potential Energy Surfaces

    PubMed Central

    Cembran, Alessandro; Song, Lingchun; Mo, Yirong; Gao, Jiali

    2010-01-01

    A multistate density functional theory in the framework of the valence bond model is described. The method is based on a block-localized density functional theory (BLDFT) for the construction of valence-bond-like diabatic electronic states and is suitable for the study of electron transfer reactions and for the representation of reactive potential energy surfaces. The method is equivalent to a valence bond theory with the treatment of the localized configurations by using density functional theory (VBDFT). In VBDFT, the electron densities and energies of the valence bond states are determined by BLDFT. A functional estimate of the off-diagonal matrix elements of the VB Hamiltonian is proposed, making use of the overlap integral between Kohn–Sham determinants and the exchange-correlation functional for the ground state substituted with the transition (exchange) density. In addition, we describe an approximate approach, in which the off-diagonal matrix element is computed by wave function theory using block-localized Kohn–Sham orbitals. The key feature is that the electron density of the adiabatic ground state is not directly computed nor used to obtain the ground-state energy; the energy is determined by diagonalization of the multistate valence bond Hamiltonian. This represents a departure from the standard single-determinant Kohn–Sham density functional theory. The multistate VBDFT method is illustrated by the bond dissociation of H2+ and a set of three nucleophilic substitution reactions in the DBH24 database. In the dissociation of H2+, the VBDFT method yields the correct asymptotic behavior as the two protons stretch to infinity, whereas approximate functionals fail badly. For the SN2 nucleophilic substitution reactions, the hybrid functional B3LYP severely underestimates the barrier heights, while the approximate two-state VBDFT method overcomes the self-interaction error, and overestimates the barrier heights. Inclusion of the ionic state in a three

  2. 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

  3. 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.

    PubMed

    Chen, Xun; Chen, Zhenhua; Wu, Wei

    2014-11-21

    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. PMID:25416880

  4. Trends in Aromatic Oxidation Reactions Catalyzed by Cytochrome P450 Enzymes: A Valence Bond Modeling.

    PubMed

    Shaik, Sason; Milko, Petr; Schyman, Patric; Usharani, Dandamudi; Chen, Hui

    2011-02-01

    The mixed density functional theory (DFT) and valence bond study described herein focuses on the activation of 17 benzene derivatives by the active species of Cytochrome P450, so-called Compound I (Cpd I), as well as by the methoxy radical, as a potentially simple model of Cpd I (Jones, J. P.; Mysinger, M.; Korzekwa, K. R. Drug Metab. Dispos. 2002, 30, 7-12). Valence bond modeling is employed to rationalize the P450 mechanism and its spin-state selectivity from first principles of electronic structure and to predict activation energies independently, using easily accessible properties of the reactants: the singlet-triplet excitation energies, the ionization potentials of the aromatics, and the electron affinity of Cpd I and/or of the methoxy radical. It is shown that the valence bond model rationalizes all the mechanistic aspects and predicts activation barriers (for 35 reactions) with reasonable accuracy compared to the DFT barriers with an average deviation of ±1.0 kcal·mol(-1) (for DFT barriers, see: Bathelt, C. M.; Ridder, L.; Mulholland, A. J.; Harvey, J. N. Org. Biomol. Chem. 2004, 2, 2998-3005). The valence bond modeling also reveals the mechanistic similarities between the P450 Cpd I and methoxy reactions and enables one to make predictions of barriers for reactions from other studies. PMID:26596155

  5. Electronic Structure of pi Systems: Part II. The Unification of Huckel and Valence Bond Theories.

    ERIC Educational Resources Information Center

    Fox, Marye Anne; Matsen, F. A.

    1985-01-01

    Presents a new view of the electronic structure of pi systems that unifies molecular orbital and valence bond theories. Describes construction of electronic structure diagrams (central to this new view) which demonstrate how configuration interaction can improve qualitative predictions made from simple Huckel theory. (JN)

  6. Comment on ``Valence-bond theory and the evaluation of electronic energy matrix elements between nonorthogonal Slater determinants''

    NASA Astrophysics Data System (ADS)

    Gallup, G. A.

    1986-07-01

    In a recent article [Phys. Rev. A 31, 2107 (1985)] Leasure and Balint-Kurti claim to give a more efficient algorithm than any previously available for determining matrix elements of the Hamiltonian in valence-bond calculations. Actually, an algorithm of no significant difference and the same efficiency has been available since 1972 and has been applied to valence-bond calculations.

  7. Numerical studies of AKLT valence bond solids in one, two and three dimensions

    NASA Astrophysics Data System (ADS)

    Wierschem, Keola; Beach, Kevin

    The fixed-point valence bond solids of Affleck, Kennedy, Lieb and Tasaki (the so-called AKLT states) have become archetypes of symmetry protected topological order. These states are constructed by first placing M valence bonds on each pair of neighboring lattice points, and then symmetrizing the Mz resulting spin-1/2 degrees of freedom at each lattice site into a combined spin- S degree of freedom with 2 S = Mz (where M is the multiplicity of the AKLT state and z is the lattice coordination number). Using Monte Carlo sampling of the AKLT wavefunctions in the loop gas framework, we directly calculate correlation functions and energy gap estimators for these states in one, two and three dimensions. We also study the behavior of the so-called strange correlator, which has been proposed as a measure of symmetry protected topological order.

  8. Quantum computational capability of a 2D valence bond solid phase

    SciTech Connect

    Miyake, Akimasa

    2011-07-15

    Highlights: > Our model is the 2D valence bond solid phase of a quantum antiferromagnet. > Universal quantum computation is processed by measurements of quantum correlations. > An intrinsic complexity of strongly-correlated quantum systems could be a resource. - Abstract: Quantum phases of naturally-occurring systems exhibit distinctive collective phenomena as manifestation of their many-body correlations, in contrast to our persistent technological challenge to engineer at will such strong correlations artificially. Here we show theoretically that quantum correlations exhibited in the 2D valence bond solid phase of a quantum antiferromagnet, modeled by Affleck, Kennedy, Lieb, and Tasaki (AKLT) as a precursor of spin liquids and topological orders, are sufficiently complex yet structured enough to simulate universal quantum computation when every single spin can be measured individually. This unveils that an intrinsic complexity of naturally-occurring 2D quantum systems-which has been a long-standing challenge for traditional computers-could be tamed as a computationally valuable resource, even if we are limited not to create newly entanglement during computation. Our constructive protocol leverages a novel way to herald the correlations suitable for deterministic quantum computation through a random sampling, and may be extensible to other ground states of various 2D valence bond phases beyond the AKLT state.

  9. 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.

  10. The Pairwise Correlated Generalized Valence Bond Model of Electronic Structure I; The Estimation of Pair Energies from Orbital Overlaps

    PubMed Central

    Petersson, G. A.

    1974-01-01

    A new method for the accurate a priori calculation of atomic and molecular energies is proposed. The new method agrees with experiment to within less than 1 kcal/mole in all cases examined thus far, and is applicable to excited states and to transition states for chemical reactions. Since the new method corrects the results of generalized valence bond calculations for the effects of electron pair correlations, we call the new method the pairwise correlated generalized valence bond method. PMID:16592172

  11. Comments on valence-bond structures and charge-shift + recoupled-pair bonding for symmetrical 4-electron 3-centre bonding units

    NASA Astrophysics Data System (ADS)

    Harcourt, Richard D.

    2016-07-01

    Consideration is given to two charge-shift bonding schemes for a symmetrical 4-electron 3-centre hyperbonding unit with three overlapping atomic orbitals. One of these schemes includes the other scheme and the Hach-Rundle-Pimentel 3-centre molecular orbital model as special cases. SF4 and [Cu(H2O)6]2+ are used to illustrate aspects of charge-shift bonding and recoupled-pair bonding theory by generating the increased-valence structures that are associated with the preferred scheme.

  12. Electron density, exchange-correlation density, and bond characterization from the perspective of the valence-bond theory. II. Numerical results

    NASA Astrophysics Data System (ADS)

    Rincón, Luis; Alvarellos, J. E.; Almeida, Rafael

    2005-06-01

    In this work we have analyzed the bond character of a series of representative diatomic molecules, using valence bond and the atoms in molecules points of view. This is done using generalized valence-bond calculations. We have also employed more exigent levels, as configuration interaction with single and double excitations and complete active space self-consistent field calculations, in order to validate the generalized valence-bond results. We have explored the possibility that the known delocalization index, and a parameter that measures the excess or defect population within a given atomic basin, can be considered as indicators of the character of bond interaction. We conclude that for a proper description of the bond character, the global behavior of both the charge and two-electron densities should be considered.

  13. Strongly correlated valence electrons and core-level chemical bonding of Lithium at terapascal pressures

    NASA Astrophysics Data System (ADS)

    Hu, Anguang; Zhang, Fan

    2015-03-01

    As the simplest pure metal, lithium exhibits some novel properties on electrical conductivity and crystal structures under high pressure. All-electron density functional theory simulations, recently developed by using the linear combination of localized Slater atomic orbitals, revealed that the bandwidth of its valence bands remains almost unchanged within about 3.5 eV even up to a terapascal pressure range. This indicates that the development from delocalized to strongly correlated electronic systems takes place under compression, resulting in metal-semiconductor and superconductivity transitions together with a sequence of new high-pressure crystal phases, discovered experimentally. In contrast to the valence bands, the core-level bands become broadening up to about 10 eV at terapascal pressures. It means the transformation from chemical non-bonding to bonding for core electrons. Thus, dense lithium under compression can be characterized as core-level chemical bonding and a completely new class of strongly correlated materials with narrow bands filled in s-electron shells only.

  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. Resonant valence bond states in zinc vacancies induce the ferromagnetism of ZnO

    NASA Astrophysics Data System (ADS)

    Sun, Shih-Jye

    2016-05-01

    A theoretical model was proposed to investigate the mechanism of ferromagnetism in ZnO as well as to simulate the experimental result that the ferromagnetism can be enhanced by UV irradiation as UV photon energy is equivalent to the band gap. In the model, the spin moments arise from the trapped electrons in oxygen vacancy states and coexist with the itinerant electrons which reside in zinc vacancy states and fall into resonant valence bond states. Charge exchange between the conduction band of ZnO and both vacancy states makes electrons on both vacancy states delocalized and results in a decrease of the ferromagnetism as well.

  16. Competing valence bond and symmetry-breaking Mott states of spin-3/2 fermions on a honeycomb lattice

    NASA Astrophysics Data System (ADS)

    Jakab, D.; Szirmai, E.; Lewenstein, M.; Szirmai, G.

    2016-02-01

    We investigate magnetic properties of strongly interacting four component spin-3/2 ultracold fermionic atoms in the Mott insulator limit with one particle per site in an optical lattice with honeycomb symmetry. In this limit, atomic tunneling is virtual, and only the atomic spins can exchange. We find a competition between symmetry-breaking and liquidlike disordered phases. Particularly interesting are valence bond states with bond centered magnetizations, situated between the ferromagnetic and conventional valence bond phases. In the framework of a mean-field theory, we calculate the phase diagram and identify an experimentally relevant parameter region where a homogeneous SU(4) symmetric Affleck-Kennedy-Lieb-Tasaki-like valence bond state is present.

  17. Implementation of umbrella integration within the framework of the empirical valence bond approach

    PubMed Central

    Chakravorty, Dhruva K.; Kumarasiri, Malika; Soudackov, Alexander V.; Hammes-Schiffer, Sharon

    2009-01-01

    The umbrella integration method for calculating the potential of mean force (PMF) for a chemical reaction is implemented within the empirical valence bond (EVB) framework. In this implementation, the PMF is generated along the energy gap reaction coordinate, and the biasing potential is the difference between the mapping potential, which is defined to be a linear combination of the valence bond state energies, and the EVB ground state energy. The umbrella integration method is based on the derivative of the PMF with respect to the reaction coordinate. An analytical expression for this derivative applicable to certain types of EVB potentials is presented. The advantages of the umbrella integration method are illustrated by the application of both umbrella integration and the weighted histogram analysis method to the hydride transfer reaction catalyzed by the enzyme dihydrofolate reductase. This application demonstrates that the umbrella integration method reduces the statistical errors, converges efficiently, and does not require significantly overlapping windows. A modified version of the weighted histogram analysis method that shares these advantages is also proposed and implemented. PMID:19319209

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

    PubMed

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

    2015-12-31

    We show numerically that the "deconfined" quantum critical point between the Néel antiferromagnet and the columnar valence-bond solid, for a square lattice of spin 1/2, has an emergent SO(5) symmetry. This symmetry allows the Néel 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)×SU(2)]/Z(2) symmetry that appears in the scaling limit for the spin-1/2 Heisenberg chain. The emergent SO(5) symmetry is strong evidence that the phase transition in the (2+1)-dimensional 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 (noncompact CP(1) model). The result indicates that in three dimensions there is an SO(5)-symmetric conformal field theory that has no relevant singlet operators, so is radically different from conventional Wilson-Fisher-type conformal field theories. PMID:26765019

  19. Empirical valence bond models for reactive potential energy surfaces: a parallel multilevel genetic program approach.

    PubMed

    Bellucci, Michael A; Coker, David F

    2011-07-28

    We describe a new method for constructing empirical valence bond potential energy surfaces using a parallel multilevel genetic program (PMLGP). Genetic programs can be used to perform an efficient search through function space and parameter space to find the best functions and sets of parameters that fit energies obtained by ab initio electronic structure calculations. Building on the traditional genetic program approach, the PMLGP utilizes a hierarchy of genetic programming on two different levels. The lower level genetic programs are used to optimize coevolving populations in parallel while the higher level genetic program (HLGP) is used to optimize the genetic operator probabilities of the lower level genetic programs. The HLGP allows the algorithm to dynamically learn the mutation or combination of mutations that most effectively increase the fitness of the populations, causing a significant increase in the algorithm's accuracy and efficiency. The algorithm's accuracy and efficiency is tested against a standard parallel genetic program with a variety of one-dimensional test cases. Subsequently, the PMLGP is utilized to obtain an accurate empirical valence bond model for proton transfer in 3-hydroxy-gamma-pyrone in gas phase and protic solvent. PMID:21806098

  20. Generalized Valence Bond Description of Chalcogen-Nitrogen Compounds. III. Why the NO-OH and NS-OH Bonds Are So Different.

    PubMed

    Takeshita, Tyler Y; Dunning, Thom H

    2016-09-01

    Crabtree et al. recently reported the microwave spectrum of nitrosyl-O-hydroxide (trans-NOOH), an isomer of nitrous acid, and found that this molecule has the longest O-O bond ever observed: 1.9149 Å ± 0.0005 Å. This is in marked contrast to the structure of the valence isoelectronic trans-NSOH molecule, which has a normal NS-OH bond length and strength. Generalized valence bond calculations show that the long bond in trans-NOOH is the result of a weak through-pair interaction that singlet couples the spins of the electrons in singly occupied orbitals on the hydroxyl radical and nitrogen atom, an interaction that is enhanced by the intervening lone pair of the oxygen atom in NO. The NS-OH bond is the result of the formation of a stable recoupled pair bond dyad, which accounts for both its length and strength. PMID:27501366

  1. Nonorthogonal orbital based N-body reduced density matrices and their applications to valence bond theory. II. An efficient algorithm for matrix elements and analytical energy gradients in VBSCF method.

    PubMed

    Chen, Zhenhua; Chen, Xun; Wu, Wei

    2013-04-28

    In this paper, by applying the reduced density matrix (RDM) approach for nonorthogonal orbitals developed in the first paper of this series, efficient algorithms for matrix elements between VB structures and energy gradients in valence bond self-consistent field (VBSCF) method were presented. Both algorithms scale only as nm(4) for integral transformation and d(2)n(β)(2) for VB matrix elements and 3-RDM evaluation, while the computational costs of other procedures are negligible, where n, m, d, and n(β )are the numbers of variable occupied active orbitals, basis functions, determinants, and active β electrons, respectively. Using tensor properties of the energy gradients with respect to the orbital coefficients presented in the first paper of this series, a partial orthogonal auxiliary orbital set was introduced to reduce the computational cost of VBSCF calculation in which orbitals are flexibly defined. Test calculations on the Diels-Alder reaction of butadiene and ethylene have shown that the novel algorithm is very efficient for VBSCF calculations. PMID:23635124

  2. A modified two-state empirical valence bond model for proton transport in aqueous solutions

    SciTech Connect

    Mabuchi, Takuya; Fukushima, Akinori; Tokumasu, Takashi

    2015-07-07

    A detailed analysis of the proton solvation structure and transport properties in aqueous solutions is performed using classical molecular dynamics simulations. A refined two-state empirical valence bond (aTS-EVB) method, which is based on the EVB model of Walbran and Kornyshev and the anharmonic water force field, is developed in order to describe efficiently excess proton transport via the Grotthuss mechanism. The new aTS-EVB model clearly satisfies the requirement for simpler and faster calculation, because of the simplicity of the two-state EVB algorithm, while providing a better description of diffusive dynamics of the excess proton and water in comparison with the previous two-state EVB models, which significantly improves agreement with the available experimental data. The results of activation energies for the excess proton and water calculated between 300 and 340 K (the temperature range used in this study) are also found to be in good agreement with the corresponding experimental data.

  3. A modified two-state empirical valence bond model for proton transport in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Mabuchi, Takuya; Fukushima, Akinori; Tokumasu, Takashi

    2015-07-01

    A detailed analysis of the proton solvation structure and transport properties in aqueous solutions is performed using classical molecular dynamics simulations. A refined two-state empirical valence bond (aTS-EVB) method, which is based on the EVB model of Walbran and Kornyshev and the anharmonic water force field, is developed in order to describe efficiently excess proton transport via the Grotthuss mechanism. The new aTS-EVB model clearly satisfies the requirement for simpler and faster calculation, because of the simplicity of the two-state EVB algorithm, while providing a better description of diffusive dynamics of the excess proton and water in comparison with the previous two-state EVB models, which significantly improves agreement with the available experimental data. The results of activation energies for the excess proton and water calculated between 300 and 340 K (the temperature range used in this study) are also found to be in good agreement with the corresponding experimental data.

  4. Block correlated second order perturbation theory with a generalized valence bond reference function

    SciTech Connect

    Xu, Enhua; Li, Shuhua

    2013-11-07

    The block correlated second-order perturbation theory with a generalized valence bond (GVB) reference (GVB-BCPT2) is proposed. In this approach, each geminal in the GVB reference is considered as a “multi-orbital” block (a subset of spin orbitals), and each occupied or virtual spin orbital is also taken as a single block. The zeroth-order Hamiltonian is set to be the summation of the individual Hamiltonians of all blocks (with explicit two-electron operators within each geminal) so that the GVB reference function and all excited configuration functions are its eigenfunctions. The GVB-BCPT2 energy can be directly obtained without iteration, just like the second order Møller–Plesset perturbation method (MP2), both of which are size consistent. We have applied this GVB-BCPT2 method to investigate the equilibrium distances and spectroscopic constants of 7 diatomic molecules, conformational energy differences of 8 small molecules, and bond-breaking potential energy profiles in 3 systems. GVB-BCPT2 is demonstrated to have noticeably better performance than MP2 for systems with significant multi-reference character, and provide reasonably accurate results for some systems with large active spaces, which are beyond the capability of all CASSCF-based methods.

  5. 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.

  6. Effective field theory for one-dimensional valence-bond-solid phases and their symmetry protection

    NASA Astrophysics Data System (ADS)

    Fuji, Yohei

    2016-03-01

    We investigate valence-bond-solid (VBS) phases in one-dimensional spin systems by an effective field theory developed by Schulz [Phys. Rev. B 34, 6372 (1986), 10.1103/PhysRevB.34.6372]. While the distinction among the VBS phases is often understood in terms of different entanglement structures protected by certain symmetries, we adopt a different but more fundamental point of view, that is, different VBS phases are separated by a gap closing under certain symmetries. In this way, the effective field theory reproduces the known three symmetries: time reversal, bond-centered inversion, and dihedral group of π spin rotations. It also predicts that there exists another symmetry: site-centered inversion combined with a spin rotation by π . We demonstrate that the last symmetry gives distinct trivial phases, which cannot be characterized by their entanglement structure, in terms of a simple perturbative analysis in a spin chain. We also discuss several applications of the effective field theory to the phase transitions among VBS phases in microscopic models and an extension of the Lieb-Schultz-Mattis theorem to non-translational-invariant systems.

  7. Is it True That the Normal Valence-Length Correlation Is Irrelevant for Metal-Metal Bonds?

    PubMed

    Singh, Vijay; Dixit, Mudit; Kosa, Monica; Major, Dan Thomas; Levi, Elena; Aurbach, Doron

    2016-04-01

    The most intriguing feature of metal-metal bonds in inorganic compounds is an apparent lack of correlation between the bond order and the bond length. In this study, we combine a variety of literature data obtained by quantum chemistry and our results based on the empirical bond valence model (BVM), to confirm for the first time the existence of a normal exponential correlation between the effective bond order (EBO) and the length of the metal-metal bonds. The difference between the EBO and the formal bond order is attributed to steric conflict between the (TM)n cluster (TM=transition metal) and its environment. This conflict, affected mainly by structural type, should cause high lattice strains, but electron redistribution around TM atoms, evident from the BVM calculations, results in a full or partial strain relaxation. PMID:26929001

  8. 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

  9. Structural and magnetic properties of Ba2LuMoO6: a valence bond glass.

    PubMed

    Coomer, Fiona C; Cussen, Edmund J

    2013-02-27

    We report here the synthesis of the site ordered double perovskite Ba(2)LuMoO(6). Rietveld refinement of room temperature powder x-ray diffraction measurements indicates that it crystallizes in the cubic space group Fm3m, with a = 8.3265(1) Å. Powder neutron diffraction data indicate that, unusually, this cubic symmetry is maintained down to 2 K, with [Formula: see text], Mo(5+) ions situated on the frustrated face-centred cubic lattice. Despite dc-susceptibility measurements showing Curie-Weiss behaviour with strong antiferromagnetic interactions at T ≥ 200 K, there is no evidence of long range magnetic ordering at 2 K. At T ≤ 50 K, susceptibility measurements indicate a loss in moment to ∼18% of the expected value, and there is a corresponding loss in the magnitude of the magnetic exchange. The structural and magnetic properties of this compound are compared with the related compound Ba(2)YMoO(6), which is a valence bond glass. PMID:23343826

  10. Resonating valence bond and {sigma}-charge density wave phases in a benzannulated phenalenyl radical.

    SciTech Connect

    Bag, P.; Itkis, M. E.; .Pal, S. K; Donnadieu, B.; Tham, F. S.; Park, H.; Schlueter, J. A.; Siegrist, T.; Haddon, R. C.; Materials Science Division; Univ. of California of Riverside; Florida State Univ.

    2010-01-01

    We report the preparation of the first benzannulated phenalenyl neutral radical conductor (18), and we show that the compound displays unprecedented solid state behavior: the structure is dominated by two sets of intermolecular interactions: (1) a {pi}-chain structure with superimposed {pi}-overlap of the benzannulated phenalenyls along [0 0 1], and (2) an interchain overlap involving a pair of carbon atoms (C4) along [0 1 0]. The {pi}-chain-type stacking motif is reminiscent of previously reported phenalenyl radicals and the room temperature structure (space group P2/c) together with the conductivity of {sigma}{sub RT} = 0.03 S/cm and the Pauli-like magnetic susceptibility are best described by the resonating valence bond (RVB) model. The interchain interaction is unstable with respect to the formation of a {sigma}-charge density wave ({sigma}-CDW) involving pairs of C4 carbon atoms between adjacent radicals and this phase is characterized by the P2{sub 1}/c space group which involves a doubling of the unit cell along the [0 1 0] direction. The RVB and CDW phases compete for structural occupancy throughout the whole temperature range (15-293 K) with the RVB phase predominating at 15 and 293 K and the {sigma}-CDW phase achieving a maximum structural occupancy of about 60% at 150 K where it produces clearly discernible effects on the magnetism and conductivity.

  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.

    PubMed

    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. PMID:25296795

  12. Electronic Structure and Bonding in Co-Based Single and Mixed Valence Oxides: A Quantum Chemical Perspective.

    PubMed

    Singh, Vijay; Major, Dan Thomas

    2016-04-01

    The mixed valence cobalt oxide, Co3O4, is a potential candidate as a photovoltaic (PV) material, which also exhibits intriguing chemical and catalytic properties. Here, we present a comparative study of the electronic, magnetic, and chemical bonding properties of mixed valence Co3O4 (i.e., Co(2+/3+)) with the related single valence CoO (i.e., Co(2+)) and Co2O3 (i.e., Co(3+)) oxides using density functional theory (DFT). We have employed a range of theoretical methods, including pure DFT, DFT+U, and a range-separated exchange-correlation functional (HSE06). We compare the electronic structure and band gap of the oxide materials, with available photoemission spectroscopy and optical band gaps. Our calculations suggest that the bonding between Co(3+) and O(2-) ions in Co2O3 and Co3O4 and Co(2+) and O(2-) ions in CoO and Co3O4 are rather different. We find that Co2O3 and Co3O4 are weakly correlated materials, whereas CoO is a strongly correlated material. Furthermore, our computed one-electron energy level diagrams reveal that strong Co-O antibonding states are present at the top of the valence band for all the cobalt oxides, hinting at a defect tolerant capacity in these materials. These results, which give a detailed picture of the chemical bonding in related single and mixed valence cobalt oxides, may serve as a guide to enhance the PV or photoelectrochemical activity of Co3O4, by reducing its internal defect states or changing its electronic structure by doping or alloying with suitable elements. PMID:27010797

  13. CLASSICAL TRAJECTORY MODELS FOR ELECTRONICALLY NON-ADIABATIC COLLISION PROCESSES: A CLASSICAL VALENCE BOND MODEL FOR ELECTRONIC DEGREES OF FREEDOM

    SciTech Connect

    Miller, William H.; Orel, Ann E.

    1980-11-01

    A classical interpretation of the Dirac-Van Vleck spin version of valence bond theory is used to obtain a classical model for electronic degrees of freedom within the valence bond framework. The approach is illustrated by deriving the explicit forms of the classical Hamiltonians, involving electronic and heavy particle degrees of freedom, for the H-H{sub 2}, F-H{sub 2} , and O-H{sub 2} systems. It is also shown how the initial conditions for both electronic and heavy particle degrees of freedom are chosen to carry out a classical trajectory simulation of collision processes. The attractive feature of this model is that it is as eaaily applicable to electronically non-adiabatic processes as it is to adiabatic ones.

  14. Emergence of superconductivity, valence bond order and Mott insulators in Pd[(dmit)2] based organic salts

    NASA Astrophysics Data System (ADS)

    Kee, Hae-Young

    2014-03-01

    The EtMe3P and EtMe3Sb nearly triangular organic salts are distinguished from most other Pd[(dmit)2] based salts, as they display valence bond and no long range order, respectively. Under pressure, a superconducting phase is revealed in EtMe3P near the boundary of valence bond order. We use slave-rotor theory with an enlarged unit cell to study competition between uniform and broken translational symmetry states, offering a theoretical framework capturing the superconducting, valence bond order, spin liquid, and metallic phases on an isotropic triangular lattice. Our finite temperature phase diagram manifests a remarkable resemblance to the phase diagram of the EtMe3P salt, where the re-entrant transitions of the type insulator-metal-insulator can be explained by an entropy difference between metal and the U(1) spin liquid. We find that the superconducting pairing symmetry is d +/- id , and predict different temperature dependences of the specific heat between the spin liquid and metal. Canadian Institute for Advanced Research, NSERC of Canada.

  15. Transitions to valence-bond solid order in a honeycomb lattice antiferromagnet

    NASA Astrophysics Data System (ADS)

    Pujari, Sumiran; Alet, Fabien; Damle, Kedar

    2015-03-01

    We use quantum Monte Carlo methods to study the ground-state phase diagram of a S =1 /2 honeycomb lattice magnet in which a nearest-neighbor antiferromagnetic exchange J (favoring Néel order) competes with two different multispin interaction terms: a six-spin interaction Q3 that favors columnar valence-bond solid (VBS) order, and a four-spin interaction Q2 that favors staggered VBS order. For Q3˜Q2≫J , we establish that the competition between the two different VBS orders stabilizes Néel order in a large swath of the phase diagram even when J is the smallest energy scale in the Hamiltonian. When Q3≫(Q2,J ) [ Q2≫(Q3,J ) ], this model exhibits at zero temperature phase transition from the Néel state to a columnar (staggered) VBS state. We establish that the Néel-columnar VBS transition is continuous for all values of Q2, and that critical properties along the entire phase boundary are well characterized by critical exponents and amplitudes of the noncompact CP1 (NCCP1) theory of deconfined criticality, similar to what is observed on a square lattice. However, a surprising threefold anisotropy of the phase of the VBS order parameter at criticality, whose presence was recently noted at the Q2=0 deconfined critical point, is seen to persist all along this phase boundary. We use a classical analogy to explore this by studying the critical point of a three-dimensional X Y model with a fourfold anisotropy field which is known to be weakly irrelevant at the three-dimensional X Y critical point. In this case, we again find that the critical anisotropy appears to saturate to a nonzero value over the range of sizes accessible to our simulations.

  16. Chemical composition, crystal structure, and their relationships with the intrinsic properties of spinel-type crystals based on bond valences.

    PubMed

    Liu, Xiao; Wang, Hao; Lavina, Barbara; Tu, Bingtian; Wang, Weimin; Fu, Zhengyi

    2014-06-16

    Spinel-type crystals may possess complex and versatile chemical composition and crystal structure, which leads to difficulty in constructing relationships among the chemical composition, crystal structure, and intrinsic properties. In this work, we develop new empirical methods based on bond valences to estimate the intrinsic properties, namely, compressibility and thermal expansion of complex spinel-type crystals. The composition-weighted average of bond force constants in tetrahedral and octahedral coordination polyhedra is derived as a function of the composition-weighted average of bond valences, which can be calculated according to the experimental chemical composition and crystal structural parameters. We discuss the coupled effects of tetrahedral and octahedral frameworks on the aforementioned intrinsic properties. The bulk modulus could be quantitatively calculated from the composition-weighted average of bond force constants in tetrahedral and octahedral coordination polyhedra. In contrast, a quantitative estimation of the thermal expansion coefficient could be obtained from the composition-weighted average of bond force constants in octahedral coordination polyhedra. These empirical methods have been validated by the results obtained for a new complex quaternary spinel-type oxynitride Mg0.268Al2.577O3.733N0.267 as well as MgAl2O4 and Al2.85O3.45N0.55 from the literature. Further, these empirical methods have the potential to be extensively applied in other types of complex crystals. PMID:24871452

  17. Spin Nematics, Valence-Bond Solids, and Spin Liquids in SO(N) Quantum Spin Models on the Triangular Lattice.

    PubMed

    Kaul, Ribhu K

    2015-10-01

    We introduce a simple model of SO(N) spins with two-site interactions which is amenable to quantum Monte Carlo studies without a sign problem on nonbipartite lattices. We present numerical results for this model on the two-dimensional triangular lattice where we find evidence for a spin nematic at small N, a valence-bond solid at large N, and a quantum spin liquid at intermediate N. By the introduction of a sign-free four-site interaction, we uncover a rich phase diagram with evidence for both first-order and exotic continuous phase transitions. PMID:26550748

  18. Reliability of the pair-defect-sum approximation for the strength of valence-bond orbitals

    PubMed Central

    Pauling, Linus; Herman, Zelek S.; Kamb, Barclay J.

    1982-01-01

    The pair-defect-sum approximation to the bond strength of a hybrid orbital (angular wave functions only) is compared to the rigorous value as a function of bond angle for seven types of bonding situations, with between three and eight bond directions equivalent by geometrical symmetry operations and with only one independent bond angle. The approximation is seen to be an excellent one in all cases, and the results provide a rationale for the application of this approximation to a variety of problems. PMID:16593167

  19. Correlation of molecular valence- and K-shell photoionization resonances with bond lengths

    NASA Technical Reports Server (NTRS)

    Sheehy, J. A.; Gil, T. J.; Winstead, C. L.; Farren, R. E.; Langhoff, P. W.

    1989-01-01

    The relationship between the interatomic distance and the positions of valence-shell and K-shell sigma(asterisk) photoionization resonances is investigated theoretically for the molecules C2, F2, N2, O2, CO, NO, C2H2, C2H4, C2H6, HCN, H2CO, N20, CO2, and C2N2. The results of molecular-orbital computations are presented in three-dimensional diagrams, which are shown to be similar to the wave functions of a particle in a cylindrical well, confirming the validity of free-electron molecular-orbital (FEMO) approximations for modeling the potential along the symmetry axis. FEMO orbital energies and resonance positions are found to be in good agreement with previous theoretical and experimental results. Also included is a Feshbach-Fano analysis of the relevance of virtual-valence orbitals to the appearance of single-channel resonances in molecular photoionization cross sections.

  20. Internal-strain effect on the valence band of strained silicon and its correlation with the bond angles

    SciTech Connect

    Inaoka, Takeshi Yanagisawa, Susumu; Kadekawa, Yukihiro

    2014-02-14

    By means of the first-principles density-functional theory, we investigate the effect of relative atom displacement in the crystal unit cell, namely, internal strain on the valence-band dispersion of strained silicon, and find close correlation of this effect with variation in the specific bond angles due to internal strain. We consider the [111] ([110]) band dispersion for (111) ((110)) biaxial tensility and [111] ([110]) uniaxial compression, because remarkably small values of hole effective mass m* can be obtained in this dispersion. Under the practical condition of no normal stress, biaxial tensility (uniaxial compression) involves additional normal compression (tensility) and internal strain. With an increase in the internal-strain parameter, the energy separation between the highest and second-highest valence bands becomes strikingly larger, and the highest band with conspicuously small m* extends remarkably down to a lower energy region, until it intersects or becomes admixed with the second band. This is closely correlated with the change in the specific bond angles, and this change can reasonably explain the above enlargement of the band separation.

  1. Plaquette valence-bond solid in the square-lattice J1-J2 antiferromagnet Heisenberg model: A bond operator approach

    NASA Astrophysics Data System (ADS)

    Doretto, R. L.

    2014-03-01

    We study the plaquette valence-bond solid phase of the spin-1/2J1-J2 antiferromagnet Heisenberg model on the square lattice within the bond-operator theory. We start by considering four S =1/2 spins on a single plaquette and determine the bond operator representation for the spin operators in terms of singlet, triplet, and quintet boson operators. The formalism is then applied to the J1-J2 model and an effective interacting boson model in terms of singlets and triplets is derived. The effective model is analyzed within the harmonic approximation and the previous results of Zhitomirsky and Ueda [Phys. Rev. B 54, 9007 (1996), 10.1103/PhysRevB.54.9007] are recovered. By perturbatively including cubic (triplet-triplet-triplet and singlet-triplet-triplet) and quartic interactions, we find that the plaquette valence-bond solid phase is stable within the parameter region 0.340.48J1, it is related to a singlet-singlet excitation at the X =(π/2,0) point of the tetramerized Brillouin zone.

  2. On the Nature of Bonding in Parallel Spins in Monovalent Metal Clusters.

    PubMed

    Danovich, David; Shaik, Sason

    2016-05-27

    As we approach the Lewis model centennial, it may be timely to discuss novel bonding motifs. Accordingly, this review discusses no-pair ferromagnetic (NPFM) bonds that hold together monovalent metallic atoms using exclusively parallel spins. Thus, without any traditional electron-pair bonds, the bonding energy per atom in these clusters can reach 20 kcal mol(-1). This review describes the origins of NPFM bonding using a valence bond (VB) analysis, which shows that this bonding motif arises from bound triplet electron pairs that are delocalized over all the close neighbors of a given atom in the cluster. The VB model accounts for the tendency of NPFM clusters to assume polyhedral shapes with rather high symmetry and for the very steep rise of the bonding energy per atom. The advent of NPFM clusters offers new horizons in chemistry of highly magnetic species sensitive to magnetic and electric fields. PMID:27070320

  3. On the Nature of Bonding in Parallel Spins in Monovalent Metal Clusters

    NASA Astrophysics Data System (ADS)

    Danovich, David; Shaik, Sason

    2016-05-01

    As we approach the Lewis model centennial, it may be timely to discuss novel bonding motifs. Accordingly, this review discusses no-pair ferromagnetic (NPFM) bonds that hold together monovalent metallic atoms using exclusively parallel spins. Thus, without any traditional electron-pair bonds, the bonding energy per atom in these clusters can reach 20 kcal mol-1. This review describes the origins of NPFM bonding using a valence bond (VB) analysis, which shows that this bonding motif arises from bound triplet electron pairs that are delocalized over all the close neighbors of a given atom in the cluster. The VB model accounts for the tendency of NPFM clusters to assume polyhedral shapes with rather high symmetry and for the very steep rise of the bonding energy per atom. The advent of NPFM clusters offers new horizons in chemistry of highly magnetic species sensitive to magnetic and electric fields.

  4. Spectral Correspondence to the Evolution of Chemical Bond and Valence Band in Oxidation

    NASA Astrophysics Data System (ADS)

    Sun, Chang Q.; Zhang, Sam; Hing, Peter; Wei, Jun; Xie, Hong; Wee, Andrew T. S.

    Spectroscopy covering energies around Fermi level of a metal is of particular interest as it does give direct information of bond forming and its consequence on the energy states (DOS). However, the origin of some outstanding spectral features from metal surface with chemisorbed oxygen has not yet been well established. It is shown in this letter that a bond-to-band model for oxidation enables the nature of a sum of spectral features to be consistently defined. All the spectral changes in the STS, XPS, UPS, photoemission spectroscopy (PES) and the thermal desorption spectroscopy (TDS) are classified by four DOS features around Fermi level and three bonding processes. Such a definition leads not only to new knowledge of the nature of O-metal interaction but also to a direct understanding of the bond-and-band forming dynamics.

  5. Analysis of the bond-valence method for calculating (29) Si and (31) P magnetic shielding in covalent network solids.

    PubMed

    Holmes, Sean T; Alkan, Fahri; Iuliucci, Robbie J; Mueller, Karl T; Dybowski, Cecil

    2016-07-01

    (29) Si and (31) P magnetic-shielding tensors in covalent network solids have been evaluated using periodic and cluster-based calculations. The cluster-based computational methodology employs pseudoatoms to reduce the net charge (resulting from missing co-ordination on the terminal atoms) through valence modification of terminal atoms using bond-valence theory (VMTA/BV). The magnetic-shielding tensors computed with the VMTA/BV method are compared to magnetic-shielding tensors determined with the periodic GIPAW approach. The cluster-based all-electron calculations agree with experiment better than the GIPAW calculations, particularly for predicting absolute magnetic shielding and for predicting chemical shifts. The performance of the DFT functionals CA-PZ, PW91, PBE, rPBE, PBEsol, WC, and PBE0 are assessed for the prediction of (29) Si and (31) P magnetic-shielding constants. Calculations using the hybrid functional PBE0, in combination with the VMTA/BV approach, result in excellent agreement with experiment. © 2016 Wiley Periodicals, Inc. PMID:27117609

  6. 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.

  7. Electronic Model for CoO2 Layer Based Systems: Chiral Resonating Valence Bond Metal and Superconductivity

    NASA Astrophysics Data System (ADS)

    Baskaran, G.

    2003-08-01

    Takada et al. have reported superconductivity in layered NaxCoO2yH2O (Tc≈5 K). We model a reference neutral CoO2 layer as an orbitally nondegenerate spin-1/2 antiferromagnetic Mott insulator on a triangular lattice and NaxCoO2yH2O as electron doped Mott insulators described by a t-J model. It is suggested that at optimal doping chiral spin fluctuations enhanced by the dopant dynamics lead to a gapful d-wave superconducting state. A chiral resonating valence bond (RVB) metal, a parity and time (PT) reversal violating state with condensed RVB gauge fields, with a possible weak ferromagnetism, and low temperature p-wave superconductivity are also suggested at higher dopings.

  8. The Quadruple Bonding in C2 Reproduces the Properties of the Molecule.

    PubMed

    Shaik, Sason; Danovich, David; Braida, Benoit; Hiberty, Philippe C

    2016-03-14

    Ever since Lewis depicted the triple bond for acetylene, triple bonding has been considered as the highest limit of multiple bonding for main elements. Here we show that C2 is bonded by a quadruple bond that can be distinctly characterized by valence-bond (VB) calculations. We demonstrate that the quadruply-bonded structure determines the key observables of the molecule, and accounts by itself for about 90% of the molecule's bond dissociation energy, and for its bond lengths and its force constant. The quadruply-bonded structure is made of two strong π bonds, one strong σ bond and a weaker fourth σ-type bond, the bond strength of which is estimated as 17-21 kcal mol(-1). Alternative VB structures with double bonds; either two π bonds or one π bond and one σ bond lie at 129.5 and 106.1 kcal mol(-1), respectively, above the quadruply-bonded structure, and they collapse to the latter structure given freedom to improve their double bonding by dative σ bonding. The usefulness of the quadruply-bonded model is underscored by "predicting" the properties of the (3)Σ+u state. C2's very high reactivity is rooted in its fourth weak bond. Thus, carbon and first-row main elements are open to quadruple bonding! PMID:26880488

  9. Insights into the Electronic Structure of Ozone and Sulfur Dioxide from Generalized Valence Bond Theory: Addition of Hydrogen Atoms.

    PubMed

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

    2016-05-01

    Ozone (O3) and sulfur dioxide (SO2) are valence isoelectronic species, yet their properties and reactivities differ dramatically. In particular, O3 is highly reactive, whereas SO2 is chemically relatively stable. In this paper, we investigate serial addition of hydrogen atoms to both the terminal atoms of O3 and SO2 and to the central atom of these species. It is well-known that the terminal atoms of O3 are much more amenable to bond formation than those of SO2. We show that the differences in the electronic structure of the π systems in the parent triatomic species account for the differences in the addition of hydrogen atoms to the terminal atoms of O3 and SO2. Further, we find that the π system in SO2, which is a recoupled pair bond dyad, facilitates the addition of hydrogen atoms to the sulfur atom, resulting in stable HSO2 and H2SO2 species. PMID:27070292

  10. Geometry of trigonal boron coordination sphere in boronic acids derivatives - a bond-valence vector model approach.

    PubMed

    Czerwińska, Karolina; Madura, Izabela D; Zachara, Janusz

    2016-04-01

    The systematic analysis of the geometry of three-coordinate boron in boronic acid derivatives with a common [CBO2] skeleton is presented. The study is based on the bond-valence vector (BVV) model [Zachara (2007). Inorg. Chem. 46, 9760-9767], a simple tool for the identification and quantitative estimation of both steric and electronic factors causing deformations of the coordination sphere. The empirical bond-valence (BV) parameters in the exponential equation [Brown & Altermatt (1985). Acta Cryst. B41, 244-247] rij and b, for B-O and B-C bonds were determined using data deposited in the Cambridge Structural Database. The values obtained amount to rBO = 1.364 Å, bBO = 0.37 Å, rBC = 1.569 Å, bBC = 0.28 Å, and they were further used in the calculation of BVV lengths. The values of the resultant BVV were less than 0.10 v.u. for 95% of the set comprising 897 [CBO2] fragments. Analysis of the distribution of BVV components allowed for the description of subtle in- and out-of plane deviations from the `ideal' (sp(2)) geometry of boron coordination sphere. The distortions specific for distinct groups of compounds such as boronic acids, cyclic and acyclic esters, benzoxaboroles and hemiesters were revealed. In cyclic esters the direction of strains was found to be controlled by the ring size effect. It was shown that the syn or anti location of substituents on O atoms is decisive for the deformations direction for both acids and acyclic esters. The greatest strains were observed in the case of benzoxaboroles which showed the highest deviation from the zero value of the resultant BVV. The out-of-plane distortions, described by the vz component of the resultant BVV, were ascertained to be useful in the identification of weak secondary interactions on the fourth coordination site of the boron centre. PMID:27048726

  11. 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

  12. Valence-bond solid as the quantum ground state in honeycomb layered urusovite CuAl (As O4)O

    NASA Astrophysics Data System (ADS)

    Vasiliev, A. N.; Volkova, O. S.; Zvereva, E. A.; Koshelev, A. V.; Urusov, V. S.; Chareev, D. A.; Petkov, V. I.; Sukhanov, M. V.; Rahaman, B.; Saha-Dasgupta, T.

    2015-04-01

    The synthetic mineral urusovite CuAl (As O4)O was prepared through the wet chemistry route and characterized over a wide temperature range in terms of studies of magnetization, specific heat, and X-band electron spin resonance. The basic structural units of the compound are distorted square pyramids Cu O5 assembled into corrugated honeycomb layers separated by As O4 and Al O4 tetrahedrons. Both thermodynamic and resonant measurements indicate that CuAl (As O4)O is a spin gap system with a gap of ˜350 K . The electronic structure calculations performed within the framework of density functional theory suggest a weakly interacting dimer model with antiferromagnetic signs for both intradimer and interdimer superexchange interactions. This establishes the valence bond solid as the quantum ground state of the title compound. The pronounced discrepancy between experimental data and calculations within the weakly interacting dimer model at elevated temperatures is ascribed in part to the steep increase of the intradimer exchange interaction parameter driven by the thermal expansion effects.

  13. Multistate empirical valence bond study of temperature and confinement effects on proton transfer in water inside hydrophobic nanochannels.

    PubMed

    Tahat, Amani; Martí, Jordi

    2016-07-01

    Microscopic characteristics of an aqueous excess proton in a wide range of thermodynamic states, from low density amorphous ices (down to 100 K) to high temperature liquids under the critical point (up to 600 K), placed inside hydrophobic graphene slabs at the nanometric scale (with interplate distances between 3.1 and 0.7 nm wide) have been analyzed by means of molecular dynamics simulations. Water-proton and carbon-proton forces were modeled with a multistate empirical valence bond method. Densities between 0.07 and 0.02 Å(-3) have been considered. As a general trend, we observed a competition between effects of confinement and temperature on structure and dynamical properties of the lone proton. Confinement has strong influence on the local structure of the proton, whereas the main effect of temperature on proton properties is observed on its dynamics, with significant variation of proton transfer rates, proton diffusion coefficients, and characteristic frequencies of vibrational motions. Proton transfer is an activated process with energy barriers between 1 and 10 kJ/mol for both proton transfer and diffusion, depending of the temperature range considered and also on the interplate distance. Arrhenius-like behavior of the transfer rates and of proton diffusion are clearly observed for states above 100 K. Spectral densities of proton species indicated that in all states Zundel-like and Eigen-like complexes survive at some extent. © 2016 Wiley Periodicals, Inc. PMID:27189810

  14. Low-energy physical properties of high- Tc superconducting Cu oxides: A comparison between the resonating valence bond and experiments

    NASA Astrophysics Data System (ADS)

    Yang, Kai-Yu; Shih, C. T.; Chou, C. P.; Huang, S. M.; Lee, T. K.; Xiang, T.; Zhang, F. C.

    2006-06-01

    In a recent review by Anderson and co-workers, it was pointed out that an early resonating valence bond (RVB) theory is able to explain a number of unusual properties of high-temperature superconducting (SC) Cu oxides. Here we extend previous calculations to study more systematically the low-energy physical properties of the plain vanilla d -wave RVB state, and to compare the results with the available experiments. We use a renormalized mean-field theory combined with variational Monte Carlo and power Lanczos methods to study the RVB state of an extended t-J model in a square lattice with parameters suitable for the hole-doped Cu oxides. The physical observable quantities we study include the specific heat, the linear residual thermal conductivity, the in-plane magnetic penetration depth, the quasiparticle energy at the antinode (π,0) , the superconducting energy gap, the quasiparticle spectra, and the Drude weights. The traits of nodes (including kF , the Fermi velocity vF , and the velocity along Fermi surface v2 ), and the SC order parameter are studied. Comparisons of the theory and the experiments in cuprates show an overall qualitative agreement, especially on their doping dependences.

  15. 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 ρ(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

  16. 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.

  17. The nature of chemical bonds from PNOF5 calculations.

    PubMed

    Matxain, Jon M; Piris, Mario; Uranga, Jon; Lopez, Xabier; Merino, Gabriel; Ugalde, Jesus M

    2012-06-18

    Natural orbital functional theory (NOFT) is used for the first time in the analysis of different types of chemical bonds. Concretely, the Piris natural orbital functional PNOF5 is used. It provides a localization scheme that yields an orbital picture which agrees very well with the empirical valence shell electron pair repulsion theory (VSEPR) and Bent's rule, as well as with other theoretical pictures provided by valence bond (VB) or linear combination of atomic orbitals-molecular orbital (LCAO-MO) methods. In this context, PNOF5 provides a novel tool for chemical bond analysis. In this work, PNOF5 is applied to selected molecules that have ionic, polar covalent, covalent, multiple (σ and π), 3c-2e, and 3c-4e bonds. PMID:22615195

  18. An Effective Hamiltonian Molecular Orbital-Valence Bond (MOVB) Approach for Chemical Reactions Applied to the Nucleophilic Substitution Reaction of Hydrosulfide Ion and Chloromethane

    PubMed Central

    Song, Lingchun; Mo, Yirong; Gao, Jiali

    2009-01-01

    An effective Hamiltonian mixed molecular orbital and valence bond (EH-MOVB) method is described to obtain an accurate potential energy surface for chemical reactions. Building upon previous results on the construction of diabatic and adiabatic potential surfaces using ab initio MOVB theory, we introduce a diabatic-coupling scaling factor to uniformly scale the ab initio off-diagonal matrix element H12 such that the computed energy of reaction from the EH-MOVB method is in agreement with the target value. The scaling factor is very close to unity, resulting in minimal alteration of the potential energy surface of the original MOVB model. Furthermore, the relative energy between the reactant and product diabatic states in the EH-MOVB method can be improved to match the experimental energy of reaction. A key ingredient in the EH-MOVB theory is that the off-diagonal matrix elements are functions of all degrees of freedom of the system and the overlap matrix is explicitly evaluated. The EH-MOVB method has been applied to the nucleophilic substitution reaction between hydrosulfide and chloromethane to illustrate the methodology and the results were matched to reproduce the results from ab initio valence bond self-consistent valence bond (VBSCF) calculations. The diabatic coupling (the off-diagonal matrix element in the generalized secular equation) has small variations along the minimum energy reaction path in the EH-MOVB model, whereas it shows a maximum value at the transition state and has nearly zero values in the regions of the ion-dipole complexes from VBSCF calculations. The difference in the diabatic coupling stabilization is attributed to the large overlap integral in the computationally efficient MOVB method. PMID:20047006

  19. An Effective Hamiltonian Molecular Orbital-Valence Bond (MOVB) Approach for Chemical Reactions Applied to the Nucleophilic Substitution Reaction of Hydrosulfide Ion and Chloromethane.

    PubMed

    Song, Lingchun; Mo, Yirong; Gao, Jiali

    2009-01-01

    An effective Hamiltonian mixed molecular orbital and valence bond (EH-MOVB) method is described to obtain an accurate potential energy surface for chemical reactions. Building upon previous results on the construction of diabatic and adiabatic potential surfaces using ab initio MOVB theory, we introduce a diabatic-coupling scaling factor to uniformly scale the ab initio off-diagonal matrix element H(12) such that the computed energy of reaction from the EH-MOVB method is in agreement with the target value. The scaling factor is very close to unity, resulting in minimal alteration of the potential energy surface of the original MOVB model. Furthermore, the relative energy between the reactant and product diabatic states in the EH-MOVB method can be improved to match the experimental energy of reaction. A key ingredient in the EH-MOVB theory is that the off-diagonal matrix elements are functions of all degrees of freedom of the system and the overlap matrix is explicitly evaluated. The EH-MOVB method has been applied to the nucleophilic substitution reaction between hydrosulfide and chloromethane to illustrate the methodology and the results were matched to reproduce the results from ab initio valence bond self-consistent valence bond (VBSCF) calculations. The diabatic coupling (the off-diagonal matrix element in the generalized secular equation) has small variations along the minimum energy reaction path in the EH-MOVB model, whereas it shows a maximum value at the transition state and has nearly zero values in the regions of the ion-dipole complexes from VBSCF calculations. The difference in the diabatic coupling stabilization is attributed to the large overlap integral in the computationally efficient MOVB method. PMID:20047006

  20. 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 (Θ = -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 σ 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 σ 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

  1. Generalized valence bond description of the ground states (X(1)Σg(+)) of homonuclear pnictogen diatomic molecules: N2, P2, and As2.

    PubMed

    Xu, Lu T; Dunning, Thom H

    2015-06-01

    The ground state, X1Σg+, of N2 is a textbook example of a molecule with a triple bond consisting of one σ and two π bonds. This assignment, which is usually rationalized using molecular orbital (MO) theory, implicitly assumes that the spins of the three pairs of electrons involved in the bonds are singlet-coupled (perfect pairing). However, for a six-electron singlet state, there are five distinct ways to couple the electron spins. The generalized valence bond (GVB) wave function lifts this restriction, including all of the five spin functions for the six electrons involved in the bond. For N2, we find that the perfect pairing spin function is indeed dominant at Re but that it becomes progressively less so from N2 to P2 and As2. Although the perfect pairing spin function is still the most important spin function in P2, the importance of a quasi-atomic spin function, which singlet couples the spins of the electrons in the σ orbitals while high spin coupling those of the electrons in the π orbitals on each center, has significantly increased relative to N2 and, in As2, the perfect pairing and quasi-atomic spin couplings are on essentially the same footing. This change in the spin coupling of the electrons in the bonding orbitals down the periodic table may contribute to the rather dramatic decrease in the strengths of the Pn2 bonds from N2 to As2 as well as in the increase in their chemical reactivity and should be taken into account in more detailed analyses of the bond energies in these species. We also compare the spin coupling in N2 with that in C2, where the quasi-atomic spin coupling dominants around Re. PMID:26575549

  2. 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.

  3. Qgui: A high-throughput interface for automated setup and analysis of free energy calculations and empirical valence bond simulations in biological systems.

    PubMed

    Isaksen, Geir Villy; Andberg, Tor Arne Heim; Åqvist, Johan; Brandsdal, Bjørn Olav

    2015-07-01

    Structural information and activity data has increased rapidly for many protein targets during the last decades. In this paper, we present a high-throughput interface (Qgui) for automated free energy and empirical valence bond (EVB) calculations that use molecular dynamics (MD) simulations for conformational sampling. Applications to ligand binding using both the linear interaction energy (LIE) method and the free energy perturbation (FEP) technique are given using the estrogen receptor (ERα) as a model system. Examples of free energy profiles obtained using the EVB method for the rate-limiting step of the enzymatic reaction catalyzed by trypsin are also shown. In addition, we present calculation of high-precision Arrhenius plots to obtain the thermodynamic activation enthalpy and entropy with Qgui from running a large number of EVB simulations. PMID:26080356

  4. 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 α-PbO, β-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

  5. On the efficiency of VBSCF algorithms, a comment on "An efficient algorithm for energy gradients and orbital optimization in valence bond theory".

    PubMed

    van Lenthe, J H; Broer-Braam, H B; Rashid, Z

    2012-03-30

    We comment on the paper [Song et al., J. Comput. Chem. 2009, 30, 399]. and discuss the efficiency of the orbital optimization and gradient evaluation in the Valence Bond Self Consistent Field (VBSCF) method. We note that Song et al. neglect to properly reference Broer et al., who published an algorithm [Broer and Nieuwpoort, Theor. Chim. Acta 1988, 73, 405] to use a Fock matrix to compute a matrix element between two different determinants, which can be used for an orbital optimization. Further, Song et al. publish a misleading comparison with our VBSCF algorithm [Dijkstra and van Lenthe, J. Chem. Phys. 2000, 113, 2100; van Lenthe et al., Mol. Phys. 1991, 73, 1159] to enable them to favorably compare their algorithm with ours. We give detail timings in terms of different orbital types in the calculation and actual timings for the example cases. PMID:22278948

  6. Atomic Structure and Valence: Level II, Unit 10, Lesson 1; Chemical Bonding: Lesson 2; The Table of Elements: Lesson 3; Electrolysis: Lesson 4. Advanced General Education Program. A High School Self-Study Program.

    ERIC Educational Resources Information Center

    Manpower Administration (DOL), Washington, DC. Job Corps.

    This self-study program for high-school level contains lessons on: Atomic Structure and Valence, Chemical Bonding, The Table of Elements, and Electrolysis. Each of the lessons concludes with a Mastery Test to be completed by the student. (DB)

  7. 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.

  8. Using the constrained DFT approach in generating diabatic surfaces and off diagonal empirical valence bond terms for modeling reactions in condensed phases.

    PubMed

    Hong, Gongyi; Rosta, Edina; Warshel, Arieh

    2006-10-01

    The empirical valence bond (EVB) model provides an extremely powerful way for modeling and analyzing chemical reactions in solutions and proteins. However, this model is based on the unverified assumption that the off diagonal elements of the EVB Hamiltonian do not change significantly upon transfer of the reacting system from one phase to another. This ad hoc assumption has been rationalized by its consistency with empirically observed linear free energy relationships, as well as by other qualitative considerations. Nevertheless, this assumption has not been rigorously established. The present work explores the validity of the above EVB key assumption by a rigorous numerical approach. This is done by exploiting the ability of the frozen density functional theory (FDFT) and the constrained density functional theory (CDFT) models to generate convenient diabatic states for QM/MM treatments, and thus to examine the relationship between the diabatic and adiabatic surfaces, as well as the corresponding effective off diagonal elements. It is found that, at least for the test case of S(N)()2 reactions, the off diagonal element does not change significantly upon moving from the gas phase to solutions and thus the EVB assumption is valid and extremely useful. PMID:17004821

  9. 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 (Δ/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.

  10. 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. β-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 β-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.

  11. A minimalistic approach to static and dynamic electron correlations: Amending generalized valence bond method with extended random phase approximation correlation correction

    NASA Astrophysics Data System (ADS)

    Chatterjee, Koushik; Pastorczak, Ewa; Jawulski, Konrad; Pernal, Katarzyna

    2016-06-01

    A perfect-pairing generalized valence bond (GVB) approximation is known to be one of the simplest approximations, which allows one to capture the essence of static correlation in molecular systems. In spite of its attractive feature of being relatively computationally efficient, this approximation misses a large portion of dynamic correlation and does not offer sufficient accuracy to be generally useful for studying electronic structure of molecules. We propose to correct the GVB model and alleviate some of its deficiencies by amending it with the correlation energy correction derived from the recently formulated extended random phase approximation (ERPA). On the examples of systems of diverse electronic structures, we show that the resulting ERPA-GVB method greatly improves upon the GVB model. ERPA-GVB recovers most of the electron correlation and it yields energy barrier heights of excellent accuracy. Thanks to a balanced treatment of static and dynamic correlation, ERPA-GVB stays reliable when one moves from systems dominated by dynamic electron correlation to those for which the static correlation comes into play.

  12. 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. β-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 β-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

  13. First-order superfluid to valence-bond solid phase transitions in easy-plane SU (N ) magnets for small N

    NASA Astrophysics Data System (ADS)

    D'Emidio, Jonathan; Kaul, Ribhu K.

    2016-02-01

    We consider the easy-plane limit of bipartite SU (N ) Heisenberg Hamiltonians, which have a fundamental representation on one sublattice and the conjugate to fundamental on the other sublattice. For N =2 the easy plane limit of the SU(2) Heisenberg model is the well-known quantum X Y model of a lattice superfluid. We introduce a logical method to generalize the quantum X Y model to arbitrary N , which keeps the Hamiltonian sign-free. We show that these quantum Hamiltonians have a world-line representation as the statistical mechanics of certain tightly packed loop models of N colors in which neighboring loops are disallowed from having the same color. In this loop representation we design an efficient Monte Carlo cluster algorithm for our model. We present extensive numerical results for these models on the two dimensional square lattice, where we find the nearest neighbor model has superfluid order for N ≤5 and valence-bond order for N >5 . By introducing SU (N ) easy-plane symmetric four-spin couplings we are able to tune across the superfluid-VBS phase boundary for all N ≤5 . We present clear evidence that this quantum phase transition is first order for N =2 and N =5 , suggesting that easy-plane deconfined criticality runs away generically to a first-order transition for small N .

  14. Connecting a new non-adiabatic vibrational mass to the bonding mechanism of LiH: A quantum superposition of ionic and covalent states

    NASA Astrophysics Data System (ADS)

    Diniz, Leonardo G.; Alijah, Alexander; Adamowicz, Ludwik; Mohallem, José R.

    2015-07-01

    Non-adiabatic vibrational calculations performed with the accuracy of 0.2 cm-1 spanning the whole energy spectrum up to the dissociation limit for 7LiH are reported. A so far unknown v = 23 energy level is predicted. The key feature of the approach used in the calculations is a valence-bond (VB) based procedure for determining the effective masses of the two vibrating atoms, which depend on the internuclear distance, R. It is found that all LiH electrons participate in the vibrational motion. The R-dependent masses are obtained from the analysis of the simple VB two-configuration ionic-covalent representation of the electronic wave function. These findings are consistent with an interpretation of the chemical bond in LiH as a quantum mechanical superposition of one-electron ionic and covalent states.

  15. Spectroscopic constants of diatomic molecules computed correcting Hartree-Fock or general-valence-bond potential-energy curves with correlation-energy functionals

    NASA Astrophysics Data System (ADS)

    Pérez-Jordá, José M.; San-Fabián, Emilio; Moscardó, Federico

    1992-04-01

    The Kohn-Sham energy with exact exchange [using the exact Hartree-Fock (HF) exchange but an approximate correlation-energy functional] may be computed very accurately by adding the correlation obtained from the HF density to the total HF energy. Three density functionals are used: local spin density (LSD), LSD with self-interaction correction, and LSD with generalized gradient correction. This scheme has been extended (Lie-Clementi, Colle-Salvetti, and Moscardo-San-Fabian) to be used with general-valence-bond (GVB) energies and wave functions, so that the extra correlation included in the GVB energy is not counted again. The effect of all these approximate correlations on HF or GVB spectroscopic constants (Re,ωe, and De) is studied. Approximate relations showing how correlation affects them are derived, and may be summarized as follows: (1) the effect on Re and ωe depends only on the correlation derivative at Re, and (2) the effect on De depends mainly on the correlation difference between quasidissociated and equilibrium geometries. A consequence is that all the correlation corrections tested here give larger ωe and De and shorter Re than the uncorrected HF or GVB values. This trend is correct for De for both HF and GVB. For Re and ωe, it is correct in most cases for GVB, but it often fails for the HF cases. A comparison is made with Kohn-Sham calculations with both exchange and correlation approximated. As a final conclusion, it is found that, within the present scheme, a qualitatively correct HF or GVB potential-energy curve, together with a correlation-energy approximation with correct dissociation behavior, is crucial for obtaining good estimates of spectroscopic constants.

  16. 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.

  17. Analysis of Bonding Patterns in the Valence Isoelectronic series O3, S3, 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) π-bonding interaction and a (L-R) π-antibonding interaction. This finding supports the previously proposed "partial biradical" interpretation of these triatomic systems, which had recently been challenged.

  18. 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...

  19. Combined valence bond-molecular mechanics potential-energy surface and direct dynamics study of rate constants and kinetic isotope effects for the H +C2H6 reaction

    NASA Astrophysics Data System (ADS)

    Chakraborty, Arindam; Zhao, Yan; Lin, Hai; Truhlar, Donald G.

    2006-01-01

    This article presents a multifaceted study of the reaction H +C2H6→H2+C2H5 and three of its deuterium-substituted isotopologs. First we present high-level electronic structure calculations by the W1, G3SX, MCG3-MPWB, CBS-APNO, and MC-QCISD/3 methods that lead to a best estimate of the barrier height of 11.8±0.5kcal/mol. Then we obtain a specific reaction parameter for the MPW density functional in order that it reproduces the best estimate of the barrier height; this yields the MPW54 functional. The MPW54 functional, as well as the MPW60 functional that was previously parametrized for the H +CH4 reaction, is used with canonical variational theory with small-curvature tunneling to calculate the rate constants for all four ethane reactions from 200 to 2000 K. The final MPW54 calculations are based on curvilinear-coordinate generalized-normal-mode analysis along the reaction path, and they include scaled frequencies and an anharmonic C-C bond torsion. They agree with experiment within 31% for 467-826 K except for a 38% deviation at 748 K; the results for the isotopologs are predictions since these rate constants have never been measured. The kinetic isotope effects (KIEs) are analyzed to reveal the contributions from subsets of vibrational partition functions and from tunneling, which conspire to yield a nonmonotonic temperature dependence for one of the KIEs. The stationary points and reaction-path potential of the MPW54 potential-energy surface are then used to parametrize a new kind of analytical potential-energy surface that combines a semiempirical valence bond formalism for the reactive part of the molecule with a standard molecular mechanics force field for the rest; this may be considered to be either an extension of molecular mechanics to treat a reactive potential-energy surface or a new kind of combined quantum-mechanical/molecular mechanical (QM/MM) method in which the QM part is semiempirical valence bond theory; that is, the new potential

  20. Resolving CuO chain and CuO2 plane contributions to the YBa2Cu3O7 -δ valence band by standing-wave excited hard x-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Thiess, S.; Lee, T.-L.; Aruta, C.; Lin, C. T.; Venturini, F.; Brookes, N. B.; Cowie, B. C. C.; Zegenhagen, J.

    2015-08-01

    We analyzed the valence band (VB) of the 90 K high-temperature superconductor YBa2Cu3O7 -δ by photoelectron spectroscopy under standing-wave excitation employing hard x rays. Precisely positioning the standing-wave intensity in the unit cell allows selectively probing the VB yield from the CuO chains and CuO2 planes, respectively. Both contribute strongly over the whole VB but the spectral weight of the planes is significantly higher than the chains within about 2 eV from the Fermi level. In the x-ray regime, the major contribution to the VB emission is coming from Cu 3 d .

  1. Fabrication of VB2/air cells for electrochemical testing.

    PubMed

    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

  2. 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

  3. Nature of the Xe(VI)-N Bonds in F6 XeNCCH3 and F6 Xe(NCCH3)2 and the Stereochemical Activity of Their Xenon Valence Electron Lone Pairs.

    PubMed

    Haner, Jamie; Matsumoto, Kazuhiko; Mercier, Hélène P A; Schrobilgen, Gary J

    2016-03-24

    The recently reported syntheses and X-ray crystal structures of the highly endothermic compounds F6XeNCCH3 and F6Xe(NCCH3)2 ⋅CH3CN provide the first, albeit weakly covalent, Xe(VI)-N bonds. The XeF6 unit of F6 XeNCCH3 possesses distorted octahedral (C3v ) symmetry similar to gas-phase XeF6 , whereas the XeF6 unit of F6 Xe(NCCH3)2 ⋅CH3CN possesses C2v symmetry. Herein, the natural bond orbital (NBO), atoms in molecules (AIM), electron localization function (ELF), and molecular electrostatic potential surface (MEPS) analyses show that the Xe valence electron lone pairs (VELPs) of both compounds are stereochemically active. The Xe VELPS are diffuse and ineffectively screen their Xe cores so that the Xe VELP positions correspond to the most electrophilic regions of the MEPS, which enables the opposing N VELP of CH3CN to coordinate to this region. These bonds are predominantly electrostatic in nature and are interpreted as σ-hole interactions. PMID:26918266

  4. Consequences of Optimal Bond Valence on Structural Rigidity and Improved Luminescence Properties in SrxBa2-xSiO4:Eu2+ Orthosilicate Phosphors

    SciTech Connect

    Denault, Kristin A.; Brgoch, Jakoah; Gaultois, Michael W.; Mikhailovsky, Alexander; Petry, Ralf; Winkler, Holger; DenBaars, Steven P.; Seshadri, Ram

    2014-08-19

    The orthosilicate phosphors SrxBa2–xSiO4:Eu2+ have now been known for over four decades and have found extensive recent use in solid-state white lighting. It is well-recognized in the literature and in practice that intermediate compositions in the solid-solutions between the orthosilicates Sr2SiO4 and Ba2SiO4 yield the best phosphor hosts when the thermal stability of luminescence is considered. We employ a combination of synchrotron X-ray diffraction, total scattering measurements, density functional theory calculations, and low-temperature heat capacity measurements, in conjunction with detailed temperature- and time-resolved studies of luminescence properties to understand the origins of the improved luminescence properties. We observe that in the intermediate compositions, the two cation sites in the crystal structure are optimally bonded as determined from bond valence sum calculations. Optimal bonding results in a more rigid lattice, as established by the intermediate compositions possessing the highest Debye temperature, which are determined experimentally from low-temperature heat capacity measurements. Greater rigidity in turn results in the highest luminescence efficiency for intermediate compositions at elevated temperatures.

  5. Geometrical frustration in the spin liquid β'-Me3EtSb[Pd(dmit)2]2 and the valence-bond solid Me3EtP[Pd(dmit)2]2.

    PubMed

    Scriven, E P; Powell, B J

    2012-08-31

    We show that the electronic structures of the title compounds predicted by density functional theory are well described by tight binding models. We determine the frustration ratio, J'/J, of the Heisenberg model on the anisotropic triangular lattice, which describes the spin degrees of freedom in the Mott insulating phase for a range of Pd(dmit)2 salts. All of the antiferromagnetic materials studied have J'/J is < or approximately equal to 0.5 or J'/J > or approximately equal to 0.9, and all salts with 0.5 < or approximately equal to J'/J < or approximately equal to 0.9 are known, experimentally, to be charge ordered valence-bond solids or spin liquids. PMID:23002879

  6. Direct infrared imaging of VB 8

    NASA Technical Reports Server (NTRS)

    Skrutskie, M. F.; Forret, W. J.; Shure, M. A.

    1987-01-01

    Near-infrared images of VB 8 taken at K (2.2 microns) and L-prime (3.75 microns) during a period of good seeing at the IRTF show no evidence of the brown dwarf companion reported by McCarthy et al. (1985). Any companion 1.0 arcsec away from the primary must be at least 4 mag fainter than the primary at K and 3 mag fainter at L-prime in order to escape detection. A faint nebula centered on the star with scattering properties similar to a nebula detected near another main-sequence M star, Lalande 21185 (reported by McCarthy in 1986), may account for the extended emission detected by speckle observations.

  7. 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

  8. Unified studies of chemical bonding structures and resonant scattering in light neutron-excess systems, 10,12Be.

    PubMed

    Ito, Makoto; Ikeda, Kiyomi

    2014-09-01

    The generalized two-center cluster model (GTCM), which can treat covalent, ionic and atomic configurations in general systems with two inert cores plus valence nucleons, is formulated in the basis of the microscopic cluster model. In this model, the covalent configurations constructed by the molecular orbital (MO) method and the atomic (or ionic) configuration obtained by the valence bonding (VB) method can be handled in a consistent manner. The GTCM is applied to the light neutron-rich system (10,12)Be = α + α + Xn (X = 2, 4). The continuous and smooth changes of the neutron orbits from the covalent MO states to the ionic VB states are clearly observed in the adiabatic energy surfaces (AESs), which are the energy curves obtained with a variation of the α-α distance. The energy levels obtained from the AESs nicely reproduce the recent observations over a wide energy region. The individual spectra are characterized in terms of chemical-bonding-like structures, such as the covalent MO or ionic VB structures, according to analysis of their intrinsic wave functions. From the analysis of AESs, the formation of the mysterious 0(2)(+) states in (10,12)Be, which have anomalously small excitation energies in comparison to a naive shell-model prediction, is investigated. A large enhancement in a monopole transition from a ground MO state to an ionic α + (6,8)He VB state is found, which seems to be consistent with a recent observation. In the unbound region, the structure problem, which handles the total system of α + α + Xn (X = 2, 4) as a bound or quasi-bound state, and the reaction problem, induced by the collision of an asymptotic VB state of α + (6,8)He, are combined by the GTCM. The properties of unbound resonant states are discussed in close connection to the reaction mechanism, and some enhancement factors originating from the properties of the intrinsic states are predicted in the reaction observables. PMID:25222183

  9. 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.

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

    SciTech Connect

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

    2015-09-14

    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 π-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.

  11. 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 π-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.

  12. Coulombic Models in Chemical Bonding.

    ERIC Educational Resources Information Center

    Sacks, Lawrence J.

    1986-01-01

    Compares the coulumbic point charge model for hydrogen chloride with the valence bond model. It is not possible to assign either a nonpolar or ionic canonical form of the valence bond model, while the covalent-ionic bond distribution does conform to the point charge model. (JM)

  13. 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

  14. Highly efficient perturbative + variational strategy based on orthogonal valence bond theory for the evaluation of magnetic coupling constants. Application to the trinuclear Cu(ii) site of multicopper oxidases.

    PubMed

    Tenti, Lorenzo; Maynau, Daniel; Angeli, Celestino; Calzado, Carmen J

    2016-07-21

    A new strategy based on orthogonal valence-bond analysis of the wave function combined with intermediate Hamiltonian theory has been applied to the evaluation of the magnetic coupling constants in two AF systems. This approach provides both a quantitative estimate of the J value and a detailed analysis of the main physical mechanisms controlling the coupling, using a combined perturbative + variational scheme. The procedure requires a selection of the dominant excitations to be treated variationally. Two methods have been employed: a brute-force selection, using a logic similar to that of the CIPSI approach, or entanglement measures, which identify the most interacting orbitals in the system. Once a reduced set of excitations (about 300 determinants) is established, the interaction matrix is dressed at the second-order of perturbation by the remaining excitations of the CI space. The diagonalization of the dressed matrix provides J values in good agreement with experimental ones, at a very low-cost. This approach demonstrates the key role of d → d* excitations in the quantitative description of the magnetic coupling, as well as the importance of using an extended active space, including the bridging ligand orbitals, for the binuclear model of the intermediates of multicopper oxidases. The method is a promising tool for dealing with complex systems containing several active centers, as an alternative to both pure variational and DFT approaches. PMID:27336417

  15. An investigation report about the lack of VB1

    PubMed Central

    Zhu, Hangju

    2016-01-01

    From August 1 to September 26, 2012, 30 workers who had the symptom of edema in both lower limbs were reported in Yancheng, Four severe edemas in both lower limbs workers were sent to the hospital, and one person of the workers died. The epidemiology investigation and laboratory testing (in the urine loading tests, the concentration of VB1 of the workers living in the factory for more than half of the year decreased far below the normal values) were conducted to explore the cause. Furthermore, after one-week intramuscular injection of thiamine treatment, the clinical symptoms of the workers had been improved greatly. Finally, the lake of the thiamine (VB1) was considered to be the reason of this incident.

  16. An investigation report about the lack of VB1.

    PubMed

    Zhu, Hangju; Sun, Guiju; Zhu, Baoli

    2016-08-01

    From August 1 to September 26, 2012, 30 workers who had the symptom of edema in both lower limbs were reported in Yancheng, Four severe edemas in both lower limbs workers were sent to the hospital, and one person of the workers died. The epidemiology investigation and laboratory testing (in the urine loading tests, the concentration of VB1 of the workers living in the factory for more than half of the year decreased far below the normal values) were conducted to explore the cause. Furthermore, after one-week intramuscular injection of thiamine treatment, the clinical symptoms of the workers had been improved greatly. Finally, the lake of the thiamine (VB1) was considered to be the reason of this incident. PMID:27621883

  17. 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…

  18. Micro-valences: perceiving affective valence in everyday objects.

    PubMed

    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

  19. 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.

  20. 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.

  1. 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

  2. Vb-type cyclones and their role in extreme precipitation events in Central Europe

    NASA Astrophysics Data System (ADS)

    Messmer, Martina; José Gómez-Navarro, Juan; Raible, Christoph C.

    2015-04-01

    Extreme weather situations are of major relevance for society, since they lead to great economical and personal damage. In Central Europe, one important source of extreme precipitation accompanied by large flooding events is the so-called Vb-event, classified by W. J. Van Bebber in 1891. Vb-events are defined as cyclones developing over the western Mediterranean that move north eastward. They can uptake large amounts of moisture, which is then transported towards the Alps and Central Europe, inducing heavy precipitation and flooding events. Despite their importance the relevant processes triggering Vb-events and their impact in extreme precipitation are not yet fully understood. The overall goal of this study research is to understand the dynamics of the past events and to provide a reliable climatology, which would provide a first guess for future behaviour of these potentially disastrous situations. A cyclone detection and tracking tool is applied to ERA Interim reanalysis (1979-2013) in order to identify the most prominent Vb-situations. Vb-events are detected and tracked in the geopotential height at 850 hPa. Subsequently, the cyclones are automatically filtered with criteria based on the origin and end of the track, which allows us discarding those paths that should not be considered as Vb-events. Precipitation in the ERA Interim and E-OBS database is used to evaluate the precipitation amounts corresponding to each case and to assess the consistency between datasets. ERA Interim and E-OBS data consistently indicate that there is great variability in precipitation amounts within different Vb-events. While it is expected that Vb-events are associated with extreme precipitation, this is only true for about one quarter of all cases. Nevertheless around 15% of extreme precipitation days (99 percentile) over the Alpine region are triggered by Vb-events. In order to obtain a better understanding of the large variability in Vb-events, the ten heaviest and lowest

  3. Valence and diffuse-bound anions of noble-gas complexes with uracil

    NASA Astrophysics Data System (ADS)

    Streit, Lívia; Dolgounitcheva, O.; Zakrzewski, V. G.; Ortiz, J. V.

    2012-11-01

    Valence-bound (VB) and diffuse-bound (DB) anions of noble-gas (Ar, Kr, and Xe) complexes with uracil have been studied with ab initio methods. MP2 optimizations revealed minima corresponding to anions of both kinds in each case. Coupled-cluster singles and doubles with perturbative triples, CCSD(T), and electron propagator single-point calculations were performed in order to assess vertical and adiabatic electron detachment energies of these complexes. Ab initio electron propagator calculations employed the outer valence Green's function and partial third-order approximations, and the algebraic diagrammatic construction in third order. Basis set effects have been systematically examined. DB anions of all three complexes were adiabatically bound, with calculated adiabatic electron attachment energies below 0.06 eV. Corresponding vertical electron detachment energies were below 0.1 eV. As to VB anions, only the Xe complex had a positive adiabatic electron detachment energy, of 0.01 eV, with a corresponding vertical electron detachment energy of 0.6 eV. These computational findings are consistent with the interpretation of results previously obtained experimentally by Hendricks et al.

  4. Reversible conversion of valence-tautomeric copper metal-organic frameworks dependent single-crystal-to-single-crystal oxidation/reduction: a redox-switchable catalyst for C-H bonds activation reaction.

    PubMed

    Huang, Chao; Wu, Jie; Song, Chuanjun; Ding, Ran; Qiao, Yan; Hou, Hongwei; Chang, Junbiao; Fan, Yaoting

    2015-06-28

    Upon single-crystal-to-single-crystal (SCSC) oxidation/reduction, reversible structural transformations take place between the anionic porous zeolite-like Cu(I) framework and a topologically equivalent neutral Cu(I)Cu(II) mixed-valent framework. The unique conversion behavior of the Cu(I) framework endowed it as a redox-switchable catalyst for the direct arylation of heterocycle C-H bonds. PMID:25994106

  5. 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

  6. Cloning and DNA sequence analysis of an aac(3)-Vb gene from Serratia marcescens.

    PubMed Central

    Rather, P N; Mierzwa, R; Hare, R S; Miller, G H; Shaw, K J

    1992-01-01

    The AAC(3)-V resistance mechanism is characterized by high-level resistance to the aminoglycosides gentamicin, netilmicin, 2'-N-ethylnetilmicin, and 6'-N-ethylnetilmicin and moderate resistance levels to tobramycin. Serratia marcescens 82041944 contains an AA(3)-V resistance mechanism as determined from aminoglycoside resistance profiles. This strain, however, does not exhibit hybridization with a probe derived from the previously cloned aac(3)-Va gene, (R. Allmansberger, B. Bräu, and W. Piepersberg, Mol. Gen. Genet. 198:514-520, 1985). High-pressure liquid chromatography analysis of the acetylation products of sisomicin carried out by extracts of S. marcescens 82041944 have demonstrated the presence of an AAC(3) enzyme. We have cloned the gene encoding this acetyltransferase and have designated it aac(3)-Vb. Nucleotide sequence comparisons show that the aac(3)-Va and aac(3)-Vb genes are 72% identical. The predicted AAC(3)-Vb protein is 28,782 Da. Comparisons of the deduced amino acid sequences show 75% identity and 84% similarity between the AAC(3)-Va and AAC(3)-Vb proteins. The use of a DNA fragment internal to the aac(3)-Vb as a hybridization probe demonstrated that the aac(3)-Vb gene is very rare in clinical isolates possessing an AAC(3)-V mechanism. PMID:1444303

  7. Removal of Vanadium from Molten Aluminum-Part I. Analysis of VB2 Formation

    NASA Astrophysics Data System (ADS)

    Khaliq, Abdul; Rhamdhani, Muhammad Akbar; Brooks, Geoffrey A.; Grandfield, John F.

    2014-04-01

    Aluminum has been used as an alternative to copper for electrical conductor applications. However, the presence of certain impurities in aluminum, such as V, Ti, Zr, Cr, and Fe, has detrimental effect on its electrical conductivity. These impurities can be removed by the addition of an Al-B master alloy containing AlB2 or AlB12 phase, known as boron treatment. The detailed mechanism of borides formation, however, is not well understood. In the current study, a systematic investigation of vanadium diborides (VB2) formation in the Al-V-B alloys was carried out. The study comprised thermodynamic assessment and experimental investigation on the Al-V-B system under typical industrial processing conditions. It was predicted from thermodynamic analysis that VB2 are stable borides of V and do not dissolve readily in the temperatures ranging from 948 K to 1173 K (675 °C to 900 °C). The experimental investigation showed that the mechanism of VB2 formation and V removal in an Al-V-B system is complex as it involves a number of steps such as chemical reaction, mass transfers in bulk liquid and inside the VB2 ring, and diffusions of B and V through the VB2 layer. Comparative analysis of thermodynamic and experimental results showed that the aluminum alloys were far from equilibrium and that the overall process was limited by the kinetics of B diffusion through the VB2 ring.

  8. Mixed Valence Niobium

    NASA Astrophysics Data System (ADS)

    Keating, Steven James

    1992-01-01

    The structural, crystal-chemical, and electrical properties of perovskites are reviewed, with respect to metallic phases similar to tungsten bronze. Phase diagrams are presented for the SrO-NbO-NbO_{2.5 } and SrNbO_3-KNbO _3-rm Sr_{0.5}NbO _3 ternaries, and for the SrNbO_3 -rm Sr_{0.5}NbO_3 binary. The influence of oxygen partial pressure, temperature, melting, and solid solutions affecting the perovskite phase rm Sr_{x}NbO _3 (0.75 <= x < 1.0) are detailed. The phase rm Sr_5Nb_4O_{15-y} (0.0 <= y <= 1.04) is discussed and XRD data are presented. The effects of A-cation substitutions in the rm A_{x}NbO_3 (A = K^+, Ba^{2+ }, Sr^{2+}, La^{3+}, Gd^ {3+}, Y^{3+} ) perovskite have been investigated. Large ions such as K^+ and Ba^ {2+} cause x to approach unity, whereas smaller ions such as Sr^{2+} and La^{3+} increase the ability of the A-site to accommodate vacancies (i.e. x < 1). Ba^{2+} results in an increase in the lattice parameter of the perovskite, whereas K^+ (which requires oxidation of Nb^{4+} to Nb^{5+}) results in a lattice parameter decrease, even though it has an ionic radius similar to Ba^{2+} . A unique relationship between unit cell volume and valence is established, suggesting that the oxidation state of the NbO_6 network dictates the lattice parameters and stability of the perovskite. The resistivity variation for rm Sr_{x}NbO_3, (Ba,Sr)NbO _3, (K,Sr)NbO_3, and (rm K_{0.5}Sr_ {0.5})NbO_3 indicates metallic behavior between 298K and 77K. Resistivity increased as the Nb was oxidized from Nb^{4+} to Nb^{5+}, but metallic properties persisted to at least Nb^ {5+}/(Nb^{5+} + Nb^{4+}) = 0.5. The influence of the exchanges Sr^{2+} = Ba^{2+} and V_{rm A} + Sr ^{2+} = 2K^+ on the electrical resistivity of the perovskite suggests ordering or band structure effects which are orders of magnitude stronger than those observed in metal alloys. Magnetic susceptibility measurements indicate Pauli-paramagnetism. At low temperature (<15K), the paramagnetic

  9. 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…

  10. 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 ΔE{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 ΔE{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, ΔE{sub B,CL} − ΔE{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 ΔE{sub V}{sup CNL} = 2.65 ± 0.3 eV agrees well with the experimental ΔE{sub V}.

  11. Evaluation of valence band top and electron affinity of SiO2 and Si-based semiconductors using X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Fujimura, Nobuyuki; Ohta, Akio; Makihara, Katsunori; Miyazaki, Seiichi

    2016-08-01

    An evaluation method for the energy level of the valence band (VB) top from the vacuum level (VL) for metals, dielectrics, and semiconductors from the results of X-ray photoelectron spectroscopy (XPS) is presented for the accurate determination of the energy band diagram for materials of interest. In this method, the VB top can be determined by the energy difference between the onset of VB signals and the cut-off energy for secondary photoelectrons by considering the X-ray excitation energy (hν). The energy level of the VB top for three kinds of Si-based materials (H-terminated Si, wet-cleaned 4H-SiC, and thermally grown SiO2) has been investigated by XPS under monochromatized Al Kα radiation (hν = 1486.6 eV). We have also demonstrated the determination of the electron affinity for the samples by this measurement technique in combination with the measured and reported energy bandgaps (E g).

  12. Valence quark spin distribution functions

    SciTech Connect

    Nathan Isgur

    1998-09-01

    The hyperfine interactions of the constituent quark model provide a natural explanation for many nucleon properties, including the {Delta} - N splitting, the charge radius of the neutron, and the observation that the proton's quark distribution function ratio d(x)/u(x) {r_arrow} 0 as x {r_arrow} 1. The hyperfine-perturbed quark model also makes predictions for the nucleon spin-dependent distribution functions. Precision measurements of the resulting asymmetries A{sub 1}{sup p}(x) and A{sub 1}{sup n}(x) in the valence region can test this model and thereby the hypothesis that the valence quark spin distributions are ''normal''.

  13. 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

  14. Sensitivity Experiments on the Impact of Vb-Cyclones to Ocean Temperature and Soil Moisture Changes

    NASA Astrophysics Data System (ADS)

    Messmer, Martina; José Gómez-Navarro, Juan; Raible, Christoph C.

    2016-04-01

    Cyclones developing over the western Mediterranean and move northeastward are a major source of extreme weather and responsible for heavy precipitation over Central Europe. Gaining insight into these processes is crucial to improve the projection of changes in frequency and severity of these so-called Vb-cyclones under future climate change scenarios. This study explores the impact of climate change on Vb-events through a number of idealized sensitivity experiments that assess the role of the sea surface temperature (SST) and soil moisture and their contribution to the moisture content in the atmosphere in recent Vb-events. To achieve this task, we use the Weather Research and Forecasting model (WRF) to dynamically downscale the ERA Interim reanalysis, simulating five prominent Vb-events that led to extreme precipitation in Central Europe. WRF allows simulating a physical consistent response of Vb-cyclones to different SSTs and soil water volumes. The changes in SSTs are designed to follow the expected temperature changes in a future climate scenario. Additionally the corresponding uncertainty in such projections is considered. Results indicate that although an increase of the Mediterranean SSTs leads to increased precipitation over Central Europe, e.g. 136% greater precipitation in the +5 K experiment compared to the control simulation, a change in the high-impact region of Vb-events at the northern side of the Alps is not found. This counter-intuitive behavior seems to be related to the increase of atmospheric instability over the artificially heated SSTs. Thereby, precipitation notably increases over the east Adriatic coast in response to warmer SSTs, which corresponds to the first location where the air is lifted. However, Vb-events become less destructive in their high-impact region, due to high loss of atmospheric water. Further experiments demonstrate that changing the SSTs of the Atlantic invokes almost no reaction (around 1% change) with respect to

  15. Characterization of Vc-Vb Particles Reinforced Fe-Based Composite Coatings Produced by Laser Cladding

    NASA Astrophysics Data System (ADS)

    Qu, K. L.; Wang, X. H.; Wang, Z. K.

    2016-03-01

    In situ synthesized VC-VB particles reinforced Fe-based composite coatings were produced by laser beam melting mixture of ferrovanadium (Fe-V) alloy, boron carbide (B4C), CaF2 and Fe-based self-melting powders. The results showed that VB particles with black regular and irregular blocky shape and VC with black flower-like shape were uniformly distributed in the coatings. The type, amount, and size of the reinforcements were influenced by the content of FeV40 and B4C powders. Compared to the substrate, the hardness and wear resistance of the composite coatings were greatly improved.

  16. 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.

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

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Seals and stoppings (III, V-A, and V-B mines... NONMETAL MINES Safety Standards for Methane in Metal and Nonmetal Mines Ventilation § 57.22218 Seals and stoppings (III, V-A, and V-B mines). (a) All seals, and those stoppings that separate main intake from...

  18. 30 CFR 57.22218 - Seals and stoppings (III, 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 Seals and stoppings (III, V-A, and V-B mines... NONMETAL MINES Safety Standards for Methane in Metal and Nonmetal Mines Ventilation § 57.22218 Seals and stoppings (III, V-A, and V-B mines). (a) All seals, and those stoppings that separate main intake from...

  19. 30 CFR 57.22218 - Seals and stoppings (III, V-A, and V-B mines).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Seals and stoppings (III, V-A, and V-B mines... NONMETAL MINES Safety Standards for Methane in Metal and Nonmetal Mines Ventilation § 57.22218 Seals and stoppings (III, V-A, and V-B mines). (a) All seals, and those stoppings that separate main intake from...

  20. 30 CFR 57.22218 - Seals and stoppings (III, 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 Seals and stoppings (III, V-A, and V-B mines... NONMETAL MINES Safety Standards for Methane in Metal and Nonmetal Mines Ventilation § 57.22218 Seals and stoppings (III, V-A, and V-B mines). (a) All seals, and those stoppings that separate main intake from...

  1. 30 CFR 57.22218 - Seals and stoppings (III, V-A, and V-B mines).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Seals and stoppings (III, V-A, and V-B mines... NONMETAL MINES Safety Standards for Methane in Metal and Nonmetal Mines Ventilation § 57.22218 Seals and stoppings (III, V-A, and V-B mines). (a) All seals, and those stoppings that separate main intake from...

  2. 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 π 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

  3. Aesthetic valence of visual illusions

    PubMed Central

    Stevanov, Jasmina; Marković, Slobodan; Kitaoka, Akiyoshi

    2012-01-01

    Visual illusions constitute an interesting perceptual phenomenon, but they also have an aesthetic and affective dimension. We hypothesized that the illusive nature itself causes the increased aesthetic and affective valence of illusions compared with their non-illusory counterparts. We created pairs of stimuli. One qualified as a standard visual illusion whereas the other one did not, although they were matched in as many perceptual dimensions as possible. The phenomenal quality of being an illusion had significant effects on “Aesthetic Experience” (fascinating, irresistible, exceptional, etc), “Evaluation” (pleasant, cheerful, clear, bright, etc), “Arousal” (interesting, imaginative, complex, diverse, etc), and “Regularity” (balanced, coherent, clear, realistic, etc). A subsequent multiple regression analysis suggested that Arousal was a better predictor of Aesthetic Experience than Evaluation. The findings of this study demonstrate that illusion is a phenomenal quality of the percept which has measurable aesthetic and affective valence. PMID:23145272

  4. THE VALENCE OF CORPUSCULAR PROTEINS.

    PubMed

    Gorin, M H; Mover, L S

    1942-07-20

    BY THE USE OF TWO EXTREME MODELS: a hydrated sphere and an unhydrated rod the valence (net charge) of corpuscular proteins can be successfully calculated from electric mobility data by the Debye-Hückel theory (modified to include the effect of the ions in the ion atmosphere) in conjunction with the electrophoretic theory of Henry. As pointed out by Abramson, this permits a comparison with values for the valence from titration data. Electrometric titration measurements of serum albumin B (Kekwick) have been determined at several ionic strengths. These results, together with the available data in the literature for serum albumin B, egg albumin, and beta-lactoglobulin have been used to compare values for the valence calculated from measurements of titration, electrophoresis, and membrane potentials. The results indicate that the usual interpretation of titration curves is open to serious question. By extrapolation of the titration data to zero ionic strength and protein concentration, there results an "intrinsic" net charge curve describing the binding of H(+) (OH(-)) ion alone. This curve agrees closely, in each case, with values of the valence calculated from mobility data (which in turn are in close accord with those estimated from membrane potential measurements). The experimental titration curves in the presence of appreciable quantities of ions and protein deviate widely from the ideal curve. It is suggested that, under these conditions, binding of undissociated acid (base) leads to erroneous values for the net charge. This binding would not affect the electrophoretic mobility. Values of the net charge obtained by the two extreme models from electrophoretic data are in agreement within 15 to 20 per cent. The agreement between the cylindrical model and the titration data is somewhat better in each case than with the sphere; i.e., this comparison enables a choice to be made between asymmetry and hydration in the interpretation of results from sedimentation and

  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. 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.

  7. Geometrical requirements for transition-metal-centered aromatic boron wheels: the case of VB10(-).

    PubMed

    Li, Wei-Li; Romanescu, Constantin; Piazza, Zachary A; Wang, Lai-Sheng

    2012-10-21

    A class of transition-metal-centered aromatic boron wheels (D(nh)-M©B(n)(q-)) have been recently produced and characterized according to an electronic design principle. Here we investigate the interplay between electronic and geometric requirements for the molecular wheels using the case of VB(10)(-), which is isoelectronic to the decacoordinated molecular wheels, Ta©B(10)(-) and Nb©B(10)(-). Photoelectron spectra of VB(10)(-) are observed to be broad and complicated with relatively low electron binding energies, in contrast to the simple and high electron binding energies observed for the molecular wheels of its heavier congeners. An unbiased global minimum search found the most stable isomer of VB(10)(-) to be a singlet "boat"-like structure (C(2)), in which the V atom is coordinated to a quasi-planar B(10) unit. A similar triplet C(2v) boat-like isomer is found to be almost degenerate to the C(2) structure, whereas the beautiful molecular wheel structure, D(10h)-V©B(10)(-), is significantly higher in energy on the potential energy surface. Therefore, even though the VB(10)(-) system fulfills the electronic requirement to form a D(10h)-M©B(10)(-) aromatic molecular wheel, the V atom is too small to stabilize the ten-membered boron ring. PMID:22968622

  8. 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

  9. Bearer channel control protocol for the dynamic VB5.2 interface in ATM access networks

    NASA Astrophysics Data System (ADS)

    Fragoulopoulos, Stratos K.; Mavrommatis, K. I.; Venieris, Iakovos S.

    1996-12-01

    In the multi-vendor systems, a customer connected to an Access network (AN) must be capable of selecting a specific Service Node (SN) according to the services the SN provides. The multiplicity of technologically varying AN calls for the definition of a standard reference point between the AN and the SN widely known as the VB interface. Two versions are currently offered. The VB5.1 is simpler to implement but is not as flexible as the VB5.2, which supports switched connections. The VB5.2 functionality is closely coupled to the Broadband Bearer Channel Connection Protocol (B-BCCP). The B-BCCP is used for conveying the necessary information for dynamic resource allocation, traffic policing and routing in the AN as well as for information exchange concerning the status of the AN before a new call is established by the SN. By relying on such a protocol for the exchange of information instead of intercepting and interpreting signalling messages in the AN, the architecture of the AN is simplified because the functionality related to processing is not duplicated. In this paper a prominent B- BCCP candidate is defined, called the Service node Access network Interaction Protocol.

  10. Proteolytic activity of Enterococcus faecalis VB63F for reduction of allergenicity of bovine milk proteins.

    PubMed

    Biscola, V; Tulini, F L; Choiset, Y; Rabesona, H; Ivanova, I; Chobert, J-M; Todorov, S D; Haertlé, T; Franco, B D G M

    2016-07-01

    With the aim of screening proteolytic strains of lactic acid bacteria to evaluate their potential for the reduction of allergenicity of the major bovine milk proteins, we isolated a new proteolytic strain of Enterococcus faecalis (Ent. faecalis VB63F) from raw bovine milk. The proteases produced by this strain had strong activity against caseins (αS1-, αS2-, and β-casein), in both skim milk and sodium caseinate. However, only partial hydrolysis of whey proteins was observed. Proteolysis of Na-caseinate and whey proteins, observed after sodium dodecyl sulfate-PAGE, was confirmed by analysis of peptide profiles by reversed-phase HPLC. Inhibition of proteolysis with EDTA indicated that the proteases produced by Ent. faecalis VB63F belonged to the group of metalloproteases. The optimal conditions for their activity were 42°C and pH 6.5. The majority of assessed virulence genes were absent in Ent. faecalis VB63F. The obtained results suggest that Ent. faecalis VB63F could be efficient in reducing the immunoreactivity of bovine milk proteins. PMID:27179865

  11. Bonding study of TiC and TiN. I. High-precision x-ray-diffraction determination of the valence-electron density distribution, Debye-Waller temperature factors, and atomic static displacements in TiC0.94 and TiN0.99

    NASA Astrophysics Data System (ADS)

    Dunand, A.; Flack, H. D.; Yvon, K.

    1985-02-01

    Single-crystal, high-precision, high-resolution x-ray-diffraction measurements of the substoichiometric refractory compounds TiC and TiN have been performed with AgKα radiation. Severe anisotropic general extinction affects the intense low-order reflections. Inhomogeneity in the mosaic spread and domain size produces small but significant differences between reflection and antireflection for the same plane of diffraction. These effects have been modeled and refined together with a scale factor, isotropic thermal parameters, a population parameter of the nonmetal site, the amplitude of metal-atom static displacements around nonmetal vacancies, and an atomic model which includes occupancy factors of the separate orbital contributions of the valence electrons combined with κ expansion-contraction parameters. At convergence, the ``agreement indices'' (or ``reliability factors'') were R=0.0025 for TiC0.94 and R=0.0023 for TiN0.99. The refined population parameters indicate a chemical composition of TiC0.939(9) and TiN0.99(2). The mean-square amplitudes of thermal vibrations, Ti=0.002 38(2) AṦ, C=0.003 35(8) AṦ, Ti=0.002 94(1) AṦ, and N=0.003 08(12) AṦ are consistent with the respective atomic masses. 36% of the metal atoms in TiC0.94 are involved in a relaxation around the nonmetal vacancies, being displaced from their sublattice sites by 0.097(2) Å along [100]. No evidence for static displacements was found in TiN0.99. The valence-electron density distribution can be described satisfactorily in terms of deformed atoms. No buildup of charge density occurs between atomic sites. Our analysis, similar to a Mulliken partitioning, shows first that ionicity is important, with a charge transfer from the metal to the nonmetal of [2.1(4)]e in the carbide and [1.9(4)]e in the nitride, and secondly that the charge asphericity around the metal atoms is larger in the former than in the latter, while no departure from spherical symmetry is

  12. Superconductivity in the liquid-dimer valence-bond state

    SciTech Connect

    Ioffe, L.B.; Larkin, A.I. )

    1989-10-01

    Introducing an unambiguous prescription which converts singlet dimers into quasidipoles, we describe the low-energy excitations in the liquid-dimer state as fluctuations of the average dipole moment. The exchange of these fluctuations leads to a long-range interaction between holes in this state. This interaction favors the two-particle Bose condensate and destroys the order parameter of the one-particle Bose condensate even at zero temperature.

  13. ChsVb, a class VII chitin synthase involved in septation, is critical for pathogenicity in Fusarium oxysporum.

    PubMed

    Martín-Urdíroz, Magdalena; Roncero, M Isabel G; González-Reyes, José Antonio; Ruiz-Roldán, Carmen

    2008-01-01

    A new myosin motor-like chitin synthase gene, chsVb, has been identified in the vascular wilt fungus Fusarium oxysporum f. sp. lycopersici. Phylogenetic analysis of the deduced amino acid sequence of the chsVb chitin synthase 2 domain (CS2) revealed that ChsVb belongs to class VII chitin synthases. The ChsVb myosin motor-like domain (MMD) is shorter than the MMD of class V chitin synthases and does not contain typical ATP-binding motifs. Targeted disrupted single (DeltachsVb) and double (DeltachsV DeltachsVb) mutants were unable to infect and colonize tomato plants or grow invasively on tomato fruit tissue. These strains were hypersensitive to compounds that interfere with fungal cell wall assembly, produced lemon-like shaped conidia, and showed swollen balloon-like structures in hyphal subapical regions, thickened walls, aberrant septa, and intrahyphal hyphae. Our results suggest that the chsVb gene is likely to function in polarized growth and confirm the critical importance of cell wall integrity in the complex infection process of this fungus. PMID:17993572

  14. 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…

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

    NASA Astrophysics Data System (ADS)

    Bredtmann, Timm; Ivanov, Misha; Dixit, Gopal

    2014-11-01

    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.

  16. 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.

  17. 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

  18. Rab11a and myosin Vb regulate recycling of the M4 muscarinic acetylcholine receptor.

    PubMed

    Volpicelli, Laura A; Lah, James J; Fang, Guofu; Goldenring, James R; Levey, Allan I

    2002-11-15

    Agonist-induced internalization followed by subsequent return to the cell surface regulates G-protein-coupled receptor (GPCR) activity. Because the cellular responsiveness to ligand depends on the balance between receptor degradation and recycling, it is crucial to identify the molecules involved in GPCR recovery to the cell surface. In this study, we identify mechanisms involved in the recycling of the M4 subtype of muscarinic acetylcholine receptor. M4 is highly expressed in the CNS, plays a role in locomotor activity, and is a novel therapeutic target for neurologic and psychiatric disorders. Previous studies show that, after cholinergic stimulation, M4 internalizes from the cell surface to endosomes in cell culture and the rat brain. Here, we show that, after activation, M4 traffics to transferrin receptor- and Rab11a-positive perinuclear endosomes. Expression of the constitutively GDP-bound, inactive mutant Rab11aS25N inhibits M4 trafficking to recycling endosomes. Expression of the C-terminal tail of myosin Vb, a Rab11a effector, enhances M4 accumulation in perinuclear endosomes. Both Rab11aS25N and the myosin Vb tail impair M4 recycling. The results demonstrate that GPCR recycling is mediated through a discrete pathway using both Rab11a and myosin Vb. PMID:12427833

  19. 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.

  20. Cluster ion distributions and correlation with fragment valence in laser-induced mass spectra of oxides

    SciTech Connect

    Michiels, E.; Bijbels, R.

    1984-06-01

    Laser microprobe mass analysis (LAMMA) spectra are described for binary oxides belonging to different groups in the periodic table. The positive and negative cluster ion distributions show a strong correlation with the valence electron configuration of the metal in the oxide. The bond dissociation energy of the MO/sup +/ ion also affects the intensity distributions. 20 references, 10 figures.

  1. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

    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

  3. 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}Σ{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.

  4. 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

  5. The Chemical Bond in C2.

    PubMed

    Hermann, Markus; Frenking, Gernot

    2016-03-14

    Quantum chemical calculations using the complete active space of the valence orbitals have been carried out for Hn CCHn (n=0-3) and N2 . The quadratic force constants and the stretching potentials of Hn CCHn have been calculated at the CASSCF/cc-pVTZ level. The bond dissociation energies of the C-C bonds of C2 and HC≡CH were computed using explicitly correlated CASPT2-F12/cc-pVTZ-F12 wave functions. The bond dissociation energies and the force constants suggest that C2 has a weaker C-C bond than acetylene. The analysis of the CASSCF wavefunctions in conjunction with the effective bond orders of the multiple bonds shows that there are four bonding components in C2 , while there are only three in acetylene and in N2 . The bonding components in C2 consist of two weakly bonding σ bonds and two electron-sharing π bonds. The bonding situation in C2 can be described with the σ bonds in Be2 that are enforced by two π bonds. There is no single Lewis structure that adequately depicts the bonding situation in C2 . The assignment of quadruple bonding in C2 is misleading, because the bond is weaker than the triple bond in HC≡CH. PMID:26756311

  6. 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

  7. 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

  8. 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.

  9. 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)

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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

  15. 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

  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. 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 (ϕc) of trans-cis photoisomerization of P2VB were calculated in different organic solvents. The photoreactivity of P2VB are also studied PMMA matrix.

  18. 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

  19. The valence-fluctuating ground state of plutonium

    SciTech Connect

    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.

    2015-07-10

    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. In addition, 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.

  20. 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.

  1. A Valence Tautomeric Dinuclear Copper Tetrakisguanidine Complex.

    PubMed

    Wiesner, Sven; Wagner, Arne; Kaifer, Elisabeth; Himmel, Hans-Jörg

    2016-07-18

    We report on the first valence tautomeric dinuclear copper complex, featuring 2,3,5,6-tetrakis(tetramethylguanidino)pyridine as a bridging redox-active GFA (guanidino-functionalized aromatic) ligand. The preferred electronic structure of the complex is massively influenced by the environment. In the solid state and in nonpolar solvents a paramagnetic, dinuclear Cu(II) complex with a neutral GFA ligand is present. In polar solvents, the electronic structure changes to a diamagnetic, dinuclear Cu(I) complex with a twofold-oxidized GFA ligand. Using acetone as a solvent, both electronic structures are accessible due to a temperature-dependent equilibrium between the two valence tautomeric complexes. Our results pave the way for a broader use of valence tautomeric transition-metal complexes in catalytic reactions since anionic coligands can now be tolerated owing to the neutral/positively charged GFA ligand. PMID:27310335

  2. 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.

  3. Painlevé analysis, nonlocal symmetry and explicit interaction solutions for supersymmetric mKdVB equation

    NASA Astrophysics Data System (ADS)

    Ren, Bo

    2016-08-01

    The N = 1 supersymmetric mKdVB system is transformed to a coupled bosonic system by using the bosonization approach. By a singularity structure analysis, the bosonized supersymmetric mKdVB (BSmKdVB) equation admits the Painlevé property. Starting from the standard truncated Painlevé method, the nonlocal symmetry for the BSmKdVB equation is obtained. To solve the first Lie's principle related with the nonlocal symmetry, the nonlocal symmetry is localized to the Lie point symmetry by introducing multiple new fields. Thanks to localization processes, similarity reductions for the prolonged systems are studied by the Lie point symmetry method. The interaction solutions among solitons and other complicated waves including Painlevé II waves and periodic cnoidal waves are given through the reduction theorems. The soliton-cnoidal wave interaction solutions are explicitly given by using the mapping and deformation method. The concrete soliton-cnoidal interaction solutions are displayed both in analytical and graphical ways.

  4. 30 CFR 57.22314 - Flow-control devices (V-A and V-B mines).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Flow-control devices (V-A and V-B mines). 57.22314 Section 57.22314 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... MINES Safety Standards for Methane in Metal and Nonmetal Mines Equipment § 57.22314 Flow-control...

  5. 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…

  6. Mixed Valence and Spin Fluctuations in Cerium

    NASA Astrophysics Data System (ADS)

    Andraka, Bohdan

    The pseudobinary alloys Ce(Ni(,x)Co(,1-x))(,2), (Ce(,x)La(,1-x))Ni(,2) and (Ce(,x)Y(,1-x))Ni(,2), where 0 < x < 1, have been studied. The room temperature lattice constant, the magnetic susceptibility in the 6 to 300 K temperature range, the low temperature specific heat in the 0.4 to 25 K range and the electrical resistivity in the 0.4 to 300 K range were measured. Additionally, X -ray absorption around L(,3) edge has been studied using the synchroton radiation. Both, thermodynamic and L(,3) probes yield similar results for the changes of valence of Ce across these systems. We have established that Ce is in the saturated valence state in the Ce(Ni(,x)Co(,1 -x))(,2) for x < 0.25. The valence decreases with x in the 0.25 to 1 concentration range. Similarly, the valence of Ce decreases in the (Ce, Y)Ni(,2) systems upon substitution of Y for Ce. The results obtained for the (Ce(,x)La(,1 -x))Ni(,2) system are interpreted in terms of changes of the Ce('3+) impurity levels. Spin fluctuations due to the 3d electrons play an important role in these systems.

  7. 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

  8. Measurement of valence-band offset at native oxide/BaSi2 interfaces by hard x-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Takabe, Ryota; Du, Weijie; Ito, Keita; Takeuchi, Hiroki; Toko, Kaoru; Ueda, Shigenori; Kimura, Akio; Suemasu, Takashi

    2016-01-01

    Undoped n-type BaSi2 films were grown on Si(111) by molecular beam epitaxy, and the valence band (VB) offset at the interface between the BaSi2 and its native oxide was measured by hard x-ray photoelectron spectroscopy (HAXPES) at room temperature. HAXPES enabled us to investigate the electronic states of the buried BaSi2 layer non-destructively thanks to its large analysis depth. We performed the depth-analysis by varying the take-off angle (TOA) of photoelectrons as 15°, 30°, and 90° with respect to the sample surface and succeeded to obtain the VB spectra of the BaSi2 and the native oxide separately. The VB maximum was located at -1.0 eV from the Fermi energy for the BaSi2 and -4.9 eV for the native oxide. We found that the band bending did not occur near the native oxide/BaSi2 interface. This result was clarified by the fact that the core-level emission peaks did not shift regardless of TOA (i.e., analysis depth). Thus, the barrier height of the native oxide for the minority-carriers in the undoped n-BaSi2 (holes) was determined to be 3.9 eV. No band bending in the BaSi2 close to the interface also suggests that the large minority-carrier lifetime in undoped n-BaSi2 films capped with native oxide is attributed not to the band bending in the BaSi2, which pushes away photogenerated minority carriers from the defective surface region, but to the decrease of defective states by the native oxide.

  9. 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…

  10. A corpuscular picture of electrons in chemical bond.

    PubMed

    Ando, Koji

    2016-03-28

    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. Its accuracy for describing potential energy curves of chemical bonds in ground and excited states of spin singlet and triplet is examined. PMID:27036429

  11. A corpuscular picture of electrons in chemical bond

    NASA Astrophysics Data System (ADS)

    Ando, Koji

    2016-03-01

    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. Its accuracy for describing potential energy curves of chemical bonds in ground and excited states of spin singlet and triplet is examined.

  12. 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(<ρ(rc)>/r)-0.19, connecting the average experimental bond lengths, , with the average accumulation of the electron density at the bond critical point, <ρ(rc)>, 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(ρ(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 ρ(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, σ, power law expression σ = [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, <ρ(rc)> = 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

  13. Gaining control over rare earth valence fluctuations

    SciTech Connect

    Wohlleben, D.

    1987-05-31

    This paper briefly deals with the problem of narrow band materials. It addresses a new theoretical approach to the fluctuation of valence electrons in rare earth elements. It is believed that the phenomena of interest arize from an instability of the partially filled d or f shell of certain atoms when they are put into a metallic host. The theoretical models which dominate the scene work with two local d or f states on one hand and a structureless sea of free conduction electrons on the other. This procedure ignores at least half of the essential physics; the other held is kept alive in the term valence fluctuation. Basically, what the prevalent models ignore is that, in all these systems, the entire atoms as the source of the anomalies are being dealt with, not just their f shells. In other words, there is important structure in the sea of conduction electrons.

  14. 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) ν, with ν ≃ 1.6, as x approaches one.

  15. Influence of VB group doped TiO2 on photovoltaic performance of dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Liu, Jia; Duan, Yandong; Zhou, Xiaowen; Lin, Yuan

    2013-07-01

    Dye-sensitized solar cell with VB group (vanadium (V), niobium (Nb) and tantalum (Ta)) doped TiO2 prepared by hydrothermal method shows a higher photovoltaic efficiency compared with the undoped TiO2. All the VB doping shift the flat band potential positively and increase the doping density which is investigated by Mott-Schottky plot. The positive shift of flat band potential improves the driving force of injecting electron from the LUMO of dye to the conduction band of TiO2 and the photocurrent. On the other hand, the increase of doping density accelerates transfer rate of electrons in TiO2 than the un-doped, which is confirmed by intensity-modulated photocurrent. V-, Nb-, Ta-doped TiO2 exhibited photovoltaic performance with 7.80%, 8.33%, 8.18%, respectively, compared with that of the cells based on pure TiO2 (7.42%).

  16. 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.

  17. Pattern classification of valence in depression.

    PubMed

    Habes, I; Krall, S C; Johnston, S J; Yuen, K S L; Healy, D; Goebel, R; Sorger, B; Linden, D E J

    2013-01-01

    Neuroimaging biomarkers of depression have potential to aid diagnosis, identify individuals at risk and predict treatment response or course of illness. Nevertheless none have been identified so far, potentially because no single brain parameter captures the complexity of the pathophysiology of depression. Multi-voxel pattern analysis (MVPA) may overcome this issue as it can identify patterns of voxels that are spatially distributed across the brain. Here we present the results of an MVPA to investigate the neuronal patterns underlying passive viewing of positive, negative and neutral pictures in depressed patients. A linear support vector machine (SVM) was trained to discriminate different valence conditions based on the functional magnetic resonance imaging (fMRI) data of nine unipolar depressed patients. A similar dataset obtained in nine healthy individuals was included to conduct a group classification analysis via linear discriminant analysis (LDA). Accuracy scores of 86% or higher were obtained for each valence contrast via patterns that included limbic areas such as the amygdala and frontal areas such as the ventrolateral prefrontal cortex. The LDA identified two areas (the dorsomedial prefrontal cortex and caudate nucleus) that allowed group classification with 72.2% accuracy. Our preliminary findings suggest that MVPA can identify stable valence patterns, with more sensitivity than univariate analysis, in depressed participants and that it may be possible to discriminate between healthy and depressed individuals based on differences in the brain's response to emotional cues. PMID:24179819

  18. Pattern classification of valence in depression☆

    PubMed Central

    Habes, I.; Krall, S.C.; Johnston, S.J.; Yuen, K.S.L.; Healy, D.; Goebel, R.; Sorger, B.; Linden, D.E.J.

    2013-01-01

    Neuroimaging biomarkers of depression have potential to aid diagnosis, identify individuals at risk and predict treatment response or course of illness. Nevertheless none have been identified so far, potentially because no single brain parameter captures the complexity of the pathophysiology of depression. Multi-voxel pattern analysis (MVPA) may overcome this issue as it can identify patterns of voxels that are spatially distributed across the brain. Here we present the results of an MVPA to investigate the neuronal patterns underlying passive viewing of positive, negative and neutral pictures in depressed patients. A linear support vector machine (SVM) was trained to discriminate different valence conditions based on the functional magnetic resonance imaging (fMRI) data of nine unipolar depressed patients. A similar dataset obtained in nine healthy individuals was included to conduct a group classification analysis via linear discriminant analysis (LDA). Accuracy scores of 86% or higher were obtained for each valence contrast via patterns that included limbic areas such as the amygdala and frontal areas such as the ventrolateral prefrontal cortex. The LDA identified two areas (the dorsomedial prefrontal cortex and caudate nucleus) that allowed group classification with 72.2% accuracy. Our preliminary findings suggest that MVPA can identify stable valence patterns, with more sensitivity than univariate analysis, in depressed participants and that it may be possible to discriminate between healthy and depressed individuals based on differences in the brain's response to emotional cues. PMID:24179819

  19. Human Amygdala Represents the Complete Spectrum of Subjective Valence

    PubMed Central

    Jin, Jingwen; Zelano, Christina; Gottfried, Jay A.

    2015-01-01

    Although the amygdala is a major locus for hedonic processing, how it encodes valence information is poorly understood. Given the hedonic potency of odor stimuli and the amygdala's anatomical proximity to the peripheral olfactory system, we combined high-resolution fMRI with pattern-based multivariate techniques to examine how valence information is encoded in the amygdala. Ten human subjects underwent fMRI scanning while smelling 9 odorants that systematically varied in perceived valence. Representational similarity analyses showed that amygdala codes the entire dimension of valence, ranging from pleasantness to unpleasantness. This unidimensional representation significantly correlated with self-reported valence ratings but not with intensity ratings. Furthermore, within-trial valence representations evolved over time, prioritizing earlier differentiation of unpleasant stimuli. Together, these findings underscore the idea that both spatial and temporal features uniquely encode pleasant and unpleasant odor valence in the amygdala. The availability of a unidimensional valence code in the amygdala, distributed in both space and time, would create greater flexibility in determining the pleasantness or unpleasantness of stimuli, providing a mechanism by which expectation, context, attention, and learning could influence affective boundaries for guiding behavior. SIGNIFICANCE STATEMENT Our findings elucidate the mechanisms of affective processing in the amygdala by demonstrating that this brain region represents the entire valence dimension from pleasant to unpleasant. An important implication of this unidimensional valence code is that pleasant and unpleasant valence cannot coexist in the amygdale because overlap of fMRI ensemble patterns for these two valence extremes obscures their unique content. This functional architecture, whereby subjective valence maps onto a pattern continuum between pleasant and unpleasant poles, offers a robust mechanism by which context

  20. Draft Genome Sequence of Colistin-Resistant Acinetobacter baumannii Strain VB22595 Isolated from a Central Line-Associated Bloodstream Infection.

    PubMed

    Veeraraghavan, Balaji; Anandan, Shalini; Ragupathi, Naveen Kumar Devanga; Vijayakumar, Saranya; Sethuvel, Dhiviya Prabaa Muthuirulandi; Biswas, Indranil

    2016-01-01

    Acinetobacter baumannii is an important emerging pathogen that causes health care-associated infections. In this study, we determined the genome of a multidrug-resistant clinical strain, VB22595, isolated from a hospital in Southern India. The draft genome indicates that strain VB22595 encodes a genome of ~3.92 Mb in size and does not contain plasmid derived MCR-1 for colistin resistance. PMID:27516521

  1. 30 CFR 57.22231 - Actions at 0.25 percent methane (I-B, II-B, V-B, and VI mines).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Actions at 0.25 percent methane (I-B, II-B, V-B, and VI mines). 57.22231 Section 57.22231 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION... Actions at 0.25 percent methane (I-B, II-B, V-B, and VI mines). If methane reaches 0.25 percent in...

  2. 30 CFR 57.22238 - Actions at 2.0 percent methane (I-B, II-B, V-B, and VI mines).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Actions at 2.0 percent methane (I-B, II-B, V-B, and VI mines). 57.22238 Section 57.22238 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION... Actions at 2.0 percent methane (I-B, II-B, V-B, and VI mines). If methane reaches 2.0 percent in the...

  3. 30 CFR 57.22238 - Actions at 2.0 percent methane (I-B, II-B, V-B, and VI mines).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Actions at 2.0 percent methane (I-B, II-B, V-B, and VI mines). 57.22238 Section 57.22238 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION... Actions at 2.0 percent methane (I-B, II-B, V-B, and VI mines). If methane reaches 2.0 percent in the...

  4. 30 CFR 57.22238 - Actions at 2.0 percent methane (I-B, II-B, V-B, and VI mines).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Actions at 2.0 percent methane (I-B, II-B, V-B, and VI mines). 57.22238 Section 57.22238 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION... Actions at 2.0 percent methane (I-B, II-B, V-B, and VI mines). If methane reaches 2.0 percent in the...

  5. 30 CFR 57.22231 - Actions at 0.25 percent methane (I-B, II-B, V-B, and VI mines).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Actions at 0.25 percent methane (I-B, II-B, V-B, and VI mines). 57.22231 Section 57.22231 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION... Actions at 0.25 percent methane (I-B, II-B, V-B, and VI mines). If methane reaches 0.25 percent in...

  6. 30 CFR 57.22231 - Actions at 0.25 percent methane (I-B, II-B, V-B, and VI mines).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Actions at 0.25 percent methane (I-B, II-B, V-B, and VI mines). 57.22231 Section 57.22231 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION... Actions at 0.25 percent methane (I-B, II-B, V-B, and VI mines). If methane reaches 0.25 percent in...

  7. 30 CFR 57.22238 - Actions at 2.0 percent methane (I-B, II-B, V-B, and VI mines).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Actions at 2.0 percent methane (I-B, II-B, V-B, and VI mines). 57.22238 Section 57.22238 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION... Actions at 2.0 percent methane (I-B, II-B, V-B, and VI mines). If methane reaches 2.0 percent in the...

  8. 30 CFR 57.22231 - Actions at 0.25 percent methane (I-B, II-B, V-B, and VI mines).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Actions at 0.25 percent methane (I-B, II-B, V-B, and VI mines). 57.22231 Section 57.22231 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION... Actions at 0.25 percent methane (I-B, II-B, V-B, and VI mines). If methane reaches 0.25 percent in...

  9. 30 CFR 57.22231 - Actions at 0.25 percent methane (I-B, II-B, V-B, and VI mines).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Actions at 0.25 percent methane (I-B, II-B, V-B... AND NONMETAL MINES Safety Standards for Methane in Metal and Nonmetal Mines Ventilation § 57.22231 Actions at 0.25 percent methane (I-B, II-B, V-B, and VI mines). If methane reaches 0.25 percent in...

  10. 30 CFR 57.22238 - Actions at 2.0 percent methane (I-B, II-B, V-B, and VI mines).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Actions at 2.0 percent methane (I-B, II-B, V-B... AND NONMETAL MINES Safety Standards for Methane in Metal and Nonmetal Mines Ventilation § 57.22238 Actions at 2.0 percent methane (I-B, II-B, V-B, and VI mines). If methane reaches 2.0 percent in the...

  11. Draft Genome Sequence of Colistin-Resistant Acinetobacter baumannii Strain VB22595 Isolated from a Central Line-Associated Bloodstream Infection

    PubMed Central

    Veeraraghavan, Balaji; Anandan, Shalini; Ragupathi, Naveen Kumar Devanga; Vijayakumar, Saranya; Sethuvel, Dhiviya Prabaa Muthuirulandi

    2016-01-01

    Acinetobacter baumannii is an important emerging pathogen that causes health care-associated infections. In this study, we determined the genome of a multidrug-resistant clinical strain, VB22595, isolated from a hospital in Southern India. The draft genome indicates that strain VB22595 encodes a genome of ~3.92 Mb in size and does not contain plasmid derived MCR-1 for colistin resistance. PMID:27516521

  12. Development of a GMP Phase III purification process for VB4-845, an immunotoxin expressed in E. coli using high cell density fermentation.

    PubMed

    Premsukh, Arjune; Lavoie, Joelle M; Cizeau, Jeannick; Entwistle, Joycelyn; MacDonald, Glen C

    2011-07-01

    VB4-845 is a recombinant immunotoxin comprised of an anti-epithelial cell adhesion molecule (EpCAM) scFv fused to a truncated form of the bacterial toxin, Pseudomonas exotoxin A. VB4-845, purified from TB fed-batch fermentation, showed clinical efficacy when administered locally to treat non-muscle invasive bladder cancer (NMIBC) and squamous cell carcinomas of the head and neck (SCCHN). Here, we describe the implementation of an Escherichia coli high cell density (HCD) cultivation and purification process for VB4-845. HCD cultivation was a prerequisite for achieving higher yields necessary for Phase III clinical trials and commercialization. Using this process, the VB4-845 titer in the supernatant was increased by 30-fold over the original TB fed-batch cultivation. To obtain clinical grade material, a process involving a five-step column purification procedure was implemented and led to an overall recovery of ∼ 40%. VB4-845 purity of >97% was achieved after the first three columns following the removal of low-molecular weight product-related impurities and aggregates. Endotoxins were effectively separated from VB4-845 on the Q-columns and by washing the Ni-column with a detergent buffer while host cell proteins were removed using ceramic hydroxyapatite. Comparability studies demonstrated that the purified product from the Phase III process was identical to the Phase II reference standard produced using TB fed-batch fermentation. PMID:21421055

  13. A comparative study of dissociation of thymidine molecules following valence or core photoionization

    NASA Astrophysics Data System (ADS)

    Itälä, E.; Huels, M. A.; Rachlew, E.; Kooser, K.; Hägerth, T.; Kukk, E.

    2013-11-01

    We have studied the fragmentation of gas phase thymidine following valence and core ionization using synchrotron radiation, combined with electron energy and ion mass resolved detection in coincidence. To identify certain fragment masses 13C labelled thymidine was also used. We find that in large part, the photofragmentation of thymidine can be described as separated thymine and 2-deoxy-d-ribose cations. However, also the intact thymidine radical cation, formation of intact base and sugar cations from glycosidic bond cleavage and several new thymidine-specific fragments are observed after valence ionization. Conversely, at the photoionization of C 1s electrons neither parent thymidine cations nor any fragments above 55 amu were detected, and only ion pairs with small masses survive core ionization, Auger decay and the subsequent Coulomb separation of the DNA sub-unit. This demonstrates the genotoxic nature of soft x-rays which in cells induce complex clustered damage similar to those yielded by heavy particles.

  14. 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 σ- versus π-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

  15. Energy Correlation among Three Photoelectrons Emitted in Core-Valence-Valence Triple Photoionization of Ne

    SciTech Connect

    Hikosaka, Y.; Soejima, K.; Lablanquie, P.; Penent, F.; Palaudoux, J.; Andric, L.; Shigemasa, E.; Suzuki, I. H.; Nakano, M.; Ito, K.

    2011-09-09

    The direct observation of triple photoionization involving one inner shell and two valence electrons is reported. The energy distribution of the three photoelectrons emitted from Ne is obtained using a very efficient multielectron coincidence method using the magnetic bottle electron spectroscopic technique. A predominance of the direct path to triple photoionization for the formation of Ne{sup 3+} in the 1s2s{sup 2}2p{sup 4} configuration is observed. It is demonstrated that the energy distribution evolves with photon energy and indicates a significant difference with triple photoionization involving only valence electrons.

  16. Energy Correlation among Three Photoelectrons Emitted in Core-Valence-Valence Triple Photoionization of Ne

    NASA Astrophysics Data System (ADS)

    Hikosaka, Y.; Lablanquie, P.; Penent, F.; Palaudoux, J.; Andric, L.; Soejima, K.; Shigemasa, E.; Suzuki, I. H.; Nakano, M.; Ito, K.

    2011-09-01

    The direct observation of triple photoionization involving one inner shell and two valence electrons is reported. The energy distribution of the three photoelectrons emitted from Ne is obtained using a very efficient multielectron coincidence method using the magnetic bottle electron spectroscopic technique. A predominance of the direct path to triple photoionization for the formation of Ne3+ in the 1s2s22p4 configuration is observed. It is demonstrated that the energy distribution evolves with photon energy and indicates a significant difference with triple photoionization involving only valence electrons.

  17. Energy correlation among three photoelectrons emitted in core-valence-valence triple photoionization of Ne.

    PubMed

    Hikosaka, Y; Lablanquie, P; Penent, F; Palaudoux, J; Andric, L; Soejima, K; Shigemasa, E; Suzuki, I H; Nakano, M; Ito, K

    2011-09-01

    The direct observation of triple photoionization involving one inner shell and two valence electrons is reported. The energy distribution of the three photoelectrons emitted from Ne is obtained using a very efficient multielectron coincidence method using the magnetic bottle electron spectroscopic technique. A predominance of the direct path to triple photoionization for the formation of Ne3+ in the 1s 2s2 2p4 configuration is observed. It is demonstrated that the energy distribution evolves with photon energy and indicates a significant difference with triple photoionization involving only valence electrons. PMID:22026663

  18. Institutional Bonding.

    ERIC Educational Resources Information Center

    Allard, M. June

    Institutional bonding was examined at a public, urban commuter college with exceptionally high attrition and visibly low morale. Changes in bonding and attrition were measured 6 years after a 2-year effort to develop school identity and student feelings of membership. It was found that a simple index of campus morale is provided by level of…

  19. 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

  20. 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.

  1. Myosin Vb uncoupling from RAB8A and RAB11A elicits microvillus inclusion disease

    PubMed Central

    Knowles, Byron C.; Roland, Joseph T.; Krishnan, Moorthy; Tyska, Matthew J.; Lapierre, Lynne A.; Dickman, Paul S.; Goldenring, James R.; Shub, Mitchell D.

    2014-01-01

    Microvillus inclusion disease (MVID) is a severe form of congenital diarrhea that arises from inactivating mutations in the gene encoding myosin Vb (MYO5B). We have examined the association of mutations in MYO5B and disruption of microvillar assembly and polarity in enterocytes. Stable MYO5B knockdown (MYO5B-KD) in CaCo2-BBE cells elicited loss of microvilli, alterations in junctional claudins, and disruption of apical and basolateral trafficking; however, no microvillus inclusions were observed in MYO5B-KD cells. Expression of WT MYO5B in MYO5B-KD cells restored microvilli; however, expression of MYO5B-P660L, a MVID-associated mutation found within Navajo populations, did not rescue the MYO5B-KD phenotype but induced formation of microvillus inclusions. Microvilli establishment required interaction between RAB8A and MYO5B, while loss of the interaction between RAB11A and MYO5B induced microvillus inclusions. Using surface biotinylation and dual immunofluorescence staining in MYO5B-KD cells expressing mutant forms of MYO5B, we observed that early microvillus inclusions were positive for the sorting marker SNX18 and derived from apical membrane internalization. In patients with MVID, MYO5B-P660L results in global changes in polarity at the villus tips that could account for deficits in apical absorption, loss of microvilli, aberrant junctions, and losses in transcellular ion transport pathways, likely leading to the MVID clinical phenotype of neonatal secretory diarrhea. PMID:24892806

  2. Cyclic Di-GMP-Regulated Periplasmic Proteolysis of a Pseudomonas aeruginosa Type Vb Secretion System Substrate

    PubMed Central

    Cooley, Richard B.; Smith, T. Jarrod; Leung, Wilfred; Tierney, Valerie; Borlee, Bradley R.; O'Toole, George A.

    2015-01-01

    ABSTRACT We previously identified a second-messenger-regulated signaling system in the environmental bacterium Pseudomonas fluorescens which controls biofilm formation in response to levels of environmental inorganic phosphate. This system contains the transmembrane cyclic di-GMP (c-di-GMP) receptor LapD and the periplasmic protease LapG. LapD regulates LapG and controls the ability of this protease to process a large cell surface adhesin protein, LapA. While LapDG orthologs can be identified in diverse bacteria, predictions of LapG substrates are sparse. Notably, the opportunistic pathogen Pseudomonas aeruginosa harbors LapDG orthologs, but neither the substrate of LapG nor any associated secretion machinery has been identified to date. Here, we identified P. aeruginosa CdrA, a protein known to mediate cell-cell aggregation and biofilm maturation, as a substrate of LapG. We also demonstrated LapDG to be a minimal system sufficient to control CdrA localization in response to changes in the intracellular concentration of c-di-GMP. Our work establishes this biofilm signaling node as a regulator of a type Vb secretion system substrate in a clinically important pathogen. IMPORTANCE Here, the biological relevance of a conserved yet orphan signaling system in the opportunistic pathogen Pseudomonas aeruginosa is revealed. In particular, we identified the adhesin CdrA, the cargo of a two-partner secretion system, as a substrate of a periplasmic protease whose activity is controlled by intracellular c-di-GMP levels and a corresponding transmembrane receptor via an inside-out signaling mechanism. The data indicate a posttranslational control mechanism of CdrA via c-di-GMP, in addition to its established transcriptional regulation via the same second messenger. PMID:26100041

  3. Separability Between Valence and Conduction Bands in Transition Metal Clusters

    SciTech Connect

    Apra, Edoardo; Carter, Emily A.; Fortunelli, Alessandro

    2004-07-30

    Simplified theories of transition metal electronic structure have been postulated for many decades. Here we test one such approximation, namely separate treatments of d (valence) and s/p (conduction) electrons in transition metal clusters, within a density functional formalism. Two different basic approaches are considered: (a) an independent-band approximation, in which the d- and s/p-bands interact only via the ?-dependent components of the Kohn-Sham operator; and (b) a more realistic approximation, in which the lowest-energy d- and s/p-orbitals (separately derived) are allowed to interact through explicit off-diagonal coupling matrix elements. Results are presented for the energy differences among three structural forms (icosahedral, cuboctahedral and truncated decahedral) of 13-atom Ni and Pt clusters. We demonstrate that an explicit decoupling of the d- and s/p-bands does not produce accurate results for the clusters considered here, not even for nickel, i.e., the transition metal for which d-s/p mixing should be at its minimum. By contrast, allowing the lowest energy orbitals of the two separate bands to interact improves the results considerably, and assures a fair description of metal-metal bonding. This suggests simplified models that exclude explicit d-s/p coupling should be employed with caution.

  4. Valence tautomerism in synthetic models of cytochrome P450.

    PubMed

    Das, Pradip Kumar; Samanta, Subhra; McQuarters, Ashley B; Lehnert, Nicolai; Dey, Abhishek

    2016-06-14

    CytP450s have a cysteine-bound heme cofactor that, in its as-isolated resting (oxidized) form, can be conclusively described as a ferric thiolate species. Unlike the native enzyme, most synthetic thiolate-bound ferric porphyrins are unstable in air unless the axial thiolate ligand is sterically protected. Spectroscopic investigations on a series of synthetic mimics of cytP450 indicate that a thiolate-bound ferric porphyrin coexists in organic solutions at room temperature (RT) with a thiyl-radical bound ferrous porphyrin, i.e., its valence tautomer. The ferric thiolate state is favored by greater enthalpy and is air stable. The ferrous thiyl state is favored by entropy, populates at RT, and degrades in air. These ground states can be reversibly interchanged at RT by the addition or removal of water to the apolar medium. It is concluded that hydrogen bonding and local electrostatics protect the resting oxidized cytP450 active site from degradation in air by stabilizing the ferric thiolate ground state in contrast to its synthetic analogs. PMID:27302948

  5. Valence and excited states of LiH-

    NASA Astrophysics Data System (ADS)

    Gutsev, Gennady L.; Nooijen, Marcel; Bartlett, Rodney J.

    1998-03-01

    Valence and excited dipole-bound states of the LiH- anion are calculated with the recently developed electron-attachment equation-of-motion coupled-cluster technique. It is found that the first dipole-bound state of LiH- corresponds to the second dissociation channel LiH--->Li-(1S)+H(2S). The second (excited) dipole-bound state of LiH- is below the neutral ground-state potential energy curve only for some range of the Li-H internuclear distance. This state appears at bond lengths larger than ~2.0 Å and decays at Li-H distances longer than ~4.2 Å, where the dipole moment of LiH becomes smaller than the critical value of 2.5 D. The adiabatic electron affinity of LiH calculated at the coupled-cluster level with the iterative inclusion of all single, double, and triple excitations and a large atomic natural orbital basis set is 0.327 eV, almost matching the recently obtained experimental value of 0.342+/-0.012 eV.

  6. The valence-fluctuating ground state of plutonium

    DOE PAGESBeta

    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; et al

    2015-07-10

    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. In addition, our study reveals that the ground state of plutonium is governed bymore » 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.« less

  7. Experimental study of the valence band of Bi2Se3

    DOE PAGESBeta

    Gao, Yi-Bin; He, Bin; Parker, David; Androulakis, Ioannis; Heremans, Joseph P.

    2014-09-26

    The valence band of Bi2Se3 is investigated with Shubnikov - de Haas measurements, galvanomagnetic and thermoelectric transport. At low hole concentration, the hole Fermi surface is closed and box-like, but at higher concentrations it develops tube-like extensions that are open. The experimentally determined density-of-states effective mass is lighter than density-functional theory calculations predict; while we cannot give a definitive explanation for this, we suspect that the theory may lack sufficient precision to compute room-temperature transport properties, such as the Seebeck coefficient, in solids in which there are Van der Waals interlayer bonds.

  8. 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.

  9. 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.

  10. Strong Constraints to the Putative Planet Candidate around VB 10 Using Doppler Spectroscopy

    NASA Astrophysics Data System (ADS)

    Anglada-Escudé, Guillem; Shkolnik, Evgenya L.; Weinberger, Alycia J.; Thompson, Ian B.; Osip, David J.; Debes, John H.

    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-1 while their standard deviation is 250 m s-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 ~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 ~ 2.5 m jup for a companion with a period shorter than one year and moderate eccentricities. Based on observations collected with the 6.5 m Magellan Telescopes located at Las Campanas Observatory, Chile, at the W. M. Keck Observatory, and the Canada-France-Hawaii Telescope (CFHT). The Keck Observatory is operated as a scientific partnership between the California Institute of Technology, the University of California, and NASA, and was made possible by the generous financial support of the W. M. Keck

  11. 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

  12. Distinguishing Bonds.

    PubMed

    Rahm, Martin; Hoffmann, Roald

    2016-03-23

    The energy change per electron in a chemical or physical transformation, ΔE/n, may be expressed as Δχ̅ + Δ(VNN + ω)/n, where Δχ̅ is the average electron binding energy, a generalized electronegativity, ΔVNN is the change in nuclear repulsions, and Δω is the change in multielectron interactions in the process considered. The last term can be obtained by the difference from experimental or theoretical estimates of the first terms. Previously obtained consequences of this energy partitioning are extended here to a different analysis of bonding in a great variety of diatomics, including more or less polar ones. Arguments are presented for associating the average change in electron binding energy with covalence, and the change in multielectron interactions with electron transfer, either to, out, or within a molecule. A new descriptor Q, essentially the scaled difference between the Δχ̅ and Δ(VNN + ω)/n terms, when plotted versus the bond energy, separates nicely a wide variety of bonding types, covalent, covalent but more correlated, polar and increasingly ionic, metallogenic, electrostatic, charge-shift bonds, and dispersion interactions. Also, Q itself shows a set of interesting relations with the correlation energy of a bond. PMID:26910496

  13. Relationship Between Infrared Intensity Theories: Electro-Optical Parameters And Bond Polar Parameters

    NASA Astrophysics Data System (ADS)

    Galabov, Boris; Dudev, T.

    1989-12-01

    Mathematical and physical aspects are analysed of the relationship between two theoretical formulations of infrared intensities employing parameters associated with chemical bonds: the valence optical theory and bond polar parameters method. Parallel applications of the two theories in analysing experimental IR intensity data for methylchloride are presented.

  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. Effect of phenyl and benzyl group in heterocyclic dithiocarbamates on the ZnS 4N chromophore: Synthesis, spectral, valence-bond parameters and single crystal X-ray structural studies on (pyridine)bis(1,2,3,4-tetrahydroquinolinedithiocarbamato)zinc(II) and (pyridine)bis(1,2,3,4-tetrahydroisoquinolinedithiocarbamato)zinc(II)

    NASA Astrophysics Data System (ADS)

    Srinivasan, N.; Thirumaran, S.; Ciattini, Samuele

    2009-03-01

    Two Zn(II)dithiocarbamates with ZnS 4N chromophores have been synthesized ([Zn(thqdtc) 2(py)] ( 1) and [Zn(thiqdtc) 2(py)] ( 2) (where thqdtc = 1,2,3,4-tetrahydroquinolinedithiocarbamate, thiqtc = 1,2,3,4-tetrahydroisoquinolinedithiocarbamate and py = pyridine)) from [Zn(thqdtc) 2] ( 3) and [Zn(thiqdtc) 2] ( 4), respectively. Their structures and properties have been characterized by IR and NMR spectra. The structures of both the complexes were determined by single crystal X-ray crystallography. The observed deshielding of the H-2 protons for 1 and 3 and H-1 and H-3 protons for 2 and 4 in the 1H NMR spectra is attributed to the drift of electrons from the nitrogen of the NR 2 group, forcing a high electron density towards sulfur via the thioureide π-system. In the 13C NMR spectra, the most important thioureide (N 13CS 2) carbon signals are observed in the region 204-207 ppm. The upfield shift of NCS 2 carbon signal for 1 (204.2 ppm) from the chemical shift value of 2 (206.9 ppm) is due to electron withdrawing resonance effect of phenyl ring thereby decreasing the double bond character in tetrahydroquinolinedithiocarbamate, whereas benzyl group in tetrahydroisoquinolinedithiocarbamate cannot participate in resonance delocalization in the same way. Single crystal X-ray structural analysis of 1 and 2 showed that the zinc atom is pentacoordinated with four sulfur atoms from the dithiocarbamate ligands and one nitrogen atom from the pyridine. VBS values support the correctness of the determined structure. The lower VBS value of 2 is due to the steric effect exerted by the thiqdtc. The phenyl and benzyl group in the heterocyclic dithiocarbamates influences the electronic properties of 1 and 2. The shift of ν C- N(thioureide) and thioureide N 13CS 2 carbon signals are correlated with the electronic effects of the dithiocarbamate ligands.

  16. Architectural Representation of Valence in the Limbic System.

    PubMed

    Namburi, Praneeth; Al-Hasani, Ream; Calhoon, Gwendolyn G; Bruchas, Michael R; Tye, Kay M

    2016-06-01

    In order to thrive, animals must be able to recognize aversive and appetitive stimuli within the environment and subsequently initiate appropriate behavioral responses. This assignment of positive or negative valence to a stimulus is a key feature of emotional processing, the neural substrates of which have been a topic of study for several decades. Until recently, the result of this work has been the identification of specific brain regions, such as the basolateral amygdala (BLA) and nucleus accumbens (NAc), as important to valence encoding. The advent of modern tools in neuroscience has allowed further dissection of these regions to identify specific populations of neurons signaling the valence of environmental stimuli. In this review, we focus upon recent work examining the mechanisms of valence encoding, and provide a model for the systematic investigation of valence within anatomically-, genetically-, and functionally defined populations of neurons. PMID:26647973

  17. Yankee bonds

    SciTech Connect

    Delaney, P. )

    1993-10-01

    Yankee and Euromarket bonds may soon find their way into the financing of power projects in Latin America. For developers seeking long-term commitments under build, own, operate, and transfer (BOOT) power projects in Latin America, the benefits are substantial.

  18. Towards an understanding of the bonding in polyoxometalates through bond order and bond energy analysis.

    PubMed

    Bridgeman, Adam J; Cavigliasso, Germán

    2003-01-01

    The molecular and electronic structures of transition metal complexes, [MOCl5]n- (n = 2 for M = V,Nb,Ta and n = 1 for Mo,W) and mixed-metal polyoxometalates, [M'M5O19]3-V,Nb,Ta, M = Mo,W) containing a single terminal oxo group on each metal, and of complexes of the uranyl ion [UO2]2+, [UO2(H2O)5]2+ and [UO2Cl4]2-, have been calculated using density functional methods. The calculated structures of the complexes are in good agreement with available experimental parameters. For the mixed-metal hexametalates, for which no crystallographic data is available, the calculations predict a small tetragonal compression of the clusters with only minor structural changes compared to the parent molybdate and tungstate. The metal oxygen bonding in these anions has been probed using Mayer-Mulliken, bond energy and atoms in molecule analyses (AIM). These methods provide a consistent description of the bonding in polyoxometalates. The terminal bonds between transition metal or uranium and oxygen atoms have large sigma and pi components with the pi contributions exceeding the sigma bonding. The transition metals utilize their d orbitals almost exclusively to bond to oxygen whilst uranium uses both its 5f and 6d orbitals. Oxygen atom charges increase and covalency indexes decrease with coordination number, with a marked separation of these terms according to the oxygen atom type. The total valency and AIM energies of the oxygen atoms are predicted to be almost constant for all types of oxygen site. The constancy of the bonding power of the oxygen atoms appears to be an important factor in determining the gross structures and details of the bonding in polyoxometalates. The Mayer Mulliken approach provides direct characterization of the bonding power of atoms and the extent of the interaction between pairs of atoms that is consistent with the results of the considerably more computationally demanding bond energy and AIM approaches. PMID:14527219

  19. 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

  20. Bond-length distributions for ions bonded to oxygen: alkali and alkaline-earth metals

    PubMed Central

    Gagné, Olivier Charles; Hawthorne, Frank Christopher

    2016-01-01

    ]-coordination. For alkali-metal and alkaline-earth-metal ions, there is a positive correlation between cation coordination number and the grand mean incident bond-valence sum at the central cation, the values varying from 0.84 v.u. for [5]K+ to 1.06 v.u. for [8]Li+, and from 1.76 v.u. for [7]Ba2+ to 2.10 v.u. for [12]Sr2+. Bond-valence arguments suggest coordination numbers higher than [12] for K+, Rb+, Cs+ and Ba2+. PMID:27484381

  1. Bond-length distributions for ions bonded to oxygen: alkali and alkaline-earth metals.

    PubMed

    Gagné, Olivier Charles; Hawthorne, Frank Christopher

    2016-08-01

    [4]- and [6]-coordination, Na(+) in [4]- and [6]-coordination. For alkali-metal and alkaline-earth-metal ions, there is a positive correlation between cation coordination number and the grand mean incident bond-valence sum at the central cation, the values varying from 0.84 v.u. for ([5])K(+) to 1.06 v.u. for ([8])Li(+), and from 1.76 v.u. for ([7])Ba(2+) to 2.10 v.u. for ([12])Sr(2+). Bond-valence arguments suggest coordination numbers higher than [12] for K(+), Rb(+), Cs(+) and Ba(2+). PMID:27484381

  2. In-silico bonding schemes to encode chemical bonds involving sharing of electrons in molecular structures.

    PubMed

    Punnaivanam, Sankar; Sathiadhas, Jerome Pastal Raj; Panneerselvam, Vinoth

    2016-05-01

    Encoding of covalent and coordinate covalent bonds in molecular structures using ground state valence electronic configuration is achieved. The bonding due to electron sharing in the molecular structures is described with five fundamental bonding categories viz. uPair-uPair, lPair-uPair, uPair-lPair, vPair-lPair, and lPair-lPair. The involvement of lone pair electrons and the vacant electron orbitals in chemical bonding are explained with bonding schemes namely "target vacant promotion", "source vacant promotion", "target pairing promotion", "source pairing promotion", "source cation promotion", "source pairing double bond", "target vacant occupation", and "double pairing promotion" schemes. The bonding schemes are verified with a chemical structure editor. The bonding in the structures like ylides, PCl5, SF6, IF7, N-Oxides, BF4(-), AlCl4(-) etc. are explained and encoded unambiguously. The encoding of bonding in the structures of various organic compounds, transition metals compounds, coordination complexes and metal carbonyls is accomplished. PMID:27041446

  3. Fast and accurate predictions of covalent bonds in chemical space.

    PubMed

    Chang, K Y Samuel; Fias, Stijn; Ramakrishnan, Raghunathan; von Lilienfeld, O Anatole

    2016-05-01

    We assess the predictive accuracy of perturbation theory based estimates of changes in covalent bonding due to linear alchemical interpolations among molecules. We have investigated σ bonding to hydrogen, as well as σ and π bonding between main-group elements, occurring in small sets of iso-valence-electronic molecules with elements drawn from second to fourth rows in the p-block of the periodic table. Numerical evidence suggests that first order Taylor expansions of covalent bonding potentials can achieve high accuracy if (i) the alchemical interpolation is vertical (fixed geometry), (ii) it involves elements from the third and fourth rows of the periodic table, and (iii) an optimal reference geometry is used. This leads to near linear changes in the bonding potential, resulting in analytical predictions with chemical accuracy (∼1 kcal/mol). Second order estimates deteriorate the prediction. If initial and final molecules differ not only in composition but also in geometry, all estimates become substantially worse, with second order being slightly more accurate than first order. The independent particle approximation based second order perturbation theory performs poorly when compared to the coupled perturbed or finite difference approach. Taylor series expansions up to fourth order of the potential energy curve of highly symmetric systems indicate a finite radius of convergence, as illustrated for the alchemical stretching of H2 (+). Results are presented for (i) covalent bonds to hydrogen in 12 molecules with 8 valence electrons (CH4, NH3, H2O, HF, SiH4, PH3, H2S, HCl, GeH4, AsH3, H2Se, HBr); (ii) main-group single bonds in 9 molecules with 14 valence electrons (CH3F, CH3Cl, CH3Br, SiH3F, SiH3Cl, SiH3Br, GeH3F, GeH3Cl, GeH3Br); (iii) main-group double bonds in 9 molecules with 12 valence electrons (CH2O, CH2S, CH2Se, SiH2O, SiH2S, SiH2Se, GeH2O, GeH2S, GeH2Se); (iv) main-group triple bonds in 9 molecules with 10 valence electrons (HCN, HCP, HCAs, HSiN, HSi

  4. Fast and accurate predictions of covalent bonds in chemical space

    NASA Astrophysics Data System (ADS)

    Chang, K. Y. Samuel; Fias, Stijn; Ramakrishnan, Raghunathan; von Lilienfeld, O. Anatole

    2016-05-01

    We assess the predictive accuracy of perturbation theory based estimates of changes in covalent bonding due to linear alchemical interpolations among molecules. We have investigated σ bonding to hydrogen, as well as σ and π bonding between main-group elements, occurring in small sets of iso-valence-electronic molecules with elements drawn from second to fourth rows in the p-block of the periodic table. Numerical evidence suggests that first order Taylor expansions of covalent bonding potentials can achieve high accuracy if (i) the alchemical interpolation is vertical (fixed geometry), (ii) it involves elements from the third and fourth rows of the periodic table, and (iii) an optimal reference geometry is used. This leads to near linear changes in the bonding potential, resulting in analytical predictions with chemical accuracy (˜1 kcal/mol). Second order estimates deteriorate the prediction. If initial and final molecules differ not only in composition but also in geometry, all estimates become substantially worse, with second order being slightly more accurate than first order. The independent particle approximation based second order perturbation theory performs poorly when compared to the coupled perturbed or finite difference approach. Taylor series expansions up to fourth order of the potential energy curve of highly symmetric systems indicate a finite radius of convergence, as illustrated for the alchemical stretching of H 2+ . Results are presented for (i) covalent bonds to hydrogen in 12 molecules with 8 valence electrons (CH4, NH3, H2O, HF, SiH4, PH3, H2S, HCl, GeH4, AsH3, H2Se, HBr); (ii) main-group single bonds in 9 molecules with 14 valence electrons (CH3F, CH3Cl, CH3Br, SiH3F, SiH3Cl, SiH3Br, GeH3F, GeH3Cl, GeH3Br); (iii) main-group double bonds in 9 molecules with 12 valence electrons (CH2O, CH2S, CH2Se, SiH2O, SiH2S, SiH2Se, GeH2O, GeH2S, GeH2Se); (iv) main-group triple bonds in 9 molecules with 10 valence electrons (HCN, HCP, HCAs, HSiN, HSi

  5. 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

  6. Intramolecular interactions of L-phenylalanine: Valence ionization spectra and orbital momentum distributions of its fragment molecules.

    PubMed

    Ganesan, Aravindhan; Wang, Feng; Falzon, Chantal

    2011-02-01

    Intramolecular interactions between fragments of L-phenylalanine, i.e., phenyl and alaninyl, have been investigated using dual space analysis (DSA) quantum mechanically. Valence space photoelectron spectra (PES), orbital energy topology and correlation diagram, as well as orbital momentum distributions (MDs) of L-phenylalanine, benzene and L-alanine are studied using density functional theory methods. While fully resolved experimental PES of L-phenylalanine is not yet available, our simulated PES reproduces major features of the experimental measurement. For benzene, the simulated orbital MDs for 1e(1g) and 1a(2u) orbitals also agree well with those measured using electron momentum spectra. Our theoretical models are then applied to reveal intramolecular interactions of the species on an orbital base, using DSA. Valence orbitals of L-phenylalanine can be essentially deduced into contributions from its fragments such as phenyl and alaninyl as well as their interactions. The fragment orbitals inherit properties of their parent species in energy and shape (ie., MDs). Phenylalanine orbitals show strong bonding in the energy range of 14-20 eV, rather than outside of this region. This study presents a competent orbital based fragments-in-molecules picture in the valence space, which supports the fragment molecular orbital picture and building block principle in valence space. The optimized structures of the molecules are represented using the recently developed interactive 3D-PDF technique. PMID:20806261

  7. Valence-electron spectral change and charge transfer mechanism of CaSi 2 during CaSi 2H 2O reaction

    NASA Astrophysics Data System (ADS)

    Abe, S.; Nakayama, H.; Nishino, T.; Iida, S.

    1997-04-01

    The changes in the valence electron states of CaSi 2 during the chemical reaction with H 2O have been investigated by Auger valence electron spectroscopy (AVES). The drastic changes in the valence electron spectra of 3s and 3p states, which are caused by the oxidization of the Si atoms in CaSi 2, were observed in Si[2s, 2p, V] spectra for CaSi 2 after the reaction. In particular, the Si[2s, 2p, V] spectra of CaSi 2 samples reacted with H 2O at 60 or 80°C for 3 h were almost similar to that of SiO 2. The peak shift of Ca[2p, 3p, 3p] Auger transition toward the lower energy side has been observed, suggesting the formation of bonds between Ca 3p and O orbitals. New peaks due to CaO or CaOH bonds also appeared in the valence electron region of Ca[2p, 3p, V] Auger transition. The charge transfer and the chemical-bond formation can be well demonstrated by AVES during the CaSi 2H 2O reaction.

  8. Diffusion bonding

    DOEpatents

    Anderson, Robert C.

    1976-06-22

    1. A method for joining beryllium to beryllium by diffusion bonding, comprising the steps of coating at least one surface portion of at least two beryllium pieces with nickel, positioning a coated surface portion in a contiguous relationship with an other surface portion, subjecting the contiguously disposed surface portions to an environment having an atmosphere at a pressure lower than ambient pressure, applying a force upon the beryllium pieces for causing the contiguous surface portions to abut against each other, heating the contiguous surface portions to a maximum temperature less than the melting temperature of the beryllium, substantially uniformly decreasing the applied force while increasing the temperature after attaining a temperature substantially above room temperature, and maintaining a portion of the applied force at a temperature corresponding to about maximum temperature for a duration sufficient to effect the diffusion bond between the contiguous surface portions.

  9. 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.

  10. Valence band anticrossing in GaBixAs1-x

    NASA Astrophysics Data System (ADS)

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

    2007-07-01

    The optical properties of GaBixAs1-x(0.04valence 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.

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

    PubMed Central

    2015-01-01

    Transition-metal Kβ 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, Kβ 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 Kβ″ 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

  12. 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.

  13. Combining symmetry-separated and bent-bond spin-coupled models of cylindrically symmetric multiple bonding

    NASA Astrophysics Data System (ADS)

    Penotti, Fabio E.; Cooper, David L.

    2015-07-01

    We examine the symmetry properties of spin-coupled (or full generalised valence bond) wavefunctions for C2H2 and N2. The symmetry-separated (σ,π) and bent-bond (ω) solutions are totally symmetric only in the D4h and D3h subgroups of D∞h, respectively. Two fairly different strategies are explored for imposing full cylindrical symmetry, with one of them (small nonorthogonal configuration interaction calculations involving rotated versions of the wavefunction) turning out to be somewhat preferable on energetic grounds to the other one (application of additional spin constraints to a single spatial configuration). It is also shown that mixing together the cylindrically symmetric symmetry-separated and bent-bond spin-coupled models leads to relatively small energy improvements unless the valence orbitals in each type of configuration are reoptimised.

  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. 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)

  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. Emotional valence and the free-energy principle.

    PubMed

    Joffily, Mateus; Coricelli, Giorgio

    2013-01-01

    The free-energy principle has recently been proposed as a unified Bayesian account of perception, learning and action. Despite the inextricable link between emotion and cognition, emotion has not yet been formulated under this framework. A core concept that permeates many perspectives on emotion is valence, which broadly refers to the positive and negative character of emotion or some of its aspects. In the present paper, we propose a definition of emotional valence in terms of the negative rate of change of free-energy over time. If the second time-derivative of free-energy is taken into account, the dynamics of basic forms of emotion such as happiness, unhappiness, hope, fear, disappointment and relief can be explained. In this formulation, an important function of emotional valence turns out to regulate the learning rate of the causes of sensory inputs. When sensations increasingly violate the agent's expectations, valence is negative and increases the learning rate. Conversely, when sensations increasingly fulfil the agent's expectations, valence is positive and decreases the learning rate. This dynamic interaction between emotional valence and learning rate highlights the crucial role played by emotions in biological agents' adaptation to unexpected changes in their world. PMID:23785269

  18. Bonded Lubricants

    NASA Technical Reports Server (NTRS)

    1977-01-01

    Another spinoff to the food processing industry involves a dry lubricant developed by General Magnaplate Corp. of Linden, N.J. Used in such spacecraft as Apollo, Skylab and Viking, the lubricant is a coating bonded to metal surfaces providing permanent lubrication and corrosion resistance. The coating lengthens equipment life and permits machinery to be operated at greater speed, thus increasing productivity and reducing costs. Bonded lubricants are used in scores of commercia1 applications. They have proved particularly valuable to food processing firms because, while increasing production efficiency, they also help meet the stringent USDA sanitation codes for food-handling equipment. For example, a cookie manufacturer plagued production interruptions because sticky batter was clogging the cookie molds had the brass molds coated to solve the problem. Similarly, a pasta producer faced USDA action on a sanitation violation because dough was clinging to an automatic ravioli-forming machine; use of the anti-stick coating on the steel forming plates solved the dual problem of sanitation deficiency and production line downtime.

  19. Many-body calculation of the valence photoemission spectrum of Fe(CO)5

    NASA Astrophysics Data System (ADS)

    Ohno, M.; von Niessen, W.

    1991-07-01

    The valence photoemission spectrum of Fe(CO)5 is calculated by the ADC(3) Green's function method. The overall agreement with the experiment is good. It is shown that the quasiparticle picture (QPP) for the outer and inner valence levels (except the 8a`2 level) derived primarily from CO ligand orbitals breaks down completely due to the one-hole/two-hole-one-particle (1h/2h1p) charge transfer (CT) coupling in the bonded system. Compared to Ni(CO)4 the many-electron effect is much stronger in Fe(CO)5. In Cr(CO)6 and Fe(CO)5 the 3d shell is incompletely filled, but in contrast to Cr(CO)6 in Fe(CO)5 there is no significant contribution from the local metal excitations. It is shown that for the 8a■2 level the 1h state is still more stable than the 2h1p states. Consequently the main line (with an intensity of 0.76) is interpreted as the 1h state where the screening charge resides on the bonding orbital which is more polarized toward the ligand than in the ground state. The satellites are dominated by 2h1p configurations where the bonding to antibonding shake-up excitations occur. For the other CO derived levels the strong mixing of 1h and 2h1p configurations leads to the breakdown of the QPP of the ionization and thus a distinction between main line and satellite line becomes meaningless. For most of the levels, the strong dynamical metal-ligand CT hole-particle excitations, where the creation of two holes in the same metal orbital is involved, lead to the breakdown of the QPP of the ionization. A similar strong many-electron effect is also found in Cr(CO)6. For most of the outer and inner valence levels of these molecules, the QPP of the ionization breaks down.

  20. 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…

  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. Does fluorine participate in halogen bonding?

    PubMed

    Eskandari, Kiamars; Lesani, Mina

    2015-03-16

    When R is sufficiently electron withdrawing, the fluorine in the R-F molecules could interact with electron donors (e.g., ammonia) and form a noncovalent bond (F⋅⋅⋅N). Although these interactions are usually categorized as halogen bonding, our studies show that there are fundamental differences between these interactions and halogen bonds. Although the anisotropic distribution of electronic charge around a halogen is responsible for halogen bond formations, the electronic charge around the fluorine in these molecules is spherical. According to source function analysis, F is the sink of electron density at the F⋅⋅⋅N BCP, whereas other halogens are the source. In contrast to halogen bonds, the F⋅⋅⋅N interactions cannot be regarded as lump-hole interactions; there is no hole in the valence shell charge concentration (VSCC) of fluorine. Although the quadruple moment of Cl and Br is mainly responsible for the existence of σ-holes, it is negligibly small in the fluorine. Here, the atomic dipole moment of F plays a stabilizing role in the formation of F⋅⋅⋅N bonds. Interacting quantum atoms (IQA) analysis indicates that the interaction between halogen and nitrogen in the halogen bonds is attractive, whereas it is repulsive in the F⋅⋅⋅N interactions. Virial-based atomic energies show that the fluorine, in contrast to Cl and Br, stabilize upon complex formation. According to these differences, it seems that the F⋅⋅⋅N interactions should be referred to as "fluorine bond" instead of halogen bond. PMID:25652256

  3. Taboo, emotionally valenced, and emotionally neutral word norms.

    PubMed

    Janschewitz, Kristin

    2008-11-01

    Although taboo words are used to study emotional memory and attention, no easily accessible normative data are available that compare taboo, emotionally valenced, and emotionally neutral words on the same scales. Frequency, inappropriateness, valence, arousal, and imageability ratings for taboo, emotionally valenced, and emotionally neutral words were made by 78 native-English-speaking college students from a large metropolitan university. The valenced set comprised both positive and negative words, and the emotionally neutral set comprised category-related and category-unrelated words. To account for influences of demand characteristics and personality factors on the ratings, frequency and inappropriateness measures were decomposed into raters' personal reactions to the words versus raters' perceptions of societal reactions to the words (personal use vs. familiarity and offensiveness vs. tabooness, respectively). Although all word sets were rated higher in familiarity and tabooness than in personal use and offensiveness, these differences were most pronounced for the taboo set. In terms of valence, the taboo set was most similar to the negative set, although it yielded higher arousal ratings than did either valenced set. Imageability for the taboo set was comparable to that of both valenced sets. The ratings of each word are presented for all participants as well as for single-sex groups. The inadequacies of the application of normative data to research that uses emotional words and the conceptualization of taboo words as a coherent category are discussed. Materials associated with this article may be accessed at the Psychonomic Society's Archive of Norms, Stimuli, and Data, www.psychonomic.org/archive. PMID:19001397

  4. 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, β = 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.

  5. The electronic structure and optical properties of organic mixed valence anion radicals

    SciTech Connect

    Liberko, C.A.

    1992-01-01

    The electronic structure of planar and helical organic mixed valence anion radicals was studied. Cyanoimine derivatives of planar diquinones were synthesized and studied by electrochemical methods. Their anion radicals were generated electrochemically and found to be stable in air. These species had electronic absorptions in the near infrared region. The Visible and near infrared spectra as well as IR vibrational data are consistent with delocalized anion radicals. The molecular orbital energy level coefficients obtained from PPP semi-empirical molecular orbital calculations on neutral quinones, imides and cyanoimine derivatives of quinones, were used to correlate experimental data of their anion radicals. The calculation correlated the long wavelength absorptions of the anion radicals confirming that the absorptions arise from electronic transitions in delocalized species. The calculation was also valuable for assigning ESR hyperfine splittings. Including minor geometric perturbations in the calculation provides a method of predicting localization in mixed valence ion radicals. Helicene diquinones were studied by cyclic voltammetry. Their anion radicals, generated electrochemically, were studied by visible, near infrared, and ESR spectroscopies. The anion radicals were found to have electronic absorptions in the near infrared region tailing into the infrared. PPP calculations were consistent with the experimental data only if transannular interaction between the ends of the helix was included. The calculations and experimental observations are consistent with an electronic structure in which the anion radical is not only delocalized around the helix but also between the ends of the helix bonding them together in a Mobius fashion.

  6. Phase behavior and critical activated dynamics of limited-valence DNA nanostars.

    PubMed

    Biffi, Silvia; Cerbino, Roberto; Bomboi, Francesca; Paraboschi, Elvezia Maria; Asselta, Rosanna; Sciortino, Francesco; Bellini, Tommaso

    2013-09-24

    Colloidal particles with directional interactions are key in the realization of new colloidal materials with possibly unconventional phase behaviors. Here we exploit DNA self-assembly to produce bulk quantities of "DNA stars" with three or four sticky terminals, mimicking molecules with controlled limited valence. Solutions of such molecules exhibit a consolution curve with an upper critical point, whose temperature and concentration decrease with the valence. Upon approaching the critical point from high temperature, the intensity of the scattered light diverges with a power law, whereas the intensity time autocorrelation functions show a surprising two-step relaxation, somehow reminiscent of glassy materials. The slow relaxation time exhibits an Arrhenius behavior with no signs of criticality, demonstrating a unique scenario where the critical slowing down of the concentration fluctuations is subordinate to the large lifetime of the DNA bonds, with relevant analogies to critical dynamics in polymer solutions. The combination of equilibrium and dynamic behavior of DNA nanostars demonstrates the potential of DNA molecules in diversifying the pathways toward collective properties and self-assembled materials, beyond the range of phenomena accessible with ordinary molecular fluids. PMID:24019470

  7. Design-atom approach for the QM/MM covalent boundary: A design-carbon atom with five valence electrons

    PubMed Central

    Xiao, Chuanyun; Zhang, Yingkai

    2009-01-01

    A critical issue underlying the accuracy and applicability of the combined quantum mechanical/molecular mechanical (QM/MM) methods is how to describe the QM/MM boundary across covalent bonds. Inspired by the ab initio pseudo-potential theory, here we introduce a novel design-atom approach for a more fundamental and transparent treatment of this QM/MM covalent boundary problem. The main idea is to replace the boundary atom of the active part with a design-atom, which has a different number of valence electrons but very similar atomic properties. By modifying the Troullier-Martins scheme, which has been widely employed to construct norm-conserving pseudo-potentials for density functional calculations, we have successfully developed a design-carbon atom with five valence electrons. Tests on a series of molecules yield very good structural and energetic results, and indicate its transferability in describing a variety of chemical bonds, including double and triple bonds. PMID:17902888

  8. Theory of Valence Transition in BiNiO3

    NASA Astrophysics Data System (ADS)

    Naka, Makoto; Seo, Hitoshi; Motome, Yukitoshi

    2016-02-01

    Motivated by the colossal negative thermal expansion recently found in BiNiO3 , the valence transition accompanied by the charge transfer between the Bi and Ni sites is theoretically studied. We introduce an effective model for Bi -6 s and Ni -3 d orbitals taking into account the valence skipping of Bi cations, and investigate the ground-state and finite-temperature phase diagrams within the mean-field approximation. We find that the valence transition is caused by commensurate locking of the electron filling in each orbital associated with charge and magnetic orderings, and the critical temperature and the nature of the transitions are strongly affected by the relative energy between the Bi and Ni levels and the effective electron-electron interaction in the Bi sites. The obtained phase diagram well explains the temperature- and pressure-driven valence transitions in BiNiO3 and the systematic variation of valence states for a series of Bi and Pb perovskite oxides.

  9. Semantic memory: distinct neural representations for abstractness and valence.

    PubMed

    Skipper, Laura M; Olson, Ingrid R

    2014-03-01

    The hypothesis that abstract words are grounded in emotion has been supported by behavioral research and corpus studies of English words. A recent neuroimaging study reported that a single brain region, the rostral anterior cingulate cortex (rACC), is responsive to abstract words, and is furthermore modulated by the emotional valence. This finding is surprising because the rACC is not commonly associated with semantic processing. It is possible that the effects observed were driven not by abstractness, but rather by valence, since the abstract words used in that study were significantly more emotional than the concrete words. We tested this hypothesis by presenting participants with words that were abstract/concrete, as well as emotionally valenced/neutral in a 2×2 factorial design. Activations to emotional words overlapped with both abstract and concrete activations throughout the brain. An ROI analysis revealed that the rACC was responsive to valence, not abstractness, when concreteness and valence unconfounded. PMID:24561187

  10. Optical Study of Archetypical Valence-Fluctuating Eu Systems

    NASA Astrophysics Data System (ADS)

    Guritanu, V.; Seiro, S.; Sichelschmidt, J.; Caroca-Canales, N.; Iizuka, T.; Kimura, S.; Geibel, C.; Steglich, F.

    2012-12-01

    We have investigated the optical conductivity of the prominent valence-fluctuating compounds EuIr2Si2 and EuNi2P2 in the infrared energy range to get new insights into the electronic properties of valence-fluctuating systems. For both compounds, we observe upon cooling the formation of a renormalized Drude response, a partial suppression of the optical conductivity below 100meV, and the appearance of a midinfrared peak at 0.15eV for EuIr2Si2 and 0.13 eV for EuNi2P2. Most remarkably, our results show a strong similarity with the optical spectra reported for many Ce- or Yb-based heavy-fermion metals and intermediate valence systems, although the phase diagrams and the temperature dependence of the valence differ strongly between Eu systems and Ce- or Yb-based systems. This suggests that the hybridization between 4f and conduction electrons, which is responsible for the properties of Ce and Yb systems, plays an important role in valence-fluctuating Eu systems.

  11. Theory of Valence Transition in BiNiO_{3}.

    PubMed

    Naka, Makoto; Seo, Hitoshi; Motome, Yukitoshi

    2016-02-01

    Motivated by the colossal negative thermal expansion recently found in BiNiO_{3}, the valence transition accompanied by the charge transfer between the Bi and Ni sites is theoretically studied. We introduce an effective model for Bi-6s and Ni-3d orbitals taking into account the valence skipping of Bi cations, and investigate the ground-state and finite-temperature phase diagrams within the mean-field approximation. We find that the valence transition is caused by commensurate locking of the electron filling in each orbital associated with charge and magnetic orderings, and the critical temperature and the nature of the transitions are strongly affected by the relative energy between the Bi and Ni levels and the effective electron-electron interaction in the Bi sites. The obtained phase diagram well explains the temperature- and pressure-driven valence transitions in BiNiO_{3} and the systematic variation of valence states for a series of Bi and Pb perovskite oxides. PMID:26894723

  12. A New Conformation With an Extraordinarily Long, 3.04 Å Two-Electron, Six-Center Bond Observed for the π-[TCNE]2 (2-) Dimer in [NMe4 ]2 [TCNE]2 (TCNE=Tetracyanoethylene).

    PubMed

    Graham, Adora G; Mota, Fernando; Shurdha, Endrit; Rheingold, Arnold L; Novoa, Juan J; Miller, Joel S

    2015-09-14

    [NMe4 ]2 [TCNE]2 (TCNE=tetracyanoethenide) formed from the reaction of TCNE and (NMe4 )CN in MeCN has νCN IR absorptions at 2195, 2191, 2172, and 2156 cm(-1) and a νCC absorption at 1383 cm(-1) that are characteristic of reduced TCNE. The TCNEs have an average central CC distance of 1.423 Å that is also characteristic of reduced TCNE. The reduced TCNE forms a previously unknown non-eclipsed, centrosymmetric π-[TCNE]2 (2-) dimer with nominal C2 symmetry, 12 sub van der Waals interatomic contacts <3.3 Å, a central intradimer separation of 3.039(3) Å, and comparable intradimer C⋅⋅⋅N distances of 3.050(3) and 2.984(3) Å. The two pairs of central C⋅⋅⋅C atoms form a ∢C-C⋅⋅⋅C-C of 112.6° that is substantially greater than the 0° observed for the eclipsed D2h π-[TCNE]2 (2-) dimer possessing a two-electron, four-center (2e(-) /4c) bond with two C⋅⋅⋅C components from a molecular orbital (MO) analysis. A MO study combining CAS(2,2)/MRMP2/cc-pVTZ and atoms-in-molecules (AIM) calculations indicates that the non-eclipsed, C2 π-[TCNE]2 (2-) dimer exhibits a new type of a long, intradimer bond involving one strong C⋅⋅⋅C and two weak C⋅⋅⋅N components, that is, a 2e(-) /6c bond. The C2 π-[TCNE]2 (2-) conformer has a singlet, diamagnetic ground state with a thermally populated triplet excited state with J/kB =1000 K (700 cm(-1) ; 86.8 meV; 2.00 kcal mol(-1) ; H=-2 JSa ⋅Sb ); at the CAS(2,2)/MBMP2 level the triplet is computed to be 9.0 kcal mol(-1) higher in energy than the closed-shell singlet ground state. The results from CAS(2,2)/NEVPT2/cc-pVTZ calculations indicate that the C2 and D2h conformers have two different local metastable minima with the C2 conformer being 1.3 kcal mol(-1) less stable. The different natures of the C2 and D2h conformers are also noted from the results of valence bond (VB) qualitative diagram that shows a 10e(-) /6c bond with one C⋅⋅⋅C and two C⋅⋅⋅N bonding

  13. 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.

  14. Metal-metal interactions in weakly coupled mixed-valence E- and Z-diferrocenylethylene complexes.

    PubMed

    Chen, Y J; Pan, D S; Chiu, C F; Su, J X; Lin, S J; Kwan, K S

    2000-03-01

    To study metal-to-metal interactions in mixed-valence states of two weakly coupling ferrocenyl groups assembled in E or Z conformation on an ethylenic double bond, E-1,2-dimethyldiferrocenylethylene (1), Z-1,2-dimethyldi-ferrocenylethylene (2), and 1,2-diferrocenylcyclohexene (3) were synthesized and structurally characterized. Crystals of 1 are triclinic, P1, with a = 7.494(9) A, b = 10.801(3) A, c = 11.971(2) A, alpha = 102.17(2) degrees, beta = 106.12(9) degrees, gamma = 90.42(2) degrees, V = 907.8 A3, and Z = 2. Crystals of 2 are monoclinic, P2(1)/c, with a = 13.601(8) A, b = 11.104(4) A, c = 13.732(1) A, beta = 114.26(7) degrees, V = 1890.8(3) A3, and Z = 4. Crystals of 3 are orthorhombic, P2(1)2(1)2(1), with a = 5.766(2) A, b = 13.090(1) A, c = 26.695(2) A, V = 2014.9(3) A3, and Z = 4. Intervalence transition spectra (IT) and electrochemical data have been determined and compared with those of diferrocenyl-benzene (para, ortho, and meta). The comproportionation constants in nitrobenzene at 25 degrees C were found to be 490 and 813 for 1 and 3, respectively. That of 2 was not measured because of the fact that 2+ isomerizes rapidly in all solvents tested, yielding nearly a racemic mixture of E and Z conformers. This finding helps to clear the paradoxical phenomenon between experimental results of mixed-valence complexes of E- and Z-1,2-bis(1'-ethyl-1-ferrocenyl)-1,2-dimethylethylene and theories. The stability of the mixed-valence species was discussed in terms of resonance delocalization, Coulomb repulsion energy, inductive effect, magnetic interaction, structural factors, and statistical factor. According to our analysis based on the Hush formalism, the contribution due to Coulomb repulsion energy dominates the overall stability of the mixed-valence state in 1+, 2+, and 3+. Stabilization that arises from resonance delocalization is only minor and contributes less than 4% to the overall stability, even in 3+ where linked Cp rings and the ethylenic plane are

  15. The effect of object-valence relations on automatic evaluation.

    PubMed

    Moran, Tal; Bar-Anan, Yoav

    2013-01-01

    Two experiments tested the effect of co-occurrence of a target object with affective stimuli on automatic evaluation of the target when the relation between the target and the affective stimuli suggests that they have opposite valence. Participants learned about targets that ended an unpleasant noise or a pleasant music. The valence of such targets is opposite to the valence of the affective stimuli that co-occur with them. Participants reported preference for targets that ended noise over targets that ended music, but automatic evaluation measures revealed the opposite preference. This suggests that automatic evaluation is sensitive to co-occurrence between stimuli more than to the relation between the stimuli, and that relational information has a stronger influence on deliberate evaluation than on automatic evaluation. These conclusions support the associative-propositional evaluation model (Gawronski & Bodenhausen, 2006), and add evidence regarding the sensitivity of the evaluative-conditioning effect to relational information. PMID:23072334

  16. Valence Electronic Structure of Aqueous Solutions: Insights from Photoelectron Spectroscopy

    NASA Astrophysics Data System (ADS)

    Seidel, Robert; Winter, Bernd; Bradforth, Stephen E.

    2016-05-01

    The valence orbital electron binding energies of water and of embedded solutes are crucial quantities for understanding chemical reactions taking place in aqueous solution, including oxidation/reduction, transition-metal coordination, and radiation chemistry. Their experimental determination based on liquid-photoelectron spectroscopy using soft X-rays is described, and we provide an overview of valence photoelectron spectroscopy studies reported to date. We discuss principal experimental aspects and several theoretical approaches to compute the measured binding energies of the least tightly bound molecular orbitals. Solutes studied are presented chronologically, from simple electrolytes, via transition-metal ion solutions and several organic and inorganic molecules, to biologically relevant molecules, including aqueous nucleotides and their components. In addition to the lowest vertical ionization energies, the measured valence photoelectron spectra also provide information on adiabatic ionization energies and reorganization energies for the oxidation (ionization) half-reaction. For solutes with low solubility, resonantly enhanced ionization provides a promising alternative pathway.

  17. Valence Electronic Structure of Aqueous Solutions: Insights from Photoelectron Spectroscopy.

    PubMed

    Seidel, Robert; Winter, Bernd; Bradforth, Stephen E

    2016-05-27

    The valence orbital electron binding energies of water and of embedded solutes are crucial quantities for understanding chemical reactions taking place in aqueous solution, including oxidation/reduction, transition-metal coordination, and radiation chemistry. Their experimental determination based on liquid-photoelectron spectroscopy using soft X-rays is described, and we provide an overview of valence photoelectron spectroscopy studies reported to date. We discuss principal experimental aspects and several theoretical approaches to compute the measured binding energies of the least tightly bound molecular orbitals. Solutes studied are presented chronologically, from simple electrolytes, via transition-metal ion solutions and several organic and inorganic molecules, to biologically relevant molecules, including aqueous nucleotides and their components. In addition to the lowest vertical ionization energies, the measured valence photoelectron spectra also provide information on adiabatic ionization energies and reorganization energies for the oxidation (ionization) half-reaction. For solutes with low solubility, resonantly enhanced ionization provides a promising alternative pathway. PMID:27023757

  18. 30 CFR 57.22222 - Ventilation materials (I-A, I-B, I-C, II-A, III, V-A, and V-B mines).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ....22222 Ventilation materials (I-A, I-B, I-C, II-A, III, V-A, and V-B mines). Brattice cloth and ventilation tubing shall be approved by MSHA in accordance with 30 CFR part 7, or shall bear a BC or VT... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Ventilation materials (I-A, I-B, I-C, II-A,...

  19. 30 CFR 57.22202 - Main fans (I-A, I-B, I-C, II-A, III, V-A, and V-B mines).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... reverse airstream shall be approved by MSHA under the appliable requirements of 30 CFR part 18; (2) Drive... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Main fans (I-A, I-B, I-C, II-A, III, V-A, and V... Main fans (I-A, I-B, I-C, II-A, III, V-A, and V-B mines). (a) Main fans shall be— (1) Installed on...

  20. 30 CFR 57.22202 - Main fans (I-A, I-B, I-C, II-A, III, V-A, and V-B mines).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... reverse airstream shall be approved by MSHA under the appliable requirements of 30 CFR part 18; (2) Drive... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Main fans (I-A, I-B, I-C, II-A, III, V-A, and V... Main fans (I-A, I-B, I-C, II-A, III, V-A, and V-B mines). (a) Main fans shall be— (1) Installed on...

  1. 30 CFR 57.22202 - Main fans (I-A, I-B, I-C, II-A, III, 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 Main fans (I-A, I-B, I-C, II-A, III, V-A, and V-B mines). 57.22202 Section 57.22202 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 MINES Safety Standards for...

  2. 30 CFR 57.22202 - Main fans (I-A, I-B, I-C, II-A, III, V-A, and V-B mines).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Main fans (I-A, I-B, I-C, II-A, III, V-A, and V-B mines). 57.22202 Section 57.22202 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 MINES Safety Standards for...

  3. 30 CFR 57.22202 - Main fans (I-A, I-B, I-C, II-A, III, V-A, and V-B mines).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... reverse airstream shall be approved by MSHA under the appliable requirements of 30 CFR part 18; (2) Drive... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Main fans (I-A, I-B, I-C, II-A, III, V-A, and V... Main fans (I-A, I-B, I-C, II-A, III, V-A, and V-B mines). (a) Main fans shall be— (1) Installed on...

  4. 30 CFR 57.22201 - Mechanical ventilation (I-A, I-B, I-C, II-A, II-B, III, IV, V-A, and V-B mines).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Mechanical ventilation (I-A, I-B, I-C, II-A, II-B, III, IV, V-A, and V-B mines). 57.22201 Section 57.22201 Mineral Resources MINE SAFETY AND HEALTH....22201 Mechanical ventilation (I-A, I-B, I-C, II-A, II-B, III, IV, V-A, and V-B mines). All mines...

  5. Bond formation effects on the metal-insulator transition in the half-filled kagome Hubbard model

    NASA Astrophysics Data System (ADS)

    Higa, Ryota; Asano, Kenichi

    2016-06-01

    We study the metal-insulator transition in the half-filled Hubbard model on a Kagome lattice using the variational cluster approximation. The strong coupling limit of the model corresponds to the S =1 /2 Kagome Heisenberg antiferromagnet, which is known to have a singlet ground state, although its detail is still debated. As the results of the cluster methods generally depend much on the choice of the unit cluster, we have chosen the clusters that are compatible with these singlet ground states in the strong coupling case found so far, which basically consist of even number of sites. It is found that the correlated electrons on the Kagome lattice have a strong tendency to form valence-bond structures, which are the resonation of electrons on a single bond or several bonds forming loops. The zero-temperature metal-insulator transition at some interaction strength is possibly driven by the formation of such short range valence bonds and shows a second order character, which is distinctive from the Brinkman-Rice scenario. The electrons on these valence bonds further localizes onto each site as the interaction increases, and the valence bonds of electrons finally turn into magnetic singlet bonds between localized S =1 /2 spins, which are consistent with the ground states of the Kagome antiferromagnet.

  6. 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.

  7. THM growth of (Cd, Mn)Te single crystal with the source ingot synthesized by VB method

    NASA Astrophysics Data System (ADS)

    Liang, Wei; Qin, Kaifeng; Zhang, Jijun; Meng, Hua; Wu, Wenqi; Liang, Xiaoyan; Min, Jiahua; Wang, Linjun

    2015-06-01

    The (Cd0.9, Mn0.1)Te crystal was grown by the Traveling Heater method (THM) from the indium-doped source ingot (Cd0.9, Mn0.1)Te which had been synthesized by the Vertical Bridgman (VB) method. The indium-doped (Cd0.9, Mn0.1)Te single crystal with the diameter of 31 mm and length of 130 mm was obtained. The variation of the Mn content was about ±1% along the length of (Cd, Mn)Te: In ingot, and the concentration of Te inclusions in the crystal was ~104 cm-3 with the average diameter of 8-12 μm. Te solvent showed purifying effects during the THM crystal growth, and the indium dopant distributed along the crystal with the concentration of 6.8-10 ppm. IR transmittance and PL spectrum measurements revealed that the as-grown (Cd, Mn)Te crystal possessed high crystalline quality, and its resistivity was up to 6.2×109 Ω cm. Under the 59.5 keV 241Am irradiation, the planar (Cd, Mn)Te detector showed an energy resolution of 12.7%.

  8. Blister formation on 13Cr2MoNbVB ferritic-martensitic steel exposed to hydrogen plasma

    NASA Astrophysics Data System (ADS)

    Nikitin, A. V.; Tolstolutskaya, G. D.; Ruzhytskyi, V. V.; Voyevodin, V. N.; Kopanets, I. E.; Karpov, S. A.; Vasilenko, R. L.; Garner, F. A.

    2016-09-01

    The influence of pre-irradiation specimen deformation level on surface blister formation and sub-surface cracking of dual-phase 13Cr2MoNbVB ferritic-martensitic steel was studied using glow discharge hydrogen plasma with ion energy of 1 keV to fluences of 2 × 1025 H/m2. Protium was used for most studies, but deuterium was used for measuring the depth dependence of hydrogen diffusion. Formation of blisters was observed in the temperature range 230-340 K. It was found that pre-irradiation deformation caused changes in the threshold fluences of blister formation and also in blister size distribution. Subsurface cracks located on grain boundaries far beyond the implantation zone were formed concurrently with blisters, arising from hydrogen diffusion and trapping at defects. It was observed that cracks as long as 1 mm in length were formed in 95% deformed steel at depths up to 500 μm from surface.

  9. Valence-differential spectroscopy of Co-Fe cyanide films

    NASA Astrophysics Data System (ADS)

    Moritomo, Y.; Nakada, F.; Kurihara, Y.

    2009-03-01

    Electrochromism is extensively investigated for practical application of display and memory devices. To develop the material, reliable information on the optical and electronic properties of the solid film is indispensable. Here, we propose valence-differential spectroscopy that can selectively extract the spectral components related to the oxidized/reduced metal site. We applied the spectroscopy to Co2+-Fe2+δ and Co2+δ-Fe2+ cyanide films with finely control of averaged valence (δ) of the transition metal by external electric pulses. The spectroscopy revealed transition energy E, width Γ, and oscillator strength f of the spectral components related to the transition metal.

  10. A diabatic representation including both valence nonadiabatic interactions and spin-orbit effects for reaction dynamics.

    PubMed

    Valero, Rosendo; Truhlar, Donald G

    2007-09-01

    provides a multibond generalization of the switch between Hund's cases in diatomic spectroscopy. The spin-orbit matrix elements in this representation are taken equal to their atomic values times a scaling function that depends on the internuclear distances. The spin-valence diabatic potential energy matrix is suitable for semiclassical dynamics simulations. Diagonalization of this matrix produces the spin-coupled adiabatic energies. For the sake of illustration, diabatic potential energy matrices are constructed along bond-fission coordinates for the HBr and the BrCH(2)Cl molecules. Comparison of the spin-coupled adiabatic energies obtained from the spin-valence diabatics with those obtained by ab initio calculations with geometry-dependent spin-orbit matrix elements shows that the new method is sufficiently accurate for practical purposes. The method formulated here should be most useful for systems with a large number of atoms, especially heavy atoms, and/or a large number of spin-coupled electronic states. PMID:17691756

  11. 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)

  12. What Determines Bond Costs. Municipal Bonds Series.

    ERIC Educational Resources Information Center

    Young, Douglas; And Others

    Public officials in small towns who participate infrequently in the bond market need information about bond financing. This publication, one in a series of booklets published by the Western Rural Development Center using research gathered between 1967-77, discusses factors influencing the marketability and cost of bond financing for towns and…

  13. Variations in the Nature of Triple Bonds: The N2, HCN, and HC2H Series.

    PubMed

    Xu, Lu T; Dunning, Thom H

    2016-07-01

    The inertness of molecular nitrogen and the reactivity of acetylene suggest there are significant variations in the nature of triple bonds. To understand these differences, we performed generalized valence bond as well as more accurate electronic structure calculations on three molecules with putative triple bonds: N2, HCN, and HC2H. The calculations predict that the triple bond in HC2H is quite different from the triple bond in N2, with HCN being an intermediate case but closer to N2 than HC2H. The triple bond in N2 is a traditional triple bond with the spins of the electrons in the bonding orbital pairs predominantly singlet coupled in the GVB wave function (92%). In HC2H, however, there is a substantial amount of residual CH(a(4)Σ(-)) fragment coupling in the triple bond at its equilibrium geometry with the contribution of the perfect pairing spin function dropping to 82% (77% in a full valence GVB calculation). This difference in the nature of the triple bond in N2 and HC2H may well be responsible for the differences in the reactivities of N2 and HC2H. PMID:27299373

  14. Puzzles in bonding and spectroscopy: the case of dicarbon.

    PubMed

    Macrae, Roderick M

    2016-01-01

    The unstable molecule C₂ has been of interest since its identification as the source of the "Swan band" features observable in the spectra offlames, carbon arcs, white dwarf stars, and comets, and it continues to serve as a focal point for experimental and theoretical discovery. Recent spectroscopic work has identified a quintet state of the molecule for the first time, while new insights into the bond order of C₂ in its ground state have been provided by sophisticated computational methods based on valence bond theory. This article gives a review of spectroscopic and computational work on C₂ including both historical background and the most recent discoveries. PMID:27120813

  15. Photofragmentation of a DNA nucleoside thymidine; valence- vs. core ionization

    NASA Astrophysics Data System (ADS)

    Itälä, E.; Kooser, K.; Hägerth, T.; Rachlew, E.; Huels, M. A.; Kukk, E.

    2012-11-01

    The photofragmentation of free thymidine molecule has been studied using combined electron- and ion spectroscopy. The results show that valence- and core ionization processes produce very different fragmentation patterns and that regardless of the photon energy, the photoionization leads almost always to dissociation of the thymidine molecule.

  16. 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

  17. 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…

  18. 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…

  19. 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…

  20. Effective valence proton numbers for nuclei with Z˜64

    NASA Astrophysics Data System (ADS)

    Fu, G. J.; Jiang, H.; Zhao, Y. M.; Arima, A.

    2011-09-01

    The subshell effect for nuclei with proton number Z˜ 64 has been known for many years. The most economic way to consider this effect is to use the effective valence proton number. In this Brief Report we extract effective valence proton numbers for nuclei in this region by using the systematics of the first 2+ energies (E21+) of even-even nuclei, the ratios of the first 4+ and 6+ state energies with respect to E21+ (R4 and R6), the B(E2) values, the quadrupole deformation parameters e2, and anomalous g factors of the 21+ state for even-even nuclei. It is noticed that these physical quantities saturate when NpNn, the product of the valence proton number and the valence neutron number, is large enough; on the other hand, they go to saturation at different “speeds.” We show that the subshell effect is more evident for E21+ and yrast state energy ratios (R4 and R6), and relatively less for other quantities.

  1. Tagging Multiple Emotional Stimuli: Negative Valence Has Little Benefit

    ERIC Educational Resources Information Center

    Watson, Derrick G.; Blagrove, Elisabeth

    2012-01-01

    Six experiments examined the influence of emotional valence on the tagging and enumeration of multiple targets. Experiments 1, 5 and 6 found that there was no difference in the efficiency of tagging/enumerating multiple negative or positive stimuli. Experiment 2 showed that, when neutral-expression face distractors were present, enumerating…

  2. 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…

  3. 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)

  4. 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.

  5. Correlation between valence electronic structure and magnetic properties in RCo5 (R = rare earth) intermetallic compound

    NASA Astrophysics Data System (ADS)

    Zhi-Qin, Xue; Yong-Quan, Guo

    2016-06-01

    The magnetisms of RCo5 (R = rare earth) intermetallics are systematically studied with the empirical electron theory of solids and molecules (EET). The theoretical moments and Curie temperatures agree well with experimental ones. The calculated results show strong correlations between the valence electronic structure and the magnetic properties in RCo5 intermetallic compounds. The moments of RCo5 intermetallics originate mainly from the 3d electrons of Co atoms and 4f electrons of rare earth, and the s electrons also affect the magnetic moments by the hybridization of d and s electrons. It is found that moment of Co atom at 2c site is higher than that at 3g site due to the fact that the bonding effect between R and Co is associated with an electron transformation from 3d electrons into covalence electrons. In the heavy rare-earth-based RCo5 intermetallics, the contribution to magnetic moment originates from the 3d and 4f electrons. The covalence electrons and lattice electrons also affect the Curie temperature, which is proportional to the average moment along the various bonds. Project supported by the National Natural Science Foundation of China (Grant No. 11274110).

  6. Vibrational effects on valence electron momentum distributions of CH{sub 2}F{sub 2}

    SciTech Connect

    Watanabe, Noboru; Yamazaki, Masakazu; Takahashi, Masahiko

    2014-12-28

    We report an electron momentum spectroscopy study of vibrational effects on the electron momentum distributions for the outer valence orbitals of difluoromethane (CH{sub 2}F{sub 2}). The symmetric noncoplanar (e,2e) experiment has been performed at an incident electron energy of 1.2 keV. Furthermore, a theoretical calculation of the electron momentum distributions of the CH{sub 2}F{sub 2} molecule has been carried out with vibrational effects being involved. It is shown from comparisons between experiment and theory that it is essential to take into account influences of the CH{sub 2} asymmetric stretching and CH{sub 2} rocking vibrational modes for a proper understanding of the electron momentum distribution of the 2b{sub 1} orbital having the CH-bonding character. The results of CH{sub 2}F{sub 2}and additional theoretical calculations for (CH{sub 3}){sub 2}O and H{sub 2}CO molecules strongly suggest that vibrational effects on electron momentum distributions tend to be appreciable for non-total symmetry molecular orbitals delocalized over some equivalent CH-bond sites.

  7. Vibrational effects on valence electron momentum distributions of CH2F2.

    PubMed

    Watanabe, Noboru; Yamazaki, Masakazu; Takahashi, Masahiko

    2014-12-28

    We report an electron momentum spectroscopy study of vibrational effects on the electron momentum distributions for the outer valence orbitals of difluoromethane (CH2F2). The symmetric noncoplanar (e,2e) experiment has been performed at an incident electron energy of 1.2 keV. Furthermore, a theoretical calculation of the electron momentum distributions of the CH2F2 molecule has been carried out with vibrational effects being involved. It is shown from comparisons between experiment and theory that it is essential to take into account influences of the CH2 asymmetric stretching and CH2 rocking vibrational modes for a proper understanding of the electron momentum distribution of the 2b1 orbital having the CH-bonding character. The results of CH2F2and additional theoretical calculations for (CH3)2O and H2CO molecules strongly suggest that vibrational effects on electron momentum distributions tend to be appreciable for non-total symmetry molecular orbitals delocalized over some equivalent CH-bond sites. PMID:25554158

  8. 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.

  9. Nature of atomic bonding and atomic structure in the phase-change Ge2Sb2Te5 glass.

    PubMed

    Xu, M; Cheng, Y Q; Sheng, H W; Ma, E

    2009-11-01

    Using electronic structure calculations, we demonstrate a global valence alternation in the amorphous Ge2Sb2Te5, a prototype phase-change alloy for data storage. The resulting p bonding profoundly influences the local atomic structure, leading to right-angle components similar to those in the crystalline counterpart of this chalcogenide glass. The dominance of p bonding is revealed by (i) distributions of the coordination number (CN) and the bond angle, for truly bonded atoms determined based on the electron localization function, and (ii) a direct evaluation of the p (and s) orbital occupation probability for the CN=3 Ge atoms that form 90 degree bonds with neighbors. PMID:20365937

  10. An inducible mouse model for microvillus inclusion disease reveals a role for myosin Vb in apical and basolateral trafficking

    PubMed Central

    Schneeberger, Kerstin; Vogel, Georg F.; Teunissen, Hans; van Ommen, Domenique D.; Begthel, Harry; El Bouazzaoui, Layla; van Vugt, Anke H. M.; Beekman, Jeffrey M.; Klumperman, Judith; Müller, Thomas; Janecke, Andreas; Gerner, Patrick; Huber, Lukas A.; Hess, Michael W.; Clevers, Hans; van Es, Johan H.; Nieuwenhuis, Edward E. S.; Middendorp, Sabine

    2015-01-01

    Microvillus inclusion disease (MVID) is a rare intestinal enteropathy with an onset within a few days to months after birth, resulting in persistent watery diarrhea. Mutations in the myosin Vb gene (MYO5B) have been identified in the majority of MVID patients. However, the exact pathophysiology of MVID still remains unclear. To address the specific role of MYO5B in the intestine, we generated an intestine-specific conditional Myo5b-deficient (Myo5bfl/fl;Vil-CreERT2) mouse model. We analyzed intestinal tissues and cultured organoids of Myo5bfl/fl;Vil-CreERT2 mice by electron microscopy, immunofluorescence, and immunohistochemistry. Our data showed that Myo5bfl/fl;Vil-CreERT2 mice developed severe diarrhea within 4 d after tamoxifen induction. Periodic Acid Schiff and alkaline phosphatase staining revealed subapical accumulation of intracellular vesicles in villus enterocytes. Analysis by electron microscopy confirmed an almost complete absence of apical microvilli, the appearance of microvillus inclusions, and enlarged intercellular spaces in induced Myo5bfl/fl;Vil-CreERT2 intestines. In addition, we determined that MYO5B is involved not only in apical but also basolateral trafficking of proteins. The analysis of the intestine during the early onset of the disease revealed that subapical accumulation of secretory granules precedes occurrence of microvillus inclusions, indicating involvement of MYO5B in early differentiation of epithelial cells. By comparing our data with a novel MVID patient, we conclude that our mouse model completely recapitulates the intestinal phenotype of human MVID. This includes severe diarrhea, loss of microvilli, occurrence of microvillus inclusions, and subapical secretory granules. Thus, loss of MYO5B disturbs both apical and basolateral trafficking of proteins and causes MVID in mice. PMID:26392529

  11. An inducible mouse model for microvillus inclusion disease reveals a role for myosin Vb in apical and basolateral trafficking.

    PubMed

    Schneeberger, Kerstin; Vogel, Georg F; Teunissen, Hans; van Ommen, Domenique D; Begthel, Harry; El Bouazzaoui, Layla; van Vugt, Anke H M; Beekman, Jeffrey M; Klumperman, Judith; Müller, Thomas; Janecke, Andreas; Gerner, Patrick; Huber, Lukas A; Hess, Michael W; Clevers, Hans; van Es, Johan H; Nieuwenhuis, Edward E S; Middendorp, Sabine

    2015-10-01

    Microvillus inclusion disease (MVID) is a rare intestinal enteropathy with an onset within a few days to months after birth, resulting in persistent watery diarrhea. Mutations in the myosin Vb gene (MYO5B) have been identified in the majority of MVID patients. However, the exact pathophysiology of MVID still remains unclear. To address the specific role of MYO5B in the intestine, we generated an intestine-specific conditional Myo5b-deficient (Myo5bfl/fl;Vil-CreERT2) mouse model. We analyzed intestinal tissues and cultured organoids of Myo5bfl/fl;Vil-CreERT2 mice by electron microscopy, immunofluorescence, and immunohistochemistry. Our data showed that Myo5bfl/fl;Vil-CreERT2 mice developed severe diarrhea within 4 d after tamoxifen induction. Periodic Acid Schiff and alkaline phosphatase staining revealed subapical accumulation of intracellular vesicles in villus enterocytes. Analysis by electron microscopy confirmed an almost complete absence of apical microvilli, the appearance of microvillus inclusions, and enlarged intercellular spaces in induced Myo5bfl/fl;Vil-CreERT2 intestines. In addition, we determined that MYO5B is involved not only in apical but also basolateral trafficking of proteins. The analysis of the intestine during the early onset of the disease revealed that subapical accumulation of secretory granules precedes occurrence of microvillus inclusions, indicating involvement of MYO5B in early differentiation of epithelial cells. By comparing our data with a novel MVID patient, we conclude that our mouse model completely recapitulates the intestinal phenotype of human MVID. This includes severe diarrhea, loss of microvilli, occurrence of microvillus inclusions, and subapical secretory granules. Thus, loss of MYO5B disturbs both apical and basolateral trafficking of proteins and causes MVID in mice. PMID:26392529

  12. Using Multiple Bonding Strategies.

    PubMed

    Larson, Thomas D

    2015-01-01

    There are many ways to bond to tooth structure, some micro-mechanical some chemical, some a combination. Different dentin bonding materials have different bonding strengths to differently prepared surfaces, and because of differences in their nature, different areas of tooth structure present peculiar bonding challenges. This paper will review a variety of material types, elucidating their particular bonding strengths and commenting on improved bonding strategies to increase durability, strength, and favorable pulpal response. In this discussion, resin dentin bonding systems, glass ionomers, Gluma, resin cements, and newer combined products will br reviewed. PMID:26485903

  13. Intramolecular Hydrogen Bonds in Low-Molecular-Weight Polyethylene Glycol.

    PubMed

    Kozlowska, Mariana; Goclon, Jakub; Rodziewicz, Pawel

    2016-04-18

    We used static DFT calculations to analyze, in detail, the intramolecular hydrogen bonds formed in low-molecular-weight polyethylene glycol (PEG) with two to five repeat subunits. Both red-shifted O-H⋅⋅⋅O and blue-shifting C-H⋅⋅⋅O hydrogen bonds, which control the structural flexibility of PEG, were detected. To estimate the strength of these hydrogen bonds, the quantum theory of atoms in molecules was used. Car-Parrinello molecular dynamics simulations were used to mimic the structural rearrangements and hydrogen-bond breaking/formation in the PEG molecule at 300 K. The time evolution of the H⋅⋅⋅O bond length and valence angles of the formed hydrogen bonds were fully analyzed. The characteristic hydrogen-bonding patterns of low-molecular-weight PEG were described with an estimation of their lifetime. The theoretical results obtained, in particular the presence of weak C-H⋅⋅⋅O hydrogen bonds, could serve as an explanation of the PEG structural stability in the experimental investigation. PMID:26864943

  14. 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…

  15. Distinct Brain Systems Underlie the Processing of Valence and Arousal of Affective Pictures

    ERIC Educational Resources Information Center

    Nielen, M. M. A.; Heslenfeld, D. J.; Heinen, K.; Van Strien, J. W.; Witter, M. P.; Jonker, C.; Veltman, D. J.

    2009-01-01

    Valence and arousal are thought to be the primary dimensions of human emotion. However, the degree to which valence and arousal interact in determining brain responses to emotional pictures is still elusive. This functional MRI study aimed to delineate neural systems responding to valence and arousal, and their interaction. We measured neural…

  16. 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…

  17. 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…

  18. 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.

  19. Valence band orbital polarization in III-V ferromagnetic semiconductors

    NASA Astrophysics Data System (ADS)

    Freeman, A. A.; Edmonds, K. W.; van der Laan, G.; Campion, R. P.; Rushforth, A. W.; Farley, N. R. S.; Johal, T. K.; Foxon, C. T.; Gallagher, B. L.; Rogalev, A.; Wilhelm, F.

    2008-02-01

    The element-specific technique of x-ray magnetic circular dichroism (XMCD) is used to directly determine the magnitude and character of the valence band orbital magnetic moments in (III,Mn)As ferromagnetic semiconductors. A distinct dichroism is observed at the AsK absorption edge, yielding an As4p orbital magnetic moment of around -0.1μB per valence band hole, which is strongly influenced by strain, indicating its crucial influence on the magnetic anisotropy. The dichroism at the GaK edge is much weaker. The K edge XMCD signals for Mn and As both have positive sign, which indicates the important contribution of Mn4p states to the MnK edge spectra.

  20. Valence-band states of ion-bombarded polystyrene

    SciTech Connect

    Terrasi, A. ); Foti, G. ); Hwu, Y. ); Margaritondo, G. )

    1991-08-01

    Ion-bombarded polystyrene with a 0.5-keV Ar{sup +} beam has been investigated by means of photoelectron spectroscopy performed with synchrotron radiation. After a dose of 10{sup 15} ions/cm{sup 2} the evolution of the valence band of the bombarded sample towards an amorphous carbonlike configuration is reported. From the analysis of valence-band spectra we estimated the out-diffusion of hydrogen and showed that its electronic states remain well identified and stable until the hydrogen presence is about 35% with respect to the pristine sample. Finally, comparison with mass spectroscopy measurements on deuterated polystyrene has been performed to determine hydrogen evolution during the ion irradiation.

  1. Attosecond photoionization dynamics with stimulated core-valence transitions

    NASA Astrophysics Data System (ADS)

    You, Jhih-An; Rohringer, Nina; Dahlström, Jan Marcus

    2016-03-01

    We investigate ionization of neon atoms by an isolated attosecond pump pulse in the presence of two coherent extreme ultraviolet or x-ray probe fields. The probe fields are tuned to a core-valence transition in the residual ion and induce spectral shearing of the photoelectron distributions. We show that the photoelectron-ion coincidence signal contains an interference pattern that depends on the temporal structure of the attosecond pump pulse and the stimulated core-valence transition. Many-body perturbation theory is used to compute "atomic response times" for the processes and we find strikingly different behavior for stimulation to the outer-core hole (2 p ↔2 s ) and stimulation to the inner-core hole (2 p ↔1 s ). The response time of the inner-core transition is found to be comparable to that of state-of-the-art laser-based characterization techniques for attosecond pulses.

  2. Tagging multiple emotional stimuli: negative valence has little benefit.

    PubMed

    Watson, Derrick G; Blagrove, Elisabeth

    2012-06-01

    Six experiments examined the influence of emotional valence on the tagging and enumeration of multiple targets. Experiments 1, 5 and 6 found that there was no difference in the efficiency of tagging/enumerating multiple negative or positive stimuli. Experiment 2 showed that, when neutral-expression face distractors were present, enumerating negative targets was faster overall, but was only more efficient for small numbers of targets. Experiments 3 and 4 determined that this negative target advantage was most likely caused by increased attentional guidance to negatively-valenced stimuli and was not based on simple visual feature differences. The findings suggest that a multiple-target negative stimulus advantage will only occur under conditions of attentional competition, and for relatively small numbers of targets. The results are discussed in relation to theories of multiple- and single-item processing, threat-priority mechanisms, and the types of representations that support different attentional tasks. PMID:22201468

  3. Interchannel coupling effects in the valence photoionization of SF6

    NASA Astrophysics Data System (ADS)

    Jose, Jobin; Lucchese, Robert; Rescigno, Tom

    2014-05-01

    The complex Kohn and polyatomic Schwinger variational techniques have been employed to illustrate the interchannel coupling correlation effects in the valence photoionization dynamics of SF6. Partial photoionization cross sections and asymmetry parameters of six valence subshells (1t1 g, 5t1 u, 1t2 u, 3eg, 1t2 g, 4t1 u) are discussed in the framework of several theoretical and experimental studies. The complex Kohn results are in rather good agreement with experimental results, indicative of the fact that the interchannel coupling effects alter the photoionization dynamics significantly. We find that the dominant effect of interchannel coupling is to reduce the magnitude of shape resonant cross sections near threshold and to induce resonant features in other channels to which resonances are coupled.

  4. Briefly Assessing Repetitive Thought Dimensions: Valence, Purpose, and Total.

    PubMed

    Segerstrom, Suzanne C; Hardy, Jaime K; Evans, Daniel R; Boggero, Ian A; Alden, Lynn E; Stanton, Annette L

    2016-10-01

    Discrete forms of repetitive thought (RT), such as worry and reflection, can be characterized along basic dimensions of valence (positive vs. negative) and purpose (searching vs. solving). In addition, people can be characterized as high or low in their tendency to engage in RT. This dimensional model has been demanding to assess, and a smaller number of items that could stand in for a large battery would make measurement more accessible. Using four samples (N = 1,588), eight items that assess RT valence, purpose, and total in a circumplex model were identified. Across these and other samples, the dimensions were adequately reliable and valid with regard to assessment via large RT battery, other measures of RT, and depressive symptoms. The accessibility of dimensional assessment of RT using this smaller number of items should facilitate work on questions about the qualities of RT that predict mental and physical health. PMID:26019299

  5. Emotional valence and arousal interact in attentional control.

    PubMed

    Jefferies, Lisa N; Smilek, Daniel; Eich, Eric; Enns, James T

    2008-03-01

    A recent study demonstrated that observers' ability to identify targets in a rapid visual sequence was enhanced when they simultaneously listened to happy music. In the study reported here, we examined how the emotion-attention relationship is influenced by changes in both mood valence (negative vs. positive) and arousal (low vs. high). We used a standard induction procedure to generate calm, happy, sad, and anxious moods in participants. Results for an attentional blink task showed no differences in first-target accuracy, but second-target accuracy was highest for participants with low arousal and negative affect (sad), lowest for those with strong arousal and negative affect (anxious), and intermediate for those with positive affect regardless of their arousal (calm, happy). We discuss implications of this valence-arousal interaction for the control of visual attention. PMID:18315803

  6. 29 CFR 2580.412-20 - Use of existing bonds, separate bonds and additional bonding.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 9 2010-07-01 2010-07-01 false Use of existing bonds, separate bonds and additional..., separate bonds and additional bonding. (a) Additional bonding. Section 13 neither prevents additional... or separate bond. (b) Use of existing bonds. Insofar as a bond currently in use is adequate to...

  7. 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.

  8. On the valence fluctuation in the early actinide metals

    DOE PAGESBeta

    Soderlind, P.; Landa, A.; Tobin, J. G.; Allen, P.; Medling, S.; Booth, C. H.; Bauer, E. D.; Cooley, J. C.; Sokaras, D.; Weng, T. -C.; et al

    2015-12-15

    In this study, recent X-ray measurements suggest a degree of valence fluctuation in plutonium and uranium intermetallics. We are applying a novel scheme, in conjunction with density functional theory, to predict 5f configuration fractions of states with valence fluctuations for the early actinide metals. For this purpose we perform constrained integer f-occupation calculations for the α phases of uranium, neptunium, and plutonium metals. For plutonium we also investigate the δ phase. The model predicts uranium and neptunium to be dominated by the f3 and f4 configurations, respectively, with only minor contributions from other configurations. For plutonium (both α and δmore » phase) the scenario is dramatically different. Here, the calculations predict a relatively even distribution between three valence configurations. The δ phase has a greater configuration fraction of f6 compared to that of the α phase. The theory is consistent with the interpretations of modern X-ray experiments and we present resonant X-ray emission spectroscopy results for α-uranium.« less

  9. 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 (1σ) 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

  10. 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

  11. Interchannel coupling effects in the valence photoionization of SF6

    NASA Astrophysics Data System (ADS)

    Jose, J.; Lucchese, R. R.; Rescigno, T. N.

    2014-05-01

    The complex Kohn and polyatomic Schwinger variational techniques have been employed to illustrate the interchannel coupling correlation effects in the valence photoionization dynamics of SF6. Partial photoionization cross sections and asymmetry parameters of six valence subshells (1t1g, 5t1u, 1t2u, 3eg, 1t2g, 4t1u) are discussed in the framework of several theoretical and experimental studies. The complex Kohn results are in rather good agreement with experimental results, indicative of the fact that the interchannel coupling effects alter the photoionization dynamics significantly. We find that the dominant effect of interchannel coupling is to reduce the magnitude of shape resonant cross sections near the threshold and to induce resonant features in other channels to which resonances are coupled. The long-standing issue concerning ordering of the valence orbitals is addressed and confirmed 4t1u61t2g63eg4(5t1u6+1t2u6) 1t1g6 as the most likely ordering.

  12. Optoelectronic properties of valence-state-controlled amorphous niobium oxide

    NASA Astrophysics Data System (ADS)

    Onozato, Takaki; Katase, Takayoshi; Yamamoto, Akira; Katayama, Shota; Matsushima, Koichi; Itagaki, Naho; Yoshida, Hisao; Ohta, Hiromichi

    2016-06-01

    In order to understand the optoelectronic properties of amorphous niobium oxide (a-NbO x ), we have investigated the valence states, local structures, electrical resistivity, and optical absorption of a-NbO x thin films with various oxygen contents. It was found that the valence states of Nb ion in a-NbO x films can be controlled from 5+  to 4+  by reducing oxygen pressure during film deposition at room temperature, together with changing the oxide-ion arrangement around Nb ion from Nb2O5-like to NbO2-like local structure. As a result, a four orders of magnitude reduction in the electrical resistivity of a-NbO x films was observed with decreasing oxygen content, due to the carrier generation caused by the appearance and increase of an oxygen-vacancy-related subgap state working as an electron donor. The tunable optoelectronic properties of a-NbO x films by valence-state-control with oxygen-vacancy formation will be useful for potential flexible optoelectronic device applications.

  13. 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.

  14. Optoelectronic properties of valence-state-controlled amorphous niobium oxide.

    PubMed

    Onozato, Takaki; Katase, Takayoshi; Yamamoto, Akira; Katayama, Shota; Matsushima, Koichi; Itagaki, Naho; Yoshida, Hisao; Ohta, Hiromichi

    2016-06-29

    In order to understand the optoelectronic properties of amorphous niobium oxide (a-NbO x ), we have investigated the valence states, local structures, electrical resistivity, and optical absorption of a-NbO x thin films with various oxygen contents. It was found that the valence states of Nb ion in a-NbO x films can be controlled from 5+  to 4+  by reducing oxygen pressure during film deposition at room temperature, together with changing the oxide-ion arrangement around Nb ion from Nb2O5-like to NbO2-like local structure. As a result, a four orders of magnitude reduction in the electrical resistivity of a-NbO x films was observed with decreasing oxygen content, due to the carrier generation caused by the appearance and increase of an oxygen-vacancy-related subgap state working as an electron donor. The tunable optoelectronic properties of a-NbO x films by valence-state-control with oxygen-vacancy formation will be useful for potential flexible optoelectronic device applications. PMID:27168317

  15. 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.

  16. On the valence fluctuation in the early actinide metals

    SciTech Connect

    Soderlind, P.; Landa, A.; Tobin, J. G.; Allen, P.; Medling, S.; Booth, C. H.; Bauer, E. D.; Cooley, J. C.; Sokaras, D.; Weng, T. -C.; Nordlund, D.

    2015-12-15

    In this study, recent X-ray measurements suggest a degree of valence fluctuation in plutonium and uranium intermetallics. We are applying a novel scheme, in conjunction with density functional theory, to predict 5f configuration fractions of states with valence fluctuations for the early actinide metals. For this purpose we perform constrained integer f-occupation calculations for the α phases of uranium, neptunium, and plutonium metals. For plutonium we also investigate the δ phase. The model predicts uranium and neptunium to be dominated by the f3 and f4 configurations, respectively, with only minor contributions from other configurations. For plutonium (both α and δ phase) the scenario is dramatically different. Here, the calculations predict a relatively even distribution between three valence configurations. The δ phase has a greater configuration fraction of f6 compared to that of the α phase. The theory is consistent with the interpretations of modern X-ray experiments and we present resonant X-ray emission spectroscopy results for α-uranium.

  17. 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

  18. 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.

  19. Korteweg-deVries-Burgers (KdVB) equation in a five component cometary plasma with kappa described electrons and ions

    NASA Astrophysics Data System (ADS)

    Michael, Manesh; Willington, Neethu T.; Jayakumar, Neethu; Sebastian, Sijo; Sreekala, G.; Venugopal, Chandu

    2016-07-01

    We investigate the existence of ion-acoustic shock waves in a five component cometary plasma consisting of positively and negatively charged oxygen ions, kappa described hydrogen ions, hot solar electrons, and slightly colder cometary electrons. The KdVB equation has been derived for the system, and its solution plotted for different kappa values, oxygen ion densities, as well as the temperature ratios for the ions. It is found that the amplitude of the shock wave decreases with increasing kappa values. The strength of the shock profile decreases with increasing temperatures of the positively charged oxygen ions and densities of negatively charged oxygen ions.

  20. Superatomic orbitals in sixteen-coordinate M@Li16 bonded by metallic bonds.

    PubMed

    Gu, Xiao; Chen, Guo-hong; Ji, Min; Yao, Yong-xin; Gong, Xin-gao

    2012-04-21

    Based on density-functional calculation and genetic algorithm structure search, we propose a series of 16-coordinate core-shell clusters: M@Li(16)(M = Ca, Sr, Ba, Ti, Zr, Hf). A tetrahedral (T(d)) structure with an outer shell of 16 lithium atoms and one enclosed heavy atom is found to be the global minimum in the structural exploration of BaLi(16) based on genetic algorithm. This structure also has lower energy compared to the other isomers we employed in all the MLi(16) clusters. In this structure, the atoms are bonded together by metallic bonds with alkali (IA) and alkaline-earth (IIA) metal atoms. Their corresponding first electronic shells are closed with significant energy gaps because their total numbers of valence electrons fulfil the 18-electron rule. Such a combination could be extended to 20-electron systems by enclosing IVB elements. With simple valence electrons and highly symmetric structures, superatomic molecular orbitals are identified in all of the T(d) clusters. PMID:22437545

  1. Excitations of one-valence-proton, one-valence-neutron nucleus {sup 210}Bi from cold-neutron capture

    SciTech Connect

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

    2015-10-15

    The low-spin structure of one-proton, one-neutron {sup 210}Bi nucleus was investigated in cold-neutron capture reaction on {sup 209}Bi. The γ-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 {sup 210}Bi 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{sup −} octupole vibration in {sup 208}Pb which provides also the possibility of testing the calculations involving the core excitations.

  2. Si-Si bond as a deep trap for electrons and holes in silicon nitride

    NASA Astrophysics Data System (ADS)

    Karpushin, A. A.; Sorokin, A. N.; Gritsenko, V. A.

    2016-02-01

    A two-stage model of the capture of electrons and holes in traps in amorphous silicon nitride Si3N4 has been proposed. The electronic structure of a "Si-Si bond" intrinsic defect in Si3N4 has been calculated in the tight-binding approximation without fitting parameters. The properties of the Si-Si bond such as a giant cross section for capture of electrons and holes and a giant lifetime of trapped carriers have been explained. It has been shown that the Si-Si bond in the neutral state gives shallow levels near the bottom of the conduction band and the top of the valence band, which have a large cross section for capture. The capture of an electron or a hole on this bond is accompanied by the shift of shallow levels by 1.4-1.5 eV to the band gap owing to the polaron effect and a change in the localization region of valence electrons of atoms of the Si-Si bond. The calculations have been proposed with a new method for parameterizing the matrix elements of the tightbinding Hamiltonian taking into account a change in the localization region of valence electrons of an isolated atom incorporated into a solid.

  3. Ferromagnetic bond of Li10 cluster: An alternative approach in terms of effective ferromagnetic sites.

    PubMed

    Donoso, Roberto; Rössler, Jaime; Llano-Gil, Sandra; Fuentealba, Patricio; Cárdenas, Carlos

    2016-09-01

    In this work, a model to explain the unusual stability of atomic lithium clusters in their highest spin multiplicity is presented and used to describe the ferromagnetic bonding of high-spin Li10 and Li8 clusters. The model associates the (lack of-)fitness of Heisenberg Hamiltonian with the degree of (de-)localization of the valence electrons in the cluster. It is shown that a regular Heisenberg Hamiltonian with four coupling constants cannot fully explain the energy of the different spin states. However, a more simple model in which electrons are located not at the position of the nuclei but at the position of the attractors of the electron localization function succeeds in explaining the energy spectrum and, at the same time, explains the ferromagnetic bond found by Shaik using arguments of valence bond theory. In this way, two different points of view, one more often used in physics, the Heisenberg model, and the other in chemistry, valence bond, come to the same answer to explain those atypical bonds. PMID:27608996

  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. Metal-Metal Bonds in Biology

    PubMed Central

    Lindahl, Paul A.

    2011-01-01

    Nickel-containing carbon monoxide dehydrogenases, acetyl-CoA synthases, nickel-iron hydrogenases, and diron hydrogenases are distinct metalloenzymes yet they share a number of important characteristics. All are O2-sensitive, with active-sites composed of iron and/or nickel ions coordinated primarily by sulfur ligands. In each case, two metals are juxtaposed at the “heart” of the active site, within range of forming metal-metal bonds. These active-site clusters exhibit multielectron redox abilities and must be reductively activated for catalysis. Reduction potentials are milder than expected based on formal oxidation state changes. When reductively activated, each cluster attacks an electrophilic substrate via an oxidative addition reaction. This affords a two-electron-reduced substrate bound to one or both metals of an oxidized cluster. M-M bonds have been established in hydrogenases where they serve to initiate the oxidative addition of protons and perhaps stabilize active sites in multiple redox states. The same may be true of the CODH and ACS active sites – Ni-Fe and Ni-Ni bonds in these sites may play critical roles in catalysis, stabilizing low-valence states and initiating oxidative addition of CO2 and methyl group cations, respectively. In this article, the structural and functional commonalities of these metalloenzyme active sites are described, and the case is made for the formation and use of metal-metal bonds in each enzyme mentioned. As a post-script, the importance of Fe-Fe bonds in the nitrogenase FeMoco active site is discussed. PMID:22119810

  6. 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.

  7. Entrapping a Group-VB Transition Metal, Vanadium, within an Endohedral Metallofullerene: V(x)Sc(3-x)N@I(h)-C80 (x = 1, 2).

    PubMed

    Wei, Tao; Wang, Song; Lu, Xing; Tan, Yuanzhi; Huang, Jing; Liu, Fupin; Li, Qunxiang; Xie, Suyuan; Yang, Shangfeng

    2016-01-13

    So far the entrapped metals for the isolated endohedral metallofullerenes (EMFs) are primarily limited to rare earth metals, whereas except group-IVB metals, whether it is possible to entrap other d-block transition metals remains unclear. Herein we report the successful entrapment of the group-VB transition metal vanadium(V) into fullerene cage, affording the heretofore unknown V-containing EMFs. Two novel V-containing EMFs--V(x)Sc(3-x)N@C80 (x = 1, 2)--were isolated, and their molecular structures were unambiguously determined by X-ray crystallography to be I(h)(7)-C80 cage entrapping the planar VSc2N/V2ScN clusters. V(x)Sc(3-x)N@I(h)(7)-C80 (x = 1, 2) were further characterized by UV-vis-NIR and ESR spectroscopies and electrochemistry, revealing that the electronic and magnetic properties of V(x)Sc(3-x)N@I(h)(7)-C80 (x = 1, 2) are tunable upon varying the number of entrapped V atoms (i.e., x value). The molecular structures and electronic properties of V(x)Sc(3-x)N@I(h)(7)-C80 (x = 1, 2) were further compared with those of the reported analogous EMFs based on lanthanide metals and the adjacent group-IVB transition metal Ti, revealing the peculiarity of the group-VB transition metal V-based EMFs. PMID:26645852

  8. Rapid adhesive bonding concepts

    NASA Technical Reports Server (NTRS)

    Stein, B. A.; Tyeryar, J. R.; Hodges, W. T.

    1984-01-01

    Adhesive bonding in the aerospace industry typically utilizes autoclaves or presses which have considerable thermal mass. As a consequence, the rates of heatup and cooldown of the bonded parts are limited and the total time and cost of the bonding process is often relatively high. Many of the adhesives themselves do not inherently require long processing times. Bonding could be performed rapidly if the heat was concentrated in the bond lines or at least in the adherends. Rapid adhesive bonding concepts were developed to utilize induction heating techniques to provide heat directly to the bond line and/or adherends without heating the entire structure, supports, and fixtures of a bonding assembly. Bonding times for specimens are cut by a factor of 10 to 100 compared to standard press bonding. The development of rapid adhesive bonding for lap shear specimens (per ASTM D1003 and D3163), for aerospace panel bonding, and for field repair needs of metallic and advanced fiber reinforced polymeric matrix composite structures are reviewed.

  9. Bonding Effects on the Slip Differences in the B 1 Monocarbides

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    Differences in plasticity are usually attributed to significant changes in crystalline symmetry or the strength of the interatomic bonds. In the B 1 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.

  10. Generally Contracted Valence-Core/Valence Basis Sets for Use with Relativistic Effective Core Potentials and Spin-Orbit Coupling Operators

    SciTech Connect

    Ermler, Walter V.; Tilson, Jeffrey L.

    2012-12-15

    A procedure for structuring generally contracted valence-core/valence basis sets of Gaussian-type functions for use with relativistic effective core potentials (gcv-c/v-RECP basis sets) is presented. Large valence basis sets are enhanced using a compact basis set derived for outer core electrons in the presence of small-core RECPs. When core electrons are represented by relativistic effective core potentials (RECPs), and appropriate levels of theory, these basis sets are shown to provide accurate representations of atomic and molecular valence and outer-core electrons. Core/valence polarization and correlation effects can be calculated using these basis sets through standard methods for treating electron correlation. Calculations of energies and spectra for Ru, Os, Ir, In and Cs are reported. Spectroscopic constants for RuO2+, OsO2+, Cs2 and InH are calculated and compared with experiment.

  11. Valence state parameters of all transition metal atoms in metalloproteins--development of ABEEMσπ fluctuating charge force field.

    PubMed

    Yang, Zhong-Zhi; Wang, Jian-Jiang; Zhao, Dong-Xia

    2014-09-01

    To promote accuracy of the atom-bond electronegativity equalization method (ABEEMσπ) fluctuating charge polarizable force fields, and extend it to include all transition metal atoms, a new parameter, the reference charge is set up in the expression of the total energy potential function. We select over 700 model molecules most of which model metalloprotein molecules that come from Protein Data Bank. We set reference charges for different apparent valence states of transition metals and calibrate the parameters of reference charges, valence state electronegativities, and valence state hardnesses for ABEEMσπ through linear regression and least square method. These parameters can be used to calculate charge distributions of metalloproteins containing transition metal atoms (Sc-Zn, Y-Cd, and Lu-Hg). Compared the results of ABEEMσπ charge distributions with those obtained by ab initio method, the quite good linear correlations of the two kinds of charge distributions are shown. The reason why the STO-3G basis set in Mulliken population analysis for the parameter calibration is specially explained in detail. Furthermore, ABEEMσπ method can also quickly and quite accurately calculate dipole moments of molecules. Molecular dynamics optimizations of five metalloproteins as the examples show that their structures obtained by ABEEMσπ fluctuating charge polarizable force field are very close to the structures optimized by the ab initio MP2/6–311G method. This means that the ABEEMσπ/MM can now be applied to molecular dynamics simulations of systems that contain metalloproteins with good accuracy. PMID:25042901

  12. The site occupation and valence of Mn ions in the crystal lattice of Sr{sub 4}Al{sub 14}O{sub 25} and its deep red emission for high color-rendering white light-emitting diodes

    SciTech Connect

    Chen, Lei; Xue, Shaochan; Chen, Xiuling; Bahader, Ali; Deng, Xiaorong; Zhao, Erlong; Jiang, Yang; Chen, Shifu; Chan, Ting-Shan; Zhao, Zhi; Zhang, Wenhua

    2014-12-15

    Highlights: • Different valences of Mn ions in Sr{sub 4}Al{sub 14}O{sub 25} were identified using XANES and EPR. • Red luminescence was attributed to Mn{sup 4+} occupying the center of AlO{sub 6} octahedron. • The Mn{sup 3+} incorporated in the center of AlO{sub 4} tetrahedron was non-luminescent. • The bond-valence theory was used to analyze the effective valences of cations. • A white LED device with CRI up to Ra 93.23 was packaged by using the red phosphor. - Abstract: The synthesis and component of red phosphor, Sr{sub 4}Al{sub 14}O{sub 25}: Mn, were optimized for application in white light-emitting diodes. The microstructure and morphology were investigated by the X-ray diffraction and scanning electron microscopy. Different valences of Mn ions in Sr{sub 4}Al{sub 14}O{sub 25} were discriminated using the electron paramagnetic resonance and X-ray absorption near-edge structure spectroscopy techniques. The bond-valence theory was used to analyze the effective valences of Sr{sup 2+} and Al{sup 3+} in Sr{sub 4}Al{sub 14}O{sub 25}. As a result, the strong covalence of Al{sup 3+} in the AlO{sub 4} tetrahedron other than in the AlO{sub 6} octahedron is disclosed. The deep red emission is attributed to Mn{sup 4+} occupying the center of AlO{sub 6} octahedron. The mechanism of energy transfer is mainly through dipole–dipole interaction, revealed by the analyses of critical distance and concentration quench. A high color rendering white LED prototype with color-rendering index up to Ra 93.23 packaged by using the red phosphor demonstrates its applicability.

  13. 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

  14. Valence-quark distribution functions in the kaon and pion

    NASA Astrophysics Data System (ADS)

    Chen, Chen; Chang, Lei; Roberts, Craig D.; Wan, Shaolong; Zong, Hong-Shi

    2016-04-01

    We describe expressions for pion and kaon dressed-quark distribution functions that incorporate contributions from gluons which bind quarks into these mesons and hence overcome a flaw of the commonly used handbag approximation. The distributions therewith obtained are purely valence in character, ensuring that dressed quarks carry all the meson's momentum at a characteristic hadronic scale and vanish as (1 -x )2 when Bjorken-x →1 . Comparing such distributions within the pion and kaon, it is apparent that the size of S U (3 ) -flavor symmetry breaking in meson parton distribution functions is modulated by the flavor dependence of dynamical chiral symmetry breaking. Corrections to these leading-order formulas may be divided into two classes, responsible for shifting dressed-quark momentum into glue and sea quarks. Working with available empirical information, we build an algebraic framework that is capable of expressing the principal impact of both classes of corrections. This enables a realistic comparison with experiment which allows us to identify and highlight basic features of measurable pion and kaon valence-quark distributions. We find that whereas roughly two thirds of the pion's light-front momentum is carried by valence dressed quarks at a characteristic hadronic scale; this fraction rises to 95% in the kaon; evolving distributions with these features to a scale typical of available Drell-Yan data produces a kaon-to-pion ratio of u -quark distributions that is in agreement with the single existing data set, and predicts a u -quark distribution within the pion that agrees with a modern reappraisal of π N Drell-Yan data. Precise new data are essential in order to validate this reappraisal and because a single modest-quality measurement of the kaon-to-pion ratio cannot be considered definitive.

  15. Bonding thermoplastic polymers

    DOEpatents

    Wallow, Thomas I.; Hunter, Marion C.; Krafcik, Karen Lee; Morales, Alfredo M.; Simmons, Blake A.; Domeier, Linda A.

    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.

  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. Creating σ-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 σ-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 σ-hole is another manifestation of the bond activation-reinforcement (BAR) rule. The appearance of a σ-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 σ-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

  18. Aging and long-term memory for emotionally valenced events.

    PubMed

    Breslin, Carolyn W; Safer, Martin A

    2013-06-01

    In 2008, 1103 ardent Boston Red Sox fans answered questions about their team's 2003 loss and 2004 win in baseball championship games with archrival New York Yankees. Contrary to predictions based on socioemotional selectivity theory, there were no significant interactions of age and event valence for accuracy in remembering event details, or for self-reported subjective vividness and rehearsal of the memories. Fans 65 years and older tended to remember feeling only sad about the 2003 loss, whereas fans 25 years and under tended to remember feeling both sad and angry. Individuals may remember emotional feelings based on remembered goals about an event. PMID:22888956

  19. Pion and kaon valence-quark parton distribution functions

    NASA Astrophysics Data System (ADS)

    Nguyen, Trang; Bashir, Adnan; Roberts, Craig D.; Tandy, Peter C.

    2011-06-01

    A rainbow-ladder truncation of QCD’s Dyson-Schwinger equations, constrained by existing applications to hadron physics, is employed to compute the valence-quark parton distribution functions of the pion and kaon. Comparison is made to π-N Drell-Yan data for the pion’s u-quark distribution and to Drell-Yan data for the ratio uK(x)/uπ(x): the environmental influence of this quantity is a parameter-free prediction, which agrees well with existing data. Our analysis unifies the computation of distribution functions with that of numerous other properties of pseudoscalar mesons.

  20. Pion and kaon valence-quark parton distribution functions.

    SciTech Connect

    Nguyen, T.; Bashir, A.; Roberts, C. D.; Tandy, P. C.

    2011-06-16

    A rainbow-ladder truncation of QCD's Dyson-Schwinger equations, constrained by existing applications to hadron physics, is employed to compute the valence-quark parton distribution functions of the pion and kaon. Comparison is made to {pi}-N Drell-Yan data for the pion's u-quark distribution and to Drell-Yan data for the ratio u{sub K}(x)/u{sub {pi}}(x): the environmental influence of this quantity is a parameter-free prediction, which agrees well with existing data. Our analysis unifies the computation of distribution functions with that of numerous other properties of pseudoscalar mesons.

  1. Pion and kaon valence-quark parton distribution functions

    SciTech Connect

    Nguyen, Trang; Bashir, Adnan; Roberts, Craig D.; Tandy, Peter C.

    2011-06-15

    A rainbow-ladder truncation of QCD's Dyson-Schwinger equations, constrained by existing applications to hadron physics, is employed to compute the valence-quark parton distribution functions of the pion and kaon. Comparison is made to {pi}-N Drell-Yan data for the pion's u-quark distribution and to Drell-Yan data for the ratio u{sub K}(x)/u{sub {pi}}(x): the environmental influence of this quantity is a parameter-free prediction, which agrees well with existing data. Our analysis unifies the computation of distribution functions with that of numerous other properties of pseudoscalar mesons.

  2. Torsionally controlled electronic coupling in mixed-valence oxodimolybdenum nitrosyl scorpionates--a DFT study.

    PubMed

    Romańczyk, Piotr P; Noga, Klemens; Włodarczyk, Andrzej J; Nitek, Wojciech; Broclawik, Ewa

    2010-09-01

    The density functional theory (DFT) method has been used to study the electronic communication in strongly interacting oxo-bridged di-{Mo(II,I)(NO(+))}(3+,2+) complexes stabilized by tris(3-methylpyrazol-1-yl)borate, [Tp(Me)](-) (dihydroxy 1' and its modified analogs), having fully localized valences on the two Mo centers (Class I), despite a short (ca. 3.8 A) Mo...Mo distance. Structural and electrochemical (separation between the redox potentials Delta(red/ox)E(1/2)) properties and IR spectra (in particular the nu(NO) frequencies) obtained from the B3LYP calculations for 1' are successfully related to experimental values. Strongly twisted geometry with the (O)N-Mo1...Mo2-N(O) angle close to 90 degrees (confirmed by DFT modeling performed for 1'(-1,0,+1) and X-ray diffraction study of [{Mo(NO)(Tp(Me2))(OH)}(2)(mu-O)](-) (1) presented herein) is a common, though so far not fully understood, structural feature of this class of mu-oxo species, in contrast to the closely related {Mo(V)(=O)}(3+) analogs. This study shows that the orthogonality of the local equatorial planes for the two Mo centers may be rationalized by the electronic structure, namely from the balance between the destabilizing repulsion of the Mo-based (d, pi(x)*)(b) electron pairs versus a favorable but relatively weak electron delocalization. Strongly repelling electron pairs avoid each other, which enforces the twisted geometries and blocks the electron delocalization. Steric hindrance (a nonbonding repulsion of the adjacent Tp(x) ligands and the weak hydrogen-bonding interactions, i.e., OH...ON, OH...OH, and C-H...O((NO/OH))) is shown not to be decisive since neither the removal of the inner 3-Me groups of [Tp(Me)](-) in complex 1' nor the substitution of OH groups by OCH(3) ligands did substantially influence the dihedral twist angle in the minimum energy structure. Yet the relative orientation of the {Mo(NO)}(2+,3+) cores along with the position of the bridging oxygen (significantly bent upon

  3. Simple Bond Cleavage

    SciTech Connect

    Gary S. Groenewold

    2005-08-01

    Simple bond cleavage is a class of fragmentation reactions in which a single bond is broken, without formation of new bonds between previously unconnected atoms. Because no bond making is involved, simple bond cleavages are endothermic, and activation energies are generally higher than for rearrangement eliminations. The rate of simple bond cleavage reactions is a strong function of the internal energy of the molecular ion, which reflects a loose transition state that resembles reaction products, and has a high density of accessible states. For this reason, simple bond cleavages tend to dominate fragmentation reactions for highly energized molecular ions. Simple bond cleavages have negligible reverse activation energy, and hence they are used as valuable probes of ion thermochemistry, since the energy dependence of the reactions can be related to the bond energy. In organic mass spectrometry, simple bond cleavages of odd electron ions can be either homolytic or heterolytic, depending on whether the fragmentation is driven by the radical site or the charge site. Simple bond cleavages of even electron ions tend to be heterolytic, producing even electron product ions and neutrals.

  4. Control of valence and conduction band energies in layered transition metal phosphates via surface functionalization.

    PubMed

    Lentz, Levi C; Kolb, Brian; Kolpak, Alexie M

    2016-05-18

    Layered transition metal phosphates and phosphites (TMPs) are a class of materials composed of layers of 2D sheets bound together via van der Waals interactions and/or hydrogen bonds. Explored primarily for use in proton transfer, their unique chemical tunability also makes TMPs of interest for forming large-scale hybrid materials. Further, unlike many layered materials, TMPs can readily be solution exfoliated to form single 2D sheets or bilayers, making them exciting candidates for a variety of applications. However, the electronic properties of TMPs have largely been unstudied to date. In this work, we use first-principles computations to investigate the atomic and electronic structure of TMPs with a variety of stoichiometries. We demonstrate that there exists a strong linear relationship between the band gap and the ionic radius of the transition metal cation in these materials, and show that this relationship, which opens opportunities for engineering new compositions with a wide range of band gaps, arises from constraints imposed by the phosphorus-oxygen bond geometry. In addition, we find that the energies of the valence and conduction band edges can be systematically tuned over a range of ∼3 eV via modification of the functional group extending from the phosphorus. Based on the Hammett constant of this functional group, we identify a simple, predictive relationship for the ionization potential and electron affinity of layered TMPs. Our results thus provide guidelines for systematic design of TMP-derived functional materials, which may enable new approaches for optimizing charge transfer in electronics, photovoltaics, electrocatalysts, and other applications. PMID:27157509

  5. Charge density waves and local states in quasi-one-dimensional mixed valence inorganic complexes

    NASA Astrophysics Data System (ADS)

    Conradson, S. D.; Stroud, M. A.; Zietlow, M. H.; Swanson, B. I.; Baeriswyl, D.; Bishop, A. R.

    1988-02-01

    The ground state structures and local states associated with chemical defects in quasi-one-dimensional halogen ( X) bridged transition metal ( M) mixed valence solids of MX and MMX type have been studied. An adiabatic Hartree-Fock theoretical framework is presented and representative members are classified. The MX materials provide a class whose strong electron-phonon coupling usually favors a charge-density-wave (CDW) ground state. However, the coupling strength can be chemically tuned (e.g., by extension to MMX systems) or altered by pressure, driving the ground state structures towards, e.g., a bond-order-wave (BOW) phase. Electron-phonon driven self-trapped states are expected in both the CDW or BOW regimes. Resonance Raman spectra of the MMX solid K 4[Pt 2(P 2O 5H 2) 4Cl]·H 2O show, in addition to the homogeneous ground state modes, sharp new features with excitation profiles shifted to the red of the intervalence-charge-transfer (IVCT) band. We attribute these new bands to a local polaron state formed by oxidation of the Pt 2Cl chain by a chemical defect. The observed spectral characteristics of this local state are in good agreement with theoretical predictions.

  6. Solvent-Triggered Cis/Trans Isomerism in Cobalt Dioxolene Chemistry: Distinguishing Effects of Packing on Valence Tautomerism.

    PubMed

    Panja, Anangamohan; Jana, Narayan Ch; Bauzá, Antonio; Frontera, Antonio; Mathonière, Corine

    2016-09-01

    In this article, the synthesis and X-ray crystal structures of two cis/trans isomers of valence tautomeric (VT) cobalt dioxolene compounds are reported. The cis isomer (1) was isolated from the polar protic methanol solvent as a kinetic product, whereas the less polar nonprotic solvent acetone yielded the trans isomer (2). It should be noted that, although some coordination polymers involving cobalt bis(dioxolene) with the cis disposition are known for bridging ancillary ligands, such an arrangement is unprecedented for mononuclear compounds. A careful study of intermocular interactions revealed that the methanol solvent does not have much influence on the crystal growth in 1, whereas acetone forms strong halogen-bonding interactions that are crucial in the solid-state architecture of 2. This behavior can likely be used in crystal engineering to design new organic-inorganic hybrid materials. The energy difference between the two isomers was examined using DFT calculations, confirming that the trans form is in the thermodynamic state whereas the cis isomer is a kinetic product that can be converted into the trans isomer with time. Finally, both isomers exhibit solvent loss at elevated temperatures that is accompanied by a change in magnetic properties, associated with an irreversible valence tautomerism. Our results highlight the crucial role of the solvents for the isolation of cis/trans isomers in cobalt dioxolene chemistry, as well as the distinguishing effects of intermolecular forces and the solid-state packing on VT behavior. PMID:27557848

  7. +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.

  8. 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

  9. Ignoring real faces: effects of valence, threat, and salience.

    PubMed

    Blagrove, Elisabeth; Watson, Derrick G

    2014-04-01

    Facial stimuli have been shown to accrue a special status within visual processing, particularly when attention is prioritized to one face over another on the basis of affective content. This has been examined in relation to the ability of faces to guide or hold attention, or to resist attentional suppression. Previous work has shown that schematic faces can only be partially ignored and that the emotional valence of to-be-ignored faces has little effect. Given recent debates concerning the use of schematic faces, here we examined the ease with which photorealistic faces could be ignored. Although we found evidence of a partial preview benefit for these stimuli, the findings were complex, with stimulus salience, valence, and threat content interacting to affect both the strength of the benefit and target detection efficiency (Exps. 1-3). Experiment 4 then clarified the effects of physical salience and perceived stimulus similarity in the previous experiments, demonstrating that a combination of these factors is likely to account for the search patterns observed. PMID:24435898

  10. Tunable topological valence in nematic shells on spherocylindrical colloidal particles

    NASA Astrophysics Data System (ADS)

    de Oliveira, E. J. L.; de Oliveira, I. N.; Lyra, M. L.; Mirantsev, L. V.

    2016-01-01

    We perform molecular dynamics simulations of the orientational ordering on nematic shells delimited by spherocylindrical nanoscopic colloidal particles. We show that under conditions of degenerate planar anchoring, the equilibrium director field structure in these shells exhibits pairs of +1 /2 topological defects at the poles of spherical cups in the absence of an external electric field. In addition, a certain number of pairs of ±1 /2 defects occurs on the spherical cups far from the poles, thus resulting in a total of eight valence spots. A strong field applied along the main spherocylindrical axis removes the ±1 /2 defect pairs while it coalesces the polar ones into a single +1 topological defect. A strong transverse field destroys all defects on the spherical cups but generates four +1 /2 defects in the cylindrical part. Therefore, an external field can be used to control the number of valence centers in spherocylindrical nematic shells, thus unveiling their capability of acting as multivalent building blocks for nanophotonic devices.

  11. 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

  12. 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

  13. Energetics and thermodynamic stability of the mixed valence ytterbium germanides.

    PubMed

    Balducci, G; Brutti, S; Ciccioli, A; Gigli, G; Palenzona, A; Pani, M

    2007-05-17

    The results of an experimental study concerning the thermodynamic stability of the Yb germanides, described as intermediate valence compounds, complemented by a computational investigation for the Yb3Ge5 compound are reported. These compounds belong to the rare earth (RE) tetrelides (tetrel = Si, Ge, i.e., group 14 elements), a class of intermetallic materials showing unusual and promising physical properties (giant magnetocaloric effect, magnetostriction, and magnetoresistence). The high-temperature decomposition reactions of the Yb-Ge intermediate phases were studied experimentally by means of the KEMS (Knudsen effusion mass spectrometry) and KEWL (Knudsen effusion weight loss) techniques. From the reaction enthalpies derived by measuring the Yb(g) decomposition pressures as a function of temperature, the heats of formation of five out of six of the intermediate phases in the Yb-Ge system were calculated. From the computational side, the stability of the Yb3Ge5(s) compound has been investigated by DFT-LCAO-B3LYP (density functional theory-linear combination of atomic orbitals-hybrid b3lyp exchange-correlation functional) first principles calculations deriving its equilibrium geometry and the enthalpy of formation at 0 K in relation to the intermediate valence state of Yb in the lattice. PMID:17444673

  14. Coupled-cluster based basis sets for valence correlation calculations

    NASA Astrophysics Data System (ADS)

    Claudino, Daniel; Gargano, Ricardo; Bartlett, Rodney J.

    2016-03-01

    Novel basis sets are generated that target the description of valence correlation in atoms H through Ar. The new contraction coefficients are obtained according to the Atomic Natural Orbital (ANO) procedure from CCSD(T) (coupled-cluster singles and doubles with perturbative triples correction) density matrices starting from the primitive functions of Dunning et al. [J. Chem. Phys. 90, 1007 (1989); ibid. 98, 1358 (1993); ibid. 100, 2975 (1993)] (correlation consistent polarized valence X-tuple zeta, cc-pVXZ). The exponents of the primitive Gaussian functions are subject to uniform scaling in order to ensure satisfaction of the virial theorem for the corresponding atoms. These new sets, named ANO-VT-XZ (Atomic Natural Orbital Virial Theorem X-tuple Zeta), have the same number of contracted functions as their cc-pVXZ counterparts in each subshell. The performance of these basis sets is assessed by the evaluation of the contraction errors in four distinct computations: correlation energies in atoms, probing the density in different regions of space via (-3 ≤ n ≤ 3) in atoms, correlation energies in diatomic molecules, and the quality of fitting potential energy curves as measured by spectroscopic constants. All energy calculations with ANO-VT-QZ have contraction errors within "chemical accuracy" of 1 kcal/mol, which is not true for cc-pVQZ, suggesting some improvement compared to the correlation consistent series of Dunning and co-workers.

  15. Coupled-cluster based basis sets for valence correlation calculations.

    PubMed

    Claudino, Daniel; Gargano, Ricardo; Bartlett, Rodney J

    2016-03-14

    Novel basis sets are generated that target the description of valence correlation in atoms H through Ar. The new contraction coefficients are obtained according to the Atomic Natural Orbital (ANO) procedure from CCSD(T) (coupled-cluster singles and doubles with perturbative triples correction) density matrices starting from the primitive functions of Dunning et al. [J. Chem. Phys. 90, 1007 (1989); ibid. 98, 1358 (1993); ibid. 100, 2975 (1993)] (correlation consistent polarized valence X-tuple zeta, cc-pVXZ). The exponents of the primitive Gaussian functions are subject to uniform scaling in order to ensure satisfaction of the virial theorem for the corresponding atoms. These new sets, named ANO-VT-XZ (Atomic Natural Orbital Virial Theorem X-tuple Zeta), have the same number of contracted functions as their cc-pVXZ counterparts in each subshell. The performance of these basis sets is assessed by the evaluation of the contraction errors in four distinct computations: correlation energies in atoms, probing the density in different regions of space via ⟨r(n)⟩ (-3 ≤ n ≤ 3) in atoms, correlation energies in diatomic molecules, and the quality of fitting potential energy curves as measured by spectroscopic constants. All energy calculations with ANO-VT-QZ have contraction errors within "chemical accuracy" of 1 kcal/mol, which is not true for cc-pVQZ, suggesting some improvement compared to the correlation consistent series of Dunning and co-workers. PMID:26979680

  16. Microscopic Examinations of Co Valences and Spin States in Electron-Doped LaCoO3

    NASA Astrophysics Data System (ADS)

    Tomiyasu, Keisuke; Koyama, Syun-Ichi; Watahiki, Masanori; Sato, Mika; Nishihara, Kazuki; Takahashi, Yuki; Onodera, Mitsugi; Iwasa, Kazuaki; Nojima, Tsutomu; Nojiri, Hiroyuki; Okamoto, Jun; Huang, Di-Jing; Yamasaki, Yuuichi; Nakao, Hironori; Murakami, Youichi

    2016-09-01

    We studied the Co valences and spin states in electron-doped LaCo1-yTeyO3 by measuring X-ray absorption spectra and electron spin resonance. The low-temperature insulating state involves the low-spin Co3+ state (S = 0) and the high-spin Co2+ state, where the latter is described by g = 3.8 and jeff = 1/2. The results, in concurrence with the electron-hole asymmetry confirmed in the electrical resistivity, coincide with the spin-blockade phenomenon in this system. Furthermore, we discuss the g factor in terms of the strong covalent-bonding nature and consider multiple origins of this phenomenon.

  17. Weak bond screening system

    NASA Astrophysics Data System (ADS)

    Chuang, S. Y.; Chang, F. H.; Bell, J. R.

    Consideration is given to the development of a weak bond screening system which is based on the utilization of a high power ultrasonic (HPU) technique. The instrumentation of the prototype bond strength screening system is described, and the adhesively bonded specimens used in the system developmental effort are detailed. Test results obtained from these specimens are presented in terms of bond strength and level of high power ultrasound irradiation. The following observations were made: (1) for Al/Al specimens, 2.6 sec of HPU irradiation will screen weak bond conditions due to improper preparation of bonding surfaces; (2) for composite/composite specimens, 2.0 sec of HPU irradiation will disrupt weak bonds due to under-cured conditions; (3) for Al honeycomb core with composite skin structure, 3.5 sec of HPU irradiation will disrupt weak bonds due to bad adhesive or oils contamination of bonding surfaces; and (4) for Nomex honeycomb with Al skin structure, 1.3 sec of HPU irradiation will disrupt weak bonds due to bad adhesive.

  18. A continuous mapping between space and valence with left- and right-handers.

    PubMed

    Freddi, Sébastien; Brouillet, Thibaut; Cretenet, Joël; Heurley, Loïc P; Dru, Vincent

    2016-06-01

    In this research, we examined whether emotional valence could correspond to a continuous lateral bias in space, according to a mental metaphor that establishes the mapping between a concrete domain (space) and an abstract one (valence). Because acting with one's dominant hand is associated with fluency and positive valence (the bodily specificity hypothesis, or BSH), we asked strong right- and left-handers to perform two spatial location tasks using emotional faces with seven levels of valence. We hypothesized and showed through two studies that, according to the BSH, extreme valenced stimuli (as compared to moderate and weak ones) would be located more at the extremity of a horizontal line, according to the correspondences between handedness and the different valences of the stimuli. This research establishes that spatial and continuous mapping of emotions was obtained while controlling for motivational direction. PMID:26428669

  19. 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

  20. First-Order Structural Change Accompanied by Yb Valence Transition in YbInCu4

    NASA Astrophysics Data System (ADS)

    Tsutsui, Satoshi; Sugimoto, Kunihisa; Tsunoda, Ryoma; Hirose, Yusuke; Mito, Takeshi; Settai, Rikio; Mizumaki, Masaichiro

    2016-06-01

    A diffraction experiment using high-energy X-rays was carried out on YbInCu4. Below the Yb valence transition temperature, the splitting of Bragg peaks was detected in high-order reflections. No superlattice reflections accompanying the valence ordering were found below the transition temperature. These experimental findings indicate that a structural change from a cubic structure to a tetragonal structure without valence ordering occurs at the transition temperature. Such a structural change free from any valence ordering is difficult to understand only in terms of Yb valence degrees of freedom. This means that the structural change may be related to electronic symmetries such as quadrupolar degrees of freedom as well as to the change in Yb valence.

  1. Processing negative valence of word pairs that include a positive word.

    PubMed

    Itkes, Oksana; Mashal, Nira

    2016-09-01

    Previous research has suggested that cognitive performance is interrupted by negative relative to neutral or positive stimuli. We examined whether negative valence affects performance at the word or phrase level. Participants performed a semantic decision task on word pairs that included either a negative or a positive target word. In Experiment 1, the valence of the target word was congruent with the overall valence conveyed by the word pair (e.g., fat kid). As expected, response times were slower in the negative condition relative to the positive condition. Experiment 2 included target words that were incongruent with the overall valence of the word pair (e.g., fat salary). Response times were longer for word pairs whose overall valence was negative relative to positive, even though these word pairs included a positive word. Our findings support the Cognitive Primacy Hypothesis, according to which emotional valence is extracted after conceptual processing is complete. PMID:26008637

  2. 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}.

  3. Bonded semiconductor substrate

    DOEpatents

    Atwater, Jr.; Harry A. , Zahler; James M.

    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.

  4. 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.

  5. Structural evolution and valence electron-state change during ultra thin silicon-oxide growth

    NASA Astrophysics Data System (ADS)

    Shimizu, A.; Abe, S.; Nakayama, H.; Nishino, T.; Iida, S.

    2000-06-01

    We have studied valence electron-state changes of Si during initial oxidation of Si(111) clean surface, HF-treated Si(001) and Si(111) surfaces by Auger valence electron spectroscopy (AVES). The results showed that the valence electron-state changes during initial oxidation were sensitively reflected in Si[2s,2p,V] (V=3s,3p) AVES spectra and that they depended on both initial surface treatment and surface orientation. The local valence electron-states, local density of states in other words, showed the characteristic-structure evolution depending on the initial surface treatment and surface orientation.

  6. 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.

  7. Energy pulse bonding

    NASA Technical Reports Server (NTRS)

    Smith, G. C.

    1972-01-01

    To eliminate many of the present termination problems a technique called energy pulse bonding (EPB) was developed. The process demonstrated the capability of: (1) joining conductors without prior removal of insulations, (2) joining conductors without danger of brittle intermetallics, (3) increased joint temperature capability, (4) simultaneous formation of several bonds, (5) capability of higher joint density, and (6) a production oriented process. The following metals were successfully bonded in the solid state: copper, beryllium copper, phosphor bronze, aluminum, brass, and Kovar.

  8. BONDING ALUMINUM METALS

    DOEpatents

    Noland, R.A.; Walker, D.E.

    1961-06-13

    A process is given for bonding aluminum to aluminum. Silicon powder is applied to at least one of the two surfaces of the two elements to be bonded, the two elements are assembled and rubbed against each other at room temperature whereby any oxide film is ruptured by the silicon crystals in the interface; thereafter heat and pressure are applied whereby an aluminum-silicon alloy is formed, squeezed out from the interface together with any oxide film, and the elements are bonded.

  9. 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.

  10. Influence of alloy microstructure on the microshear bond strength of basic alloys to a resin luting cement.

    PubMed

    Bauer, José; Costa, José Ferreira; Carvalho, Ceci Nunes; Souza, Douglas Nesadal de; Loguercio, Alessandro Dourado; Grande, Rosa Helena Miranda

    2012-01-01

    The aim of this study was to evaluate the influence of microstructure and composition of basic alloys on their microshear bond strength (µSBS) to resin luting cement. The alloys used were: Supreme Cast-V (SC), Tilite Star (TS), Wiron 99 (W9), VeraBond II (VBII), VeraBond (VB), Remanium (RM) and IPS d.SIGN 30 (IPS). Five wax patterns (13 mm in diameter and 4mm height) were invested, and cast in a centrifugal casting machine for each basic alloy. The specimens were embedded in resin, polished with a SiC paper and sandblasted. After cleaning the metal surfaces, six tygon tubes (0.5 mm height and 0.75 mm in diameter) were placed on each alloy surface, the resin cement (Panavia F) was inserted, and the excess was removed before light-curing. After storage (24 h/37°C), the specimens were subjected to µSBS testing (0.5 mm/min). The data were subjected to a one-way repeated measures analysis of variance and Turkey's test (α=0.05). After polishing, their microstructures were revealed with specific conditioners. The highest µSBS (mean/standard deviation in MPa) were observed in the alloys with dendritic structure, eutectic formation or precipitation: VB (30.6/1.7), TS (29.8/0.9), SC (30.6/1.7), with the exception of IPS (31.1/0.9) which showed high µSBS but no eutectic formation. The W9 (28.1/1.5), VBII (25.9/2.0) and RM (25.9/0.9) showed the lowest µSBS and no eutectic formation. It seems that alloys with eutectic formation provide the highest µSBS values when bonded to a light-cured resin luting cement. PMID:23306223

  11. Many-body calculation of the valence photoemission spectrum of Cr(CO)6

    NASA Astrophysics Data System (ADS)

    Ohno, M.; von Niessen, W.; Tarantelli, F.

    1992-01-01

    The valence photoemission spectrum of Cr(CO)6 is calculated by the third-order algebraic-diagrammatic-construction Green's-function method. The overall agreement with experiment is good. It is shown that the quasiparticle picture of the levels derived primarily from the CO 1π and 4(5)σ levels begins to break down or breaks down completely due to one-hole (1h) and two hole-one-particle (2h1p) charge transfer (CT) and local metal excitation coupling in the bonded system. Compared to Ni(CO)4, the many-electron effect in Cr(CO)6 is much stronger. Because of the incompletely filled 3d shell, there is a significant contribution from the local metal excitations. It is shown that for the 2t2g, 8t1u, 5eg, 1t1g, 1t2u, 7t1u, 8a1g, and 7a1g levels the 1h state is still more stable than the 2h1p states. Consequently, the main line (with an intensity of 0.6-0.7) is interpreted as the 1h state, where the screening charge resides on the bonding orbital, which is more polarized toward the ligand than in the ground state. The satellites are dominated by 2h1p configurations where the bonding-to-antibonding shake-up excitations occur. For the 1t2g, 4eg, and 6t1u levels, the strong mixing of 1h and 2h1p configurations leads to the breakdown of the quasiparticle picture of the ionization and thus a distinction between the main line and satellite line becomes meaningless. For the 1t2g level, the strong 1t-12g⇆2t-22g3t2g CT excitation, where the excitations occur in the orbital space of the same symmetry, creating two holes in the same orbital, leads to the breakdown of the quasiparticle picture of the ionization.

  12. Expectation modulates neural representations of valence throughout the human brain.

    PubMed

    Ramayya, Ashwin G; Pedisich, Isaac; Kahana, Michael J

    2015-07-15

    The brain's sensitivity to unexpected gains or losses plays an important role in our ability to learn new behaviors (Rescorla and Wagner, 1972; Sutton and Barto, 1990). Recent work suggests that gains and losses are ubiquitously encoded throughout the human brain (Vickery et al., 2011), however, the extent to which reward expectation modulates these valence representations is not known. To address this question, we analyzed recordings from 4306 intracranially implanted electrodes in 39 neurosurgical patients as they performed a two-alternative probability learning task. Using high-frequency activity (HFA, 70-200 Hz) as an indicator of local firing rates, we found that expectation modulated reward-related neural activity in widespread brain regions, including regions that receive sparse inputs from midbrain dopaminergic neurons. The strength of unexpected gain signals predicted subjects' abilities to encode stimulus-reward associations. Thus, neural signals that are functionally related to learning are widely distributed throughout the human brain. PMID:25937489

  13. Valence quark polarization in the nucleon and the deuteron data

    NASA Astrophysics Data System (ADS)

    Arash, Firooz; Taghavi-Shahri, Fatemeh

    2008-10-01

    Within the framework of the so-called valon model, we argue that a substantial part of the nucleon spin, about 40%, is carried by the polarized valence quarks. The remaining is the result of cancelations between gluon polarization and the orbital angular momentum, where the gluon polarization is the dominant one. It is shown that the sea quark contributions to the spin of any hadron is simply marginal and consistent with zero. Our findings point to a substantially smaller value for a8 than inferred from hyperon β decay, suggesting that full SU (3) symmetric assumption needs to be reconsidered. New and emerging experimental data tend to support this finding. Finally, we show that within the model presented here the experimental data on the polarized structure functions g1p,n,d are reproduced.

  14. 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

  15. The contribution of chromatic and achromatic valence to spectral saturation.

    PubMed

    Fuld, K

    1991-01-01

    The spectral efficiency of the achromatic and opponent chromatic channels was measured in three subjects by use of heterochromatic flicker photometry and hue cancellation, respectively. Heterochromatic brightness matching was also used for measuring achromatic spectral efficiency. These data were then used to predict spectral saturation based on Hurvich and Jameson's (1957; Psychological Review, 64, 384-404) opponent colors model. A standard color-naming procedure and a saturation matching technique were used for measures of spectral saturation. The ratio of saturation of short-wave to long-wave lights was found to be less than that predicted by the linear valence model. Allowing for nonlinearity at the opponent site of the yellow-blue channel plus a desaturating signal from the rods provided a good fit between data and theory. PMID:2017884

  16. 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.

  17. Time flies with music whatever its emotional valence.

    PubMed

    Droit-Volet, Sylvie; Bigand, Emmanuel; Ramos, Danilo; Bueno, José Lino Oliveira

    2010-10-01

    The present study used a temporal bisection task to investigate whether music affects time estimation differently from a matched auditory neutral stimulus, and whether the emotional valence of the musical stimuli (i.e., sad vs. happy music) modulates this effect. The results showed that, compared to sine wave control music, music presented in a major (happy) or a minor (sad) key shifted the bisection function toward the right, thus increasing the bisection point value (point of subjective equality). This indicates that the duration of a melody is judged shorter than that of a non-melodic control stimulus, thus confirming that "time flies" when we listen to music. Nevertheless, sensitivity to time was similar for all the auditory stimuli. Furthermore, the temporal bisection functions did not differ as a function of musical mode. PMID:20674884

  18. Fullerene valence photoemission time delay near ionization cavity minima

    NASA Astrophysics Data System (ADS)

    Magrakvelidze, Maia; Anstine, Dylan; Dixit, Gopal; Madjet, Mohamed; Chakraborty, Himadri

    2015-05-01

    We investigate photoemission quantum phases and associated Wigner-Smith time delays for HOMO and HOMO-1 electrons of a C60 molecule using time-dependent local density approximation (TDLDA). The interference oscillations in C60 valence emissions produce series of minima whose energy separation depends on the molecular size. We show that the quantum phase associated with these minima exhibits rapid variations due to electron correlations, causing rich structures in the photoemission time delay. Besides fullerenes, the detection of photoemission minima in metal clusters suggests a possible universality of the phenomenon in cluster systems, or even quantum dots, that confine finite-sized electron gas. The work predicts a new research direction to apply attosecond metrology, such as RABITT, in the world of nanosystems. This work was supported by the U.S. National Science Foundation.

  19. A density functional for core-valence correlation energy

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    A density functional, ɛCV-DFT(ρc, ρv), describing the core-valence correlation energy has been constructed as a linear combination of ɛLY Pcorr(ρc), ɛV WN5corr(ρc, ρv), ɛPBEcorr(ρc, ρv), ɛSlaterex(ρc, ρv), ɛHCTHex(ρc, ρv), ɛHFex(ρc, ρv), and F CV -DFT (" separators=" N i , Z i ) , 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 ɛCV-DFT(ρc, ρv) 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 ɛCV-DFT(ρc, ρv) 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.

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

    PubMed

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

    2015-12-01

    A density functional, εCV-DFT(ρc, ρv), describing the core-valence correlation energy has been constructed as a linear combination of εLY P (corr)(ρc), εV WN5 (corr)(ρc, ρv), εPBE (corr)(ρc, ρv), εSlater (ex)(ρc, ρv), εHCTH (ex)(ρc, ρv), εHF (ex)(ρc, ρv), 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 εCV-DFT(ρc, ρv) 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 εCV-DFT(ρc, ρv) 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

  1. Interfacial bonding stability

    NASA Technical Reports Server (NTRS)

    Boerio, J.

    1984-01-01

    Interfacial bonding stability by in situ ellipsometry was investigated. It is found that: (1) gamma MPS is an effective primer for bonding ethylene vinyl acetate (EVA) to aluminum; (2) ellipsometry is an effective in situ technique for monitoring the stability of polymer/metal interfaces; (3) the aluminized back surface of silicon wafers contain significant amounts of silicon and may have glass like properties.

  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. Earth-Bonding.

    ERIC Educational Resources Information Center

    Norgaard, Jim

    1988-01-01

    Defines "earth bonding" as dynamic interaction between individual and physical environment. Examines methods and goals of traditional environmental education. Describes development of five-day camping workshop for 11 outdoor education teachers. Describes how workshop facilitated earth bonding for teachers. Calls for further research in "bonding…

  5. 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.

  6. Halogen bonding anion recognition.

    PubMed

    Brown, Asha; Beer, Paul D

    2016-07-01

    A halogen bond is an attractive non-covalent interaction between an electrophilic region in a covalently bonded halogen atom and a Lewis base. While these interactions have long been exploited as a tool in crystal engineering their powerful ability to direct supramolecular self-assembly and molecular recognition processes in solution has, until recently, been overlooked. During the last decade however an ever-increasing number of studies on solution-phase halogen-bond-mediated anion recognition processes has emerged. This Feature Article summarises advancements which have been made thus far in this rapidly developing research area. We survey the use of iodoperfluoroarene, haloimidazolium and halotriazole/triazolium halogen-bond-donor motifs in anion receptor design, before providing an account of our research into the application of mechanically interlocked rotaxane and catenane frameworks as halogen bonding anion host systems. PMID:27273600

  7. 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.

  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. Metal-Metal Bonding in Uranium-Group 10 Complexes.

    PubMed

    Hlina, Johann A; Pankhurst, James R; Kaltsoyannis, Nikolas; Arnold, Polly L

    2016-03-16

    Heterobimetallic complexes containing short uranium-group 10 metal bonds have been prepared from monometallic IU(IV)(OAr(P)-κ(2)O,P)3 (2) {[Ar(P)O](-) = 2-tert-butyl-4-methyl-6-(diphenylphosphino)phenolate}. The U-M bond in IU(IV)(μ-OAr(P)-1κ(1)O,2κ(1)P)3M(0), M = Ni (3-Ni), Pd (3-Pd), and Pt (3-Pt), has been investigated by experimental and DFT computational methods. Comparisons of 3-Ni with two further U-Ni complexes XU(IV)(μ-OAr(P)-1κ(1)O,2κ(1)P)3Ni(0), X = Me3SiO (4) and F (5), was also possible via iodide substitution. All complexes were characterized by variable-temperature NMR spectroscopy, electrochemistry, and single crystal X-ray diffraction. The U-M bonds are significantly shorter than any other crystallographically characterized d-f-block bimetallic, even though the ligand flexes to allow a variable U-M separation. Excellent agreement is found between the experimental and computed structures for 3-Ni and 3-Pd. Natural population analysis and natural localized molecular orbital (NLMO) compositions indicate that U employs both 5f and 6d orbitals in covalent bonding to a significant extent. Quantum theory of atoms-in-molecules analysis reveals U-M bond critical point properties typical of metallic bonding and a larger delocalization index (bond order) for the less polar U-Ni bond than U-Pd. Electrochemical studies agree with the computational analyses and the X-ray structural data for the U-X adducts 3-Ni, 4, and 5. The data show a trend in uranium-metal bond strength that decreases from 3-Ni down to 3-Pt and suggest that exchanging the iodide for a fluoride strengthens the metal-metal bond. Despite short U-TM (transition metal) distances, four other computational approaches also suggest low U-TM bond orders, reflecting highly transition metal localized valence NLMOs. These are more so for 3-Pd than 3-Ni, consistent with slightly larger U-TM bond orders in the latter. Computational studies of the model systems (PH3)3MU(OH)3I (M = Ni, Pd) reveal

  10. Metal–Metal Bonding in Uranium–Group 10 Complexes

    PubMed Central

    2016-01-01

    Heterobimetallic complexes containing short uranium–group 10 metal bonds have been prepared from monometallic IUIV(OArP-κ2O,P)3 (2) {[ArPO]− = 2-tert-butyl-4-methyl-6-(diphenylphosphino)phenolate}. The U–M bond in IUIV(μ-OArP-1κ1O,2κ1P)3M0, M = Ni (3–Ni), Pd (3–Pd), and Pt (3–Pt), has been investigated by experimental and DFT computational methods. Comparisons of 3–Ni with two further U–Ni complexes XUIV(μ-OArP-1κ1O,2κ1P)3Ni0, X = Me3SiO (4) and F (5), was also possible via iodide substitution. All complexes were characterized by variable-temperature NMR spectroscopy, electrochemistry, and single crystal X-ray diffraction. The U–M bonds are significantly shorter than any other crystallographically characterized d–f-block bimetallic, even though the ligand flexes to allow a variable U–M separation. Excellent agreement is found between the experimental and computed structures for 3–Ni and 3–Pd. Natural population analysis and natural localized molecular orbital (NLMO) compositions indicate that U employs both 5f and 6d orbitals in covalent bonding to a significant extent. Quantum theory of atoms-in-molecules analysis reveals U–M bond critical point properties typical of metallic bonding and a larger delocalization index (bond order) for the less polar U–Ni bond than U–Pd. Electrochemical studies agree with the computational analyses and the X-ray structural data for the U–X adducts 3–Ni, 4, and 5. The data show a trend in uranium–metal bond strength that decreases from 3–Ni down to 3–Pt and suggest that exchanging the iodide for a fluoride strengthens the metal–metal bond. Despite short U–TM (transition metal) distances, four other computational approaches also suggest low U–TM bond orders, reflecting highly transition metal localized valence NLMOs. These are more so for 3–Pd than 3–Ni, consistent with slightly larger U–TM bond orders in the latter. Computational studies of the model systems (PH3)3MU(OH)3I

  11. Dissociable Modulation of Overt Visual Attention in Valence and Arousal Revealed by Topology of Scan Path

    PubMed Central

    Ni, Jianguang; Jiang, Huihui; Jin, Yixiang; Chen, Nanhui; Wang, Jianhong; Wang, Zhengbo; Luo, Yuejia; Ma, Yuanye; Hu, Xintian

    2011-01-01

    Emotional stimuli have evolutionary significance for the survival of organisms; therefore, they are attention-grabbing and are processed preferentially. The neural underpinnings of two principle emotional dimensions in affective space, valence (degree of pleasantness) and arousal (intensity of evoked emotion), have been shown to be dissociable in the olfactory, gustatory and memory systems. However, the separable roles of valence and arousal in scene perception are poorly understood. In this study, we asked how these two emotional dimensions modulate overt visual attention. Twenty-two healthy volunteers freely viewed images from the International Affective Picture System (IAPS) that were graded for affective levels of valence and arousal (high, medium, and low). Subjects' heads were immobilized and eye movements were recorded by camera to track overt shifts of visual attention. Algebraic graph-based approaches were introduced to model scan paths as weighted undirected path graphs, generating global topology metrics that characterize the algebraic connectivity of scan paths. Our data suggest that human subjects show different scanning patterns to stimuli with different affective ratings. Valence salient stimuli (with neutral arousal) elicited faster and larger shifts of attention, while arousal salient stimuli (with neutral valence) elicited local scanning, dense attention allocation and deep processing. Furthermore, our model revealed that the modulatory effect of valence was linearly related to the valence level, whereas the relation between the modulatory effect and the level of arousal was nonlinear. Hence, visual attention seems to be modulated by mechanisms that are separate for valence and arousal. PMID:21494331

  12. 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…

  13. Intrasubject Predictions of Occupational Preference: The Effect of Manipulating Components of the Valence Model

    ERIC Educational Resources Information Center

    Muchinsky, Paul M.; Taylor, M. Susan

    1976-01-01

    The purposes of this study were (1) to test whether the occupational preferences of senior psychology majors could be predicted using a within-subjects analysis of Vroom's model; (2) to examine the predictive validity of valence and instrumentality measures, and (3) to compare the predictive validity of the weighted and unweighted valence models.…

  14. 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…

  15. Age influences the relation between subjective valence ratings and emotional word use during autobiographical memory retrieval.

    PubMed

    Ford, Jaclyn H; DiGirolamo, Marissa A; Kensinger, Elizabeth A

    2016-09-01

    Recent research reveals an age-related increase in positive autobiographical memory retrieval using a number of positivity measures, including valence ratings and positive word use. It is currently unclear whether the positivity shift in each of these measures co-occurs, or if age uniquely influences multiple components of autobiographical memory retrieval. The current study examined the correspondence between valence ratings and emotional word use in young and older adults' autobiographical memories. Positive word use in narratives was associated with valence ratings only in young adults' narratives. Older adults' narratives contained a consistent level of positive word use regardless of valence rating, suggesting that positive words and concepts may be chronically accessible to older adults during memory retrieval, regardless of subjective valence. Although a relation between negative word use in narratives and negative valence ratings was apparent in both young and older adults, it was stronger in older adults' narratives. These findings confirm that older adults do vary their word use in accordance with subjective valence, but they do so in a way that is different from young adults. The results also point to a potential dissociation between age-related changes in subjective valence and in positive word use. PMID:26274398

  16. Metal to metal multiple bonds in ordered assemblies

    PubMed Central

    Chisholm, Malcolm H.

    2007-01-01

    The synthesis and properties of metal–metal (MM) quadruply bonded compounds of molybdenum and tungsten in liquid crystalline phases are described. Covalently linked MM quadruply bonded complexes, dimers of dimers, are shown to give rise to mixed valence complexes upon oxidation and the degree of electron delocalization is shown to be correlated with the M2δ bridge π interactions. Class III behavior or complete delocalization is observed to M2 to M2 distances of up to 14 Å. When the M2 unit is attached to oligothiophenes via a carboxylate tether, the photophysical properties of the thienyl units are greatly modified due to M2δ–thienyl π conjugation and spin–orbit coupling. This leads to long-lived emissive states and electroluminescence in solid-state devices. PMID:17299047

  17. 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.

  18. Electronic, optical and bonding properties of MgCO 3

    NASA Astrophysics Data System (ADS)

    Hossain, Faruque M.; Dlugogorski, B. Z.; Kennedy, E. M.; Belova, I. V.; Murch, Graeme E.

    2010-05-01

    The electronic, optical and bonding properties of MgCO 3 (magnesite, rhombohedral calcite-type structure) are calculated using a first-principles density-functional theory (DFT) method considering the exchange-correlation function within the local density approximation (LDA) and the generalized gradient approximation (GGA). The indirect band gap of magnesite is estimated to be 5.0 eV, which is underestimated by ˜1.0 eV. The fundamental absorption edge, which indicates the exact optical transitions from occupied valence bands to the unoccupied conduction band, is estimated by calculating the photon energy dependent imaginary part of the dielectric function using scissors approximations (rigid shift of unoccupied bands). The optical properties show consistent results with the experimental calcite-type structure and also show a considerable optical anisotropy of the magnesite structure. The density of states and Mulliken population analyses reveal the bonding nature between the atoms.

  19. Examining the role of emotional valence of mind wandering: All mind wandering is not equal.

    PubMed

    Banks, Jonathan B; Welhaf, Matthew S; Hood, Audrey V B; Boals, Adriel; Tartar, Jaime L

    2016-07-01

    To evaluate the role of emotional valence on the impact of mind wandering on working memory (WM) and sustained attention, we reanalyzed data from three independently conducted studies that examined the impact of stress on WM (Banks & Boals, 2016; Banks, Welhaf, & Srour, 2015) and sustained attention (Banks, Tartar, & Welhaf, 2014). Across all studies, participants reported the content of their thoughts at random intervals during the WM or sustained attention task. Thought probes in all studies included a core set of response options for task-unrelated thoughts (TUTs) that were negatively, positively, or neutrally emotionally valenced. In line with theories of emotional valenced stimuli on capture of attention, results suggest negatively valenced TUTs, but not positively valenced TUTs, were related to poorer WM and sustained attention in two studies. Neutral TUTs were related to poorer WM but not sustained attention performance. Implications for models of mind wandering are discussed. PMID:27310109

  20. Influence of emotional valence and arousal on the spread of activation in memory.

    PubMed

    Jhean-Larose, Sandra; Leveau, Nicolas; Denhière, Guy

    2014-11-01

    Controversy still persists on whether emotional valence and arousal influence cognitive activities. Our study sought to compare how these two factors foster the spread of activation within the semantic network. In a lexical decision task, prime words were varied depending on the valence (pleasant or unpleasant) or on the level of emotional arousal (high or low). Target words were carefully selected to avoid semantic priming effects, as well as to avoid arousing specific emotions (neutral). Three SOA durations (220, 420 and 720 ms) were applied across three independent groups. Results indicate that at 220 ms, the effect of arousal is significantly higher than the effect of valence in facilitating spreading activation while at 420 ms, the effect of valence is significantly higher than the effect of arousal in facilitating spreading activation. These findings suggest that affect is a sequential process involving the successive intervention of arousal and valence. PMID:24715543

  1. Fractional valency and kink conduction mechanism in quasi-one-dimensional molecular systems

    SciTech Connect

    Ovchinnikov, A.A.; Ukrainskii, T.I.

    1987-09-01

    The authors consider the connection between fractional valence and electrical conductivity of donor-acceptor molecular crystals for which one-dimensional anisotropy is characteristic and seek to answer the observation that donor-acceptor crystals with fractional valence display higher conductivity than those with integral valence by proving, using a Hamiltonian and a Wigner lattice for the crystal, that donor-acceptor molecular crystals with fractional valence have some additional degeneracy in the ground state and that this circumstance is responsible for the existence in such systems of electronic excitations of the kink type which, in the general case, carry a fractional charge and may provide high electrical conductivity. Their qualitative analysis of Wigner lattices for the real molecular crystals TTF-TCNQ and NMP-TCNQ, compared against organic semiconductors, shows that energy-degenerate structures exist for ionic valences of one half, one third, and two thirds.

  2. Valence fluctuations of europium in the boride Eu4Pd29+x B8

    NASA Astrophysics Data System (ADS)

    Gumeniuk, Roman; Schnelle, Walter; Ahmida, Mahmoud A.; Abd-Elmeguid, Mohsen M.; Kvashnina, Kristina O.; Tsirlin, Alexander A.; Leithe-Jasper, Andreas; Geibel, Christoph

    2016-03-01

    We synthesized a high-quality sample of the boride Eu4Pd29+x B8 (x  =  0.76) and studied its structural and physical properties. Its tetragonal structure was solved by direct methods and confirmed to belong to the Eu4Pd29B8 type. All studied physical properties indicate a valence fluctuating Eu state, with a valence decreasing continuously from about 2.9 at 5 K to 2.7 at 300 K. Maxima in the T dependence of the susceptibility and thermopower at around 135 K and 120 K, respectively, indicate a valence fluctuation energy scale on the order of 300 K. Analysis of the magnetic susceptibility evidences some inconsistencies when using the ionic interconfigurational fluctuation (ICF) model, thus suggesting a stronger relevance of hybridization between 4f and valence electrons compared to standard valence-fluctuating Eu systems.

  3. 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

  4. Valence fluctuations of europium in the boride Eu4Pd(29+x)B8.

    PubMed

    Gumeniuk, Roman; Schnelle, Walter; Ahmida, Mahmoud A; Abd-Elmeguid, Mohsen M; Kvashnina, Kristina O; Tsirlin, Alexander A; Leithe-Jasper, Andreas; Geibel, Christoph

    2016-03-23

    We synthesized a high-quality sample of the boride Eu4Pd(29+x)B8 (x  =  0.76) and studied its structural and physical properties. Its tetragonal structure was solved by direct methods and confirmed to belong to the Eu4Pd29B8 type. All studied physical properties indicate a valence fluctuating Eu state, with a valence decreasing continuously from about 2.9 at 5 K to 2.7 at 300 K. Maxima in the T dependence of the susceptibility and thermopower at around 135 K and 120 K, respectively, indicate a valence fluctuation energy scale on the order of 300 K. Analysis of the magnetic susceptibility evidences some inconsistencies when using the ionic interconfigurational fluctuation (ICF) model, thus suggesting a stronger relevance of hybridization between 4f and valence electrons compared to standard valence-fluctuating Eu systems. PMID:26895077

  5. Skin-depth lattice strain, core-level trap depression and valence charge polarization of Al surfaces

    NASA Astrophysics Data System (ADS)

    Wang, Yan; Bo, Maolin; Liu, Yonghui; Guo, Yongling; Wang, Haibin; Yue, Jian; Huang, Yongli

    2016-01-01

    Clarifying the origin for surface core-level shift (SCLS) and gaining quantitative information regarding the coordination-resolved local strain, binding energy (BE) shift and cohesive energy change have been a challenge. Here, we show that a combination of the bond order-length-strength (BOLS) premise, X-ray photoelectron spectroscopy (XPS) and the ab initio density functional theory (DFT) calculations of aluminum (Al) 2p3/2 energy shift of Al surfaces has enabled us to derive such information, namely, (i) the 2p3/2 energy of an isolated Al atom (72.146 ± 0.003eV) and its bulk shift (0.499 eV); (ii) the skin lattice contracts by up to 12.5% and the BE density increases by 70%; and (iii) the cohesive energy drops up to 38%. It is affirmed that the shorter and stronger bonds between under-coordinated atoms provide a perturbation to the Hamiltonian and hence lead to the local strain, quantum entrapment and valence charge polarization. Findings should help in understanding the phenomena of surface pre-melting and skin-high elasticity, in general.

  6. The Halogen Bond

    PubMed Central

    2016-01-01

    The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design. PMID:26812185

  7. The Halogen Bond.

    PubMed

    Cavallo, Gabriella; Metrangolo, Pierangelo; Milani, Roberto; Pilati, Tullio; Priimagi, Arri; Resnati, Giuseppe; Terraneo, Giancarlo

    2016-02-24

    The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design. PMID:26812185

  8. Development of wavelength-dispersive soft X-ray emission spectrometers for transmission electron microscopes--an introduction of valence electron spectroscopy for transmission electron microscopy.

    PubMed

    Terauchi, Masami; Koike, Masato; Fukushima, Kurio; Kimura, Atsushi

    2010-01-01

    Two types of wavelength-dispersive soft X-ray spectrometers, a high-dispersion type and a conventional one, for transmission electron microscopes were constructed. Those spectrometers were used to study the electronic states of valence electrons (bonding electrons). Both spectrometers extended the acceptable energy regions to higher than 2000 eV. The best energy resolution of 0.08 eV was obtained for an Al L-emission spectrum by using the high-dispersion type spectrometer. By using the spectrometer, C K-emission of carbon allotropes, Cu L-emission of Cu(1-x)Zn(x) alloys and Pt M-emission spectra were presented. The FWHM value of 12 eV was obtained for the Pt Malpha-emission peak. The performance of the conventional one was also presented for ZnS and a section specimen of a multilayer device. W-M and Si-K emissions were clearly resolved. Soft X-ray emission spectroscopy based on transmission electron microscopy (TEM) has an advantage for obtaining spectra from a single crystalline specimen with a defined crystal setting. As an example of anisotropic soft X-ray emission, C K-emission spectra of single crystalline graphite with different crystal settings were presented. From the spectra, density of states of pi- and sigma-bondings were separately derived. These results demonstrated a method to analyse the electronic states of valence electrons of materials in the nanometre scale based on TEM. PMID:20371492

  9. Synthesis and characterization of MnCrO4, a new mixed-valence antiferromagnet.

    PubMed

    Nalbandyan, Vladimir B; Zvereva, Elena A; Yalovega, Galina E; Shukaev, Igor L; Ryzhakova, Anastasiya P; Guda, Alexander A; Stroppa, Alessandro; Picozzi, Silvia; Vasiliev, Alexander N; Whangbo, Myung-Hwan

    2013-10-21

    A new orthorhombic phase, MnCrO4, isostructural with MCrO4 (M = Mg, Co, Ni, Cu, Cd) was prepared by evaporation of an aqueous solution, (NH4)2Cr2O7 + 2 Mn(NO3)2, followed by calcination at 400 °C. It is characterized by redox titration, Rietveld analysis of the X-ray diffraction pattern, Cr K edge and Mn K edge XANES, ESR, magnetic susceptibility, specific heat and resistivity measurements. In contrast to the high-pressure MnCrO4 phase where both cations are octahedral, the new phase contains Cr in a tetrahedral environment suggesting the charge balance Mn(2+)Cr(6+)O4. However, the positions of both X-ray absorption K edges, the bond lengths and the ESR data suggest the occurrence of some mixed-valence character in which the mean oxidation state of Mn is higher than 2 and that of Cr is lower than 6. Both the magnetic susceptibility and the specific heat data indicate an onset of a three-dimensional antiferromagnetic order at TN ≈ 42 K, which was confirmed also by calculating the spin exchange interactions on the basis of first principles density functional calculations. Dynamic magnetic studies (ESR) corroborate this scenario and indicate appreciable short-range correlations at temperatures far above TN. MnCrO4 is a semiconductor with activation energy of 0.27 eV; it loses oxygen on heating above 400 °C to form first Cr2O3 plus Mn3O4 and then Mn1.5Cr1.5O4 spinel. PMID:24090277

  10. Valence Tautomerism in One-Dimensional Coordination Polymers.

    PubMed

    Drath, Olga; Gable, Robert W; Moubaraki, Boujemaa; Murray, Keith S; Poneti, Giordano; Sorace, Lorenzo; Boskovic, Colette

    2016-05-01

    The combination of the divergent bis-pyridyl linking ligands 1,2-bis(4-pyridyl)ethane (1,2-bpe), 4,4'-trans-azopyridine (azpy), and 1,3-bis(4-pyridyl)propane (1,3-bpp) with cobalt and 3,5-di-tert-butyldioxolene (3,5-dbdiox) ligands has afforded the complexes [Co(3,5-dbdiox)2(1,2-bpe)]∞ (1), [Co(3,5-dbdiox)2(azpy)]∞ (2), [trans-Co(3,5-dbdiox)2(1,3-bpp)]∞ (3a), and [cis-Co(3,5-dbdiox)2(1,3-bpp)]∞ (3b). All species are 1D coordination polymers that crystallize as solvated forms; the geometric isomers 3a,b cocrystallize. Complexes 1, 2, and 3a exhibit around the Co centers a trans disposition of the N-donor atoms from the pyridyl linkers, while an unusual cis disposition is evident in 3b. Single-crystal X-ray structural analysis at 100 or 130 K of solvated forms of these complexes indicates that all complexes possess the {Co(III)(3,5-dbcat)(3,5-dbsq)} (3,5-dbcat = 3,5-di-tert-butylcatecholate; 3,5-dbsq = 3,5-di-tert-butylsemiquinonate) charge distribution at the temperature of data collection. Variable-temperature magnetic susceptibility studies reveal that 1, 1·1.5MeCN·2H2O, 2·2EtOH, and 3·MeCN·H2O (3 = 3a·3b) all exhibit thermally induced valence tautomeric (VT) transitions above 200 K. Multiple heating and cooling cycles indicate that in some cases the behavior is strongly dependent on desolvation processes. Most notably, further desolvation of 1·1.5MeCN·2H2O above 340 K affords χmT values that suggest unusual ferromagnetic coupling in the {hs-Co(II)(3,5-dbsq)2} valence tautomer. Compound 3·MeCN·H2O exhibits a two-step VT transition that may be ascribed to the presence of the cis and trans geometric isomers. Compounds 1, 1·1.5MeCN·2H2O, 2·2EtOH, and 3·MeCN·H2O all also exhibit a single photoinduced VT transition, comparable to those generally observed for nonpolymeric cobalt-dioxolene complexes. PMID:27058604

  11. 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

    2015-12-28

    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 σ-back-donation, which influences the stability and sigma-donicity of these complexes. PMID:26489888

  12. Bonding aerogels with polyurethanes

    SciTech Connect

    Matthews, F.M.; Hoffman, D.M.

    1989-11-01

    Aerogels, porous silica glasses with ultra-fine cell size (30nm), are made by a solution gelation (sol-gel) process. The resulting gel is critical point dried to densities from 0.15--0.60 g/cc. This material is machinable, homogeneous, transparent, coatable and bondable. To bond aerogel an adhesive should have long cure time, no attack on the aerogel structure, and high strength. Several epoxies and urethanes were examined to determine if they satisfied these conditions. Bond strengths above 13 psi were found with double bubble and DP-110 epoxies and XI-208/ODA-1000 and Castall U-2630 urethanes. Hardman Kalex Tough Stuff'' A-85 hardness urethane gave 18 psi bond strength. Hardman A-85, Tuff-Stuff'' was selected for further evaluation because it produced bond strengths comparable to the adherend cohesive strength. 5 refs., 2 figs.

  13. Junk-Bond Colleges.

    ERIC Educational Resources Information Center

    Van Der Werf, Martin

    2003-01-01

    Describes how a long-predicted decline in the fortunes of small private colleges is beginning to show up in the bond market, as the number of colleges now rated in the junk category has nearly doubled. (EV)

  14. 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.

  15. Valence calculations of lanthanide anion binding energies: a comprehensive study

    NASA Astrophysics Data System (ADS)

    O'Malley, Steven M.; Beck, Donald R.

    2009-05-01

    We have applied a methodology of universal jls restrictions on the 4f^n subgroup of relativistic configuration-interaction calculations of progressively more complex lanthanide anionsootnotetextS. M. O'Malley and D. R. Beck, Phys. Rev. A 77, 012505 (2008).^,ootnotetextS. M. O'Malley and D. R. Beck, Phys. Rev. A 78, 012510 (2008).^,ootnotetextS. M. O'Malley and D. R. Beck, Phys. Rev. A, in press.. Our completed study of the row predicts bound 6p attachments to all lanthanide ground state configurations except Yb, additional 6p attachments to excited opposite parity configurations in Tb and Lu, and 6s attachments to excited open-6s thresholds in La, Ce, Pr, and Gd. In total we predict more than 100 bound states for the lanthanide anions, and we hope this comprehensive study encourages further experimentalootnotetexte.g. V. T. Davis et al., Nucl. Instrum. Methods Phys. Res. B 241, 118 (2005).^,ootnotetexte.g. C. W. Walter et al., Phys. Rev. A 76, 052702 (2007). interest in these anions. Such measurements will be useful in ``fine tuning'' these ab initio binding energies to account for missing core-valence correlation and the approximations that were necessary in these complex calculations.

  16. Valence Band Anticrossing in GaBixAs1-x

    NASA Astrophysics Data System (ADS)

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

    2007-03-01

    Recently, significant attention has been devoted to exploring the large bandgap bowing and spin-orbit splitting in GaBixAs1-x. alloys. We attribute the origins of these effects to a restructuring of the alloy valence band induced by an anticrossing interaction between the delocalized GaAs p-like states and the resonant localized Bi p-like states. Hybridization of like-symmetry states leads to the splitting of the heavy hole, light hole and spin-orbit split-off bands into sets of E+ and E- subbands. The splitting is confirmed experimentally by photomodulated reflectance spectroscopy in alloys with Bi concentrations up to x = 0.084. The bandgap bowing is a direct consequence of the strong upward shift of the uppermost heavy and light hole E+ bands with increasing Bi concentration, while the much slower ascent of the spin-orbit split-off E+ band produces the large rise in the spin-orbit splitting energy.

  17. Valence Band Control of Metal Silicide Films via Stoichiometry.

    PubMed

    Streller, Frank; Qi, Yubo; Yang, Jing; Mangolini, Filippo; Rappe, Andrew M; Carpick, Robert W

    2016-07-01

    The unique electronic and mechanical properties of metal silicide films render them interesting for advanced materials in plasmonic devices, batteries, field-emitters, thermoelectric devices, transistors, and nanoelectromechanical switches. However, enabling their use requires precisely controlling their electronic structure. Using platinum silicide (PtxSi) as a model silicide, we demonstrate that the electronic structure of PtxSi thin films (1 ≤ x ≤ 3) can be tuned between metallic and semimetallic by changing the stoichiometry. Increasing the silicon content in PtxSi decreases the carrier density according to valence band X-ray photoelectron spectroscopy and theoretical density of states (DOS) calculations. Among all PtxSi phases, Pt3Si offers the highest DOS due to the modest shift of the Pt5d manifold away from the Fermi edge by only 0.5 eV compared to Pt, rendering it promising for applications. These results, demonstrating tunability of the electronic structure of thin metal silicide films, suggest that metal silicides can be designed to achieve application-specific electronic properties. PMID:27322019

  18. Delocalization and Valence Tautomerism in Vanadium Tris(iminosemiquinone) Complexes.

    PubMed

    Bendix, Jesper; Clark, Kensha Marie

    2016-02-18

    To survey the noninnocence of bis(arylimino) acenaphthene (BIAN) ligands (L) in complexes with early metals, the homoleptic vanadium complex, [V(L)3 ] (1), and its monocation, [V(L)3 ]PF6 (2), were synthesized. These complexes were found to have a very rich electronic behavior, whereby 1 displays strong electronic delocalization and 2 can be observed in unprecedented valence tautomeric forms. The oxidation states of the metal and ligand components in these complexes were assigned by using spectroscopic, crystallographic, and magnetic analyses. Complex 1 was identified as [V(IV) (L(red) )(L(.) )2 ] (L(red) =N,N'-bis(3,5-dimethylphenylamido)acenaphthylene; L(.) =N,N'-bis(3,5-dimethylphenylimino)acenaphthenesemiquinonate). Complex 2 was determined to be [V(V) (L(red) )(L(.) )2 ](+) at T<150 K and [V(IV) (L(.) )3 ](+) at T>150 K. Cyclic voltammetry experiments reveal six quasi-reversible processes, thus indicating the potential of this metal-ligand combination in catalysis or materials applications. PMID:26799365

  19. 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.

  20. 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 ℏ Ω , 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 ℏ Ω 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 ℏ Ω model space with the exact no-core shell-model results in the 4 ℏ Ω model space for the A =18 and A =19 systems and find good agreement.

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

    PubMed Central

    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 be manipulated factorially. False memories increased with age for unpresented semantic associates of word lists, and net accuracy (the ratio of true memory to total memory) decreased with age. These surprising developmental trends were more pronounced for negatively-valenced materials than for positively-valenced materials, they were more pronounced for high-arousal materials than for low-arousal materials, and developmental increases in the effects of arousal were small in comparison to developmental increases in the effects of valence. These findings have ramifications for legal applications of false-memory research: Materials that share the emotional hallmark of crimes (events that are negatively valenced and arousing) produced the largest age increases in false memory and the largest age declines in net accuracy. PMID:20547393

  2. High and low roads to odor valence? A choice response-time study.

    PubMed

    Olofsson, Jonas K; Bowman, Nicholas E; Gottfried, Jay A

    2013-10-01

    Valence and edibility are two important features of olfactory perception, but it remains unclear how they are read out from an olfactory input. For a given odor object (e.g., the smell of rose or garlic), does perceptual identification of that object necessarily precede retrieval of information about its valence and edibility, or alternatively, are these processes independent? In the present study, we studied rapid, binary perceptual decisions regarding odor detection, object identity, valence, and edibility for a set of common odors. We found that decisions regarding odor-object identity were faster than decisions regarding odor valence or edibility, but slower than detection. Mediation analysis revealed that odor valence and edibility decision response times were predicted by a model in which odor-object identity served as a mediator along the perceptual pathway from detection to both valence and edibility. According to this model, odor valence is determined through both a "low road" that bypasses odor objects and a "high road" that utilizes odor-object information. Edibility evaluations are constrained to processing via the high road. The results outline a novel causal framework that explains how major perceptual features might be rapidly extracted from odors through engagement of odor objects early in the processing stream. PMID:23875569

  3. Lying about the Valence of Affective Pictures: An fMRI Study

    PubMed Central

    Lee, Tatia M. C.; Lee, Tiffany M. Y.; Raine, Adrian; Chan, Chetwyn C. H.

    2010-01-01

    The neural correlates of lying about affective information were studied using a functional magnetic resonance imaging (fMRI) methodology. Specifically, 13 healthy right-handed Chinese men were instructed to lie about the valence, positive or negative, of pictures selected from the International Affective Picture System (IAPS) while their brain activity was scanned by a 3T Philip Achieva scanner. The key finding is that the neural activity associated with deception is valence-related. Comparing to telling the truth, deception about the valence of the affectively positive pictures was associated with activity in the inferior frontal, cingulate, inferior parietal, precuneus, and middle temporal regions. Lying about the valence of the affectively negative pictures, on the other hand, was associated with activity in the orbital and medial frontal regions. While a clear valence-related effect on deception was observed, common neural regions were also recruited for the process of deception about the valence of the affective pictures. These regions included the lateral prefrontal and inferior parietal regions. Activity in these regions has been widely reported in fMRI studies on deception using affectively-neutral stimuli. The findings of this study reveal the effect of valence on the neural activity associated with deception. Furthermore, the data also help to illustrate the complexity of the neural mechanisms underlying deception. PMID:20811624

  4. Vivid: How valence and arousal influence word processing under different task demands.

    PubMed

    Delaney-Busch, Nathaniel; Wilkie, Gianna; Kuperberg, Gina

    2016-06-01

    In this study, we used event-related potentials to examine how different dimensions of emotion-valence and arousal-influence different stages of word processing under different task demands. In two experiments, two groups of participants viewed the same single emotional and neutral words while carrying out different tasks. In both experiments, valence (pleasant, unpleasant, and neutral) was fully crossed with arousal (high and low). We found that the task made a substantial contribution to how valence and arousal modulated the late positive complex (LPC), which is thought to reflect sustained evaluative processing (particularly of emotional stimuli). When participants performed a semantic categorization task in which emotion was not directly relevant to task performance, the LPC showed a larger amplitude for high-arousal than for low-arousal words, but no effect of valence. In contrast, when participants performed an overt valence categorization task, the LPC showed a large effect of valence (with unpleasant words eliciting the largest positivity), but no effect of arousal. These data show not only that valence and arousal act independently to influence word processing, but that their relative contributions to prolonged evaluative neural processes are strongly influenced by the situational demands (and by individual differences, as revealed in a subsequent analysis of subjective judgments). PMID:26833048

  5. Stochastic QM/MM Models for Proton Transport in Condensed Phase: An Empirical Valence Bond (EVB) Approach

    NASA Astrophysics Data System (ADS)

    Burykin, Anton; Braun-Sand, Sonja; Warshel, Arieh

    2005-03-01

    Proton transport (PT) plays a major role in biophysics in general and bioenergetics in particular. In view of the crucial role of biological PT processes it is important to gain a quantitative molecular understanding of the factors that control such processes. While modeling actual time-dependent PT in biological systems one has to deal with up to microsecond time scales which are not accessible to QM/MM methods. In order to overcome this problem we have developed a new type of hybrid quantum/classical approach which combines explicit QM (EVB) representation of the chain of donor and acceptors and implicit representation (via the effective coordinates) of the environment (the rest of the protein/water system). The dynamics of the whole QM/MM system is described by stochastic (langevin) equations. This model takes into account the correct physics of proton charge delocalization and the reorganization of solvent polar groups during the PT process. The description of QM/MM langevin dynamics method is given and several applications to biological systems (PT in Gramicidin A channel and Carbonic Anhydrase) are presented.

  6. The Effect of Action Valence and Race on 3- to 8-Year-Old Children's Social Cognitive Judgments

    ERIC Educational Resources Information Center

    Arterberry, Martha E.; Hughes, Brittany C.; Mejia, Barbara

    2015-01-01

    The present study investigated children's judgments of actions as a function of the valence of the action and the race of the actor. Three- to 8-year-old children were read an illustrated storybook in which 1 character did not share (a negatively valenced action) and the other character was helpful (a positively valenced action). The race of the…

  7. 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…

  8. Positively Valenced Stimuli Facilitate Creative Novel Metaphoric Processes by Enhancing Medial Prefrontal Cortical Activation

    PubMed Central

    Subramaniam, Karuna; Beeman, Mark; Faust, Miriam; Mashal, Nira

    2013-01-01

    A metaphor is a figure of speech in which a subject is symbolic of another unrelated object. In the present study, we examined neural patterns associated with both novel unfamiliar and conventional familiar metaphoric processing, and how these patterns are modulated by affective valence. Prior to fMRI scanning, participants received a list of word pairs (novel unfamiliar metaphors as well as conventional familiar metaphors) and were asked to denote the valence (positive, negative, or neutral) of each word pair. During scanning, participants had to decide whether the word pairs formed meaningful or meaningless expressions. Results indicate that participants were faster and more accurate at deciding that positively valenced metaphors were meaningful compared to neutral metaphors. These behavioral findings were accompanied by increased activation in the medial prefrontal cortex (mPFC), posterior cingulate cortex (PCC), and the right inferior parietal lobe (RIPL). Specifically, positively valenced novel unfamiliar metaphors elicited activation in these brain regions in addition to the left superior temporal gyrus when compared to neutral novel metaphors. We also found that the mPFC and PCC mediated the processing of positively valenced metaphors when compared to negatively valenced metaphors. Positively valenced conventional metaphors, however, elicited different neural signatures when contrasted with either neutral or negatively valenced conventional metaphors. Together, our results indicate that positively valenced stimuli facilitate creative metaphoric processes (specifically novel metaphoric processes) by mediating attention and cognitive control processes required for the access, integration, and selection of semantic associations via modulation of the mPFC. The present study is important for the development of neural accounts of emotion-cognition interactions required for creativity, language, and successful social functioning in general. PMID:23637686

  9. Valence anions in complexes of adenine and 9-methyladenine with formic acid: stabilization by intermolecular proton transfer.

    PubMed

    Mazurkiewicz, Kamil; Harańczyk, Maciej; Gutowski, Maciej; Rak, Janusz; Radisic, Dunja; Eustis, Soren N; Wang, Di; Bowen, Kit H

    2007-02-01

    Photoelectron spectra of adenine-formic acid (AFA(-)) and 9-methyladenine-formic acid (MAFA(-)) anionic complexes have been recorded with 2.540 eV photons. These spectra reveal broad features with maxima at 1.5-1.4 eV that indicate formation of stable valence anions in the gas phase. The neutral and anionic complexes of adenine/9-methyladenine and formic acid were also studied computationally at the B3LYP, second-order Møller-Plesset, and coupled-cluster levels of theory with the 6-31++G** and aug-cc-pVDZ basis sets. The neutral complexes form cyclic hydrogen bonds, and the most stable dimers are bound by 17.7 and 16.0 kcal/mol for AFA and MAFA, respectively. The theoretical results indicate that the excess electron in both AFA(-) and MAFA(-) occupies a pi* orbital localized on adenine/9-methyladenine, and the adiabatic stability of the most stable anions amounts to 0.67 and 0.54 eV for AFA(-) and MAFA(-), respectively. The attachment of the excess electron to the complexes induces a barrier-free proton transfer (BFPT) from the carboxylic group of formic acid to a N atom of adenine or 9-methyladenine. As a result, the most stable structures of the anionic complexes can be characterized as neutral radicals of hydrogenated adenine (9-methyladenine) solvated by a deprotonated formic acid. The BFPT to the N atoms of adenine may be biologically relevant because some of these sites are not involved in the Watson-Crick pairing scheme and are easily accessible in the cellular environment. We suggest that valence anions of purines might be as important as those of pyrimidines in the process of DNA damage by low-energy electrons. PMID:17263404

  10. 27 CFR 24.147 - Operations bond or unit bond.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Operations bond or unit bond. 24.147 Section 24.147 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY LIQUORS WINE Establishment and Operations Bonds and Consents of Surety § 24.147 Operations bond or unit...

  11. 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.

  12. 30 CFR 57.22501 - Personal electric lamps (I-A, I-B, I-C, II-A, II-B, III, IV, V-A, and V-B mines).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Personal electric lamps (I-A, I-B, I-C, II-A... Illumination § 57.22501 Personal electric lamps (I-A, I-B, I-C, II-A, II-B, III, IV, V-A, and V-B mines). Electric lamps used for personal illumination shall be approved by MSHA under the requirements of 30...

  13. 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...

  14. 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...

  15. 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.

  16. Asymmetric bifurcated halogen bonds.

    PubMed

    Novák, Martin; Foroutan-Nejad, Cina; Marek, Radek

    2015-03-01

    Halogen bonding (XB) is being extensively explored for its potential use in advanced materials and drug design. Despite significant progress in describing this interaction by theoretical and experimental methods, the chemical nature remains somewhat elusive, and it seems to vary with the selected system. In this work we present a detailed DFT analysis of three-center asymmetric halogen bond (XB) formed between dihalogen molecules and variously 4-substituted 1,2-dimethoxybenzene. The energy decomposition, orbital, and electron density analyses suggest that the contribution of electrostatic stabilization is comparable with that of non-electrostatic factors. Both terms increase parallel with increasing negative charge of the electron donor molecule in our model systems. Depending on the orientation of the dihalogen molecules, this bifurcated interaction may be classified as 'σ-hole - lone pair' or 'σ-hole - π' halogen bonds. Arrangement of the XB investigated here deviates significantly from a recent IUPAC definition of XB and, in analogy to the hydrogen bonding, the term bifurcated halogen bond (BXB) seems to be appropriate for this type of interaction. PMID:25656525

  17. Evidence for equilibrium gels of valence-limited particles.

    PubMed

    Dudukovic, Nikola A; Zukoski, Charles F

    2014-10-21

    We explore the formation and structure of gels produced from solutions of the aromatic dipeptide derivative molecule fluorenylmethoxycarbonyl-diphenylalanine (Fmoc-FF) in dimethyl sulfoxide (DMSO). Mixing these solutions with water results in the self-assembly of Fmoc-FF molecules into space-filling fibrous networks, exhibiting mechanical properties characteristic of gels. Using confocal fluorescence microscopy, we observe the gel transition in situ and find that, upon the addition of water, the solution undergoes a rapid transition to a non-equilibrium state forming ∼ 2 μm spheres, followed by the formation of fibers 5-10 nm in diameter, nucleating at a sphere surface and expanding into the solution as the remaining spheres dissolve, extending the network. The gel aging process is associated with the network becoming increasingly uniform through apparent redissolution/reaggregation of the Fmoc-FF molecules, corresponding to the observed increase in the elastic modulus to a plateau value. We demonstrate that this increase in uniformity and elastic modulus can be expedited by controlling the temperature of the system, as well as that these gels are thermally reversible, further indicating that the system is in equilibrium in its fibrous network state. X-ray scattering information suggests that the packing of the molecules within a fiber is based on π-π stacking of β-sheets, consistent with models proposed in the literature for similar systems, implying that each particle (molecule) possesses a limited number of interaction sites. These observations provide experimental evidence that these low molecular weight gelator molecules can be considered valence-limited "patchy" particles, which associate at low enough temperature to form equilibrium gels. PMID:25155031

  18. Valence, arousal, and task effects in emotional prosody processing

    PubMed Central

    Paulmann, Silke; Bleichner, Martin; Kotz, Sonja A.

    2013-01-01

    Previous research suggests that emotional prosody processing is a highly rapid and complex process. In particular, it has been shown that different basic emotions can be differentiated in an early event-related brain potential (ERP) component, the P200. Often, the P200 is followed by later long lasting ERPs such as the late positive complex. The current experiment set out to explore in how far emotionality and arousal can modulate these previously reported ERP components. In addition, we also investigated the influence of task demands (implicit vs. explicit evaluation of stimuli). Participants listened to pseudo-sentences (sentences with no lexical content) spoken in six different emotions or in a neutral tone of voice while they either rated the arousal level of the speaker or their own arousal level. Results confirm that different emotional intonations can first be differentiated in the P200 component, reflecting a first emotional encoding of the stimulus possibly including a valence tagging process. A marginal significant arousal effect was also found in this time-window with high arousing stimuli eliciting a stronger P200 than low arousing stimuli. The P200 component was followed by a long lasting positive ERP between 400 and 750 ms. In this late time-window, both emotion and arousal effects were found. No effects of task were observed in either time-window. Taken together, results suggest that emotion relevant details are robustly decoded during early processing and late processing stages while arousal information is only reliably taken into consideration at a later stage of processing. PMID:23801973

  19. Surface analysis in composite bonding

    NASA Technical Reports Server (NTRS)

    Messick, D. L.; Wightman, J. P.

    1982-01-01

    The role of the interfacial region in determining the bond strength and durability of composite bonds is discussed. The characterization of a variety of carbon fibers including Celion 6000 using both scanning electron microscopy and X-ray photoelectron spectroscopy is discussed. The emphasis is on composite bonding, that is, the adhesive bonding between composites in contrast to fiber-matrix interaction. The primary objective of the research is the characterization of composite surfaces before adhesive bonding and after fracture of bonded specimens. Work done on the analysis of composite samples pretreated in a number of ways prior to bonding is detailed.

  20. C-H...Cl relevant discrepancy on structure, magnetic and electronic conductivity of two mixed-valence Cu{sup I}Cu{sup II} coordination polymers

    SciTech Connect

    Shi Ling; Yang Ping; Huang Guang; Li Qian; Wang Ning; Wu Jianzhong; Yu Ying

    2011-07-15

    Two mixed-valence Cu{sup I}Cu{sup II} coordination polymers [Cu{sup I}Cu{sup II}(qdiol)ClL]{sub n} (qdiol{sup 2-}=2,3-dioxyquinoxalinate, L=2,2'-bipyridine, 1; L=1,10-phenanthroline, 2) were obtained in basic ethanolic solution of CuCl{sub 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{sup II}, qdiol{sup 2-} and L are identical in both complexes. But the Cu{sup I} ions are two- and three-coordinated, and the Cl{sup -} 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. - Graphical Abstract: Subtly different C-H...Cl bonding nature leads to diverse coordination modes and supramolecular networks, as well as physical properties of two Cu{sup I}Cu{sup II} coordination polymers with similar compositions. Highlights: > Two new Cu(I)-Cu(II) mixed-valence coordination polymers are obtained. > Environments of Cu(I) and Cl are different caused by C-H...Cl H-bonding. > Supramolecular networks are hence diverse. > Magnetic and semiconducting properties are influenced by the structures.

  1. 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.

  2. Insulation bonding test system

    NASA Technical Reports Server (NTRS)

    Beggs, J. M.; Johnston, G. D.; Coleman, A. D.; Portwood, J. N.; Saunders, J. M.; Redmon, J. W.; Porter, A. C. (Inventor)

    1984-01-01

    A method and a system for testing the bonding of foam insulation attached to metal is described. The system involves the use of an impacter which has a calibrated load cell mounted on a plunger and a hammer head mounted on the end of the plunger. When the impacter strikes the insulation at a point to be tested, the load cell measures the force of the impact and the precise time interval during which the hammer head is in contact with the insulation. This information is transmitted as an electrical signal to a load cell amplifier where the signal is conditioned and then transmitted to a fast Fourier transform (FFT) analyzer. The FFT analyzer produces energy spectral density curves which are displayed on a video screen. The termination frequency of the energy spectral density curve may be compared with a predetermined empirical scale to determine whether a igh quality bond, good bond, or debond is present at the point of impact.

  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.

    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.

  4. Pion form factor using domain wall valence quarks and asqtad sea quarks

    SciTech Connect

    George Fleming; Frederic Bonnet; Robert Edwards; Randal Lewis; David Richards

    2004-09-01

    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.

  5. 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

  6. 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...

  7. Mixed-valence trinuclear manganese clusters: Influence of the electronic transfer on the magnetic properties

    NASA Astrophysics Data System (ADS)

    Gomez-Garcia, C. J.; Coronado, E.; Pourroy, G.

    1990-05-01

    The magnetic behavior of mixed-valence trinuclear clusters d4-d4-d5 is discussed on the basis of a model which takes into account valence delocalization and Heisenberg exchange. This model considers the competing effect between the electronic transfer and the localization of the extra electron due to an asymmetry of the triangular entity. The magnetic properties of the mixed-valence oxo-centered Mn(II)-Mn(III)-Mn(III) complexes formulated as Mn3O(O2CR)6L3 (R=Me, L=pyridine) are discussed on the basis of the developed model, supporting a significant intramolecular electron transfer. A comparison of these results to those previously reported by assuming a valence-trapped model is given.

  8. Dissociating motivational direction and affective valence: specific emotions alter central motor processes.

    PubMed

    Coombes, Stephen A; Cauraugh, James H; Janelle, Christopher M

    2007-11-01

    We aimed to clarify the relation between affective valence and motivational direction by specifying how central and peripheral components of extension movements are altered according to specific unpleasant affective states. As predicted, premotor reaction time was quicker for extension movements initiated during exposure to attack than for extension movements initiated during exposure to all other valence categories (mutilation, erotic couples, opposite-sex nudes, neutral humans, household objects, blank). Exposure to erotic couples and mutilations yielded greater peak force than exposure to images of attack, neutral humans, and household objects. Finally, motor reaction time and peak electromyographic amplitude were not altered by valence. These findings indicate that unpleasant states do not unilaterally prime withdrawal movements, and that the quick execution of extension movements during exposure to threatening images is due to rapid premotor, rather than motor, reaction time. Collectively, our findings support the call for dissociating motivational direction and affective valence. PMID:17958705

  9. Rare earth 4f hybridization with the GaN valence band

    NASA Astrophysics Data System (ADS)

    Wang, Lu; Mei, Wai-Ning; McHale, S. R.; McClory, J. W.; Petrosky, J. C.; Wu, J.; Palai, R.; Losovyj, Y. B.; Dowben, P. A.

    2012-11-01

    The placement of the Gd, Er and Yb 4f states within the GaN valence band has been explored by both experiment and theory. The 4d-4f photoemission resonances for various rare-earth(RE)-doped GaN thin films (RE = Gd, Er, Yb) provide an accurate depiction of the occupied 4f state placement within the GaN. The resonant photoemission show that the major Er and Gd RE 4f weight is at about 5-6 eV below the valence band maximum, similar to the 4f weights in the valence band of many other RE-doped semiconductors. For Yb, there is a very little resonant enhancement of the valence band of Yb-doped GaN, consistent with a large 4f14-δ occupancy. The placement of the RE 4f levels is in qualitative agreement with theoretical expectations.

  10. The rare earth 4 f hybridization with the GaN valence band

    NASA Astrophysics Data System (ADS)

    Wang, Lu; Mei, Wai-Ning; McHale, Steve; McClory, John; Petrosky, James; Wu, J.; Palai, Ratnakar; Losovyj, Yaroslav; Dowben, Peter

    2013-03-01

    The placement of the Gd, Er, and Yb 4f states within the GaN valence band has been explored by both experiment and theory. The 4 d - 4 f photoemission resonances for various rare earth doped GaN thin films (RE = Gd, Er, Yb) provide an accurate depiction of the occupied 4 f state placement within the GaN. The resonant photoemission show that the major Er and Gd rare earth 4 f weight is at about 5-6 eV below the valence band maximum, similar to the 4 f weights in the valence band of many other rare earth doped semiconductors. For Yb, there is very little resonant enhancement of the valence band of Yb doped GaN, consistent with a largely 4f 14 - δ occupancy. The placement of the rare earth 4 f levels is in qualitative agreement with theoretical expectations.

  11. 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

  12. Metallic Adhesion and Bonding

    NASA Technical Reports Server (NTRS)

    Ferrante, J.; Smith, J. R.; Rose, J. H.

    1984-01-01

    Although metallic adhesion has played a central part in much tribological speculation, few quantitative theoretical calculations are available. This is in part because of the difficulties involved in such calculations and in part because the theoretical physics community is not particularly involved with tribology. The calculations currently involved in metallic adhesion are summarized and shown that these can be generalized into a scaled universal relationship. Relationships exist to other types of covalent bonding, such as cohesive, chemisorptive, and molecular bonding. A simple relationship between surface energy and cohesive energy is offered.

  13. Magnetic properties of mixed-valence tetranuclear iron clusters: electron transfer versus exchange interactions

    NASA Astrophysics Data System (ADS)

    Borras-Almenar, J. J.; Coronado, E.; Georges, R.; Gómez-García, C. J.

    1992-02-01

    In order to obtain the energy levels of a mixed-valence [Fe 4S 4] 3+ cubane-type cluster, we develop a model that takes into account the electron delocalization within the cluster as well as the superexchange interactions. Trends of level pattern are discussed as a function of the sign and magnitude of transfer intergrals, and compared with those obtained on mixed-valence dimers and trimers.

  14. Hadronic physics with domain-wall valence and improved staggered sea quarks

    SciTech Connect

    D. B. Renner; W. Schroers; R. Edwards; G. T. Fleming; Ph. Hagler; J. W. Negele; K. Orginos; A. V. Pochinski; D. Richards

    2004-06-01

    With the advent of chiral fermion formulations, the simulation of light valence quarks has finally become realistic for numerical simulations of lattice QCD. The simulation of light dynamical quarks, however, remains one of the major challenges and is still an obstacle to realistic simulations. We attempt to meet this challenge using a hybrid combination of Asqtad sea quarks and domain-wall valence quarks. Initial results for the proton form factor and the nucleon axial coupling are presented.

  15. Strangeness in the Nucleon or the quark model beyond the valence approximation

    SciTech Connect

    Nathan Isgur

    1999-01-01

    Simple arguments based on unitarity indicate that meson loops diagrams, induced by an underlying qq pair creation process, should badly disturb the phenomenologically successful spectroscopy and dynamics of the valence quark model, including such simple but mysterious regularities as the OZI rule. The author discusses some recent progress in adding pair creation to the valence quark model in a way which provides rationale for the quark model's success.

  16. Theoretical study of valence orbital response to guanine tautomerization in coordinate and momentum spaces

    NASA Astrophysics Data System (ADS)

    Yang, Zejin; Duffy, Patrick; Zhu, Quan; Takahashi, Masahiko; Wang, Feng

    2015-10-01

    The binding energy spectra and electron momentum spectra of eight stable guanine tautomers are calculated in the complete valence space. The present results show that the canonical keto (C=O) guanine N(9)H tautomer (GU1) possesses the largest dipole moment, molecular electronic spatial extent, molecular hardness value, and the minimum first vertical ionization potential (VIP). Valence orbital profile investigations find that several orbitals remain almost unchanged during tautomerization, such as frontier highest occupied molecular orbital 39a and 18a. Several orbitals with interchanged order and inverse direction in charge spatial orientations are also detected. Outer valence orbitals (with smaller VIPs) show more complex orbital shapes in the momentum space than those of inner ones (larger VIPs) due mainly to the relatively strong inter-orbital interaction and delocalized electronic distributions. Proton rotation along C-O(H) and C-N(H) axes within hexagonal ring causes smaller influence to orbital profiles than those of proton migration within pentagonal and/or hexagonal rings. Orbital variation trends between enol (GU3-GU5) and keto (GU1, GU2, GU6-GU8) tautomers are observed, including the signature orbitals of enol form, the variation tendency of total orbital intensity, and the variation order of the maximum orbital intensity. In the outer valence momentum space (outside 26a), orbital composed by pz electrons show single peak with a gradual increasing peak site from 0.5 a.u. of inner valence orbital to 1.0 a.u. of outer valence orbital, whereas orbitals composed by px,y electrons form double peaks with respective sites at about 0.5 and 1.5 a.u., only three px,y-orbitals present single peaks (33a,34a,36a). The general variation trends in the complete valence space for all the valence orbitals on their intensities, peak sites, and orbital components are concluded.

  17. 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.

  18. 29 CFR 2580.412-20 - Use of existing bonds, separate bonds and additional bonding.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... bonding. 2580.412-20 Section 2580.412-20 Labor Regulations Relating to Labor (Continued) EMPLOYEE BENEFITS SECURITY ADMINISTRATION, DEPARTMENT OF LABOR TEMPORARY BONDING RULES UNDER THE EMPLOYEE RETIREMENT INCOME SECURITY ACT OF 1974 TEMPORARY BONDING RULES General Bond Rules § 2580.412-20 Use of existing...

  19. 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.

  20. A general valence asymmetry in similarity: Good is more alike than bad.

    PubMed

    Koch, Alex; Alves, Hans; Krüger, Tobias; Unkelbach, Christian

    2016-08-01

    The density hypothesis (Unkelbach, Fiedler, Bayer, Stegmüller, & Danner, 2008) claims a general higher similarity of positive information to other positive information compared with the similarity of negative information to other negative information. This similarity asymmetry might explain valence asymmetries on all levels of cognitive processing. The available empirical evidence for this general valence asymmetry in similarity suffers from a lack of direct tests, low representativeness, and possible confounding variables (e.g., differential valence intensity, frequency, familiarity, or concreteness of positive and negative stimuli). To address these problems, Study 1 first validated the spatial arrangement method (SpAM) as a similarity measure. Using SpAM, Studies 2-6 found the proposed valence asymmetry in large, representative samples of self- and other-generated words (Studies 2a/2b), for words of consensual and idiosyncratic valence (Study 3), for words from 1 and many independent information sources (Study 4), for real-life experiences (Study 5), and for large data sets of verbal (i.e., ∼14,000 words reported by Warriner, Kuperman, & Brysbaert, 2013) and visual information (i.e., ∼1,000 pictures reported in the IAPS; Lang, Bradley, & Cuthbert, 2005; Study 6). Together, these data support a general valence asymmetry in similarity, namely that good is more alike than bad. (PsycINFO Database Record PMID:26866655