WorldWideScience

Sample records for bond valence model

  1. The chemical bond in inorganic chemistry the bond valence model

    CERN Document Server

    Brown, I David

    2016-01-01

    The bond valence model is a version of the ionic model in which the chemical constraints are expressed in terms of localized chemical bonds formed by the valence charge of the atoms. Theorems derived from the properties of the electrostatic flux predict the rules obeyed by both ionic and covalent bonds. They make quantitative predictions of coordination number, crystal structure, bond lengths and bond angles. Bond stability depends on the matching of the bonding strengths of the atoms, while the conflicting requirements of chemistry and space lead to the structural instabilities responsible for the unusual physical properties displayed by some materials. The model has applications in many fields ranging from mineralogy to molecular biology.

  2. The itinerant resonating-valence-bond model for superconductivity

    International Nuclear Information System (INIS)

    Liu, S.H.

    1987-08-01

    It has been proposed by Anderson that the pairing interaction in high temperature superconductors La/sub 2-x/ Sr/sub x/ Cuo 4 and Yba 2 Cu 3 O/sub 7-x/ is magnetic in origin, and the recent discovery of antiferromagnetic ordering in La 2 CuO 4 has been regarded as strong evidence in support of this so-called resonating-valence-bond (RVB) model. Close examination of the ordered state of this material reveals that it is an itinerant antiferromagnet. Accordingly, the superconducting properties must also be studied using the itinerant model approach, rather than the local moment model discussed so far in literature. This paper reports an approximate solution of the itinerant RVB model of superconductivity. It is shown that superconductivity can take place in a narrow region of the parameter space, and that the fluctuating local exchange field causes the superconducting state to be gapless. 19 refs

  3. Modelling of Ion Transport in Solids with a General Bond Valence Based Force-Field

    OpenAIRE

    S. Adams; R.P. Rao

    2010-01-01

    Empirical bond length - bond valence relations provide insight into the link between structure of and ion transport in solid electrolytes. Building on our earlier systematic adjustment of bond valence (BV) parameters to the bond softness, here we discuss how the squared BV mismatch can be linked to the absolute energy scale and used as a general Morse-type interaction potential for analyzing low-energy pathways in ion conducting solid or mixed conductors either by an energy landscape approach...

  4. Modelling of Ion Transport in Solids with a General Bond Valence Based Force-Field

    Directory of Open Access Journals (Sweden)

    S. Adams

    2010-12-01

    Full Text Available Empirical bond length - bond valence relations provide insight into the link between structure of and ion transport in solid electrolytes. Building on our earlier systematic adjustment of bond valence (BV parameters to the bond softness, here we discuss how the squared BV mismatch can be linked to the absolute energy scale and used as a general Morse-type interaction potential for analyzing low-energy pathways in ion conducting solid or mixed conductors either by an energy landscape approach or by molecular dynamics (MD simulations. For a wide range of Lithium oxides we could thus model ion transport revealing significant differences to an earlier geometric approach. Our novel BV-based force-field has also been applied to investigate a range of mixed conductors, focusing on cathode materials for lithium ion battery (LIB applications to promote a systematic design of LIB cathodes that combine high energy density with high power density. To demonstrate the versatility of the new BV-based force-field it is applied in exploring various strategies to enhance the power performance of safe low cost LIB materials (LiFePO4, LiVPO4F, LiFeSO4F, etc..

  5. A new simplifying approach to molecular geometry description: the vectorial bond-valence model.

    Science.gov (United States)

    Harvey, Miguel Angel; Baggio, Sergio; Baggio, Ricardo

    2006-12-01

    A method to describe, analyze and even predict the coordination geometries of metal complexes is proposed, based on previous well established concepts such as bond valence and valence-shell electron-pair repulsion (VSEPR). The idea behind the method is the generalization of the scalar bond-valence concept into a vector quantity, the bond-valence vector (BVV), with the innovation that the multidentate ligands are represented by their resultant BVVs. Complex n-ligand coordination spheres (frequently indescribable at the atomic level) reduce to much simpler ones when analyzed in BVV space, with the bonus of a better applicability of the VSEPR predictions. The geometrical implications of the BVV description are analyzed for the cases of n=2 and 3 (n=number of ligands), and the validity of its predictions, checked for a large number of metal complexes.

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

    Science.gov (United States)

    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.

  7. Physics of Resonating Valence Bond Spin Liquids

    Science.gov (United States)

    Wildeboer, Julia Saskia

    This thesis will investigate various aspects of the physics of resonating valence bond spin liquids. After giving an introduction to the world that lies beyond Landau's priciple of symmetry breaking, e.g. giving an overview of exotic magnetic phases and how they can be described and (possibly) found, we will study a spin-rotationally invariant model system with a known parent Hamiltonian, and argue its ground state to lie within a highly sought after exotic phase, namely the Z2 quantum spin liquid phase. A newly developed numerical procedure --Pfaffian Monte Carlo-- will be introduced to amass evidence that our model Hamiltonian indeed exhibits a Z2 quantum spin liquid phase. Subsequently, we will prove a useful mathematical property of the resonating valence bond states: these states are shown to be linearly independent. Various lattices are investigated concerning this property, and its applications and usefullness are discussed. Eventually, we present a simplified model system describing the interplay of the well known Heisenberg interaction and the Dzyaloshinskii-Moriya (DM) interaction term acting on a sawtooth chain. The effect of the interplay between the two interaction couplings on the phase diagram is investigated. To do so, we employ modern techniques such as the density matrix renormalization group (DMRG) scheme. We find that for weak DM interaction the system exhibits valence bond order. However, a strong enough DM coupling destroys this order.

  8. The variational subspace valence bond method

    Energy Technology Data Exchange (ETDEWEB)

    Fletcher, Graham D. [Argonne National Laboratory, 9700 South Cass Ave., Lemont, Illinois 60439 (United States)

    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.

  9. Valence bond solids for SU(n) spin chains: Exact models, spinon confinement, and the Haldane gap

    International Nuclear Information System (INIS)

    Greiter, Martin; Rachel, Stephan

    2007-01-01

    To begin with, we introduce several exact models for SU(3) spin chains: First is a translationally invariant parent Hamiltonian involving four-site interactions for the trimer chain, with a threefold degenerate ground state. We provide numerical evidence that the elementary excitations of this model transform under representation 3 of SU(3) if the original spins of the model transform under representation 3. Second is a family of parent Hamiltonians for valence bond solids of SU(3) chains with spin representations 6, 10, and 8 on each lattice site. We argue that of these three models, only the latter two exhibit spinon confinement and, hence, a Haldane gap in the excitation spectrum. We generalize some of our models to SU(n). Finally, we use the emerging rules for the construction of valence bond solid states to argue that models of antiferromagnetic chains of SU(n) spins, in general, possess a Haldane gap if the spins transform under a representation corresponding to a Young tableau consisting of a number of boxes λ which is divisible by n. If λ and n have no common divisor, the spin chain will support deconfined spinons and not exhibit a Haldane gap. If λ and n have a common divisor different from n, it will depend on the specifics of the model including the range of the interaction

  10. Emergent spin-1 trimerized valence bond crystal in the spin-1/2 Heisenberg model on the star lattice

    Science.gov (United States)

    Ran, Shi-Ju; Li, Wei; Gong, Shou-Shu; Weichselbaum, Andreas; von Delft, Jan; Su, Gang

    2018-02-01

    We explore the frustrated spin-1/2 Heisenberg model on the star lattice with antiferromagnetic (AF) couplings inside each triangle and ferromagnetic (FM) intertriangle couplings (Jefrustration from the AF interactions inside each triangle, but trigger a fully gapped inversion-symmetry-breaking trimerized valence bond crystal (TVBC) with emergent spin-1 degrees of freedom. We discover that with strengthening Je, the system exhibits a universal scaling behavior either with or without a magnetic field h : the order parameter, the five critical fields that separate the Je-h ground-state phase diagram into six phases, and the excitation gap obtained by low-temperature specific heat, all depend exponentially on Je. Our work implies that the spin-1 VBCs can be stabilized by introducing small FM couplings in the geometrically frustrated spin-1/2 systems.

  11. Analysis Of Chemical Bonding Using Ab Initio Valence Bond Theory

    NARCIS (Netherlands)

    Engelberts, J.J.

    2017-01-01

    In this thesis, theoretical chemical research is presented in which the Valence Bond (VB) Theory plays a central role. For the last three chapters, the VB method is used, in combination with Magnetically Induced Ring Currents, to analyze the aromaticity of several conjugated molecules. The

  12. Two states are not enough: quantitative evaluation of the valence-bond intramolecular charge-transfer model and its use in predicting bond length alternation effects.

    Science.gov (United States)

    Jarowski, Peter D; Mo, Yirong

    2014-12-15

    The structural weights of the canonical resonance contributors used in the Two-state valence-bond charge-transfer model, neutral (N, R1) and ionic (VB-CT, R2), to the ground states and excited states of a series of linear dipolar intramolecular charge-transfer chromophores containing a buta-1,3-dien-1,4-diyl bridge have been computed by using the block-localized wavefunction (BLW) method at the B3LYP/6-311+G(d) level to provide the first quantitative assessment of this simple model. Ground- and excited-state analysis reveals surprisingly low ground-state structural weights for the VB-CT resonance form using either this Two-state model or an expanded Ten-state model. The VB-CT state is found to be more prominent in the excited state. Individual resonance forms were structurally optimized to understand the origins of the bond length alternation (BLA) of the bridging unit. Using a Wheland energy-based weighting scheme, the weighted average of the optimized bond lengths with the Two-state model was unable to reproduce the BLA features with values 0.04 to 0.02 Å too large compared to the fully delocalized (FD) structure (BLW: ca. -0.13 to -0.07 Å, FD: ca. -0.09 to -0.05 Å). Instead, an expanded Ten-state model fit the BLA values of the FD structure to within only 0.001 Å of FD. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Seniority Number in Valence Bond Theory.

    Science.gov (United States)

    Chen, Zhenhua; Zhou, Chen; Wu, Wei

    2015-09-08

    In this work, a hierarchy of valence bond (VB) methods based on the concept of seniority number, defined as the number of singly occupied orbitals in a determinant or an orbital configuration, is proposed and applied to the studies of the potential energy curves (PECs) of H8, N2, and C2 molecules. It is found that the seniority-based VB expansion converges more rapidly toward the full configuration interaction (FCI) or complete active space self-consistent field (CASSCF) limit and produces more accurate PECs with smaller nonparallelity errors than its molecular orbital (MO) theory-based analogue. Test results reveal that the nonorthogonal orbital-based VB theory provides a reverse but more efficient way to truncate the complete active Hilbert space by seniority numbers.

  14. Semiempirical search for oxide superconductors based on bond valence sums

    International Nuclear Information System (INIS)

    Tanaka, S.; Fukushima, N.; Niu, H.; Ando, K.

    1992-01-01

    Relationships between crystal structures and electronic states of layered transition-metal oxides are analyzed in the light of bond valence sums. Correlations between the superconducting transition temperature T c and the bond-valence-sum parameters are investigated for the high-T c cuprate compounds. Possibility of making nonsuperconducting oxides superconducting is discussed. (orig.)

  15. Resonating Valence Bond wavefunctions for electronic simulations

    Science.gov (United States)

    Sorella, Sandro

    2007-03-01

    We discuss several progress for the simulation of strongly correlated electrons, based on an efficient implementation of the Resonating Valence Bond (RVB) theory with Quantum Monte Carlo (QMC). Due to very important advances[1] in the energy optimization of strongly correlated variational wave functions, it is now possible to optimize several variational parameters with remarkable efficiency even within a stochastic approach such as QMC. In this way it is possible to describe very accurately the electronic correlation by a first principle many-body wave function, that can be extended to fairly large electronic systems. Indeed a remarkable improvement of the Hartree-Fock theory is provided by the so called RVB wave function introduced by P.W. Anderson in the context of High-Tc superconductivity[2]. For instance, by means of this paradigm, it has been possible to perform a realistic and accurate simulation of the benzene dimer, where we have found that the RVB correlation of the benzene ring plays a crucial role in the dimer bonding[3,4]. Finally we consider the still controversial low-temperature and high-pressure phase diagram of Hydrogen by using the same RVB wavefunction. We use a novel second order Langevin dynamics by introducing a consistent friction tensor, allowing to remain in thermal equilibrium even with very noisy forces, namely determined by QMC with very short runs. This allows us to simulate finite temperature systems (˜100 H) with very high efficiency, while the variational parameters are consistently optimized during the ionic dynamics. *[1] See C. J. Umrigar, J. Toulouse, C. Filippi, S. Sorella and R. G. Hennig, cond-mat/0611094 and references therein. *[2] P. W. Anderson Science 235, 1196 (1987). *[3] M. Casula, C. Attaccalite and S. Sorella J. Chem. Phys. 121 7110 (2004). *[4] S. Sorella, M. Casula and D. Rocca in preparation. *[5] C. Attaccalite and S. Sorella in preparation.

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

    Science.gov (United States)

    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)

  17. Orbital imaging and assessment of different orbital models for the valence shell of methanol. Comparison of electron momentum spectroscopy measurements with near-Hartree-Fock limit, MRSD-CI, localized valence bond and density functional theory

    Science.gov (United States)

    Rolke, J.; Zheng, Y.; Brion, C. E.; Shi, Z.; Wolfe, Saul; Davidson, E. R.

    1999-06-01

    The momentum distributions of the valence orbitals of methanol have been studied by electron momentum spectroscopy (EMS) and Hartree-Fock (HF), multi-reference singles and doubles configuration interaction (MRSD-CI), localized valence bond (VB) and density functional theory (DFT) calculations. The experiment was performed using a multichannel EMS spectrometer at a total energy of 1200 eV plus the binding energy. Binding-energy spectra measured in the energy range of 6-47 eV are presented for the azimuthal angles φ=0° and φ=8°. Synthetic binding-energy spectra from Green's function and HF calculations for the azimuthal angles φ=0° and φ=8° in the 6-47 eV energy region are also compared to experiment. In the inner valence region strong splitting of the 4a' and 3a' ionization is observed due to final-state electron correlation effects. The measured momentum profiles are compared with HF calculations at the level of the target HF approximation using basis sets ranging from simple (STO-3G) to large (110-GTO and Trun-pV5Z). DFT calculations at the level of the target Kohn-Sham approximation employing the local density approximation or hybrid functional methods and the large Trun-pV5Z basis set are also compared to experiment. The effects of electron correlation and relaxation are also investigated in the outer valence region by MRSD-CI calculations of the full ion-neutral overlap amplitude using the 110-G(CI) basis set. The shapes of all momentum profiles are well predicted by higher level theory. Some small discrepancy still exists between all theoretical treatments and experiment in the low-momentum region for the HOMO 2a″ orbital. MRSD-CI or DFT (i.e. correlated) methods are needed to adequately describe the shape of the 7a' and (6a'+1a″) momentum profiles. The s-type character in the 5a' momentum profile is underestimated by HF theory and overemphasized by density functional theory (DFT). The 110-G(CI) calculation best predicts the shape for the 5a

  18. Reply to ``Ab initio valence-bond theory''

    Science.gov (United States)

    Balint-Kurti, G. G.

    1986-07-01

    In our paper [S. C. Leasure and G. G. Balint-Kurti, Phys. Rev. A 31, 2107 (1985)], we presented a new procedure for calculating Hamiltonian matrix elements between Slater determinants constructed from nonorthogonal orbitals. This is the central problem of valence-bond theory.

  19. Topology of electron charge density for chemical bonds from valence bond theory: a probe of bonding types.

    Science.gov (United States)

    Zhang, Lixian; Ying, Fuming; Wu, Wei; Hiberty, Philippe C; Shaik, Sason

    2009-01-01

    To characterize the nature of bonding we derive the topological properties of the electron charge density of a variety of bonds based on ab initio valence bond methods. The electron density and its associated Laplacian are partitioned into covalent, ionic, and resonance components in the valence bond spirit. The analysis provides a density-based signature of bonding types and reveals, along with the classical covalent and ionic bonds, the existence of two-electron bonds in which most of the bonding arises from the covalent-ionic resonance energy, so-called charge-shift bonds. As expected, the covalent component of the Laplacian at the bond critical point is found to be largely negative for classical covalent bonds. In contrast, for charge-shift bonds, the covalent part of the Laplacian is small or positive, in agreement with the weakly attractive or repulsive character of the covalent interaction in these bonds. On the other hand, the resonance component of the Laplacian is always negative or nearly zero, and it increases in absolute value with the charge-shift character of the bond, in agreement with the decrease of kinetic energy associated with covalent-ionic mixing. A new interpretation of the topology of the total density at the bond critical point is proposed to characterize covalent, ionic, and charge-shift bonding from the density point of view.

  20. The New Resonating Valence Bond Method for Ab-Initio Electronic Simulations

    OpenAIRE

    Sorella, Sandro; Zen, Andrea

    2013-01-01

    The Resonating Valence Bond theory of the chemical bond was introduced soon after the discovery of quantum mechanics and has contributed to explain the role of electron correlation within a particularly simple and intuitive approach where the chemical bond between two nearby atoms is described by one or more singlet electron pairs. In this chapter Pauling's resonating valence bond theory of the chemical bond is revisited within a new formulation, introduced by P.W. Anderson after the discover...

  1. Resonating valence bond states in the PEPS formalism

    Science.gov (United States)

    Schuch, Norbert; Poilblanc, Didier; Cirac, J. Ignacio; Pérez-García, David

    2012-09-01

    We study resonating valence bond (RVB) states in the projected entangled pair states (PEPS) formalism. Based on symmetries in the PEPS description, we establish relations between the toric code state, the orthogonal dimer state, and the SU(2) singlet RVB state on the kagome lattice: We prove the equivalence of toric code and dimer state, and devise an interpolation between the dimer state and the RVB state. This interpolation corresponds to a continuous path in Hamiltonian space, proving that the RVB state is the fourfold degenerate ground state of a local Hamiltonian on the (finite) kagome lattice. We investigate this interpolation using numerical PEPS methods, studying the decay of correlation functions, the change of overlap, and the entanglement spectrum, none of which exhibits signs of a phase transition.

  2. Atoms in Valence Bond – AiVB : synopsis and test results

    NARCIS (Netherlands)

    Zielinski, M.L.; van Lenthe, J.H.

    2010-01-01

    The Atoms in Valence Bond (AiVB) method, a new approach in the Valence Bond, is introduced. This approach combines the ideas behind the early Atoms in Molecules (AIM) developments, e.g. by Moffit [21], to understand a molecular wave function in terms of proper atomic wave functions, with the

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

    International Nuclear Information System (INIS)

    Miyake, Akimasa

    2011-01-01

    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.

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

    International Nuclear Information System (INIS)

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

    2009-01-01

    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.

  5. Valence bond solid formalism for d-level one-way quantum computation

    International Nuclear Information System (INIS)

    Clark, Sean

    2006-01-01

    The d-level or qudit one-way quantum computer (d1WQC) is described using the valence bond solid formalism and the generalized Pauli group. This formalism provides a transparent means of deriving measurement patterns for the implementation of quantum gates in the computational model. We introduce a new universal set of qudit gates and use it to give a constructive proof of the universality of d1WQC. We characterize the set of gates that can be performed in one parallel time step in this model

  6. Resonating-valence-bond superconductors with fermionic projected entangled pair states

    NARCIS (Netherlands)

    Poilblanc, D.; Corboz, P.; Schuch, N.; Cirac, J.I.

    2014-01-01

    We construct a family of simple fermionic projected entangled pair states (fPEPS) on the square lattice with bond dimension D=3 which are exactly hole-doped resonating valence bond (RVB) wave functions with short-range singlet bonds. Under doping the insulating RVB spin liquid evolves immediately

  7. Microscopic theory of the nearest-neighbor valence bond sector of the spin-1/2 kagome antiferromagnet

    Science.gov (United States)

    Ralko, Arnaud; Mila, Frédéric; Rousochatzakis, Ioannis

    2018-03-01

    The spin-1/2 Heisenberg model on the kagome lattice, which is closely realized in layered Mott insulators such as ZnCu3(OH) 6Cl2 , is one of the oldest and most enigmatic spin-1/2 lattice models. While the numerical evidence has accumulated in favor of a quantum spin liquid, the debate is still open as to whether it is a Z2 spin liquid with very short-range correlations (some kind of resonating valence bond spin liquid), or an algebraic spin liquid with power-law correlations. To address this issue, we have pushed the program started by Rokhsar and Kivelson in their derivation of the effective quantum dimer model description of Heisenberg models to unprecedented accuracy for the spin-1/2 kagome, by including all the most important virtual singlet contributions on top of the orthogonalization of the nearest-neighbor valence bond singlet basis. Quite remarkably, the resulting picture is a competition between a Z2 spin liquid and a diamond valence bond crystal with a 12-site unit cell, as in the density-matrix renormalization group simulations of Yan et al. Furthermore, we found that, on cylinders of finite diameter d , there is a transition between the Z2 spin liquid at small d and the diamond valence bond crystal at large d , the prediction of the present microscopic description for the two-dimensional lattice. These results show that, if the ground state of the spin-1/2 kagome antiferromagnet can be described by nearest-neighbor singlet dimers, it is a diamond valence bond crystal, and, a contrario, that, if the system is a quantum spin liquid, it has to involve long-range singlets, consistent with the algebraic spin liquid scenario.

  8. Potential energy surfaces for electron dynamics modeled by floating and breathing Gaussian wave packets with valence-bond spin-coupling: An analysis of high-harmonic generation spectrum

    Science.gov (United States)

    Ando, Koji

    2018-03-01

    A model of localized electron wave packets (EWPs), floating and breathing Gaussians with non-orthogonal valence-bond spin-coupling, is applied to compute the high-harmonic generation (HHG) spectrum from a LiH molecule induced by an intense laser pulse. The characteristic features of the spectrum, a plateau up to 50 harmonic-order and a cutoff, agreed well with those from the previous time-dependent complete active-space self-consistent-field calculation [T. Sato and K. L. Ishikawa, Phys. Rev. A 91, 023417 (2015)]. In contrast to the conventional molecular orbital picture in which the Li 2s and H 1s atomic orbitals are strongly mixed, the present calculation indicates that an incoherent sum of responses of single electrons reproduces the HHG spectrum, in which the contribution from the H 1s electron dominates the plateau and cutoff, whereas the Li 2s electron contributes to the lower frequency response. The results are comprehensive in terms of the shapes of single-electron potential energy curves constructed from the localized EWP model.

  9. Size-extensive wave functions for quantum Monte Carlo: A linear scaling generalized valence bond approach

    NARCIS (Netherlands)

    Fracchia, F.; Filippi, Claudia; Amovilli, C.

    2012-01-01

    We propose a new class of multideterminantal Jastrow–Slater wave functions constructed with localized orbitals and designed to describe complex potential energy surfaces of molecular systems for use in quantum Monte Carlo (QMC). Inspired by the generalized valence bond formalism, we elaborate a

  10. Unifying Exchange Sensitivity in Transition-Metal Spin-State Ordering and Catalysis through Bond Valence Metrics.

    Science.gov (United States)

    Gani, Terry Z H; Kulik, Heather J

    2017-11-14

    Accurate predictions of spin-state ordering, reaction energetics, and barrier heights are critical for the computational discovery of open-shell transition-metal (TM) catalysts. Semilocal approximations in density functional theory, such as the generalized gradient approximation (GGA), suffer from delocalization error that causes them to overstabilize strongly bonded states. Descriptions of energetics and bonding are often improved by introducing a fraction of exact exchange (e.g., erroneous low-spin GGA ground states are instead correctly predicted as high-spin with a hybrid functional). The degree of spin-splitting sensitivity to exchange can be understood based on the chemical composition of the complex, but the effect of exchange on reaction energetics within a single spin state is less well-established. Across a number of model iron complexes, we observe strong exchange sensitivities of reaction barriers and energies that are of the same magnitude as those for spin splitting energies. We rationalize trends in both reaction and spin energetics by introducing a measure of delocalization, the bond valence of the metal-ligand bonds in each complex. The bond valence thus represents a simple-to-compute property that unifies understanding of exchange sensitivity for catalytic properties and spin-state ordering in TM complexes. Close agreement of the resulting per-metal-organic-bond sensitivity estimates, together with failure of alternative descriptors demonstrates the utility of the bond valence as a robust descriptor of how differences in metal-ligand delocalization produce differing relative energetics with exchange tuning. Our unified description explains the overall effect of exact exchange tuning on the paradigmatic two-state FeO + /CH 4 reaction that combines challenges of spin-state and reactivity predictions. This new descriptor-sensitivity relationship provides a path to quantifying how predictions in transition-metal complex screening are sensitive to the

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

    Science.gov (United States)

    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.

  12. The role of the 5f valence orbitals of early actinides in chemical bonding

    Science.gov (United States)

    Vitova, T.; Pidchenko, I.; Fellhauer, D.; Bagus, P. S.; Joly, Y.; Pruessmann, T.; Bahl, S.; Gonzalez-Robles, E.; Rothe, J.; Altmaier, M.; Denecke, M. A.; Geckeis, H.

    2017-01-01

    One of the long standing debates in actinide chemistry is the level of localization and participation of the actinide 5f valence orbitals in covalent bonds across the actinide series. Here we illuminate the role of the 5f valence orbitals of uranium, neptunium and plutonium in chemical bonding using advanced spectroscopies: actinide M4,5 HR-XANES and 3d4f RIXS. Results reveal that the 5f orbitals are active in the chemical bonding for uranium and neptunium, shown by significant variations in the level of their localization evidenced in the spectra. In contrast, the 5f orbitals of plutonium appear localized and surprisingly insensitive to different bonding environments. We envisage that this report of using relative energy differences between the 5fδ/ϕ and 5fπ*/5fσ* orbitals as a qualitative measure of overlap-driven actinyl bond covalency will spark activity, and extend to numerous applications of RIXS and HR-XANES to gain new insights into the electronic structures of the actinide elements. PMID:28681848

  13. Bonding and Molecular Geometry without Orbitals- The Electron Domain Model

    Science.gov (United States)

    Gillespie, Ronald J.; Spencer, James N.; Moog, Richard S.

    1996-07-01

    An alternative to the conventional valence bond approach to bonding and geometry-the electron domain model-is presented. This approach avoids some of the problems with the standard approach and presents fewer difficulties for the student, while still providing a physical basis for the VSEPR model and a link to the valence bond model. The electron domain model also emphasizes the importance of the Pauli principle in understanding the chemical bond and molecular geometry. A letter from Derek W. Smith in our April 2000 issue addresses the above.

  14. Valence XPS structure and chemical bond in Cs2UO2Cl4

    Directory of Open Access Journals (Sweden)

    Teterin Yury A.

    2016-01-01

    Full Text Available Quantitative analysis was done of the valence electrons X-ray photoelectron spectra structure in the binding energy (BE range of 0 eV to ~35 eV for crystalline dicaesium tetrachloro-dioxouranium (VI (Cs2UO2Cl4. This compound contains the uranyl group UO2. The BE and structure of the core electronic shells (~35 eV-1250 eV, as well as the relativistic discrete variation calculation results for the UO2Cl4(D4h cluster reflecting U close environment in Cs2UO2Cl4 were taken into account. The experimental data show that many-body effects due to the presence of cesium and chlorine contribute to the outer valence (0-~15 eV BE spectral structure much less than to the inner valence (~15 eV-~35 eV BE one. The filled U5f electronic states were theoretically calculated and experimentally confirmed to be present in the valence band of Cs2UO2Cl4. It corroborates the suggestion on the direct participation of the U5f electrons in the chemical bond. Electrons of the U6p atomic orbitals participate in formation of both the inner (IVMO and the outer (OVMO valence molecular orbitals (bands. The filled U6p and the O2s, Cl3s electronic shells were found to make the largest contributions to the IVMO formation. The molecular orbitals composition and the sequence order in the binding energy range 0 eV-~35 eV in the UO2Cl4 cluster were established. The experimental and theoretical data allowed a quantitative molecular orbitals scheme for the UO2Cl4 cluster in the BE range 0-~35 eV, which is fundamental for both understanding the chemical bond nature in Cs2UO2Cl4 and the interpretation of other X-ray spectra of Cs2UO2Cl4. The contributions to the chemical binding for the UO2Cl4 cluster were evaluated to be: the OVMO contribution - 76%, and the IVMO contribution - 24 %.

  15. 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

    Science.gov (United States)

    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.

  16. Non-orthogonal and orthogonal valence bond wavefunctions in the hydrogen molecule: the diabatic view

    Science.gov (United States)

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

    2013-07-01

    The ability of the valence bond (VB) approach to describe a molecular system in 'chemical terms' finds its theoretical justification in the fact that the VB wavefunctions are supposed to be diabatic, i.e. with a well-defined nature, not depending on the nuclear geometry. The intimate nature of the VB wavefunctions is here analysed by computing the non-adiabatic coupling for the simple, paradigmatic case of the hydrogen (H2) molecule. This analysis reveals that the neutral and ionic VB wavefunctions cannot be considered as diabatic states, given that they present a large non-adiabatic coupling. The diabatic states, obtained by a suitable transformation of the VB wavefunctions, are found to be the wavefunctions of the orthogonal VB (OVB) approach, which therefore gains a legitimacy in the analysis of the composition of the adiabatic wavefunctions. Such an analysis has some bearing on the description of the nature of the chemical bond in H2: the neutral structure gives a dissociative curve and the bond is due to the stabilisation brought by the ionic structure that mixes together with the neutral structure in the ground state wavefunction at short internuclear distances. The ability of the (at first glance) neutral VB wavefunction based on the 1s orbitals to describe in a compact way the ground state (and therefore the chemical bond) is ascribed to an almost optimal mixing in this wavefunction of the diabatic neutral and ionic states at all internuclear distances.

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

    Science.gov (United States)

    Yang, Fan; Yao, Hong

    2012-10-05

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

  18. A Definition of the Magnetic Transition Temperature Using Valence Bond Theory.

    Science.gov (United States)

    Jornet-Somoza, Joaquim; Deumal, Mercè; Borge, Juan; Robb, Michael A

    2018-03-01

    Macroscopic magnetic properties are analyzed using Valence Bond theory. Commonly the critical temperature T C for magnetic systems is associated with a maximum in the energy-based heat capacity C p (T). Here a more broadly applicable definition of the magnetic transition temperature T C is described using the spin moment expectation value (i.e., applying the spin exchange density operator) instead of energy. Namely, the magnetic capacity C s (T) reflects variation in the spin multiplicity as a function of temperature, which is shown to be related to ∂[χT(T)]/∂T. Magnetic capacity C s (T) depends on long-range spin interactions that are not relevant in the energy-based heat capacity C p (T). Differences between C s (T) and C p (T) are shown to be due to spin order/disorder within the crystal that can be monitored via a Valence Bond analysis of the corresponding magnetic wave function. Indeed the concept of the Boltzmann spin-alignment order is used to provide information about the spin correlation between magnetic units. As a final illustration, the critical temperature is derived from the magnetic capacity for several molecular magnets presenting different magnetic topologies that have been experimentally studied. A systematic shift between the transition temperatures associated with C s (T) and C p (T) is observed. It is demonstrated that this shift can be attributed to the loss of long-range spin correlation. This suggests that the magnetic capacity C s (T) can be used as a predictive tool for the magnetic topology and thus for the synthetic chemists.

  19. Some considerations about bond indices in non-orthogonal bases and the MO calculation of valence and oxidation number

    International Nuclear Information System (INIS)

    Giambiagi, M.S. de; Giambiagi, M.; Jorge, F.E.

    1984-01-01

    In order to guarantee the desired invariance properties of bond indices, the importance of expliciting the tensor character of the matrices concerned, so as to deal with a contraction in the tensor sense between a covariant index and a contravariant one is shown. An MO valence definition using Wiberg's indices is generalized to non-orthogonal bases and a straightforward definition of oxidation numbers is proposed. IEH calculations of their magnitudes for some appropriate examples are performed: they emphasize the role of 'secondary' bonds in N and C-containing compounds; the hydrogen behaviour in half-bonds and strong H-bonds is satisfactorily accounted for; valence and oxidation number values are assigned to Fe, Co and Ni in a few complexes. (Author) [pt

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  2. On the weaknesses of the valence shell electron pair repulsion (VSEPR) model

    Science.gov (United States)

    Røeggen, Inge

    1986-07-01

    The validity of the valence shell electron pair repulsion model (VSEPR) is discussed within the framework of an antisymmetric product of strongly orthogonal geminals (APSG). It is shown that when a molecule is partitioned onto fragments consisting of a central fragment, lone pairs, bond pairs, and ligands, the total APSG energy including the nuclear repulsion terms, can be written as a sum of intra- and interfragment energies. The VSEPR terms can be identified as three out of 13 different energy components. The analysis is applied to the water molecule. Six of the neglected energy components in the VSEPR model have a larger variation with the bond angle than the terms which are included in the model. According to this analysis it is difficult to consider the VSEPR model as a valid framework for discussing molecular equilibrium geometries. It is suggested that energy fragment analysis might represent an alternative model.

  3. The Nature of the Idealized Triple Bonds Between Principal Elements and the σ Origins of Trans-Bent Geometries-A Valence Bond Study.

    Science.gov (United States)

    Ploshnik, Elina; Danovich, David; Hiberty, Philippe C; Shaik, Sason

    2011-04-12

    We describe herein a valence bond (VB) study of 27 triply bonded molecules of the general type X≡Y, where X and Y are main element atoms/fragments from groups 13-15 in the periodic table. The following conclusions were derived from the computational data: (a) Single π-bond and double π-bond energies for the entire set correlate with the "molecular electronegativity", which is the sum of the X and Y electronegativites for X≡Y. The correlation with the molecular electronegativity establishes a simple rule of periodicity: π-bonding strength generally increases from left to right in a period and decreases down a column in the periodic table. (b) The σ frame invariably prefers trans bending, while π-bonding gets destabilized and opposes the trans distortion. In HC≡CH, the π-bonding destabilization overrides the propensity of the σ frame to distort, while in the higher row molecules, the σ frame wins out and establishes trans-bent molecules with 2(1)/2 bonds, in accord with recent experimental evidence based on solid state (29)Si NMR of the Sekiguchi compound. Thus, in the trans-bent molecules "less bonds pay more". (c) All of the π bonds show significant bonding contributions from the resonance energy due to covalent-ionic mixing. This quantity is shown to correlate linearly with the corresponding "molecular electronegativity" and to reflect the mechanism required to satisfy the equilibrium condition for the bond. The π bonds for molecules possessing high molecular electronegativity are charge-shift bonds, wherein bonding is dominated by the resonance energy of the covalent and ionic forms, rather than by either form by itself.

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

    Science.gov (United States)

    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.

  5. Actinides in silicate glasses and melts and on mineral surfaces: information on local co-ordination environments from XAFS spectroscopy and bond valence theory

    International Nuclear Information System (INIS)

    Brown, G.E.Jr.; Farges, F.; Brown, G.E.Jr.; Farges, F.; Bargar, J.R.; Farges, F.; Thomson Berbeco, H.

    2002-01-01

    The impact of actinides on the environment is mitigated by their interaction with particle surfaces and by incorporation into suitable waste forms. In both cases, a fundamental knowledge of the local co-ordination environment of actinide ions is essential for understanding their stability in various near-surface environments under a range of conditions. When actinide ions are sorbed on mineral surfaces, the extent to which the ions are immobilised depends on the type of surface complex or solid precipitate that forms. When incorporated into a glass or crystalline waste form, the stability of the actinide will depend in part on its redox state and local co-ordination environment. In both cases, XAFS spectroscopy can provide unique information on the number and types of first and, in certain cases, more distant neighbours, and their geometric arrangement (including inter-atomic distances and a measure of their disorder). When this structural information from XAFS spectroscopy is combined with Pauling bond valence theory and modem bond valences corrected for bond length variations, it is also possible to develop plausible models for their medium-range co-ordination environments (out to ≅ 4 Angstrom radial distance around the actinide) for both sorbed actinide ions and those present in a silicate glass or melt. We discuss results from several XAFS studies of the naturally occurring actinides uranium and thorium in sorption samples, silicate glasses and silicate melts at high temperature. (authors)

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

    Science.gov (United States)

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

    2016-05-05

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Inaoka, Takeshi, E-mail: inaoka@phys.u-ryukyu.ac.jp; Yanagisawa, Susumu; Kadekawa, Yukihiro [Department of Physics and Earth Sciences, Faculty of Science, University of the Ryukyus, 1 Senbaru, Nishihara, Okinawa 903-0213 (Japan)

    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.

  8. The Valency Theory: The Human Bond From A New Psychoanalytic Perspective

    OpenAIRE

    Med Hafsi

    2008-01-01

    The present paper discusses some psychoanalytical conceptions concerning what links people to each other, or the human bond. Psychoanalysis, can be regarded as a science dealing basically with, although not directly, the human bond or link linking the person with his external and internal objects. The fact that this bond is in perpetualtransformation, and therefore can be apprehended from different angles has led to various psychoanalytical conceptions or theories which are more complementary...

  9. In-medium pion valence distributions in a light-front model

    International Nuclear Information System (INIS)

    Melo, J.P.B.C. de; Tsushima, K.; Ahmed, I.

    2017-01-01

    Pion valence distributions in nuclear medium and vacuum are studied in a light-front constituent quark model. The in-medium input for studying the pion properties is calculated by the quark-meson coupling model. We find that the in-medium pion valence distribution, as well as the in-medium pion valence wave function, are substantially modified at normal nuclear matter density, due to the reduction in the pion decay constant.

  10. Electronic properties and bonding in Zr Hx thin films investigated by valence-band x-ray photoelectron spectroscopy

    Science.gov (United States)

    Magnuson, Martin; Schmidt, Susann; Hultman, Lars; Högberg, Hans

    2017-11-01

    The electronic structure and chemical bonding in reactively magnetron sputtered Zr Hx (x =0.15 , 0.30, 1.16) thin films with oxygen content as low as 0.2 at.% are investigated by 4d valence band, shallow 4p core-level, and 3d core-level x-ray photoelectron spectroscopy. With increasing hydrogen content, we observe significant reduction of the 4d valence states close to the Fermi level as a result of redistribution of intensity toward the H 1s-Zr 4d hybridization region at ˜6 eV below the Fermi level. For low hydrogen content (x =0.15 , 0.30), the films consist of a superposition of hexagonal closest-packed metal (α phase) and understoichiometric δ -Zr Hx (Ca F2 -type structure) phases, while for x =1.16 , the films form single-phase Zr Hx that largely resembles that of stoichiometric δ -Zr H2 phase. We show that the cubic δ -Zr Hx phase is metastable as thin film up to x =1.16 , while for higher H contents the structure is predicted to be tetragonally distorted. For the investigated Zr H1.16 film, we find chemical shifts of 0.68 and 0.51 eV toward higher binding energies for the Zr 4 p3 /2 and 3 d5 /2 peak positions, respectively. Compared to the Zr metal binding energies of 27.26 and 178.87 eV, this signifies a charge transfer from Zr to H atoms. The change in the electronic structure, spectral line shapes, and chemical shifts as a function of hydrogen content is discussed in relation to the charge transfer from Zr to H that affects the conductivity by charge redistribution in the valence band.

  11. Low-temperature spin dynamics of a valence bond glass in Ba2YMoO6

    Science.gov (United States)

    de Vries, M. A.; Piatek, J. O.; Misek, M.; Lord, J. S.; Rønnow, H. M.; Bos, J.-W. G.

    2013-04-01

    We carried out ac magnetic susceptibility measurements and muon spin relaxation spectroscopy on the cubic double perovskite Ba2YMoO6, down to 50 mK. Below ∼1 K the muon relaxation is typical of a magnetic insulator with a spin-liquid type ground state, i.e. without broken symmetries or frozen moments. However, the ac susceptibility revealed a dilute-spin-glass-like transition below ∼1 K. Antiferromagnetically coupled Mo5+ 4d1 electrons in triply degenerate t2g orbitals are in this material arranged in a geometrically frustrated fcc lattice. Bulk magnetic susceptibility data has previously been interpreted in terms of a freezing to a heterogeneous state with non-magnetic sites where 4d1 electrons have paired in spin-singlets dimers, and residual unpaired Mo5+ 4d1 electron spins. Based on the magnetic heat capacity data it has been suggested that this heterogeneity is the result of kinetic constraints intrinsic to the physics of the pure system (possibly due to topological overprotection) leading to a self-induced glass of valence bonds between neighbouring 4d1 electrons. The muon spin relaxation (μSR) unambiguously points to a heterogeneous state with a static arrangement of unpaired electrons in a background of (valence bond) dimers between the majority of Mo5+ 4d electrons. The ac susceptibility data indicate that the residual magnetic moments freeze into a dilute-spin-glass-like state. This is in apparent contradiction with the muon-spin decoupling at 50 mK in fields up to 200 mT, which indicates that, remarkably, the time scale of the field fluctuations from the residual moments is ∼5 ns. Comparable behaviour has been observed in other geometrically frustrated magnets with spin-liquid-like behaviour and the implications of our observations on Ba2YMoO6 are discussed in this context.

  12. Coupled cluster valence bond theory for open-shell systems with application to very long range strong correlation in a polycarbene dimer.

    Science.gov (United States)

    Small, David W; Head-Gordon, Martin

    2017-07-14

    The Coupled Cluster Valence Bond (CCVB) method, previously presented for closed-shell (CS) systems, is extended to open-shell (OS) systems. The theoretical development is based on embedding the basic OS CCVB wavefunction in a fictitious singlet super-system. This approach reveals that the OS CCVB amplitude equations are quite similar to those of CS CCVB, and thus that OS CCVB requires the same level of computational effort as CS CCVB, which is an inexpensive method. We present qualitatively correct CCVB potential energy curves for all low-lying spin states of P 2 and Mn 2 + . CCVB is successfully applied to the low-lying spin states of some model linear polycarbenes, systems that appear to be a hindrance to standard density functionals. We examine an octa-carbene dimer in a side-by-side orientation, which, in the monomer dissociation limit, exhibits maximal strong correlation over the length of the polycarbene.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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. Copyright © 2015 Elsevier Inc. All rights reserved.

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

    NARCIS (Netherlands)

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

    2012-01-01

    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

  16. High energy pp and anti-pp elastic scattering in nucleon valence core model

    International Nuclear Information System (INIS)

    Islam, M.M.; Fearnley, T.

    1986-01-01

    Connection between the valence core model and the effective QCD models of nucleon structure is pointed out. Also, implication of recent anti-pp differential cross section measurements at 53 GeV on our previous calculations is discussed

  17. Bond graph modeling of centrifugal compression systems

    OpenAIRE

    Uddin, Nur; Gravdahl, Jan Tommy

    2015-01-01

    A novel approach to model unsteady fluid dynamics in a compressor network by using a bond graph is presented. The model is intended in particular for compressor control system development. First, we develop a bond graph model of a single compression system. Bond graph modeling offers a different perspective to previous work by modeling the compression system based on energy flow instead of fluid dynamics. Analyzing the bond graph model explains the energy flow during compressor surge. Two pri...

  18. How fast monoamine oxidases decompose adrenaline? Kinetics of isoenzymes A and B evaluated by empirical valence bond simulation.

    Science.gov (United States)

    Oanca, Gabriel; Stare, Jernej; Mavri, Janez

    2017-12-01

    This work scrutinizes kinetics of decomposition of adrenaline catalyzed by monoamine oxidase (MAO) A and B enzymes, a process controlling the levels of adrenaline in the central nervous system and other tissues. Experimental kinetic data for MAO A and B catalyzed decomposition of adrenaline are reported only in the form of the maximum reaction rate. Therefore, we estimated the experimental free energy barriers form the kinetic data of closely related systems using regression method, as was done in our previous study. By using multiscale simulation on the Empirical Valence Bond (EVB) level, we studied the chemical reactivity of the MAO A catalyzed decomposition of adrenaline and we obtained a value of activation free energy of 17.3 ± 0.4 kcal/mol. The corresponding value for MAO B is 15.7 ± 0.7 kcal/mol. Both values are in good agreement with the estimated experimental barriers of 16.6 and 16.0 kcal/mol for MAO A and MAO B, respectively. The fact that we reproduced the kinetic data and preferential catalytic effect of MAO B over MAO A gives additional support to the validity of the proposed hydride transfer mechanism. Furthermore, we demonstrate that adrenaline is preferably involved in the reaction in a neutral rather than in a protonated form due to considerably higher barriers computed for the protonated adrenaline substrate. The results are discussed in the context of chemical mechanism of MAO enzymes and possible applications of multiscale simulation to rationalize the effects of MAO activity on adrenaline level. © 2017 Wiley Periodicals, Inc.

  19. Levels of valence

    Directory of Open Access Journals (Sweden)

    Vera eShuman

    2013-05-01

    Full Text Available 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 (unpleasantness, goal obstructiveness/conduciveness, low or high power, self- (incongruence, 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.

  20. A valence force field-Monte Carlo algorithm for quantum dot growth modeling

    DEFF Research Database (Denmark)

    Barettin, Daniele; Kadkhodazadeh, Shima; Pecchia, Alessandro

    2017-01-01

    We present a novel kinetic Monte Carlo version for the atomistic valence force fields algorithm in order to model a self-assembled quantum dot growth process. We show our atomistic model is both computationally favorable and capture more details compared to traditional kinetic Monte Carlo models...

  1. Effect of the valence electron concentration on the bulk modulus and chemical bonding in Ta2AC and Zr2AC (A=Al, Si, and P)

    International Nuclear Information System (INIS)

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

    2005-01-01

    We have studied the effect of the valence electron concentration, on the bulk modulus and the chemical bonding in Ta 2 AC and Zr 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 2 AlC. The bulk moduli of both Ta 2 AC and Zr 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

  2. Mechatronic modeling and simulation using bond graphs

    CERN Document Server

    Das, Shuvra

    2009-01-01

    Introduction to Mechatronics and System ModelingWhat Is Mechatronics?What Is a System and Why Model Systems?Mathematical Modeling Techniques Used in PracticeSoftwareBond Graphs: What Are They?Engineering SystemsPortsGeneralized VariablesBond GraphsBasic Components in SystemsA Brief Note about Bond Graph Power DirectionsSummary of Bond Direction RulesDrawing Bond Graphs for Simple Systems: Electrical and MechanicalSimplification Rules for Junction StructureDrawing Bond Graphs for Electrical SystemsDrawing Bond Graphs for Mechanical SystemsCausalityDrawing Bond Graphs for Hydraulic and Electronic Components and SystemsSome Basic Properties and Concepts for FluidsBond Graph Model of Hydraulic SystemsElectronic SystemsDeriving System Equations from Bond GraphsSystem VariablesDeriving System EquationsTackling Differential CausalityAlgebraic LoopsSolution of Model Equations and Their InterpretationZeroth Order SystemsFirst Order SystemsSecond Order SystemTransfer Functions and Frequency ResponsesNumerical Solution ...

  3. Valency and molecular structure

    CERN Document Server

    Cartmell, E

    1977-01-01

    Valency and Molecular Structure, Fourth Edition provides a comprehensive historical background and experimental foundations of theories and methods relating to valency and molecular structures. In this edition, the chapter on Bohr theory has been removed while some sections, such as structures of crystalline solids, have been expanded. Details of structures have also been revised and extended using the best available values for bond lengths and bond angles. Recent developments are mostly noted in the chapter on complex compounds, while a new chapter has been added to serve as an introduction t

  4. A first-prototype multi-determinant X-ray constrained wavefunction approach: the X-ray constrained extremely localized molecular orbital-valence bond method.

    Science.gov (United States)

    Genoni, Alessandro

    2017-07-01

    All the current variants of Jayatilaka's X-ray constrained wavefunction (XCW) approach work within the framework of the single-determinant wavefunction ansatz. In this paper, a first-prototype multi-determinant XCW technique is proposed. The strategy assumes that the desired XCW is written as a valence-bond-like expansion in terms of pre-determined single Slater determinants constructed with extremely localized molecular orbitals. The method, which can be particularly suitable to investigate systems with a multi-reference character, has been applied to determine the weights of the resonance structures of naphthalene at different temperatures by exploiting experimental high-resolution X-ray diffraction data. The results obtained have shown that the explicit consideration of experimental structure factors in the determination of the resonance structure weights may lead to results significantly different compared with those resulting only from the simple energy minimization.

  5. 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.

    Science.gov (United States)

    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)

  6. Thai students' mental model of chemical bonding

    Science.gov (United States)

    Sarawan, Supawadee; Yuenyong, Chokchai

    2018-01-01

    This Research was finding the viewing about concept of chemical bonding is fundamental to subsequent learning of various other topics related to this concept in chemistry. Any conceptions about atomic structures that students have will be shown their further learning. The purpose of this study is to interviews conceptions held by high school chemistry students about metallic bonding and to reveal mental model of atomic structures show according to the educational level. With this aim, the questionnaire prepared making use of the literature and administered for analysis about mental model of chemical bonding. It was determined from the analysis of answers of questionnaire the 10th grade, 11th grade and 12th grade students. Finally, each was shown prompts in the form of focus cards derived from curriculum material that showed ways in which the bonding in specific metallic substances had been depicted. Students' responses revealed that learners across all three levels prefer simple, realistic mental models for metallic bonding and reveal to chemical bonding.

  7. Factor Structure of Early Smoking Experiences and Associations with Smoking Behavior: Valence or Sensitivity Model?

    Directory of Open Access Journals (Sweden)

    Stéphanie Baggio

    2013-11-01

    Full Text Available The Early Smoking Experience (ESE questionnaire is the most widely used questionnaire to assess initial subjective experiences of cigarette smoking. However, its factor structure is not clearly defined and can be perceived from two main standpoints: valence, or positive and negative experiences, and sensitivity to nicotine. This article explores the ESE’s factor structure and determines which standpoint was more relevant. It compares two groups of young Swiss men (German- and French-speaking. We examined baseline data on 3,368 tobacco users from a representative sample in the ongoing Cohort Study on Substance Use Risk Factors (C-SURF. ESE, continued tobacco use, weekly smoking and nicotine dependence were assessed. Exploratory structural equation modeling (ESEM and structural equation modeling (SEM were performed. ESEM clearly distinguished positive experiences from negative experiences, but negative experiences were divided in experiences related to dizziness and experiences related to irritations. SEM underlined the reinforcing effects of positive experiences, but also of experiences related to dizziness on nicotine dependence and weekly smoking. The best ESE structure for predictive accuracy of experiences on smoking behavior was a compromise between the valence and sensitivity standpoints, which showed clinical relevance.

  8. Understanding valence-shell electron-pair repulsion (VSEPR) theory using origami molecular models

    Science.gov (United States)

    Endah Saraswati, Teguh; Saputro, Sulistyo; Ramli, Murni; Praseptiangga, Danar; Khasanah, Nurul; Marwati, Sri

    2017-01-01

    Valence-shell electron-pair repulsion (VSEPR) theory is conventionally used to predict molecular geometry. However, it is difficult to explore the full implications of this theory by simply drawing chemical structures. Here, we introduce origami modelling as a more accessible approach for exploration of the VSEPR theory. Our technique is simple, readily accessible and inexpensive compared with other sophisticated methods such as computer simulation or commercial three-dimensional modelling kits. This method can be implemented in chemistry education at both the high school and university levels. We discuss the example of a simple molecular structure prediction for ammonia (NH3). Using the origami model, both molecular shape and the scientific justification can be visualized easily. This ‘hands-on’ approach to building molecules will help promote understanding of VSEPR theory.

  9. Photoemission in the Anderson model for rare earth compounds with floating valences

    International Nuclear Information System (INIS)

    Frota, H.O. da.

    1985-01-01

    X-ray photoemission spectra (XPS) are calculated for the spin-degenerate Anderson model of valence fluctuation compounds. Based on the renormalization group technique originally introduced by Wilson to calculate the magnetic susceptibility for the Kondo model, the numerical calculation has uniform accuracy over the entire parameter space of the Anderson model; at any given photoelectron energy, a maximum error of 4% is estimated for the calculated photoemission current. The calculated spectra display two peaks associated with the two possible x-ray induced transitions between the n f = 0,1 or 2 occupations of the f-orbital: a first ionization peak corresponding to the n f = 2 → n f = 1 transition and a second ionization peak due to the n f 1 → n f = 0 transition. (author)

  10. Understanding valence-shell electron-pair repulsion (VSEPR) theory using origami molecular models

    International Nuclear Information System (INIS)

    Saraswati, Teguh Endah; Saputro, Sulistyo; Ramli, Murni; Praseptiangga, Danar; Khasanah, Nurul; Marwati, Sri

    2017-01-01

    Valence-shell electron-pair repulsion (VSEPR) theory is conventionally used to predict molecular geometry. However, it is difficult to explore the full implications of this theory by simply drawing chemical structures. Here, we introduce origami modelling as a more accessible approach for exploration of the VSEPR theory. Our technique is simple, readily accessible and inexpensive compared with other sophisticated methods such as computer simulation or commercial three-dimensional modelling kits. This method can be implemented in chemistry education at both the high school and university levels. We discuss the example of a simple molecular structure prediction for ammonia (NH_3). Using the origami model, both molecular shape and the scientific justification can be visualized easily. This ‘hands-on’ approach to building molecules will help promote understanding of VSEPR theory. (paper)

  11. Valence Band Structure of InAs1-xBix and InSb1-xBix Alloy Semiconductors Calculated Using Valence Band Anticrossing Model

    Directory of Open Access Journals (Sweden)

    D. P. Samajdar

    2014-01-01

    Full Text Available The valence band anticrossing model has been used to calculate the heavy/light hole and spin-orbit split-off energies in InAs1-xBix and InSb1-xBix alloy systems. It is found that both the heavy/light hole, and spin-orbit split E+ levels move upwards in energy with an increase in Bi content in the alloy, whereas the split E− energy for the holes shows a reverse trend. The model is also used to calculate the reduction of band gap energy with an increase in Bi mole fraction. The calculated values of band gap variation agree well with the available experimental data.

  12. LAMMPS Framework for Dynamic Bonding and an Application Modeling DNA

    DEFF Research Database (Denmark)

    Svaneborg, Carsten

    2012-01-01

    and bond types. When breaking bonds, all angular and dihedral interactions involving broken bonds are removed. The framework allows chemical reactions to be modeled, and use it to simulate a simplistic, coarse-grained DNA model. The resulting DNA dynamics illustrates the power of the present framework.......We have extended the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) to support directional bonds and dynamic bonding. The framework supports stochastic formation of new bonds, breakage of existing bonds, and conversion between bond types. Bond formation can be controlled...... to limit the maximal functionality of a bead with respect to various bond types. Concomitant with the bond dynamics, angular and dihedral interactions are dynamically introduced between newly connected triplets and quartets of beads, where the interaction type is determined from the local pattern of bead...

  13. Liquid-solid transition in the bond particle model for elemental semiconductors

    International Nuclear Information System (INIS)

    Badirkhan, Z.; Tosi, M.P.; Rovere, M.

    1991-07-01

    Freezing of Silicon and Germanium involves a reconstruction of covalent tetrahedral bonds from a metallic liquid having density and coordination then the solid. We first contrast the metallic liquid structure of Germanium with that of its semiconducting amorphous state, in order to emphasize the changes in the atomic structure factor that arise from reconstruction of the interatomic bonds. We then use the density wave theory of freezing to discuss the liquid-solid transition within a pseudoclassical model, which describes the liquid structure by means of partial structure factors giving the pair correlations between atoms and bond particles. The phase transition is viewed as a freezing of the bonds driven by tetrahedrally constrained attractions between ionic cores and valence electrons and accompanied by an opening of the structure to allow long-range connectivity of tetrahedral atomic units. Quantitative calculations on the bond particle model illustrate the relationship between the liquid structure and the microscopic Fourier components of the single-particle densities of atoms and bonds. In further support of this picture, we also present calculations for freezing of a liquid having the density and the atomic structure of compacted amorphous Germanium. (author). 25 refs, 2 figs, 2 tabs

  14. Model analysis of molecular conformations in terms of weak interactions between non bonded atoms

    International Nuclear Information System (INIS)

    Lombardi, E.

    1988-01-01

    The aim of the present paper is to establish a reliable basis for the evaluation of stable conformations and rotational barriers for molecules, with possible applications to systems of biological interest. It is proceeded in two steps: first, the effect of chemical environment on orbitals of a given atom is studied for diatomic units, adopting a valence-bond approach and considering, as prototypes, the two simplest series of diatomic molecules with one valence electron each, i.e. the alkali diatomics and the alkali hydrides. In the model, the orbital of the hydrogen atom by a simple (''1S'') gaussian function, the valence orbital of an alkali atom by a function (r 2 -a 2 ) times a simple gaussian (''2S'' gaussian). Dissociation energies D e and equilibrium distances R e are calculated using a scanning procedure. Agreement with experiment is quantitative for the alkali diatomics. For alkali hydrides, good agreement is obtained only if validity of a rule β e R e =constant, for the two atoms separately, is postulated; β e is the characteristic parameter of a ''1S'' gaussian (hydrogen) or a ''2S'' gaussian (alkali atom) function. In a second step, the authors assume validity of the same rule in conformational analysis for any single bonded A-B molecule with A=C, O, N, P, Si, Ge and B=H, or a halogen atom. Gauge β e values for H, F and C are obtained by fitting experimental rotational barriers in C 2 H 6 , C 2 F 6 and C 3 H 8 . Stable conformation of, and barriers to rotation in, ethane-like rotors are determined, applying first-order exchange perturbation theory, in terms of two- and many-center exchange interactions in cluster of non-bonded atoms. Some 60 molecules are analyzed. Agreement with experiments is strikngly good except for a few systematic deviation. Reasons for such discrepancies are discussed

  15. Calculation of fluctuations and photoemission properties in a tetrahedral-cluster model for an intermediate-valence system

    International Nuclear Information System (INIS)

    Reich, A.; Falicov, L.M.

    1986-01-01

    An exact solution of a four-site tetrahedral-crystal model, the smallest face-centered-cubic crystal, is presented in the case of an intermediate-valence system. The model consists of the following: (a) one extended orbital and one localized orbital per atom, (b) an interatomic transfer term between extended orbitals, (c) an interatomic hybridization between the localized and extended orbitals, (d) strong intra-atomic Coulomb repulsion between opposite-spin localized states, and (e) intermediate-strength intra-atomic Coulomb repulsion between the localized and extended states. These competing effects are examined as they manifest themselves in the intermediate-valence, photoemission, inverse-photoemission, and thermodynamic properties

  16. Decision-making deficits in patients with chronic schizophrenia: Iowa Gambling Task and Prospect Valence Learning model

    OpenAIRE

    Kim, Myung-Sun; Kang,Bit-Na; Lim,Jae Young

    2016-01-01

    Myung-Sun Kim,1 Bit-Na Kang,1 Jae Young Lim2 1Department of Psychology, Sungshin Women’s University, Seoul, Republic of Korea; 2Department of Psychiatry, Keyo Medical Foundation, Keyo Hospital, Uiwang, Republic of Korea Purpose: Decision-making is the process of forming preferences for possible options, selecting and executing actions, and evaluating the outcome. This study used the Iowa Gambling Task (IGT) and the Prospect Valence Learning (PVL) model to investigate deficits in r...

  17. Wavelet-based study of valence?arousal model of emotions on EEG signals with LabVIEW

    OpenAIRE

    Guzel Aydin, Seda; Kaya, Turgay; Guler, Hasan

    2016-01-01

    This paper illustrates the wavelet-based feature extraction for emotion assessment using electroencephalogram (EEG) signal through graphical coding design. Two-dimensional (valence?arousal) emotion model was studied. Different emotions (happy, joy, melancholy, and disgust) were studied for assessment. These emotions were stimulated by video clips. EEG signals obtained from four subjects were decomposed into five frequency bands (gamma, beta, alpha, theta, and delta) using ?db5? wavelet functi...

  18. Applicability of a valence fluctuation model to the observed physical property response of actinide materials

    International Nuclear Information System (INIS)

    Sandenaw, T.A.

    1978-01-01

    It is shown that the physical property behavior of the light actinide elements, U, Np, and Pu, and certain of their alloys, is like that of known mixed-valence, R.E. metallic compounds. It is inferred that interconfiguration fluctuation (ICF) theory should also be applicable to actinide materials

  19. Using the Circumplex Model of Affect to Study Valence and Arousal Ratings of Emotional Faces by Children and Adults with Autism Spectrum Disorders

    OpenAIRE

    Tseng, Angela; Bansal, Ravi; Liu, Jun; Gerber, Andrew J.; Goh, Suzanne; Posner, Jonathan; Colibazzi, Tiziano; Algermissen, Molly; Chiang, I-Chin; Russell, James A.; Peterson, Bradley S.

    2014-01-01

    The Affective Circumplex Model holds that emotions can be described as linear combinations of two underlying, independent neurophysiological systems (arousal, valence). Given research suggesting individuals with autism spectrum disorders (ASD) have difficulty processing emotions, we used the circumplex model to compare how individuals with ASD and typically-developing (TD) individuals respond to facial emotions. Participants (51 ASD, 80 TD) rated facial expressions along arousal and valence d...

  20. Predictive Models for the Free Energy of Hydrogen Bonded Complexes with Single and Cooperative Hydrogen Bonds.

    Science.gov (United States)

    Glavatskikh, Marta; Madzhidov, Timur; Solov'ev, Vitaly; Marcou, Gilles; Horvath, Dragos; Varnek, Alexandre

    2016-12-01

    In this work, we report QSPR modeling of the free energy ΔG of 1 : 1 hydrogen bond complexes of different H-bond acceptors and donors. The modeling was performed on a large and structurally diverse set of 3373 complexes featuring a single hydrogen bond, for which ΔG was measured at 298 K in CCl 4 . The models were prepared using Support Vector Machine and Multiple Linear Regression, with ISIDA fragment descriptors. The marked atoms strategy was applied at fragmentation stage, in order to capture the location of H-bond donor and acceptor centers. Different strategies of model validation have been suggested, including the targeted omission of individual H-bond acceptors and donors from the training set, in order to check whether the predictive ability of the model is not limited to the interpolation of H-bond strength between two already encountered partners. Successfully cross-validating individual models were combined into a consensus model, and challenged to predict external test sets of 629 and 12 complexes, in which donor and acceptor formed single and cooperative H-bonds, respectively. In all cases, SVM models outperform MLR. The SVM consensus model performs well both in 3-fold cross-validation (RMSE=1.50 kJ/mol), and on the external test sets containing complexes with single (RMSE=3.20 kJ/mol) and cooperative H-bonds (RMSE=1.63 kJ/mol). © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Studies of valence-bond based quantum mechanical potential-energy surfaces. I. H2 + D2 exchange reaction. II. LiH + H → Li + H2 and LiH + D → LiD + H reactions

    International Nuclear Information System (INIS)

    Freihaut, B.H.

    1975-01-01

    The first phase of this investigation involved the construction of a perfect pairing valence-bond (VB) quantum mechanical potential-energy surfaces for the (H 2 D 2 ) system to compare its results for various geometries to the other prior formulations of such. A plausible four-body pathway for the H 2 --D 2 exchange reaction as shown by a semiempirical Huckel method was explored by the current valence-bond procedure. The second phase of the present investigation involves the formation of a VB based potential-energy surface for the LiH + H → Li + H 2 and LiH + D → LiD + H reaction systems for geometries compatible for a three-center reaction mechanism. No energy acceptable four-body reaction pathway was found for the H 2 --D 2 exchange system. Good agreement was demonstrated with previous ''ab initio'' configuration interaction (CI) studies for the various geometries tested. The square configuration for the H 4 system yielded the lowest barrier height of all the four-body geometries tested although it was still considerably higher than the experimental activation energy for the (H 2 ,D 2 ) system. The barrier height energy for the linear LiH--H configuration agreed well with the one previous work on this system. The barrier height for the LiH--H system increases as the Li--H--H bond angle decreases from 180 0 to 90 0 as well as the Li--H distance at the saddle point. The VB method used herein showed markedly good comparison with recent full CI calculations on the lithium-hydrogen system especially in view of the very limited basis set used in the VB procedure

  2. Theoretical study of one-electron bonds in a series of high-spin lithium-beryllium-hydrogen clusters: ?Valence shell single-electron repulsion? rule and electron localization function analysis

    Science.gov (United States)

    Chaquin, Patrick; Chevreau, Hilaire

    A series of high-spin clusters containing Li, H, and Be in which the valence shell molecular orbitals (MOs) are occupied by a single electron has been characterized using ab initio and density functional theory (DFT) calculations. A first type (5Li2, n+1LiHn+ (n = 2-5), 8Li2H6+) possesses only one electron pair in the lowest MO, with bond energies of ?3 kcal/mol. In a second type, all the MOs are singly occupied, which results in highly excited species that nevertheless constitute a marked minimum on their potential energy surface (PES). Thus, it is possible to design a larger panel of structures (8LiBe, 7Li2, 8Li2-, 4LiH+, 6BeH2+, n+3LiHn+ (n = 3, 4), n+2LiHn2+ (n = 4-6), 8Li2H2+, 9Li2H42+, 22Li3Be3 and 22Li6H63+), single-electron equivalent to doublet ?classical? molecules ranging from CO to C6H6. The geometrical structure is studied in relation to the valence shell single-electron repulsion (VSEPR) theory and the electron localization function (ELF) is analyzed, revealing a striking similarity with the corresponding structure having paired electrons.

  3. Phase separation and valence instabilities in cuprate superconductors: Effective one-band-model approach

    Science.gov (United States)

    Simón, M. E.; Aligia, A. A.

    1996-06-01

    We study the Cu-O valence instability (VI) and the related phase separation (PS) driven by Cu-O nearest-neighbor repulsion Upd, using an effective extended one-band Hubbard (Heff) obtained from the extended three-band Hubbard, through an appropriate low-energy reduction. Heff is solved by exact diagonalization of a square cluster with 10 unit cells and also within a slave-boson mean-field theory. Its parameters depend on doping for Upd≠0 and on-site O repulsion Up≠0. The results using both techniques coincide in that there is neither VI nor PS for doping values levels xUpd>~2 eV. The PS region begins for Upd>~2 at large doping x>~0.6 and increases with increasing Upd. The PS also increases with increasing on-site Cu repulsion Ud.

  4. Upper Secondary Teachers' Knowledge for Teaching Chemical Bonding Models

    Science.gov (United States)

    Bergqvist, Anna; Drechsler, Michal; Chang Rundgren, Shu-Nu

    2016-01-01

    Researchers have shown a growing interest in science teachers' professional knowledge in recent decades. The article focuses on how chemistry teachers impart chemical bonding, one of the most important topics covered in upper secondary school chemistry courses. Chemical bonding is primarily taught using models, which are key for understanding…

  5. Wavelet-based study of valence-arousal model of emotions on EEG signals with LabVIEW.

    Science.gov (United States)

    Guzel Aydin, Seda; Kaya, Turgay; Guler, Hasan

    2016-06-01

    This paper illustrates the wavelet-based feature extraction for emotion assessment using electroencephalogram (EEG) signal through graphical coding design. Two-dimensional (valence-arousal) emotion model was studied. Different emotions (happy, joy, melancholy, and disgust) were studied for assessment. These emotions were stimulated by video clips. EEG signals obtained from four subjects were decomposed into five frequency bands (gamma, beta, alpha, theta, and delta) using "db5" wavelet function. Relative features were calculated to obtain further information. Impact of the emotions according to valence value was observed to be optimal on power spectral density of gamma band. The main objective of this work is not only to investigate the influence of the emotions on different frequency bands but also to overcome the difficulties in the text-based program. This work offers an alternative approach for emotion evaluation through EEG processing. There are a number of methods for emotion recognition such as wavelet transform-based, Fourier transform-based, and Hilbert-Huang transform-based methods. However, the majority of these methods have been applied with the text-based programming languages. In this study, we proposed and implemented an experimental feature extraction with graphics-based language, which provides great convenience in bioelectrical signal processing.

  6. Unicorns in the world of chemical bonding models.

    Science.gov (United States)

    Frenking, Gernot; Krapp, Andreas

    2007-01-15

    The appearance and the significance of heuristically developed bonding models are compared with the phenomenon of unicorns in mythical saga. It is argued that classical bonding models played an essential role for the development of the chemical science providing the language which is spoken in the territory of chemistry. The advent and the further development of quantum chemistry demands some restrictions and boundary conditions for classical chemical bonding models, which will continue to be integral parts of chemistry. Copyright (c) 2006 Wiley Periodicals, Inc.

  7. Macroeconomic Stability in a Model with Bond Transaction Services

    Directory of Open Access Journals (Sweden)

    Massimiliano Marzo

    2018-02-01

    Full Text Available Cochrane (2014 shows that high-powered money balances and short-term government bonds can be considered as perfect substitutes for the U.S economy during the past twenty years. We build on this claim and consider a variant of the standard cashless new-Keynesian model with two types of government bonds, which can be thought of as short- and long-term bonds. The first one has a macroeconomic role in the sense that it provides transaction services in addition to generating a yield. The other type of government bond pays only an interest rate. Consistent with previous findings, the Taylor principle is not a panacea for equilibrium determinacy in a model without money. When the government bond market matters beyond the need for fiscal solvency, monetary policy rules do not need to comply with the Taylor principle for unique equilibria to exist.

  8. Bond graph model-based fault diagnosis of hybrid systems

    CERN Document Server

    Borutzky, Wolfgang

    2015-01-01

    This book presents a bond graph model-based approach to fault diagnosis in mechatronic systems appropriately represented by a hybrid model. The book begins by giving a survey of the fundamentals of fault diagnosis and failure prognosis, then recalls state-of-art developments referring to latest publications, and goes on to discuss various bond graph representations of hybrid system models, equations formulation for switched systems, and simulation of their dynamic behavior. The structured text: • focuses on bond graph model-based fault detection and isolation in hybrid systems; • addresses isolation of multiple parametric faults in hybrid systems; • considers system mode identification; • provides a number of elaborated case studies that consider fault scenarios for switched power electronic systems commonly used in a variety of applications; and • indicates that bond graph modelling can also be used for failure prognosis. In order to facilitate the understanding of fault diagnosis and the presented...

  9. Application of Bond Graph Modeling for Photovoltaic Module Simulation

    Directory of Open Access Journals (Sweden)

    Madi S.

    2016-01-01

    Full Text Available In this paper, photovoltaic generator is represented using the bond-graph methodology. Starting from the equivalent circuit the bond graph and the block diagram of the photovoltaic generator have been derived. Upon applying bond graph elements and rules a mathematical model of the photovoltaic generator is obtained. Simulation results of this obtained model using real recorded data (irradiation and temperature at the Renewable Energies Development Centre in Bouzaréah – Algeria are obtained using MATLAB/SMULINK software. The results have compared with datasheet of the photovoltaic generator for validation purposes.

  10. X-ray scattering and the chemical bond in N2 and CN

    NARCIS (Netherlands)

    Groenewegen, P.P.M.; Zeevalkink, J.; Feil, D.

    1971-01-01

    X-ray scattering from the chemical bond within N2 and CN- has been studied in detail. Differences in scattering from these systems, derived from bonding and non-bonding models, are characterized by R values of ~ 0.04. Partitioning of the scattering into core and valence electron parts clearly

  11. Ab initio valence calculations in chemistry

    CERN Document Server

    Cook, D B

    1974-01-01

    Ab Initio Valence Calculations in Chemistry describes the theory and practice of ab initio valence calculations in chemistry and applies the ideas to a specific example, linear BeH2. Topics covered include the Schrödinger equation and the orbital approximation to atomic orbitals; molecular orbital and valence bond methods; practical molecular wave functions; and molecular integrals. Open shell systems, molecular symmetry, and localized descriptions of electronic structure are also discussed. This book is comprised of 13 chapters and begins by introducing the reader to the use of the Schrödinge

  12. Using the Circumplex Model of Affect to Study Valence and Arousal Ratings of Emotional Faces by Children and Adults with Autism Spectrum Disorders

    Science.gov (United States)

    Tseng, Angela; Bansal, Ravi; Liu, Jun; Gerber, Andrew J.; Goh, Suzanne; Posner, Jonathan; Colibazzi, Tiziano; Algermissen, Molly; Chiang, I-Chin; Russell, James A.; Peterson, Bradley S.

    2014-01-01

    The Affective Circumplex Model holds that emotions can be described as linear combinations of two underlying, independent neurophysiological systems (arousal, valence). Given research suggesting individuals with autism spectrum disorders (ASD) have difficulty processing emotions, we used the circumplex model to compare how individuals with ASD and…

  13. Reactive Force Fields via Explicit Valency

    Science.gov (United States)

    Kale, Seyit

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

  14. Valencies of the lanthanides

    OpenAIRE

    Johnson, David A.; Nelson, Peter G.

    2018-01-01

    The valencies of the lanthanides vary more than was once thought. In addition to valencies associated with a half-full shell, there are valencies associated with a quarter- and three-quarter-full shell. This can be explained on the basis of Slater’s theory of many-electron atoms. The same theory explains the variation in complexing constants in the trivalent state (the “tetrad effect”). Valency in metallic and organometallic compounds is also discussed.

  15. Political Culture and Covalent Bonding. A Conceptual Model of Political Culture Change

    Directory of Open Access Journals (Sweden)

    Camelia Florela Voinea

    2015-01-01

    Full Text Available Our class of models aims at explaining the dynamics of political attitude change by means of the dynamic changes in values, beliefs, norms and knowledge with which it is associated. The model constructs a political culture perspective over the relationship between macro and micro levels of a society and polity. The model defines the bonding mechanism as a basic mechanism of the political culture change by taking inspiration from the valence bonding theory in Chemistry, which has inspired the elaboration of the mechanisms and processes underlying the political culture emergence and the political culture control over the relationship between macro-level political entities and the micro-level individual agents. The model introduces operational definitions of the individual agent in political culture terms. The simulation model is used for the study of emergent political culture change phenomena based on individual interactions (emergent or upward causation as well as the ways in which the macro entities and emergent phenomena influence in turn the behaviors of individual agents (downward causation. The model is used in the ongoing research concerning the quality of democracy and political participation of the citizens in the Eastern European societies after the Fall of Berlin Wall. It is particularly aimed at explaining the long-term effect of the communist legacy and of the communist polity concept and organization onto the political mentalities and behaviors of the citizens with respect to democratic institutions and political power. The model has major implications in political socialization, political involvement, political behavior, corruption and polity modeling.

  16. Computational Tools To Model Halogen Bonds in Medicinal Chemistry.

    Science.gov (United States)

    Ford, Melissa Coates; Ho, P Shing

    2016-03-10

    The use of halogens in therapeutics dates back to the earliest days of medicine when seaweed was used as a source of iodine to treat goiters. The incorporation of halogens to improve the potency of drugs is now fairly standard in medicinal chemistry. In the past decade, halogens have been recognized as direct participants in defining the affinity of inhibitors through a noncovalent interaction called the halogen bond or X-bond. Incorporating X-bonding into structure-based drug design requires computational models for the anisotropic distribution of charge and the nonspherical shape of halogens, which lead to their highly directional geometries and stabilizing energies. We review here current successes and challenges in developing computational methods to introduce X-bonding into lead compound discovery and optimization during drug development. This fast-growing field will push further development of more accurate and efficient computational tools to accelerate the exploitation of halogens in medicinal chemistry.

  17. Nucleophilic Aromatic Addition in Ionizing Environments: Observation and Analysis of New C-N Valence Bonds in Complexes between Naphthalene Radical Cation and Pyridine.

    Science.gov (United States)

    Peverati, Roberto; Platt, Sean P; Attah, Isaac K; Aziz, Saaudallah G; El-Shall, M Samy; Head-Gordon, Martin

    2017-08-30

    Radical organic ions can be stabilized by complexation with neutral organics via interactions that can resemble chemical bonds, but with much diminished bond energies. Those interactions are a key factor in cluster growth and polymerization reactions in ionizing environments such as regions of the interstellar medium and solar nebulae. Such radical cation complexes between naphthalene (Naph) and pyridine (Pyr) are characterized using mass-selected ion mobility experiments. The measured enthalpy of binding of the Naph +• (Pyr) heterodimer (20.9 kcal/mol) exceeds that of the Naph +• (Naph) homodimer (17.8 kcal/mol). The addition of 1-3 more pyridine molecules to the Naph +• (Pyr) heterodimer gives 10-11 kcal/mol increments in binding enthalpy. A rich array of Naph +• (Pyr) isomers are characterized by electronic structure calculations. The calculated Boltzmann distribution at 400 K yields an enthalpy of binding in reasonable agreement with experiment. The global minimum is a distonic cation formed by Pyr attack on Naph +• at the α-carbon, changing its hybridization from sp 2 to distorted sp 3 . The measured collision cross section in helium for the Naph +• (Pyr) heterodimer of 84.9 ± 2.5 Å 2 at 302 K agrees well with calculated angle-averaged cross sections (83.9-85.1 Å 2 at 302 K) of the lowest energy distonic structures. A remarkable 16 kcal/mol increase in the binding energy between Naph +• (Pyr) and Bz +• (Pyr) (Bz is benzene) is understood by energy decomposition analysis. A similar increase in binding from Naph +• (NH 3 ) to Naph +• (Pyr) (as well as between Bz +• (NH 3 ) and Bz +• (Pyr)) is likewise rationalized.

  18. Probing molecular adsorbates with core-level spectroscopies: Electronic structure and bonding models

    Science.gov (United States)

    Fohlisch, Alexander

    Resonantly excited X-ray emission spectroscopy has been applied to study the valence electronic structure of molecular adsorbates in an atom specific and orbital symmetry selective manner. In combination with ab initio cluster calculations, electronic structure and bonding models have been derived. Existing models of surface chemical bonding have been reviewed and partially revised. Most notably, the bonding mechanism of carbon monoxide (CO) on transition and noble metals has been revised and is found to be the result of a strong covalent interaction between the CO orbitals and the metal bands within each orbital symmetry. A characteristic allylic configuration is found in the π system and strong polarization within the σ system. The equilibrium properties of adsorbed CO are the direct result of a balance between the repulsive σ-interaction and the attractive π-interaction both in terms of the total energy and the local bond properties. The bonding of ammonia (NH3) on the Cu(110) surface is found to be dominated by a large covalent interaction, which contrasts the previous model of a strong electrostatic interaction. Furthermore, adsorbate-adsorbate interaction leads to a tilted adsorption geometry. Ethylene (C2H4) on Cu(110) is adsorbed in the di-σ configuration, according to the generally accepted Dewar Chatt Duncanson model for hydrocarbon adsorption. The application and interpretation of resonantly excited X-ray emission on these systems also required a thorough discussion of the spectroscopic process. Another topic was the vibrational fine structure in the X-ray photoemission core-level main lines of adsorbed molecules. The observation of the vibrational fine structure in molecular adsorbates is remarkable, as it was previously thought impossible to observe due to solid state broadening contributions. A detailed analysis of the vibrational fine structure and the line profile makes it possible to study the electronic and geometric properties of the core

  19. Modeling the Conditional Covariance between Stock and Bond Returns

    NARCIS (Netherlands)

    P. de Goeij (Peter); W.A. Marquering (Wessel)

    2002-01-01

    textabstractTo analyze the intertemporal interaction between the stock and bond market returns, we allow the conditional covariance matrix to vary over time according to a multivariate GARCH model similar to Bollerslev, Engle and Wooldridge (1988). We extend the model such that it allows for

  20. An affective circumplex model of neural systems subserving valence, arousal, and cognitive overlay during the appraisal of emotional faces.

    Science.gov (United States)

    Gerber, Andrew J; Posner, Jonathan; Gorman, Daniel; Colibazzi, Tiziano; Yu, Shan; Wang, Zhishun; Kangarlu, Alayar; Zhu, Hongtu; Russell, James; Peterson, Bradley S

    2008-01-01

    Increasing evidence supports the existence of distinct neural systems that subserve two dimensions of affect--arousal and valence. Ten adult participants underwent functional magnetic resonance imaging during which they were presented a range of standardized faces and then asked, during the scan, to rate the emotional expressions of the faces along the dimensions of arousal and valence. Lower ratings of arousal accompanied greater activity in the amygdala complex, cerebellum, dorsal pons, and right medial prefrontal cortex (mPFC). More negative ratings of valence accompanied greater activity in the dorsal anterior cingulate (dACC) and parietal cortices. Extreme ratings of valence (highly positive and highly negative ratings) accompanied greater activity in the temporal cortex and fusiform gyrus. Building on an empirical literature which suggests that the amygdala serves as a salience and ambiguity detector, we interpret our findings as showing that a face rated as having low arousal is more ambiguous and a face rated as having extreme valence is more personally salient. This explains how both low arousal and extreme valence lead to greater activation of an ambiguity/salience system subserved by the amygdala, cerebellum, and dorsal pons. In addition, the right medial prefrontal cortex appears to down-regulate individual ratings of arousal, whereas the fusiform and related temporal cortices seem to up-regulate individual assessments of extreme valence when individual ratings are studied relative to group reference ratings for each stimulus. The simultaneous assessment of the effects of arousal and valence proved essential for the identification of neural systems contributing to the processing of emotional faces.

  1. An Affective Circumplex Model of Neural Systems Subserving Valence, Arousal, & Cognitive Overlay During the Appraisal of Emotional Faces

    Science.gov (United States)

    Gerber, Andrew J.; Posner, Jonathan; Gorman, Daniel; Colibazzi, Tiziano; Yu, Shan; Wang, Zhishun; Kangarlu, Alayar; Zhu, Hongtu; Russell, James; Peterson, Bradley S.

    2008-01-01

    Increasing evidence supports the existence of distinct neural systems that subserve two dimensions of affect – arousal and valence. Ten adult participants underwent functional magnetic resonance imaging during which they were presented a range of standardized faces and then asked, during the scan, to rate the emotional expressions of the faces along the dimensions of arousal and valence. Lower ratings of arousal accompanied greater activity in the amygdala complex, cerebellum, dorsal pons, and right medial prefrontal cortex. More negative ratings of valence accompanied greater activity in the dorsal anterior cingulate and parietal cortices. Extreme ratings of valence (highly positive and highly negative ratings) accompanied greater activity in the temporal cortex and fusiform gyrus. Building on an empirical literature which suggests that the amygdala serves as a salience and ambiguity detector, we interpret our findings as showing that a face rated has having low arousal is more ambiguous and a face rated as having extreme valence is more personally salient. This explains how both low arousal and extreme valence lead to greater activation of an ambiguity/salience system subserved by the amygdala, cerebellum, and dorsal pons. In addition, the right medial prefrontal cortex appears to down-regulate individual ratings of arousal, whereas the fusiform and related temporal cortices seem to up-regulate individual assessments of extreme valence when individual ratings are studied relative to group reference ratings for each stimulus. The simultaneous assessment of the effects of arousal and valence proved essential for the identification of neural systems contributing to the processing of emotional faces. PMID:18440572

  2. Teaching VSEPR: The Plastic Egg Model.

    Science.gov (United States)

    Birk, James P.; Abbassain, Soraya

    1996-01-01

    Describes the construction of a versatile, accessible, and inexpensive model to demonstrate the Valence-Shell Electron-Pair Repulsion Theory (VSEPR). Depicts the different orientation of valence electrons in an atom and the geometry of bonds and lone pairs in molecules. Offers the advantage of easily distinguishing lone pairs from bonds and…

  3. Fuzzy Case-Based Reasoning in Product Style Acquisition Incorporating Valence-Arousal-Based Emotional Cellular Model

    Directory of Open Access Journals (Sweden)

    Fuqian Shi

    2012-01-01

    Full Text Available Emotional cellular (EC, proposed in our previous works, is a kind of semantic cell that contains kernel and shell and the kernel is formalized by a triple- L = , where P denotes a typical set of positive examples relative to word-L, d is a pseudodistance measure on emotional two-dimensional space: valence-arousal, and δ is a probability density function on positive real number field. The basic idea of EC model is to assume that the neighborhood radius of each semantic concept is uncertain, and this uncertainty will be measured by one-dimensional density function δ. In this paper, product form features were evaluated by using ECs and to establish the product style database, fuzzy case based reasoning (FCBR model under a defined similarity measurement based on fuzzy nearest neighbors (FNN incorporating EC was applied to extract product styles. A mathematical formalized inference system for product style was also proposed, and it also includes uncertainty measurement tool emotional cellular. A case study of style acquisition of mobile phones illustrated the effectiveness of the proposed methodology.

  4. Hirshfeld atom refinement for modelling strong hydrogen bonds.

    Science.gov (United States)

    Woińska, Magdalena; Jayatilaka, Dylan; Spackman, Mark A; Edwards, Alison J; Dominiak, Paulina M; Woźniak, Krzysztof; Nishibori, Eiji; Sugimoto, Kunihisa; Grabowsky, Simon

    2014-09-01

    High-resolution low-temperature synchrotron X-ray diffraction data of the salt L-phenylalaninium hydrogen maleate are used to test the new automated iterative Hirshfeld atom refinement (HAR) procedure for the modelling of strong hydrogen bonds. The HAR models used present the first examples of Z' > 1 treatments in the framework of wavefunction-based refinement methods. L-Phenylalaninium hydrogen maleate exhibits several hydrogen bonds in its crystal structure, of which the shortest and the most challenging to model is the O-H...O intramolecular hydrogen bond present in the hydrogen maleate anion (O...O distance is about 2.41 Å). In particular, the reconstruction of the electron density in the hydrogen maleate moiety and the determination of hydrogen-atom properties [positions, bond distances and anisotropic displacement parameters (ADPs)] are the focus of the study. For comparison to the HAR results, different spherical (independent atom model, IAM) and aspherical (free multipole model, MM; transferable aspherical atom model, TAAM) X-ray refinement techniques as well as results from a low-temperature neutron-diffraction experiment are employed. Hydrogen-atom ADPs are furthermore compared to those derived from a TLS/rigid-body (SHADE) treatment of the X-ray structures. The reference neutron-diffraction experiment reveals a truly symmetric hydrogen bond in the hydrogen maleate anion. Only with HAR is it possible to freely refine hydrogen-atom positions and ADPs from the X-ray data, which leads to the best electron-density model and the closest agreement with the structural parameters derived from the neutron-diffraction experiment, e.g. the symmetric hydrogen position can be reproduced. The multipole-based refinement techniques (MM and TAAM) yield slightly asymmetric positions, whereas the IAM yields a significantly asymmetric position.

  5. Meson productions at large transverse momentum in core-valence parton model

    CERN Document Server

    Biyajima, M

    1976-01-01

    A quark parton model with an impulse approximation is presented for describing from small momentum to large momentum phenomena in inclusive reactions. An annihilation process by quark-antiquark collision and a pair creation process by gluon-gluon collision are assumed to be dominant. By making use of these two diagrams the authors can explain the particle ratios in addition to the various large p/sub T/-distributions at FNAL and CERN-ISR. Model calculations suggests that gluon collisions are playing an important role as well as quark-antiquark annihilation process. (24 refs).

  6. Measuring affect at work based on the valence and arousal circumplex model.

    Science.gov (United States)

    Madrid, Hector P; Patterson, Malcolm G

    2014-01-01

    Affective states have become a central topic of interest in research on organizational behavior. Recently, scholars have been paying more attention to the proposals of the Circumplex Model (Russell, 1980) in order to gain a finer grained understanding of job-related affect. However, the limited availability of well-validated measures to test this model in work settings, particularly in non English-speaking populations, is still a major drawback. Using three samples of English-speaking and Spanish-speaking workers, this article offers the cross-validation of the Multi-Affect Indicator (Warr, 2007) between the original English version and its corresponding translation into Spanish. Multi-group Structural Equation Modeling supported the instrument's structure and its invariance between the two languages (English: χ2 = 65.56, df = 48, p = .05; RMSEA = .06; CFI = .97; Spanish: χ2 = 68.68, df = 48, p = .03; RMSEA = .05; CFI = .97). Furthermore, Circular Stochastic Modeling supported the theoretically proposed circumplex representation (χ2 = 139.85, df = 51, p < .01; χ2/df = 2.74, RMSEA = .06). Thus, this study offers an instrument that provides a more accurate approximation to affect at work, both in English and in another of the major language communities in the world, the Spanish-speaking population.

  7. Modified bond model for shear in slabs under concentrated loads

    NARCIS (Netherlands)

    Lantsoght, E.O.L.; Van der Veen, C.; De Boer, A.

    2015-01-01

    Slabs subjected to concentrated loads close to supports, as occurring for truck loads on slab bridges, are less studied than beams in shear or slab-column connections in punching. To predict the shear capacity for this case, the Bond Model for concentric punching shear was studied initially.

  8. Estimating Structural Models of Corporate Bond Prices in Indonesian Corporations

    Directory of Open Access Journals (Sweden)

    Lenny Suardi

    2014-08-01

    Full Text Available This  paper  applies  the  maximum  likelihood  (ML  approaches  to  implementing  the structural  model  of  corporate  bond,  as  suggested  by  Li  and  Wong  (2008,  in  Indonesian corporations.  Two  structural  models,  extended  Merton  and  Longstaff  &  Schwartz  (LS models,  are  used  in  determining  these  prices,  yields,  yield  spreads  and  probabilities  of default. ML estimation is used to determine the volatility of irm value. Since irm value is unobserved variable, Duan (1994 suggested that the irst step of ML estimation is to derive the likelihood function for equity as the option on the irm value. The second step is to ind parameters such as the drift and volatility of irm value, that maximizing this function. The irm value itself is extracted by equating the pricing formula to the observed equity prices. Equity,  total  liabilities,  bond  prices  data  and  the  irm's  parameters  (irm  value,  volatility of irm value, and default barrier are substituted to extended Merton and LS bond pricing formula in order to valuate the corporate bond.These models are implemented to a sample of 24 bond prices in Indonesian corporation during  period  of  2001-2005,  based  on  criteria  of  Eom,  Helwege  and  Huang  (2004.  The equity  and  bond  prices  data  were  obtained  from  Indonesia  Stock  Exchange  for  irms  that issued equity and provided regular inancial statement within this period. The result shows that both models, in average, underestimate the bond prices and overestimate the yields and yield spread. ";} // -->activate javascript

  9. Decision-making deficits in patients with chronic schizophrenia: Iowa Gambling Task and Prospect Valence Learning model.

    Science.gov (United States)

    Kim, Myung-Sun; Kang, Bit-Na; Lim, Jae Young

    2016-01-01

    Decision-making is the process of forming preferences for possible options, selecting and executing actions, and evaluating the outcome. This study used the Iowa Gambling Task (IGT) and the Prospect Valence Learning (PVL) model to investigate deficits in risk-reward related decision-making in patients with chronic schizophrenia, and to identify decision-making processes that contribute to poor IGT performance in these patients. Thirty-nine patients with schizophrenia and 31 healthy controls participated. Decision-making was measured by total net score, block net scores, and the total number of cards selected from each deck of the IGT. PVL parameters were estimated with the Markov chain Monte Carlo sampling scheme in OpenBugs and BRugs, its interface to R, and the estimated parameters were analyzed with the Mann-Whitney U-test. The schizophrenia group received significantly lower total net scores compared to the control group. In terms of block net scores, an interaction effect of group × block was observed. The block net scores of the schizophrenia group did not differ across the five blocks, whereas those of the control group increased as the blocks progressed. The schizophrenia group obtained significantly lower block net scores in the fourth and fifth blocks of the IGT and selected cards from deck D (advantageous) less frequently than the control group. Additionally, the schizophrenia group had significantly lower values on the utility-shape, loss-aversion, recency, and consistency parameters of the PVL model. These results indicate that patients with schizophrenia experience deficits in decision-making, possibly due to failure in learning the expected value of each deck, and incorporating outcome experiences of previous trials into expectancies about options in the present trial.

  10. An Algebraic Model for the Pion's Valence-Quark GPD: A Probe for a Consistent Extension Beyond DGLAP Region Via Radon Transform Inversion

    Science.gov (United States)

    Chouika, Nabil; Mezrag, Cédric; Moutarde, Hervé; Rodríguez-Quintero, José

    2017-07-01

    We briefly report on a recent computation, with the help of a fruitful algebraic model, sketching the pion valence dressed-quark generalized parton distribution. Then, preliminary, we introduce on a sensible procedure to get reliable results in both Dokshitzer-Gribov-Lipatov-Altarelli-Parisi and Efremov-Radyushkin-Brodsky-Lepage kinematical regions, grounded on the GPD overlap representation and its parametrization of a Radon transform of the so-called double distribution.

  11. Ionic conduction, bond valence analysis of structure–property relationships of NaHoP{sub 2}O{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Béjaoui, Anis, E-mail: bejaoui-anis@hotmail.fr; Horchani-Naifer, Karima; Férid, Mokhtar

    2013-08-15

    Single crystals of NaHoP{sub 2}O{sub 7} diphosphate have been prepared by the flux method and its structural and physical properties have been investigated. It crystallizes in the monoclinic system with the space group P2{sub 1}/n and its parameters are: a=8.6796(4) Å, b=5.3677(2) Å, c=13.6904(6) Å, β=106.120° (2), V=612.75 (5) Å{sup 3}, Z=4. The structure of NaHoP{sub 2}O{sub 7} consists of a three-dimensional framework of HoO{sub 6} octahedra, linked by P{sub 2}O{sub 7} diphosphate units, forming tunnels running parallel to [0 1 0], which are occupied by Na atoms. The infrared and Raman vibrational spectra have been investigated. Activation energy was obtained from Arrhenius plots (Ln σT versus 1000/T) and found to be 1.27 eV. The coupling of the structural analysis with the BVS model for NaHoP{sub 2}O{sub 7} has better interpret the measurements of the ionic conductivity and the most probably transport pathway model was determined. - Graphical abstract: Schematic representation of the structural arrangement of NaHoP{sub 2}O{sub 7} shows the sodium conduction pathway along the [0 1 0] direction. Highlights: • Single crystals of NaHoP{sub 2}O{sub 7} were prepared by flux method and characterized by single-crystal X-ray data. • The conductivity and loss spectra were analysed in order explain the mechanism of conduction. • The most probably conduction pathway are determined.

  12. Bond Graph Modeling and Simulation of Mechatronic Systems

    DEFF Research Database (Denmark)

    Habib, Tufail; Nielsen, Kjeld; Jørgensen, Kaj Asbjørn

    2012-01-01

    One of the demanding steps in the design and development of Mechatronic systems is to develop the initial model to visualize the response of a system. The Bond Graph (BG) method is a graphical approach for the design of multidomain systems. That is ideal for visualizing the essential characterist......One of the demanding steps in the design and development of Mechatronic systems is to develop the initial model to visualize the response of a system. The Bond Graph (BG) method is a graphical approach for the design of multidomain systems. That is ideal for visualizing the essential...... characteristics of a system. This paper explores the BG method as a modeling approach to develop Mechatronic systems; a case study about the Radar Antenna pedestal drive system is comprehensively addressed. Flow of energy between different functional elements of the system and their causalities are analyzed...

  13. A Bond Graph Approach for the Modeling and Simulation of a Buck Converter

    Directory of Open Access Journals (Sweden)

    Rached Zrafi

    2018-01-01

    Full Text Available This paper deals with the modeling of bond graph buck converter systems. The bond graph formalism, which represents a heterogeneous formalism for physical modeling, is used to design a sub-model of a power MOSFET and PiN diode switchers. These bond graph models are based on the device’s electrical elements. The application of these models to a bond graph buck converter permit us to obtain an invariant causal structure when the switch devices change state. This paper shows the usefulness of the bond graph device’s modeling to simulate an implicit bond graph buck converter.

  14. Decision-making deficits in patients with chronic schizophrenia: Iowa Gambling Task and Prospect Valence Learning model

    Directory of Open Access Journals (Sweden)

    Kim MS

    2016-04-01

    Full Text Available Myung-Sun Kim,1 Bit-Na Kang,1 Jae Young Lim2 1Department of Psychology, Sungshin Women’s University, Seoul, Republic of Korea; 2Department of Psychiatry, Keyo Medical Foundation, Keyo Hospital, Uiwang, Republic of Korea Purpose: Decision-making is the process of forming preferences for possible options, selecting and executing actions, and evaluating the outcome. This study used the Iowa Gambling Task (IGT and the Prospect Valence Learning (PVL model to investigate deficits in risk-reward related decision-making in patients with chronic schizophrenia, and to identify decision-making processes that contribute to poor IGT performance in these patients. Materials and methods: Thirty-nine patients with schizophrenia and 31 healthy controls participated. Decision-making was measured by total net score, block net scores, and the total number of cards selected from each deck of the IGT. PVL parameters were estimated with the Markov chain Monte Carlo sampling scheme in OpenBugs and BRugs, its interface to R, and the estimated parameters were analyzed with the Mann–Whitney U-test.Results: The schizophrenia group received significantly lower total net scores compared to the control group. In terms of block net scores, an interaction effect of group × block was observed. The block net scores of the schizophrenia group did not differ across the five blocks, whereas those of the control group increased as the blocks progressed. The schizophrenia group obtained significantly lower block net scores in the fourth and fifth blocks of the IGT and selected cards from deck D (advantageous less frequently than the control group. Additionally, the schizophrenia group had significantly lower values on the utility-shape, loss-aversion, recency, and consistency parameters of the PVL model. Conclusion: These results indicate that patients with schizophrenia experience deficits in decision-making, possibly due to failure in learning the expected value of each deck

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

    Science.gov (United States)

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

    1983-01-01

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

  16. Pathogen Mutation Modeled by Competition Between Site and Bond Percolation

    Science.gov (United States)

    Hébert-Dufresne, Laurent; Patterson-Lomba, Oscar; Goerg, Georg M.; Althouse, Benjamin M.

    2013-03-01

    While disease propagation is a main focus of network science, its coevolution with treatment has yet to be studied in this framework. We present a mean-field and stochastic analysis of an epidemic model with antiviral administration and resistance development. We show how this model maps to a coevolutive competition between site and bond percolation featuring hysteresis and both second- and first-order phase transitions. The latter, whose existence on networks is a long-standing question, imply that a microscopic change in infection rate can lead to macroscopic jumps in expected epidemic size.

  17. A generalization of the bond fluctuation model to viscoelastic environments

    International Nuclear Information System (INIS)

    Fritsch, Christian C

    2014-01-01

    A lattice-based simulation method for polymer diffusion in a viscoelastic medium is presented. This method combines the eight-site bond fluctuation model with an algorithm for the simulation of fractional Brownian motion on the lattice. The method applies to unentangled self-avoiding chains and is probed for anomalous diffusion exponents α between 0.7 and 1.0. The simulation results are in very good agreement with the predictions of the generalized Rouse model of a self-avoiding chain polymer in a viscoelastic medium. (paper)

  18. A structural bond strength model for glass durability

    International Nuclear Information System (INIS)

    Feng, Xiangdong; Metzger, T.B.

    1996-01-01

    A glass durability model, structural bond strength (SBS) model was developed to correlate glass durability with its composition. This model assumes that the strengths of the bonds between cations and oxygens and the structural roles of the individual elements in the glass arc the predominant factors controlling the composition dependence of the chemical durability of glasses. The structural roles of oxides in glass are classified as network formers, network breakers, and intermediates. The structural roles of the oxides depend upon glass composition and the redox state of oxides. Al 2 O 3 , ZrO 2 , Fe 2 O 3 , and B 2 O 3 are assigned as network formers only when there are sufficient alkalis to bind with these oxides. CaO can also improve durability by sharing non-bridging oxygen with alkalis, relieving SiO 2 from alkalis. The percolation phenomenon in glass is also taken into account. The SBS model is applied to correlate the 7-day product consistency test durability of 42 low-level waste glasses with their composition with an R 2 of 0.87, which is better than 0.81 obtained with an eight-coefficient empirical first-order mixture model on the same data set

  19. FE modeling of Cu wire bond process and reliability

    NARCIS (Netherlands)

    Yuan, C.A.; Weltevreden, E.R.; Akker, P. van den; Kregting, R.; Vreugd, J. de; Zhang, G.Q.

    2011-01-01

    Copper based wire bonding technology is widely accepted by electronic packaging industry due to the world-wide cost reduction actions (compared to gold wire bond). However, the mechanical characterization of copper wire differs from the gold wire; hence the new wire bond process setting and new bond

  20. Bond Energies in Models of the Schrock Metathesis Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Vasiliu, Monica; Li, Shenggang; Arduengo, Anthony J.; Dixon, David A.

    2011-06-23

    Heats of formation, adiabatic and diabatic bond dissociation energies (BDEs) of the model Schrock-type metal complexes M(NH)(CRR)(OH)₂ (M = Cr, Mo, W; CRR = CH₂, CHF, CF₂) and MO₂(OH)₂ compounds, and Brønsted acidities and fluoride affinities for the M(NH)(CH₂)(OH) ₂ transition metal complexes are predicted using high level CCSD(T) calculations. The metallacycle intermediates formed by reaction of C₂H4 with M(NH)-(CH₂)(OH)2 and MO₂(OH)₂ are investigated at the same level of theory. Additional corrections were added to the complete basis set limit to obtain near chemical accuracy ((1 kcal/mol). A comparison between adiabatic and diabatic BDEs is made and provides an explanation of trends in the BDEs. Electronegative groups bonded on the carbenic carbon lead to less stable Schrock-type complexes as the adiabatic BDEs ofMdCF₂ andMdCHF bonds are much lower than theMdCH₂ bonds. The Cr compounds have smaller BDEs than theWorMo complexes and should be less stable. Different M(NH)(OH)₂(C₃H₆) and MO(OH)₂(OC₂H4) metallacycle intermediates are investigated, and the lowest-energy metallacycles have a square pyramidal geometry. The results show that consideration of the singlet_triplet splitting in the carbene in the initial catalyst as well as in the metal product formed by the retro [2+2] cycloaddition is a critical component in the design of an effective olefin metathesis catalyst in terms of the parent catalyst and the groups being transferred.

  1. Influence of chain topology and bond potential on the glass transition of polymer chains simulated with the bond fluctuation model

    Energy Technology Data Exchange (ETDEWEB)

    Freire, J J [Departamento de Ciencias y Tecnicas FisicoquImicas, Facultad de Ciencias, Universidad Nacional de Educacion a Distancia (UNED), Senda del Rey 9, 28040 Madrid (Spain)], E-mail: jfreire@invi.uned.es

    2008-07-16

    The bond fluctuation model with a bond potential has been applied to investigation of the glass transition of linear chains and chains with a regular disposition of small branches. Cooling and subsequent heating curves are obtained for the chain energies and also for the mean acceptance probability of a bead jump. In order to mimic different trends to vitrification, a factor B gauging the strength of the bond potential with respect to the long-range potential (i.e. the intramolecular or intermolecular potential between indirectly bonded beads) has been introduced. (A higher value of B leads to a preference for the highest bond lengths and a higher total energy, implying a greater tendency to vitrify.) Different cases have been considered for linear chains: no long-range potential, no bond potential and several choices for B. Furthermore, two distinct values of B have been considered for alternate bonds in linear chains. In the case of the branched chains, mixed models with different values of B for bonds in the main chain and in the branches have also been investigated. The possible presence of ordering or crystallization has been characterized by calculating the collective light scattering function of the different samples after annealing at a convenient temperature below the onset of the abrupt change in the curves associated with a thermodynamic transition. It is concluded that ordering is inherited more efficiently in the systems with branched chains and also for higher values of B. The branched molecules with the highest B values in the main chain bonds exhibit two distinct transitions in the heating curves, which may be associated with two glass transitions. This behavior has been detected experimentally for chains with relatively long flexible branches.

  2. THE VALENCE OF CORPUSCULAR PROTEINS.

    Science.gov (United States)

    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

  3. Probing Transient Valence Orbital Changes with Picosecond Valence-to-Core X-ray Emission Spectroscopy

    DEFF Research Database (Denmark)

    March, Anne Marie; Assefa, Tadesse A.; Boemer, Christina

    2017-01-01

    it a powerful technique for molecular studies in a wide variety of environments. A picosecond-time-resolved measurement of the complete Is X-ray emission spectrum captures the transient photoinduced changes and includes the weak valence-to-core (vtc) emission lines that correspond to transitions from occupied......We probe the dynamics of valence electrons in photoexcited [Fe(terpy)2]2+ in solution to gain deeper insight into the Fe ligand bond changes. We use hard X-ray emission spectroscopy (XES), which combines element specificity and high penetration with sensitivity to orbital structure, making...

  4. Valence band structure and density of states effective mass model of biaxial tensile strained silicon based on k · p theory

    International Nuclear Information System (INIS)

    Kuang Qian-Wei; Liu Hong-Xia; Wang Shu-Long; Qin Shan-Shan; Wang Zhi-Lin

    2011-01-01

    After constructing a stress and strain model, the valence bands of in-plane biaxial tensile strained Si is calculated by k · p method. In the paper we calculate the accurate anisotropy valance bands and the splitting energy between light and heavy hole bands. The results show that the valance bands are highly distorted, and the anisotropy is more obvious. To obtain the density of states (DOS) effective mass, which is a very important parameter for device modeling, a DOS effective mass model of biaxial tensile strained Si is constructed based on the valance band calculation. This model can be directly used in the device model of metal—oxide semiconductor field effect transistor (MOSFET). It also a provides valuable reference for biaxial tensile strained silicon MOSFET design. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  5. Analysis of valence XPS and AES of (PP, P4VP, PVME, PPS, PTFE) polymers by DFT calculations using the model molecules

    Science.gov (United States)

    Endo, Kazunaka; Shimada, Shingo; Kato, Nobuhiko; Ida, Tomonori

    2016-10-01

    We simulated valence X-ray photoelectron spectra (VXPS) of five [(CH2CH(CH3))n {poly(propyrene) PP}, ((CH2CH(C5NH4))n {poly(4-vinyl-pyridine) P4VP}, (CH2CHO(CH3))n {poly(vinyl methyl ether) PVME}, (C6H4S)n {poly(phenylene) sulphide PPS}, (CF2CF2)n {poly(tetrafluoroethylene) PTFE}] polymers by density-functional theory (DFT) calculations using the model oligomers. The spectra reflect the differences in the chemical structures between each polymer, since the peak intensities of valence band spectra are seen to be due to photo-ionization cross-section of (C, N, O, S, F) atoms by considering the orbital energies and cross-section values of the polymer models, individually. In the Auger electron spectra (AES) simulations, theoretical kinetic energies of the AES are obtained with our modified calculation method. The modified kinetic energies correspond to two final-state holes at the ground state and at the transition-state in DFT calculations, respectively. Experimental peaks of (C, N, O)- KVV, and S L2,3VV AES for each polymer are discussed in detail by our modified calculation method.

  6. Temperature effects in the valence fluctuation of europium intermetallic compounds

    International Nuclear Information System (INIS)

    Menezes, O.L.T. de; Troper, A.; Gomes, A.A.

    1978-03-01

    A previously reported model for valence fluctuations in europium compound in order to account for thermal occupation effect. Experimental results are critically discussed and new experiments are suggested

  7. Advances in modeling and design of adhesively bonded systems

    CERN Document Server

    Kumar, S

    2013-01-01

    The book comprehensively charts a way for industry to employ adhesively bonded joints to make systems more efficient and cost-effective Adhesively bonded systems have found applications in a wide spectrum of industries (e.g., aerospace, electronics, construction, ship building, biomedical, etc.) for a variety of purposes. Emerging adhesive materials with improved mechanical properties have allowed adhesion strength approaching that of the bonded materials themselves. Due to advances in adhesive materials and the many potential merits that adhesive bonding offers, adhesive bonding has replac

  8. Bond angle variations in XH3 [X = N, P, As, Sb, Bi]: the critical role of Rydberg orbitals exposed using a diabatic state model.

    Science.gov (United States)

    Reimers, Jeffrey R; McKemmish, Laura K; McKenzie, Ross H; Hush, Noel S

    2015-10-14

    Ammonia adopts sp(3) hybridization (HNH bond angle 108°) whereas the other members of the XH3 series PH3, AsH3, SbH3, and BiH3 instead prefer octahedral bond angles of 90-93°. We use a recently developed general diabatic description for closed-shell chemical reactions, expanded to include Rydberg states, to understand the geometry, spectroscopy and inversion reaction profile of these molecules, fitting its parameters to results from Equation of Motion Coupled-Cluster Singles and Doubles (EOM-CCSD) calculations using large basis sets. Bands observed in the one-photon absorption spectrum of NH3 at 18.3 eV, 30 eV, and 33 eV are reassigned from Rydberg (formally forbidden) double excitations to valence single-excitation resonances. Critical to the analysis is the inclusion of all three electronic states in which two electrons are placed in the lone-pair orbital n and/or the symmetric valence σ* antibonding orbital. An illustrative effective two-state diabatic model is also developed containing just three parameters: the resonance energy driving the high-symmetry planar structure, the reorganization energy opposing it, and HXH bond angle in the absence of resonance. The diabatic orbitals are identified as sp hybrids on X; for the radical cations XH3(+) for which only 2 electronic states and one conical intersection are involved, the principle of orbital following dictates that the bond angle in the absence of resonance is acos(-1/5) = 101.5°. The multiple states and associated multiple conical intersection seams controlling the ground-state structure of XH3 renormalize this to acos[3 sin(2)(2(1/2)atan(1/2))/2 - 1/2] = 86.7°. Depending on the ratio of the resonance energy to the reorganization energy, equilibrium angles can vary from these limiting values up to 120°, and the anomalously large bond angle in NH3 arises because the resonance energy is unexpectedly large. This occurs as the ordering of the lowest Rydberg orbital and the σ* orbital swap, allowing

  9. THE HYBRID BOND GRAPHS MODELLING ON ANTI LOCK BRAKING SYSTEM SLIDING MODE

    OpenAIRE

    Dragana Trajković; Slobodan Stefanović

    2016-01-01

    This paper presents application of the hybrid bond graphs modeling and simulation laboratory anti-lock braking model using Dymola. It is shown on this practical example that the use of Dymola software package will simplify the modeling and simulation. The results and simulation obtained by the hybrid bond graph modeling are presented in this paper.

  10. THE HYBRID BOND GRAPHS MODELLING ON ANTI LOCK BRAKING SYSTEM SLIDING MODE

    Directory of Open Access Journals (Sweden)

    Dragana Trajković

    2016-04-01

    Full Text Available This paper presents application of the hybrid bond graphs modeling and simulation laboratory anti-lock braking model using Dymola. It is shown on this practical example that the use of Dymola software package will simplify the modeling and simulation. The results and simulation obtained by the hybrid bond graph modeling are presented in this paper.

  11. Valence skipping driven superconductivity and charge Kondo effect

    International Nuclear Information System (INIS)

    Yanagisawa, Takashi; Hase, Izumi

    2013-01-01

    Highlights: •Valence skipping in metallic compounds can give rise to an unconventional superconductivity. •Several elements in the periodic table show valence skipping (or valence missing), for example, Bi forms the compounds in valence states +3 and +5. •The doping of valence skipping elements will induce superconductivity and this will lead to a possibility of high temperature superconductivity. •We consider the Wolf model with negative-U impurities, and show a phase diagram including superconducting phase. •There is a high temperature region near the boundary. -- Abstract: Valence skipping in metallic compounds can give rise to an unconventional superconductivity. Several elements in the periodic table show valence skipping (or valence missing), for example, Bi forms the compounds in valence states +3 and +5. The doping of valence skipping elements will induce superconductivity and this will lead to a possibility of high temperature superconductivity. We consider the Wolf model with negative-U impurities, and show a phase diagram including superconducting phase. The superconducting state is changed into a metallic state with a local singlet as the attractive interaction |U| increases. There is a high temperature region near the boundary

  12. Pauli forces and the valence shell electron pair repulsion model for H/sub 2/O and NH/sub 3/

    Energy Technology Data Exchange (ETDEWEB)

    Edmiston, C.; Bartleson, J.; Jarvie, J.

    1986-06-25

    It is shown that the two effects of antisymmetry (Pauli exclusion principle) within the correct SCF wavefunctions cannot bend linear H/sub 2/O or planar NH/sub 3/ without classical electronic coulombic repulsion (CER) between LMO charge clouds in the SCF energy expression. These two effects are the orthogonality of the molecular orbitals (MOs) and the electron-exchange interactions between the LMOs. This result is in direct contradiction to the presently accepted valence shell electron pair repulsion (VSEPR) model, which attributes the geometries of molecules to Pauli forces between localized electron pairs. It is argued that the Walsh MO energy correlation diagrams, based on the integral Hellmann-Feynman theorem, are a more correct simple model for molecular geometries.

  13. Learning probabilistic models of hydrogen bond stability from molecular dynamics simulation trajectories

    KAUST Repository

    Chikalov, Igor

    2011-02-15

    Background: Hydrogen bonds (H-bonds) play a key role in both the formation and stabilization of protein structures. They form and break while a protein deforms, for instance during the transition from a non-functional to a functional state. The intrinsic strength of an individual H-bond has been studied from an energetic viewpoint, but energy alone may not be a very good predictor.Methods: This paper describes inductive learning methods to train protein-independent probabilistic models of H-bond stability from molecular dynamics (MD) simulation trajectories of various proteins. The training data contains 32 input attributes (predictors) that describe an H-bond and its local environment in a conformation c and the output attribute is the probability that the H-bond will be present in an arbitrary conformation of this protein achievable from c within a time duration ?. We model dependence of the output variable on the predictors by a regression tree.Results: Several models are built using 6 MD simulation trajectories containing over 4000 distinct H-bonds (millions of occurrences). Experimental results demonstrate that such models can predict H-bond stability quite well. They perform roughly 20% better than models based on H-bond energy alone. In addition, they can accurately identify a large fraction of the least stable H-bonds in a conformation. In most tests, about 80% of the 10% H-bonds predicted as the least stable are actually among the 10% truly least stable. The important attributes identified during the tree construction are consistent with previous findings.Conclusions: We use inductive learning methods to build protein-independent probabilistic models to study H-bond stability, and demonstrate that the models perform better than H-bond energy alone. 2011 Chikalov et al; licensee BioMed Central Ltd.

  14. A new model for diffusion bonding and its application to duplex alloys

    Energy Technology Data Exchange (ETDEWEB)

    Orhan, N. [Firat Univ., Elazig (Turkey). Dept. of Metall.; Aksoy, M.; Eroglu, M. [Department of Metallurgical and Materials Engineering, Faculty of Engineering, University of Firat, Elazig (Turkey)

    1999-11-01

    Diffusion bonding is an advanced bonding process in which two materials, similar or dissimilar, can be bonded in solid state. This provides to bond materials in a wide range from low carbon steels to ceramics and composites which cannot be bonded with conventional welding methods. One of the major advantages of this method is to produce new bimetal or dissimilar material couples. The process is diffusion-based and occurs in solid state and because of its increasing use as a commercial process. The estimation of final bonding time is very important but difficult without experiments for many materials. In this study, therefore, a new mathematical model is presented to predict the final bonding time for a sound bonding interface prior to bonding practice. Being different from the previous models, this model assumes a new surface morphology as a sine wave and a new creep mechanism for duplex alloys. The mechanisms operating during diffusion bonding are based on those in pressure sintering studies but here mass transfer by evaporation has been ignored. The driving forces and rate terms for those mechanisms have been altered to reflect the difference of the geometries of the two processes. Also the effect of grain size has been included in the model in case of joining fine-grained materials. In determining diffusion coefficients for duplex alloys, Darken's equation for binary alloys has been used. Depending on this new approach, it was shown that a more realistic final bonding time could be predicted for duplex alloys by comparing the results from this new model with those from the previous ones. As a result, it was determined that the new model could be used in order to estimate the final bonding time of the duplex alloys for a sound bond interface and the relationships between its parameters safely. The predictions from this new model show a very good agreement between practice and theory. (orig.)

  15. Learning Probabilistic Models of Hydrogen Bond Stability from Molecular Dynamics Simulation Trajectories

    KAUST Repository

    Chikalov, Igor

    2011-04-02

    Hydrogen bonds (H-bonds) play a key role in both the formation and stabilization of protein structures. H-bonds involving atoms from residues that are close to each other in the main-chain sequence stabilize secondary structure elements. H-bonds between atoms from distant residues stabilize a protein’s tertiary structure. However, H-bonds greatly vary in stability. They form and break while a protein deforms. For instance, the transition of a protein from a nonfunctional to a functional state may require some H-bonds to break and others to form. The intrinsic strength of an individual H-bond has been studied from an energetic viewpoint, but energy alone may not be a very good predictor. Other local interactions may reinforce (or weaken) an H-bond. This paper describes inductive learning methods to train a protein-independent probabilistic model of H-bond stability from molecular dynamics (MD) simulation trajectories. The training data describes H-bond occurrences at successive times along these trajectories by the values of attributes called predictors. A trained model is constructed in the form of a regression tree in which each non-leaf node is a Boolean test (split) on a predictor. Each occurrence of an H-bond maps to a path in this tree from the root to a leaf node. Its predicted stability is associated with the leaf node. Experimental results demonstrate that such models can predict H-bond stability quite well. In particular, their performance is roughly 20% better than that of models based on H-bond energy alone. In addition, they can accurately identify a large fraction of the least stable H-bonds in a given conformation. The paper discusses several extensions that may yield further improvements.

  16. Analysis of the putative Cr-Cr quintuple bond in Ar'CrCrAr' (Ar' = C6H3-2,6(C6H3-2,6-Pr(i)2)2 based on the combined natural orbitals for chemical valence and extended transition state method.

    Science.gov (United States)

    Ndambuki, Sylvester; Ziegler, Tom

    2012-07-16

    The nature of the putative Cr-Cr quintuple bond in Ar'CrCrAr' (Ar' = C(6)H(3)-2,6(C(6)H(3)-2,6-Pr(i)(2))(2)) is investigated with the help of a newly developed energy and density decomposition scheme. The new approach combines the extended transition state (ETS) energy decomposition method with the natural orbitals for chemical valence (NOCV) density decomposition scheme within the same theoretical framework. The results show that in addition to the five bonding components (σ(2)π(2)π'(2)δ(2)δ'(2)) of the Cr-Cr bond, the quintuple bond is augmented by secondary Cr-C interactions involving the Cr-ipso-carbon of the flanking aryl rings. The presence of isopropyl groups (Pr(i)) is further shown to stabilize Ar'CrCrAr' by 20 kcal/mol compared to the two Ar'Cr monomers through stabilizing van der Waals dispersion interactions.

  17. Bonding and interaction of molecules with surfaces

    International Nuclear Information System (INIS)

    Ellis, D.E.

    1988-01-01

    In this lecture it is intended to discuss some general features of bonding and interaction of molecules with surfaces. The geometry of surface complexes is sufficiently difficult and the interaction mechanisms are sufficiently subtle. That all possible theoretical models need to be exploited such as: i) Semiempirical - including Huckel molecular orbital theory; ii)first principles including self-consistent-field Hartree-Fock and Local Density approaches; iii)explicitly correlated, including C.I., Generalized Valence Bond, Coupled Cluster Perturbation Theory and Many Body Perturbation Theory. (A.C.A.S.) [pt

  18. System Response Analysis and Model Order Reduction, Using Conventional Method, Bond Graph Technique and Genetic Programming

    Directory of Open Access Journals (Sweden)

    Lubna Moin

    2009-04-01

    Full Text Available This research paper basically explores and compares the different modeling and analysis techniques and than it also explores the model order reduction approach and significance. The traditional modeling and simulation techniques for dynamic systems are generally adequate for single-domain systems only, but the Bond Graph technique provides new strategies for reliable solutions of multi-domain system. They are also used for analyzing linear and non linear dynamic production system, artificial intelligence, image processing, robotics and industrial automation. This paper describes a unique technique of generating the Genetic design from the tree structured transfer function obtained from Bond Graph. This research work combines bond graphs for model representation with Genetic programming for exploring different ideas on design space tree structured transfer function result from replacing typical bond graph element with their impedance equivalent specifying impedance lows for Bond Graph multiport. This tree structured form thus obtained from Bond Graph is applied for generating the Genetic Tree. Application studies will identify key issues and importance for advancing this approach towards becoming on effective and efficient design tool for synthesizing design for Electrical system. In the first phase, the system is modeled using Bond Graph technique. Its system response and transfer function with conventional and Bond Graph method is analyzed and then a approach towards model order reduction is observed. The suggested algorithm and other known modern model order reduction techniques are applied to a 11th order high pass filter [1], with different approach. The model order reduction technique developed in this paper has least reduction errors and secondly the final model retains structural information. The system response and the stability analysis of the system transfer function taken by conventional and by Bond Graph method is compared and

  19. Structured modeling of systems using bond graphs (Automation); Modelisation structuree des systemes avec les bond graphs (automatique)

    Energy Technology Data Exchange (ETDEWEB)

    Verge, M.; Jaume, D.

    2004-10-01

    The creation of new products requires the knowledge of the physical phenomena involved. Starting from models difficult to design, simple simulations are necessary before the first realizations. This book explains the modeling of dynamical systems from different technologies: mechanical, hydraulic, electric, thermal. The proposed modeling is based on the bond graph approach which is characterized by power conservation. This approach allows to design the model as the encapsulation of several elementary models exchanging energy. The efficiency of softwares and the need of model libraries have contributed to the fast spreading of this method in the industry. After a theoretical first part, the second part of the book presents some industrial examples where the design of models is integrally detailed and for which simulations have been performed. (J.S.)

  20. Chemical bonding in hypervalent molecules: is the octet rule relevant?

    Science.gov (United States)

    Noury, Stéphane; Silvi, Bernard; Gillespie, Ronald J

    2002-04-22

    The bonding in a large number of hypervalent molecules of P, As, S, Se, Te, Cl, and Br with the ligands F, Cl, O, CH(3), and CH(2) has been studied using the topological analysis of the electron localization function ELF. This function partitions the electron density of a molecule into core and valence basins and further classifies valence basins according to the number of core basins with which they have a contact. The number and geometry of these basins is generally in accord with the VSEPR model. The population of each basin can be obtained by integration, and so, the total population of the valence shell of an atom can be obtained as the sum of the populations of all the valence basins which share a boundary with its core basin. It was found that the population of the V(A, X) disynaptic basin corresponding to the bond, where A is the central atom and X the ligand, varies with the electronegativity of the ligand from approximately 2.0 for a weakly electronegative ligand such as CH(3) to less than 1.0 for a ligand such as F. We find that the total population of the valence shell of a hypervalent atom may vary from close to 10 for a period 15 element and close to 12 for a group 16 element to considerably less than 8 for an electronegative ligand such as F. For example, the phosphorus atom in PF(5) has a population of 5.37 electrons in its valence shell, whereas the arsenic atom in AsMe5 has a population of 9.68 electrons in its valence shell. By definition, hypervalent atoms do not obey the Lewis octet rule. They may or may not obey a modified octet rule that has taken the place of the Lewis octet rule in many recent discussions and according to which an atom in a molecule always has fewer than 8 electrons in its valence shell. We show that the bonds in hypervalent molecules are very similar to those in corresponding nonhypervalent (Lewis octet) molecules. They are all polar bonds ranging from weakly to strongly polar depending on the electronegativity of the

  1. Modelling Callable Annuity Bonds with Interest-Only Optionality

    DEFF Research Database (Denmark)

    Holst, Anders; Nalholm, Morten

    In this paper an investigation of the pricing of callable annuities with interest-only(I-O) optionality is conducted. First the I-O optionality feature of callable annuities isintroduced. Next an algorithm for pricing callable annuities with I-O optionality usingthe finite difference methodology......, is formulated. This is then used to investigate optimalstrategies of I-O bonds and impacts on prices from the I-O optionality. It is found thatthe I-O feature necessitates a simultaneous valuation of all elements of the callable I-Obond. Following this, the Greeks of the I-O bond are investigated. It is found...

  2. Analysis, Modeling and Simulation of Mechatronic Systems using the Bond Graph Method

    Directory of Open Access Journals (Sweden)

    A. Alabakhshizadeh

    2011-01-01

    Full Text Available The Bond Graph is the proper choice of physical system used for: (i Modeling which can be applied to systems combining multidisciplinary energy domains, (ii Analysis to provide a great value proposition for finding the algebraic loops within the system enabling the process of troubleshooting and eliminating the defects by using the proper component(s to fix the causality conflict even without being acquainted in the proper system, and (iii Simulation facilitated through derived state space equations from the Bond Graph model is solved using industrial simulation software, such as 20-Sim. The Bond Graph technique is a graphical language of modeling, in which component energy ports are connected by bonds that specify the transfer of energy between system components. Following a brief introduction of the Bond Graph methodology and techniques, two separate case studies are comprehensively addressed. The first case study is a systematic implementation of a fourth order electrical system and conversion to mechanical system while the second case study presents modeling of the Dielectric Electro Active Polymer (DEAP actuator. Building the systematic Bond Graph of multifaceted system and ease of switching between different domains are aims of the first case study while the second study shows how a complex mechatronic system could be analyzed and built by the Bond Graph. The respective Bond Graphs in each case is evaluated in the light of mathematical equations and simulations. Excellent correlation has been achieved between the simulation results and proper system equations.

  3. Bond dissociation enthalpies of a pinoresinol lignin model compound

    Science.gov (United States)

    Thomas Elder

    2014-01-01

    ABSTRACT: The pinoresinol unit is one of the principal interunit linkages in lignin. As such, its chemistry and properties are of major importance in understanding the behavior or the polymer. This work examines the homolytic cleavage of the pinoresinol system, representing the initial step in thermal degradation. The bond dissociation enthalpy of this reaction has...

  4. A Model of Girls' School Delinquency: School Bonding and Reputation

    Science.gov (United States)

    Lee, Sang Min; Smith-Adcock, Sondra

    2005-01-01

    Using a longitudinal national database, the authors conducted a path analysis of girls' school delinquency to determine the indirect and direct effects of socioeconomic status, parental involvement, bonding to school, and girls' self-perception of reputation on school delinquency during middle school and high school. Self-perception of reputation…

  5. Chemical bond fundamental aspects of chemical bonding

    CERN Document Server

    Frenking, Gernot

    2014-01-01

    This is the perfect complement to ""Chemical Bonding - Across the Periodic Table"" by the same editors, who are two of the top scientists working on this topic, each with extensive experience and important connections within the community. The resulting book is a unique overview of the different approaches used for describing a chemical bond, including molecular-orbital based, valence-bond based, ELF, AIM and density-functional based methods. It takes into account the many developments that have taken place in the field over the past few decades due to the rapid advances in quantum chemica

  6. Architectural Representation of Valence in the Limbic System

    Science.gov (United States)

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

    2016-01-01

    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

  7. Charge reversal and surface charge amplification in asymmetric valence restricted primitive model planar electric double layers in the modified Poisson-Boltzmann theory

    Directory of Open Access Journals (Sweden)

    L.B. Bhuiyan

    2017-12-01

    Full Text Available The modified Poisson-Boltzmann theory of the restricted primitive model double layer is revisited and recast in a fresh, slightly broader perspective. Derivation of relevant equations follow the techniques utilized in the earlier MPB4 and MPB5 formulations and clarifies the relationship between these. The MPB4, MPB5, and a new formulation of the theory are employed in an analysis of the structure and charge reversal phenomenon in asymmetric 2:1/1:2 valence electrolytes. Furthermore, polarization induced surface charge amplification is studied in 3:1/1:3 systems. The results are compared to the corresponding Monte Carlo simulations. The theories are seen to predict the "exact" simulation data to varying degrees of accuracy ranging from qualitative to almost quantitative. The results from a new version of the theory are found to be of comparable accuracy as the MPB5 results in many situations. However, in some cases involving low electrolyte concentrations, theoretical artifacts in the form of un-physical "shoulders" in the singlet ionic distribution functions are observed.

  8. Teaching Molecular Geometry with the VSEPR Model

    Science.gov (United States)

    Gillespie, Ronald J.

    2004-01-01

    The first introduction to molecular geometry should be through the simple and easily understood VSEPR model, as the Valence Bond Theory and MO Theory suffer from limitations as far as understanding molecular geometry is concerned. The VSEPR model gives a perfectly satisfactory description of the bonding that follows directly from the Lewis model…

  9. Calibration of short rate term structure models from bid-ask coupon bond prices

    Science.gov (United States)

    Gomes-Gonçalves, Erika; Gzyl, Henryk; Mayoral, Silvia

    2018-02-01

    In this work we use the method of maximum entropy in the mean to provide a model free, non-parametric methodology that uses only market data to provide the prices of the zero coupon bonds, and then, a term structure of the short rates. The data used consists of the prices of the bid-ask ranges of a few coupon bonds quoted in the market. The prices of the zero coupon bonds obtained in the first stage, are then used as input to solve a recursive set of equations to determine a binomial recombinant model of the short term structure of the interest rates.

  10. Automated Modeling and Simulation Using the Bond Graph Method for the Aerospace Industry

    Science.gov (United States)

    Granda, Jose J.; Montgomery, Raymond C.

    2003-01-01

    Bond graph modeling was originally developed in the late 1950s by the late Prof. Henry M. Paynter of M.I.T. Prof. Paynter acted well before his time as the main advantage of his creation, other than the modeling insight that it provides and the ability of effectively dealing with Mechatronics, came into fruition only with the recent advent of modern computer technology and the tools derived as a result of it, including symbolic manipulation, MATLAB, and SIMULINK and the Computer Aided Modeling Program (CAMPG). Thus, only recently have these tools been available allowing one to fully utilize the advantages that the bond graph method has to offer. The purpose of this paper is to help fill the knowledge void concerning its use of bond graphs in the aerospace industry. The paper first presents simple examples to serve as a tutorial on bond graphs for those not familiar with the technique. The reader is given the basic understanding needed to appreciate the applications that follow. After that, several aerospace applications are developed such as modeling of an arresting system for aircraft carrier landings, suspension models used for landing gears and multibody dynamics. The paper presents also an update on NASA's progress in modeling the International Space Station (ISS) using bond graph techniques, and an advanced actuation system utilizing shape memory alloys. The later covers the Mechatronics advantages of the bond graph method, applications that simultaneously involves mechanical, hydraulic, thermal, and electrical subsystem modeling.

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

    Science.gov (United States)

    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 mediate the…

  12. Modeling cytoskeletal flow over adhesion sites: competition between stochastic bond dynamics and intracellular relaxation

    International Nuclear Information System (INIS)

    Sabass, Benedikt; Schwarz, Ulrich S

    2010-01-01

    In migrating cells, retrograde flow of the actin cytoskeleton is related to traction at adhesion sites located at the base of the lamellipodium. The coupling between the moving cytoskeleton and the stationary adhesions is mediated by the continuous association and dissociation of molecular bonds. We introduce a simple model for the competition between the stochastic dynamics of elastic bonds at the moving interface and relaxation within the moving actin cytoskeleton represented by an internal viscous friction coefficient. Using exact stochastic simulations and an analytical mean field theory, we show that the stochastic bond dynamics lead to biphasic friction laws as observed experimentally. At low internal dissipation, stochastic bond dynamics lead to a regime of irregular stick-and-slip motion. High internal dissipation effectively suppresses cooperative effects among bonds and hence stabilizes the adhesion.

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

    Science.gov (United States)

    Brysbaert, Marc; Warriner, Amy Beth

    2014-01-01

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

  14. 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.

    Science.gov (United States)

    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.

  15. Modeling single molecule junction mechanics as a probe of interface bonding

    Science.gov (United States)

    Hybertsen, Mark S.

    2017-03-01

    Using the atomic force microscope based break junction approach, applicable to metal point contacts and single molecule junctions, measurements can be repeated thousands of times resulting in rich data sets characterizing the properties of an ensemble of nanoscale junction structures. This paper focuses on the relationship between the measured force extension characteristics including bond rupture and the properties of the interface bonds in the junction. A set of exemplary model junction structures has been analyzed using density functional theory based calculations to simulate the adiabatic potential surface that governs the junction elongation. The junction structures include representative molecules that bond to the electrodes through amine, methylsulfide, and pyridine links. The force extension characteristics are shown to be most effectively analyzed in a scaled form with maximum sustainable force and the distance between the force zero and force maximum as scale factors. Widely used, two parameter models for chemical bond potential energy versus bond length are found to be nearly identical in scaled form. Furthermore, they fit well to the present calculations of N-Au and S-Au donor-acceptor bonds, provided no other degrees of freedom are allowed to relax. Examination of the reduced problem of a single interface, but including relaxation of atoms proximal to the interface bond, shows that a single-bond potential form renormalized by an effective harmonic potential in series fits well to the calculated results. This allows relatively accurate extraction of the interface bond energy. Analysis of full junction models shows cooperative effects that go beyond the mechanical series inclusion of the second bond in the junction, the spectator bond that does not rupture. Calculations for a series of diaminoalkanes as a function of molecule length indicate that the most important cooperative effect is due to the interactions between the dipoles induced by the donor

  16. On a Corporate Bond Pricing Model with Credit Rating Migration Risksand Stochastic Interest Rate

    Directory of Open Access Journals (Sweden)

    Jin Liang

    2017-10-01

    Full Text Available In this paper we study a corporate bond-pricing model with credit rating migration and astochastic interest rate. The volatility of bond price in the model strongly depends on potential creditrating migration and stochastic change of the interest rate. This new model improves the previousexisting models in which the interest rate is considered to be a constant. The existence, uniquenessand regularity of the solution for the model are established. Moreover, some properties includingthe smoothness of the free boundary are obtained. Furthermore, some numerical computations arepresented to illustrate the theoretical results.

  17. Determinants of the Government Bond Yield in Spain: A Loanable Funds Model

    Directory of Open Access Journals (Sweden)

    Yu Hsing

    2015-07-01

    Full Text Available This paper applies demand and supply analysis to examine the government bond yield in Spain. The sample ranges from 1999.Q1 to 2014.Q2. The EGARCH model is employed in empirical work. The Spanish government bond yield is positively associated with the government debt/GDP ratio, the short-term Treasury bill rate, the expected inflation rate, the U.S. 10 year government bond yield and a dummy variable representing the debt crisis and negatively affected by the GDP growth rate and the expected nominal effective exchange rate.

  18. Bond graphs for modelling, control and fault diagnosis of engineering systems

    CERN Document Server

    2017-01-01

    This book presents theory and latest application work in Bond Graph methodology with a focus on: • Hybrid dynamical system models, • Model-based fault diagnosis, model-based fault tolerant control, fault prognosis • and also addresses • Open thermodynamic systems with compressible fluid flow, • Distributed parameter models of mechanical subsystems. In addition, the book covers various applications of current interest ranging from motorised wheelchairs, in-vivo surgery robots, walking machines to wind-turbines.The up-to-date presentation has been made possible by experts who are active members of the worldwide bond graph modelling community. This book is the completely revised 2nd edition of the 2011 Springer compilation text titled Bond Graph Modelling of Engineering Systems – Theory, Applications and Software Support. It extends the presentation of theory and applications of graph methodology by new developments and latest research results. Like the first edition, this book addresses readers in a...

  19. An Interactive Teaching System for Bond Graph Modeling and Simulation in Bioengineering

    Science.gov (United States)

    Roman, Monica; Popescu, Dorin; Selisteanu, Dan

    2013-01-01

    The objective of the present work was to implement a teaching system useful in modeling and simulation of biotechnological processes. The interactive system is based on applications developed using 20-sim modeling and simulation software environment. A procedure for the simulation of bioprocesses modeled by bond graphs is proposed and simulators…

  20. Attachment style in the context of clinical and health psychology : A proposal for the assessment of valence, incongruence, and accessibility of attachment representations in various working models

    NARCIS (Netherlands)

    Gerlsma, Coby; Luteijn, Frans

    By combining the Adult Attachment interview and the Autobiographical Memory Test, a structured interview was developed as a 'quick and dirty' measure for the assessment of attachment representations in clinical settings. The interview intends to assess valence, incongruence, and accessibility of the

  1. Theory of Valence Transition in BiNiO$_3$

    OpenAIRE

    Naka, Makoto; Seo, Hitoshi; Motome, Yukitoshi

    2015-01-01

    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 with 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...

  2. Estimating the Term Structure With a Semiparametric Bayesian Hierarchical Model: An Application to Corporate Bonds1

    Science.gov (United States)

    Cruz-Marcelo, Alejandro; Ensor, Katherine B.; Rosner, Gary L.

    2011-01-01

    The term structure of interest rates is used to price defaultable bonds and credit derivatives, as well as to infer the quality of bonds for risk management purposes. We introduce a model that jointly estimates term structures by means of a Bayesian hierarchical model with a prior probability model based on Dirichlet process mixtures. The modeling methodology borrows strength across term structures for purposes of estimation. The main advantage of our framework is its ability to produce reliable estimators at the company level even when there are only a few bonds per company. After describing the proposed model, we discuss an empirical application in which the term structure of 197 individual companies is estimated. The sample of 197 consists of 143 companies with only one or two bonds. In-sample and out-of-sample tests are used to quantify the improvement in accuracy that results from approximating the term structure of corporate bonds with estimators by company rather than by credit rating, the latter being a popular choice in the financial literature. A complete description of a Markov chain Monte Carlo (MCMC) scheme for the proposed model is available as Supplementary Material. PMID:21765566

  3. NMR studies of strong hydrogen bonds in enzymes and in a model compound

    Science.gov (United States)

    Harris, T. K.; Zhao, Q.; Mildvan, A. S.

    2000-09-01

    Hydrogen bond lengths on enzymes have been derived with high precision (≤±0.05 Å) from both the proton chemical shifts (δ) and the fractionation factors (φ) of the proton involved and were compared with those obtained from protein X-ray crystallography. Hydrogen bond lengths derived from proton chemical shifts were obtained from a correlation of 59 O-H⋯O hydrogen bond lengths, measured by small molecule high resolution X-ray crystallography, with chemical shifts determined by solid-state NMR in the same crystals [A. McDermott, C.F. Ridenour, Encyclopedia of NMR, Wiley, Sussex, England, 1996, 3820pp]. Hydrogen bond lengths were independently obtained from fractionation factors which yield distances between the two proton wells in quartic double minimum potential functions [M.M. Kreevoy, T.M. Liang, J. Am. Chem. Soc. 102 (1980) 3315]. The high precision hydrogen bond lengths derived from their corresponding NMR-measured proton chemical shifts and fractionation factors agree well with each other and with those reported in protein X-ray structures within the larger errors (±0.2-0.8 Å) in lengths obtained by protein X-ray crystallography. The increased precision in measurements of hydrogen bond lengths by NMR has provided insight into the contributions of short, strong hydrogen bonds to catalysis for several enzymes including ketosteroid isomerase, triosephosphate isomerase, and serine proteases. The O-H⋯O hydrogen bond length derived from the proton chemical shift in a model dihydroxy-naphthalene compound in aqueous solution agreed well with lengths of such hydrogen bonds determined by high resolution, small molecule X-ray diffraction.

  4. Magnetic Phase Transitions in Quantum Ising Model with Annealed Antiferromagnetic Bond Randomness

    Science.gov (United States)

    Shi, Zhu-pei; Tao, Rui-bao

    1990-06-01

    The effect of annealed antiferromagnetic bond randomness on the phase transitions of the Quantum Ising Model (QIM) is studied by using mean-field renormalization group method. It is argued that bond randomness drastically alters multicritical phase diagram via transverse field. Multicritical points and coexistence region of ferromagnetic and antiferromagnetic case exist only at weak transverse field, and are entirely eliminated at strong transverse field. The coexistence region diminishes in reducing the fluctuation interaction. This physical picture demonstrates that the competition between transverse field and exchange interaction and fluctuation interaction via bond randomness play an important role in generating multiphase structure. Another consequence of competition is that tricritical points of first-second order phase transitions are not entirely eliminated by bond randomness in two-dimensional QIM. The project supported by the Foundation of Doctoral Education.

  5. Modeling and Simulation of a Wind Turbine Driven Induction Generator Using Bond Graph

    Directory of Open Access Journals (Sweden)

    Lachouri Abderrazak

    2015-12-01

    Full Text Available The objective of this paper is to investigate the modelling and simulation of wind turbine applied on induction generator with bond graph methodology as   a graphical and multi domain approach. They provide a precise and unambiguous modelling tool, which allows for the specification of hierarchical physical structures. The paper begins with an introduction to the bond graphs technique, followed by an implementation of the wind turbine model. Simulation results illustrate the simplified system response obtained using the 20-sim software.

  6. Incommmensurability and Unconventional Superconductor to Insulator Transition in the Hubbard Model with Bond-Charge Interaction

    Science.gov (United States)

    Aligia, A. A.; Anfossi, A.; Arrachea, L.; Degli Esposti Boschi, C.; Dobry, A. O.; Gazza, C.; Montorsi, A.; Ortolani, F.; Torio, M. E.

    2007-11-01

    We determine the quantum phase diagram of the one-dimensional Hubbard model with bond-charge interaction X in addition to the usual Coulomb repulsion U>0 at half-filling. For large enough Xmodel shows three phases. For large U the system is in the spin-density wave phase as in the usual Hubbard model. As U decreases, there is first a spin transition to a spontaneously dimerized bond-ordered wave phase and then a charge transition to a novel phase in which the dominant correlations at large distances correspond to an incommensurate singlet superconductor.

  7. Analysis of surface bond lengths reported for chemisorption on metal surfaces

    Science.gov (United States)

    Mitchell, K. A. R.

    1985-01-01

    A review is given of bond length information available from the techniques of surface crystallography (particularly with LEED, SEXAFS and photoelectron diffraction) for chemisorption on well-defined surfaces of metals (M). For adsorbed main-group atoms (X), measured X-M interatomic distances for 38 combinations of X and M have been assessed with a bond order-bond length relation in combination with the Schomaker-Stevenson approach for determining single-bond lengths. When the surface bond orders are fixed primarily by the valency of X, this approach appears to provide a simple framework for predicing X-M surface bond lengths. Further, in cases where agreement has been reached from different surface crystallographic techniques, this framework has the potential for assessing refinements to the surface bonding model (e.g. in determining the roles of the effective surface valency of M, and of coordinate bonding and supplementary π bonding between X and M). Preliminary comparisons of structural data are also given for molecular adsorption (CO and ethylidyne) and for the chemisorption of other metal atoms.

  8. The Measurement of the Relationship between Taiwan’s Bond Funds’ Net Flow and the Investment Risk -Threshold Autoregressive Model

    OpenAIRE

    Wo-Chiang Lee; Joe-Ming Lee

    2014-01-01

    This article applies the threshold autoregressive model to investigate the relationship between bond funds’ net flow and investment risk in Taiwan. Our empirical findings show that bond funds’ investors are concerned about the investment return and neglect the investment risk. In particular, when expanding the size of the bond funds, fund investors believe that the fund cannot lose any money on investment products. In order to satisfy investors, bond fund managers only target short-term retur...

  9. Moving beyond Definitions: What Student-Generated Models Reveal about Their Understanding of Covalent Bonding and Ionic Bonding

    Science.gov (United States)

    Luxford, Cynthia J.; Bretz, Stacey Lowery

    2013-01-01

    Chemistry students encounter a variety of terms, definitions, and classification schemes that many instructors expect students to memorize and be able to use. This research investigated students' descriptions of ionic and covalent bonding beyond definitions in order to explore students' knowledge about chemical bonding. Using Johnstone's Multiple…

  10. DNA Self-Assembly and Computation Studied with a Coarse-grained Dynamic Bonded Model

    DEFF Research Database (Denmark)

    Svaneborg, Carsten; Fellermann, Harold; Rasmussen, Steen

    2012-01-01

    We utilize a coarse-grained directional dynamic bonding DNA model [C. Svaneborg, Comp. Phys. Comm. (In Press DOI:10.1016/j.cpc.2012.03.005)] to study DNA self-assembly and DNA computation. In our DNA model, a single nucleotide is represented by a single interaction site, and complementary sites can...

  11. Parental Bonds, Attachment Anxiety, Media Susceptibility, and Body Dissatisfaction: A Mediation Model

    Science.gov (United States)

    Patton, Sarah C.; Beaujean, A. Alexander; Benedict, Helen E.

    2014-01-01

    The developmental trajectory of body image dissatisfaction is unclear. Researchers have investigated sociocultural and developmental risk factors; however, the literature needs an integrative etiological model. In 2009, Cheng and Mallinckrodt proposed a dual mediation model, positing that poor-quality parental bonds, via the mechanisms of…

  12. Pseudo-Bond Graph model for the analysis of the thermal behavior of buildings

    Directory of Open Access Journals (Sweden)

    Merabtine Abdelatif

    2013-01-01

    Full Text Available In this work, a simplified graphical modeling tool, which in some extent can be considered in halfway between detailed physical and Data driven dynamic models, has been developed. This model is based on Bond Graphs approach. This approach has the potential to display explicitly the nature of power in a building system, such as a phenomenon of storage, processing and dissipating energy such as Heating, Ventilation and Air-Conditioning (HVAC systems. This paper represents the developed models of the two transient heat conduction problems corresponding to the most practical cases in building envelope, such as the heat transfer through vertical walls, roofs and slabs. The validation procedure consists of comparing the results obtained with this model with analytical solution. It has shown very good agreement between measured data and Bond Graphs model simulation. The Bond Graphs technique is then used to model the building dynamic thermal behavior over a single zone building structure and compared with a set of experimental data. An evaluation of indoor temperature was carried out in order to check our Bond Graphs model.

  13. Modeling, Control and Analyze of Multi-Machine Drive Systems using Bond Graph Technique

    Directory of Open Access Journals (Sweden)

    J. Belhadj

    2006-03-01

    Full Text Available In this paper, a system viewpoint method has been investigated to study and analyze complex systems using Bond Graph technique. These systems are multimachine multi-inverter based on Induction Machine (IM, well used in industries like rolling mills, textile, and railway traction. These systems are multi-domains, multi-scales time and present very strong internal and external couplings, with non-linearity characterized by a high model order. The classical study with analytic model is difficult to manipulate and it is limited to some performances. In this study, a “systemic approach” is presented to design these kinds of systems, using an energetic representation based on Bond Graph formalism. Three types of multimachine are studied with their control strategies. The modeling is carried out by Bond Graph and results are discussed to show the performances of this methodology

  14. Numerical modelling of two HMX-based plastic-bonded explosives at the mesoscale

    OpenAIRE

    Handley, Caroline A.

    2011-01-01

    Mesoscale models are needed to predict the effect of changes to the microstructure of plastic-bonded explosives on their shock initiation and detonation behaviour. This thesis describes the considerable progress that has been made towards a mesoscale model for two HMX-based explosives PBX9501 and EDC37. In common with previous work in the literature, the model is implemented in hydrocodes that have been designed for shock physics and detonation modelling. Two relevant physics effects, heat co...

  15. Hole energy and momentum distributions in valence bands

    International Nuclear Information System (INIS)

    Laan, G. van der.

    1982-01-01

    In order to understand the electrical and magnetic properties of solids, the knowledge of the density of states and the dispersion relation of the valence bands is indispensable. This thesis offers some alternative methods to obtain information about the nature of the valence band. Part A deals with the energy distribution of the photoelectrons. A simple model, which explains the core hole satellite structure in compounds with large correlation effects between the valence band holes and the created photo-hole, is outlined. CuCl, CuX 2 (X = F Cl and Br) are studied, by photoemission and Auger electron spectroscopies in determining the valence band properties. Part B deals with the simultaneous measurement of the energy and the wave vector of the emitted electrons. A practical example is given for the determination of the dispersion relation in copper. The measurements of a surface resonance band and the distribution of the secondary electrons are also reported. (Auth.)

  16. A Unified Bond Graph Modeling Approach for the Ejection Phase of the Cardiovascular System

    Directory of Open Access Journals (Sweden)

    LUBNA MOIN

    2016-07-01

    Full Text Available In this paper the unified Bond Graph model of the left ventricle ejection phase is presented, simulated and validated. The integro-differential and ordinary differential equations obtained from the bond graph models are simulated using ODE45 (Ordinary Differential Equation Solver on MATLAB and Simulink. The results, thus, obtained are compared with CVS (Cardiovascular System physiological data present in Simbiosys (a software for simulating biological systems and also with the CVS Wiggers diagram of heart cycle. As the cardiac activity is a multi domain process that includes mechanical, hydraulic, chemical and electrical events; therefore, for modeling such systems a unified modeling approach is needed. In this paper the unified Bond Graph model of the left ventricle ejection phase is proposed. The Bond Graph conventionalism approach is a graphical method principally powerful to portray multi-energy systems, as it is formulated on the portrayal of power exchanges. The model takes into account a simplified description of the left ventricle which is close to the medical investigation promoting the apperception and the dialogue between engineers and physiologists.

  17. Bond-Slip Models for FPR-Concrete Interfaces Subjected to Moisture Conditions

    Directory of Open Access Journals (Sweden)

    Justin Shrestha

    2017-01-01

    Full Text Available Environmental related durability issues have been of great concerns in the structures strengthened with the fiber reinforced polymers (FRPs. In marine environment, moisture is one of the dominant factors that adversely affect the material properties and the bond interfaces. Several short-term and long-term laboratory experimental investigations have been conducted to study such behaviors but, still, there are insufficient constitutive bond models which could incorporate moisture exposure conditions. This paper proposed a very simple approach in determining the nonlinear bond-slip models for the FRP-concrete interface considering the effect of moisture conditions. The proposed models are based on the strain results of the experimental investigation conducted by the authors using 6 different commercial FRP systems exposed to the moisture conditions for the maximum period of 18 months. The exposure effect in the moisture conditions seems to have great dependency on the FRP system. Based on the contrasting differences in the results under moisture conditions, separate bond-slip models have been proposed for the wet-layup FRP and prefabricated FRP systems. As for the verification of the proposed model under moisture conditions, predicted pull-out load was compared with the experimental pull-out load. The results showed good agreement for all the FRP systems under investigation.

  18. A nonabelian vortex-bond model of hadrons

    International Nuclear Information System (INIS)

    Patkos, A.

    1976-10-01

    The nature of non-Abelian theories for magnetic quark confinement is discussed. Using the internal holonomy group method the properties of infinitely long, straight, static vortices of cylindrical symmetry are investigated. For defining the conserved gauge-invariant charges the concept of ''the measuring matrices'' is used. It is shown for a general class of models that the most general vortex-like configurations can always be transformed to Abelian form. The introduction of Dirac-type monopoles and the stability problem in case of small amplitude oscillations are also discussed. (Sz. N.Z.)

  19. Identification of parameters of cohesive elements for modeling of adhesively bonded joints of epoxy composites

    Directory of Open Access Journals (Sweden)

    Kottner R.

    2013-12-01

    Full Text Available Adhesively bonded joints can be numerically simulated using the cohesive crack model. The critical strain energy release rate and the critical opening displacement are the parameters which must be known when cohesive elements in MSC.Marc software are used. In this work, the parameters of two industrial adhesives Hunstman Araldite 2021 and Gurit Spabond 345 for bonding of epoxy composites are identified. Double Cantilever Beam (DCB and End Notched Flexure (ENF test data were used for the identification. The critical opening displacements were identified using an optimization algorithm where the tests and their numerical simulations were compared.

  20. Developing a laser shockwave model for characterizing diffusion bonded interfaces

    Science.gov (United States)

    Lacy, Jeffrey M.; Smith, James A.; Rabin, Barry H.

    2015-03-01

    The US National Nuclear Security Agency has a Global Threat Reduction Initiative (GTRI) with the goal of reducing the worldwide use of high-enriched uranium (HEU). A salient component of that initiative is the conversion of research reactors from HEU to low enriched uranium (LEU) fuels. An innovative fuel is being developed to replace HEU in high-power research reactors. The new LEU fuel is a monolithic fuel made from a U-Mo alloy foil encapsulated in Al-6061 cladding. In order to support the fuel qualification process, the Laser Shockwave Technique (LST) is being developed to characterize the clad-clad and fuel-clad interface strengths in fresh and irradiated fuel plates. LST is a non-contact method that uses lasers for the generation and detection of large amplitude acoustic waves to characterize interfaces in nuclear fuel plates. However, because the deposition of laser energy into the containment layer on a specimen's surface is intractably complex, the shock wave energy is inferred from the surface velocity measured on the backside of the fuel plate and the depth of the impression left on the surface by the high pressure plasma pulse created by the shock laser. To help quantify the stresses generated at the interfaces, a finite element method (FEM) model is being utilized. This paper will report on initial efforts to develop and validate the model by comparing numerical and experimental results for back surface velocities and front surface depressions in a single aluminum plate representative of the fuel cladding.

  1. Sugar-peptidic bond interactions: spectroscopic characterization of a model system.

    Science.gov (United States)

    Camiruaga, Ander; Usabiaga, Imanol; Insausti, Aran; León, Iker; Fernández, José A

    2017-05-17

    Sugars are small carbohydrates which play numerous roles in living organisms such as storage of energy or as structural components. Modifications of specific sites within the glycan chain can modulate a carbohydrate's overall biological function as it happens with nucleic acids and proteins. Hence, identifying discrete carbohydrate modifications and understanding their biological effects is essential. A study of such processes requires of a deep knowledge of the interaction mechanism at the molecular level. Here, we use a combination of laser spectroscopy in jets and quantum mechanical calculations to characterize the interaction between phenyl-β-d-glucopyranoside and N-methylacetamide as a model to understand the interaction between a sugar and a peptide bond. The most stable structure of the molecular aggregate shows that the main interaction between the peptide fragment and the sugar proceeds via a C[double bond, length as m-dash]OH-O2 hydrogen bond. A second conformer was also found, in which the peptide establishes a C[double bond, length as m-dash]OH-O6 hydrogen bond with the hydroxymethyl substituent of the sugar unit. All the conformers present an additional interaction point with the aromatic ring. This particular preference of the peptide for the hydroxyl close to the aromatic ring could explain why glycogenin uses tyrosine in order to convert glucose into glycogen by exposing the O4H hydroxyl group for the other glucoses for the polymerization to take place.

  2. Simulating Ru L3-edge X-ray absorption spectroscopy with time-dependent density functional theory: model complexes and electron localization in mixed-valence metal dimers.

    Science.gov (United States)

    Van Kuiken, Benjamin E; Valiev, Marat; Daifuku, Stephanie L; Bannan, Caitlin; Strader, Matthew L; Cho, Hana; Huse, Nils; Schoenlein, Robert W; Govind, Niranjan; Khalil, Munira

    2013-05-30

    Ruthenium L3-edge X-ray absorption (XA) spectroscopy probes unoccupied 4d orbitals of the metal atom and is increasingly being used to investigate the local electronic structure in ground and excited electronic states of Ru complexes. The simultaneous development of computational tools for simulating Ru L3-edge spectra is crucial for interpreting the spectral features at a molecular level. This study demonstrates that time-dependent density functional theory (TDDFT) is a viable and predictive tool for simulating ruthenium L3-edge XA spectroscopy. We systematically investigate the effects of exchange correlation functional and implicit and explicit solvent interactions on a series of Ru(II) and Ru(III) complexes in their ground and electronic excited states. The TDDFT simulations reproduce all of the experimentally observed features in Ru L3-edge XA spectra within the experimental resolution (0.4 eV). Our simulations identify ligand-specific charge transfer features in complicated Ru L3-edge spectra of [Ru(CN)6](4-) and Ru(II) polypyridyl complexes illustrating the advantage of using TDDFT in complex systems. We conclude that the B3LYP functional most accurately predicts the transition energies of charge transfer features in these systems. We use our TDDFT approach to simulate experimental Ru L3-edge XA spectra of transition metal mixed-valence dimers of the form [(NC)5M(II)-CN-Ru(III)(NH3)5](-) (where M = Fe or Ru) dissolved in water. Our study determines the spectral signatures of electron delocalization in Ru L3-edge XA spectra. We find that the inclusion of explicit solvent molecules is necessary for reproducing the spectral features and the experimentally determined valencies in these mixed-valence complexes. This study validates the use of TDDFT for simulating Ru 2p excitations using popular quantum chemistry codes and providing a powerful interpretive tool for equilibrium and ultrafast Ru L3-edge XA spectroscopy.

  3. International Space Station Centrifuge Rotor Models A Comparison of the Euler-Lagrange and the Bond Graph Modeling Approach

    Science.gov (United States)

    Nguyen, Louis H.; Ramakrishnan, Jayant; Granda, Jose J.

    2006-01-01

    The assembly and operation of the International Space Station (ISS) require extensive testing and engineering analysis to verify that the Space Station system of systems would work together without any adverse interactions. Since the dynamic behavior of an entire Space Station cannot be tested on earth, math models of the Space Station structures and mechanical systems have to be built and integrated in computer simulations and analysis tools to analyze and predict what will happen in space. The ISS Centrifuge Rotor (CR) is one of many mechanical systems that need to be modeled and analyzed to verify the ISS integrated system performance on-orbit. This study investigates using Bond Graph modeling techniques as quick and simplified ways to generate models of the ISS Centrifuge Rotor. This paper outlines the steps used to generate simple and more complex models of the CR using Bond Graph Computer Aided Modeling Program with Graphical Input (CAMP-G). Comparisons of the Bond Graph CR models with those derived from Euler-Lagrange equations in MATLAB and those developed using multibody dynamic simulation at the National Aeronautics and Space Administration (NASA) Johnson Space Center (JSC) are presented to demonstrate the usefulness of the Bond Graph modeling approach for aeronautics and space applications.

  4. The use of symmetrized valence and relative motion coordinates for crystal potentials

    DEFF Research Database (Denmark)

    McMurry, H. L.; Hansen, Flemming Yssing

    1980-01-01

    Symmetrized valence coordinates are linear combinations of conventional valence coordinates which display the symmetry of a set of atoms bound by the valence bonds. Relative motion coordinates are relative translations, or relative rotations, of two or more strongly bonded groups of atoms among...... which relatively weak forces act. They are useful for expressing interactions between molecules in molecular crystals and should be chosen, also, to reflect the symmetry of the interacting groups. Since coordinates defined by these procedures possess elements of symmetry in common with the bonding...... interaction constants coupling coordinates of unlike symmetry with regard to the crystal point group are necessarily zero. They may be small, also, for coordinates which belong to different representations of the local symmetry when this is not the same as for the crystal. Procedures are given for defining...

  5. Computational insight into relations between electronic and vibrational polarizabilities within the two-state valence-bond charge-transfer model

    Czech Academy of Sciences Publication Activity Database

    Zalesny, R.; Bartkowiak, W.; Toman, Petr; Leszczynski, J.

    2007-01-01

    Roč. 337, 1-3 (2007), s. 77-80 ISSN 0301-0104 Grant - others:Polish Committee for Scientific Research and the Ministry of Education, Youth, and Sports of the Czech Republic(PL) CZ25 Institutional research plan: CEZ:AV0Z40500505 Keywords : polarizability * first hyperpolarizability * second hyperpolarizability * nonlinear optical properties Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.805, year: 2007

  6. Thermal recombination: Beyond the valence quark approximation

    Energy Technology Data Exchange (ETDEWEB)

    Mueller, B. [Department of Physics, Duke University, Durham, NC 27708 (United States); Fries, R.J. [School of Physics and Astronomy, University of Minnesota, Minneapolis, MN 55455 (United States)]. E-mail: fries@physics.umn.edu; Bass, S.A. [Department of Physics, Duke University, Durham, NC 27708 (United States); RIKEN BNL Research Center, Brookhaven National Laboratory, Upton, NY 11973 (United States)

    2005-07-07

    Quark counting rules derived from recombination models agree well with data on hadron production at intermediate transverse momenta in relativistic heavy-ion collisions. They convey a simple picture of hadrons consisting only of valence quarks. We discuss the inclusion of higher Fock states that add sea quarks and gluons to the hadron structure. We show that, when recombination occurs from a thermal medium, hadron spectra remain unaffected by the inclusion of higher Fock states. However, the quark number scaling for elliptic flow is somewhat affected. We discuss the implications for our understanding of data from the Relativistic Heavy Ion Collider.

  7. Molecular invariants: atomic group valence

    International Nuclear Information System (INIS)

    Mundim, K.C.; Giambiagi, M.; Giambiagi, M.S. de.

    1988-01-01

    Molecular invariants may be deduced in a very compact way through Grassman algebra. In this work, a generalized valence is defined for an atomic group; it reduces to the Known expressions for the case of an atom in a molecule. It is the same of the correlations between the fluctions of the atomic charges qc and qd (C belongs to the group and D does not) around their average values. Numerical results agree with chemical expectation. (author) [pt

  8. Theoretical modeling of infrared spectra of the hydrogen and deuterium bond in aspirin crystal

    Science.gov (United States)

    Ghalla, Houcine; Rekik, Najeh; Michta, Anna; Oujia, Brahim; Flakus, Henryk T.

    2010-01-01

    An extended quantum theoretical approach of the ν IR lineshape of cyclic dimers of weakly H-bonded species is proposed. We have extended a previous approach [M.E.-A. Benmalti, P. Blaise, H.T. Flakus, O. Henri-Rousseau, Chem. Phys. 320 (2006) 267] by accounting for the anharmonicity of the slow mode which is described by a "Morse" potential in order to reproduce the polarized infrared spectra of the hydrogen and deuterium bond in acetylsalicylic acid (aspirin) crystals. From comparison of polarized IR spectra of isotopically neat and isotopically diluted aspirin crystals it resulted that centrosymmetric aspirin dimer was the bearer of the crystal main spectral properties. In this approach, the adiabatic approximation is performed for each separate H-bond bridge of the dimer and a strong non-adiabatic correction is introduced into the model via the resonant exchange between the fast mode excited states of the two moieties. Within the strong anharmonic coupling theory, according to which the X-H→⋯Y high-frequency mode is anharmonically coupled to the H-bond bridge, this model incorporated the Davydov coupling between the excited states of the two moieties, the quantum direct and indirect dampings and the anharmonicity for the H-bond bridge. The spectral density is obtained within the linear response theory by Fourier transform of the damped autocorrelation functions. The evaluated spectra are in fairly good agreement with the experimental ones by using a minimum number of independent parameters. The effect of deuteration has been well reproduced by reducing simply the angular frequency of the fast mode and the anharmonic coupling parameter.

  9. Links between the charge model and bonded parameter force constants in biomolecular force fields

    Science.gov (United States)

    Cerutti, David S.; Debiec, Karl T.; Case, David A.; Chong, Lillian T.

    2017-10-01

    The ff15ipq protein force field is a fixed charge model built by automated tools based on the two charge sets of the implicitly polarized charge method: one set (appropriate for vacuum) for deriving bonded parameters and the other (appropriate for aqueous solution) for running simulations. The duality is intended to treat water-induced electronic polarization with an understanding that fitting data for bonded parameters will come from quantum mechanical calculations in the gas phase. In this study, we compare ff15ipq to two alternatives produced with the same fitting software and a further expanded data set but following more conventional methods for tailoring bonded parameters (harmonic angle terms and torsion potentials) to the charge model. First, ff15ipq-Qsolv derives bonded parameters in the context of the ff15ipq solution phase charge set. Second, ff15ipq-Vac takes ff15ipq's bonded parameters and runs simulations with the vacuum phase charge set used to derive those parameters. The IPolQ charge model and associated protocol for deriving bonded parameters are shown to be an incremental improvement over protocols that do not account for the material phases of each source of their fitting data. Both force fields incorporating the polarized charge set depict stable globular proteins and have varying degrees of success modeling the metastability of short (5-19 residues) peptides. In this particular case, ff15ipq-Qsolv increases stability in a number of α -helices, correctly obtaining 70% helical character in the K19 system at 275 K and showing appropriately diminishing content up to 325 K, but overestimating the helical fraction of AAQAA3 by 50% or more, forming long-lived α -helices in simulations of a β -hairpin, and increasing the likelihood that the disordered p53 N-terminal peptide will also form a helix. This may indicate a systematic bias imparted by the ff15ipq-Qsolv parameter development strategy, which has the hallmarks of strategies used to develop

  10. Steel-concrete bond model for the simulation of reinforced concrete structures

    International Nuclear Information System (INIS)

    Mang, Chetra

    2015-01-01

    Reinforced concrete structure behavior can be extremely complex in the case of exceeding the cracking threshold. The composite characteristics of reinforced concrete structure should be finely presented especially in the distribution stress zone between steel-concrete at their interface. In order to compute the industrial structures, a perfect relation hypothesis between steel and concrete is supposed in which the complex phenomenon of the two-material relation is not taken into account. On the other hand, this perfect relation is unable to predict the significant disorders, the repartition, and the distribution of the cracks, which is directly linked to the steel. In literature, several numerical methods are proposed in order to finely study the concrete-steel bond behavior, but these methods give many difficulties in computing complex structures in 3D. With the results obtained in the thesis framework of Torre-Casanova (2012), the new concrete-steel bond model has been developed to improve performances (iteration numbers and computational time) and the representation (cyclic behavior) of the initial one. The new model has been verified with analytical solution of steel-concrete tie and validated with the experimental results. The new model is equally tested with the structural scale to compute the shear wall behavior in the French national project (CEOS.fr) under monotonic load. Because of the numerical difficulty in post-processing the crack opening in the complex crack formation, a new crack opening method is also developed. This method consists of using the discontinuity of relative displacement to detect the crack position or using the slip sign change between concrete-steel. The simulation-experiment comparison gives validation of not only the new concrete-steel bond model but also the new crack post-processing method. Finally, the cyclic behavior of the bond law with the non-reduced envelope is adopted and integrated in the new bond model in order to take

  11. Linear finite-difference bond graph model of an ionic polymer actuator

    Science.gov (United States)

    Bentefrit, M.; Grondel, S.; Soyer, C.; Fannir, A.; Cattan, E.; Madden, J. D.; Nguyen, T. M. G.; Plesse, C.; Vidal, F.

    2017-09-01

    With the recent growing interest for soft actuation, many new types of ionic polymers working in air have been developed. Due to the interrelated mechanical, electrical, and chemical properties which greatly influence the characteristics of such actuators, their behavior is complex and difficult to understand, predict and optimize. In light of this challenge, an original linear multiphysics finite difference bond graph model was derived to characterize this ionic actuation. This finite difference scheme was divided into two coupled subparts, each related to a specific physical, electrochemical or mechanical domain, and then converted into a bond graph model as this language is particularly suited for systems from multiple energy domains. Simulations were then conducted and a good agreement with the experimental results was obtained. Furthermore, an analysis of the power efficiency of such actuators as a function of space and time was proposed and allowed to evaluate their performance.

  12. Spin-splitting calculation for zincblende semiconductors using an atomic bond-orbital model.

    Science.gov (United States)

    Kao, Hsiu-Fen; Lo, Ikai; Chiang, Jih-Chen; Chen, Chun-Nan; Wang, Wan-Tsang; Hsu, Yu-Chi; Ren, Chung-Yuan; Lee, Meng-En; Wu, Chieh-Lung; Gau, Ming-Hong

    2012-10-17

    We develop a 16-band atomic bond-orbital model (16ABOM) to compute the spin splitting induced by bulk inversion asymmetry in zincblende materials. This model is derived from the linear combination of atomic-orbital (LCAO) scheme such that the characteristics of the real atomic orbitals can be preserved to calculate the spin splitting. The Hamiltonian of 16ABOM is based on a similarity transformation performed on the nearest-neighbor LCAO Hamiltonian with a second-order Taylor expansion k at the Γ point. The spin-splitting energies in bulk zincblende semiconductors, GaAs and InSb, are calculated, and the results agree with the LCAO and first-principles calculations. However, we find that the spin-orbit coupling between bonding and antibonding p-like states, evaluated by the 16ABOM, dominates the spin splitting of the lowest conduction bands in the zincblende materials.

  13. Modeling on-column reduction of trisulfide bonds in monoclonal antibodies during protein A chromatography.

    Science.gov (United States)

    Ghose, Sanchayita; Rajshekaran, Rupshika; Labanca, Marisa; Conley, Lynn

    2017-01-06

    Trisulfides can be a common post-translational modification in many recombinant monoclonal antibodies. These are a source of product heterogeneity that add to the complexity of product characterization and hence, need to be reduced for consistent product quality. Trisulfide bonds can be converted to the regular disulfide bonds by incorporating a novel cysteine wash step during Protein A affinity chromatography. An empirical model is developed for this on-column reduction reaction to compare the reaction rates as a function of typical operating parameters such as temperature, cysteine concentration, reaction time and starting level of trisulfides. The model presented here is anticipated to assist in the development of optimal wash conditions for the Protein A step to effectively reduce trisulfides to desired levels. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. BCS superconductivity in mixed valence and heavy fermion superconductors

    Science.gov (United States)

    Gor'kov, Lev P.; Barzykin, Victor

    2005-03-01

    We consider competition of Kondo effect and s-wave superconductivity in heavy fermion and mixed valence superconductors, using the slave boson 1/N approach for the periodic Anderson model. Similar to the well known results for single-impurity Kondo effect in superconductors, we have found that re-entrant behavior of the superconducting transition temperature, Tc, should be observed in heavy fermion superconductors as a function of model parameters or concentration of impurities. Suppression of Tc in mixed valence superconductors is much weaker, without re-entrant behavior of Tc. Our results have most validity in the low-temperature regime.

  15. An Analytical Model for Predicting the Stress Distributions within Single-Lap Adhesively Bonded Beams

    Directory of Open Access Journals (Sweden)

    Xiaocong He

    2014-01-01

    Full Text Available An analytical model for predicting the stress distributions within single-lap adhesively bonded beams under tension is presented in this paper. By combining the governing equations of each adherend with the joint kinematics, the overall system of governing equations can be obtained. Both the adherends and the adhesive are assumed to be under plane strain condition. With suitable boundary conditions, the stress distribution of the adhesive in the longitudinal direction is determined.

  16. Effect of Bond-Diluted on Spin-32 Transverse Ising Model with Crystal Field

    Science.gov (United States)

    Jiang, Wei; Lu, Zhan-Hong; Wei, Guo-Zhu; Du, An

    2002-08-01

    The magnetic properties of the bond-diluted spin-3/2 transverse Ising model with the presence of a crystal field on the honeycomb lattice are studied within the framework of the effective field theory with correlations. The interactions Jij are assumed to be independent random variables with distribution P(Jij)=pδ(Jij-J)+(1-p)δ(Jij). The project supported by the Foundation of the Ministry of Education of China under Grant No. 99026

  17. Nonlinear finite element modeling of concrete deep beams with openings strengthened with externally-bonded composites

    International Nuclear Information System (INIS)

    Hawileh, Rami A.; El-Maaddawy, Tamer A.; Naser, Mohannad Z.

    2012-01-01

    Highlights: ► A 3D nonlinear FE model is developed of RC deep beams with web openings. ► We used cohesion elements to simulate bond. ► The developed FE model is suitable for analysis of such complex structures. -- Abstract: This paper aims to develop 3D nonlinear finite element (FE) models for reinforced concrete (RC) deep beams containing web openings and strengthened in shear with carbon fiber reinforced polymer (CFRP) composite sheets. The web openings interrupted the natural load path either fully or partially. The FE models adopted realistic materials constitutive laws that account for the nonlinear behavior of materials. In the FE models, solid elements for concrete, multi-layer shell elements for CFRP and link elements for steel reinforcement were used to simulate the physical models. Special interface elements were implemented in the FE models to simulate the interfacial bond behavior between the concrete and CFRP composites. A comparison between the FE results and experimental data published in the literature demonstrated the validity of the computational models in capturing the structural response for both unstrengthened and CFRP-strengthened deep beams with openings. The developed FE models can serve as a numerical platform for performance prediction of RC deep beams with openings strengthened in shear with CFRP composites.

  18. A New Material Model for 2D FE Analysis of Adhesively Bonded Composite Joints

    Directory of Open Access Journals (Sweden)

    Libin ZHAO

    2014-12-01

    Full Text Available Effective and convenient stress analysis techniques play important roles in the analysis and design of adhesively bonded composite joints. A new material model is presented at the level of composite ply according to the orthotropic elastic mechanics theory and plane strain assumption. The model proposed has the potential to reserve nature properties of laminates with ply-to-ply modeling. The equivalent engineering constants in the model are obtained only by the material properties of unidirectional composites. Based on commercial FE software ABAQUS, a 2D FE model of a single-lap adhesively bonded joint was established conveniently by using the new model without complex modeling process and much professional knowledge. Stress distributions in adhesive were compared with the numerical results by Tsai and Morton and interlaminar stresses between adhesive and adherents were compared with the results from a detailed 3D FE analysis. Good agreements in both cases verify the validity of the proposed model. DOI: http://dx.doi.org/10.5755/j01.ms.20.4.5960

  19. Bond and CDS Pricing via the Stochastic Recovery Black-Cox Model

    Directory of Open Access Journals (Sweden)

    Albert Cohen

    2017-04-01

    Full Text Available Building on recent work incorporating recovery risk into structural models by Cohen & Costanzino (2015, we consider the Black-Cox model with an added recovery risk driver. The recovery risk driver arises naturally in the context of imperfect information implicit in the structural framework. This leads to a two-factor structural model we call the Stochastic Recovery Black-Cox model, whereby the asset risk driver At defines the default trigger and the recovery risk driver Rt defines the amount recovered in the event of default. We then price zero-coupon bonds and credit default swaps under the Stochastic Recovery Black-Cox model. Finally, we compare our results with the classic Black-Cox model, give explicit expressions for the recovery risk premium in the Stochastic Recovery Black-Cox model, and detail how the introduction of separate but correlated risk drivers leads to a decoupling of the default and recovery risk premiums in the credit spread. We conclude this work by computing the effect of adding coupons that are paid continuously until default, and price perpetual (consol bonds in our two-factor firm value model, extending calculations in the seminal paper by Leland (1994.

  20. Crossover and valence band Kβ X-rays of chromium oxides

    International Nuclear Information System (INIS)

    Fazinic, Stjepko; Mandic, Luka; Kavcic, Matjaz; Bozicevic, Iva

    2011-01-01

    Kβ X-ray spectra of chromium metal and selected chromium oxides were measured twice using medium resolution flat crystal spectrometer and high resolution spectrometer employing Johansson geometry after excitation with 2 MeV proton beams. The positions and intensities of crossover (Kβ'') and valence (Kβ 2,5 ) band X-rays relative to the primary Kβ X-ray components were extracted in a consistent way. The results were compared with the existing data obtained by proton and photon induced ionization mechanisms and theoretical predictions. The obtained results in peak relative positions and intensities were analyzed in order to study dependence on the chromium oxidation states and chromium-oxygen bond lengths in selected chromium oxides. Our results obtained by both spectrometers confirm that the linear trend observed for the valence peak relative energy shift as a function of chromium oxidation number does not depend on the experimental resolution. Experimental results for normalized intensities (i.e. relative intensities divided with the number of chromium-oxygen pairs) of crossover and valence band X-rays obtained by both spectrometers are in very good agreement, and follow exponential relationship with the average Cr-O bond lengths in corresponding chromium oxides. The observed trends in crossover and valence X-rays normalized intensities could be used to measure the average chromium-oxygen bond length in various chromium oxides, with the sum of both crossover and valence X-ray normalized intensities being the most sensitive measure.

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

    Science.gov (United States)

    Naka, Makoto; Seo, Hitoshi; Motome, Yukitoshi

    2016-02-05

    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.

  2. Theory of Valence Transition in BiNiO3

    Science.gov (United States)

    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.

  3. Modeling the vapor-liquid equilibria of polymer-solvent mixtures: Systems with complex hydrogen bonding behavior

    DEFF Research Database (Denmark)

    Tsivintzelis, Ioannis; Kontogeorgis, Georgios

    2009-01-01

    The vapor–liquid equilibria of binary polymer–solvent systems was modeled using the Non-Random Hydrogen Bonding (NRHB) model. Mixtures of poly(ethylene glycol), poly(propylene glycol), poly(vinyl alcohol) and poly(vinyl acetate) with various solvents were investigated, while emphasis was put...... on hydrogen bonding systems, in which functional groups of the polymer chain can self-associate or cross-associate with the solvent molecules. Effort has been made to explicitly account for all hydrogen bonding interactions. The results reveal that the NRHB model offers a flexible approach to account...

  4. Influence of heterogeneity on rock strength and stiffness using discrete element method and parallel bond model

    Directory of Open Access Journals (Sweden)

    Spyridon Liakas

    2017-08-01

    Full Text Available The particulate discrete element method (DEM can be employed to capture the response of rock, provided that appropriate bonding models are used to cement the particles to each other. Simulations of laboratory tests are important to establish the extent to which those models can capture realistic rock behaviors. Hitherto the focus in such comparison studies has either been on homogeneous specimens or use of two-dimensional (2D models. In situ rock formations are often heterogeneous, thus exploring the ability of this type of models to capture heterogeneous material behavior is important to facilitate their use in design analysis. In situ stress states are basically three-dimensional (3D, and therefore it is important to develop 3D models for this purpose. This paper revisits an earlier experimental study on heterogeneous specimens, of which the relative proportions of weaker material (siltstone and stronger, harder material (sandstone were varied in a controlled manner. Using a 3D DEM model with the parallel bond model, virtual heterogeneous specimens were created. The overall responses in terms of variations in strength and stiffness with different percentages of weaker material (siltstone were shown to agree with the experimental observations. There was also a good qualitative agreement in the failure patterns observed in the experiments and the simulations, suggesting that the DEM data enabled analysis of the initiation of localizations and micro fractures in the specimens.

  5. Bond graph modeling and simulation of impact dynamics of an automotive crash

    International Nuclear Information System (INIS)

    Khurshid, A.; Malik, M.A.

    2007-01-01

    With increase in the speeds of automotives, safety has become more and more important aspect of designers to care for. Thus, it is necessary to design the automobile body structure keeping in view all the safety requirements. As a result of the above-mentioned facts, in the recent years, the designers in making automotives more safe, more collision resistant and crash worthy have focused increased attention on designing automotives, which provides greater protection for the drivers and the passengers in case of an accident. Before a new model is launched into the market, a complete collision analysis is carried out to check the damage reduction capabilities and impact protection of automotives in case of an accident. Research in the field of automotive collision and impact analysis is a continuing activity and dedicated groups of engineers are devoting their full time and efforts for this. In this research work, the main attention is focused to provide a detailed knowledge about automotive collision analysis. The objective of this research paper is to develop an understanding of the automotive collision response. For this, we have done a simulation experiment in which, on a railroad, a train car is separated from a train and is moving towards two stationary train cars. By using a bond graph model of the system its state-space equations are found. Then by using software, the simulation is carried out. The bond graph method is a graphical presentation of the power flow using bonds. (author)

  6. Solid-liquid interdiffusion (SLID) bonding in the Au-In system: experimental study and 1D modelling

    Science.gov (United States)

    Deillon, Léa; Hessler-Wyser, Aïcha; Hessler, Thierry; Rappaz, Michel

    2015-12-01

    Au-In bonds with a nominal composition of about 60 at.% In were fabricated for use in wafer-level packaging of MEMS. The microstructure of the bonds was studied by scanning electron microscopy. The bond hermeticity was then assessed using oxidation of Cu thin discs predeposited within the sealed packages. The three intermetallic compounds AuIn2, AuIn and Au7In3 were observed. Their thickness evolution during bonding and after subsequent heat treatment was successfully modelled using a finite difference model of diffusion, thermodynamic data and diffusion coefficients calibrated from isothermal diffusion couples. 17% of the packages were hermetic and, although the origin of the leaks could not be clearly identified, it appeared that hermeticity was correlated with the unevenness of the metallisation and/or wafer and the fact that the bonds shrink due to density differences as the relative fractions of the various phases gradually evolve.

  7. Solid-liquid interdiffusion (SLID) bonding in the Au–In system: experimental study and 1D modelling

    International Nuclear Information System (INIS)

    Deillon, Léa; Hessler-Wyser, Aïcha; Hessler, Thierry; Rappaz, Michel

    2015-01-01

    Au–In bonds with a nominal composition of about 60 at.% In were fabricated for use in wafer-level packaging of MEMS. The microstructure of the bonds was studied by scanning electron microscopy. The bond hermeticity was then assessed using oxidation of Cu thin discs predeposited within the sealed packages. The three intermetallic compounds AuIn 2 , AuIn and Au 7 In 3 were observed. Their thickness evolution during bonding and after subsequent heat treatment was successfully modelled using a finite difference model of diffusion, thermodynamic data and diffusion coefficients calibrated from isothermal diffusion couples. 17% of the packages were hermetic and, although the origin of the leaks could not be clearly identified, it appeared that hermeticity was correlated with the unevenness of the metallisation and/or wafer and the fact that the bonds shrink due to density differences as the relative fractions of the various phases gradually evolve. (paper)

  8. Measurement and modelling of hydrogen bonding in 1-alkanol plus n-alkane binary mixtures

    DEFF Research Database (Denmark)

    von Solms, Nicolas; Jensen, Lars; Kofod, Jonas L.

    2007-01-01

    Two equations of state (simplified PC-SAFT and CPA) are used to predict the monomer fraction of 1-alkanols in binary mixtures with n-alkanes. It is found that the choice of parameters and association schemes significantly affects the ability of a model to predict hydrogen bonding in mixtures, eve...... studies, which is clarified in the present work. New hydrogen bonding data based on infrared spectroscopy are reported for seven binary mixtures of alcohols and alkanes. (C) 2007 Elsevier B.V. All rights reserved....... though pure-component liquid densities and vapour pressures are predicted equally accurately for the associating compound. As was the case in the study of pure components, there exists some confusion in the literature about the correct interpretation and comparison of experimental data and theoretical...

  9. Postpartum Bonding Disorder: Factor Structure, Validity, Reliability and a Model Comparison of the Postnatal Bonding Questionnaire in Japanese Mothers of Infants

    Directory of Open Access Journals (Sweden)

    Yukiko Ohashi

    2016-08-01

    Full Text Available Negative attitudes of mothers towards their infant is conceptualized as postpartum bonding disorder, which leads to serious health problems in perinatal health care. However, its measurement still remains to be standardized. Our aim was to examine and confirm the psychometric properties of the Postnatal Bonding Questionnaire (PBQ in Japanese mothers. We distributed a set of questionnaires to community mothers and studied 392 mothers who returned the questionnaires at 1 month after childbirth. Our model was compared with three other models derived from previous studies. In a randomly halved sample, an exploratory factor analysis yielded a three-factor structure: Anger and Restrictedness, Lack of Affection, and Rejection and Fear. This factor structure was cross-validated by a confirmatory factor analysis using the other halved sample. The three subscales showed satisfactory internal consistency. The three PBQ subscale scores were correlated with depression and psychological abuse scores. Their test–retest reliability between day 5 and 1 month after childbirth was measured by intraclass correlation coefficients between 0.76 and 0.83. The Akaike Information Criteria of our model was better than the original four-factor model of Brockington. The present study indicates that the PBQ is a reliable and valid measure of bonding difficulties of Japanese mothers with neonates.

  10. Shock-induced electrical activity in polymeric solids. A mechanically induced bond scission model

    International Nuclear Information System (INIS)

    Graham, R.A.

    1979-01-01

    When polymeric solids are subjected to high-pressure shock loading, two anomalous electrical phenomena, shock-induced conduction and shock-induced polarization, are observed. The present paper proposes a model of mechanically induced bond scission within the shock front to account for the effects. An experimental study of shock-induced polarization in poly(pyromellitimide) (Vespel SP-1) is reported for shock compressions from 17 to 23% (pressures from 2.5 to 5.4 GPa). Poly(pyromellitimide) is found to be a strong generator of such polarization and the polarization is found to reflect an irreversible or highly hysteretic process. The present measurements are combined with prior measurements to establish a correlation between monomer structure and strength of shock-induced polarization; feeble signals are observed in the simpler monomer repeat units of poly(tetrafluoroethylene) and polyethylene while the strongest signals are observed in more complex monomers of poly(methyl methacrylate) and poly(pyromellitimide). It is also noted that there is an apparent correlation between shock-induced conduction and shock-induced polarization. Such shock-induced electrical activity is also found to be well correlated with the propensity for mechanical bond scission observed in experiments carried out in conventional mechanochemical studies. The bond scission model can account for characteristics observed for electrical activity in shock-loaded polymers and their correlation to monomer structure. Localization of elastic energy within the monomer repeat unit or along the main chain leads to the different propensities for bond scission and resulting shock-induced electrical activity

  11. Conduction Mechanism of Valence Change Resistive Switching Memory: A Survey

    Directory of Open Access Journals (Sweden)

    Ee Wah Lim

    2015-09-01

    Full Text Available Resistive switching effect in transition metal oxide (TMO based material is often associated with the valence change mechanism (VCM. Typical modeling of valence change resistive switching memory consists of three closely related phenomena, i.e., conductive filament (CF geometry evolution, conduction mechanism and temperature dynamic evolution. It is widely agreed that the electrochemical reduction-oxidation (redox process and oxygen vacancies migration plays an essential role in the CF forming and rupture process. However, the conduction mechanism of resistive switching memory varies considerably depending on the material used in the dielectric layer and selection of electrodes. Among the popular observations are the Poole-Frenkel emission, Schottky emission, space-charge-limited conduction (SCLC, trap-assisted tunneling (TAT and hopping conduction. In this article, we will conduct a survey on several published valence change resistive switching memories with a particular interest in the I-V characteristic and the corresponding conduction mechanism.

  12. The multimedia models for the evaluation of exposure bond to the atmospheric emissions of classified installations

    International Nuclear Information System (INIS)

    Bonnard, R.

    2001-12-01

    Risk assessment and environmental impacts studies are realized to preserve the public health. Today one of the most used approach is the use of an atmospheric dispersion model to assess the risks. The data are then injected in a calculation software of exposure bond to polluted soils, to evaluate the risks of non direct exposure. This report details and evaluates the models corresponding to the need: the methodology for assessing Health Risks associated with multiple pathways of exposure to combustor, human health risk assessment proto col for hazardous waste combustion facilities, EUSES, CALTOX, MEPAS, MEND-TOX, RESRAD, MMSOILS, FRAMES-HWIR, PC-GEMS and TRIM. (A.L.B.)

  13. Kernel density estimation applied to bond length, bond angle, and torsion angle distributions.

    Science.gov (United States)

    McCabe, Patrick; Korb, Oliver; Cole, Jason

    2014-05-27

    We describe the method of kernel density estimation (KDE) and apply it to molecular structure data. KDE is a quite general nonparametric statistical method suitable even for multimodal data. The method generates smooth probability density function (PDF) representations and finds application in diverse fields such as signal processing and econometrics. KDE appears to have been under-utilized as a method in molecular geometry analysis, chemo-informatics, and molecular structure optimization. The resulting probability densities have advantages over histograms and, importantly, are also suitable for gradient-based optimization. To illustrate KDE, we describe its application to chemical bond length, bond valence angle, and torsion angle distributions and show the ability of the method to model arbitrary torsion angle distributions.

  14. Valence shell charge concentration (VSCC) evolution: a tool to investigate the transformations within a VSCC throughout a chemical reaction.

    Science.gov (United States)

    Cortés-Guzmán, Fernando; Gómez, Rosa María; Rocha-Rinza, Tomas; Sánchez-Obregón, María Azucena; Guevara-Vela, José Manuel

    2011-11-17

    Theoretical studies about reaction mechanisms are usually limited to the determination of the energetic paths that connect reactants, transition states, and products. Recently, our group proposed the structural evolution, which has provided insights about the molecular structure changes occurring along a reaction path. Structural evolution may be defined as the development of a chemical reaction system across the partitioning of the nuclear configuration space into a finite number of structural regions defined on account of the topology of a scalar field, e.g., the electron density. In this paper, we present a tool to investigate within the framework of the Quantum Theory of Atoms in Molecules the evolvement of the Valence Shell Charge Concentration, the VSCC evolution, which is the description of the changes of electron density concentrations and depletions around the bonding area of an atom. The VSCC evolution provides supplementary information to the structural evolution because it allows the analysis of valence shells within a structural region, i.e., a subset of R(Q) with the same connectivity among the atoms forming a molecule. This new approach constitutes also a complement to the Valence-Shell Electron Pair Repulsion (VSEPR) model because it gives an account of the adjustments of electron pairs in the valence shell of an atom across a chemical reaction. The insertion reaction in the hydroformylation reaction of ethylene, the reduction of cyclohexanone with lithium aluminum hydride, the oxidation of methanol with chlorochromate, and the bimolecular nucleophilic substitution of CH(3)F with F(-) are used as representatives examples of the application of the VSCC evolution. Overall, this paper shows how the VSCC evolution through an analysis of the modifications of local charge concentrations and depletions in individual steps of a chemical reaction gives new insights about these processes.

  15. Fe–Mn alloys: A mixed-bond spin-1/2 Ising model version

    Energy Technology Data Exchange (ETDEWEB)

    Freitas, A.S. [Departamento de Física, Universidade Federal de Sergipe, 49100-000 São Cristovão, SE (Brazil); Albuquerque, Douglas F. de, E-mail: douglas@ufs.br [Departamento de Física, Universidade Federal de Sergipe, 49100-000 São Cristovão, SE (Brazil); Departamento de Matemática, Universidade Federal de Sergipe, 49100-000 São Cristovão, SE (Brazil); Moreno, N.O. [Departamento de Física, Universidade Federal de Sergipe, 49100-000 São Cristovão, SE (Brazil)

    2014-06-01

    In this work, we apply the mixed-bond spin-1/2 Ising model to study the magnetic properties of Fe–Mn alloys in the α phase by employing the effective field theory (EFT). Here, we suggest a new approach to the ferromagnetic coupling between nearest neighbours Fe–Fe that depends on the ratio between the Mn–Mn coupling and the Fe–Mn coupling and of second power of the Mn concentration q in contrast to linear dependence considered in the other articles. Also, we propose a new probability distribution for binary alloys with mixed-bonds based on the distribution for ternary alloys and we obtain a very good agreement for all considered values of q in T–q plane, in particular for q>0.11. - Highlights: • We apply the mixed-bond spin-1/2 to study the properties of Fe–Mn. • We employ the EFT and suggest a new approach to ferromagnetic coupling. • The new probability distribution is considered. • The phase diagram is obtained for all values of q in T–q plane.

  16. Fe–Mn alloys: A mixed-bond spin-1/2 Ising model version

    International Nuclear Information System (INIS)

    Freitas, A.S.; Albuquerque, Douglas F. de; Moreno, N.O.

    2014-01-01

    In this work, we apply the mixed-bond spin-1/2 Ising model to study the magnetic properties of Fe–Mn alloys in the α phase by employing the effective field theory (EFT). Here, we suggest a new approach to the ferromagnetic coupling between nearest neighbours Fe–Fe that depends on the ratio between the Mn–Mn coupling and the Fe–Mn coupling and of second power of the Mn concentration q in contrast to linear dependence considered in the other articles. Also, we propose a new probability distribution for binary alloys with mixed-bonds based on the distribution for ternary alloys and we obtain a very good agreement for all considered values of q in T–q plane, in particular for q>0.11. - Highlights: • We apply the mixed-bond spin-1/2 to study the properties of Fe–Mn. • We employ the EFT and suggest a new approach to ferromagnetic coupling. • The new probability distribution is considered. • The phase diagram is obtained for all values of q in T–q plane

  17. Effective valence as the control parameter of the superconducting ...

    African Journals Online (AJOL)

    In this paper, we have demonstrated that the effective valence of iron can be used as the control parameter to tune the Tc of this family of superconducting materials. This is achieved by postulating that our model of spin fluctuation which has been used to successfully account for the superconductivity in the cuprates in Ref.

  18. AVE bond index in the H-bond of the Watson-Crick pairs

    International Nuclear Information System (INIS)

    Giambiagi, M.; Giambiagi, M.S. de; Barroso Filho, W.

    1981-01-01

    The normal Watson-Crick base pairs are treated as super-molecules. The properties of the electronic distribution along the N-H...Y bonds are studied in an all-valence-electrons calculation, through a bond index formula devised for non-orthogonal basis. Eletronic density diagrams of the adenine-uracil base pair are analysed. (Auhor) [pt

  19. Bonding Strength Effects in Hydro-Mechanical Coupling Transport in Granular Porous Media by Pore-Scale Modeling

    Directory of Open Access Journals (Sweden)

    Zhiqiang Chen

    2016-03-01

    Full Text Available The hydro-mechanical coupling transport process of sand production is numerically investigated with special attention paid to the bonding effect between sand grains. By coupling the lattice Boltzmann method (LBM and the discrete element method (DEM, we are able to capture particles movements and fluid flows simultaneously. In order to account for the bonding effects on sand production, a contact bond model is introduced into the LBM-DEM framework. Our simulations first examine the experimental observation of “initial sand production is evoked by localized failure” and then show that the bonding or cement plays an important role in sand production. Lower bonding strength will lead to more sand production than higher bonding strength. It is also found that the influence of flow rate on sand production depends on the bonding strength in cemented granular media, and for low bonding strength sample, the higher the flow rate is, the more severe the erosion found in localized failure zone becomes.

  20. Method of modelization assistance with bond graphs and application to qualitative diagnosis of physical systems

    International Nuclear Information System (INIS)

    Lucas, B.

    1994-05-01

    After having recalled the usual diagnosis techniques (failure index, decision tree) and those based on an artificial intelligence approach, the author reports a research aimed at exploring the knowledge and model generation technique. He focuses on the design of an aid to model generation tool and aid-to-diagnosis tool. The bond graph technique is shown to be adapted to the aid to model generation, and is then adapted to the aid to diagnosis. The developed tool is applied to three projects: DIADEME (a diagnosis system based on physical model), the improvement of the SEXTANT diagnosis system (an expert system for transient analysis), and the investigation on an Ariane 5 launcher component. Notably, the author uses the Reiter and Greiner algorithm

  1. Cleavage of C-O bonds in lignin model compounds catalyzed by methyldioxorhenium in homogeneous phase.

    Science.gov (United States)

    Harms, Reentje G; Markovits, Iulius I E; Drees, Markus; Herrmann, H C Mult Wolfgang A; Cokoja, Mirza; Kühn, Fritz E

    2014-02-01

    Methyldioxorhenium (MDO)-catalyzed C-O bond cleavage of a variety of lignin β-O-4-model compounds yields phenolic and aldehydic compounds in homogeneous phase under mild reaction conditions. MDO is in situ generated by reduction of methyltrioxorhenium (MTO) and is remarkably stable under the applied reaction conditions allowing its reuse for least five times without significant activity loss. Based on the observed and isolated intermediates, 17 O- and 2 H-isotope labeling experiments, DFT calculations, and several spectroscopic studies, a reaction mechanism is proposed. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Phase transitions in mixed valence systems

    Energy Technology Data Exchange (ETDEWEB)

    Gor`kov, L.P. [Florida State Univ., Tallahassee, FL (United States). Nat. High Magnetic Field Lab.]|[Rossijskaya Akademiya Nauk, Moscow (Russian Federation). Inst. Teoreticheskoj Fiziki

    1996-07-01

    The experimental properties of URu{sub 2}Si{sub 2} are briefly discussed to demonstrate that the lattice degrees of freedom may be tightly involved into the mixed valence phenomenon and the heavy fermion behavior. Instead of describing the f-electrons in terms of rigid single ion orbitals, we emphasize the importance of the lattice effects in localization of an f-electron near the given site. In view that so many pertinent interactions and parameters are involved, a phenomenological approach to the problem is discussed in terms of the generalized Anderson model for single centers. Implications of the picture to the symmetry considerations are discussed in some more details for URu{sub 2}Si{sub 2}. Some features of the Kondo insulator state are also discussed to indicate that they may also be compatible with the developed views. (orig.).

  3. Network flow model of force transmission in unbonded and bonded granular media.

    Science.gov (United States)

    Tordesillas, Antoinette; Tobin, Steven T; Cil, Mehmet; Alshibli, Khalid; Behringer, Robert P

    2015-06-01

    An established aspect of force transmission in quasistatic deformation of granular media is the existence of a dual network of strongly versus weakly loaded particles. Despite significant interest, the regulation of strong and weak forces through the contact network remains poorly understood. We examine this aspect of force transmission using data on microstructural fabric from: (I) three-dimensional discrete element models of grain agglomerates of bonded subspheres constructed from in situ synchrotron microtomography images of silica sand grains under unconfined compression and (II) two-dimensional assemblies of unbonded photoelastic circular disks submitted to biaxial compression under constant volume. We model force transmission as a network flow and solve the maximum flow-minimum cost (MFMC) problem, the solution to which yields a percolating subnetwork of contacts that transmits the "maximum flow" (i.e., the highest units of force) at "least cost" (i.e., the dissipated energy from such transmission). We find the MFMC describes a two-tier hierarchical architecture. At the local level, it encapsulates intraconnections between particles in individual force chains and in their conjoined 3-cycles, with the most common configuration having at least one force chain contact experiencing frustrated rotation. At the global level, the MFMC encapsulates interconnections between force chains. The MFMC can be used to predict most of the force chain particles without need for any information on contact forces, thereby suggesting the network flow framework may have potential broad utility in the modeling of force transmission in unbonded and bonded granular media.

  4. Bond Graph Modelling for Fault Detection and Isolation of an Ultrasonic Linear Motor

    Directory of Open Access Journals (Sweden)

    Mabrouk KHEMLICHE

    2010-12-01

    Full Text Available In this paper Bond Graph modeling, simulation and monitoring of ultrasonic linear motors are presented. Only the vibration of piezoelectric ceramics and stator will be taken into account. Contact problems between stator and rotor are not treated here. So, standing and travelling waves will be briefly presented since the majority of the motors use another wave type to generate the stator vibration and thus obtain the elliptic trajectory of the points on the surface of the stator in the first time. Then, electric equivalent circuit will be presented with the aim for giving a general idea of another way of graphical modelling of the vibrator introduced and developed. The simulations of an ultrasonic linear motor are then performed and experimental results on a prototype built at the laboratory are presented. Finally, validation of the Bond Graph method for modelling is carried out, comparing both simulation and experiment results. This paper describes the application of the FDI approach to an electrical system. We demonstrate the FDI effectiveness with real data collected from our automotive test. We introduce the analysis of the problem involved in the faults localization in this process. We propose a method of fault detection applied to the diagnosis and to determine the gravity of a detected fault. We show the possibilities of application of the new approaches to the complex system control.

  5. Models for mean bonding length, melting point and lattice thermal expansion of nanoparticle materials

    Energy Technology Data Exchange (ETDEWEB)

    Omar, M.S., E-mail: dr_m_s_omar@yahoo.com [Department of Physics, College of Science, University of Salahaddin-Erbil, Arbil, Kurdistan (Iraq)

    2012-11-15

    Graphical abstract: Three models are derived to explain the nanoparticles size dependence of mean bonding length, melting temperature and lattice thermal expansion applied on Sn, Si and Au. The following figures are shown as an example for Sn nanoparticles indicates hilly applicable models for nanoparticles radius larger than 3 nm. Highlights: ► A model for a size dependent mean bonding length is derived. ► The size dependent melting point of nanoparticles is modified. ► The bulk model for lattice thermal expansion is successfully used on nanoparticles. -- Abstract: A model, based on the ratio number of surface atoms to that of its internal, is derived to calculate the size dependence of lattice volume of nanoscaled materials. The model is applied to Si, Sn and Au nanoparticles. For Si, that the lattice volume is increases from 20 Å{sup 3} for bulk to 57 Å{sup 3} for a 2 nm size nanocrystals. A model, for calculating melting point of nanoscaled materials, is modified by considering the effect of lattice volume. A good approach of calculating size-dependent melting point begins from the bulk state down to about 2 nm diameter nanoparticle. Both values of lattice volume and melting point obtained for nanosized materials are used to calculate lattice thermal expansion by using a formula applicable for tetrahedral semiconductors. Results for Si, change from 3.7 × 10{sup −6} K{sup −1} for a bulk crystal down to a minimum value of 0.1 × 10{sup −6} K{sup −1} for a 6 nm diameter nanoparticle.

  6. Models for mean bonding length, melting point and lattice thermal expansion of nanoparticle materials

    International Nuclear Information System (INIS)

    Omar, M.S.

    2012-01-01

    Graphical abstract: Three models are derived to explain the nanoparticles size dependence of mean bonding length, melting temperature and lattice thermal expansion applied on Sn, Si and Au. The following figures are shown as an example for Sn nanoparticles indicates hilly applicable models for nanoparticles radius larger than 3 nm. Highlights: ► A model for a size dependent mean bonding length is derived. ► The size dependent melting point of nanoparticles is modified. ► The bulk model for lattice thermal expansion is successfully used on nanoparticles. -- Abstract: A model, based on the ratio number of surface atoms to that of its internal, is derived to calculate the size dependence of lattice volume of nanoscaled materials. The model is applied to Si, Sn and Au nanoparticles. For Si, that the lattice volume is increases from 20 Å 3 for bulk to 57 Å 3 for a 2 nm size nanocrystals. A model, for calculating melting point of nanoscaled materials, is modified by considering the effect of lattice volume. A good approach of calculating size-dependent melting point begins from the bulk state down to about 2 nm diameter nanoparticle. Both values of lattice volume and melting point obtained for nanosized materials are used to calculate lattice thermal expansion by using a formula applicable for tetrahedral semiconductors. Results for Si, change from 3.7 × 10 −6 K −1 for a bulk crystal down to a minimum value of 0.1 × 10 −6 K −1 for a 6 nm diameter nanoparticle.

  7. Vison Condensation and Bond Density Wave Order in the Cuprates

    Science.gov (United States)

    Patel, Aavishkar; Allais, Andrea; Chowdhury, Debanjan; Sachdev, Subir

    We consider Z2 spin liquids on the square lattice. These can undergo a confinement transition to a valence bond solid (VBS) phase via the condensation of vortex excitations carrying Z2 magnetic flux (visons). The resulting condensed phase is described by a fully frustrated Ising model (FFIM) on the dual square lattice, with additional couplings allowed by symmetries. We argue that such a model can also apply to confinement transitions out of the fractionalized Fermi liquid (FL*) states of doped antiferromagnets. We study the low energy states of such a model and discuss their implications for the incommensurate d-form factor bond density wave order observed in several recent experiments on the cuprate superconductors.

  8. Graphs with many valencies and few eigenvalues

    NARCIS (Netherlands)

    van Dam, Edwin; Koolen, J.H.; Xia, Zheng-Jiang

    Dom de Caen posed the question whether connected graphs with three distinct eigenvalues have at most three distinct valencies. We do not answer this question, but instead construct connected graphs with four and five distinct eigenvalues and arbitrarily many distinct valencies. The graphs with four

  9. Dissociable modulation of overt visual attention in valence and arousal revealed by topology of scan path.

    Directory of Open Access Journals (Sweden)

    Jianguang Ni

    Full Text Available 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.

  10. A continuum-based model capturing size effects in polymer bonds

    International Nuclear Information System (INIS)

    Diebels, S; Johlitz, M; Steeb, H; Chatzouridou, A; Batal, J; Possart, W

    2007-01-01

    It is known from applications that the mechanical behaviour of polymer bonds does not only depend on the properties of the polymer itself but also on the substrate. Therefore, the mechanical behaviour, i.e. the stiffness, of a polymer joint becomes thickness dependent. In the present work we describe experiments performed on polymer joints and we develop a continuum-based model which is able to describe the experimentally observed size effects without suggesting the microstructure in detail. The continuum mechanical model is enhanced by a scalar-valued structure parameter which describes all the effects taking place in the boundary layer which arises near the substrate. It is shown that the model parameters can be determined on the basis of simple shear experiments performed on polymer layers of different thickness

  11. Finite Element Bond Modeling for Indented Wires in Pretensioned Concrete Crossties

    Science.gov (United States)

    2016-04-12

    Indented wires have been increasingly employed by : concrete crosstie manufacturers to improve the bond between : prestressing steel reinforcements and concrete, as bond can : affect several critical performance measures, including transfer : length,...

  12. Chemical modelling of complex organic molecules with peptide-like bonds in star-forming regions

    Science.gov (United States)

    Quénard, David; Jiménez-Serra, Izaskun; Viti, Serena; Holdship, Jonathan; Coutens, Audrey

    2018-02-01

    Peptide bonds (N-C = O) play a key role in metabolic processes since they link amino acids into peptide chains or proteins. Recently, several molecules containing peptide-like bonds have been detected across multiple environments in the interstellar medium, growing the need to fully understand their chemistry and their role in forming larger pre-biotic molecules. We present a comprehensive study of the chemistry of three molecules containing peptide-like bonds: HNCO, NH2CHO, and CH3NCO. We also included other CHNO isomers (HCNO, HOCN) and C2H3NO isomers (CH3OCN, CH3CNO) to the study. We have used the UCLCHEM gas-grain chemical code and included in our chemical network all possible formation/destruction pathways of these peptide-like molecules recently investigated either by theoretical calculations or in laboratory experiments. Our predictions are compared to observations obtained towards the proto-star IRAS 16293-2422 and the L1544 pre-stellar core. Our results show that some key reactions involving the CHNO and C2H3NO isomers need to be modified to match the observations. Consistently with recent laboratory findings, hydrogenation is unlikely to produce NH2CHO on grain surfaces, while a combination of radical-radical surface reactions and gas-phase reactions is a better alternative. In addition, better results are obtained for NH2CHO when a slightly higher activation energy of 25 K is considered for the gas-phase reaction NH2 + H2CO → NH2CHO + H. Finally, our modelling shows that the observed correlation between NH2CHO and HNCO in star-forming regions may come from the fact that HNCO and NH2CHO react to temperature in the same manner rather than from a direct chemical link between the two species.

  13. Intramolecular hydrogen bond: Can it be part of the basis set of ...

    Indian Academy of Sciences (India)

    It has been shown earlier1 that the relaxed force constants (RFCs) could be used as a measure of bond strength only when the bonds form a part of the complete valence internal coordinates (VIC) basis. However, if the bond is not a part of the complete VIC basis, its RFC is not necessarily a measure of bond strength.

  14. 3D Modeling of Ultrasonic Wave Interaction with Disbonds and Weak Bonds

    Science.gov (United States)

    Leckey, C.; Hinders, M.

    2011-01-01

    Ultrasonic techniques, such as the use of guided waves, can be ideal for finding damage in the plate and pipe-like structures used in aerospace applications. However, the interaction of waves with real flaw types and geometries can lead to experimental signals that are difficult to interpret. 3-dimensional (3D) elastic wave simulations can be a powerful tool in understanding the complicated wave scattering involved in flaw detection and for optimizing experimental techniques. We have developed and implemented parallel 3D elastodynamic finite integration technique (3D EFIT) code to investigate Lamb wave scattering from realistic flaws. This paper discusses simulation results for an aluminum-aluminum diffusion disbond and an aluminum-epoxy disbond and compares results from the disbond case to the common artificial flaw type of a flat-bottom hole. The paper also discusses the potential for extending the 3D EFIT equations to incorporate physics-based weak bond models for simulating wave scattering from weak adhesive bonds.

  15. Effects of water contamination on the supercooled dynamics of a hydrogen-bonded model glass former.

    Science.gov (United States)

    Sjöström, Johan; Bergman, Rikard; Wadell, Carl; Moberg, Tobias; Swenson, Jan; Mattsson, Johan

    2011-03-03

    Broad-band dielectric spectroscopy is a commonly used tool in the study of glass-forming liquids. The high sensitivity of the technique together with the wide range of probed time scales makes it a powerful method for investigating the relaxation spectra of liquids. One particularly important class of glass-forming liquids that is often studied using this technique consists of liquids dominated by hydrogen (H) bond interactions. When investigating such liquids, particular caution has to be taken during sample preparation due to their often highly hygroscopic nature. Water can easily be absorbed from the atmosphere, and dielectric spectroscopy is a very sensitive probe of such contamination due to the large dipole moment of water. Our knowledge concerning the effects of small quantities of water on the dielectric properties of these commonly investigated liquids is limited. We here demonstrate the effects due to the presence of small amounts of water on the dielectric response of a typical H-bonded model glass former, tripropylene glycol. We show how the relaxation processes present in the pure liquid are affected by addition of water, and we find that a characteristic water induced relaxation response is observed for water contents as low as 0.15 wt%. We stress the importance of careful purification of hygroscopic liquids before experiments and quantify what the effects are if such procedures are not undertaken. © 2011 American Chemical Society

  16. Enzymatic Transformation and Bonding of Sulfonamide Antibiotics to Model Humic Substances

    Directory of Open Access Journals (Sweden)

    J. Schwarz

    2015-01-01

    Full Text Available Sulfonamides are consumed as pharmaceutical antibiotics and reach agricultural soils with excreta used as fertilizer. Subsequently, nonextractable residues rapidly form in soil, which has been researched in a couple of studies. To further elucidate conditions, strength, and mechanisms of the fixation to soil humic substances, three selected sulfonamides were investigated using the biochemical oligomerization of substituted phenols as a model for the humification process. Catechol, guaiacol, and vanillin were enzymatically reacted using laccase from Trametes versicolor. In the presence of the substituted phenols alone, the concentration of sulfonamides decreased. This decrease was even more pronounced when additional laccase was present. Upon the enzymatic oligomerization of the substituted phenols to a humic-like structure the sulfonamides were sorbed, transformed, sequestered, and nonextractable bound. Sulfonamides were transformed depending on their molecular properties. Fractions of different bonding strength were determined using a sequential extraction procedure. Isolated nonextractable products were analyzed by chromatographic, spectroscopic, and calorimetric methods to identify coupling and bonding mechanisms of the sulfonamides. Differential scanning calorimetry measurements suggested cross-linking of such incorporated sulfonamides in humic oligomers. Nuclear magnetic resonance spectroscopy measurements showed clear differences between the vanillin-sulfapyridine oligomer and the parent sulfapyridine indicating bound residue formation through covalent binding.

  17. Implementation of strength and burn models for plastic-bonded explosives and propellants

    Energy Technology Data Exchange (ETDEWEB)

    Reaugh, J E

    2009-05-07

    We have implemented the burn model in LS-DYNA. At present, the damage (porosity and specific surface area) is specified as initial conditions. However, history variables that are used by the strength model are reserved as placeholders for the next major revision, which will be a completely interactive model. We have implemented an improved strength model for explosives based on a model for concrete. The model exhibits peak strength and subsequent strain softening in uniaxial compression. The peak strength increases with increasing strain rate and/or reduced ambient temperature. Under triaxial compression compression, the strength continues to increase (or at least not decrease) with increasing strain. This behaviour is common to both concrete and polymer-bonded explosives (PBX) because the microstructure of these composites is similar. Both have aggregate material with a broad particle size distribution, although the length scale for concrete aggregate is two orders of magnitude larger than for PBX. The (cement or polymer) binder adheres to the aggregate, and is both pressure and rate sensitive. There is a larger bind binder content in concrete, compared to the explosive, and the aggregates have different hardness. As a result we expect the parameter values to differ, but the functional forms to be applicable to both. The models have been fit to data from tests on an AWE explosive that is HMX based. The decision to implement the models in LS-DYNA was based on three factors: LS-DYNA is used routinely by the AWE engineering analysis group and has a broad base of experienced users; models implemented in LS-DYNA can be transferred easily to LLNL's ALE 3D using a material model wrapper developed by Rich Becker; and LS-DYNA could accommodate the model requirements for a significant number of additional history variables without the significant time delay associated with code modification.

  18. On triangle meshes with valence dominant vertices

    KAUST Repository

    Morvan, Jean-Marie

    2018-02-16

    We study triangulations $\\\\cal T$ defined on a closed disc $X$ satisfying the following condition: In the interior of $X$, the valence of all vertices of $\\\\cal T$ except one of them (the irregular vertex) is $6$. By using a flat singular Riemannian metric adapted to $\\\\cal T$, we prove a uniqueness theorem when the valence of the irregular vertex is not a multiple of $6$. Moreover, for a given integer $k >1$, we exhibit non isomorphic triangulations on $X$ with the same boundary, and with a unique irregular vertex whose valence is $6k$.

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

    Science.gov (United States)

    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. Copyright (c) 2006 Wiley Periodicals, Inc.

  20. From test data to FE code: a straightforward strategy for modelling the structural bonding interface

    Directory of Open Access Journals (Sweden)

    M. A. Lepore

    2017-01-01

    Full Text Available A straightforward methodology for modelling the cohesive zone (CZM of an adhesively bonded joint is developed, by using a commercial finite element code and experimental outcomes from standard fracture tests, without defining a damage law explicitly. The in-house developed algorithm implements a linear interpolated cohesive relationship, obtained from literature data, and calculates the damage at each step increment. The algorithm is applicable both to dominant mode I or dominant mode II debonding simulations. The hypothesis of unloading stages occurrence is also considered employing an irreversible behaviour with elastic damaged reloading. A case study for validation is presented, implementing the algorithm in the commercial finite element method (FEM software Abaqus®. Numerical simulation of dominant mode I fracture loading provides with satisfactory results.

  1. ANALYTICAL MODEL OF DAMAGED AIRCRAFT SKIN BONDED REPAIRS ASSUMING THE MATERIAL PROPERTIES DEGRADATION

    Directory of Open Access Journals (Sweden)

    2016-01-01

    Full Text Available The search of optimal variants for composite repair patches allows to increase the service life of a damaged air- plane structure. To sensibly choose the way of repair, it is necessary to have a computational complex to predict the stress- strain condition of "structure-adhesive-patch" system and to take into account the damage growth considering the material properties change. The variant of the computational complex based on inclusion method is proposed.For calculation purposes the repair bonded joint is divided into two areas: a metal plate with patch-shaped hole and a "patch-adhesive layer-skin" composite plate (inclusion.Calculation stages:Evaluation of the patch influence to the skin stress-strain condition, stress distribution between skin and patch in the case of no damage. Calculation of the stress-strain condition is performed separately for the skin with hole and for the inclusion; solutions are coupled based on strain compatibility.Definition of the damage growth parameters at new stress-strain condition due to bonded patch existence. Skincrack stress intensity factors are found to identify the crack growth velocity. Patch is modelled as a set of "springs" bridging the crack.Degradation analysis of elasticity properties for the patch material.Repair effectiveness is evaluated with respect to crack growth velocity reduction in the initial material in compari- son with the case of the patch absence.Calculation example for the crack repair effectiveness depending on number of loading cycles for the 7075-T6 aluminum skin is given. Repair patches are carbon-epoxy, glass-epoxy and boron-epoxy material systems with quasi- isotropic layup and GLARE hybrid metal-polymeric material.The analysis shows the high effectiveness of the carbon-epoxy patch. Due to low stiffness, the glass-epoxy patchdemonstrates the least effectiveness. GLARE patch containing the fiberglass plies oriented across the crack has the same effectiveness as the carbon and

  2. Theory for the mixed-valence state

    International Nuclear Information System (INIS)

    Varma, C.M.

    1979-01-01

    A theory is presented which explains why mixed-valence compounds behave as two component Fermi liquids, and why TmSe orders magnetically while the other known mixed-valence compounds do not. The variation of Tsub(N) and the field Hsub(T) to obtain ferromagnetic alignment with changing Tm 2+ /Tm 3+ ratio is quantitatively explained. For Tm 2+ concentration > = 0.3, TmSe is predicted to order ferromagnetically

  3. Valence nucleons in self-consistent fields

    International Nuclear Information System (INIS)

    Di Toro, M.; Lomnitz-Adler, J.

    1978-01-01

    An iterative approach to determine directly the best Hartree-Fock one-body density rho is extended by expressing rho in terms of a core and a valence part and allowing for general crossings of occupied and unoccupied levels in the valence part. Results are shown for 152 Sm and a microscopic analysis of the core structure of deformed light nuclei is carried out. (author)

  4. Modeling the Solid-Liquid Equilibrium in Pharmaceutical-Solvent Mixtures: Systems with Complex Hydrogen Bonding Behvaior

    DEFF Research Database (Denmark)

    Tsivintzelis, Ioannis; Economou, Ioannis; Kontogeorgis, Georgios

    2009-01-01

    A methodology is suggested for modeling the phase equilibria of complex chemical mixtures with an equation of state (EoS) for the case where only limited experimental data exist. The complex hydrogen bonding behavior is explicitly accounted for and the corresponding parameters are adopted from...... simpler molecules of similar chemical structure and/or are fitted to Hansen's partial solubility parameters. The methodology is applied to modeling the solubility of three pharmaceuticals, namely acetanilide, phenacetin, and paracetamol, using the nonrandom hydrogen bonding (NRHB) EoS. In all cases...... and solid state, Delta Cp = Cp-l - Cps, in the determination of solid chemical potential and, also, of the polymorphism of drugs....

  5. Contributions of the Model of Modelling Diagram to the Learning of Ionic Bonding: Analysis of A Case Study

    Science.gov (United States)

    Mendonça, Paula Cristina Cardoso; Justi, Rosária

    2011-08-01

    Current proposals for science education recognise the importance of students' involvement in activities aimed at favouring the understanding of science as a human, dynamic and non-linear construct. Modelling-based teaching is one of the alternatives through which to address such issues. Modelling-based teaching activities for ionic bonding were introduced. This topic was chosen because of both the high incidence of students' alternative conceptions and its abstract nature, which justify the need for understanding complex models. The diagram Model of Modelling was used as a theoretical construct during the development of the teaching activities, which were implemented in a Brazilian medium level public school class (16-18 years old students). The data collected were the written material and models produced by the students, the content-knowledge tests, the video-recording of the lessons, and the observations and field notes of both the teacher and the researcher who observed the lessons. The analysis of such data enabled the production of case studies for each of the student groups. In this paper, we analyse one of the case studies, looking for evidence about the way that specific elements of the teaching strategy supported students' learning. It supported our belief in the use of the Model of Modelling diagram as a theoretical construct with which to develop and analyse modelling-based teaching activities.

  6. Theory of Valence Transitions in Ytterbium and Europium Intermetallics

    International Nuclear Information System (INIS)

    Zlatic, V.; Freericks, J.K.

    2001-01-01

    The exact solution of the multi-component Falicov-Kimball model in infinite-dimensions is presented and used to discuss a new fixed point of valence fluctuating intermetallics with Yb and Eu ions. In these compounds, temperature, external magnetic field, pressure, or chemical pressure induce a transition between a metallic state with the f-ions in a mixed-valent (non-magnetic) configuration and a semi-metallic state with the f-ions in an integral-valence (paramagnetic) configuration. The zero-field transition occurs at the temperature T V , while the zero-temperature transition sets in at the critical field H c . We present the thermodynamic and dynamic properties of the model for an arbitrary concentration of d- and f -electrons. For large U, we find a MI transition, triggered by the temperature or field- induced change in the f-occupancy. (author)

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

    Science.gov (United States)

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

    2016-01-01

    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 4 samples (N = 1588), 8 items were identified that assess RT valence, purpose, and total in a circumplex model. 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

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

    Science.gov (United States)

    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. © The Author(s) 2015.

  9. Br and O···Cl halogen bonds in some small model molecular systems

    Indian Academy of Sciences (India)

    as halogen bond acceptor with X-Y (X = Cl, Br; Y = CF3, CF2H, CFH2, CN, CCH, CCCN) as halogen bond donors. The strength of interaction energy for O··· Br halogen-bonded complexes varies from −2.16 to −5.26kcal/mol while for O··· Cl complexes, it is between −1.65 to −3.67kcal/mol, which indicate the. O··· Br bond to ...

  10. Quantitative modeling assesses the contribution of bond strengthening, rebinding and force sharing to the avidity of biomolecule interactions.

    Directory of Open Access Journals (Sweden)

    Valentina Lo Schiavo

    Full Text Available Cell adhesion is mediated by numerous membrane receptors. It is desirable to derive the outcome of a cell-surface encounter from the molecular properties of interacting receptors and ligands. However, conventional parameters such as affinity or kinetic constants are often insufficient to account for receptor efficiency. Avidity is a qualitative concept frequently used to describe biomolecule interactions: this includes incompletely defined properties such as the capacity to form multivalent attachments. The aim of this study is to produce a working description of monovalent attachments formed by a model system, then to measure and interpret the behavior of divalent attachments under force. We investigated attachments between antibody-coated microspheres and surfaces coated with sparse monomeric or dimeric ligands. When bonds were subjected to a pulling force, they exhibited both a force-dependent dissociation consistent with Bell's empirical formula and a force- and time-dependent strengthening well described by a single parameter. Divalent attachments were stronger and less dependent on forces than monovalent ones. The proportion of divalent attachments resisting a force of 30 piconewtons for at least 5 s was 3.7 fold higher than that of monovalent attachments. Quantitative modeling showed that this required rebinding, i.e. additional bond formation between surfaces linked by divalent receptors forming only one bond. Further, experimental data were compatible with but did not require stress sharing between bonds within divalent attachments. Thus many ligand-receptor interactions do not behave as single-step reactions in the millisecond to second timescale. Rather, they exhibit progressive stabilization. This explains the high efficiency of multimerized or clustered receptors even when bonds are only subjected to moderate forces. Our approach provides a quantitative way of relating binding avidity to measurable parameters including bond

  11. Modelling of Non-Linear Pilot Disinfection Water System: A Bond Graph Approach

    Directory of Open Access Journals (Sweden)

    Naoufel ZITOUNI

    2012-08-01

    Full Text Available The ultraviolet (UV irradiations are used to solve the bacteriological problem of the drinking water quality. A discharge-gas lamp is used to produce this type of irradiation. The UV lamp is fed by photovoltaic (PV energy via electronic ballast composed by an inverter, a transformer and resonant circuit (RLC. The aim of this work is to give a useful global model of the system. In particular, we introduce the complicated UV lamp model and the water disinfection kinetics, where the radiant energy flux emitted by the discharge-gas lamp and the arc voltage are a complex functions of the current and time. This system is intended to be mainly used in rural zones, the photovoltaic modules as source of energy is an adequate solution. To optimise the power transfer from the PV array to ballast and UV lamp, a Maximum Power Point Tracking (MPPT device may be located between PV array and the loads. In this paper, we developed a bond-graph model which gives the water quality from UV flow, gas type, pressure, lamp current and geometrical characteristic. Finally reliable simulations are established and compared with experimental tests.

  12. Incorporation of Hydrogen Bond Angle Dependency into the Generalized Solvation Free Energy Density Model.

    Science.gov (United States)

    Ma, Songling; Hwang, Sungbo; Lee, Sehan; Acree, William E; No, Kyoung Tai

    2018-03-30

    To describe the physically realistic solvation free energy surface of a molecule in a solvent, a generalized version of the solvation free energy density (G-SFED) calculation method has been developed. In the G-SFED model, the contribution from the hydrogen bond (HB) between a solute and a solvent to the solvation free energy was calculated as the product of the acidity of the donor and the basicity of the acceptor of an HB pair. The acidity and basicity parameters of a solute were derived using the summation of acidities and basicities of the respective acidic and basic functional groups of the solute, and that of the solvent was experimentally determined. Although the contribution of HBs to the solvation free energy could be evenly distributed to grid points on the surface of a molecule, the G-SFED model was still inadequate to describe the angle dependency of the HB of a solute with a polarizable continuum solvent. To overcome this shortcoming of the G-SFED model, the contribution of HBs was formulated using the geometric parameters of the grid points described in the HB coordinate system of the solute. We propose an HB angle dependency incorporated into the G-SFED model, i.e., the G-SFED-HB model, where the angular-dependent acidity and basicity densities are defined and parametrized with experimental data. The G-SFED-HB model was then applied to calculate the solvation free energies of organic molecules in water, various alcohols and ethers, and the log P values of diverse organic molecules, including peptides and a protein. Both the G-SFED model and the G-SFED-HB model reproduced the experimental solvation free energies with similar accuracy, whereas the distributions of the SFED on the molecular surface calculated by the G-SFED and G-SFED-HB models were quite different, especially for molecules having HB donors or acceptors. Since the angle dependency of HBs was included in the G-SFED-HB model, the SFED distribution of the G-SFED-HB model is well described

  13. Discrete kink dynamics in hydrogen-bonded chains: The two-component model

    DEFF Research Database (Denmark)

    Karpan, V.M.; Zolotaryuk, Yaroslav; Christiansen, Peter Leth

    2004-01-01

    -proton interaction in the hydrogen bond. (ii) a harmonic coupling between the protons in adjacent hydrogen bonds, and (iii) a harmonic coupling between the nearest-neighbor heavy ions (an isolated diatomic chain with the lowest acoustic band) or instead a harmonic on-site potential for the heavy ions (a diatomic...

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  15. Hue opponency: chromatic valence functions, individual differences, cortical winner-take-all opponent modeling, and the relationship between spikes and sensitivity.

    Science.gov (United States)

    Billock, Vincent A

    2018-04-01

    Neural spike rate data are more restricted in range than related psychophysical data. For example, several studies suggest a compressive (roughly cube root) nonlinear relationship between wavelength-opponent spike rates in primate midbrain and color appearance in humans, two rather widely separated domains. This presents an opportunity to partially bridge a chasm between these two domains and to probe the putative nonlinearity with other psychophysical data. Here neural wavelength-opponent data are used to create cortical competition models for hue opponency. This effort led to creation of useful models of spiking neuron winner-take-all (WTA) competition and MAX selection. When fed with actual primate data, the spiking WTA models generate reasonable wavelength-opponent spike rate behaviors. An average psychophysical observer for red-green and blue-yellow opponency is curated from eight applicable studies in the refereed and dissertation literatures, with cancellation data roughly every 10 nm in 18 subjects for yellow-blue opponency and 15 subjects for red-green opponency. A direct mapping between spiking neurons with broadband wavelength sensitivity and human psychophysical luminance yields a power law exponent of 0.27, similar to the cube root nonlinearity. Similarly, direct mapping between the WTA model opponent spike rates and psychophysical opponent data suggests power law relationships with exponents between 0.24 and 0.41.

  16. What factors affect the regioselectivity of oxidation by cytochrome p450? A DFT study of allylic hydroxylation and double bond epoxidation in a model reaction.

    Science.gov (United States)

    de Visser, Sam P; Ogliaro, François; Sharma, Pankaz K; Shaik, Sason

    2002-10-02

    . Chem., Int. Ed. 2001, 40, 2874-2878) that tunes its reactivity and selectivity patterns in response to the protein environment in which it is accommodated. A valence bond (VB) model, akin to "redox mesomerism" (Bernadou, J.; Fabiano, A.-S.; Robert, A.; Meunier, B. J. Am. Chem. Soc. 1994, 116, 9375-9376), is constructed and enables the description of a chameleon transition state. It shows that the good donor ability of the thiolate ligand and the acceptor ability of the iron porphyrin create mixed-valent situations that endow the transition state with a great sensitivity to external perturbations as in the protein pocket. The model is used to discuss the computed results and to relate them to experimental findings.

  17. A 3-D microstructural level model for analyzing the response of polymer bonded explosives

    Science.gov (United States)

    Hardin, David; Zhou, Min

    2011-06-01

    A three-dimensional finite element model is developed to study the microstructural level response of polymer-bonded explosives (PBX) under impact loading. The study focuses on the effect of the morphology and packing of energetic grains on the overall thermomechanical response of the composites. A cohesive finite element method (CFEM) is utilized to account for failure in the form of debonding between the HMX grains and the polymer matrix. Frictional heating along crack faces is tracked through a contact algorithm. Microstructures with cubic and multifaceted three-dimensional polygonal granules with packing densities between 0.42 and 0.74 are generated and used. Both 2D and 3D calculations are carried to analyze the differences between the models. To ensure consistency, the 2D microstructures are sections of the 3D microstructures. In this presentation, we will discuss differences in results from the 2D and 3D calculations, with a particular focus on the progression of damage and heating under impact loading.

  18. DEM investigation of weathered rocks using a novel bond contact model

    Directory of Open Access Journals (Sweden)

    Zhenming Shi

    2015-06-01

    Full Text Available The distinct element method (DEM incorporated with a novel bond contact model was applied in this paper to shed light on the microscopic physical origin of macroscopic behaviors of weathered rock, and to achieve the changing laws of microscopic parameters from observed decaying properties of rocks during weathering. The changing laws of macroscopic mechanical properties of typical rocks were summarized based on the existing research achievements. Parametric simulations were then conducted to analyze the relationships between macroscopic and microscopic parameters, and to derive the changing laws of microscopic parameters for the DEM model. Equipped with the microscopic weathering laws, a series of DEM simulations of basic laboratory tests on weathered rock samples was performed in comparison with analytical solutions. The results reveal that the relationships between macroscopic and microscopic parameters of rocks against the weathering period can be successfully attained by parametric simulations. In addition, weathering has a significant impact on both stress–strain relationship and failure pattern of rocks.

  19. Numerical modelling of the bonding process for wind turbine blades: model validation

    DEFF Research Database (Denmark)

    Uzal, Anil; Spangenberg, Jon; W. Nielsen, Michael

    numerical modelis developed in order to analyse adhesive propagation in squeeze flow problems with 3-D flow effects.The model is validated by comparison with an experiment where a rectangular prism shaped adhesivesample is squeezed between two parallel plates. In the numerical model the rheological...

  20. A Mechanics Model for Sensors Imperfectly Bonded to the Skin for Determination of the Young's Moduli of Epidermis and Dermis

    Science.gov (United States)

    Yuan, J. H.; Shi, Y.; Pharr, M.; Feng, X.; Rogers, John A.; Huang, Yonggang

    2016-01-01

    A mechanics model is developed for the encapsulated piezoelectric thin-film actuators/sensors system imperfectly bonded to the human skin to simultaneously determine the Young's moduli of the epidermis and dermis as well as the thickness of epidermis. PMID:27330219

  1. Variation of sigma-hole magnitude with M valence electron population in MX(n)Y(4-n) molecules (n = 1-4; M = C, Si, Ge; X, Y = F, Cl, Br).

    Science.gov (United States)

    McDowell, Sean A C; Joseph, Jerelle A

    2014-01-14

    Sigma holes are described as electron-deficient regions on atoms, particularly along the extension of covalent bonds, due to non-uniform electron density distribution on the surface of these atoms. A computational study of MX(n)Y(4-n) molecules (n = 1-4; M = C, Si, Ge; X, Y = F, Cl, Br) was undertaken and it is shown that the relative sigma hole potentials on M due to X-M and Y-M can be adequately explained in terms of the variation in the valence electron population of the central M atom. A model is proposed for the depletion of the M valence electron population which explains the trends in sigma hole strengths, especially those that cannot be accounted for solely on the basis of relative electronegativities.

  2. Theoretical calculations of valence states in Fe-Mo compounds

    International Nuclear Information System (INIS)

    Estrada, F; Navarro, O; Noverola, H; Suárez, J R; Avignon, M

    2014-01-01

    The half-metallic ferromagnetic double perovskite compound Sr 2 FeMoO 6 is considered as an important material for spintronic applications. It appears to be fundamental to understand the role of electronic parameters controlling the half-metallic ground state. Fe-Mo double perovskites usually present some degree of Fe/Mo disorder which generally increases with doping. In this work, we study the valence states of Fe-Mo cations in the off-stoichiometric system Sr 2 Fe 1+x Mo 1−x O 6 (−1 ≤ x ≤ 1/3) with disorder. Our results for Fe and Mo valence states are obtained using the Green functions and the renormalization perturbation expansion method. The model is based on a correlated electron picture with localized Fe-spins and conduction Mo-electrons interacting with the local spins via a double-exchange-type mechanism

  3. The role of the autonomic nervous system in hypertension: a bond graph model study

    International Nuclear Information System (INIS)

    Chen, Shuzhen; Gong, Yuexian; Dai, Kaiyong; Sui, Meirong; Yu, Yi; Ning, Gangmin; Zhang, Shaowen

    2008-01-01

    A bond graph model of the cardiovascular system with embedded autonomic nervous regulation was developed for a better understanding of the role of the autonomic nervous system (ANS) in hypertension. The model is described by a pump model of the heart and a detailed representation of the head and neck, pulmonary, coronary, abdomen and extremity circulation. It responds to sympathetic and parasympathetic activities by modifying systemic peripheral vascular resistance, heart rate, ventricular end-systolic elastance and venous unstressed volumes. The impairment of ANS is represented by an elevation of the baroreflex set point. The simulation results show that, compared with normotensive, in hypertension the systolic and diastolic blood pressure (SBP/DBP) rose from 112/77 mmHg to 144/94 mmHg and the left ventricular wall thickness (LVWT) increased from 10 mm to 12.74 mm. In the case that ANS regulation was absent, both the SBP and DBP further increased by 8 mmHg and the LVWT increased to 13.22 mm. The results also demonstrate that when ANS regulation is not severely damaged, e.g. the baroreflex set point is 97 mmHg, it still has an effect in preventing the rapid rise of blood pressure in hypertension; however, with the worsening of ANS regulation, its protective role weakens. The results agree with human physiological and pathological features in hemodynamic parameters and carotid baroreflex function curves, and indicate the role of ANS in blood pressure regulation and heart protection. In conclusion, the present model may provide a valid approach to study the pathophysiological conditions of the cardiovascular system and the mechanism of ANS regulation

  4. Low-temperature bonded glass-membrane microfluidic device for in vitro organ-on-a-chip cell culture models

    Science.gov (United States)

    Pocock, Kyall J.; Gao, Xiaofang; Wang, Chenxi; Priest, Craig; Prestidge, Clive A.; Mawatari, Kazuma; Kitamori, Takehiko; Thierry, Benjamin

    2015-12-01

    The integration of microfluidics with living biological systems has paved the way to the exciting concept of "organson- a-chip", which aims at the development of advanced in vitro models that replicate the key features of human organs. Glass based devices have long been utilised in the field of microfluidics but the integration of alternative functional elements within multi-layered glass microdevices, such as polymeric membranes, remains a challenge. To this end, we have extended a previously reported approach for the low-temperature bonding of glass devices that enables the integration of a functional polycarbonate porous membrane. The process was initially developed and optimised on specialty low-temperature bonding equipment (μTAS2001, Bondtech, Japan) and subsequently adapted to more widely accessible hot embosser units (EVG520HE Hot Embosser, EVG, Austria). The key aspect of this method is the use of low temperatures compatible with polymeric membranes. Compared to borosilicate glass bonding (650 °C) and quartz/fused silica bonding (1050 °C) processes, this method maintains the integrity and functionality of the membrane (Tg 150 °C for polycarbonate). Leak tests performed showed no damage or loss of integrity of the membrane for up to 150 hours, indicating sufficient bond strength for long term cell culture. A feasibility study confirmed the growth of dense and functional monolayers of Caco-2 cells within 5 days.

  5. [Emotional valence of words in schizophrenia].

    Science.gov (United States)

    Jalenques, I; Enjolras, J; Izaute, M

    2013-06-01

    Emotion recognition is a domain in which deficits have been reported in schizophrenia. A number of emotion classification studies have indicated that emotion processing deficits in schizophrenia are more pronounced for negative affects. Given the difficulty of developing material suitable for the study of these emotional deficits, it would be interesting to examine whether patients suffering from schizophrenia are responsive to positively and negatively charged emotion-related words that could be used within the context of remediation strategies. The emotional perception of words was examined in a clinical experiment involving schizophrenia patients. This emotional perception was expressed by the patients in terms of the valence associated with the words. In the present study, we investigated whether schizophrenia patients would assign the same negative and positive valences to words as healthy individuals. Twenty volunteer, clinically stable, outpatients from the Psychiatric Service of the University Hospital of Clermont-Ferrand were recruited. Diagnoses were based on DSM-IV criteria. Global psychiatric symptoms were assessed using the Positive and Negative Symptoms Scale (PANSS). The patients had to evaluate the emotional valence of a set of 300 words on a 5-point scale ranging from "very unpleasant" to "very pleasant". . The collected results were compared with those obtained by Bonin et al. (2003) [13] from 97 University students. Correlational analyses of the two studies revealed that the emotional valences were highly correlated, i.e. the schizophrenia patients estimated very similar emotional valences. More precisely, it was possible to examine three separate sets of 100 words each (positive words, neutral words and negative words). The positive words that were evaluated were the more positive words from the norms collected by Bonin et al. (2003) [13], and the negative words were the more negative examples taken from these norms. The neutral words

  6. A systematic Monte Carlo simulation study of the primitive model planar electrical double layer over an extended range of concentrations, electrode charges, cation diameters and valences

    Directory of Open Access Journals (Sweden)

    Mónika Valiskó

    2018-02-01

    Full Text Available The purpose of this study is to provide data for the primitive model of the planar electrical double layer, where ions are modeled as charged hard spheres, the solvent as an implicit dielectric background (with dielectric constant ϵ = 78.5, and the electrode as a smooth, uniformly charged, hard wall. We use canonical and grand canonical Monte Carlo simulations to compute the concentration profiles, from which the electric field and electrostatic potential profiles are obtained by solving Poisson’s equation. We report data for an extended range of parameters including 1:1, 2:1, and 3:1 electrolytes at concentrations c = 0.0001 − 1 M near electrodes carrying surface charges up to σ = ±0.5 Cm−2. The anions are monovalent with a fixed diameter d− = 3 Å, while the charge and diameter of cations are varied in the range z+ = 1, 2, 3 and d+ = 1.5, 3, 6, and 9 Å (the temperature is 298.15 K. We provide all the raw data in the supplementary material.

  7. Investigation of the structure of core-coupled odd-proton copper nuclei in fpg valence space using the projected shell model

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, Anuradha; Singh, Suram; Bharti, Arun [University of Jammu, Department of Physics and Electronics, Jammu (India); Khosa, S.K. [Central University of Jammu, Department of Physics and Astronomical Sciences, Jammu (India); Bhat, G.H.; Sheikh, J.A. [University of Kashmir, Department of Physics, Srinagar (India)

    2017-01-15

    By employing a systematically parametrized Hamiltonian and the best fit of the various input parameters, high-spin yrast energy states for an isotopic chain of odd mass {sup 59-69}Cu nuclei have been investigated by using a novel computational quantum mechanical framework-projected shell model. Comparison of calculations and experiments yields good agreement. The present study of various intriguing nuclear structure properties along the yrast lines in these odd proton isotopes reflects some interesting informative nuclear physics results. The calculations successfully describe the formation of the yrast level structures from multi-quasi-particle configurations based on πf x νg bands for {sup 59-69}Cu isotopes. The present calculations indicate the evolution of the nuclear structure near the magic nuclei, Ni, and also provide an indication of coexistence of both, collective as well as single-particle, levels for {sup 69}Cu nucleus at N=40. (orig.)

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

    Energy Technology Data Exchange (ETDEWEB)

    Cieplicka-Oryńczak, N. [INFN sezione di Milano, Via Celoria 16, 20133 Milano (Italy); Institute of Nuclear Physics, Polish Academy of Sciences, PL-31342 Kraków (Poland); Fornal, B.; Szpak, B. [Institute of Nuclear Physics, Polish Academy of Sciences, PL-31342 Kraków (Poland); Leoni, S.; Bottoni, S. [INFN sezione di Milano, Via Celoria 16, 20133 Milano (Italy); Università degli Studi di Milano, Via Celoria 16, 20133 Milano (Italy); Bazzacco, D. [Dipartimento di Fisica e Astronomia dell’Università, I-35131 Padova (Italy); INFN Sezione di Padova, I-35131 Padova (Italy); Blanc, A.; Jentschel, M.; Köster, U.; Mutti, P.; Soldner, T. [Institute Laue-Langevin, 6, rue Jules Horowitz, 38042 Grenoble Cedex 9 (France); Bocchi, G. [Università degli Studi di Milano, Via Celoria 16, 20133 Milano (Italy); France, G. de [GANIL, Bd. Becquerel, BP 55027, 14076 CAEN Cedex 05 (France); Simpson, G. [LPSC, Université Joseph Fourier Grenoble 1, CNRS/IN2P3, Institut National Polytechnique de Grenoble, F-38026 Grenoble Cedex (France); Ur, C. [INFN Sezione di Padova, Via F. Marzolo 8, I-35131 Padova (Italy); Urban, W. [Faculty of Physics, University of Warsaw, ul. Hoża 69, 02-681, Warszawa (Poland)

    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.

  9. Particle-phonon excitations in valence-neutron and valence-proton nuclei around 146Gd

    International Nuclear Information System (INIS)

    Collatz, R.D.

    1994-07-01

    The present thesis deals with the one-valence-particle nuclei 147 Tb and 151 Er. The main purpose of the study was, to study characteristic properties of the particle-phonon excitations of these nuclei. In the one-valence-proton nucleus 147 Tb from the πh 11/2 x3 - septet only the 15/2 + and 17/2 + Yrast states were known, which underly a strong diagonal exchange interaction. At mass separators in β decay experiments of the 1/2 + and the 11/2 -147 Dy activities and in in-beam experiments layed out on excitation of states above the Yrast line with 6 Li beams the nucleus 147 Tb was spectroscoped. The combination of these three data sets made the nearly complete covering of the spin range from 1/2 to 27/2 of the low-lying states in 147 Tb possible. At the whole in this nucleus more than 100 hitherto unknown states could be placed and farly characterized. The unusually manifold data allowed to identify beside the complete πh 11/2 x3 - septet also very much further particlexphonon states. Furthermore in the excitation range between 2.5 and 4 MeV numerous three-quasiparticle excitations were observed and in very sufficient way described by parameter-free shell-model calculations. A further important result is the manifestation of a neutron-one-particle-one-hole state with I=27/2, which lies with 3.7 MeV excitation close to the Yrast line. (orig./HSI)

  10. In Situ Imaging during Compression of Plastic Bonded Explosives for Damage Modeling

    Directory of Open Access Journals (Sweden)

    Virginia W. Manner

    2017-06-01

    Full Text Available The microstructure of plastic bonded explosives (PBXs is known to influence behavior during mechanical deformation, but characterizing the microstructure can be challenging. For example, the explosive crystals and binder in formulations such as PBX 9501 do not have sufficient X-ray contrast to obtain three-dimensional data by in situ, absorption contrast imaging. To address this difficulty, we have formulated a series of PBXs using octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX crystals and low-density binder systems. The binders were hydroxyl-terminated polybutadiene (HTPB or glycidyl azide polymer (GAP cured with a commercial blend of acrylic monomers/oligomers. The binder density is approximately half of the HMX, allowing for excellent contrast using in situ X-ray computed tomography (CT imaging. The samples were imaged during unaxial compression using micro-scale CT in an interrupted in situ modality. The rigidity of the binder was observed to significantly influence fracture, crystal-binder delamination, and flow. Additionally, 2D slices from the segmented 3D images were meshed for finite element simulation of the mesoscale response. At low stiffness, the binder and crystal do not delaminate and the crystals move with the material flow; at high stiffness, marked delamination is noted between the crystals and the binder, leading to very different mechanical properties. Initial model results exhibit qualitatively similar delamination.

  11. Finite element bond models for seven-wire prestressing strands in concrete crossties.

    Science.gov (United States)

    2015-03-23

    Seven-wire strands are commonly used in pretensioned : concrete ties, but its bonding mechanism with concrete needs : further examination to provide a better understanding of some : concrete tie failure modes. As a key component in the finite : eleme...

  12. Bond graph modelling of engineering systems: theory, applications and software support

    National Research Council Canada - National Science Library

    Borutzky, Wolfgang; Margolis, Donald L

    2011-01-01

    ... way such that analytical or computer response predictions can be straightforwardly carried out. Bond graphs are a concise pictorial representation of all types of interacting energetic systems. In my experience working with engineers on the development of complex systems it is obvious that these systems suffer from thermal problems, structural problems, vibration and noise problems, and control and stability issues that do not fit into a single discipline. Bond graphs provide the link by which all these different ...

  13. Br and O···Cl halogen bonds in some small model molecular systems

    Indian Academy of Sciences (India)

    Abstract. Halogen bonding interactions of type X···O=C are important in various fields including bio- logical systems. In this work, theoretical calculations were carried out using B3LYP/6-31++G**, MP2/6-. 31++G** and MP2/aug-cc-pVDZ methods on a series of O··· X halogen bonds between CH2O and CH3CHO as halogen ...

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

    Directory of Open Access Journals (Sweden)

    C. Mezrag

    2015-02-01

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

  15. The determinants of bond angle variability in protein/peptide backbones: A comprehensive statistical/quantum mechanics analysis.

    Science.gov (United States)

    Improta, Roberto; Vitagliano, Luigi; Esposito, Luciana

    2015-11-01

    The elucidation of the mutual influence between peptide bond geometry and local conformation has important implications for protein structure refinement, validation, and prediction. To gain insights into the structural determinants and the energetic contributions associated with protein/peptide backbone plasticity, we here report an extensive analysis of the variability of the peptide bond angles by combining statistical analyses of protein structures and quantum mechanics calculations on small model peptide systems. Our analyses demonstrate that all the backbone bond angles strongly depend on the peptide conformation and unveil the existence of regular trends as function of ψ and/or φ. The excellent agreement of the quantum mechanics calculations with the statistical surveys of protein structures validates the computational scheme here employed and demonstrates that the valence geometry of protein/peptide backbone is primarily dictated by local interactions. Notably, for the first time we show that the position of the H(α) hydrogen atom, which is an important parameter in NMR structural studies, is also dependent on the local conformation. Most of the trends observed may be satisfactorily explained by invoking steric repulsive interactions; in some specific cases the valence bond variability is also influenced by hydrogen-bond like interactions. Moreover, we can provide a reliable estimate of the energies involved in the interplay between geometry and conformations. © 2015 Wiley Periodicals, Inc.

  16. Diffusion-bonded 16MND5-Inconel 690-316LN junction: elaboration and process residual stresses modeling

    International Nuclear Information System (INIS)

    Martinez, Michael

    1999-01-01

    The objective of this research thesis is, on the one hand, to elaborate and to characterise a bonded junction of 16MND5 and 316LN steels, and, on the other hand, to develop a simulation tool for the prediction of microstructures after bonding, as well as residual stresses related to this process. The author first reports the study of the use of diffusion bonding by hot isostatic pressing (HIP diffusion bonding) for the bonding of 16MND5 (steel used in French PWR vessel) and 316LN (austenitic stainless steel used in piping), in order to obtain junctions adapted to a use within PWRs. In this case, the use of an Inconel insert material appeared to be necessary to avoid stainless steel carburization. Thus, inserts in Inconel 600 and 690 have been tested. The objective has then been to develop a realistic calculation of residual stresses in this assembly. These stresses are stimulated by quenching. The author notably studied the simulation of temperature dependent phase transformations, and stress induced phase transformations. An existing model is validated and applied to HIP and quenching cycles. The last part reports the calculation of residual stresses by simulation of the mechanical response of the three-component material cooled from 900 C to room temperature and thus submitted to a loading of thermal origin (dilatation) and metallurgical origin (phase transformations in the 16MND5). The effect of carbon diffusion on mechanical properties has also been taken into account. The author discusses problems faced by existing models, and explains the choice of conventional macro-mechanical models. The three materials are supposed to have a plastic-viscoplastic behaviour with isotropic and kinematic strain hardening, and this behaviour is identified between 20 and 900 C [fr

  17. Nonideal anion displacement, band gap variation, and valence band splitting in Cu-In-Se compounds

    International Nuclear Information System (INIS)

    Reena Philip, Rachel; Pradeep, B.

    2005-01-01

    Polycrystalline thin films of ternary chalcopyrite CuInSe 2 and defect compounds CuIn 3 Se 5 and CuIn 5 Se 8 are prepared in vacuum by three-source coevaporation method. Structural and optical characterizations of the films are done using X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDAX), and optical absorbance spectra measurements. With variation in the composition of CuInSe 2 , a change over from p-type to n-type conductivity is observed (as noted by the hot probe method). The deformation parameters and the anion displacements are calculated from the X-ray diffraction data, and the cation-anion bond lengths are deduced. The dependence of band gap variation on nonideal anion displacement in the ternary compounds and the effect of Se-p-Cu-d repulsion on band gap are studied. The threefold optical structure observed in the fundamental absorption region of the absorption spectra is analysed to extract the valence band splitting parameters. Hopfields quasi-cubic model adapted for chalcopyrites with tetragonal deformation is used to determine the crystal field splittings and spin orbit splittings, and the linear hybridization model is used to calculate the percentage of d-orbital and p-orbital contribution to hybridization in the compounds under consideration

  18. Effect of Oxidation Degree on Valence Change and Distribution of Octahedral Fe Element in Biotite

    Directory of Open Access Journals (Sweden)

    Li Ziqian

    2017-01-01

    Full Text Available In this paper, the valence change and distribution of iron elements in octahedral vacancies of biotite were studied in the oxidation process. The biotite and saturated barium nitrate solution were mixed in dilute hydrochloric acid under hydrothermal reaction conditions, the solid after reaction was used as the test sample. Firstly, the remainder potassium and iron content were measured by atomic absorption spectrometry(AAS. Secondly, the state of iron along with oxidation degree increased was analyzed, in addition, the phase composition and the change of layer spacing in samples was detected by X-ray diffraction(XRD. Thirdly, The variation mode of Si-O bond were characterized by Fourier transform infrared spectroscopy(FT-IR.This research was adopted hydrogen ions in diluted hydrochloric acid and nitrate ions in barium nitrate to provide oxidation environment for reaction, and the oxidation degree was controlled by adjusted the amount of hydrogen ion introduced. We found out that the amount of hydrogen ion is positively correlated with oxidation degree in biotite, and the deeper oxidation degree in biotite, the lower electronegativity of singer layer. Potassium and iron element would be release out of micaceous structure during the biotite oxidation. The higher the oxidation degree is, the greater the releasing happen. The charge density combining Fe oxidation and releasing firstly increased then decreased with the oxidation degree turned greater. During the oxidation, the Si-O vibrated would change from parallel layer vibration model to vertical vibration model.

  19. Explicit consideration of spatial hydrogen bonding direction for activity coefficient prediction based on implicit solvation calculations.

    Science.gov (United States)

    Chen, Wei-Lin; Lin, Shiang-Tai

    2017-08-09

    The activity coefficient of a chemical in a mixture is important in understanding the thermodynamic properties and non-ideality of the mixture. The COSMO-SAC model based on the result of quantum mechanical implicit solvation calculations has been shown to provide reliable predictions of activity coefficients for mixed fluids. However, it is found that the prediction accuracy is in general inferior for associating fluids. Existing methods for describing the hydrogen-bonding interaction consider the strength of the interaction based only on the polarity of the screening charges, neglecting the fact that the formation of hydrogen bonds requires a specific orientation between the donor and acceptor pairs. In this work, we propose a new approach that takes into account the spatial orientational constraints in hydrogen bonds. Based on the Valence Shell Electron Pair Repulsion (VSEPR) theory, the molecular surfaces associated with the formation of hydrogen bonds are limited to those in the projection of the lone pair electrons of hydrogen bond acceptors, in addition to the polarity of the surface screening charges. Our results show that this new directional hydrogen bond approach, denoted as the COSMO-SAC(DHB) model, requires fewer universal parameters and is significantly more accurate and reliable compared to previous models for a variety of properties, including vapor-liquid equilibria (VLE), infinite dilution activity coefficient (IDAC) and water-octanol partition coefficient (K ow ).

  20. A New Graphical Model for Proton NMR (Deshielding over a Carbon-Carbon Double Bond to Replace the Shielding Cone Model

    Directory of Open Access Journals (Sweden)

    Justin D. Brown

    2000-11-01

    Full Text Available The long-held “shielding cone” model of the through-space NMR shielding effect of a carbon-carbon double bond predicts only the effect of the magnetic anisotropy of the double bond; it ignores other important contributors to the overall shielding. GIAO-SCF and GIAO-MP2 calculations have been performed on a simple model system, methane moved sequentially above ethene or 2-methylpropene. These calculations permit the net NMR shielding surface to be mapped. Based on those results, a new and very different graphical model for predicting the effect of a proton’s position relative to a carbon-carbon double bond on its chemical shift is presented.

  1. Explicit solvation effects on the conventional resonance model for protonated imine, carbonyl, and thiocarbonyl compounds

    Science.gov (United States)

    Braïda, Benoît; Hiberty, Philippe C.

    The conventional resonance model describes carbonyls, imines, and thiocarbonyls, as well as their protonated analogues, by a superposition of two valence bond structures. Ab initio Breathing-Orbital Valence Bond computations on formaldehyde, formimine, and thioformaldehyde as well as their protonated forms are performed to directly quantify the weights of their valence bond structures. Following a gas phase study that showed that protonation significantly increases the weight of the carbenic form relative to the π polar-covalent bonded form (Braida, et al., Org Lett, 2008, 10, 1951), the present work estimates the influence of a polar protic solvent, modelized by water. Solvation effects are modeled explicitly by performing VB calculations on supersystems made of the organic substrate surrounded by four water molecules. It is shown that protonation significantly increases the polarity of the C=X π bond in all three cases (X = O, NH, S) in solvated phase, in line with the known acceleration of nucleophilic additions on these compounds by acidic catalysis. Moreover, solvation significantly enhances the polarity of the C=X π bond in the protonated forms of formaldehyde and thioformaldehyde, but has practically no effect on the C=X π bond of protonated formimine.

  2. Dynamic fracture of adhesively bonded composite structures using cohesive zone models

    Science.gov (United States)

    Makhecha, Dhaval P.

    material model to be used in an explicit code (LS-DYNA). Dynamic simulations of the standard test configurations for Mode I (Double Cantilever Beam) and Mode II (End Load Split) are carried out using the explicit code. Verification of these coupon tests leads to the crash analysis of realistic structures like the square composite tube. Analyses of bonded and unbonded square tubes are presented. These tubes shows a very uncharacteristic failure mode: the composite material disintegrates on impact, and this has been captured in the analysis. Disadvantages of the interface element approach are well documented in the literature. An alternative method, known as the Extended Finite Element Method (XFEM), is implemented here through an eight-noded quadrilateral plane strain element. The method, based on the partition-of-unity, is used to study simple test configuration like the three-point bend problem and a double cantilever beam. Functionally graded materials are also simulated and the results are compared to the experimental results available in the literature.

  3. Charge-dependent non-bonded interaction methods for use in quantum mechanical modeling of condensed phase reactions

    Science.gov (United States)

    Kuechler, Erich R.

    Molecular modeling and computer simulation techniques can provide detailed insight into biochemical phenomena. This dissertation describes the development, implementation and parameterization of two methods for the accurate modeling of chemical reactions in aqueous environments, with a concerted scientific effort towards the inclusion of charge-dependent non-bonded non-electrostatic interactions into currently used computational frameworks. The first of these models, QXD, modifies interactions in a hybrid quantum mechanical/molecular (QM/MM) mechanical framework to overcome the current limitations of 'atom typing' QM atoms; an inaccurate and non-intuitive practice for chemically active species as these static atom types are dictated by the local bonding and electrostatic environment of the atoms they represent, which will change over the course of the simulation. The efficacy QXD model is demonstrated using a specific reaction parameterization (SRP) of the Austin Model 1 (AM1) Hamiltonian by simultaneously capturing the reaction barrier for chloride ion attack on methylchloride in solution and the solvation free energies of a series of compounds including the reagents of the reaction. The second, VRSCOSMO, is an implicit solvation model for use with the DFTB3/3OB Hamiltonian for biochemical reactions; allowing for accurate modeling of ionic compound solvation properties while overcoming the discontinuous nature of conventional PCM models when chemical reaction coordinates. The VRSCOSMO model is shown to accurately model the solvation properties of over 200 chemical compounds while also providing smooth, continuous reaction surfaces for a series of biologically motivated phosphoryl transesterification reactions. Both of these methods incorporate charge-dependent behavior into the non-bonded interactions variationally, allowing the 'size' of atoms to change in meaningful ways with respect to changes in local charge state, as to provide an accurate, predictive and

  4. Affective Priming with Associatively Acquired Valence

    Science.gov (United States)

    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…

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

    Science.gov (United States)

    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

  6. Modeling of the Diffusion Bond for SPF/DB Titanium Hollow Structures

    Directory of Open Access Journals (Sweden)

    Xianghai Chai

    2015-01-01

    Full Text Available Diffusion-bonded titanium hollow warren structures have been successfully applied in aircraft engine components, such as fan blade, and OGV, while the optimal design of the hollow warren structure to improve its impact resistance, especially under bird-strike event, has been a challenge. In this work, a series of impact tests and numerical simulations are carried out to investigate the effect of key geometric features on the overall impact strength of a panel-shaped titanium hollow warren structure. Based on experimental and numerical studies, a quantitative relationship between diffusion bonding seam strength and the overall impact strength is developed. Meanwhile, key geometric factors affecting the resultant bonding seam strength for a typical manufacturing process are identified. This work provides useful references for the optimal design to increase impact resistance for aircraft engine hollow warren structure components.

  7. Analysis of the physical properties of trehalose-water-lithium iodide based on the bond strength coordination number fluctuation model

    International Nuclear Information System (INIS)

    Sahara; Jean L Ndeugueu; Masaru Aniya

    2010-01-01

    The temperature dependence of the viscosity of trehalose-water-lithium iodide system has been investigated by the mean of the Bond Strength Coordination Number Fluctuation (BSCNF) model. The result indicates that by increasing the trehalose content, maintaining the content of LiI constant, the fragility decreases due to the increase of the connectivity between the structural units. Our analysis suggests also that the fragility of the system is controlled by the amount of water in the composition. By increasing the water content, the total bond strength decreases and its fluctuation increases, resulting in the increase of the fragility. Based on the analysis of the obtained parameters of the BSCNF model, a physical interpretation of the VFT parameters reported in a previous study has been given. (author)

  8. Reducing the negative valence of stressful memories through emotionally valenced, modality-specific tasks

    NARCIS (Netherlands)

    Tadmor, Avia; McNally, Richard J; Engelhard, Iris M

    2016-01-01

    BACKGROUND AND OBJECTIVES: People who perform a cognitively demanding secondary task while recalling a distressing memory often experience the memory as less emotional, vivid, or accurate during subsequent recollections. In this experiment, we tested whether the emotional valence (positive versus

  9. Substituent Effects on the Stability of Thallium and Phosphorus Triple Bonds: A Density Functional Study.

    Science.gov (United States)

    Lu, Jia-Syun; Yang, Ming-Chung; Su, Ming-Der

    2017-07-05

    Three computational methods (M06-2X/Def2-TZVP, B3PW91/Def2-TZVP and B3LYP/LANL2DZ+dp) were used to study the effect of substitution on the potential energy surfaces of RTl≡PR (R = F, OH, H, CH₃, SiH₃, SiMe(Si t Bu₃)₂, Si i PrDis₂, Tbt (=C₆H₂-2,4,6-(CH(SiMe₃)₂)₃), and Ar* (=C₆H₃-2,6-(C₆H₂-2, 4,6- i -Pr₃)₂)). The theoretical results show that these triply bonded RTl≡PR compounds have a preference for a bent geometry (i.e., ∠R⎼Tl⎼P ≈ 180° and ∠Tl⎼P⎼R ≈ 120°). Two valence bond models are used to interpret the bonding character of the Tl≡P triple bond. One is model [I], which is best described as TlP. This interprets the bonding conditions for RTl≡PR molecules that feature small ligands. The other is model [II], which is best represented as TlP. This explains the bonding character of RTl≡PR molecules that feature large substituents. Irrespective of the types of substituents used for the RTl≡PR species, the theoretical investigations (based on the natural bond orbital, the natural resonance theory, and the charge decomposition analysis) demonstrate that their Tl≡P triple bonds are very weak. However, the theoretical results predict that only bulkier substituents greatly stabilize the triply bonded RTl≡PR species, from the kinetic viewpoint.

  10. The role of H-bond in the high-pressure chemistry of model molecules

    Science.gov (United States)

    Fanetti, Samuele; Citroni, Margherita; Dziubek, Kamil; Medre Nobrega, Marcelo; Bini, Roberto

    2018-03-01

    Pressure is an extraordinary tool to modify direction and strength of intermolecular interactions with important consequences on the chemical stability of molecular materials. The decrease of the distance among nearest neighbour molecules can give rise to reactive configurations reflecting the crystal arrangement and leading to association processes. In this context, the role of the H-bonds is very peculiar because their usual strengthening with rising pressure does not necessarily configure a decrease of the reaction activation energy but, on the contrary, can give rise to an anomalous stability of the system. In spite of this central role, the mechanisms by which a chemical reaction is favoured or prevented by H-bonding under high pressure conditions is a poorly explored field. Here we review a few studies where the chemical behaviour of simple molecular systems under static compression was related to the H-bonding evolution with pressure. These results are able to clarify a wealth of changes of the chemical and physical properties caused by the strengthening with pressure of the H-bonding network and provide additional tools to understand the mechanisms of high-pressure reactivity, a mandatory step to make these synthetic methods of potential interest for applicative purposes.

  11. Electron momentum distributions and binding energies for the valence orbitals of hydrogen bromide and hydrogen iodide

    International Nuclear Information System (INIS)

    Brion, C.E.; McCarthy, I.E.; Suzuki, I.H.; Weigold, E.; Williams, G.R.J.; Bedford, K.L.; Kunz, A.B.; Weidman, R.

    1981-12-01

    The electron binding energy spectra and momentum distributions have been obtained for the valence orbitals of HBr and HI using noncoplanar symmetric electron coincidence spectroscopy at 1200eV. The weakly bonding inner valence ns orbitals, which have not been previously observed, have their spectroscopic (pole) strength severely split among a number of ion states. For HBr the strength of the main inner valence (ns) transition is 0.42 0.03 whereas for HI it is 0.37 0.04, in close agreement with that observed for the valence s orbitals of the corresponding isoelectronic inert gas atoms. The spectroscopic strength for the two outermost orbitals is found to be close to unity, in agreement with many body Green's function calculations. The measured momentum distributions are compared with several spherically averaged MO momentum distributions, as well as (for HBr) with a Green's function calculation of the generalized overlap amplitude (GOA). The GOA momentum distributions are in excellent agreement with the HBr data, both in shape and relative magnitude. Not all of the MO momentum distributions are in reasonable agreement with the data. Comparison is also made with the calculated momentum distributions for Kr, Br, Xe and I

  12. Effects of cement thickness and bonding on the failure loads of CAD/CAM ceramic crowns: multi-physics FEA modeling and monotonic testing.

    Science.gov (United States)

    May, Liliana G; Kelly, J Robert; Bottino, Marco A; Hill, Thomas

    2012-08-01

    To determine the influence of cement thickness and ceramic/cement bonding on stresses and failure of CAD/CAM crowns, using both multi-physics finite element analysis and monotonic testing. Axially symmetric FEA models were created for stress analysis of a stylized monolithic crown having resin cement thicknesses from 50 to 500 μm under occlusal loading. Ceramic-cement interface was modeled as bonded or not-bonded (cement-dentin as bonded). Cement polymerization shrinkage was simulated as a thermal contraction. Loads necessary to reach stresses for radial cracking from the intaglio surface were calculated by FEA. Experimentally, feldspathic CAD/CAM crowns based on the FEA model were machined having different occlusal cementation spaces, etched and cemented to dentin analogs. Non-bonding of etched ceramic was achieved using a thin layer of poly(dimethylsiloxane). Crowns were loaded to failure at 5 N/s, with radial cracks detected acoustically. Failure loads depended on the bonding condition and the cement thickness for both FEA and physical testing. Average fracture loads for bonded crowns were: 673.5 N at 50 μm cement and 300.6N at 500 μm. FEA stresses due to polymerization shrinkage increased with the cement thickness overwhelming the protective effect of bonding, as was also seen experimentally. At 50 μm cement thickness, bonded crowns withstood at least twice the load before failure than non-bonded crowns. Occlusal "fit" can have structural implications for CAD/CAM crowns; pre-cementation spaces around 50-100 μm being recommended from this study. Bonding benefits were lost at thickness approaching 450-500 μm due to polymerization shrinkage stresses. Copyright © 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  13. On The Nature of the Halogen Bond.

    Science.gov (United States)

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

    2014-09-09

    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.

  14. Bond dissociation energies and radical stabilization energies associated with model peptide-backbone radicals.

    Science.gov (United States)

    Wood, Geoffrey P F; Moran, Damian; Jacob, Rebecca; Radom, Leo

    2005-07-21

    Bond dissociation energies (BDEs) and radical stabilization energies (RSEs) have been calculated for a series of models that represent a glycine-containing peptide-backbone. High-level methods that have been used include W1, CBS-QB3, U-CBS-QB3, and G3X(MP2)-RAD. Simpler methods used include MP2, B3-LYP, BMK, and MPWB1K in association with the 6-311+G(3df,2p) basis set. We find that the high-level methods produce BDEs and RSEs that are in good agreement with one another. Of the simpler methods, RBMK and RMPWB1K achieve good accuracy for BDEs and RSEs for all the species that were examined. For monosubstituted carbon-centered radicals, we find that the stabilizing effect (as measured by RSEs) of carbonyl substituents (CX=O) ranges from 24.7 to 36.9 kJ mol(-1), with the largest stabilization occurring for the CH=O group. Amino groups (NHY) also stabilize a monosubstituted alpha-carbon radical, with the calculated RSEs ranging from 44.5 to 49.5 kJ mol(-1), the largest stabilization occurring for the NH2 group. In combination, NHY and CX=O substituents on a disubstituted carbon-centered radical produce a large stabilizing effect ranging from 82.0 to 125.8 kJ mol(-1). This translates to a captodative (synergistic) stabilization of 12.8 to 39.4 kJ mol(-1). For monosubstituted nitrogen-centered radicals, we find that the stabilizing effect of methyl and related (CH2Z) substituents ranges from 25.9 to 31.7 kJ mol(-1), the largest stabilization occurring for the CH3 group. Carbonyl substituents (CX=O) destabilize a nitrogen-centered radical relative to the corresponding closed-shell molecule, with the calculated RSEs ranging from -30.8 to -22.3 kJ mol(-1), the largest destabilization occurring for the CH=O group. In combination, CH2Z and CX=O substituents at a nitrogen radical center produce a destabilizing effect ranging from -19.0 to -0.2 kJ mol(-1). This translates to an additional destabilization associated with disubstitution of -18.6 to -7.8 kJ mol(-1).

  15. Fundamentals of fiber bonding in thermally point-bonded nonwovens

    Science.gov (United States)

    Chidambaram, Aparna

    Thermal point bonding (TPB) uses heat and pressure to bond a web of fibers at discrete points imparting strength to the manufactured fabric. This process significantly reduces the strength and elongation of the bridging fibers between bond points while strengthening the web. Single fiber experiments were performed with four structurally different polypropylene fibers to analyze the inter-relationships between fiber structure, fiber properties and bonding process. Two fiber types had a low birefringence sheath or surface layer while the remaining had uniform birefringence profiles through their thickness. Bonds were formed between isolated pairs of fibers by subjecting the fibers to a calendering process and simulating TPB process conditions. The dependence of bond strength on bonding temperature and on the type of fiber used was evaluated. Fiber strengths before and after bonding were measured and compared to understand the effect of bonding on fiber strength. Additionally, bonded fiber strength was compared to the strength of single fibers which had experienced the same process conditions as the bonded pairs. This comparison estimated the effect of mechanical damage from pressing fibers together with steel rolls while creating bonds in TPB. Interfiber bond strength increased with bonding temperature for all fiber types. Fiber strength decreased with increasing bonding temperature for all fiber types except for one type of low birefringent sheath fibers. Fiber strength degradation was unavoidable at temperatures required for successful bonding. Mechanical damage from compression of fibers between rolls was an insignificant factor in this strength loss. Thermal damage during bonding was the sole significant contributor to fiber strength degradation. Fibers with low birefringence skins formed strong bonds with minimal fiber strength loss and were superior to fibers without such surface layers in TPB performance. A simple model to predict the behavior of a two-bond

  16. The thermodynamic stability of hydrogen bonded and cation bridged complexes of humic acid models-A theoretical study

    International Nuclear Information System (INIS)

    Aquino, Adelia J.A.; Tunega, Daniel; Pasalic, Hasan; Haberhauer, Georg; Gerzabek, Martin H.; Lischka, Hans

    2008-01-01

    Hydrogen bonded and cation bridged complexation of poly(acrylic acid) oligomers, representing a model compound for humic acids, with acetic acid and the herbicide (4-chloro-2-methylphenoxy) acetic acid (MCPA) have been studied by means of density functional theory. Solvation effects were computed by means of a combination of microsolvation (explicit insertion of water molecules) and global solvation (polarizable continuum approach). The stability of hydrogen bonded complexes in solution is characterized by a strong competition between solute and solvent molecules. The cation bridged complexes of the negatively charged (deprotonated) ligands were found to be strongly favored explaining the capability of humic acids to fixate anionic species from soil solutions and the ability to form cross-linking structures within the humic acid macromolecules

  17. Magnetic-field-induced valence transition in rare-earth systems

    Indian Academy of Sciences (India)

    In the present work we investigate the scaling behavior observed experimentally based on an electronic model which has not yet been attempted. 2. The model and approximation. The Hamiltonian of the periodic Anderson model (PAM) with Falicov–Kimball term used to describe both continuous and discontinuous valence ...

  18. Evaluative conditioning induces changes in sound valence

    Directory of Open Access Journals (Sweden)

    Anna C. Bolders

    2012-04-01

    Full Text Available Evaluative Conditioning (EC has hardly been tested in the auditory domain, but it is a potentially valuable research tool. In Experiment 1 we investigated whether the affective evaluation of short environmental sounds can be changed using affective words as unconditioned stimuli (US. Congruence effects on an affective priming task (APT for conditioned sounds demonstrated successful EC. Subjective ratings for sounds paired with negative words changed accordingly. In Experiment 2 we investigated whether the acquired valence remains stable after repeated presentation of the conditioned sound without the US or whether extinction occurs. The acquired affective value remained present, albeit weaker, even after 40 extinction trials. These results warrant the use of EC to study processing of short environmental sounds with acquired valence, even if this requires repeated stimulus presentations. This paves the way for studying processing of affective environmental sounds while effectively controlling low level-stimulus properties.

  19. Human Amygdala Represents the Complete Spectrum of Subjective Valence

    Science.gov (United States)

    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. Analytical modeling of mixed-Mode bending behavior of asymmetric adhesively bonded pultruded GFRP joints

    Czech Academy of Sciences Publication Activity Database

    Ševčík, Martin; Shahverdi, M.; Hutař, Pavel; Vassilopoulos, Anastasios P.

    2015-01-01

    Roč. 147, OCT (2015), s. 228-242 ISSN 0013-7944 R&D Projects: GA MŠk(CZ) ED1.1.00/02.0068; GA MŠk(CZ) EE2.3.30.0063 Institutional support: RVO:68081723 Keywords : Mixed-Mode delamination * Asymmetric joint * Adhesively bonded joint * Failure criterion * Analytical prediction * GFRP Subject RIV: JL - Materials Fatigue, Friction Mechanics Impact factor: 2.024, year: 2015

  1. 5th International Conference on Valence Fluctuations

    CERN Document Server

    Malik, S

    1987-01-01

    During the Koln meeting (August 28-31, 1984), Irdia was chosen as the venue for the next International Conference on Valence Fluctuations. lhis was in recognition ard appreciation of the work done, both experimental ard theoretical, by the Irdian scientists in this area during the last decade. We decided to hold this Conference in the month of January, 1987 at Bangalore. lhe subject of Valence Fluctuations has kept itself alive ard active as it has provided many shocks ard suprises particularly among the Ce- ard U-based intermetallies. lhe richness of many interesting physical phenomena occurring in mixed valent materials, the flexibility of modifying their physical properties (by alloying, for example) ard the possibility of synthesizing a wide variety of new such materials seem to be the key factors in this regard. Barely six months before this Conference, an International Conference on Anomalous Rare Earths and Actinides (ICAREA) had been held at Grenoble (July, 1986) which also focussed on mixed valence a...

  2. Architecture-based multiscale computational modeling of plant cell wall mechanics to examine the hydrogen-bonding hypothesis of the cell wall network structure model.

    Science.gov (United States)

    Yi, Hojae; Puri, Virendra M

    2012-11-01

    A primary plant cell wall network was computationally modeled using the finite element approach to study the hypothesis of hemicellulose (HC) tethering with the cellulose microfibrils (CMFs) as one of the major load-bearing mechanisms of the growing cell wall. A computational primary cell wall network fragment (10 × 10 μm) comprising typical compositions and properties of CMFs and HC was modeled with well-aligned CMFs. The tethering of HC to CMFs is modeled in accordance with the strength of the hydrogen bonding by implementing a specific load-bearing connection (i.e. the joint element). The introduction of the CMF-HC interaction to the computational cell wall network model is a key to the quantitative examination of the mechanical consequences of cell wall structure models, including the tethering HC model. When the cell wall network models with and without joint elements were compared, the hydrogen bond exhibited a significant contribution to the overall stiffness of the cell wall network fragment. When the cell wall network model was stretched 1% in the transverse direction, the tethering of CMF-HC via hydrogen bonds was not strong enough to maintain its integrity. When the cell wall network model was stretched 1% in the longitudinal direction, the tethering provided comparable strength to maintain its integrity. This substantial anisotropy suggests that the HC tethering with hydrogen bonds alone does not manifest sufficient energy to maintain the integrity of the cell wall during its growth (i.e. other mechanisms are present to ensure the cell wall shape).

  3. Parental Bonding

    Directory of Open Access Journals (Sweden)

    T. Paul de Cock

    2014-08-01

    Full Text Available Estimating the early parent–child bonding relationship can be valuable in research and practice. Retrospective dimensional measures of parental bonding provide a means for assessing the experience of the early parent–child relationship. However, combinations of dimensional scores may provide information that is not readily captured with a dimensional approach. This study was designed to assess the presence of homogeneous groups in the population with similar profiles on parental bonding dimensions. Using a short version of the Parental Bonding Instrument (PBI, three parental bonding dimensions (care, authoritarianism, and overprotection were used to assess the presence of unobserved groups in the population using latent profile analysis. The class solutions were regressed on 23 covariates (demographics, parental psychopathology, loss events, and childhood contextual factors to assess the validity of the class solution. The results indicated four distinct profiles of parental bonding for fathers as well as mothers. Parental bonding profiles were significantly associated with a broad range of covariates. This person-centered approach to parental bonding has broad utility in future research which takes into account the effect of parent–child bonding, especially with regard to “affectionless control” style parenting.

  4. Beyond molecular recognition: using a repulsive field to tune interfacial valency and binding specificity between adhesive surfaces.

    Science.gov (United States)

    Santore, Maria M; Zhang, Jun; Srivastava, Sudhanshu; Rotello, Vincent M

    2009-01-06

    Surface-bound biomolecular fragments enable "smart" materials to recognize cells and other particles in applications ranging from tissue engineering and medical diagnostics to colloidal and nanoparticle assembly. Such smart surfaces are, however, limited in their design to biomolecular selectivity. This feature article demonstrates, using a completely nonbiological model system, how specificity can be achieved for particle (and cell) binding, employing surface designs where immobilized nanoscale adhesion elements are entirely nonselective. Fundamental principles are illustrated by a model experimental system where 11 nm cationic nanoparticles on a planar negative silica surface interact with flowing negative silica microspheres having 1.0 and 0.5 microm diameters. In these systems, the interfacial valency, defined as the number of cross-bonds needed to capture flowing particles, is tunable through ionic strength, which alters the range of the background repulsion and therefore the effective binding strength of the adhesive elements themselves. At high ionic strengths where long-range electrostatic repulsions are screened, single surface-bound nanoparticles capture microspheres, defining the univalent regime. At low ionic strengths, competing repulsions weaken the effective nanoparticle adhesion so that multiple nanoparticles are needed for microparticle capture. This article discusses important features of the univalent regime and then illustrates how multivalency produces interfacial-scale selectivity. The arguments are then generalized, providing a possible explanation for highly specific cell binding in nature, despite the degeneracy of adhesion molecules and cell types. The mechanism for the valency-related selectivity is further developed in the context of selective flocculation in the colloidal literature. Finally, results for multivalent binding are contrasted with the current thinking for interfacial design and the presentation of adhesion moieties on

  5. Memory effects of sleep, emotional valence, arousal and novelty in children.

    Science.gov (United States)

    Vermeulen, Marije C M; van der Heijden, Kristiaan B; Benjamins, Jeroen S; Swaab, Hanna; van Someren, Eus J W

    2017-06-01

    Effectiveness of memory consolidation is determined by multiple factors, including sleep after learning, emotional valence, arousal and novelty. Few studies investigated how the effect of sleep compares with (and interacts with) these other factors, of which virtually none are in children. The present study did so by repeated assessment of declarative memory in 386 children (45% boys) aged 9-11 years through an online word-pair task. Children were randomly assigned to either a morning or evening learning session of 30 unrelated word-pairs with positive, neutral or negative valenced cues and neutral targets. After immediately assessing baseline recognition, delayed recognition was recorded either 12 or 24 h later, resulting in four different assessment schedules. One week later, the procedure was repeated with exactly the same word-pairs to evaluate whether effects differed for relearning versus original novel learning. Mixed-effect logistic regression models were used to evaluate how the probability of correct recognition was affected by sleep, valence, arousal, novelty and their interactions. Both immediate and delayed recognition were worse for pairs with negatively valenced or less arousing cue words. Relearning improved immediate and delayed word-pair recognition. In contrast to these effects, sleep did not affect recognition, nor did sleep moderate the effects of arousal, valence and novelty. The findings suggest a robust inclination of children to specifically forget the pairing of words to negatively valenced cue words. In agreement with a recent meta-analysis, children seem to depend less on sleep for the consolidation of information than has been reported for adults, irrespective of the emotional valence, arousal and novelty of word-pairs. © 2017 European Sleep Research Society.

  6. Dynamic modelling of the expansion cylinder of an open Joule cycle Ericsson engine: A bond graph approach

    International Nuclear Information System (INIS)

    Creyx, M.; Delacourt, E.; Morin, C.; Desmet, B.

    2016-01-01

    A dynamic model using the bond graph formalism of the expansion cylinder of an open Joule cycle Ericsson engine intended for a biomass-fuelled micro-CHP system is presented. Dynamic phenomena, such as the thermodynamic evolution of air, the instantaneous air mass flow rates linked to pressure drops crossing the valves, the heat transferred through the expansion cylinder wall and the mechanical friction losses, are included in the model. The influence on the Ericsson engine performances of the main operating conditions (intake air pressure and temperature, timing of intake and exhaust valve closing, rotational speed, mechanical friction losses and heat transfer at expansion cylinder wall) is studied. The operating conditions maximizing the performances of the Ericsson engine used in the a biomass-fuelled micro-CHP unit are an intake air pressure between 6 and 8 bar, a maximized intake air temperature, an adjustment of the intake and exhaust valve closing corresponding to an expansion cycle close to the theoretical Joule cycle, a rotational speed close to 800 rpm. The heat transfer at the expansion cylinder wall reduces the engine performances. - Highlights: • A bond graph dynamic model of the Ericsson engine expansion cylinder is presented. • Dynamic aspects are modelled: pressure drops, friction losses, wall heat transfer. • Influent factors and phenomena on the engine performances are investigated. • Expansion cycles close to the theoretical Joule cycle maximize the performances. • The heat transfer at the expansion chamber wall reduces the performances.

  7. Quantum mechanics models of the methanol dimer: OH⋯O hydrogen bonds of β-d-glucose moieties from crystallographic data.

    Science.gov (United States)

    Cintrón, Michael Santiago; Johnson, Glenn P; French, Alfred D

    2017-04-18

    The interaction of two methanol molecules, simplified models of carbohydrates and cellulose, was examined using a variety of quantum mechanics (QM) levels of theory. Energy plots for hydrogen bonding distance (H⋯O) and angle (OH⋯O) were constructed. All but two experimental structures were located in stabilized areas on the vacuum phase energy plots. Each of the 399 models was analyzed with Bader's atoms-in-molecules (AIM) theory, which showed a widespread ability by the dimer models to form OH⋯O hydrogen bonds that have bond paths and Bond Critical Points. Continuum solvation calculations suggest that a portion of the energy-stabilized structures could occur in the presence of water. A survey of the Cambridge Structural Database (CSD) for all donor-acceptor interactions in β-D-glucose moieties examined the similarities and differences among the hydroxyl groups and acetal oxygen atoms that participate in hydrogen bonds. Comparable behavior was observed for the O2H, O3H, O4H, and O6H hydroxyls, acting either as acceptors or donors. Ring O atoms showed distinct hydrogen bonding behavior that favored mid-length hydrogen bonds. Published by Elsevier Ltd.

  8. Curly arrows meet electron density transfers in chemical reaction mechanisms: from electron localization function (ELF) analysis to valence-shell electron-pair repulsion (VSEPR) inspired interpretation.

    Science.gov (United States)

    Andrés, Juan; Berski, Sławomir; Silvi, Bernard

    2016-07-07

    Probing the electron density transfers during a chemical reaction can provide important insights, making possible to understand and control chemical reactions. This aim has required extensions of the relationships between the traditional chemical concepts and the quantum mechanical ones. The present work examines the detailed chemical insights that have been generated through 100 years of work worldwide on G. N. Lewis's ground breaking paper on The Atom and the Molecule (Lewis, G. N. The Atom and the Molecule, J. Am. Chem. Soc. 1916, 38, 762-785), with a focus on how the determination of reaction mechanisms can be reached applying the bonding evolution theory (BET), emphasizing how curly arrows meet electron density transfers in chemical reaction mechanisms and how the Lewis structure can be recovered. BET that combines the topological analysis of the electron localization function (ELF) and Thom's catastrophe theory (CT) provides a powerful tool providing insight into molecular mechanisms of chemical rearrangements. In agreement with physical laws and quantum theoretical insights, BET can be considered as an appropriate tool to tackle chemical reactivity with a wide range of possible applications. Likewise, the present approach retrieves the classical curly arrows used to describe the rearrangements of chemical bonds for a given reaction mechanism, providing detailed physical grounds for this type of representation. The ideas underlying the valence-shell-electron pair-repulsion (VSEPR) model applied to non-equilibrium geometries provide simple chemical explanations of density transfers. For a given geometry around a central atom, the arrangement of the electronic domain may comply or not with the VSEPR rules according with the valence shell population of the considered atom. A deformation yields arrangements which are either VSEPR defective (at least a domain is missing to match the VSEPR arrangement corresponding to the geometry of the ligands), VSEPR compliant

  9. 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.

    Science.gov (United States)

    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

    2007-02-05

    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

  10. Homolytic bond dissociation energies for C-H bonds adjacent to sulfur and aromatic moieties: The effects of substituents of C-H bond strengths of the benzylic positions in coal model compounds

    Energy Technology Data Exchange (ETDEWEB)

    Alnajjar, M.S.; Franz, J.A. [Pacific Northwest Lab., Richland, WA (United States); Gleicher, G.J.; Truksa, S. [Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry; Bordwell, F.; Zhang, Xian-Man [Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry

    1993-09-01

    Sulfur-containing compounds are precursors for thiyl radicals at coal liquefaction temperatures due to the weakness of The and S-S bonds. Thiyl radicals play important roles in hydrogen atom shuttling between benzylic positions and catalyze the cleavage and the formation of strong C-C bonds. Although many reactions of thiyl and other sulfur-containing radicals are qualitatively understood, the homolytic bond dissociation energies (EDE`s) and the thermochemistry associated with many key high molecular weight hydrocarbon and sulfur-containing organic structures important to coal is lacking because they are inappropriate for gas-phase techniques. The measurement of BDE`s has been proven to be difficult even in the simplest of molecules.

  11. Mechatronic modeling of a 750kW fixed-speed wind energy conversion system using the Bond Graph Approach.

    Science.gov (United States)

    Khaouch, Zakaria; Zekraoui, Mustapha; Bengourram, Jamaa; Kouider, Nourreeddine; Mabrouki, Mustapha

    2016-11-01

    In this paper, we would like to focus on modeling main parts of the wind turbines (blades, gearbox, tower, generator and pitching system) from a mechatronics viewpoint using the Bond-Graph Approach (BGA). Then, these parts are combined together in order to simulate the complete system. Moreover, the real dynamic behavior of the wind turbine is taken into account and with the new model; final load simulation is more realistic offering benefits and reliable system performance. This model can be used to develop control algorithms to reduce fatigue loads and enhance power production. Different simulations are carried-out in order to validate the proposed wind turbine model, using real data provided in the open literature (blade profile and gearbox parameters for a 750 kW wind turbine). Copyright © 2016 ISA. Published by Elsevier Ltd. All rights reserved.

  12. Simulating Ru L 3 -Edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers

    Energy Technology Data Exchange (ETDEWEB)

    Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.; Bannan, Caitlin; Strader, Matthew L.; Cho, Hana; Huse, Nils; Schoenlein, Robert W.; Govind, Niranjan; Khalil, Munira

    2013-05-30

    Ruthenium L3-edge X-ray absorption (XA) spectroscopy probes unoccupied 4d orbitals of the metal atom and is increasingly being used to investigate the local electronic structure in ground and excited electronic states of Ru complexes. The simultaneous development of computational tools for simulating Ru L3-edge spectra is crucial for interpreting the spectral features at a molecular level. This study demonstrates that time-dependent density functional theory (TDDFT) is a viable and predictive tool for simulating ruthenium L3-edge XA spectroscopy. We systematically investigate the effects of exchange correlation functional and implicit and explicit solvent interactions on a series of RuII and RuIII complexes in their ground and electronic excited states. The TDDFT simulations reproduce all of the experimentally observed features in Ru L3-edge XA spectra within the experimental resolution (0.4 eV). Our simulations identify ligand-specific charge transfer features in complicated Ru L3-edge spectra of [Ru(CN)6]4- and RuII polypyridyl complexes illustrating the advantage of using TDDFT in complex systems. We conclude that the B3LYP functional most accurately predicts the transition energies of charge transfer features in these systems. We use our TDDFT approach to simulate experimental Ru L3-edge XA spectra of transition metal mixed-valence dimers of the form [(NC)5MII-CN-RuIII(NH3)5] (where M = Fe or Ru) dissolved in water. Our study determines the spectral signatures of electron delocalization in Ru L3-edge XA spectra. We find that the inclusion of explicit solvent molecules is necessary for reproducing the spectral features and the experimentally determined valencies in these mixed-valence complexes. This study validates the use of TDDFT for simulating Ru 2p excitations using popular quantum chemistry codes and providing a powerful interpretive tool for equilibrium and ultrafast Ru L3-edge XA spectroscopy.

  13. NATO Advanced Study Institute on Mixed-Valence Compounds : Theory and Applications in Chemistry, Physics, Geology, and Biology

    CERN Document Server

    1980-01-01

    It has been a decade since two seminal reviews demonstrated that mixed-valence compounds share many unique and fascinating features. The insight pro­ vided by those early works has promoted a great deal of both experimental and theoretical study. As a result of extensive efforts, our understanding of the bonding and properties of mixed-valence compounds has advanced substantially. There has been no compre­ hensive treatment of mixed-valence compounds since 1967, and the meeting convened at Oxford in September, 1979, provided a unique opportunity to examine the subject and its many ramifications. Mixed-valence compounds play an important role in many fields. Although the major impact of the subject has been in chemistry, its importance has become increasingly clear in solid state physics, geology, and biology. Extensive interest and effort in the field of molecular metals has demonstrated that mixed-valency is a prerequisite for high elec­ trical conductivity. The intense colors of many minerals have been s...

  14. Spectroscopy of 211Rn approaching the valence limit

    International Nuclear Information System (INIS)

    Davidson, P.M.; Dracoulis, G.D.; Kibedi, T.; Fabricius, B.; Baxter, A.M.; Stuchbery, A.E.; Poletti, A.R.; Schiffer, K.J.

    1993-02-01

    High spin states in 211 Rn were populated using the reaction 198 Pt( 18 O,5n) at 96 MeV. The decay was studied using γ-ray and electron spectroscopy. The known level scheme is extended up to a spin of greater than 69/2 and many non-yrast states are added. Semi-empirical shell model calculations and the properties of related states in 210 Rn and 212 Rn are used to assign configurations to some of the non-yrast states. The properties of the high spin states observed are compared to the predictions of the Multi-Particle Octupole Coupling model and the semi-empirical shell model. The maximum reasonable spin available from the valence particles and holes is 77/2 and states are observed to near this limit. 12 refs., 4 tabs., 8 figs

  15. The Relation Between Valence and Arousal in Subjective Experience Varies With Personality and Culture.

    Science.gov (United States)

    Kuppens, Peter; Tuerlinckx, Francis; Yik, Michelle; Koval, Peter; Coosemans, Joachim; Zeng, Kevin J; Russell, James A

    2017-08-01

    While in general arousal increases with positive or negative valence (a so-called V-shaped relation), there are large differences among individuals in how these two fundamental dimensions of affect are related in people's experience. In two studies, we examined two possible sources of this variation: personality and culture. In Study 1, participants (Belgian university students) recalled a recent event that was characterized by high or low valence or arousal and reported on their feelings and their personality in terms of the Five-Factor Model. In Study 2, participants from Canada, China/Hong Kong, Japan, Korea, and Spain reported on their feelings in a thin slice of time and on their personality. In Study 1, we replicated the V-shape as characterizing the relation between valence and arousal, and identified personality correlates of experiencing particular valence-arousal combinations. In Study 2, we documented how the V-shaped relation varied as a function of Western versus Eastern cultural background and personality. The results showed that the steepness of the V-shaped relation between valence and arousal increases with Extraversion within cultures, and with a West-East distinction between cultures. Implications for the personality-emotion link and research on cultural differences in affect are discussed. © 2016 Wiley Periodicals, Inc.

  16. The nature of chemical bonds from PNOF5 calculations.

    Science.gov (United States)

    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. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Off-planar geometry and structural instability of EDO-TTF explained by using the extended debye polarizability model for bond angles.

    Science.gov (United States)

    Linker, Gerrit-Jan; van Duijnen, Piet Th; van Loosdrecht, Paul H M; Broer, Ria

    2012-07-05

    The geometry of ethylenedioxy-tetrathiafulvalene, EDO-TTF, plays an important role in the metal-insulator transition in the charge transfer salt (EDO-TTF)(2)PF(6). The planar and off-planar geometrical conformations of the EDO-TTF molecules are explained using an extended Debye polarizability model for the bond angle. The geometrical structure of EDO-TTF is dictated by its four sulfur bond angles and these are, in turn, determined by the polarizability of the sulfur atoms. With Hartree-Fock and second-order Møller-Plesset perturbation theory calculations on EDO-TTF, TTF, H(2)S, and their oxygen and selenium substituted counterparts we confirm this hypothesis. The Debye polarizability model for bond angles relates directly the optimum bond angle with the polarizability of the center atom. Considering the (EDO-TTF)(2)PF(6) material in this light proves to be very fruitful.

  18. Valuation of Indonesian catastrophic earthquake bonds with generalized extreme value (GEV) distribution and Cox-Ingersoll-Ross (CIR) interest rate model

    Energy Technology Data Exchange (ETDEWEB)

    Gunardi,; Setiawan, Ezra Putranda [Mathematics Department, Gadjah Mada University (Indonesia)

    2015-12-22

    Indonesia is a country with high risk of earthquake, because of its position in the border of earth’s tectonic plate. An earthquake could raise very high amount of damage, loss, and other economic impacts. So, Indonesia needs a mechanism for transferring the risk of earthquake from the government or the (reinsurance) company, as it could collect enough money for implementing the rehabilitation and reconstruction program. One of the mechanisms is by issuing catastrophe bond, ‘act-of-God bond’, or simply CAT bond. A catastrophe bond issued by a special-purpose-vehicle (SPV) company, and then sold to the investor. The revenue from this transaction is joined with the money (premium) from the sponsor company and then invested in other product. If a catastrophe happened before the time-of-maturity, cash flow from the SPV to the investor will discounted or stopped, and the cash flow is paid to the sponsor company to compensate their loss because of this catastrophe event. When we consider the earthquake only, the amount of discounted cash flow could determine based on the earthquake’s magnitude. A case study with Indonesian earthquake magnitude data show that the probability of maximum magnitude can model by generalized extreme value (GEV) distribution. In pricing this catastrophe bond, we assumed stochastic interest rate that following the Cox-Ingersoll-Ross (CIR) interest rate model. We develop formulas for pricing three types of catastrophe bond, namely zero coupon bonds, ‘coupon only at risk’ bond, and ‘principal and coupon at risk’ bond. Relationship between price of the catastrophe bond and CIR model’s parameter, GEV’s parameter, percentage of coupon, and discounted cash flow rule then explained via Monte Carlo simulation.

  19. Valuation of Indonesian catastrophic earthquake bonds with generalized extreme value (GEV) distribution and Cox-Ingersoll-Ross (CIR) interest rate model

    International Nuclear Information System (INIS)

    Gunardi,; Setiawan, Ezra Putranda

    2015-01-01

    Indonesia is a country with high risk of earthquake, because of its position in the border of earth’s tectonic plate. An earthquake could raise very high amount of damage, loss, and other economic impacts. So, Indonesia needs a mechanism for transferring the risk of earthquake from the government or the (reinsurance) company, as it could collect enough money for implementing the rehabilitation and reconstruction program. One of the mechanisms is by issuing catastrophe bond, ‘act-of-God bond’, or simply CAT bond. A catastrophe bond issued by a special-purpose-vehicle (SPV) company, and then sold to the investor. The revenue from this transaction is joined with the money (premium) from the sponsor company and then invested in other product. If a catastrophe happened before the time-of-maturity, cash flow from the SPV to the investor will discounted or stopped, and the cash flow is paid to the sponsor company to compensate their loss because of this catastrophe event. When we consider the earthquake only, the amount of discounted cash flow could determine based on the earthquake’s magnitude. A case study with Indonesian earthquake magnitude data show that the probability of maximum magnitude can model by generalized extreme value (GEV) distribution. In pricing this catastrophe bond, we assumed stochastic interest rate that following the Cox-Ingersoll-Ross (CIR) interest rate model. We develop formulas for pricing three types of catastrophe bond, namely zero coupon bonds, ‘coupon only at risk’ bond, and ‘principal and coupon at risk’ bond. Relationship between price of the catastrophe bond and CIR model’s parameter, GEV’s parameter, percentage of coupon, and discounted cash flow rule then explained via Monte Carlo simulation

  20. Transversely Compressed Bonded Joints

    DEFF Research Database (Denmark)

    Hansen, Christian Skodborg; Schmidt, Jacob Wittrup; Stang, Henrik

    2012-01-01

    The load capacity of bonded joints can be increased if transverse pressure is applied at the interface. The transverse pressure is assumed to introduce a Coulomb-friction contribution to the cohesive law for the interface. Response and load capacity for a bonded single-lap joint was derived using...... non-linear fracture mechanics. The results indicated a good correlation between theory and tests. Furthermore, the model is suggested as theoretical base for determining load capacity of bonded anchorages with transverse pressure, in externally reinforced concrete structures....

  1. Simulant molecules with trivalent or pentavalent phosphorus atoms: bond dissociation energies and other thermodynamic and structural properties from quantum chemical models.

    Science.gov (United States)

    Hahn, David K; RaghuVeer, Krishans S; Ortiz, J V

    2011-08-04

    The CBS-QB3 and G4 thermochemical models have been used to generate energetic, structural, and spectroscopic data on a set of molecules with trivalent or pentavalent phosphorus atoms that can serve as simulants of chemical warfare agents. Based on structural data, the conformational stabilities of these molecules are explained in terms of the anomeric interaction within the OPOC and OPSC fragments. For those cases where experimental data are available, comparisons have been made between calculated and previously reported vibrational frequencies. All varieties of bond dissociation energies have been examined except those for C-H and P═O bonds. In trivalent phosphorus molecules, the O-C and S-C bonds have the lowest dissociation energies. In the pentavalent phosphorus set, the S-C bonds, followed by P-S bonds, have the lowest dissociation energies. In the fluorinated simulant molecules, the P-F bond is strongest, and the P-C or O-C bonds are weakest. © 2011 American Chemical Society

  2. Positive valence music restores executive control over sustained attention.

    Science.gov (United States)

    Baldwin, Carryl L; Lewis, Bridget A

    2017-01-01

    Music sometimes improves performance in sustained attention tasks. But the type of music employed in previous investigations has varied considerably, which can account for equivocal results. Progress has been hampered by lack of a systematic database of music varying in key characteristics like tempo and valence. The aims of this study were to establish a database of popular music varying along the dimensions of tempo and valence and to examine the impact of music varying along these dimensions on restoring attentional resources following performance of a sustained attention to response task (SART) vigil. Sixty-nine participants rated popular musical selections that varied in valence and tempo to establish a database of four musical types: fast tempo positive valence, fast tempo negative valence, slow tempo positive valence, and slow tempo negative valence. A second group of 89 participants performed two blocks of the SART task interspersed with either no break or a rest break consisting of 1 of the 4 types of music or silence. Presenting positive valence music (particularly of slow tempo) during an intermission between two successive blocks of the SART significantly decreased miss rates relative to negative valence music or silence. Results support an attentional restoration theory of the impact of music on sustained attention, rather than arousal theory and demonstrate a means of restoring sustained attention. Further, the results establish the validity of a music database that will facilitate further investigations of the impact of music on performance.

  3. Fluorescence properties of valence-controlled Eu2+ and Mn2+ ions in aluminosilicate glasses

    International Nuclear Information System (INIS)

    Van Tuyen, Ho; Nonaka, Takamasa; Yamanaka, Ken-ichi; Chau, Pham Minh; Quy Hai, Nguyen Thi; Quang, Vu Xuan; Nogami, Masayuki

    2017-01-01

    Controlling of valence states of metal ions doped in glasses has attracted considerable interest due to the possibility of looking toward optical applications. In this study, new Na 2 O-Al 2 O 3 -SiO 2 glasses were developed to dope Eu 2+ and Mn 2+ with well controlled valence states by heating in H 2 gas atmosphere, and the changes in the valence state of doped-ions and their fluorescence properties were investigated using visible and infrared optical absorption spectroscopies, X-ray absorption fine structure spectroscopy, and fluorescence spectroscopy. Among Eu 3+ , Mn 3+ and Mn 2+ ions incorporated in the as-prepared glasses, the Eu 3+ and Mn 3+ ions were reduced to Eu 2+ and Mn 2+ ions, respectively, by heating in H 2 gas and OH bonds were concurrently formed. The fluorescence spectra of glasses heated in H 2 exhibited broad emission bands at 450 and 630 nm wavelength, assigned to the Eu 2+ and Mn 2+ , respectively, ions, in which the fluorescence intensity at 450 nm was observed to decrease with increasing Mn 2+ ion content. The increased fluorescence intensities were analyzed as the energy transfer from Eu 2+ to Mn 2+ ions and the energy transfer efficiency was estimated with a concentration of Eu 2+ and Mn 2+ ions.

  4. Models of molecular geometry.

    Science.gov (United States)

    Gillespie, Ronald J; Robinson, Edward A

    2005-05-01

    Although the structure of almost any molecule can now be obtained by ab initio calculations chemists still look for simple answers to the question "What determines the geometry of a given molecule?" For this purpose they make use of various models such as the VSEPR model and qualitative quantum mechanical models such as those based on the valence bond theory. The present state of such models, and the support for them provided by recently developed methods for analyzing calculated electron densities, are reviewed and discussed in this tutorial review.

  5. DFT modeling of the electronic and magnetic structures and chemical bonding properties of intermetallic hydrides

    International Nuclear Information System (INIS)

    Al Alam, A.F.

    2009-06-01

    This thesis presents an ab initio study of several classes of intermetallics and their hydrides. These compounds are interesting from both a fundamental and an applied points of view. To achieve this aim two complementary methods, constructed within the DFT, were chosen: (i) pseudo potential based VASP for geometry optimization, structural investigations and electron localization mapping (ELF), and (ii) all-electrons ASW method for a detailed description of the electronic structure, chemical bonding properties following different schemes as well as quantities depending on core electrons such as the hyperfine field. A special interest is given with respect to the interplay between magneto-volume and chemical interactions (metal-H) effects within the following hydrided systems: binary Laves (e.g. ScFe 2 ) and Haucke (e.g. LaNi 5 ) phases on one hand, and ternary cerium based (e.g. CeRhSn) and uranium based (e.g. U 2 Ni 2 Sn) alloys on the other hand. (author)

  6. Optimal Investment in Structured Bonds

    DEFF Research Database (Denmark)

    Jessen, Pernille; Jørgensen, Peter Løchte

    The paper examines the role of structured bonds in the optimal portfolio of a small retail investor. We consider the typical structured bond essentially repacking an exotic option and a zero coupon bond, i.e. an investment with portfolio insurance. The optimal portfolio is found when the investment...... opportunities consist of a risky reference fund, a risk-free asset and a structured bond. Key model elements are the trading strategy and utility function of the investor. Our numerical results indicate structured bonds do have basis for consideration in the optimal portfolio. The product holdings...

  7. LAMMPS Framework for Directional Dynamic Bonding

    DEFF Research Database (Denmark)

    2012-01-01

    and bond types. When breaking bonds, all angular and dihedral interactions involving broken bonds are removed. The framework allows chemical reactions to be modeled, and use it to simulate a simplistic, coarse-grained DNA model. The resulting DNA dynamics illustrates the power of the present framework.......We have extended the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) to support directional bonds and dynamic bonding. The framework supports stochastic formation of new bonds, breakage of existing bonds, and conversion between bond types. Bond formation can be controlled...... to limit the maximal functionality of a bead with respect to various bond types. Concomitant with the bond dynamics, angular and dihedral interactions are dynamically introduced between newly connected triplets and quartets of beads, where the interaction type is determined from the local pattern of bead...

  8. Bond length and electric current oscillation of long linear carbon chains: Density functional theory, MpB model, and quantum spin transport studies

    International Nuclear Information System (INIS)

    Oeiras, R. Y.; Silva, E. Z. da

    2014-01-01

    Carbon linear atomic chains attached to graphene have experimentally been produced. Motivated by these results, we study the nature of the carbon bonds in these nanowires and how it affects their electrical properties. In the present study we investigate chains with different numbers of atoms and we observe that nanowires with odd number of atoms present a distinct behavior than the ones with even numbers. Using graphene nanoribbons as leads, we identify differences in the quantum transport of the chains with the consequence that even and odd numbered chains have low and high electrical conduction, respectively. We also noted a dependence of current with the wire size. We study this unexpected behavior using a combination of first principles calculations and simple models based on chemical bond theory. From our studies, the electrons of carbon nanowires present a quasi-free electron behavior and this explains qualitatively the high electrical conduction and the bond lengths with unexpected values for the case of odd nanowires. Our study also allows the understanding of the electric conduction dependence with the number of atoms and their parity in the chain. In the case of odd number chains a proposed π-bond (MpB) model describes unsaturated carbons that introduce a mobile π-bond that changes dramatically the structure and transport properties of these wires. Our results indicate that the nature of bonds plays the main role in the oscillation of quantum electrical conduction for chains with even and odd number of atoms and also that nanowires bonded to graphene nanoribbons behave as a quasi-free electron system, suggesting that this behavior is general and it could also remain if the chains are bonded to other materials

  9. Effective field treatment of the annealed bond-dilute transverse Ising model

    International Nuclear Information System (INIS)

    Silva, P.R.; Sa Barreto, F.C. de

    1983-01-01

    The dilution of the spin-1/2 transverse Ising Model is studied by means of an effective field type treatment based on an extension of Callen's relation to the present model. The thermodynamics of the diluted model is obtained and the results are shown to be an improvement over the standard mean field treatment. The results are also compared with the Monte Carlo calculation for the spin-infinite transverse Ising Model. (Author) [pt

  10. Colour and emotion: children also associate red with negative valence.

    Science.gov (United States)

    Gil, Sandrine; Le Bigot, Ludovic

    2016-11-01

    The association of colour with emotion constitutes a growing field of research, as it can affect how humans process their environment. Although there has been increasing interest in the association of red with negative valence in adults, little is known about how it develops. We therefore tested the red-negative association in children for the first time. Children aged 5-10 years performed a face categorization task in the form of a card-sorting task. They had to judge whether ambiguous faces shown against three different colour backgrounds (red, grey, green) seemed to 'feel good' or 'feel bad'. Results of logistic mixed models showed that - as previously demonstrated in adults - children across the age range provided significantly more 'feel bad' responses when the faces were given a red background. This finding is discussed in relation to colour-emotion association theories. © 2015 John Wiley & Sons Ltd.

  11. Unusual magnetic properties of mixed-valence system: multiconfigurational method theoretical study on Mn2+ cation.

    Science.gov (United States)

    Wang, Bingwu; Chen, Zhida

    2005-10-01

    The geometry structure, dissociation energy, vibrational frequencies, and low-lying spin-state energy spectrum of Mn2+ are investigated by using ab initio CASSCF/ECP10MDF, complete active space self-consistent field/atomic natural orbital basis sets (CASSCF/ANO-s), CASPT2/ECP10MDF, and second-order perturbation theory with CASSCF reference function/atomic natural orbital basis sets (CASPT2/ANO-s) levels of theory. For the ground state the dissociation energy of 1.397 eV calculated at the CASPT2/ANO-s level supports Jarrlod's experimental value of 1.39 eV. The equilibrium bond length and vibrational frequency are 2.940 A calculated at the CASPT2/ANO-s level of theory and 214.4 cm-1 calculated at the CASSCF/ANO-s level of theory, respectively. On the basis of the mixed-valence model, the Heisenberg exchange constant J(-71.2 cm-1) and the double-exchange constant B(647.7 cm-1) are extracted explicitly from the low-lying energy spectrum calculated at the higher levels of theory. The magnetic competition between the weaker Heisenberg exchange interactions and the stronger double-exchange interactions makes the ground state a 12Sigmag+ state, consistent with electron paramagnetic resonance experimental observation, which explains unusual magnetic properties of Mn2+, quite different from the antiferromagnetic ground state of Mn2 and Cr2. On the other hand, the results calculated at the higher levels of theory show the consistent antiferromagnetic Heisenberg exchange interactions between 3d-3d for Cr2, Mn2+, and Mn2.

  12. Bond markets in Africa

    Directory of Open Access Journals (Sweden)

    Yibin Mu

    2013-07-01

    Full Text Available African bond markets have been steadily growing in recent years, but nonetheless remain undeveloped. African countries would benefit from greater access to financing and deeper financial markets. This paper compiles a unique set of data on government securities and corporate bond markets in Africa. It then applies an econometric model to analyze the key determinants of African government securities market and corporate bond market capitalization. Government securities market capitalization is directly related to better institutions and interest rate volatility, and inversely related to smaller fiscal deficits, higher interest rate spreads, exchange rate volatility, and current and capital account openness. Corporate bond market capitalization is directly linked to economic size, the level of development of the economy and financial markets, better institutions, and interest rate volatility, and inversely related to higher interest rate spreads and current account openness. Policy implications follow.

  13. The introduction of hydrogen bond and hydrophobicity effects into the rotational isomeric states model for conformational analysis of unfolded peptides

    International Nuclear Information System (INIS)

    Engin, Ozge; Sayar, Mehmet; Erman, Burak

    2009-01-01

    Relative contributions of local and non-local interactions to the unfolded conformations of peptides are examined by using the rotational isomeric states model which is a Markov model based on pairwise interactions of torsion angles. The isomeric states of a residue are well described by the Ramachandran map of backbone torsion angles. The statistical weight matrices for the states are determined by molecular dynamics simulations applied to monopeptides and dipeptides. Conformational properties of tripeptides formed from combinations of alanine, valine, tyrosine and tryptophan are investigated based on the Markov model. Comparison with molecular dynamics simulation results on these tripeptides identifies the sequence-distant long-range interactions that are missing in the Markov model. These are essentially the hydrogen bond and hydrophobic interactions that are obtained between the first and the third residue of a tripeptide. A systematic correction is proposed for incorporating these long-range interactions into the rotational isomeric states model. Preliminary results suggest that the Markov assumption can be improved significantly by renormalizing the statistical weight matrices to include the effects of the long-range correlations

  14. Modeling liquid-vapor equilibria with an equation of state taking into account dipolar interactions and association by hydrogen bonding

    International Nuclear Information System (INIS)

    Perfetti, E.

    2006-11-01

    Modelling fluid-rock interactions as well as mixing and unmixing phenomena in geological processes requires robust equations of state (EOS) which must be applicable to systems containing water, gases over a broad range of temperatures and pressures. Cubic equations of state based on the Van der Waals theory (e. g. Soave-Redlich-Kwong or Peng-Robinson) allow simple modelling from the critical parameters of the studied fluid components. However, the accuracy of such equations becomes poor when water is a major component of the fluid since neither association trough hydrogen bonding nor dipolar interactions are accounted for. The Helmholtz energy of a fluid may be written as the sum of different energetic contributions by factorization of partition function. The model developed in this thesis for the pure H 2 O and H 2 S considers three contributions. The first contribution represents the reference Van der Waals fluid which is modelled by the SRK cubic EOS. The second contribution accounts for association through hydrogen bonding and is modelled by a term derived from Cubic Plus Association (CPA) theory. The third contribution corresponds to the dipolar interactions and is modelled by the Mean Spherical Approximation (MSA) theory. The resulting CPAMSA equation has six adjustable parameters, which three represent physical terms whose values are close to their experimental counterpart. This equation results in a better reproduction of the thermodynamic properties of pure water than obtained using the classical CPA equation along the vapour-liquid equilibrium. In addition, extrapolation to higher temperatures and pressure is satisfactory. Similarly, taking into account dipolar interactions together with the SRK cubic equation of state for calculating molar volume of H 2 S as a function of pressure and temperature results in a significant improvement compared to the SRK equation alone. Simple mixing rules between dipolar molecules are proposed to model the H 2 O-H 2 S

  15. An iterated GMM procedure for estimating the Campbell-Cochrane habit formation model, with an application to Danish stock and bond returns

    DEFF Research Database (Denmark)

    Engsted, Tom; Møller, Stig V.

    We suggest an iterated GMM approach to estimate and test the consumption based habit persistence model of Campbell and Cochrane (1999), and we apply the approach on annual and quarterly Danish stock and bond returns. For comparative purposes we also estimate and test the standard CRRA model...

  16. A WEAK ALKALI BOND IN (N, K–A–S–H GELS: EVIDENCE FROM LEACHING AND MODELING

    Directory of Open Access Journals (Sweden)

    FRANTIŠEK ŠKVÁRA

    2012-12-01

    Full Text Available The alkali bond in (N, K–A–S–H gels presents an up-to-date insufficiently resolved issue with significant consequences for efflorescence in alkali-activated materials. A series of experiments shows nearly all alkalis are leachable from alkaliactivated fly-ash and metakaolin in excessive amounts of deionized water. A diffusion-based model describes well the alkali leaching process. Negligible changes of the (N, K–A–S–H gel nanostructure indicate that Na,K do not form the gel backbone and H3O+ is probably the easiest substitution for the leached alkalies. Small changes in the long-term compressive strength of leached specimens support this hypothesis.

  17. Modeling and Measurement of Sustained Loading and Temperature-Dependent Deformation of Carbon Fiber-Reinforced Polymer Bonded to Concrete.

    Science.gov (United States)

    Jeong, Yoseok; Lee, Jaeha; Kim, WooSeok

    2015-01-29

    This paper aims at presenting the effects of short-term sustained load and temperature on time-dependent deformation of carbon fiber-reinforced polymer (CFRP) bonded to concrete and pull-off strength at room temperature after the sustained loading period. The approach involves experimental and numerical analysis. Single-lap shear specimens were used to evaluate temperature and short-term sustained loading effects on time-dependent behavior under sustained loading and debonding behavior under pull-off loading after a sustained loading period. The numerical model was parameterized with experiments on the concrete, FRP, and epoxy. Good correlation was seen between the numerical results and single-lap shear experiments. Sensitivity studies shed light on the influence of temperature, epoxy modulus, and epoxy thickness on the redistribution of interfacial shear stress during sustained loading. This investigation confirms the hypothesis that interfacial stress redistribution can occur due to sustained load and elevated temperature and its effect can be significant.

  18. Atom-specific look at the surface chemical bond using x-ray emission spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Nilsson, A.; Wassdahl, N.; Weinelt, M. [Uppsala Univ. (Sweden)] [and others

    1997-04-01

    CO and N{sub 2} adsorbed on the late transition metals have become prototype systems regarding the general understanding of molecular adsorption. It is in general assumed that the bonding of molecules to transition metals can be explained in terms of the interaction of the frontier HOMO and LUMO molecular orbitals with the d-orbitals. In such a picture the other molecular orbitals should remain essentially the same as in the free molecule. For the adsorption of the isoelectronic molecules CO and N{sub 2} this has led to the so called Blyholder model i.e., a synergetic {sigma} (HOMO) donor and {pi} (LUMO) backdonation bond. The authors results at the ALS show that such a picture is oversimplified. The direct observation and identification of the states related to the surface chemical bond is an experimental challenge. For noble and transition metal surfaces, the adsorption induced states overlap with the metal d valence band. Their signature is therefore often obscured by bulk substrate states. This complication has made it difficult for techniques such as photoemission and inverse photoemission to provide reliable information on the energy of chemisorption induced states and has left questions unanswered regarding the validity of the frontier orbitals concept. Here the authors show how x-ray emission spectroscopy (XES), in spite of its inherent bulk sensitivity, can be used to investigate adsorbed molecules. Due to the localization of the core-excited intermediate state, XE spectroscopy allows an atomic specific separation of the valence electronic states. Thus the molecular contributions to the surface measurements make it possible to determine the symmetry of the molecular states, i.e., the separation of {pi} and {sigma} type states. In all the authors can obtain an atomic view of the electronic states involved in the formation of the chemical bond to the surface.

  19. Modeling and Simulation of Underwater Flexible Manipulator as Raleigh Beam Using Bond Graph

    OpenAIRE

    Sumit Kumar; Sunil Kumar; Chandan Deep Singh

    2015-01-01

    This paper presents modeling and simulation of flexible robot in an underwater environment. The underwater environment completely contrasts with ground or space environment. The robot in an underwater situation is subjected to various dynamic forces like buoyancy forces, hydrostatic and hydrodynamic forces. The underwater robot is modeled as Rayleigh beam. The developed model further allows estimating the deflection of tip in two directions. The complete dynamics of the u...

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

    Science.gov (United States)

    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),…

  1. The stabilities and electron structures of Al-Mg clusters with 18 and 20 valence electrons

    Science.gov (United States)

    Yang, Huihui; Chen, Hongshan

    2017-07-01

    The spherical jellium model predicts that metal clusters having 18 and 20 valence electrons correspond to the magic numbers and will show specific stabilities. We explore in detail the geometric structures, stabilities and electronic structures of Al-Mg clusters containing 18 and 20 valence electrons by using genetic algorithm combined with density functional theories. The stabilities of the clusters are governed by the electronic configurations and Mg/Al ratios. The clusters with lower Mg/Al ratios are more stable. The molecular orbitals accord with the shell structures predicted by the jellium model but the 2S level interweaves with the 1D levels and the 2S and 1D orbitals form a subgroup. The clusters having 20 valence electrons form closed 1S21P61D102S2 shells and show enhanced stability. The Al-Mg clusters with a valence electron count of 18 do not form closed shells because one 1D orbital is unoccupied. The ionization potential and electron affinity are closely related to the electronic configurations; their values are determined by the subgroups the HOMO or LUMO belong to. Supplementary material in the form of one pdf file available from the Journal web page at http://https://doi.org/10.1140/epjd/e2017-80042-9

  2. Molecular dynamics modeling of bonding two materials by atomic scale friction stir welding

    Science.gov (United States)

    Konovalenko S., Iv.; Konovalenko, Ig. S.; Psakhie, S. G.

    2017-12-01

    Molecular dynamics model of atomic scale friction stir welding has been developed. Formation of a butt joint between two crystallites was modeled by means of rotating rigid conical tool traveling along the butt joint line. The formed joint had an intermixed atomic structure composed of atoms initially belonged to the opposite mated piece of metal. Heat removal was modeled by adding the extra viscous force to peripheral atomic layers. This technique provides the temperature control in the tool-affected zone during welding. Auxiliary vibration action was added to the rotating tool. The model provides the variation of the tool's angular velocity, amplitude, frequency and direction of the auxiliary vibration action to provide modeling different welding modes.

  3. Mechatronics by bond graphs an object-oriented approach to modelling and simulation

    CERN Document Server

    Damić, Vjekoslav

    2015-01-01

    This book presents a computer-aided approach to the design of mechatronic systems. Its subject is an integrated modeling and simulation in a visual computer environment. Since the first edition, the simulation software changed enormously, became more user-friendly and easier to use. Therefore, a second edition became necessary taking these improvements into account. The modeling is based on system top-down and bottom-up approach. The mathematical models are generated in a form of differential-algebraic equations and solved using numerical and symbolic algebra methods. The integrated approach developed is applied to mechanical, electrical and control systems, multibody dynamics, and continuous systems. .

  4. Connecting [NiFe]- and [FeFe]-hydrogenases: mixed-valence nickel-iron dithiolates with rotated structures.

    Science.gov (United States)

    Schilter, David; Rauchfuss, Thomas B; Stein, Matthias

    2012-08-20

    New mixed-valence iron-nickel dithiolates are described that exhibit structures similar to those of mixed-valence diiron dithiolates. The interaction of tricarbonyl salt [(dppe)Ni(pdt)Fe(CO)(3)]BF(4) ([1]BF(4), where dppe = Ph(2)PCH(2)CH(2)PPh(2) and pdt(2-) = -SCH(2)CH(2)CH(2)S-) with P-donor ligands (L) afforded the substituted derivatives [(dppe)Ni(pdt)Fe(CO)(2)L]BF(4) incorporating L = PHCy(2) ([1a]BF(4)), PPh(NEt(2))(2) ([1b]BF(4)), P(NMe(2))(3) ([1c]BF(4)), P(i-Pr)(3) ([1d]BF(4)), and PCy(3) ([1e]BF(4)). The related precursor [(dcpe)Ni(pdt)Fe(CO)(3)]BF(4) ([2]BF(4), where dcpe = Cy(2)PCH(2)CH(2)PCy(2)) gave the more electron-rich family of compounds [(dcpe)Ni(pdt)Fe(CO)(2)L]BF(4) for L = PPh(2)(2-pyridyl) ([2a]BF(4)), PPh(3) ([2b]BF(4)), and PCy(3) ([2c]BF(4)). For bulky and strongly basic monophosphorus ligands, the salts feature distorted coordination geometries at iron: crystallographic analyses of [1e]BF(4) and [2c]BF(4) showed that they adopt "rotated" Fe(I) centers, in which PCy(3) occupies a basal site and one CO ligand partially bridges the Ni and Fe centers. Like the undistorted mixed-valence derivatives, members of the new class of complexes are described as Ni(II)Fe(I) (S = ½) systems according to electron paramagnetic resonance spectroscopy, although with attenuated (31)P hyperfine interactions. Density functional theory calculations using the BP86, B3LYP, and PBE0 exchange-correlation functionals agree with the structural and spectroscopic data, suggesting that the spin for [1e](+) is mostly localized in a Fe(I)-centered d(z(2)) orbital, orthogonal to the Fe-P bond. The PCy(3) complexes, rare examples of species featuring "rotated" Fe centers, both structurally and spectroscopically incorporate features from homobimetallic mixed-valence diiron dithiolates. Also, when the NiS(2)Fe core of the [NiFe]-hydrogenase active site is reproduced, the "hybrid models" incorporate key features of the two major classes of hydrogenase. Furthermore, cyclic

  5. Valence changes associated with the metal-insulator transition in Bi1-xLaxNiO3

    Science.gov (United States)

    Wadati, H.; Takizawa, M.; Tran, T. T.; Tanaka, K.; Mizokawa, T.; Fujimori, A.; Chikamatsu, A.; Kumigashira, H.; Oshima, M.; Ishiwata, S.; Azuma, M.; Takano, M.

    2005-10-01

    Perovskite-type BiNiO3 is an insulating antiferromagnet in which a charge disproportionation occurs at the Bi site. La substitution for Bi suppresses the charge disproportionation and makes the system metallic. We have measured the photoemission and x-ray-absorption (XAS) spectra of Bi1-xLaxNiO3 to investigate how the electronic structure changes with La doping. From Ni 2p XAS, we observed an increase of the valence of Ni from 2+ toward 3+ . Combined with the core-level photoemission study, it was found that the average valence of Bi remains ˜4+ and that the Ni valence behaves as ˜(2+x)+ , that is, La substitution results in a hole doping at the Ni sites. In the valence-band photoemission spectra, we observed a Fermi cutoff for x>0 , consistent with the metallic behavior of the La-doped compounds. The Ni 2p XAS, Ni 2p core-level photoemission, and valence-band photoemission spectra were analyzed by configuration-interaction cluster-model calculation, and the spectral line shapes were found to be consistent with the gradual Ni2+→Ni3+ valence change.

  6. Numerical Parameter Optimization of the Ignition and Growth Model for HMX Based Plastic Bonded Explosives

    Science.gov (United States)

    Gambino, James; Tarver, Craig; Springer, H. Keo; White, Bradley; Fried, Laurence

    2017-06-01

    We present a novel method for optimizing parameters of the Ignition and Growth reactive flow (I&G) model for high explosives. The I&G model can yield accurate predictions of experimental observations. However, calibrating the model is a time-consuming task especially with multiple experiments. In this study, we couple the differential evolution global optimization algorithm to simulations of shock initiation experiments in the multi-physics code ALE3D. We develop parameter sets for HMX based explosives LX-07 and LX-10. The optimization finds the I&G model parameters that globally minimize the difference between calculated and experimental shock time of arrival at embedded pressure gauges. This work was performed under the auspices of the U.S. DOE by LLNL under contract DE-AC52-07NA27344. LLNS, LLC LLNL-ABS- 724898.

  7. Halogen Bonds in Novel Polyhalogen Monoanions.

    Science.gov (United States)

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

    2017-06-27

    Polyhalogen monoanions [X 2n+1 ] - (X=Cl and Br; n=1, 2, 3, 4, and 5) have been systematically studied using the block-localized wave function (BLW) method, which offers a valence bond (VB) analysis. For each species, the most stable isomer can be described as a central halide anion X - non-classically bonded to a number of dihalogen molecules X 2 via "halogen bonds". VB analyses confirm the dominant role of the charge-transfer interaction between the lone pair on X - and the σ-anti-bonding orbital of X 2 molecule (n→σ*) in X 3 - and higher analogues. Thus, our study demonstrates that these halogen bonds are essentially dative covalent interactions. Importantly, the charge-transfer interaction between [X 2n-1 ] - and X 2 decreases with the increasing n, in accord with the weakening of the Lewis basicity as characterized by the corresponding HOMO energy. The reduction of the charge transfer interaction underscores the reduction of covalence in halogen bonds in [X 2n+1 ] - . This tendency highlights the anti-cooperative effect in polyhalogen monoanions. All in all, the halogen bond between X - and nX 2 molecules exhibits the same trends as in X - with a single X 2 molecule. In other words, halogen bonding in the larger clusters derives from the same bonding mechanism as the [X 3 ] - anion. As such, the X - ⋅⋅⋅X 2 halogen bond at different bond lengths forms a gauge of covalence for the entire [X 2n+1 ] - family. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Influence of the spin quantum number $s$ on the zero-temperature phase transition in the square lattice $J$-$J'$ model

    OpenAIRE

    Darradi, R.; Richter, J.; Farnell, D. J. J.

    2004-01-01

    We investigate the phase diagram of the Heisenberg antiferromagnet on the square lattice with two different nearest-neighbor bonds $J$ and $J'$ ($J$-$J'$ model) at zero temperature. The model exhibits a quantum phase transition at a critical value $J'_c > J$ between a semi-classically ordered N\\'eel and a magnetically disordered quantum paramagnetic phase of valence-bond type, which is driven by local singlet formation on $J'$ bonds. We study the influence of spin quantum number $s$ on this p...

  9. Fault diagnosis of locomotive electro-pneumatic brake through uncertain bond graph modeling and robust online monitoring

    Science.gov (United States)

    Niu, Gang; Zhao, Yajun; Defoort, Michael; Pecht, Michael

    2015-01-01

    To improve reliability, safety and efficiency, advanced methods of fault detection and diagnosis become increasingly important for many technical fields, especially for safety related complex systems like aircraft, trains, automobiles, power plants and chemical plants. This paper presents a robust fault detection and diagnostic scheme for a multi-energy domain system that integrates a model-based strategy for system fault modeling and a data-driven approach for online anomaly monitoring. The developed scheme uses LFT (linear fractional transformations)-based bond graph for physical parameter uncertainty modeling and fault simulation, and employs AAKR (auto-associative kernel regression)-based empirical estimation followed by SPRT (sequential probability ratio test)-based threshold monitoring to improve the accuracy of fault detection. Moreover, pre- and post-denoising processes are applied to eliminate the cumulative influence of parameter uncertainty and measurement uncertainty. The scheme is demonstrated on the main unit of a locomotive electro-pneumatic brake in a simulated experiment. The results show robust fault detection and diagnostic performance.

  10. Modelling of Non-Linear Pilot Disinfection Water System: A Bond Graph Approach

    OpenAIRE

    Naoufel ZITOUNI; Ridha ANDOULSI; Anis SELAMI; Abdelkader MAMI; Hssen ABDENNASSEUR

    2012-01-01

    The ultraviolet (UV) irradiations are used to solve the bacteriological problem of the drinking water quality. A discharge-gas lamp is used to produce this type of irradiation. The UV lamp is fed by photovoltaic (PV) energy via electronic ballast composed by an inverter, a transformer and resonant circuit (RLC). The aim of this work is to give a useful global model of the system. In particular, we introduce the complicated UV lamp model and the water disinfection kinetics, where the radiant e...

  11. VALENCY AND SYNTACTICAL RELATION IN BIMANESS

    Directory of Open Access Journals (Sweden)

    Made Sri Satyawati

    2012-11-01

    Full Text Available This study presents the findings and descriptions of the replies to severalproblems that have not been completely and deeply discussed in the researchespreviously conducted on Bimanese. The problems are related to micro-linguistic factors,namely valency and syntactical relation in Bimanese. Both deductive and inductiveapproaches were applied to obtain satisfactory results. The main theory employed in thisstudy is Role and Reference Grammar Theory (RRG by Van Valin and J. Lapolla. It wasemployed to completely analyze the collected data in accordance with the problemsproposed in this research, and the inductive approach was employed to analyze the datain order to get novelties.In this study, clause structure is given the first priority to discuss, followed by thediscussion on operator, voice markers, nominalizers, and definiteness. Based on thepredicate category, the clause in Bimanese can be constructed with the constituents thatare under the categories of verb, noun, adjective, number, and adverb (prepositionalphrase. Based on the clause analysis, it has been found that in Bimanese there are severaloperators, each of which has different functional boundary in marking the clausemeaning. One operator may only sign nucleus, core (nucleus and argument, or core andperiphery. Bimanese has also been identified to have four linguistic states expressed byverbs that are made to make sense based on state (Aktisontrat, achievement, andaccomplishment. RRG classifies verbs into ten instead of four. However, in this study, tomake the analysis easier, verbs are classified into four. The predicate in Bimanese can beboth serial verbs and secondary verbs. It has also been found that the mechanism ofchange in valency is marked by the attachment of markers to the verbs resulting incausativity, applicativity, and resultivity. From those syntactical constructions, thesyntactical relation in Bimanese can be clearly identified. The discussion on syntacticalrelation

  12. Examination of Bond Properties through Infrared Spectroscopy and Molecular Modeling in the General Chemistry Laboratory

    Science.gov (United States)

    Csizmar, Clifford M.; Force, Dee Ann; Warner, Don L.

    2012-01-01

    A concerted effort has been made to increase the opportunities for undergraduate students to address scientific problems employing the processes used by practicing chemists. As part of this effort, an infrared (IR) spectroscopy and molecular modeling experiment was developed for the first-year general chemistry laboratory course. In the…

  13. Pricing Swaptions and Coupon Bond Options in Affine Term Structure Models

    NARCIS (Netherlands)

    Schrager, D.F.; Pelsser, A.A.J.

    2006-01-01

    We propose an approach to find an approximate price of a swaption in affine term structure models. Our approach is based on the derivation of approximate swap rate dynamics in which the volatility of the forward swap rate is itself an affine function of the factors. Hence, we remain in the affine

  14. Pricing swaptions and coupon bond options in affine term structure models

    NARCIS (Netherlands)

    Schrager, D.F.; Pelsser, A.A.J.

    2005-01-01

    We propose an approach to …nd an approximate price of a swaption in Affine Term Structure Models. Our approach is based on the derivation of approximate dynamics in which the volatility of the Forward Swap Rate is itself an affine function of the factors. Hence we remain in the Affine framework and

  15. Analytical model of asymmetrical Mixed-Mode Bending test of adhesively bonded GFRP joint

    Czech Academy of Sciences Publication Activity Database

    Ševčík, Martin; Hutař, Pavel; Vassilopoulos, Anastasios P.; Shahverdi, M.

    2015-01-01

    Roč. 9, č. 34 (2015), s. 237-246 ISSN 1971-8993 R&D Projects: GA MŠk(CZ) EE2.3.30.0063; GA ČR GA15-09347S Institutional support: RVO:68081723 Keywords : GFRP materials * Mixed-Mode bending * Fiber bridging * Analytical model Subject RIV: JL - Materials Fatigue, Friction Mechanics

  16. Of Caucasians, Asians, and Giraffes: The Influence of Categorization and Target Valence on Social Projection.

    Science.gov (United States)

    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. © 2015 by the Society for Personality and Social Psychology, Inc.

  17. Finite Element Modelling for Tensile Behaviour of Thermally Bonded Nonwoven Fabric

    Directory of Open Access Journals (Sweden)

    Gao Xiaoping

    2015-03-01

    Full Text Available A nonwoven fabric has been widely used in geotextile engineering in recent years; its tensile strength is an important behaviour. Since the fibre distributions in nonwoven fabrics are random and discontinuous, the unit-cell model of a nonwoven fabric cannot be developed to simulate its tensile behaviour. This article presents our research on using finite element method (FEM to study the tensile behaviour of a nonwoven fabric in macro-scale based on the classical laminate composite theory. The laminate orientation was considered with orientation distribution function of fibres, which has been obtained by analysing the data acquired from scanning electron microscopy with Hough Transform. The FE model of a nonwoven fabric was developed using ABAQUS software; the required engineering constants of a nonwoven fabric were obtained from experimental data. Finally, the nonwoven specimens were stretched along with machine direction and cross direction. The experimental stress-strain curves were compared with the results of FE simulations. The approximate agreement proves the validity of an FE model, which could be used to precisely simulate the stress relaxation, strain creep, bending and shear property of a nonwoven fabric.

  18. Diffusion bonding

    International Nuclear Information System (INIS)

    Anderson, R.C.

    1976-01-01

    A method is described for joining beryllium to beryllium by diffusion bonding. At least one surface portion of at least two beryllium pieces is coated with nickel. A coated surface portion is positioned in a contiguous relationship with another surface portion and subjected to an environment having an atmosphere at a pressure lower than ambient pressure. A force is applied on the beryllium pieces for causing the contiguous surface portions to abut against each other. The contiguous surface portions are heated to a maximum temperature less than the melting temperature of the beryllium, and the applied force is decreased while increasing the temperature after attaining a temperature substantially above room temperature. A portion of the applied force is maintained at a temperature corresponding to about maximum temperature for a duration sufficient to effect the diffusion bond between the contiguous surface portions

  19. An Iterated GMM Procedure for Estimating the Campbell-Cochrane Habit Formation Model, with an Application to Danish Stock and Bond Returns

    DEFF Research Database (Denmark)

    Engsted, Tom; Møller, Stig Vinther

    2010-01-01

    We suggest an iterated GMM approach to estimate and test the consumption based habit persistence model of Campbell and Cochrane, and we apply the approach on annual and quarterly Danish stock and bond returns. For comparative purposes we also estimate and test the standard constant relative risk...

  20. REMO: A new protocol to refine full atomic protein models from C-alpha traces by optimizing hydrogen-bonding networks.

    Science.gov (United States)

    Li, Yunqi; Zhang, Yang

    2009-08-15

    Protein structure prediction approaches usually perform modeling simulations based on reduced representation of protein structures. For biological utilizations, it is an important step to construct full atomic models from the reduced structure decoys. Most of the current full atomic model reconstruction procedures have defects which either could not completely remove the steric clashes among backbone atoms or generate final atomic models with worse topology similarity relative to the native structures than the reduced models. In this work, we develop a new protocol, called REMO, to generate full atomic protein models by optimizing the hydrogen-bonding network with basic fragments matched from a newly constructed backbone isomer library of solved protein structures. The algorithm is benchmarked on 230 nonhomologous proteins with reduced structure decoys generated by I-TASSER simulations. The results show that REMO has a significant ability to remove steric clashes, and meanwhile retains good topology of the reduced model. The hydrogen-bonding network of the final models is dramatically improved during the procedure. The REMO algorithm has been exploited in the recent CASP8 experiment which demonstrated significant improvements of the I-TASSER models in both atomic-level structural refinement and hydrogen-bonding network construction. 2009 Wiley-Liss, Inc.

  1. Bond-based linear indices of the non-stochastic and stochastic edge-adjacency matrix. 1. Theory and modeling of ChemPhys properties of organic molecules.

    Science.gov (United States)

    Marrero-Ponce, Yovani; Martínez-Albelo, Eugenio R; Casañola-Martín, Gerardo M; Castillo-Garit, Juan A; Echevería-Díaz, Yunaimy; Zaldivar, Vicente Romero; Tygat, Jan; Borges, José E Rodriguez; García-Domenech, Ramón; Torrens, Francisco; Pérez-Giménez, Facundo

    2010-11-01

    Novel bond-level molecular descriptors are proposed, based on linear maps similar to the ones defined in algebra theory. The kth edge-adjacency matrix (E(k)) denotes the matrix of bond linear indices (non-stochastic) with regard to canonical basis set. The kth stochastic edge-adjacency matrix, ES(k), is here proposed as a new molecular representation easily calculated from E(k). Then, the kth stochastic bond linear indices are calculated using ES(k) as operators of linear transformations. In both cases, the bond-type formalism is developed. The kth non-stochastic and stochastic total linear indices are calculated by adding the kth non-stochastic and stochastic bond linear indices, respectively, of all bonds in molecule. First, the new bond-based molecular descriptors (MDs) are tested for suitability, for the QSPRs, by analyzing regressions of novel indices for selected physicochemical properties of octane isomers (first round). General performance of the new descriptors in this QSPR studies is evaluated with regard to the well-known sets of 2D/3D MDs. From the analysis, we can conclude that the non-stochastic and stochastic bond-based linear indices have an overall good modeling capability proving their usefulness in QSPR studies. Later, the novel bond-level MDs are also used for the description and prediction of the boiling point of 28 alkyl-alcohols (second round), and to the modeling of the specific rate constant (log k), partition coefficient (log P), as well as the antibacterial activity of 34 derivatives of 2-furylethylenes (third round). The comparison with other approaches (edge- and vertices-based connectivity indices, total and local spectral moments, and quantum chemical descriptors as well as E-state/biomolecular encounter parameters) exposes a good behavior of our method in this QSPR studies. Finally, the approach described in this study appears to be a very promising structural invariant, useful not only for QSPR studies but also for similarity

  2. Plant G-Proteins Come of Age: Breaking the Bond with Animal Models.

    Science.gov (United States)

    Trusov, Yuri; Botella, José R

    2016-01-01

    G-proteins are universal signal transducers mediating many cellular responses. Plant G-protein signaling has been modeled on the well-established animal paradigm but accumulated experimental evidence indicates that G-protein-dependent signaling in plants has taken a very different evolutionary path. Here we review the differences between plant and animal G-proteins reported over past two decades. Most importantly, while in animal systems the G-protein signaling cycle is activated by seven transmembrane-spanning G-protein coupled receptors, the existence of these type of receptors in plants is highly controversial. Instead plant G-proteins have been proven to be functionally associated with atypical receptors such as the Arabidopsis RGS1 and a number of receptor-like kinases. We propose that, instead of the GTP/GDP cycle used in animals, plant G-proteins are activated/de-activated by phosphorylation/de-phosphorylation. We discuss the need of a fresh new look at these signaling molecules and provide a hypothetical model that departs from the accepted animal paradigm.

  3. Principle and modelling of Transient Current Technique for interface traps characterization in monolithic pixel detectors obtained by CMOS-compatible wafer bonding

    CERN Document Server

    Bronuzzi, J.; Moll, M.; Sallese, J.M.

    2016-01-01

    In the framework of monolithic silicon radiation detectors, a fabrication process based on a recently developed silicon wafer bonding technique at low temperature was proposed. Ideally, this new process would enable direct bonding of a read-out electronic chip wafer on a highly resistive silicon substrate wafer, which is expected to present many advantages since it would combine high performance IC's with high sensitive ultra-low doped bulk silicon detectors. But electrical properties of the bonded interface are critical for this kind of application since the mobile charges generated by radiation inside the bonded bulk are expected to transit through the interface in order to be collected by the read-out electronics. In this work, we propose to explore and develop a model for the so-called Transient Current Technique (TCT) to identify the presence of deep traps at the bonded interface. For this purpose, we consider a simple PIN diode reversely biased where the ultra-low doped active region of interest is set ...

  4. Valence, magnetism and conduction in the intermediate valence compounds: the case SmB6

    International Nuclear Information System (INIS)

    Derr, J.

    2006-09-01

    In some rare earth based compounds, the 4f level is situated so close to the Fermi level that the valence of the compound can become intermediate between two integer values. The so called 'intermediate valence' compound of Samarium hexaboride (SmB 6 ) is one typical example of the exciting physics which can result from this quantum equilibrium between two valence configurations. The first configuration (Sm 2+ ) corresponds to an insulating and non magnetic state whereas the second one (Sm 3+ ) would theoretically give a magnetic and metallic ground state. This dissertation deals with the influence of pressure on this equilibrium. Specific heat measurements under pressure evidenced a new long range magnetic ordering for pressures higher than p c ∼ 10 GPa. On another hand, transport measurements measured for the first time in good conditions of hydrostatics found a reliable and reproducible critical pressure for the insulator to metal transition equal to p c . The phase diagram of SmB 6 is now well known and the observation for the first time of a magnetic anomaly in the high pressure resistivity curves certifies that the onset of the magnetic phase really coincide with the closure of the gap. This change at the critical pressure p c is discussed in a general frame taking into account the Kondo lattice temperature as a key parameter for the renormalization of the wavefunction from one integer configuration to the other whereas the valence itself is still intermediate. This general idea seems to be valid also for other systems studied in this dissertation like SmS or TmSe and could even be valid for more general cases (Ytterbium, Cerium). In the same time, resistivity measurements under uniaxial stress were undertaken. The result is a strong anisotropy effect observed on the pressure dependence of the residual resistivity in the compound SmB 6 . The comparison with the transport under hydrostatic conditions enables us to consider a new idea for the nature of the gap

  5. A simplified indirect bonding technique

    Directory of Open Access Journals (Sweden)

    Radha Katiyar

    2014-01-01

    Full Text Available With the advent of lingual orthodontics, indirect bonding technique has become an integral part of practice. It involves placement of brackets initially on the models and then their transfer to teeth with the help of transfer trays. Problems encountered with current indirect bonding techniques used are (1 the possibility of adhesive flash remaining around the base of the brackets which requires removal (2 longer time required for the adhesive to gain enough bond strength for secure tray removal. The new simplified indirect bonding technique presented here overcomes both these problems.

  6. Multireference Configuration Interaction Methods – An Application to the Valence Isomerism in Cyclobutadieno-p-benzoquinone and its Diprotonated Form

    Directory of Open Access Journals (Sweden)

    Mario Vazdar

    2015-12-01

    Full Text Available Multireference averaged quadratic coupled cluster (MR-AQCC calculations for cyclobutadieno-p-benzoquinone indicate that valence bond isomers 1a and 1b can exist as distinct species. The energy barrier height for their interconversion are 4.6 and 4.5 kcal mol−1, respectively, what is by ca. 2 kcal mol−1 lower than in the parent cyclobutadiene, implying that they could perhaps exist only under extreme conditions, namely at very low temperatures. For double protonated cyclobutadieno-p-benzoquinone, the CASSCF calculations erroneously predict existence of two valence isomers, 2a and 2b, whereas the MR-AQCC calculations reveal that geometry of the double protonated species could be best described by structure 2b. This nicely illustrates the crucial role of dynamic correlation and the need for using a highly-correlated theoretical method including geometry optimization in studied molecules.

  7. Modeling and Measurement of Sustained Loading and Temperature-Dependent Deformation of Carbon Fiber-Reinforced Polymer Bonded to Concrete

    Science.gov (United States)

    Jeong, Yoseok; Lee, Jaeha; Kim, WooSeok

    2015-01-01

    This paper aims at presenting the effects of short-term sustained load and temperature on time-dependent deformation of carbon fiber-reinforced polymer (CFRP) bonded to concrete and pull-off strength at room temperature after the sustained loading period. The approach involves experimental and numerical analysis. Single-lap shear specimens were used to evaluate temperature and short-term sustained loading effects on time-dependent behavior under sustained loading and debonding behavior under pull-off loading after a sustained loading period. The numerical model was parameterized with experiments on the concrete, FRP, and epoxy. Good correlation was seen between the numerical results and single-lap shear experiments. Sensitivity studies shed light on the influence of temperature, epoxy modulus, and epoxy thickness on the redistribution of interfacial shear stress during sustained loading. This investigation confirms the hypothesis that interfacial stress redistribution can occur due to sustained load and elevated temperature and its effect can be significant. PMID:28787948

  8. Modeling and Measurement of Sustained Loading and Temperature-Dependent Deformation of Carbon Fiber-Reinforced Polymer Bonded to Concrete

    Directory of Open Access Journals (Sweden)

    Yoseok Jeong

    2015-01-01

    Full Text Available This paper aims at presenting the effects of short-term sustained load and temperature on time-dependent deformation of carbon fiber-reinforced polymer (CFRP bonded to concrete and pull-off strength at room temperature after the sustained loading period. The approach involves experimental and numerical analysis. Single-lap shear specimens were used to evaluate temperature and short-term sustained loading effects on time-dependent behavior under sustained loading and debonding behavior under pull-off loading after a sustained loading period. The numerical model was parameterized with experiments on the concrete, FRP, and epoxy. Good correlation was seen between the numerical results and single-lap shear experiments. Sensitivity studies shed light on the influence of temperature, epoxy modulus, and epoxy thickness on the redistribution of interfacial shear stress during sustained loading. This investigation confirms the hypothesis that interfacial stress redistribution can occur due to sustained load and elevated temperature and its effect can be significant.

  9. Positive valence music restores executive control over sustained attention

    OpenAIRE

    Baldwin, Carryl L.; Lewis, Bridget A.

    2017-01-01

    Music sometimes improves performance in sustained attention tasks. But the type of music employed in previous investigations has varied considerably, which can account for equivocal results. Progress has been hampered by lack of a systematic database of music varying in key characteristics like tempo and valence. The aims of this study were to establish a database of popular music varying along the dimensions of tempo and valence and to examine the impact of music varying along these dimensio...

  10. Modulation of motor-meaning congruity effects for valenced words

    OpenAIRE

    Brookshire, Geoffrey; Ivry, Richard; Casasanto, Daniel

    2010-01-01

    We investigated the extent to which emotionally valenced words automatically cue spatio-motor representations. Participants made speeded button presses, moving their hand upward or downward while viewing words with positive or negative valence. Only the color of the words was relevant to the response; on target trials, there was no requirement to read the words or process their meaning. In Experiment 1, upward responses were faster for positive words, and downward for negative words. This eff...

  11. Effect of valence nucleons on nuclear binding energy

    Energy Technology Data Exchange (ETDEWEB)

    Angeli, I. (Kossuth Lajos Tudomanyegyetem, Debrecen (HU))

    1991-10-01

    The nucleonic promiscuity factor P = N{sub p}N{sub n}/(N{sub p} + N{sub n}), where N{sub p}(N{sub n}) is the number of valence protons (neutrons) or holes, is shown to be a useful parameter in the description of the mass number dependence of nuclear binding energies. This means that most of the deviation from a smooth mass number dependence is caused by the isoscalar interaction between valence protons and neutrons.

  12. Bond between smooth prestressing wires and concrete : finite element model and transfer length analysis for pretensioned concrete crossties.

    Science.gov (United States)

    2014-04-03

    Pretensioned concrete ties are increasingly employed in railroad high speed : and heavy haul applications. The bond between prestressing wires or strands and : concrete plays an important role in determining the transfer length of pretensioned : conc...

  13. Modeling customer-supplier relationships by the concept of bonding: Evidence from eight different product/service markets

    DEFF Research Database (Denmark)

    Grunert, Klaus G.; Hansen, Søren Sten; Wandorf, Charlotte

    Feeling, functional, form and financial bonds are introduced as a conceptual tool to analyse relationship quality, and are operationalized as second order factors emerging from an analysis of transaction characteristics evaluated in terms of both importance and supplier proficiency. Analysis...

  14. Emotional valence and the free-energy principle.

    Directory of Open Access Journals (Sweden)

    Mateus Joffily

    Full Text Available 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.

  15. The relationship between local density and bond-orientational order during crystallization of the Gaussian core model.

    Science.gov (United States)

    Li, Yan-Wei; Sun, Zhao-Yan

    2016-02-21

    Whether nucleation is triggered by density or by bond-orientational order is one of the most hotly debated issues in recent investigations of the crystallization process. Here, we present a numerical study of the relationship between them for soft particles within the isothermal-isobaric ensemble. We compress the system and thus obtain the fluid-solid transition. By investigating locally dense-packed particles and particles with a relatively high bond-orientational order in the compressing process, we find a sharp increase of the spatial correlations for both densely packed particles and highly bond-orientational ordered particles at the phase transition point, which provide new characterization methods for the liquid-crystal transition. We also find that it is the bond-orientational order rather than density that triggers the nucleation process. The relationship between the local density and the bond-orientational order parameter is strongly affected by the characterization methods used. The local bond order parameter (q6) shows clear correlation with the local density (ρ) in the fluid stage, while the coarse-grained form (q[combining macron]6) does not correlate with ρ at all, owing to the comparable spatial scales of q6 and ρ. Nevertheless, q[combining macron]6 shows an obvious advantage in distinguishing between solid and liquid particles in our work. These results may elevate our understanding of the mechanism of the crystallization process.

  16. Cooperativity in Surface Bonding and Hydrogen Bonding of Water and Hydroxyl at Metal Surfaces

    DEFF Research Database (Denmark)

    Schiros, T.; Ogasawara, H.; Naslund, L. A.

    2010-01-01

    of the mixed phase at metal surfaces. The surface bonding can be considered to be similar to accepting a hydrogen bond, and we can thereby apply general cooperativity rules developed for hydrogen-bonded systems. This provides a simple understanding of why water molecules become more strongly bonded...... to the surface upon hydrogen bonding to OH and why the OH surface bonding is instead weakened through hydrogen bonding to water. We extend the application of this simple model to other observed cooperativity effects for pure water adsorption systems and H3O+ on metal surfaces.......We examine the balance of surface bonding and hydrogen bonding in the mixed OH + H2O overlayer on Pt(111), Cu(111), and Cu(110) via density functional theory calculations. We find that there is a cooperativity effect between surface bonding and hydrogen bonding that underlies the stability...

  17. Does fluorine participate in halogen bonding?

    Science.gov (United States)

    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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Valence Topological Charge-Transfer Indices for Dipole Moments

    Directory of Open Access Journals (Sweden)

    Francisco Torrens

    2003-01-01

    Full Text Available New valence topological charge-transfer indices are applied to the calculation of dipole moments. The algebraic and vector semisum charge-transfer indices are defined. The combination of the charge-transfer indices allows the estimation of the dipole moments. The model is generalized for molecules with heteroatoms. The ability of the indices for the description of the molecular charge distribution is established by comparing them with the dipole moments of a homologous series of phenyl alcohols. Linear and non-linear correlation models are obtained. The new charge-transfer indices improve the multivariable non-linear regression equations for the dipole moment. When comparing with previous results, the variance decreases 92%. No superposition of the corresponding Gk–Jk and GkV – JkV pairs is observed. This diminishes the risk of co-linearity. Inclusion of the oxygen atom in the p-electron system is beneficial for the description of the dipole moment, owing to either the role of the additional p orbitals provided by the heteroatom or the role of steric factors in the p-electron conjugation. Linear and non-linear correlations between the fractal dimension and various descriptors point not only to a homogeneous molecular structure but also to the ability to predict and tailor drug properties.

  19. Bond-order wave phase of the extended Hubbard model: Electronic solitons, paramagnetism, and coupling to Peierls and Holstein phonons

    Science.gov (United States)

    Kumar, Manoranjan; Soos, Zoltán G.

    2010-10-01

    The bond-order wave (BOW) phase of the extended Hubbard model (EHM) in one dimension (1D) is characterized at intermediate correlation U=4t by exact treatment of N -site systems. Linear coupling to lattice (Peierls) phonons and molecular (Holstein) vibrations are treated in the adiabatic approximation. The molar magnetic susceptibility χM(T) is obtained directly up to N=10 . The goal is to find the consequences of a doubly degenerate ground state (gs) and finite magnetic gap Em in a regular array. Degenerate gs with broken inversion symmetry are constructed for finite N for a range of V near the charge-density-wave boundary at V≈2.18t where Em≈0.5t is large. The electronic amplitude B(V) of the BOW in the regular array is shown to mimic a tight-binding band with small effective dimerization δeff . Electronic spin and charge solitons are elementary excitations of the BOW phase and also resemble topological solitons with small δeff . Strong infrared intensity of coupled molecular vibrations in dimerized 1D systems is shown to extend to the regular BOW phase while its temperature dependence is related to spin solitons. The Peierls instability to dimerization has novel aspects for degenerate gs and substantial Em that suppresses thermal excitations. Finite Em implies exponentially small χM(T) at low temperature followed by an almost linear increase with T . The EHM with U=4t is representative of intermediate correlations in quasi-1D systems such as conjugated polymers or organic ion-radical and charge-transfer salts. The vibronic and thermal properties of correlated models with BOW phases are needed to identify possible physical realizations.

  20. Valence and non-valence quark distribution function of hadrons in the val on model

    International Nuclear Information System (INIS)

    Khorramian, A.N.; Arash, F.

    2000-01-01

    We calculate the par tonic structure of constitute quark in the next-to-leading order. The structure of any hadron can be obtained thereafter using a convolution method. Such a procedure is used to generate the structure function of proton and pion in Next- to- leading order

  1. Self-assembly and glass-formation in a lattice model of telechelic polymer melts: Influence of stiffness of the sticky bonds

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Wen-Sheng, E-mail: wsxu@uchicago.edu [James Franck Institute, The University of Chicago, Chicago, Illinois 60637 (United States); Freed, Karl F., E-mail: freed@uchicago.edu [James Franck Institute, The University of Chicago, Chicago, Illinois 60637 (United States); Department of Chemistry, The University of Chicago, Chicago, Illinois 60637 (United States)

    2016-06-07

    Telechelic polymers are chain macromolecules that may self-assemble through the association of their two mono-functional end groups (called “stickers”). A deep understanding of the relation between microscopic molecular details and the macroscopic physical properties of telechelic polymers is important in guiding the rational design of telechelic polymer materials with desired properties. The lattice cluster theory (LCT) for strongly interacting, self-assembling telechelic polymers provides a theoretical tool that enables establishing the connections between important microscopic molecular details of self-assembling polymers and their bulk thermodynamics. The original LCT for self-assembly of telechelic polymers considers a model of fully flexible linear chains [J. Dudowicz and K. F. Freed, J. Chem. Phys. 136, 064902 (2012)], while our recent work introduces a significant improvement to the LCT by including a description of chain semiflexibility for the bonds within each individual telechelic chain [W.-S. Xu and K. F. Freed, J. Chem. Phys. 143, 024901 (2015)], but the physically associative (or called “sticky”) bonds between the ends of the telechelics are left as fully flexible. Motivated by the ubiquitous presence of steric constraints on the association of real telechelic polymers that impart an additional degree of bond stiffness (or rigidity), the present paper further extends the LCT to permit the sticky bonds to be semiflexible but to have a stiffness differing from that within each telechelic chain. An analytical expression for the Helmholtz free energy is provided for this model of linear telechelic polymer melts, and illustrative calculations demonstrate the significant influence of the stiffness of the sticky bonds on the self-assembly and thermodynamics of telechelic polymers. A brief discussion is also provided for the impact of self-assembly on glass-formation by combining the LCT description for this extended model of telechelic polymers with

  2. Self-assembly and glass-formation in a lattice model of telechelic polymer melts: Influence of stiffness of the sticky bonds

    International Nuclear Information System (INIS)

    Xu, Wen-Sheng; Freed, Karl F.

    2016-01-01

    Telechelic polymers are chain macromolecules that may self-assemble through the association of their two mono-functional end groups (called “stickers”). A deep understanding of the relation between microscopic molecular details and the macroscopic physical properties of telechelic polymers is important in guiding the rational design of telechelic polymer materials with desired properties. The lattice cluster theory (LCT) for strongly interacting, self-assembling telechelic polymers provides a theoretical tool that enables establishing the connections between important microscopic molecular details of self-assembling polymers and their bulk thermodynamics. The original LCT for self-assembly of telechelic polymers considers a model of fully flexible linear chains [J. Dudowicz and K. F. Freed, J. Chem. Phys. 136, 064902 (2012)], while our recent work introduces a significant improvement to the LCT by including a description of chain semiflexibility for the bonds within each individual telechelic chain [W.-S. Xu and K. F. Freed, J. Chem. Phys. 143, 024901 (2015)], but the physically associative (or called “sticky”) bonds between the ends of the telechelics are left as fully flexible. Motivated by the ubiquitous presence of steric constraints on the association of real telechelic polymers that impart an additional degree of bond stiffness (or rigidity), the present paper further extends the LCT to permit the sticky bonds to be semiflexible but to have a stiffness differing from that within each telechelic chain. An analytical expression for the Helmholtz free energy is provided for this model of linear telechelic polymer melts, and illustrative calculations demonstrate the significant influence of the stiffness of the sticky bonds on the self-assembly and thermodynamics of telechelic polymers. A brief discussion is also provided for the impact of self-assembly on glass-formation by combining the LCT description for this extended model of telechelic polymers with

  3. Study of the cross-market effects of Brexit based on the improved symbolic transfer entropy GARCH model-An empirical analysis of stock-bond correlations.

    Science.gov (United States)

    Chen, Xiurong; Tian, Yixiang; Zhao, Rubo

    2017-01-01

    In this paper, we study the cross-market effects of Brexit on the stock and bond markets of nine major countries in the world. By incorporating information theory, we introduce the time-varying impact weights based on symbolic transfer entropy to improve the traditional GARCH model. The empirical results show that under the influence of Brexit, flight-to-quality not only commonly occurs between the stocks and bonds of each country but also simultaneously occurs among different countries. We also find that the accuracy of the time-varying symbolic transfer entropy GARCH model proposed in this paper has been improved compared to the traditional GARCH model, which indicates that it has a certain practical application value.

  4. Study of the cross-market effects of Brexit based on the improved symbolic transfer entropy GARCH model-An empirical analysis of stock-bond correlations.

    Directory of Open Access Journals (Sweden)

    Xiurong Chen

    Full Text Available In this paper, we study the cross-market effects of Brexit on the stock and bond markets of nine major countries in the world. By incorporating information theory, we introduce the time-varying impact weights based on symbolic transfer entropy to improve the traditional GARCH model. The empirical results show that under the influence of Brexit, flight-to-quality not only commonly occurs between the stocks and bonds of each country but also simultaneously occurs among different countries. We also find that the accuracy of the time-varying symbolic transfer entropy GARCH model proposed in this paper has been improved compared to the traditional GARCH model, which indicates that it has a certain practical application value.

  5. Reassessing Spin-Coupled (Full Generalized Valence Bond) Descriptions of Ozone Using Three-Center Bond Indices.

    Czech Academy of Sciences Publication Activity Database

    Cooper, D.L.; Penotti, F.E.; Ponec, Robert

    2017-01-01

    Roč. 1116, Sl (2017), s. 40-49 ISSN 2210-271X Institutional support: RVO:67985858 Keywords : full GVB and spin-coupled * PI-system in O3 * domain-averaged fermi holes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.549, year: 2016

  6. Reassessing Spin-Coupled (Full Generalized Valence Bond) Descriptions of Ozone Using Three-Center Bond Indices.

    Czech Academy of Sciences Publication Activity Database

    Cooper, D.L.; Penotti, F.E.; Ponec, Robert

    2017-01-01

    Roč. 1116, Sl (2017), s. 40-49 ISSN 2210-271X Institutional support: RVO:67985858 Keywords : full GVB and spin-coupled * PI-system in O3 * domain-averaged fermi holes Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 1.549, year: 2016

  7. Valence effects on adsorption: a preliminary assessment of the effects on valence state control on sorption measurements

    International Nuclear Information System (INIS)

    Meyer, R.E.; Arnold, W.D.; Case, F.; Shiao, S.Y.; Palmer, D.A.

    1983-01-01

    Electrochemical arguments are advanced to illustrate that what is usually measured in practice is a mixed potential determined by the kinetics of the electrode processes occurring at the indicator electrode. Valence states can be altered electrochemically or by use of added chemical reagents, including redox couples which can hold the potential to relatively specific potentials. The disadvantage of added chemical reagents is that they may alter the characteristics of the sorption reactions by interaction with the sorbent. Electrochemical methods are versatile and do not add reagents, but in some caes the nuclide can adsorb on the electrode itself. A description is given of the application of the electrochemical method of valence control to determination of sorption of Np(V) on alumina. Valence state control and analysis can be used to study possible redox reactions on materials which might be used as backfill materials. A description is given of survey experiments with a number of sulfides and iron-containing materials. Valence state analysis is used on the initial solutions and leachate from acid leaches of the sorbent after the sorption experiment to help determine whether valence state change is occurring. The preliminary results indicate that on the sulfides tested, sorption occurs both with and without valence state change

  8. Bonding in phase change materials: concepts and misconceptions.

    Science.gov (United States)

    Jones, R O

    2018-04-18

    Bonding concepts originating in chemistry are surveyed from a condensed matter perspective, beginning around 1850 with 'valence' and the word 'bond' itself. The analysis of chemical data in the 19th century resulted in astonishing progress in understanding the connectivity and stereochemistry of molecules, almost without input from physicists until the development of quantum mechanics in 1925 and afterwards. The valence bond method popularized by Pauling and the molecular orbital methods of Hund, Mulliken, Bloch, and Hückel play major roles in the subsequent development, as does the central part played by the kinetic energy in covalent bonding (Ruedenberg and others). 'Metallic' (free electron) and related approaches, including pseudopotential and density functional theories, have been remarkably successful in understanding structures and bonding in molecules and solids. We discuss these concepts in the context of phase change materials, which involve the rapid and reversible transition between amorphous and crystalline states, and note the confusion that some have caused, in particular 'resonance' and 'resonant bonding'.

  9. Pressure-Induced Intermetallic Valence Transition in BiNiO3

    Science.gov (United States)

    Azuma, Masaki; Tsujimoto, Masahiko; Ishiwata, Shintaro; Isoda, Seiji; Shimakawa, Yuichi; Takano, Mikio; Carlsson, Sandra; Rodgers, Jennifer; Attfield, J. Paul; Tucker, Matthew G.

    2008-03-01

    The valence state change of BiNiO3 perovskite under pressure has been investigated by a powder neutron diffraction study and electronic state calculations. At ambient pressure, BiNiO3 has the unusual charge distribution Bi^3+0.5Bi^5+0.5Ni^2+O3 with ordering of Bi^3+ and Bi^5+ charges on the A sites of a highly distorted perovskite structure. High pressure neutron diffraction measurements and Bond valence sum calculations show that the pressure-induced melting of the charge disproportionated state leads to a simultaneous charge transfer from Ni to Bi, so that the high pressure phase is metallic Bi^3+Ni^3+O3. This unprecedented charge transfer between A and B site cations coupled to electronic instabilities at both sites leads to a variety of ground states, and it is predicted that a Ni-charge disproportionated state should also be observable. [1] M. Azuma et al., J. Am. Chem. Soc., 129, (2007) 14433.

  10. Oxygen Evolution at Manganite Perovskite Ruddlesden-Popper Type Particles: Trends of Activity on Structure, Valence and Covalence

    Directory of Open Access Journals (Sweden)

    Majid Ebrahimizadeh Abrishami

    2016-11-01

    Full Text Available An improved understanding of the correlation between the electronic properties of Mn-O bonds, activity and stability of electro-catalysts for the oxygen evolution reaction (OER is of great importance for an improved catalyst design. Here, an in-depth study of the relation between lattice structure, electronic properties and catalyst performance of the perovskite Ca1−xPrxMnO3 and the first-order RP-system Ca2−xPrxMnO4 at doping levels of x = 0, 0.25 and 0.5 is presented. Lattice structure is determined by X-ray powder diffraction and Rietveld refinement. X-ray absorption spectroscopy of Mn-L and O-K edges gives access to Mn valence and covalency of the Mn-O bond. Oxygen evolution activity and stability is measured by rotating ring disc electrode studies. We demonstrate that the highest activity and stability coincidences for systems with a Mn-valence state of +3.7, though also requiring that the covalency of the Mn-O bond has a relative minimum. This observation points to an oxygen evolution mechanism with high redox activity of Mn. Covalency should be large enough for facile electron transfer from adsorbed oxygen species to the MnO6 network; however, it should not be hampered by oxidation of the lattice oxygen, which might cause a crossover to material degradation. Since valence and covalency changes are not entirely independent, the introduction of the energy position of the eg↑ pre-edge peak in the O-K spectra as a new descriptor for oxygen evolution is suggested, leading to a volcano-like representation of the OER activity.

  11. Application of Meta-Heuristic Hybrid Artificial Intelligence Techniques for Modeling of Bonding Strength of Plywood Panels

    Directory of Open Access Journals (Sweden)

    Cenk Demirkır

    2014-04-01

    Full Text Available Plywood, which is one of the most important wood based panels, has many usage areas changing from traffic signs to building constructions in many countries. It is known that the high quality plywood panel manufacturing has been achieved with a good bonding under the optimum pressure conditions depending on adhesive type. This is a study of determining the using possibilities of modern meta-heuristic hybrid artificial intelligence techniques such as IKE and AANN methods for prediction of bonding strength of plywood panels. This study has composed of two main parts as experimental and analytical. Scots pine, maritime pine and European black pine logs were used as wood species. The pine veneers peeled at 32°C and 50°C were dried at 110°C, 140°C and 160°C temperatures. Phenol formaldehyde and melamine urea formaldehyde resins were used as adhesive types. EN 314-1 standard was used to determine the bonding shear strength values of plywood panels in experimental part of this study. Then the intuitive k-nearest neighbor estimator (IKE and adaptive artificial neural network (AANN were used to estimate bonding strength of plywood panels. The best estimation performance was obtained from MA metric for k-value=10. The most effective factor on bonding strength was determined as adhesive type. Error rates were determined less than 5% for both of the IKE and AANN. It may be recommended that proposed methods could be used in applying to estimation of bonding strength values of plywood panels.

  12. Structure, magnetism, and theoretical study of a mixed-valence Co(II)3Co(III)4 heptanuclear wheel: lack of SMM behavior despite negative magnetic anisotropy.

    Science.gov (United States)

    Chibotaru, Liviu F; Ungur, Liviu; Aronica, Christophe; Elmoll, Hani; Pilet, Guillaume; Luneau, Dominique

    2008-09-17

    A mixed-valence Co(II)/Co(III) heptanuclear wheel [Co(II)3Co(III)4(L)6(MeO)6] (LH2 = 1,1,1-trifluoro-7-hydroxy-4-methyl-5-aza-hept-3-en-2-one) has been synthesized and its crystal structure determined using single-crystal X-ray diffraction. The valence state of each cobalt ion was established by bond valence sum calculations. Studies of the temperature dependence of the magnetic susceptibility and the field dependence of the magnetization evidence ferromagnetic interactions within the compound. In order to understand the magnetic properties of this Co7 wheel, we performed ab initio calculations for each cobalt fragment at the CASSCF/CASPT2 level, including spin-orbit coupling effects within the SO-RASSI approach. The four Co(III) ions were found to be diamagnetic and to give a significant temperature-independent paramagnetic contribution to the susceptibility. The spin-orbit coupling on the three Co(II) sites leads to separations of approximately 200 cm(-1) between the ground and excited Kramers doublets, placing the Co7 wheel into a weak-exchange limit in which the lowest electronic states are adequately described by the anisotropic exchange interaction between the lowest Kramers doublets on Co(II) sites. Simulation of the exchange interaction was done within the Lines model, keeping the fully ab initio treatment of magnetic anisotropy effects on individual cobalt fragments using a recently developed methodology. A good description of the susceptibility and magnetization was obtained for nearest-neighbor (J1) and next-nearest-neighbor (J2) exchange parameters (1.5 and 5.5 cm(-1), respectively). The strong ferromagnetic interaction between distant cobalt ions arises as a result of low electron-promotion energies in the exchange bridges containing Co(III) ions. The calculations showed a large value of the magnetization along the main magnetic axis (10.1 mu(B)), which is a combined effect of the ferromagnetic exchange interaction and negative magnetic anisotropy on

  13. Space-Valence Priming with Subliminal and Supraliminal Words

    Directory of Open Access Journals (Sweden)

    Ulrich eAnsorge

    2013-02-01

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

  14. Effects of valence and divided attention on cognitive reappraisal processes.

    Science.gov (United States)

    Morris, John A; Leclerc, Christina M; Kensinger, Elizabeth A

    2014-12-01

    Numerous studies have investigated the neural substrates supporting cognitive reappraisal, identifying the importance of cognitive control processes implemented by prefrontal cortex (PFC). This study examined how valence and attention affect the processes used for cognitive reappraisal by asking participants to passively view or to cognitively reappraise positive and negative images with full or divided attention. When participants simply viewed these images, results revealed few effects of valence or attention. However, when participants engaged in reappraisal, there was a robust effect of valence, with the reappraisal of negative relative to positive images associated with more widespread activation, including within regions of medial and lateral PFC. There also was an effect of attention, with more lateral PFC recruitment when regulating with full attention and more medial PFC recruitment when regulating with divided attention. Within two regions of medial PFC and one region of ventrolateral PFC, there was an interaction between valence and attention: in these regions, divided attention reduced activity during reappraisal of positive but not negative images. Critically, participants continued to report reappraisal success even during the Divided Attention condition. These results suggest multiple routes to successful cognitive reappraisal, depending upon image valence and the availability of attentional resources. © The Author (2014). Published by Oxford University Press. For Permissions, please email: journals.permissions@oup.com.

  15. Chemical Bonding and Molecular Geometry: from Lewis to Electron Densities. Ronald J. Gillespie, Paul L.A. Popelier (Eds.); Oxford University Press, Oxford, 2001, xiii+268 pages, ISBN 01951049-X, US$ 39.50

    Science.gov (United States)

    Silvi, B.

    2002-06-01

    This small book will certainly be one of the reference textbooks on the bonding theory of the next decade. The presentation of the different models used to describe and explain the chemical bond is made in both an epistemological and historical perspective in the first five chapters. The authors clearly show the importance of the Pauli principle as the explicative key of the chemical bonding. The respective merits and limitations of the Lewis model, of the orbital picture, of the valence shell electron pair (VSEPR) and ligand close-packing model are emphasised and illustrated by examples belonging to Inorganic Chemistry. The remaining three chapters contain an elegant presentation of the 'Atoms in Molecules' theory which provides a rigorous description of the bonding on the ground of the topological analysis of the electron density distribution. The introduction of the necessary mathematical definitions is made in a very simple and pedagogical fashion, which avoids unnecessary specialised jargon. The information extracted by the AIM analysis is then used to investigate the bonding in molecules belonging to periods 2-6. It is necessary to have read this book before teaching anything on the Chemical Bonding Theory. Its presence in the library is indispensable.

  16. Environmentally dependent bond-order potentials: New ...

    Indian Academy of Sciences (India)

    Environmentally dependent bond-order potentials: New developments and applications ... for modelling amorphous structure we found that the and bond integrals are not only transferable between graphite and diamond structures but they are also strongly anisotropic due to inter-plan bonding between graphite sheets.

  17. Numerical approach of the bond stress behavior of steel bars embedded in self-compacting concrete and in ordinary concrete using beam models

    Directory of Open Access Journals (Sweden)

    F.M. Almeida Filho

    Full Text Available The present study evaluates the bond behavior between steel bars and concrete by means of a numerical analysis based on Finite Element Method. Results of a previously conducted experimental program on reinforced concrete beams subjected to monotonic loading are also presented. Two concrete types, self-compacting concrete and ordinary concrete, were considered in the study. Non-linear constitutive relations were used to represent concrete and steel in the proposed numerical model, aiming to reproduce the bond behavior observed in the tests. Experimental analysis showed similar results for the bond resistances of self-compacting and ordinary concrete, with self-compacting concrete presenting a better performance in some cases. The results given by the numerical modeling showed a good agreement with the tests for both types of concrete, especially in the pre-peak branch of the load vs. slip and load vs. displacement curves. As a consequence, the proposed numerical model could be used to estimate a reliable development length, allowing a possible reduction of the structure costs.

  18. Bond-versus-site doping models for off-chain-doped Haldane-gap system Y2BaNiO5

    International Nuclear Information System (INIS)

    Lou Jizhong; Qin Shaojin; Su Zhaobin; Yu Lu

    1998-09-01

    Using the density matrix renormalization-group technique, we calculate the impurity energy levels for two different effective models of off-chain doping for quasi-one-dimensional Heisenberg chain compound Y 2 BaNiO 5 : ferromagnetic bond doping and antiferromagnetic site spin-1/2 doping. Thresholds of the impurity strength for the appearance of localized states are found for both models. However, the ground-state and low-energy excitations for weak impurity strength are different for these two models and the difference can be detected by experiments. (author)

  19. Relation between plasmons and the valence-band density-of-states in polymethylmethacrylate - influence of ion irradiation on damage selectivity

    International Nuclear Information System (INIS)

    Moliton, J.P.; Jussiaux, C.; Trigaud, T.; Lazzaroni, R.; Lhost, O.; Bredas, J.L.; Kihn, Y.; Sevely, J.

    1996-01-01

    A physical model is presented that aims at rationalizing the selectivity of bond breakage observed when polymethylmethacrylate is irradiated by ions in the 10-500 keV energy range. This model, previously proposed by Brandt and Ritchie, is based on electronic collective effects. The coupling between the pure plasma oscillation at omega(p) and the oscillation of free electrons at [omega(k0)(2)](1/2) makes the whole electronic population resonant at the frequency omega(rp) = (omega(p)(2) + [omega(k0)(2)])(1/2). By computing the valence-band density of states, we calculate [omega(k0)(2)] and then deduce the theoretical value of omega(rp). On the other hand, we provide an experimental measurement of omega(rp) and study its dependence on ion fluence by electron-energy-loss spectroscopy. The validity of the model of Brandt and Ritchie is then discussed in the light of both theoretical and experimental data. (author)

  20. Annealing effects on recombinative activity of nickel at direct silicon bonded interface

    International Nuclear Information System (INIS)

    Kojima, Takuto; Ohshita, Yoshio; Yamaguchi, Masafumi

    2015-01-01

    By performing capacitance transient analyses, the recombination activity at a (110)/(100) direct silicon bonded (DSB) interface contaminated with nickel diffused at different temperatures, as a model of grain boundaries in multicrystalline silicon, was studied. The trap level depth from the valence band, trap density of states, and hole capture cross section peaked at an annealing temperature of 300 °C. At temperatures ⩾400 °C, the hole capture cross section increased with temperature, but the density of states remained unchanged. Further, synchrotron-based X-ray analyses, microprobe X-ray fluorescence (μ-XRF), and X-ray absorption near edge structure (XANES) analyses were performed. The analysis results indicated that the chemical phase after the sample was annealed at 200 °C was a mixture of NiO and NiSi 2

  1. Understanding Bonds - Denmark

    DEFF Research Database (Denmark)

    Rimmer, Nina Røhr

    2016-01-01

    a specified rate of interest during the life of the bond and to repay the face value of the bond (the principal) when it “matures,” or comes due. Among the types of bonds you can choose from are: Government securities, municipal bonds, corporate bonds, mortgage and asset-backed securities, federal agency...

  2. Tantalum surface oxidation: Bond relaxation, energy entrapment, and electron polarization

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Yongling [Key Laboratory of Low-Dimensional Materials and Application Technologies (Ministry of Education), Hunan Provincial Key Laboratory of Thin Film Materials and Devices, Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China); Bo, Maolin [Yangtze Normal University, College of Mechanical and Electrical Engineering, Chongqing 408100 (China); Wang, Yan [School of Information and Electronic Engineering, Hunan University of Science and Technology, Hunan 411201 (China); Liu, Yonghui [Key Laboratory of Low-Dimensional Materials and Application Technologies (Ministry of Education), Hunan Provincial Key Laboratory of Thin Film Materials and Devices, Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China); Sun, Chang Q. [NOVITAS, School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Huang, Yongli, E-mail: huangyongli@xtu.edu.cn [Key Laboratory of Low-Dimensional Materials and Application Technologies (Ministry of Education), Hunan Provincial Key Laboratory of Thin Film Materials and Devices, Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China)

    2017-02-28

    Graphical abstract: The bond, electron and energy relaxation result in core level energy shift, local densification, quantum entrapment and electron polarization of bonding electrons. - Highlights: • Increasing the oxygen coverage lowers the adsorption energy associated with lattice reconstruction. • Electrons transfer from Ta surface atoms to sp-hydrated oxygen, creating dipole moment that decreases the work function. • Oxygen chemisorption modified valence density-of-state (DOS) for Ta with four excessive DOS features: O−Ta bonding, O{sup 2−} lone pairs, Ta+ electron holes, and the lone-pair polarized Ta dipoles. • The bond, electron and energy relaxation between surface undercoordinated atoms are responsible for core level energy shift, local densification, quantum entrapment and electron polarization of bonding electrons. - Abstract: A combination of photoelectron spectrometric analysis and density functional theory calculations has enabled reconciliation of the bond-energy-electron relaxation for the Ta(100, 110, 111) surfaces chemisorbed with oxygen at different coverages. Results show that increasing oxygen coverage lowers the adsorption energy associated with lattice reconstruction. Valence electrons transfer from Ta surface atoms to oxygen to create four excessive DOS features in terms of O−Ta bonding, lone pairs of oxygen, Ta{sup +} electron holes, and polarized Ta dipoles. Oxidation proceeds in the following dynamics: oxygen gets electrons from two neighboring Ta atoms left behind Ta{sup +}; the sp{sup 3}-orbital hybridization takes place with additional two electron lone pairs, the lone pairs polarize the other two Ta neighbors becoming dipoles. X-ray photoelectron spectral analysis results in the 4f binding energy of an isolated Ta atom and its shift upon bond formation and oxidation. Exercises provide not only a promising numerical approach for the quantitative information about the bond and electronic behavior but also consistent

  3. Chemical bonding in copper-based transparent conducting oxides: CuMO{sub 2} (M = In, Ga, Sc)

    Energy Technology Data Exchange (ETDEWEB)

    Godinho, K G; Morgan, B J; Allen, J P; Scanlon, D O; Watson, G W, E-mail: scanloda@tcd.ie, E-mail: watsong@tcd.ie [School of Chemistry and CRANN, Trinity College Dublin, Dublin 2 (Ireland)

    2011-08-24

    The geometry and electronic structure of copper-based p-type delafossite transparent conducting oxides, CuMO{sub 2} (M = In, Ga, Sc), are studied using the generalized gradient approximation (GGA) corrected for on-site Coulomb interactions (GGA + U). The bonding and valence band compositions of these materials are investigated, and the origins of changes in the valence band features between group 3 and group 13 cations are discussed. Analysis of the effective masses at the valence and conduction band edge explains the experimentally reported conductivity trends.

  4. A facilitative effect of negative affective valence on working memory.

    Science.gov (United States)

    Gotoh, Fumiko; Kikuchi, Tadashi; Olofsson, Ulrich

    2010-06-01

    Previous studies have shown that negatively valenced information impaired working memory performance due to an attention-capturing effect. The present study examined whether negative valence could also facilitate working memory. Affective words (negative, neutral, positive) were used as retro-cues in a working memory task that required participants to remember colors at different spatial locations on a computer screen. Following the cue, a target detection task was used to either shift attention to a different location or keep attention at the same location as the retro-cue. Finally, participants were required to discriminate the cued color from a set of distractors. It was found that negative cues yielded shorter response times (RTs) in the attention-shift condition and longer RTs in the attention-stay condition, compared with neutral and positive cues. The results suggest that negative affective valence may enhance working memory performance (RTs), provided that attention can be disengaged.

  5. Emotional sound symbolism: Languages rapidly signal valence via phonemes.

    Science.gov (United States)

    Adelman, James S; Estes, Zachary; Cossu, Martina

    2018-03-03

    Rapidly communicating the emotional valence of stimuli (i.e., negativity or positivity) is vital for averting dangers and acquiring rewards. We therefore hypothesized that human languages signal emotions via individual phonemes (emotional sound symbolism), and more specifically that the phonemes at the beginning of the word signal its valence, as this would maximize the receiver's time to respond adaptively. Analyzing approximately 37,000 words across five different languages (English, Spanish, Dutch, German, and Polish), we found emotional sound symbolism in all five languages, and within each language the first phoneme of a word predicted its valence better than subsequent phonemes. Moreover, given that averting danger is more urgent than acquiring rewards, we further hypothesized and demonstrated that phonemes that are uttered most rapidly tend to convey negativity rather than positivity. Thus, emotional sound symbolism is an adaptation providing an early warning system in human languages, analogous to other species' alarm calls. Copyright © 2018 Elsevier B.V. All rights reserved.

  6. Contribution to the study of higher valency states of americium

    International Nuclear Information System (INIS)

    Langlet, Jean.

    1976-01-01

    Study of the chemistry of the higher valencies of americium in aqueous solutions and especially the autoreduction phenomenon. First a purification method of americium solutions is studied by precipitation, solvent extraction and ion exchange chromatography. Studies of higher valency states chemical properties are disturbed by the autoreduction phenomenon changing Am VI and Am V in Am III more stable. Stabilization of higher valency states, characterized by a steady concentration of Am VI in solution, can be done by complexation of Am VI and Am V ions or by a protecting effect of foreign ions. The original medium used has a complexing effect by SO 4 2- ions and a protecting effect by the system S 2 O 8 2- -Ag + consuming H 2 O 2 main reducing agent produced by water radiolysis. These effects are shown by the study of Am VI in acid and basic solutions. A mechanism of the stabilization effect is given [fr

  7. Direct double photoionization of the valence shell of Be

    International Nuclear Information System (INIS)

    Citrini, F.; Malegat, L.; Selles, P.; Kazansky, A.K.

    2003-01-01

    The hyperspherical R-matrix method with semiclassical outgoing waves is used to study the direct double photoionization (DPI) of the valence shell of the lightest alkaline earth-metal Be. The absolute fully integrated, singly, doubly, and triply differential cross sections obtained are compared with the single set of measurements available and with recent calculations based on the convergent close coupling and time-dependent close coupling methods. The level of agreement between all these data is very encouraging. A comparison is also made between the DPI of He and the direct DPI of the valence shell of Be. It confirms that the electron-electron correlations are stronger in the valence 2s shell of Be than in the 1s shell of He, thus contributing to a desirable clarification

  8. RKKY interaction in mixed valence system and heavy fermion superconductivity

    International Nuclear Information System (INIS)

    Fusui Liu; Gao Lin; Lin Zonghan

    1985-11-01

    The 1-D RKKY interaction of mixed valence system is given by using the thermodynamic perturbation theory. The numerical comparisons of 1-D and 3-D RKKY interaction between systems with localized magnetic moments of mixed valence and non-mixed valence show that the former is much stronger than the latter. From some analyses we propose that the heavy Fermion superconductivity comes from the RKKY interaction between two local f electrons which hop off the impurity site to become two continuum electrons. The source of the two impurity electrons hopping is the Coulomb interaction. It is also emphasized that the RKKY interaction does not disappear for the Kondo lattice, when the temperature is less than the Kondo temperature. (author)

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

    Science.gov (United States)

    Wuttisela, Karntarat

    2017-01-01

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

  10. Hexacoordinate bonding and aromaticity in silicon phthalocyanine.

    Science.gov (United States)

    Yang, Yang

    2010-12-23

    Si-E bondings in hexacoordinate silicon phthalocyanine were analyzed using bond order (BO), energy partition, atoms in molecules (AIM), electron localization function (ELF), and localized orbital locator (LOL). Bond models were proposed to explain differences between hexacoordinate and tetracoordinate Si-E bondings. Aromaticity of silicon phthalocyanine was investigated using nucleus-independent chemical shift (NICS), harmonic oscillator model of aromaticity (HOMA), conceptual density functional theory (DFT), ring critical point (RCP) descriptors, and delocalization index (DI). Structure, energy, bonding, and aromaticity of tetracoordinate silicon phthalocyanine were studied and compared with hexacoordinate one.

  11. Effective charges, the valence p-n interaction, and the IBM

    Energy Technology Data Exchange (ETDEWEB)

    Casten, R.F. (Brookhaven National Lab., Upton, NY (United States)); Wolf, A. (Brookhaven National Lab., Upton, NY (United States) Israel Atomic Energy Commission, Beersheba (Israel). Nuclear Research Center-Negev)

    1992-01-01

    There are three recent themes in nuclear structure that come together in an interesting and useful way via the concept of effective charges and the framework of the IBM. These three concepts are the importance of dynamical symmetries in describing nuclear structure and the benefits that accrue from their exploitation, secondly, the critical role of the p-n interaction in the onset and development of collectivity in nuclei, and, thirdly, the importance of the valence nucleons in determining structure and its evolution. We will illustrate this by showing that the interpretation of measured B(E2) values in the context of the dynamical symmetries of the IBM leads to new insights into the meaning of effective charges and offers new avenues to understand the role of the proton-neutron (p-n) interaction in modulating the nature of the valence space and the growth of collectivity. In particular, we will show that effective charges in valence models, such as the IBM, can be interpreted in terms of derivatives of the collectivity of the low lying levels, that is, as measures of the rate of change of collectivity as the proton and neutron numbers vary. This paper is based on recent work by the authors.

  12. Effective charges, the valence p-n interaction, and the IBM

    Energy Technology Data Exchange (ETDEWEB)

    Casten, R.F. [Brookhaven National Lab., Upton, NY (United States); Wolf, A. [Brookhaven National Lab., Upton, NY (United States)]|[Israel Atomic Energy Commission, Beersheba (Israel). Nuclear Research Center-Negev

    1992-10-01

    There are three recent themes in nuclear structure that come together in an interesting and useful way via the concept of effective charges and the framework of the IBM. These three concepts are the importance of dynamical symmetries in describing nuclear structure and the benefits that accrue from their exploitation, secondly, the critical role of the p-n interaction in the onset and development of collectivity in nuclei, and, thirdly, the importance of the valence nucleons in determining structure and its evolution. We will illustrate this by showing that the interpretation of measured B(E2) values in the context of the dynamical symmetries of the IBM leads to new insights into the meaning of effective charges and offers new avenues to understand the role of the proton-neutron (p-n) interaction in modulating the nature of the valence space and the growth of collectivity. In particular, we will show that effective charges in valence models, such as the IBM, can be interpreted in terms of derivatives of the collectivity of the low lying levels, that is, as measures of the rate of change of collectivity as the proton and neutron numbers vary. This paper is based on recent work by the authors.

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

    Science.gov (United States)

    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.

  14. Geometry of simple molecules: nonbonded interactions, not bonding orbitals, and primarily determine observed geometries.

    Science.gov (United States)

    See, R F; Dutoi, A D; McConnell, K W; Naylor, R M

    2001-03-28

    The forces responsible for the observed geometries of the YX(3) (Y = N or P; X = H, F, or Cl) molecules were studied through ab initio computations at the HF-SCF/6-31G level. The calculated molecular orbitals were grouped as contributing primarily to (a) the covalent bonds, (b) the terminal atom nonbonding electrons (for X = F or Cl), and (c) the central atom nonbonding electrons. This grouping was accomplished through 3-D plotting and an atomic population analysis of the molecular orbitals. The molecules were then moved through a X-Y-X angular range from 90 degrees to 119 degrees, in four or five degree increments. Single-point calculations were done at each increment, so as to quantify the energy changes in the molecular orbital groups as a function of geometry. These calculations show that the nonbonding electrons are much more sensitive to geometry change than are the bonding orbitals, particularly in the trihalide compounds. The molecular orbitals representing the nonbonding electrons on the terminal atoms (both valence and core electrons) contribute to the spreading forces, as they favor a wider X-Y-X angle. The contracting forces, which favor a smaller X-Y-X angle, consist of the orbitals comprising the nonbonding electrons on the central atom (again, both valence and core electrons). The observed geometry is seen as the balance point between these two sets of forces. A simple interaction-distance model of spreading and contracting forces supports this hypothesis. Highly linear trends are obtained for both the nitrogen trihalides (R(2) = 0.981) and phosphorus trihalides (R(2) = 0.992) when the opposing forces are plotted against each other. These results suggest that a revision of the popular conceptual models (hybridization and VSEPR) of molecular geometry might be appropriate.

  15. Representations of modality-general valence for videos and music derived from fMRI data.

    Science.gov (United States)

    Kim, Jongwan; Shinkareva, Svetlana V; Wedell, Douglas H

    2017-03-01

    This study tested for neural representations of valence that are shared across visual and auditory modalities referred to as modality-general representations. On a given trial participants made either affective or semantic judgments of short silent videos or music samples. For each modality valence was manipulated at three levels, positive, neutral, and negative, while controlling for the level of arousal. Whole-brain crossmodal identification of affect indicated the presence of modality-general valence representations that distinguished 1) positive from negative trials (signed valence) and 2) valenced from non-valenced trials (unsigned valence). These results generalized across the two tasks. Brain regions that were sensitive to valence states in the same way for both modalities were identified by searchlight analysis of fMRI data by comparing the correlation of voxel responses to the same and different valence conditions across the two modalities. These analyses identified seven clusters that distinguished signed valence, unsigned valence or both. Signed valence was represented in the precuneus, unsigned valence in the bilateral medial prefrontal cortex, superior temporal sulcus (STS)/postcentral, and middle frontal gyrus (MFG) and both types were represented in the STS/MFG and thalamus. These results support the idea that modality general valence is represented in a network of several locations throughout the brain. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. Multilevel analysis of facial expressions of emotion and script: self-report (arousal and valence) and psychophysiological correlates.

    Science.gov (United States)

    Balconi, Michela; Vanutelli, Maria Elide; Finocchiaro, Roberta

    2014-09-26

    The paper explored emotion comprehension in children with regard to facial expression of emotion. The effect of valence and arousal evaluation, of context and of psychophysiological measures was monitored. Indeed subjective evaluation of valence (positive vs. negative) and arousal (high vs. low), and contextual (facial expression vs. facial expression and script) variables were supposed to modulate the psychophysiological responses. Self-report measures (in terms of correct recognition, arousal and valence attribution) and psychophysiological correlates (facial electromyography, EMG, skin conductance response, SCR, and heart rate, HR) were observed when children (N = 26; mean age = 8.75 y; range 6-11 y) looked at six facial expressions of emotions (happiness, anger, fear, sadness, surprise, and disgust) and six emotional scripts (contextualized facial expressions). The competencies about the recognition, the evaluation on valence and arousal was tested in concomitance with psychophysiological variations. Specifically, we tested for the congruence of these multiple measures. Log-linear analysis and repeated measure ANOVAs showed different representations across the subjects, as a function of emotion. Specifically, children' recognition and attribution were well developed for some emotions (such as anger, fear, surprise and happiness), whereas some other emotions (mainly disgust and sadness) were less clearly represented. SCR, HR and EMG measures were modulated by the evaluation based on valence and arousal, with increased psychophysiological values mainly in response to anger, fear and happiness. As shown by multiple regression analysis, a significant consonance was found between self-report measures and psychophysiological behavior, mainly for emotions rated as more arousing and negative in valence. The multilevel measures were discussed at light of dimensional attribution model.

  17. Microscopic models for proton transfer in water and strongly hydrogen-bonded complexes with a single-well proton potential

    DEFF Research Database (Denmark)

    Kuznetsov, A.M.; Ulstrup, Jens

    2004-01-01

    A new mechanism and formalism for proton transfer in donor-acceptor complexes with long hydrogen bonds introduced recently [1], is applied to a proton transfer in liquid water. "Structural diffusion" of hydroxonium ions is regarded as totally adiabatic process, with synchronous hindered translation...... of two closest water molecules to and from the reaction complex as crucial steps. The water molecules induce a "gated" shift of the proton from the donor to the acceptor in the double-well potential with simultaneous breaking/formation of hydrogen bonds between these molecules and the proton donor...... and acceptor. The short-range and long-range proton transfer as "structural diffusion" of Zundel complexes is also considered. The theoretical formalism is illustrated with the use of Morse, exponential, and harmonic molecular potentials. This approach is extended to proton transfer in strongly hydrogen...

  18. [Connection between the evaluation of positive or negative valence and verbal responses to a lexical decision making task].

    Science.gov (United States)

    Brouillet, Thibaut; Syssau, Arielle

    2005-12-01

    Evaluation of the positive or negative valence of a stimulus is an activity that is part of any emotional experience that has been mostly studied using the affective priming paradigm. When the prime and the target have the same valence (e.g. positive prime and positive target), the target response is facilitated as a function of opposing valence conditions (e.g. negative prime and positive target). These studies show that this evaluation is automatic but depends on the nature of the task's implied response because the priming effects are only observed for positive responses, not for negative responses. This result was explained in automatic judgmental tendency model put forth by Abelson and Rosenberg (1958) and Klauer and Stern (1992). In this model, affective priming assumes there is an overlap between both responses, the first response taking precedence as a function of the prime-target valence, and the second response one that is required by the task. We are assuming that another type of response was not foreseen under this model. In fact, upon activating the valence for each of the prime-target elements, two preliminary responses would be activated before the response on the prime-target valence relationship. These responses are directly linked to the prime and target evaluation independently of the prime-target relationship. This hypothesis can be linked to the larger hypothesis whereby the evaluative process is related to two distinct motivational systems corresponding to approach and avoidance behaviour responses (Lang, Bradley, & Cuthbert, 1990; Neuman & Strack, 2000; Cacciopo, Piester & Bernston, 1993). In this study, we use the hypothesis that when a word leads to a positive valence evaluation, this favours a positive verbal response and inversely, a negative valence word favours a negative response. We are testing this hypothesis outside the affective priming paradigm to study to what extent evaluating a word, even when it is not primed, activates both

  19. Doping and bond length contributions to Mn K-edge shift in La1 ...

    Indian Academy of Sciences (India)

    ... corresponds to the shift in the center of gravity of the unoccupied Mn 4-band contributing to the Mn K-absorption edge region. This correspondence is then used to separate the doping and size contributions to the edge shift due to variation in the number of electrons in valence band and Mn-O bond lengths, respectively, ...

  20. Wire bonding in microelectronics

    CERN Document Server

    Harman, George G

    2010-01-01

    Wire Bonding in Microelectronics, Third Edition, has been thoroughly revised to help you meet the challenges of today's small-scale and fine-pitch microelectronics. This authoritative guide covers every aspect of designing, manufacturing, and evaluating wire bonds engineered with cutting-edge techniques. In addition to gaining a full grasp of bonding technology, you'll learn how to create reliable bonds at exceedingly high yields, test wire bonds, solve common bonding problems, implement molecular cleaning methods, and much more. Coverage includes: Ultrasonic bonding systems and technologies, including high-frequency systems Bonding wire metallurgy and characteristics, including copper wire Wire bond testing Gold-aluminum intermetallic compounds and other interface reactions Gold and nickel-based bond pad plating materials and problems Cleaning to improve bondability and reliability Mechanical problems in wire bonding High-yield, fine-pitch, specialized-looping, soft-substrate, and extreme-temperature wire bo...

  1. Quantum chemical studies of a model for peptide bond formation. 3. Role of magnesium cation in formation of amide and water from ammonia and glycine

    Science.gov (United States)

    Oie, T.; Loew, G. H.; Burt, S. K.; MacElroy, R. D.

    1984-01-01

    The SN2 reaction between glycine and ammonia molecules with magnesium cation Mg2+ as a catalyst has been studied as a model reaction for Mg(2+)-catalyzed peptide bond formation using the ab initio Hartree-Fock molecular orbital method. As in previous studies of the uncatalyzed and amine-catalyzed reactions between glycine and ammonia, two reaction mechanisms have been examined, i.e., a two-step and a concerted reaction. The stationary points of each reaction including intermediate and transition states have been identified and free energies calculated for all geometry-optimized reaction species to determine the thermodynamics and kinetics of each reaction. Substantial decreases in free energies of activation were found for both reaction mechanisms in the Mg(2+)-catalyzed amide bond formation compared with those in the uncatalyzed and amine-catalyzed amide bond formation. The catalytic effect of the Mg2+ cation is to stabilize both the transition states and intermediate, and it is attributed to the neutralization of the developing negative charge on the electrophile and formation of a conformationally flexible nonplanar five-membered chelate ring structure.

  2. Semiphenomenological approach to the problem of discontinuous change of valence

    International Nuclear Information System (INIS)

    Zielinski, J.

    1982-08-01

    Simple, semiphenomenological theory of the abrupt change of valence in SmS is presented. The phase transition and the softening of the phonon mode can be considered as being due to the partial decoupling of phonons from the electronic system. (author)

  3. Experimental evidence of photoinduced valence change of Fe 3 in ...

    Indian Academy of Sciences (India)

    Home; Journals; Pramana – Journal of Physics; Volume 56; Issue 5. Experimental evidence of photoinduced valence change of Fe3+ in BaTiO3 and mechanism for growth of new grating in depleted pump condition: An EPR investigation. M D Sastry M Moghbel Putcha Venkateswarlu A Darwish. Research Articles Volume ...

  4. Spin Dynamics and Magnetic Ordering in Mixed Valence Systems

    DEFF Research Database (Denmark)

    Shapiro, S. M.; Bjerrum Møller, Hans; Axe, J. D.

    1978-01-01

    Neutron scattering measurements are reported on the mixed valence compounds Ce//1// minus //xTh//x and TmSe. The chi double prime (Q, omega ) as derived from the inelastic spectra of Ce//0//. //7//4Th//0//. //2//6 shows a peak in the gamma phase near 20. 0 meV and shifts abruptly to greater than 70...

  5. Mn valence state and electrode performance of perovskite-type ...

    Indian Academy of Sciences (India)

    increase in the oxidation state of Mn ions was due to the formation of Mn4+ ions and oxygen vacancies. The addition of Cu ions to LSM systems could lead to enhanced electrode performance for oxygen reduction reactions originating from the change in valence of Mn ions. Keywords. Cu-doped LSM; electrical conductivity; ...

  6. Intervalence charge transfer transition in mixed valence complexes ...

    Indian Academy of Sciences (India)

    Keywords. Mixed valence complexes; intervalence charge transfer; rotaxane; inclusion complex; optical electron transfer; cyclodextrin. ... Further, inclusion of the bridging ligand with interrupted -electron system in a -CD cavity initiate an optical electron transfer from Fe(II) to Ru(III) which is otherwise not observed.

  7. Vection Modulates Emotional Valence of Autobiographical Episodic Memories

    Science.gov (United States)

    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…

  8. Effective valence as the control parameter of the superconducting ...

    African Journals Online (AJOL)

    One approach to investigating the superconductivity in the ironbased materials is understanding the chemical and structural parameters that can be used to tune their remarkably high Tc. In this paper, we have demonstrated that the effective valence of iron can be used as the control parameter to tune the Tc of this family of ...

  9. verbal extensions: valency decreasing extensions in the basà ...

    African Journals Online (AJOL)

    Finance

    London: Hodder. Education. Imoh, P.M., 2013. Verbal extensions: Valency increasing operations in Basà verbal system. Paper presented at the West African Languages Congress (WALC) and 26th Annual. Conference of the Linguistic Association of Nigeria (26th CLAN), 29th July to 2nd August. 2013, University of Ibadan, ...

  10. Can QTAIM topological parameters be a measure of hydrogen bonding strength?

    Science.gov (United States)

    Mo, Yirong

    2012-05-31

    The block-localized wave function (BLW) method, which is the simplest variant of ab initio valence bond (VB) theory, together with the quantum theory of atoms in molecules (QTAIM) approach, have been used to probe the intramolecular hydrogen bonding interactions in a series of representative systems of resonance-assisted hydrogen bonds (RAHBs). RAHB is characteristic of the cooperativity between the π-electron delocalization and hydrogen bonding interactions and is identified in many biological systems. While the deactivation of the π resonance in these RAHB systems by the use of the BLW method is expected to considerably weaken the hydrogen bonding strength, little change on the topological properties of electron densities at hydrogen bond critical points (HBCPs) is observed. This raises a question of whether the QTAIM topological parameters can be an effective measure of hydrogen bond strength.

  11. Vison excitations in near-critical quantum dimer models

    Science.gov (United States)

    Strübi, G.; Ivanov, D. A.

    2011-06-01

    We study vison excitations in a quantum dimer model interpolating between the Rokhsar-Kivelson models on the square and triangular lattices. In the square-lattice case, the model is known to be critical and characterized by U(1) topological quantum numbers. Introducing diagonal dimers brings the model to a Z2 resonating-valence-bond phase. We study variationally the emergence of vison excitations at low concentration of diagonal dimers, close to the critical point. We find that, in this regime, vison excitations are large in size and their structure resembles vortices in type-II superconductors.

  12. X hydrogen bonds

    Indian Academy of Sciences (India)

    sigma electrons, can be hydrogen bond acceptors.11–14. The recent IUPAC report and recommendation on hydro gen bond have recognised the diverse nature of hydro- gen bond donors and acceptors.13,14. Unlike methane, hydrogen bonding by higher alkanes has not received much attention. One of the earlier works.

  13. Parenting stress and parental bonding.

    Science.gov (United States)

    Willinger, Ulrike; Diendorfer-Radner, Gabriela; Willnauer, Ruth; Jörgl, Gudrun; Hager, Veronika

    2005-01-01

    Attachment experiences are thought to be important because of their implications for later development. The authors' aim with the questionnaire-based study was to investigate the differences between recalled parental bonding regarding 4 types of maternal and paternal bonding with respect to experienced parenting stress caused by child characteristics, parent attributes, and life events under the consideration of the child's gender and age. The authors gathered parental bonding behavior data with the German version of the Parental Bonding Instrument (PBI). The authors assessed parenting stress with their German version of the "Parenting Stress Index (PSI)." They found significant differences among 120 mothers grouped in the 4 maternal and the 4 paternal bonding types regarding parenting stress caused by child, maternal bonding: F(5, 113) = 4.13, p = .002, paternal bonding: F(5, 111) = 8.50, p mothers who themselves recalled the "optimal parental bonding type" with respect to the child and parental domain. The authors did not find any significant differences between the 4 maternal, F(5, 113) = 1.25, p = .29, and the 4 paternal, F(5, 111) = 1.87, p = .106, bonding types with respect to the life stress. According to the authors' findings, the representation of attachment relationships seems to have a special impact on the adult's capacity to cope with challenges and stress, either directly or indirectly as an internal working model of attachment. For the clinical practice, these findings seem to recommend the combination of both the PSI and PBI regarding the diagnostic of stressful mother-child system to plan an optimal intervention program.

  14. Adhesive wafer bonding

    Science.gov (United States)

    Niklaus, F.; Stemme, G.; Lu, J.-Q.; Gutmann, R. J.

    2006-02-01

    Wafer bonding with intermediate polymer adhesives is an important fabrication technique for advanced microelectronic and microelectromechanical systems, such as three-dimensional integrated circuits, advanced packaging, and microfluidics. In adhesive wafer bonding, the polymer adhesive bears the forces involved to hold the surfaces together. The main advantages of adhesive wafer bonding include the insensitivity to surface topography, the low bonding temperatures, the compatibility with standard integrated circuit wafer processing, and the ability to join different types of wafers. Compared to alternative wafer bonding techniques, adhesive wafer bonding is simple, robust, and low cost. This article reviews the state-of-the-art polymer adhesive wafer bonding technologies, materials, and applications.

  15. High-Temperature Isomerization of Benzenoid Polycyclic Aromatic Hydrocarbons. Analysis through the Bent Bond and Antiperiplanar Hypothesis Orbital Model.

    Science.gov (United States)

    Parent, Jean-François; Deslongchamps, Pierre

    2018-03-16

    L. T. Scott has discovered the 1,2-swapping of carbon and hydrogen atoms which is known to take place on benzenoid aromatics (up to ∼1000 °C range). For example, 13 C-1-naphthalene is specifically converted to 13 C-2-naphthalene, and there is evidence that this occurs through the formation of benzofulvene and a naphthalene-carbene intermediate. Application of the bent bond/antiperiplanar hypothesis leads to the postulate that higher in energy pyramidal singlet diradical intermediates can be used to propose a mechanism that rationalizes various atom rearrangements on benzenoid aromatics and related isomeric compounds.

  16. Valence band photoemission studies of clean metals

    Energy Technology Data Exchange (ETDEWEB)

    Wehner, P.S.

    1978-04-01

    The application of Angle-Resolved Photoelectron Spectroscopy (ARPES) to crystalline solids and the utilization of such studies to illuminate several questions concerning the detailed electronic structure of such materials, are discussed. Specifically, by construction of a Direct Transition (DT) model and the utilization of energy-dependent angle-resolved normal photoemission in the photon energy range 32 eV < or = h..nu.. < or = 200 eV, the bulk band structure of copper is experimentally mapped out along three different directions in the Brillouin Zone; GAMMA to K, GAMMA to L, and GAMMA to X. In addition, various effects which influence the obtainable resolution in vector k-space, namely, thermal disorder, momentum broadening, and band mixing, are discussed and are shown to place severe limitations on the applicability of the DT model. Finally, a model for Angle-Resolved X-ray Photoelectron Spectroscopy (ARXPS) based on the symmetry of the initial-state wavefunctions is presented and compared to experimental results obtained from copper single crystals.

  17. Influence of double hydrogen bonds and alkyl chains on the gelation of nonchiral polyurethane model compounds: sheets, eaves trough, tubes and oriented fibers.

    Science.gov (United States)

    Khanna, Shalini; Khan, Mostofa Kamal; Sundararajan, Pudupadi

    2009-11-17

    We describe the gelation, upon self-assembly of a series of nonchiral molecules, resulting in tubular morphology of the fibers. These are biscarbamates, which are model compounds for polyurethanes with two hydrogen bonding groups separated by a (CH(2))(6) spacer and symmetrically substituted with alkyl chains on either side varying in length from C(6) to C(18). Upon gelation, these molecules form a sheet initially. The sheets then tend to wrap, leading to tubules. Those with partial wrapping resemble eaves troughs. With the predominant growth along the hydrogen bonding direction, the energy of interaction between the molecules along this direction would be more dominant than just the van der Waals interaction in the other two, leading to asymmetry of interaction in the sheet. We rationalize such tube formation in this case on the basis of the theories [Schnur, J. M.; Ratna, B. R.; Selinger, J. V.; Singh, A.; Jyothi, G.; Easwaran, K. R. K. Science, 1994, 264, 945. Schnur, J. M. Science, 1993, 262, 166. McKierman, R. L.; Heintz, A. M.; Hsu, S. L.; Gido, S. P.; Penelle, J. Polym. Mater. Sci. Eng. 2001, 84, 416.] which were developed for amphiphilic mono and bilayers, which state that these bilayers are not at their minimal energy when they are flat, and prefer a bent state. The gelation behavior of this series with double hydrogen bond is compared with the monocarbamates with a single hydrogen bonding motif [Moniruzzaman, M.; Sundararajan, P. R. Langmuir 2005, 21, 3802.]. We attribute the tendency toward both gelation and crystallization in some cases to the competing contributions of the hydrogen bond and van der Waals interactions between the long alkyl side chains. Oriented fibers for X-ray diffraction were obtained by simply using a magnetic stir bar during gelation. It is also found that the solvents that gel with diureas [van Esch, J.; Kellogg, R. M.; Feringa, B. L. Tetrahedron Lett. 1997, 38, 281] also form gels with biscarbamates. While the biscarbamates with

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

    Science.gov (United States)

    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…

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

    Science.gov (United States)

    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…

  20. On the theory of phonoriton in cubic semiconductors with a degenerate valence band

    International Nuclear Information System (INIS)

    Nguyen Ai Viet; Nguyen Thi Que Huong; Le Qui Thong

    1992-10-01

    The ''phonoriton'' is an elementary excitation constructed from an exciton polariton and phonon in semiconductors under intense excitation by an electromagnetic wave near the exciton resonance (L.V. Keldysh and A.L. Ivanov, 1982). In this paper we develop a theory of phonoriton in direct band gap cubic semiconductor with a degenerate valence band using the simple model of J.L. Birman and B.S. Wang (1990). In addition to experimental proofs of the existence of phonoriton we propose an experiment to measure its flight time. (author). 33 refs

  1. Chemical bonding and the equilibrium composition of Grignard reagents in ethereal solutions.

    Science.gov (United States)

    Henriques, André M; Barbosa, André G H

    2011-11-10

    A thorough analysis of the electronic structure and thermodynamic aspects of Grignard reagents and its associated equilibrium composition in ethereal solutions is performed. Considering methylmagnesium halides containing fluorine, chlorine, and bromine, we studied the neutral, charged, and radical species associated with their chemical equilibrium in solution. The ethereal solvents considered, tetrahydrofuran (THF) and ethyl ether (Et(2)O), were modeled using the polarizable continuum model (PCM) and also by explicit coordination to the Mg atoms in a cluster. The chemical bonding of the species that constitute the Grignard reagent is analyzed in detail with generalized valence bond (GVB) wave functions. Equilibrium constants were calculated with the DFT/M06 functional and GVB wave functions, yielding similar results. According to our calculations and existing kinetic and electrochemical evidence, the species R(•), R(-), (•)MgX, and RMgX(2)(-) must be present in low concentration in the equilibrium. We conclude that depending on the halogen, a different route must be followed to produce the relevant equilibrium species in each case. Chloride and bromide must preferably follow a "radical-based" pathway, and fluoride must follow a "carbanionic-based" pathway. These different mechanisms are contrasted against the available experimental results and are proven to be consistent with the existing thermodynamic data on the Grignard reagent equilibria.

  2. The effects of reasoning, use of models, sex type, and their interactions on posttest achievement in chemical bonding after constant instruction

    Science.gov (United States)

    Staver, John R.; Halsted, Douglas A.

    The purpose of the authors in this study was to determine the effects of reasoning, use of models during testing, and sex type on posttest achievement in chemical bonding under controlled instruction. Eighty-four high school students taking chemistry were randomly assigned within their classes to models and no models groups for the posttest. Reasoning capabilities were assessed by the Piagetian Logical Operations Test (PLOT) (Staver & Gabel, JRST, Vol. 16, No. 6, 1979), prior to instruction. All students then received the same instruction on chemical bonding which included teacher demonstrations of concepts with three-dimensional molecular models, interspersed teacher questions during the introduction and development of concepts, student manipulation of three-dimensional molecular models during laboratory experiments, and text reading assignments on concepts prior to their instruction in class. The posttest on molecular geometry and shape contained three sections requiring memory and application (Bloom, Taxonomy of educational objective, handbook I: Cognitive domain. New York: David McKay, 1956). Data were analyzed by regression (Nie et al., Statistical package for the social sciences, 2nd ed. New York: McGraw-Hill, 1975). Results indicate that reasoning accounted for a significant portion (p sex type did not account for a significant (p > 0.05) portion of the variance on total scores or any section of posttest. The three-way interaction of reasoning, model usage, and sex type accounted for a significant portion (p < 0.05) of the variance in total scores, and in the memory and application sections of the posttest. Discussion focused on the results, conclusions, and implications for science teaching.

  3. The olfactory tubercle encodes odor valence in behaving mice.

    Science.gov (United States)

    Gadziola, Marie A; Tylicki, Kate A; Christian, Diana L; Wesson, Daniel W

    2015-03-18

    Sensory information acquires meaning to adaptively guide behaviors. Despite odors mediating a number of vital behaviors, the components of the olfactory system responsible for assigning meaning to odors remain unclear. The olfactory tubercle (OT), a ventral striatum structure that receives monosynaptic input from the olfactory bulb, is uniquely positioned to transform odor information into behaviorally relevant neural codes. No information is available, however, on the coding of odors among OT neurons in behaving animals. In recordings from mice engaged in an odor discrimination task, we report that the firing rate of OT neurons robustly and flexibly encodes the valence of conditioned odors over identity, with rewarded odors evoking greater firing rates. This coding of rewarded odors occurs before behavioral decisions and represents subsequent behavioral responses. We predict that the OT is an essential region whereby odor valence is encoded in the mammalian brain to guide goal-directed behaviors. Copyright © 2015 the authors 0270-6474/15/354515-13$15.00/0.

  4. Human Amygdala Tracks a Feature-Based Valence Signal Embedded within the Facial Expression of Surprise.

    Science.gov (United States)

    Kim, M Justin; Mattek, Alison M; Bennett, Randi H; Solomon, Kimberly M; Shin, Jin; Whalen, Paul J

    2017-09-27

    Human amygdala function has been traditionally associated with processing the affective valence (negative vs positive) of an emotionally charged event, especially those that signal fear or threat. However, this account of human amygdala function can be explained by alternative views, which posit that the amygdala might be tuned to either (1) general emotional arousal (activation vs deactivation) or (2) specific emotion categories (fear vs happy). Delineating the pure effects of valence independent of arousal or emotion category is a challenging task, given that these variables naturally covary under many circumstances. To circumvent this issue and test the sensitivity of the human amygdala to valence values specifically, we measured the dimension of valence within the single facial expression category of surprise. Given the inherent valence ambiguity of this category, we show that surprised expression exemplars are attributed valence and arousal values that are uniquely and naturally uncorrelated. We then present fMRI data from both sexes, showing that the amygdala tracks these consensus valence values. Finally, we provide evidence that these valence values are linked to specific visual features of the mouth region, isolating the signal by which the amygdala detects this valence information. SIGNIFICANCE STATEMENT There is an open question as to whether human amygdala function tracks the valence value of cues in the environment, as opposed to either a more general emotional arousal value or a more specific emotion category distinction. Here, we demonstrate the utility of surprised facial expressions because exemplars within this emotion category take on valence values spanning the dimension of bipolar valence (positive to negative) at a consistent level of emotional arousal. Functional neuroimaging data showed that amygdala responses tracked the valence of surprised facial expressions, unconfounded by arousal. Furthermore, a machine learning classifier identified

  5. Magnetism of mixed valence (LaSr) hexaferrites

    Czech Academy of Sciences Publication Activity Database

    Novák, Pavel; Knížek, Karel; Küpferling, M.; Grössinger, R.; Pieper, M.W.

    2005-01-01

    Roč. 43, - (2005), s. 509-515 ISSN 1434-6028 R&D Projects: GA ČR(CZ) GA202/03/0552 Grant - others:FWF(AT) P15700 aP16500-NO2 Institutional research plan: CEZ:AV0Z1010914 Keywords : ferrimagnetics * narrow band systems * intermediate valence solids Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.720, year: 2005

  6. Feedback Valence Affects Auditory Perceptual Learning Independently of Feedback Probability

    Science.gov (United States)

    Amitay, Sygal; Moore, David R.; Molloy, Katharine; Halliday, Lorna F.

    2015-01-01

    Previous studies have suggested that negative feedback is more effective in driving learning than positive feedback. We investigated the effect on learning of providing varying amounts of negative and positive feedback while listeners attempted to discriminate between three identical tones; an impossible task that nevertheless produces robust learning. Four feedback conditions were compared during training: 90% positive feedback or 10% negative feedback informed the participants that they were doing equally well, while 10% positive or 90% negative feedback informed them they were doing equally badly. In all conditions the feedback was random in relation to the listeners’ responses (because the task was to discriminate three identical tones), yet both the valence (negative vs. positive) and the probability of feedback (10% vs. 90%) affected learning. Feedback that informed listeners they were doing badly resulted in better post-training performance than feedback that informed them they were doing well, independent of valence. In addition, positive feedback during training resulted in better post-training performance than negative feedback, but only positive feedback indicating listeners were doing badly on the task resulted in learning. As we have previously speculated, feedback that better reflected the difficulty of the task was more effective in driving learning than feedback that suggested performance was better than it should have been given perceived task difficulty. But contrary to expectations, positive feedback was more effective than negative feedback in driving learning. Feedback thus had two separable effects on learning: feedback valence affected motivation on a subjectively difficult task, and learning occurred only when feedback probability reflected the subjective difficulty. To optimize learning, training programs need to take into consideration both feedback valence and probability. PMID:25946173

  7. Continuum-limit scaling of overlap fermions as valence quarks

    Energy Technology Data Exchange (ETDEWEB)

    Cichy, Krzysztof [Adam Mickiewicz Univ., Poznan (Poland). Faculty of Physics; Herdoiza, Gregorio; Jansen, Karl [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany). John von Neumann-Inst. fuer Computing NIC

    2009-10-15

    We present the results of a mixed action approach, employing dynamical twisted mass fermions in the sea sector and overlap valence fermions, with the aim of testing the continuum limit scaling behaviour of physical quantities, taking the pion decay constant as an example. To render the computations practical, we impose for this purpose a fixed finite volume with lattice size L{approx}1.3 fm. We also briefly review the techniques we have used to deal with overlap fermions. (orig.)

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

    Science.gov (United States)

    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.

  9. Bond-Slip Relationship for CFRP Sheets Externally Bonded to Concrete under Cyclic Loading.

    Science.gov (United States)

    Li, Ke; Cao, Shuangyin; Yang, Yue; Zhu, Juntao

    2018-02-26

    The objective of this paper was to explore the bond-slip relationship between carbon fiber-reinforced polymer (CFRP) sheets and concrete under cyclic loading through experimental and analytical approaches. Modified beam tests were performed in order to gain insight into the bond-slip relationship under static and cyclic loading. The test variables are the CFRP-to-concrete width ratio, and the bond length of the CFRP sheets. An analysis of the test results in this paper and existing test results indicated that the slope of the ascending segment of the bond-slip curve decreased with an increase in the number of load cycles, but the slip corresponding to the maximum shear stress was almost invariable as the number of load cycles increased. In addition, the rate of reduction in the slope of the ascending range of the bond-slip curve during cyclic loading decreased as the concrete strength increased, and increased as the load level or CFRP-to-concrete width ratio enhanced. However, these were not affected by variations in bond length if the residual bond length was longer than the effective bond length. A bilinear bond-slip model for CFRP sheets that are externally bonded to concrete under cyclic loading, which considered the effects of the cyclic load level, concrete strength, and CFRP-to-concrete ratio, was developed based on the existing static bond-slip model. The accuracy of this proposed model was verified by a comparison between this proposed model and test results.

  10. Incremental validity of positive and negative valence in predicting personality disorder.

    Science.gov (United States)

    Simms, Leonard J; Yufik, Tom; Gros, Daniel F

    2010-04-01

    The Big Seven model of personality includes five dimensions similar to the Big Five model as well as two evaluative dimensions—Positive Valence (PV) and Negative Valence (NV)—which reflect extremely positive and negative person descriptors, respectively. Recent theory and research have suggested that PV and NV predict significant variance in personality disorder (PD) above that predicted by the Big Five, but firm conclusions have not been possible because previous studies have been limited to only single measures of PV, NV, and the Big Five traits. In the present study, we replicated and extended previous findings using three markers of all key constructs—including PV, NV, and the Big Five—in a diverse sample of 338 undergraduates. Results of hierarchical multiple regression analyses revealed that PV incrementally predicted Narcissistic and Histrionic PDs above the Big Five and that NV nonspecifically incremented the prediction of most PDs. Implications for dimensional models of personality pathology are discussed. PsycINFO Database Record (c) 2010 APA, all rights reserved.

  11. The Origin of the Non-Additivity in Resonance-Assisted Hydrogen Bond Systems.

    Science.gov (United States)

    Lin, Xuhui; Zhang, Huaiyu; Jiang, Xiaoyu; Wu, Wei; Mo, Yirong

    2017-11-09

    The concept of resonance-assisted hydrogen bond (RAHB) has been widely accepted, and its impact on structures and energetics can be best studied computationally using the block-localized wave function (BLW) method, which is a variant of ab initio valence bond (VB) theory and able to derive strictly electron-localized structures self-consistently. In this work, we use the BLW method to examine a few molecules that result from the merging of two malonaldehyde molecules. As each of these molecules contains two hydrogen bonds, these intramolecular hydrogen bonds may be cooperative or anticooperative, depended on their relative orientations, and compared with the hydrogen bond in malonaldehyde. Apart from quantitatively confirming the concept of RAHB, the comparison of the computations with and without π resonance shows that both σ-framework and π-resonance contribute to the nonadditivity in these RAHB systems with multiple hydrogen bonds.

  12. Comparison between alkali heat treatment and sprayed hydroxyapatite coating on thermally-sprayed rough Ti surface in rabbit model: Effects on bone-bonding ability and osteoconductivity.

    Science.gov (United States)

    Kawai, Toshiyuki; Takemoto, Mitsuru; Fujibayashi, Shunsuke; Tanaka, Masashi; Akiyama, Haruhiko; Nakamura, Takashi; Matsuda, Shuichi

    2015-07-01

    In this study, we investigated the effect of different surface treatments (hydroxyapatite (HA) coating, alkali heat treatment, and no treatment) on the ability of bone to bond to a rough arc-sprayed Ti metal surface, using rabbit models. The bone-to-implant contacts for untreated, HA-coated, and alkali heat-treated implants were 21.2%, 72.1%, and 33.8% at 4 weeks, 21.8%, 70.9%, and 30.0% at 8 weeks, and 16.3%, 70.2%, and 29.9% at 16 weeks, respectively (n = 8). HA -coated implants showed significantly higher bone-to-implant contacts than the untreated and alkali heat-treated implants at all the time point, whereas alkali heat-treated implants showed significantly higher bone-to-implant contacts than untreated implants at 4 and 16 weeks. The failure loads in a mechanical test for untreated, HA coated, alkali heat-treated plates were 65.4 N, 70.7 N, and 90.8 N at 4 weeks, 76.1 N, 64.7 N, and 104.8 N at 8 weeks and 88.7 N, 92.6 N, and 118.5 N at 16 weeks, respectively (n = 8). The alkali heat-treated plates showed significantly higher failure loads than HA-coated plates at 8 and 16 weeks. The difference between HA-coated plates and untreated plates were not statistically significant at any time point. Thus HA coating, although it enables high bone-to-implant contact, may not enhance the bone-bonding properties of thermally-sprayed rough Ti metal surfaces. In contrast, alkali heat treatment can be successfully applied to thermally-sprayed Ti metal to enhance both bone-to-implant contact and bone-bonding strength. © 2014 Wiley Periodicals, Inc.

  13. On the Relationship between Bonding Theory and Youth Gang Resistance in U.S. 8th Graders: Competing Structural Equation Models with Latent Structure Indirect Effects

    Science.gov (United States)

    Vander Horst, Anthony

    2012-01-01

    In a study of 5285 8th graders from the Gang Resistance and Education Training (G.R.E.A.T.) research, this study applied Travis Hirschi's social bonding theory to examine the curriculum's efficacy in increasing conventional bonding (friends with positive peers, succeeding at education etc.) and decreasing non-conventional bonding (drug…

  14. Ferromagnetic dinuclear mixed-valence Mn(II)/Mn(III) complexes: building blocks for the higher nuclearity complexes. structure, magnetic properties, and density functional theory calculations.

    Science.gov (United States)

    Hänninen, Mikko M; Välivaara, Juha; Mota, Antonio J; Colacio, Enrique; Lloret, Francesc; Sillanpää, Reijo

    2013-02-18

    A series of six mixed-valence Mn(II)/Mn(III) dinuclear complexes were synthesized and characterized by X-ray diffraction. The reactivity of the complexes was surveyed, and structures of three additional trinuclear mixed-valence Mn(III)/Mn(II)/Mn(III) species were resolved. The magnetic properties of the complexes were studied in detail both experimentally and theoretically. All dinuclear complexes show ferromagnetic intramolecular interactions, which were justified on the basis of the electronic structures of the Mn(II) and Mn(III) ions. The large Mn(II)-O-Mn(III) bond angle and small distortion of the Mn(II) cation from the ideal square pyramidal geometry were shown to enhance the ferromagnetic interactions since these geometrical conditions seem to favor the orthogonal arrangement of the magnetic orbitals.

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

    Science.gov (United States)

    Graf, Peter; Yu, Martin

    2015-01-01

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

  16. Estimating valence from the sound of a word: Computational, experimental, and cross-linguistic evidence.

    Science.gov (United States)

    Louwerse, Max; Qu, Zhan

    2017-06-01

    It is assumed linguistic symbols must be grounded in perceptual information to attain meaning, because the sound of a word in a language has an arbitrary relation with its referent. This paper demonstrates that a strong arbitrariness claim should be reconsidered. In a computational study, we showed that one phonological feature (nasals in the beginning of a word) predicted negative valence in three European languages (English, Dutch, and German) and positive valence in Chinese. In three experiments, we tested whether participants used this feature in estimating the valence of a word. In Experiment 1, Chinese and Dutch participants rated the valence of written valence-neutral words, with Chinese participants rating the nasal-first neutral-valence words more positive and the Dutch participants rating nasal-first neutral-valence words more negative. In Experiment 2, Chinese (and Dutch) participants rated the valence of Dutch (and Chinese) written valence-neutral words without being able to understand the meaning of these words. The patterns replicated the valence patterns from Experiment 1. When the written words from Experiment 2 were transformed into spoken words, results in Experiment 3 again showed that participants estimated the valence of words on the basis of the sound of the word. The computational study and psycholinguistic experiments indicated that language users can bootstrap meaning from the sound of a word.

  17. On pleasure and thrill: the interplay between arousal and valence during visual word recognition.

    Science.gov (United States)

    Recio, Guillermo; Conrad, Markus; Hansen, Laura B; Jacobs, Arthur M

    2014-07-01

    We investigated the interplay between arousal and valence in the early processing of affective words. Event-related potentials (ERPs) were recorded while participants read words organized in an orthogonal design with the factors valence (positive, negative, neutral) and arousal (low, medium, high) in a lexical decision task. We observed faster reaction times for words of positive valence and for those of high arousal. Data from ERPs showed increased early posterior negativity (EPN) suggesting improved visual processing of these conditions. Valence effects appeared for medium and low arousal and were absent for high arousal. Arousal effects were obtained for neutral and negative words but were absent for positive words. These results suggest independent contributions of arousal and valence at early attentional stages of processing. Arousal effects preceded valence effects in the ERP data suggesting that arousal serves as an early alert system preparing a subsequent evaluation in terms of valence. Copyright © 2014 Elsevier Inc. All rights reserved.

  18. High-pressure synchrotron Mössbauer and X-ray diffraction studies: Exploring the structure-related valence fluctuation in EuNi{sub 2}P{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Li, Chunyu [Center for High Pressure Science and Technology Advanced Research, Shanghai 201203 (China); Natural Science Research Center, Academy of Fundamental and Interdisciplinary Sciences, Harbin Institute of Technology, Harbin 150080 (China); Yu, Zhenhai, E-mail: yuzh@hpstar.ac.cn [Center for High Pressure Science and Technology Advanced Research, Shanghai 201203 (China); Natural Science Research Center, Academy of Fundamental and Interdisciplinary Sciences, Harbin Institute of Technology, Harbin 150080 (China); Bi, Wenli [Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439 (United States); Department of Geology, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Zhao, Jiyong; Hu, Michael Y. [Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439 (United States); Zhao, Jinggeng [Natural Science Research Center, Academy of Fundamental and Interdisciplinary Sciences, Harbin Institute of Technology, Harbin 150080 (China); Wu, Wei [Beijing National Lab for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China); Luo, Jianlin [Beijing National Lab for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China); Collaborative Innovation Center of Quantum Matter, Beijing 100190 (China); Yan, Hao, E-mail: yanhao@hpstar.ac.cn [Center for High Pressure Science and Technology Advanced Research, Shanghai 201203 (China); Alp, Esen E. [Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439 (United States); Liu, Haozhe, E-mail: haozhe.liu@hpstar.ac.cn [Center for High Pressure Science and Technology Advanced Research, Shanghai 201203 (China); Natural Science Research Center, Academy of Fundamental and Interdisciplinary Sciences, Harbin Institute of Technology, Harbin 150080 (China)

    2016-11-15

    The high-pressure effect on valence fluctuation of the ThCr{sub 2}Si{sub 2}-type intermetallic compound EuNi{sub 2}P{sub 2} has been investigated using in situ synchrotron Mössbauer spectroscopy (SMS). The isomer shift of {sup 151}Eu in EuNi{sub 2}P{sub 2} increases monotonically with increasing pressure up to 50 GPa, suggesting a valence transition of the Eu from mixed toward trivalent. The synchrotron angle-dispersive X-ray diffraction (AD-XRD) experiment shows that EuNi{sub 2}P{sub 2} remains in the tetragonal structure up to 32.5 GPa at room temperature. We propose that the evolutions of bonding distance with pressure have an obvious effect on the valence fluctuation.

  19. Comparing possible proxies of corporate bond liquidity

    OpenAIRE

    Houweling, Patrick; Mentink, A.A.; Vorst, Ton

    2003-01-01

    textabstractWe consider eight different proxies (issued amount, coupon, listed, age, missing prices, yield volatility, number of contributors and yield dispersion) to measure corporate bond liquidity and use a five-variable model to control for interest rate risk, credit risk, maturity, rating and currency differences between bonds. The null hypothesis that liquidity risk is not priced in our data set of euro corporate bonds is rejected for seven out of eight liquidity proxies. We find signif...

  20. Decomposing European bond and equity volatility

    OpenAIRE

    Christiansen, Charlotte

    2004-01-01

    The paper investigates volatility spillover from US and aggregate European asset markets into European national asset markets. A main contribution is that bond and equity volatilities are analyzed simultaneously. A new model belonging to the "volatilityspillover" family is suggested: The conditional variance of e.g. the unexpected German stock return is divided into separate effects from the contemporaneous idiosyncratic variance of US bonds, US stocks, European bonds, European stocks, German...

  1. Osteoinductive potential and bone-bonding ability of ProRoot MTA, MTA Plus and Biodentine in rabbit intramedullary model: Microchemical characterization and histological analysis.

    Science.gov (United States)

    Gandolfi, M G; Iezzi, G; Piattelli, A; Prati, C; Scarano, A

    2017-05-01

    in medullary bone in appropriate animal model have been demonstrated by ESEM-EDX in association with OM. Good biocompatibility was evident as only slight inflammatory infiltrate and no sign of necrosis at the interface with the pre-existing bone were found. MTA Plus and ProRoot MTA exhibited bioactive potential as they can bond to bone directly without interposed connective tissue. Biodentine was replaced by newly formed bone. The results of the study demonstrate the capacity of calcium silicate cements to allow osteoid matrix deposition by activated osteoblasts and favour its biomineralization, and to achieve a direct bond between the (bioactive) materials surface and the mineralized bone matrix. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  2. Interactions between incentive valence and action information in a cued approach-avoidance task.

    Science.gov (United States)

    Hoofs, Vincent; Carsten, Thomas; Boehler, C Nico; Krebs, Ruth M

    2018-01-10

    Environmental stimuli can provoke specific response tendencies depending on their incentive valence. While some studies report positive-approach and negative-avoidance biases, others find no such mappings. To further illuminate the relationship between incentive valence and action requirement, we combined a cued monetary incentive paradigm with an approach/avoidance joystick task. Incentive type was manipulated between groups: The reward group won money, while the punishment group avoided losing money for correct and fast responses to targets following incentive cues. Depending on their orientations, targets had to be 'approached' or 'avoided'. Importantly, incentive valence (signaled by cue color) was orthogonal to action requirement (target orientation). Moreover, targets could carry valence-associated information or not (target color), which was, however, task-irrelevant. First, we observed that both valence cues (reward/punishment) improved performance compared to neutral cues, independent of the required action (approach/avoid), suggesting that advance valence cues do not necessarily produce specific action biases. Second, task-irrelevant valence associations with targets promoted action biases, with valence-associated targets facilitating approach and impairing avoid responses. Importantly, this approach bias for valence-associated targets was observed in both groups and hence occurred independently of absolute valence ('unsigned'). This rather unexpected finding might be related to the absence of a direct contrast between positive valence and negative valence within groups and the common goal to respond fast and accurately in all incentive trials. Together, our results seem to challenge the notion that monetary incentives trigger 'hard-wired' valence-action biases in that specific design choices seem to modulate the presence and/or direction of valence-action biases.

  3. Australia's Bond Home Bias

    OpenAIRE

    Anil V. Mishra; Umaru B. Conteh

    2014-01-01

    This paper constructs the float adjusted measure of home bias and explores the determinants of bond home bias by employing the International Monetary Fund's high quality dataset (2001 to 2009) on cross-border bond investment. The paper finds that Australian investors' prefer investing in countries with higher economic development and more developed bond markets. Exchange rate volatility appears to be an impediment for cross-border bond investment. Investors prefer investing in countries with ...

  4. Pressure shifts of valence and core exciton peaks in potassium iodide

    International Nuclear Information System (INIS)

    Yamada, Akio; Fukutani, Hirohito; Miyabe, Masabumi; Yagi, Kazutoshi; Kato, Hiroo; Koide, Tsuneharu; Shidara, Tetsuo; Miyahara, Tsuneaki; Sato, Shigeru.

    1985-01-01

    Hydrostatic pressure shifts of valence and core exciton peaks in KI are measured with a modulation method at about 120 K. The pressure coefficients are determined to be, in units of 10 -3 meV/bar, 17.0 and 4.7 for the valence excitons at 5.73 and 7.22 eV, and 18.8, 17.0 and -38.7 for the core excitons at 19.95, 20.20 and 21.05 eV, respectively. The pressure shifts of the lowest exciton at 5.73 eV and the core excitons are discussed with a simple model of localized transitions. Experimental results for the lowest exciton and the core excitons at 19.95 and 20.20 eV are explained well in this model, but the shift of the core exciton at 21.05 eV does not agree with the theoretical expectation. The exciton-phonon interaction term contributing to thermal shifts of the excitons is deduced from the present pressure coefficients. (author)

  5. Functionality versus dimensionality in psychological taxonomies, and a puzzle of emotional valence.

    Science.gov (United States)

    Trofimova, Irina

    2018-04-19

    This paper applies evolutionary and functional constructivism approaches to the discussion of psychological taxonomies, as implemented in the neurochemical model Functional Ensemble of Temperament (FET). FET asserts that neurochemical systems developed in evolution to regulate functional-dynamical aspects of construction of actions: orientation, selection (integration), energetic maintenance, and management of automatic behavioural elements. As an example, the paper reviews the neurochemical mechanisms of interlocking between emotional dispositions and performance capacities. Research shows that there are no specific neurophysiological systems of positive or negative affect, and that emotional valence is rather an integrative product of many brain systems during estimations of needs and the capacities required to satisfy these needs. The interlocking between emotional valence and functional aspects of performance appears to be only partial since all monoamine and opioid receptor systems play important roles in non-emotional aspects of behaviour, in addition to emotionality. This suggests that the Positive/Negative Affect framework for DSM/ICD classifications of mental disorders oversimplifies the structure of non-emotionality symptoms of these disorders. Contingent dynamical relationships between neurochemical systems cannot be represented by linear statistical models searching for independent dimensions (such as factor analysis); nevertheless, these relationships should be reflected in psychological and psychiatric taxonomies.This article is part of the theme issue 'Diverse perspectives on diversity: multi-disciplinary approaches to taxonomies of individual differences'. © 2018 The Authors.

  6. Levels and transitions in /sup 204/Pb and the four valence neutron-hole configurations

    International Nuclear Information System (INIS)

    Hanly, J.M.; Hicks, S.E.; McEllistrem, M.T.; Yates, S.W.

    1988-01-01

    Levels of the nucleus /sup 204/Pb have been investigated using the (n,n'γ) reaction, and γ rays from low-spin excited levels have been observed. Forty-three low-spin levels connected by 78 γ rays are found below 2.9 MeV, whereas only about 28 levels had previously been known. The levels below 2 MeV excitation energy are expected to be dominated by the p/sub 1/2/, f/sub 5/2/, and p/sub 3/2/ valence neutron hole excitations, and 0 + levels at 0, 1730, and 2433.1 keV are associated primarily with these configurations. These states are at almost the same excitation energies as parent 0 + excitations in /sup 206/Pb. Approximately six unnatural-parity levels are identified; this is close to the number predicted in six orbit valence-space shell model calculations. The number of natural-parity levels found, however, is almost twice that calculated with the shell model. Levels and transitions below 2 MeV excitation energy are consistent with expectations basing /sup 204/Pb states on correlated two-hole excitations dominant in /sup 206/Pb

  7. Magnetic and magnetoelastic properties of valence transition compounds based on YbInCu4 (Review Article)

    Science.gov (United States)

    Mushnikov, N. V.

    2015-12-01

    The intermetallic compound YbInCu4 undergoes an isostructural first-order valence-changing phase transition from a state with localized moments of the Yb into a Fermi liquid state with strong Kondo screening. This article reviews studies of the structure and of the electronic, magnetic, and magnetoelastic properties of compounds based on YbInCu4. The effects of alloying and pressure on such parameters of the electronic and magnetic state as the Kondo temperature, Curie paramagnetic temperature, effective magnetic moment, and valence of Yb are determined. The observational data are interpreted in terms of a single-impurity Kondo model. The magnetic anisotropy of single-crystal YbInCu4 and magnetostriction in high magnetic fields are studied. It is shown that a crystal field model for localized states of Yb3+ provides a good description of magnetic anisotropy and anisotropic magnetostriction in the high-temperature phase.

  8. A simple beam model to analyse the durability of adhesively bonded tile floorings in presence of shrinkage

    Directory of Open Access Journals (Sweden)

    S. de Miranda

    2014-07-01

    Full Text Available A simple beam model for the evaluation of tile debonding due to substrate shrinkage is presented. The tile-adhesive-substrate package is modeled as an Euler-Bernoulli beam laying on a two-layer elastic foundation. An effective discrete model for inter-tile grouting is introduced with the aim of modelling workmanship defects due to partial filled groutings. The model is validated using the results of a 2D FE model. Different defect configurations and adhesive typologies are analysed, focusing the attention on the prediction of normal stresses in the adhesive layer under the assumption of Mode I failure of the adhesive.

  9. Postpartum bonding: the role of perinatal depression, anxiety and maternal-fetal bonding during pregnancy.

    Science.gov (United States)

    Dubber, S; Reck, C; Müller, M; Gawlik, S

    2015-04-01

    Adverse effects of perinatal depression on the mother-child interaction are well documented; however, the influence of maternal-fetal bonding during pregnancy on postpartum bonding has not been clearly identified. The subject of this study was to investigate prospectively the influence of maternal-fetal bonding and perinatal symptoms of anxiety and depression on postpartum mother-infant bonding. Data from 80 women were analyzed for associations of symptoms of depression and anxiety as well as maternal bonding during pregnancy to maternal bonding in the postpartum period using the Edinburgh Postnatal Depression Scale (EPDS), the State-Trait Anxiety Inventory (STAI), the Pregnancy Related Anxiety Questionnaire (PRAQ-R), the Maternal-Fetal Attachment Scale (MFAS) and the Postpartum Bonding Questionnaire (PBQ-16). Maternal education, MFAS, PRAQ-R, EPDS and STAI-T significantly correlated with the PBQ-16. In the final regression model, MFAS and EPDS postpartum remained significant predictors of postpartum bonding and explained 20.8 % of the variance. The results support the hypothesized negative relationship between maternal-fetal bonding and postpartum maternal bonding impairment as well as the role of postpartum depressive symptoms. Early identification of bonding impairment during pregnancy and postpartum depression in mothers plays an important role for the prevention of potential bonding impairment in the early postpartum period.

  10. Crystal structures of two mixed-valence copper cyanide complexes withN-methyl-ethylenedi-amine.

    Science.gov (United States)

    Corfield, Peter W R; Sabatino, Alexander

    2017-02-01

    The crystal structures of two mixed-valence copper cyanide compounds involving N -methyl-ethylenedi-amine (meen), are described. In compound (I), poly[bis(μ 3 -cyanido-κ 3 C : C : N )tris(μ 2 -cyanido-κ 2 C : N )bis( N -methylethane-1,2-di-amine-κ 2 N , N ')tricopper(I)copper(II)], [Cu 4 (CN) 5 (C 3 H 10 N 2 ) 2 ] or Cu 4 (CN) 5 meen 2 , cyanide groups link Cu I atoms into a three-dimensional network containing open channels parallel to the b axis. In the network, two tetra-hedrally bound Cu I atoms are bonded by the C atoms of two end-on bridging CN groups to form Cu 2 (CN) 6 moieties with the Cu atoms in close contact at 2.560 (1) Å. Other trigonally bound Cu I atoms link these units together to form the network. The Cu II atoms, coordinated by two meen units, are covalently linked to the network via a cyanide bridge, and project into the open network channels. In the mol-ecular compound (II), [( N -methylethylenediamine-κ 2 N , N ')copper(II)]-μ 2 -cyanido-κ 2 C : N -[bis(cyanido-κ C )copper(I)] monohydrate, [Cu 2 (CN) 3 (C 3 H 10 N 2 ) 2 ]·H 2 O or Cu 2 (CN) 3 meen 2 ·H 2 O, a CN group connects a Cu II atom coordinated by two meen groups with a trigonal-planar Cu I atom coordinated by CN groups. The mol-ecules are linked into centrosymmetric dimers via hydrogen bonds to two water mol-ecules. In both compounds, the bridging cyanide between the Cu II and Cu I atoms has the N atom bonded to Cu II and the C atom bonded to Cu I , and the Cu II atoms are in a square-pyramidal coordination.

  11. Generalized bond percolation and statistical mechanics

    International Nuclear Information System (INIS)

    Tsallis, C.

    1978-05-01

    A generalization of traditional bond percolation is performed, in the sens that bonds have now the possibility of partially transmitting the information (a fact which leads to the concept of 'fidelity' of the bond), and also in the sens that, besides the normal tendency to equiprobability, the bonds are allowed to substantially change the information. Furthermore the fidelity is allowed, to become an aleatory variable, and the operational rules concerning the associated distribution laws are determined. Thermally quenched random bonds and the whole body of Statistical Mechanics become particular cases of this formalism, which is in general adapted to the treatment of all problems whose main characteristic is to preserve a part of the information through a long path or array (critical phenomena, regime changements, thermal random models, etc). Operationally it provides a quick method for the calculation of the equivalent probability of complex clusters within the traditional bond percolation problem [pt

  12. DETERMINANTS OF ORI001 TYPE GOVERNMENT BOND

    Directory of Open Access Journals (Sweden)

    Yosandi Yulius

    2011-09-01

    Full Text Available The need to build a strong bond market is amenable, especially after the 1997 crises. This paper analyzes the influence of deposit interest rate, foreign exchange rates, and Composite Stock Price Index on yield-to-maturity of Bond Series Retail ORI001, employing monthly data from Bloomberg information service, 2006(8 to 2008(12, using Generalized Autoregressive Conditional Heteroscedasticity type models. It finds the evidence that deposit interest rate and exchange rate have positive significant influence on the bond, and that stock index has a negative significant influence on the bond. It also finds that Deposit Interest Rate, exchange rate, and the stock index significantly influence the bond altogether.Keywords: Interest rate, exchange rate, composite stock price index, yield-to-maturity, bondJEL classification numbers: G12, G15

  13. Decomposing European bond and equity volatility

    DEFF Research Database (Denmark)

    Christiansen, Charlotte

    The paper investigates volatility spillover from US and aggregate European asset markets into European national asset markets. A main contribution is that bond and equity volatilities are analyzed simultaneously. A new model belonging to the "volatilityspillover" family is suggested......: The conditional variance of e.g. the unexpected German stock return is divided into separate effects from the contemporaneous idiosyncratic variance of US bonds, US stocks, European bonds, European stocks, German bonds, and German stocks. Significant volatility-spillover effects are found. The national bond...... (stock) volatilities are mainly influenced by bond (stock) effects. Global, regional, and local volatility effects are all important. The introduction of the euro is associated with a structural break....

  14. Vanadium, sulfur, and iron valences in melt inclusions as a window into magmatic processes: A case study at Nyamuragira volcano, Africa

    Science.gov (United States)

    Head, Elisabet; Lanzirotti, Antonio; Newville, Matthew; Sutton, Stephen

    2018-04-01

    This study describes microscale sulfur (S), vanadium (V), and iron (Fe) K-edge X-ray absorption near edge structure (μ-XANES) spectroscopy measurements on olivine-hosted melt inclusions (MI) preserved in tephras (1986 and 2006) and lavas (1938 and 1948) erupted from Nyamuragira volcano (D.R. Congo, Africa). The S, V, and Fe spectroscopic data are used to constrain the evolution of oxygen fugacity (fO2) and sulfur speciation for the entrapped melts. Melt inclusions from lavas show evidence of post-entrapment crystallization and were thus reheated prior to μ-XANES analysis. The MI from tephra show no evidence of post-entrapment crystallization and were, therefore, not reheated. Sulfur, V, and Fe μ-XANES results from 1938, 1948, and 2006 eruptive materials are all similar within analytical uncertainty and provide similar average calculated melt fO2's based on XANES oxybarometry. However, olivine-hosted MI from the 1986 tephras yield significantly different S, V, and Fe XANES spectra when compared to MI from the other eruptions, with disagreement between calculated fO2's from the three valence state oxybarometers beyond the uncertainty of the calibration models. Their V μ-XANES spectra are also significantly more ordered and yield more reduced average V valence. The S μ-XANES spectra display a significantly more intense low-energy spectral resonance, which indicates differences in Fe-S bonding character, and greater variability in their measured sulfate content. These V and S spectroscopic features are best explained by crystallization of sub-micrometer magnetite and sulfide crystallites within the 1986 inclusions. The sensitivity of XANES spectroscopy to short-range order allows these crystallites to be recognized even though they are not easily detected by imaging analysis. This shows that V and S μ-XANES are potentially highly sensitive tools for identifying the presence of volumetrically minor amounts of spinel and sulfide within inclusions extracted from

  15. Amorphous Mixed-Valence Vanadium Oxide/Exfoliated Carbon Cloth Structure Shows a Record High Cycling Stability.

    Science.gov (United States)

    Song, Yu; Liu, Tian-Yu; Yao, Bin; Kou, Tian-Yi; Feng, Dong-Yang; Liu, Xiao-Xia; Li, Yat

    2017-04-01

    Previous studies show that vanadium oxides suffer from severe capacity loss during cycling in the liquid electrolyte, which has hindered their applications in electrochemical energy storage. The electrochemical instability is mainly due to chemical dissolution and structural pulverization of vanadium oxides during charge/discharge cyclings. In this study the authors demonstrate that amorphous mixed-valence vanadium oxide deposited on exfoliated carbon cloth (CC) can address these two limitations simultaneously. The results suggest that tuning the V 4+ /V 5+ ratio of vanadium oxide can efficiently suppress the dissolution of the active materials. The oxygen-functionalized carbon shell on exfoliated CC can bind strongly with VO x via the formation of COV bonding, which retains the electrode integrity and suppresses the structural degradation of the oxide during charging/discharging. The uptake of structural water during charging and discharging processes also plays an important role in activating the electrode material. The amorphous mixed-valence vanadium oxide without any protective coating exhibits record-high cycling stability in the aqueous electrolyte with no capacitive decay in 100 000 cycles. This work provides new insights on stabilizing vanadium oxide, which is critical for the development of vanadium oxide based energy storage devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Structural, intramolecular hydrogen bonding and vibrational studies ...

    Indian Academy of Sciences (India)

    The harmonic oscillator model of aromaticity (HOMA) index elucidated the impact of hydrogen bond- ing in the ring. Intramolecular hydrogen bonding energy has been calculated from topological study. The low wavenumber vibrational modes obtained from experimental FT-Raman spectrum also supported the presence.

  17. A Direct Proof of the Resonance-Impaired Hydrogen Bond (RIHB) Concept.

    Science.gov (United States)

    Lin, Xuhui; Wu, Wei; Mo, Yirong

    2018-01-24

    The concept of resonance-enhanced hydrogen bond (RAHB) has been widely accepted and applied as it highlights the positive impact of π-conjugation on intramolecular H-bonds. However, electron delocalization is directional and there is a possibility that π-resonance goes from the H-bond acceptor to the H-bond donor, leading to a negative impact on H-bonds. Here we used the block-localized wavefunction (BLW) method which is a variant of ab initio valence bond (VB) theory and able to derive strictly electron-localized structures self-consistently, to quantify the interplay between H-bond and π-resonance in the terms of geometry, energetics and spectral properties. The comparison of geometrical optimizations with and without π-resonance shows that conjugation can indeed either enhance or weaken intramolecular H-bonds. We further experimented with various substituents attached to either the H-bond acceptor and/or H-bond donor side(s) to tune the H-bonding strength in both directions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. THREE-VALENCE-PARTICE NUCLEI IN THE 132Sn and 208 Pb REGIONS

    International Nuclear Information System (INIS)

    Benchikh, L.; Draoui, B.; Latfaoui, M.; Aissaoui, L.

    2011-01-01

    Full text: Among the nuclei of the nuclear charter, the nuclei around closed shells play a key role in understanding the effective interaction properties between nucleons far from the valley of stability; particulary, the nuclei of a few valence nucleons around doubly magic 208 28Pb126 and 132 50Sn82 nuclei. The interest of both regions 208Pb and 132Sn lies in the fact that there is a great similarity between their nuclear spectroscopic properties. The single energy gaps in both cases are comparable and the orbitals above and below these gaps are similarly ordered. Each single state in the region of 132Sn has its counterpart in that of 208Pb. An interesting predictive consequence, the interactions of the Sn region, difficult region to reach experimentally, can be estimated from their corresponding ones constructed to describe the nuclei of the Pb region. Because of the importance of the similarity existing between the spectroscopy of these two regions, we are interested in nuclei with three valence nucleons in the lead and Tin regions on the basis of experimental data (spin, parity and energy states). In this context, the theoretical study is conducted within the shell model using the MSDI interaction for the energy spectra calculations of the studied nuclei. The calculated results are in good agreement with the available experimental data and show evidence that a close resemblance between the spectroscopy of these two regions persists when moving away from the immediate neighbours of doubly magic 132Sn and 208Pb.

  19. Stress and emotional valence effects on children's versus adolescents' true and false memory.

    Science.gov (United States)

    Quas, Jodi A; Rush, Elizabeth B; Yim, Ilona S; Edelstein, Robin S; Otgaar, Henry; Smeets, Tom

    2016-01-01

    Despite considerable interest in understanding how stress influences memory accuracy and errors, particularly in children, methodological limitations have made it difficult to examine the effects of stress independent of the effects of the emotional valence of to-be-remembered information in developmental populations. In this study, we manipulated stress levels in 7-8- and 12-14-year-olds and then exposed them to negative, neutral, and positive word lists. Shortly afterward, we tested their recognition memory for the words and false memory for non-presented but related words. Adolescents in the high-stress condition were more accurate than those in the low-stress condition, while children's accuracy did not differ across stress conditions. Also, among adolescents, accuracy and errors were higher for the negative than positive words, while in children, word valence was unrelated to accuracy. Finally, increases in children's and adolescents' cortisol responses, especially in the high-stress condition, were related to greater accuracy but not false memories and only for positive emotional words. Findings suggest that stress at encoding, as well as the emotional content of to-be-remembered information, may influence memory in different ways across development, highlighting the need for greater complexity in existing models of true and false memory formation.

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

    International Nuclear Information System (INIS)

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

    1987-10-01

    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 2 O 5 H 2 ) 4 Cl)·H 2 O 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 2 Cl chain by a chemical defect. The observed spectral characteristics of this local state are in good agreement with theoretical predictions. (author). 28 refs, 4 figs, 1 tab

  1. A molecular mechanics valence force field for sulfonamides derived by ab initio methods

    Energy Technology Data Exchange (ETDEWEB)

    Nicholas, J.B.; Burke, B.J.; Hopfinger, A.J. (Univ. of Illinois, Chicago (United States)); Vance, R.; Martin, E. (DowElanco, Walnut Creek, CA (United States))

    1991-11-28

    Molecular mechanics valence force field parameters for the sulfonamide group, SO[sub 2]NH, have been derived from ab initio calculations at the RHF/6-31G* level of theory. The force field parameters were designed to be used in conjunction with existing parameters from the MM2/MMP2 force field. The new parameters are demonstrated to accurately reproduce the ab initio optimized geometries of four molecules that contain the sulfonamide group. The strategy used in force field parametrization is discussed. The conformational flexibility of the sulfonamide group has been investigated. Calculations at the RHF/6-31G* level reveal the existence of two stable conformers and that interconversion is achieved by nitrogen inversion rather than rotation about the S-N bond. The energetic effects of expanding the basis set to 6-31G** and of including MP2 and MP3 corrections for electron correlation are discussed. The geometries and Mulliken charges for the ab initio optimized structures are also reported.

  2. Valence-band of cubic semiconductors: Clifford algebra approach II

    International Nuclear Information System (INIS)

    Dargys, A

    2010-01-01

    Application of Clifford algebra in the analysis of valence-band spin properties in semiconductors is considered. In the first part (Dargys A 2009 Phys. Scr. 80 065701), for this purpose the isomorphism between multivectors and their matrix representations was used to transform the problem to Clifford algebra. Here equivalence rules are established between the spinors of Hilbert space and basis elements of the five-dimensional Clifford algebra Cl 4,1 . Then, the rules are applied to the total angular momentum components and the two-band hole Hamiltonian. The resulting biquaternionic Schroedinger equation for hole spin is solved as an example.

  3. Valence-band of cubic semiconductors: Clifford algebra approach II

    Science.gov (United States)

    Dargys, A.

    2010-07-01

    Application of Clifford algebra in the analysis of valence-band spin properties in semiconductors is considered. In the first part (Dargys A 2009 Phys. Scr. 80 065701), for this purpose the isomorphism between multivectors and their matrix representations was used to transform the problem to Clifford algebra. Here equivalence rules are established between the spinors of Hilbert space and basis elements of the five-dimensional Clifford algebra Cl4, 1. Then, the rules are applied to the total angular momentum components and the two-band hole Hamiltonian. The resulting biquaternionic Schrödinger equation for hole spin is solved as an example.

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

    Science.gov (United States)

    Majerz, Irena; Olovsson, Ivar

    2010-01-01

    The quantum-mechanically derived reaction coordinates (QMRC) for the proton transfer in O-H-O hydrogen bonds have been derived from ab initio calculations of potential-energy surfaces. A comparison is made between the QMRC and the corresponding bond-order reaction coordinates (BORC) derived by applying the Pauling bond order concept together with the principle of conservation of bond order. In agreement with earlier results for N-H-N(+) hydrogen bonds there is virtually perfect agreement between the QMRC and BORC curves for intermolecular O-H-O hydrogen bonds. For intramolecular O-H-O hydrogen bonds, the donor and acceptor parts of the molecule impose strong constraints on the O···O distance and the QMRC does not follow the BORC relation in the whole range. The neutron-determined proton positions are located close to the theoretically calculated potential-energy minima, and where the QMRC and the BORC curves coincide with each other. The results confirm the universal character of intermolecular hydrogen bonds: BORC is identical with QMRC and the proton can be moved from donor to acceptor keeping its valency equal to 1. The shape of PES for intramolecular hydrogen bonds is more complex as it is sensitive to the geometry of the molecule as well as of the hydrogen bridge. This journal is © the Owner Societies 2010

  5. The multimedia models for the evaluation of exposure bond to the atmospheric emissions of classified installations; Les modeles multimedia pour l'evaluation des expositions liees aux emissions atmospheriques des installations classees

    Energy Technology Data Exchange (ETDEWEB)

    Bonnard, R

    2001-12-15

    Risk assessment and environmental impacts studies are realized to preserve the public health. Today one of the most used approach is the use of an atmospheric dispersion model to assess the risks. The data are then injected in a calculation software of exposure bond to polluted soils, to evaluate the risks of non direct exposure. This report details and evaluates the models corresponding to the need: the methodology for assessing Health Risks associated with multiple pathways of exposure to combustor, human health risk assessment proto col for hazardous waste combustion facilities, EUSES, CALTOX, MEPAS, MEND-TOX, RESRAD, MMSOILS, FRAMES-HWIR, PC-GEMS and TRIM. (A.L.B.)

  6. An exploration of the relationship among valence, fading affect, rehearsal frequency, and memory vividness for past personal events.

    Science.gov (United States)

    Lindeman, Meghan I H; Zengel, Bettina; Skowronski, John J

    2017-07-01

    The affect associated with negative (or unpleasant) memories typically tends to fade faster than the affect associated with positive (or pleasant) memories, a phenomenon called the fading affect bias (FAB). We conducted a study to explore the mechanisms related to the FAB. A retrospective recall procedure was used to obtain three self-report measures (memory vividness, rehearsal frequency, affective fading) for both positive events and negative events. Affect for positive events faded less than affect for negative events, and positive events were recalled more vividly than negative events. The perceived vividness of an event (memory vividness) and the extent to which an event has been rehearsed (rehearsal frequency) were explored as possible mediators of the relation between event valence and affect fading. Additional models conceived of affect fading and rehearsal frequency as contributors to a memory's vividness. Results suggested that memory vividness was a plausible mediator of the relation between an event's valence and affect fading. Rehearsal frequency was also a plausible mediator of this relation, but only via its effects on memory vividness. Additional modelling results suggested that affect fading and rehearsal frequency were both plausible mediators of the relation between an event's valence and the event's rated memory vividness.

  7. Near IR overtone spectral investigations of cyclohexanol using local mode model--evidence for variation of anharmonicity with concentration due to hydrogen bonding.

    Science.gov (United States)

    John, Usha; Nair, K P R

    2005-09-01

    The near infrared vibrational overtone absorption spectrum of liquid phase cyclohexanol in carbon tetrachloride in different concentrations are examined in the region Deltav=2, 3 and 4. The free and bonded OH local mode mechanical frequency values and anharmonicity values obtained from fitting the overtones are analysed. The observation supports the conclusions drawn from earlier experimental studies on anharmonicity variation of OH-stretching vibrations of alcohols due to intermolecular hydrogen bonding. Our observation is also in agreement with the ab initio calculations on water dimer and trimer. Mechanical anharmonicity of bonded OH-stretching bands tends to increase as a consequence of strong hydrogen bonding at higher concentrations.

  8. Virtual Distance and Soundstage, and their Impacts on Experienced Emotional Valence

    DEFF Research Database (Denmark)

    Christensen, Justin

    2015-01-01

    Research from animal ethology and affective neuroscience suggest that a listener’s perceived distance from a signal source can alter their experienced emotional valence of the music. Furthermore, appraisal theories of emotion suggest that emotionally valenced responses will diverge according...... to the type of emotion presented. For these exploratory investigations, subjects listen to selected musical excerpts on speakers in combination with a tactile transducer attached to their chair. The listening sessions are recorded on EEG supported by subject feedback responses. My hypothesis is that musical...... stimuli should cause stronger valenced responses in the nearfield than at a distance. Thus, music experienced as being negatively valenced at a distance should be more negatively valenced in nearfield, and music that is experienced as having a positive valence at a distance should be more positively...

  9. A Modified Theoretical Model of Intrinsic Hardness of Crystalline Solids

    Science.gov (United States)

    Dai, Fu-Zhi; Zhou, Yanchun

    2016-01-01

    Super-hard materials have been extensively investigated due to their practical importance in numerous industrial applications. To stimulate the design and exploration of new super-hard materials, microscopic models that elucidate the fundamental factors controlling hardness are desirable. The present work modified the theoretical model of intrinsic hardness proposed by Gao. In the modification, we emphasize the critical role of appropriately decomposing a crystal to pseudo-binary crystals, which should be carried out based on the valence electron population of each bond. After modification, the model becomes self-consistent and predicts well the hardness values of many crystals, including crystals composed of complex chemical bonds. The modified model provides fundamental insights into the nature of hardness, which can facilitate the quest for intrinsic super-hard materials. PMID:27604165

  10. Relative Contribution of Odour Intensity and Valence to Moral Decisions.

    Science.gov (United States)

    Cecchetto, Cinzia; Rumiati, Raffaella Ida; Parma, Valentina

    2017-01-01

    Meta-analytic evidence showed that the chemical senses affect moral decisions. However, how odours impact on morality is currently unclear. Through a set of three studies, we assess whether and how odour intensity biases moral choices (Study 1a), its psychophysiological responses (Study 1b), as well as the behavioural and psychophysiological effects of odour valence on moral choices (Study 2). Study 1a suggests that the presence of an odour plays a role in shaping moral choice. Study 1b reveals that of two iso-pleasant versions of the same neutral odour, only the one presented sub-threshold (vs. supra-threshold) favours deontological moral choices, those based on the principle of not harming others even when such harm provides benefits. As expected, this odour intensity effect is tracked by skin conductance responses, whereas no difference in cardiac activity - proxy for the valence dimension - is revealed. Study 2 suggests that the same neutral odour presented sub-threshold increases deontological choices even when compared to iso-intense ambiguous odour, perceived as pleasant or unpleasant by half of the participants, respectively. Skin conductance responses, as expected, track odour pleasantness, but cardiac activity fails to do so. Results are discussed in the context of mechanisms alternative to disgust induction underlying moral choices.

  11. The effects of colour and valence on news evaluation.

    Science.gov (United States)

    Kaspar, Kai; Grümmer, Melanie; Kießler, Antje; Neuß, Celina; Schröter, Franziska

    2017-12-01

    Research across different fields of psychology has reported effects of colour cues on a variety of cognitive processes. Especially, the colour red has been shown to have striking influences. In the context of media reception, however, colour effects have been widely neglected so far. This study made a first step in this direction by investigating the effects of the colour red (compared with blue and grey) on the way news articles are evaluated. Two types of news were framed by a coloured border while the valence of the news content additionally varied. Based on 369 participants who read and evaluated the news articles online, we observed effects for colour cues and news valence in the absence of an interaction effect, indicating that the colour red induced approach motivation. However, only the contrast between red and grey reached statistical significance, indicating that chromatic and achromatic colours may differ in their perceived visual saliency. Overall, these results provide an important complement to previous studies and have practical implications for media researchers and producers. © 2015 International Union of Psychological Science.

  12. Relaxation and cross section effects in valence band photoemission spectroscopy

    International Nuclear Information System (INIS)

    McFeely, F.R.

    1976-09-01

    Various problems relating to the interpretation of valence band x-ray photoemission (XPS) spectra of solids are discussed. The experiments and calculations reported herein deal with the following questions: (1) To what extent do many-body effects manifest themselves in an XPS valence band spectrum, and thus invalidate a direct comparison between the photoemission energy distribution, I(E), and the density of states, N(E), calculated on the basis of ground-state one-electron theory. (2) The effect of the binding-energy-dependent photoemission cross section on I(E) at XPS energies. (3) In favorable cases indicated by (1) and (2) we examine the effect of the interaction of the crystal field with the apparent spin-orbit splittings of core levels observed in XPS spectra. (4) The use of tight binding band structure calculations to parameterize the electronic band structure from XPS and other data is described. (5) The use of high energy angle-resolved photoemission on oriented single crystals to gain orbital symmetry information is discussed. (6) The evolution of the shape of the photoemission energy distribution (of polycrystalline Cu) as a function of photon energy from 50 less than or equal h ω less than or equal 175 is discussed

  13. Diazole-based powdered cocrystal featuring a helical hydrogen-bonded network: structure determination from PXRD, solid-state NMR and computer modeling.

    Science.gov (United States)

    Sardo, Mariana; Santos, Sérgio M; Babaryk, Artem A; López, Concepción; Alkorta, Ibon; Elguero, José; Claramunt, Rosa M; Mafra, Luís

    2015-02-01

    We present the structure of a new equimolar 1:1 cocrystal formed by 3,5-dimethyl-1H-pyrazole (dmpz) and 4,5-dimethyl-1H-imidazole (dmim), determined by means of powder X-ray diffraction data combined with solid-state NMR that provided insight into topological details of hydrogen bonding connectivities and weak interactions such as CH···π contacts. The use of various 1D/2D (13)C, (15)N and (1)H high-resolution solid-state NMR techniques provided structural insight on local length scales revealing internuclear proximities and relative orientations between the dmim and dmpz molecular building blocks of the studied cocrystal. Molecular modeling and DFT calculations were also employed to generate meaningful structures. DFT refinement was able to decrease the figure of merit R(F(2)) from ~11% (PXRD only) to 5.4%. An attempt was made to rationalize the role of NH···N and CH···π contacts in stabilizing the reported cocrystal. For this purpose four imidazole derivatives with distinct placement of methyl substituents were reacted with dmpz to understand the effect of methylation in blocking or enabling certain intermolecular contacts. Only one imidazole derivative (dmim) was able to incorporate into the dmpz trimeric motif thus resulting in a cocrystal, which contains both hydrophobic (methyl groups) and hydrophilic components that self-assemble to form an atypical 1D network of helicoidal hydrogen bonded pattern, featuring structural similarities with alpha-helix arrangements in proteins. The 1:1 dmpz···dmim compound I is the first example of a cocrystal formed by two different azoles. Copyright © 2014 Elsevier Inc. All rights reserved.

  14. Ligand additivity in the valence photoelectron spectroscopy of phosphine-substituted molybdenum carbonyls

    International Nuclear Information System (INIS)

    Bursten, B.E.; Darensbourg, D.J.; Kellogg, G.E.; Lichtenberger, D.L.

    1984-01-01

    The He I valence photoelectron spectra in the 6-9-eV ionization region are reported for seven phosphine-substituted molybdenum carbonyls. The observation of vibrational structure due to excitation of a CO stretching mode in several of the spectra aids band assignment. These data are used to test the validity of the model of ligand additivity for determining the energetics of the dπ electrons in octahedral d 6 complexes. It is shown that the model successfully correlates the positions, intensities, and number of the ionization bands for the molybdenum compounds. A comparison of the results for the complexes of different phosphine ligands indicates that the trimethyl (PMe 3 ), triethyl (PEt 3 ), and tri-n-butyl (P-n-Bu 3 ) phosphines are comparable π-acceptors, but that the sigma-donor strength increases as PMe 3 3 3

  15. Copper wire bonding

    CERN Document Server

    Chauhan, Preeti S; Zhong, ZhaoWei; Pecht, Michael G

    2014-01-01

    This critical volume provides an in-depth presentation of copper wire bonding technologies, processes and equipment, along with the economic benefits and risks.  Due to the increasing cost of materials used to make electronic components, the electronics industry has been rapidly moving from high cost gold to significantly lower cost copper as a wire bonding material.  However, copper wire bonding has several process and reliability concerns due to its material properties.  Copper Wire Bonding book lays out the challenges involved in replacing gold with copper as a wire bond material, and includes the bonding process changes—bond force, electric flame off, current and ultrasonic energy optimization, and bonding tools and equipment changes for first and second bond formation.  In addition, the bond–pad metallurgies and the use of bare and palladium-coated copper wires on aluminum are presented, and gold, nickel and palladium surface finishes are discussed.  The book also discusses best practices and re...

  16. Automation of the CHARMM General Force Field (CGenFF) I: bond perception and atom typing.

    Science.gov (United States)

    Vanommeslaeghe, K; MacKerell, A D

    2012-12-21

    Molecular mechanics force fields are widely used in computer-aided drug design for the study of drug-like molecules alone or interacting with biological systems. In simulations involving biological macromolecules, the biological part is typically represented by a specialized biomolecular force field, while the drug is represented by a matching general (organic) force field. In order to apply these general force fields to an arbitrary drug-like molecule, functionality for assignment of atom types, parameters, and charges is required. In the present article, which is part I of a series of two, we present the algorithms for bond perception and atom typing for the CHARMM General Force Field (CGenFF). The CGenFF atom typer first associates attributes to the atoms and bonds in a molecule, such as valence, bond order, and ring membership among others. Of note are a number of features that are specifically required for CGenFF. This information is then used by the atom typing routine to assign CGenFF atom types based on a programmable decision tree. This allows for straightforward implementation of CGenFF's complicated atom typing rules and for equally straightforward updating of the atom typing scheme as the force field grows. The presented atom typer was validated by assigning correct atom types on 477 model compounds including in the training set as well as 126 test-set molecules that were constructed to specifically verify its different components. The program may be utilized via an online implementation at https://www.paramchem.org/ .

  17. Isolation of a mixed valence diiron hydride: evidence for a spectator hydride in hydrogen evolution catalysis.

    Science.gov (United States)

    Wang, Wenguang; Nilges, Mark J; Rauchfuss, Thomas B; Stein, Matthias

    2013-03-06

    The mixed-valence diiron hydrido complex (μ-H)Fe2(pdt)(CO)2(dppv)2 ([H1](0), where pdt =1,3-propanedithiolate and dppv = cis-1,2-C2H2(PPh2)2), was generated by reduction of the differous hydride [H1](+) using decamethylcobaltocene. Crystallographic analysis shows that [H1](0) retains the stereochemistry of its precursor, where one dppv ligand spans two basal sites and the other spans apical and basal positions. The Fe---Fe bond elongates to 2.80 from 2.66 Å, but the Fe-P bonds only change subtly. Although the Fe-H distances are indistinguishable in the precursor, they differ by 0.2 Å in [H1](0). The X-band electron paramagnetic resonance (EPR) spectrum reveals the presence of two stereoisomers, the one characterized crystallographically and a contribution of about 10% from a second symmetrical (sym) isomer wherein both dppv ligands occupy apical-basal sites. The unsymmetrical (unsym) arrangement of the dppv ligands is reflected in the values of A((31)P), which range from 31 MHz for the basal phosphines to 284 MHz for the apical phosphine. Density functional theory calculations were employed to rationalize the electronic structure of [H1](0) and to facilitate spectral simulation and assignment of EPR parameters including (1)H and (31)P hyperfine couplings. The EPR spectra of [H1](0) and [D1](0) demonstrate that the singly occupied molecular orbital is primarily localized on the Fe center with the longer bond to H, that is, Fe(II)-H···Fe(I). The coupling to the hydride is A((1)H) = 55 and 74 MHz for unsym- amd sym-[H1](0), respectively. Treatment of [H1](0) with H(+) gives 0.5 equiv of H2 and [H1](+). Reduction of D(+) affords D2, leaving the hydride ligand intact. These experiments demonstrate that the bridging hydride ligand in this complex is a spectator in the hydrogen evolution reaction.

  18. Large shift and small broadening of Br2 valence band upon dimer formation with H2O: an ab initio study.

    Science.gov (United States)

    Franklin-Mergarejo, Ricardo; Rubayo-Soneira, Jesus; Halberstadt, Nadine; Ayed, Tahra; Bernal-Uruchurtu, Margarita I; Hernández-Lamoneda, Ramón; Janda, Kenneth C

    2011-06-16

    Valence electronic excitation spectra are calculated for the H(2)O···Br(2) complex using highly correlated ab initio potentials for both the ground and the valence electronic excited states and a 2-D approximation for vibrational motion. Due to the strong interaction between the O-Br and the Br-Br stretching motions, inclusion of these vibrations is the minimum necessary for the spectrum calculation. A basis set calculation is performed to determine the vibrational wave functions for the ground electronic state and a wave packet simulation is conducted for the nuclear dynamics on the excited state surfaces. The effects of both the spin-orbit interaction and temperature on the spectra are explored. The interaction of Br(2) with a single water molecule induces nearly as large a shift in the spectrum as is observed for an aqueous solution. In contrast, complex formation has a remarkably small effect on the T = 0 K width of the valence bands due to the fast dissociation of the dihalogen bond upon excitation. We therefore conclude that the widths of the spectra in aqueous solution are mostly due to inhomogeneous broadening. © 2011 American Chemical Society

  19. Exploring Conceptual Frameworks of Models of Atomic Structures and Periodic Variations, Chemical Bonding, and Molecular Shape and Polarity: A Comparison of Undergraduate General Chemistry Students with High and Low Levels of Content Knowledge

    Science.gov (United States)

    Wang, Chia-Yu; Barrow, Lloyd H.

    2013-01-01

    The purpose of the study was to explore students' conceptual frameworks of models of atomic structure and periodic variations, chemical bonding, and molecular shape and polarity, and how these conceptual frameworks influence their quality of explanations and ability to shift among chemical representations. This study employed a purposeful sampling…

  20. The Application Effect of Learning Model Acquisition Concept Combined with Cooperative Learning STAD to the Learning Achievement, activeness, and Students Responses In Learning Chemistry Bond

    Directory of Open Access Journals (Sweden)

    Putri Ridha Ilahi

    2014-06-01

    Full Text Available Pengaruh Penerapan Model Pembelajaran Pemerolehan Konsep Dipadu Pembelajaran Kooperatif STAD terhadap Prestasi Belajar, Keaktifan, dan Respon Siswa pada Pembelajaran Ikatan Kimia Abstract: This study aims to determine differences: (1 student achievement acquisition make use of the concept of combined learning model STAD cooperative learning and student achievement using model concepts in conventional learning acquisition; (2 active students use learning model acquisition combined the concept of cooperative learning and student activity STAD learning model acquisition using the concept in the conventional learning; (3 The students 'response to the acquisition of the concept of combined learning STAD cooperative learning and students' response to the acquisition of learning concepts in conventional learning. This research uses descriptive research design and quasi-experimental design (quasy experiment design. Learning achievement data were collected using an objective test and reliability coefficient calculated by using SPSS 16 for windows Data recorded in the learning activity of students using observation sheet. Student response data to the learning model was obtained by questionnaire. Data were analyzed statistically and descriptive. The results showed: (1 student achievement using learning model acquisition combined the concept of cooperative learning STAD higher compared to student achievement using model concepts in conventional learning acquisition; (2 active students use learning model acquisition combined the concept of cooperative learning STAD higher than students' active learning model acquisition using the concept in the conventional learning; (3 The students 'response to learning acquisition combined the concept of cooperative learning STAD is more positive than the students' response to the acquisition of learning concepts in conventional learning. Key Words: acquisition of concepts, STAD, chemical bonds   Abstrak: Penelitian ini