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

    Science.gov (United States)

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

    2014-11-12

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

  3. Valence-Bond Theory and Chemical Structure.

    Science.gov (United States)

    Klein, Douglas J.; Trinajstic, Nenad

    1990-01-01

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

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

    OpenAIRE

    Adams, S.; 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...

  5. Empirical valence bond model of an SN2 reaction in polar and nonpolar solvents

    Science.gov (United States)

    Benjamin, Ilan

    2008-08-01

    A new model for the substitution nucleophilic reaction (SN2) in solution is described using the empirical valence bond (EVB) method. The model includes a generalization to three dimensions of a collinear gas phase EVB model developed by Mathis et al. [J. Mol. Liq. 61, 81 (1994)] and a parametrization of solute-solvent interactions of four different solvents (water, ethanol, chloroform, and carbon tetrachloride). The model is used to compute (in these four solvents) reaction free energy profiles, reaction and solvent dynamics, a two-dimensional reaction/solvent free energy map, as well as a number of other properties that in the past have mostly been estimated.

  6. An alternative empirical model for the relationship between the bond valence and the thermal expansion rate of chemical bonds.

    Science.gov (United States)

    Sidey, Vasyl

    2015-08-01

    The relationship between the bond valence s and the thermal expansion rate of chemical bonds (dr/dT) has been closely approximated by using the alternative three-parameter empirical model (dr/dT) = (u + vs)(-1/w), where u, v and w are the refinable parameters. Unlike the s-(dr/dT) model developed by Brown et al. [(1997), Acta Cryst. B53, 750-761], this alternative model can be optimized for particular s-(dr/dT) datasets in the least-squares refinement procedure. For routine calculations of the thermal expansion rates of chemical bonds, the alternative model with the parameters u = -63.9, v = 2581.0 and w = 0.647 can be recommended.

  7. 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..

  8. A Valence-Bond Nonequilibrium Solvation Model for a Twisting Cyanine Dye

    CERN Document Server

    McConnell, Sean; Olsen, Seth

    2014-01-01

    We study a two-state valence-bond electronic Hamiltonian model of non-equilibrium solvation during the excited-state twisting reaction of monomethine cyanines. These dyes are of interest because of the strong environment-dependent enhancement of their fluorescence quantum yield that results from suppression of competing non-radiative decay via twisted internal charge-transfer (TICT) states. For monomethine cyanines, where the ground state is a superposition of structures with different bond and charge localization, there are two twisting pathways with different charge localization in the excited state. The Hamiltonian designed to be as simple as possible consistent with a few well-enumerated assumptions. It is defined by three parameters and is a function of two $\\pi$-bond twisting angle coordinates and a single solvation coordinate. For parameters corresponding to symmetric monomethines, there are two low-energy twisting channels on the excited-state surface that lead to a manifold of twisted intramolecular ...

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

    Science.gov (United States)

    Bellucci, Michael A; Coker, David F

    2011-07-28

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

  10. A multistate empirical valence bond model for solvation and transport simulations of OH- in aqueous solutions.

    Science.gov (United States)

    Ufimtsev, Ivan S; Kalinichev, Andrey G; Martinez, Todd J; Kirkpatrick, R James

    2009-11-07

    We describe a new multistate empirical valence bond (MS-EVB) model of OH(-) in aqueous solutions. This model is based on the recently proposed "charged ring" parameterization for the intermolecular interaction of hydroxyl ion with water [Ufimtsev, et al., Chem. Phys. Lett., 2007, 442, 128] and is suitable for classical molecular simulations of OH(-) solvation and transport. The model reproduces the hydration structure of OH(-)(aq) in good agreement with experimental data and the results of ab initio molecular dynamics simulations. It also accurately captures the major structural, energetic, and dynamic aspects of the proton transfer processes involving OH(-) (aq). The model predicts an approximately two-fold increase of the OH(-) mobility due to proton exchange reactions.

  11. Hiawatha's Valence Bonding

    CERN Document Server

    Laughlin, R B

    2004-01-01

    There is increasing circumstantial evidence that the cuprate superconductors, and correlated-electron materials generally, defy simple materials categorization because of their proximity to one or more continuous zero-temperature phase transitions. This implies that the fifteen-year confusion about the cuprates is not fundamental at all but simply overinterpreted quantum criticality--an effect that seems mysterious by virtue of its hypersensitivity to perturbations, i.e. to sample imperfections in experiment and small modifications of approximation schemes in theoretical modeling, but is really just an unremarkable phase transition of some kind masquerading as something important, a sheep in wolf's clothing. This conclusion is extremely difficult for most physicists even to think about because it requires admitting that an identifiable physical phenomenon might cause the scientific method to fail in some cases. For this reason I have decided to explain the problem in a way that is nonthreatening, easy to read...

  12. Valence-bond non-equilibrium solvation model for a twisting monomethine cyanine

    Science.gov (United States)

    McConnell, Sean; McKenzie, Ross H.; Olsen, Seth

    2015-02-01

    We propose and analyze a two-state valence-bond model of non-equilibrium solvation effects on the excited-state twisting reaction of monomethine cyanines. Suppression of this reaction is thought responsible for environment-dependent fluorescence yield enhancement in these dyes. Fluorescence is quenched because twisting is accompanied via the formation of dark twisted intramolecular charge-transfer (TICT) states. For monomethine cyanines, where the ground state is a superposition of structures with different bond and charge localizations, there are two possible twisting pathways with different charge localizations in the excited state. For parameters corresponding to symmetric monomethines, the model predicts two low-energy twisting channels on the excited-state surface, which leads to a manifold of TICT states. For typical monomethines, twisting on the excited state surface will occur with a small barrier or no barrier. Changes in the solvation configuration can differentially stabilize TICT states in channels corresponding to different bonds, and that the position of a conical intersection between adiabatic states moves in response to solvation to stabilize either one channel or the other. There is a conical intersection seam that grows along the bottom of the excited-state potential with increasing solvent polarity. For monomethine cyanines with modest-sized terminal groups in moderately polar solution, the bottom of the excited-state potential surface is completely spanned by a conical intersection seam.

  13. 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.

  14. Absence of superconductivity and valence bond order in the Hubbard-Heisenberg model for organic charge-transfer solids.

    Science.gov (United States)

    Gomes, N; Clay, R T; Mazumdar, S

    2013-09-25

    A frustrated, effective ½-filled band Hubbard-Heisenberg model has been proposed for describing the strongly dimerized charge-transfer solid families κ-(ET)2X and Z[Pd(dmit)2]2. In addition to showing unconventional superconductivity, these materials also exhibit antiferromagnetism, candidate spin-liquid phases, and, in the case of Z=EtMe3P, a spin-gapped phase that has sometimes been referred to as a valence bond solid. We show that neither superconductivity nor the valence bond order phase occurs within the Hubbard-Heisenberg model. We suggest that a description based on ¼-filling, that is reached when the carrier concentration per molecule instead of per dimer is considered, thus may be appropriate.

  15. Kekulé-based Valence Bond Model.I. The Ground-state Properties of Conjugated π-Systems

    Institute of Scientific and Technical Information of China (English)

    LI,Shu-Hua(黎书华); MA,Jing(马晶); JIANG,Yuan-Sheng(江元生)

    2002-01-01

    The Kekulé-based valence bond ( VB ) method, in which the VB model is solved using covalent Kekulé structures as basis functions, is justified in the present work. This method is dimonstrated to provide satisfactory descriptions for resoance energies and bond ang lengths of benzenoid hydrocarbons, being in good agreement with SCF-MO and experimental results. In additicn, an alternative way of discyssing characters of localizedsubstructures within a polyclic benzenoid system is suggested based upon such sunokufied VB calculations. Finally,the symmetries of VB ground states for nonalternant conjugated systems are also illustrated to be obtainable through these calculations, presenting very useful information for understanding the chemical behaviors of some nonalternant conjugated molecules.

  16. Bond valence at mixed occupancy sites. I. Regular polyhedra.

    Science.gov (United States)

    Bosi, Ferdinando

    2014-10-01

    Bond valence sum calculations at mixed occupancy sites show the occurrence of systematic errors leading to apparent violations of the Valence Sum Rule (bond valence theory) in regular and unstrained bonding environments. The systematic deviation of the bond valence from the expected value is observed in the long-range structure, and is discussed from geometric and algebraic viewpoints. In the valence-length diagram, such a deviation arises from discrepancies between the intersection points of the long-range bond valences and the theoretical bond valences with the valence-length curves of involved cations. Three factors cause systematic errors in the bond valences: difference in atomic valences, bond valence parameters Ri (the length of a bond of unit valence) and bond valence parameters bi (the bond softness) between the involved cations over the same crystallographic site. One important consequence strictly related to the systematic errors is that they lead to erroneous bond strain values for mixed occupancy sites indicating underbonding or overbonding that actually does not exist.

  17. Kekulé-based Valence Bond Model.Ⅱ. Diels-Alder Reactivity of Polycyclic Aromatic Hydrocarbons

    Institute of Scientific and Technical Information of China (English)

    MA,Jing(马晶); LI,Shu-Hua(黎书华); JIANG,Yuan-Sheng(江元生)

    2002-01-01

    The Kekule-based valence bond ( VB ) method was employed to study the ground state properties of 52 polycyclic aromatic hydrocarbons. The reactivity indices defined upon our VB calculations were demonstrated to be capable of quantitatively interpreting the secnd order rate constants of the Diels-Alder reactions. The qualitative trends of the reactivities of many homologous series can be also explained based on the local aromaticity index defined in this work.

  18. Resonance and Aromaticity : An Ab Initio Valence Bond Approach

    NARCIS (Netherlands)

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

    2012-01-01

    Resonance energy is one of the criteria to measure aromaticity. The effect of the use of different orbital models is investigated in the calculated resonance energies of cyclic conjugated hydrocarbons within the framework of the ab initio Valence Bond Self-Consistent Field (VBSCF) method. The VB wav

  19. Seniority Number in Valence Bond Theory.

    Science.gov (United States)

    Chen, Zhenhua; Zhou, Chen; Wu, Wei

    2015-09-01

    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.

  20. Atoms in Valence Bond. Method, implementation and application

    NARCIS (Netherlands)

    Zielinski, M.L.

    2012-01-01

    The Atoms in Valence Bond (AiVB) approach is presented. The main goal was to develop a new and innovative approach, within the existing Valence Bond framework, to build and analyze the molecular VB wave function in terms of atoms and their atomic states, in a very user-friendly environment. The nece

  1. Mean bond-length variation in crystal structures: a bond-valence approach.

    Science.gov (United States)

    Bosi, Ferdinando

    2014-08-01

    The distortion theorem of the bond-valence theory predicts that the mean bond length 〈D〉 increases with increasing deviation of the individual bond lengths from their mean value according to the equation 〈D〉 = (D' + ΔD), where D' is the length found in a polyhedron having equivalent bonds and ΔD is the bond distortion. For a given atom, D' is expected to be similar from one structure to another, whereas 〈D〉 should vary as a function of ΔD. However, in several crystal structures 〈D〉 significantly varies without any relevant contribution from ΔD. In accordance with bond-valence theory, 〈D〉 variation is described here by a new equation: 〈D〉 = (DRU + ΔDtop + ΔDiso + ΔDaniso + ΔDelec), where DRU is a constant related to the type of cation and coordination environment, ΔDtop is the topological distortion related to the way the atoms are linked, ΔDiso is an isotropic effect of compression (or stretching) in the bonds produced by steric strain and represents the same increase (or decrease) in all the bond lengths in the coordination sphere, ΔDaniso is the distortion produced by compression and stretching of bonds in the same coordination sphere, ΔDelec is the distortion produced by electronic effects. If present, ΔDelec can be combined with ΔDaniso because they lead to the same kind of distortions in line with the distortion theorem. Each D-index, in the new equation, corresponds to an algebraic expression containing experimental and theoretical bond valences. On the basis of this study, the ΔD index defined in bond valence theory is a result of both the bond topology and the distortion theorem (ΔD = ΔDtop + ΔDaniso + ΔDelec), and D' is a result of the compression, or stretching, of bonds (D' = DRU + ΔDiso). The deficiencies present in the bond-valence theory in explaining mean bond-length variations can therefore be overcome, and the observed variations of 〈D〉 in crystal structures can be

  2. Coulombic Models in Chemical Bonding.

    Science.gov (United States)

    Sacks, Lawrence J.

    1986-01-01

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

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

    Science.gov (United States)

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

    2009-09-11

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

  4. Bond valence parameterslinearly dependent on the molybdenum oxidation states

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Based on the available crystal data, a linear correlation between R0, the bond valence parameter for a Mo-containing chemical bond, and the Mo oxidation state n was developed for the first time. Using the "universal" value of the parameter B = 0.037 nm, the linear equations of R0-n for Mo-X (X: O, S, N, Cl and F) bonds were established. The oxidation-state independent Mo-O bond valence parameters, R0 = 0.18788 nm and B = 0.03046 nm, published recently have been shown to be a special case of the linearly correlated functions. Some bond valence sum calculations in compounds containing only Mo-O bonds using these para- meters are presented.

  5. 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)

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

    Science.gov (United States)

    Deschner, Andreas; Sørensen, Erik S

    2014-09-01

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

  7. Plaquette valence bond theory of high-temperature superconductivity

    Science.gov (United States)

    Harland, Malte; Katsnelson, Mikhail I.; Lichtenstein, Alexander I.

    2016-09-01

    We present a strong-coupling approach to the theory of high-temperature superconductivity based on the observation of a quantum critical point in the plaquette within the t ,t' Hubbard model. The crossing of ground-state energies in the N =2 -4 sectors occurs for parameters close to the optimal doping. The theory predicts the maximum of the dx2-y2-wave order parameter at the border between localized and itinerant electron behaviors and gives a natural explanation for the pseudogap formation via the soft-fermion mode related to local singlet states of the plaquette in the environment. Our approach follows the general line of resonating valence-bond theory stressing a crucial role of singlets in the physics of high-Tc superconductors but focuses on the formation of local singlets, similar to phenomena observed in frustrated one-dimensional quantum spin models.

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

    Science.gov (United States)

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

    2014-03-01

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

  9. Emergence of string valence-bond-solid state in the frustrated J1-J2 transverse field Ising model on the square lattice

    Science.gov (United States)

    Sadrzadeh, M.; Haghshenas, R.; Jahromi, S. S.; Langari, A.

    2016-12-01

    We investigate the ground-state nature of the transverse field Ising model on the J1-J2 square lattice at the highly frustrated point J2/J1=0.5 . At zero field, the model has an exponentially large degenerate classical ground state, which can be affected by quantum fluctuations for nonzero field toward a unique quantum ground state. We consider two types of quantum fluctuations, harmonic ones by using linear spin-wave theory (LSWT) with single-spin-flip excitations above a long-range magnetically ordered background and anharmonic fluctuations, by employing a cluster-operator approach (COA) with multispin cluster-type fluctuations above a nonmagnetic cluster-ordered background. Our findings reveal that the harmonic fluctuations of LSWT fail to lift the extensive degeneracy as well as signaling a violation of the Hellmann-Feynman theorem. However, the string-type anharmonic fluctuations of COA are able to lift the degeneracy toward a string valence-bond-solid (VBS) state, which is obtained from an effective theory consistent with the Hellmann-Feynman theorem as well. Our results are further confirmed by implementing numerical tree tensor network simulation. The emergent nonmagnetic string VBS phase is gapped and breaks lattice rotational symmetry with only twofold degeneracy, which bears a continuous quantum phase transition at Γ /J1≅0.50 to the quantum paramagnet phase of high fields. The critical behavior is characterized by ν ≅1.0 and γ ≅0.33 exponents.

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

    Science.gov (United States)

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

    2012-05-17

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

  11. A valence bond study of three-center four-electron pi bonding: electronegativity vs electroneutrality.

    Science.gov (United States)

    DeBlase, Andrew; Licata, Megan; Galbraith, John Morrison

    2008-12-18

    Three-center four-electron (3c4e) pi bonding systems analogous to that of the ozone molecule have been studied using modern valence bond theory. Molecules studied herein consist of combinations of first row atoms C, N, and O with the addition of H atoms where appropriate in order to preserve the 3c4e pi system. Breathing orbital valence bond (BOVB) calculations were preformed at the B3LYP/6-31G**-optimized geometries in order to determine structural weights, pi charge distributions, resonance energies, and pi bond energies. It is found that the most weighted VB structure depends on atomic electronegativity and charge distribution, with electronegativity as the dominant factor. By nature, these systems are delocalized, and therefore, resonance energy is the main contributor to pi bond energies. Molecules with a single dominant VB structure have low resonance energies and therefore low pi bond energies.

  12. 1D valence bond solids in a magnetic field

    Science.gov (United States)

    Iaizzi, Adam; Sandvik, Anders W.

    2015-09-01

    A Valence bond solid (VBS) is a nonmagnetic, long-range ordered state of a quantum spin system where local spin singlets are formed in some regular pattern. We here study the competition between VBS order and a fully polarized ferromagnetic state as function of an external magnetic field in a one-dimensional extended Heisenberg model—the J-Q2 model— using stochastic series expansion (SSE) quantum Monte Carlo simulations with directed loop updates. We discuss the ground state phase diagram.

  13. Paired-permanent approach to valence bond theory

    Institute of Scientific and Technical Information of China (English)

    吴玮; 吴安安; 莫亦荣; 张乾二

    1996-01-01

    A new function called paired-permanent is defined and widely discussed, and a practicable procedure for evaluations of paired-permanents is proposed, which is similar to the Laplace method for determinants. Using the concept of paired-permanents, an efficient algorithm is presented for evaluating the Hamiltonian and overlap matrix elements in the spin-free form of valence bond (VB) theory. With the new algorithm, a spin-free wavefunction is simply written as a paired-permanent, and an overlap matrix element may be obtained by evaluating a corresponding paired-permanent. Meanwhile, the Hamiltonian matrix element is expressed in terms of the summation of the products of electronic integrals and the corresponding sub-paired-permanents

  14. Conceptual chemistry approach towards the support effect in supported vanadium oxides : Valence bond calculations on the ionicity of vanadium catalysts

    NARCIS (Netherlands)

    Fievez, Tim; De Proft, Frank; Geerlings, Paul; Weckhuysen, Bert M.; Havenith, Remco W. A.

    2011-01-01

    The concept of bond ionicity, obtained via a valence bond analysis, is invoked in the interpretation of the catalytic activity of supported vanadium oxides, in analogy with previous work conducted within the framework of conceptual DFT. For a set of model clusters representing the vanadium oxide sup

  15. 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 availab

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

    Science.gov (United States)

    Patil, Amol Baliram; Bhanage, Bhalchandra Mahadeo

    2016-06-21

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Shih-Jye, E-mail: sjs@nuk.edu.tw

    2016-05-06

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

  18. The new Resonating Valence Bond Method for ab-initio Electronic Simulations

    CERN Document Server

    Sorella, Sandro

    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 discovery of High-Tc superconductivity. It is shown that this intuitive picture of electron correlation becomes now practical and efficient, since it allows us to faithfully exploit the locality of the electron correlation, and to describe several new phases of matter, such as Mott insulators, High-Tc superconductors, and spin liquid phases.

  19. A STUDY OF TEMPERATURE-DEPENDENT VALENCE BOND STRUCTURE OF TITANIUM

    Institute of Scientific and Technical Information of China (English)

    X.B. Li; Y.Q. Xie; Y.Z. Nie; H.J. Peng; H.J. Tao; F.X. Yu

    2007-01-01

    On the basis of energy and shape method for the determination of the valence bond (VB) structures of crystal, the valence bond structure of titanium is redetermined at room temperature and calculated in the whole temperature range of 0-1943K. The outer shell electronic distribution of Ti is ec2.9907 .(sc0.4980 + dc2.4927) ef1.0093 in crystal. The temperature dependences of the VB structures of hcp and bcc phases are the same. The VB structures of hcp and bcc phases monotonically increase or decrease with the increase in temperature, but show discontinuous changes at the phase-transformation temperature 1155K.

  20. Valence-bond-solid domain walls in a 2D quantum magnet

    Science.gov (United States)

    Shao, Hui; Guo, Wenan; Sandvik, Anders

    sing quantum Monte Carlo simulations, we study properties of domain walls in a square-lattice S=1/2 Heisenberg model with additional interactions which can drive the system from an antiferromagnetic (AFM) ground state to a valence-bond solid (VBS). We study the finite-size scaling of the domain-wall energy at the putative ''deconfined'' critical AFM-VBS point, which gives access to the critical exponent governing the domain-wall width. This length-scale diverges faster than the correlation length and also is related to the scale of spinon deconfinement. Our results show additional evidence of deconfied quantum criticality and are compatible with critical exponents extracted from finite-size scaling of other quantities. NSFC Grant No. 11175018, NSF Grant No. DMR-1410126.

  1. An ab initio Valence Bond Study on Cyclopenta-Fused Naphthalenes and Fluoranthenes

    NARCIS (Netherlands)

    Havenith, R.W.A.; van Lenthe, J.H.; Jenneskens, L.W.

    2005-01-01

    To probe the effect of external cyclopenta-fusion on a naphthalene core, ab initio valence bond (VB) calculations have been performed, using strictly atomic benzene p-orbitals and p-orbitals that are allowed to delocalize, on naphthalene (1), acenaphthylene (2), pyracylene (3), cyclopenta[b,c]-acena

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

    NARCIS (Netherlands)

    Fracchia, F.; Filippi, C.; 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 coup

  3. Properties of the random-singlet phase: From the disordered Heisenberg chain to an amorphous valence-bond solid

    Science.gov (United States)

    Shu, Yu-Rong; Yao, Dao-Xin; Ke, Chih-Wei; Lin, Yu-Cheng; Sandvik, Anders W.

    2016-11-01

    We use a strong-disorder renormalization group (SDRG) method and ground-state quantum Monte Carlo (QMC) simulations to study S =1 /2 spin chains with random couplings, calculating disorder-averaged spin and dimer correlations. The QMC simulations demonstrate logarithmic corrections to the power-law decaying correlations obtained with the SDRG scheme. The same asymptotic forms apply both for systems with standard Heisenberg exchange and for certain multispin couplings leading to spontaneous dimerization in the clean system. We show that the logarithmic corrections arise in the valence-bond (singlet pair) basis from a contribution that cannot be generated by the SDRG scheme. In the model with multispin couplings, where the clean system dimerizes spontaneously, random singlets form between spinons localized at domain walls in the presence of disorder. This amorphous valence-bond solid is asymptotically a random-singlet state and only differs from the random-exchange Heisenberg chain in its short-distance properties.

  4. Valence bond study on excited states of molecules——Bonding features of the low-lying states of molecule B2

    Institute of Scientific and Technical Information of China (English)

    曹泽星; 吴玮; 张乾二

    1997-01-01

    Based on the correspondence of the molecular orbital theory and valence bond theory to the description of chemical bonds,the ah imtio valence bond (VB) calculations of the low-lying states of diatomic molecules arc realized.The calculation results for the low-lying states of B2 show that the VB calculation has clear-cut physical significance,and its simulation of the behavior of the potential energy surface about the equilibrium position is superior to that of the molecular orbital theory.The valence bond calculation involving only a few bonded tableaus can correctly re fleet the effect of electronic correlation.

  5. Effects of Magnetic Field on the Valence Bond Property of the Double-Quantum-Dot Molecule

    Institute of Scientific and Technical Information of China (English)

    王立民; 罗莹; 马本堃

    2002-01-01

    The effects of the magnetic field on the valence bond property of the double-quantum-dot molecule are numerically studied by the finite element method and perturbation approach because of the absence of cylindrical symmetry in the horizontally coupled dots. The calculation results show that the energy value of the ground state changes differently from that of the first excited state with increasing magnetic field strength, and they cross under a certain magnetic field. The increasing magnetic field makes the covalent bond state change into an ionic bond state, which agrees qualitatively with experimental results and makes ionic bond states remain. The oscillator strength of transition between covalent bond states decreases distinctly with the increasing magnetic field strength, when the molecule is irradiated by polarized light. Such a phenomenon is possibly useful for actual applications.

  6. Comparison of ion sites and diffusion paths in glasses obtained by molecular dynamics simulations and bond valence analysis

    OpenAIRE

    Muller, Christian; Zienicke, Egbert; Adams, Stefan; Habasaki, Junko; Maass, Philipp

    2006-01-01

    Based on molecular dynamics simulations of a lithium metasilicate glass we study the potential of bond valence sum calculations to identify sites and diffusion pathways of mobile Li ions in a glassy silicate network. We find that the bond valence method is not well suitable to locate the sites, but allows one to estimate the number of sites. Spatial regions of the glass determined as accessible for the Li ions by the bond valence method can capture up to 90% of the diffusion path. These regio...

  7. Nature of the chemical bond and origin of the inverted dipole moment in boron fluoride: a generalized valence bond approach.

    Science.gov (United States)

    Fantuzzi, Felipe; Cardozo, Thiago Messias; Nascimento, Marco Antonio Chaer

    2015-05-28

    The generalized product function energy partitioning (GPF-EP) method has been applied to investigate the nature of the chemical bond and the origin of the inverted dipole moment of the BF molecule. The calculations were carried out with GPF wave functions treating all of the core electrons as a single Hartree-Fock group and the valence electrons at the generalized valence bond perfect-pairing (GVB-PP) or full GVB levels, with the cc-pVTZ basis set. The results show that the chemical structure of both X (1)Σ(+) and a (3)Π states is composed of a single bond. The lower dissociation energy of the excited state is attributed to a stabilizing intraatomic singlet coupling involving the B 2sp-like lobe orbitals after bond dissociation. An increase of electron density on the B atom caused by the reorientation of the boron 2sp-like lobe orbitals is identified as the main responsible effect for the electric dipole inversion in the ground state of BF. Finally, it is shown that π back-bonding from fluorine to boron plays a minor role in the electron density displacement to the bonding region in both states. Moreover, this effect is associated with changes in the quasi-classical component of the electron density only and does not contribute to covalency in either of the states. Therefore, at least for the case of the BF molecule, the term back-bonding is misleading, since it does not contribute to the bond formation.

  8. Entanglement and SU(n) symmetry in one-dimensional valence bond solid states

    CERN Document Server

    Orus, Roman

    2011-01-01

    Here we evaluate the many-body entanglement properties of a generalized SU(n) valence bond solid state on a chain. Our results follow from a derivation of the transfer matrix of the system which, in combination with symmetry properties, allows for a new, elegant and straightforward evaluation of different entanglement measures. In particular, the geometric entanglement per block, correlation length, von Neumann and R\\'enyi entropies of a block, localizable entanglement and entanglement length are obtained in a very simple way. All our results are in agreement with previous derivations for the SU(2) case.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-05-30

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

  10. 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 %.

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

    Institute of Scientific and Technical Information of China (English)

    宋振; 刘小浪; 何丽珠; 夏志国; 刘泉林

    2015-01-01

    Bond valence method illustrates the relation between valence and length of a particular bond type. This theory has been used to predict structure information, but the effect is very limited. In this paper, two indexes, i.e., global instability index (GII) and bond strain index (BSI), are adopted as a judgment of a search-match program for prediction. The results show that with GII and BSI combined as judgment, the predicted atom positions are very close to real ones. The mechanism and validity of this searching program are also discussed. The GII&BSI distribution contour map reveals that the predicted function is a reflection of exponential feature of bond valence formula. This combined searching method may be integrated with other structure-determination method, and may be helpful in refining and testifying light atom positions.

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

    Science.gov (United States)

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

    We present an effective Z2 gauge theory that captures various competing phases in spin-1/2 kagome lattice antiferromagnets: the topological Z2 spin liquid (SL) phase, and the 12-site and 36- site valence bond solid (VBS) phases. Our effective theory is a generalization of the recent Z2 gauge theory proposed for SL phases by Wan and Tchernyshyov. In particular, we investigate possible VBS phases that arise from vison condensations in the SL. In addition to the 12-site and 36-site VBS phases, there exists 6-site VBS that is closely related to the symmetry-breaking valence bond modulation patterns observed in the recent density matrix renormalization group simulations. We find that our results have remarkable consistency with a previous study using a different Z2 gauge theory. Motivated by the lattice geometry in the recently reported vanadium oxyfluoride kagome antiferromagnet, our gauge theory is extended to incorporate lowered symmetry by inequivalent up- and down-triangles. We investigate effects of this anisotropy on the 12-site, 36-site, and 6-site VBS phases. Particularly, interesting dimer melting effects are found in the 36-site VBS. We discuss the implications of our findings and also compare the results with a different type of Z2 gauge theory used in previous studies.

  13. Mott insulator to high Tc superconductor via pressure: resonating valence bond theory and prediction of new systems.

    Science.gov (United States)

    Baskaran, G

    2003-05-16

    Mott insulator superconductor transition, via pressure and no external doping, is studied in orbitally nondegenerate spin-1 / 2 systems. It is presented as another resonating valence bond route to high T(c) superconductivity. We propose a "strong coupling" hypothesis that views long range Coulomb force driven first order Mott transition as a self-doping process that also preserves superexchange on the metal side. We present a two-species t-J model where conserved N0 doubly occupied (e(-)) sites and N0 empty sites (e(+)) hop in the background of N-2N(0) singly occupied (neutral) sites in a lattice of N sites. An equivalence to the regular t-J model is made. Some old and new systems are predicted to be candidates for pressure-induced high T(c) superconductivity.

  14. Solvent-induced red-shifts for the proton stretch vibrational frequency in a hydrogen-bonded complex. 1. A valence bond-based theoretical approach.

    Science.gov (United States)

    Kiefer, Philip M; Pines, Ehud; Pines, Dina; Hynes, James T

    2014-07-17

    A theory is presented for the proton stretch vibrational frequency νAH for hydrogen (H-) bonded complexes of the acid dissociation type, that is, AH···B ⇔ A(-)···HB(+)(but without complete proton transfer), in both polar and nonpolar solvents, with special attention given to the variation of νAH with the solvent's dielectric constant ε. The theory involves a valence bond (VB) model for the complex's electronic structure, quantization of the complex's proton and H-bond motions, and a solvent coordinate accounting for nonequilibrium solvation. A general prediction is that νAH decreases with increasing ε largely due to increased solvent stabilization of the ionic VB structure A(-)···HB(+) relative to the neutral VB structure AH···B. Theoretical νAH versus 1/ε slope expressions are derived; these differ for polar and nonpolar solvents and allow analysis of the solvent dependence of νAH. The theory predicts that both polar and nonpolar slopes are determined by (i) a structure factor reflecting the complex's size/geometry, (ii) the complex's dipole moment in the ground vibrational state, and (iii) the dipole moment change in the transition, which especially reflects charge transfer and the solution phase proton potential shapes. The experimental proton frequency solvent dependence for several OH···O H-bonded complexes is successfully accounted for and analyzed with the theory.

  15. Molecular mechanics-valence bond method for planar conjugated hydrocarbon cations.

    Science.gov (United States)

    Hall, Katherine F; Tokmachev, Andrei M; Bearpark, Michael J; Boggio-Pasqua, Martial; Robb, Michael A

    2007-10-07

    We present an extension of the molecular mechanics-valence bond (MMVB) hybrid method to study ground and excited states of planar conjugated hydrocarbon cations. Currently, accurate excited state calculations on these systems are limited to expensive ab initio studies of smaller systems: up to 15 active electrons in 16 pi orbitals with complete active space self-consistent field (CASSCF) theory using high symmetry. The new MMVB extension provides a faster, cheaper treatment to investigate larger cation systems with more than 24 active orbitals. Extension requires both new matrix elements and new parameters: In this paper we present both, for the limited planar case. The scheme is tested for the planar radical cations of benzene, naphthalene, anthracene, and phenanthrene. Calculated MMVB relative energies are in good agreement with CASSCF results for equilibrium geometries on the ground and first excited states, and conical intersections.

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

    CERN Document Server

    Azadi, Sam; Kühne, Thomas D

    2015-01-01

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

  17. A new algorithm for inactive orbital optimization in valence bond theory

    Institute of Scientific and Technical Information of China (English)

    CHEN ZhenHua; ZHANG QianEr; WU Wei

    2009-01-01

    This paper presents an efficient algorithm for energy gradients in valence bond self-consistent field (VBSCF) method with non-orthogonal orbitals.The frozen core approximation method is extended to the case of non-orthogonal orbitals.The expressions for the total energy and its gradients are presented by introducing auxiliary orbitals,where inactive orbitals are orthogonal,while active orbitals are non-orthogonal themselves but orthogonal to inactive orbitsls.It is shown that our new algorithm has a low scaling of (N_a+ 1)m~4,where N_a and m are the numbers of the active orbitals and basis functions,respectively,and is more efficient than the existing VBSCF algorithms.

  18. A new algorithm for inactive orbital optimization in valence bond theory

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    This paper presents an efficient algorithm for energy gradients in valence bond self-consistent field(VBSCF) method with non-orthogonal orbitals.The frozen core approximation method is extended to the case of non-orthogonal orbitals.The expressions for the total energy and its gradients are presented by introducing auxiliary orbitals,where inactive orbitals are orthogonal,while active orbitals are non-orthogonal themselves but orthogonal to inactive orbitals.It is shown that our new algorithm has a low scaling of(Na+1)m4,where Na and m are the numbers of the active orbitals and basis functions,respectively,and is more efficient than the existing VBSCF algorithms.

  19. Implications of the complete basis set limit in valence bond theory : a case study of molecular hydrogen

    NARCIS (Netherlands)

    Duke, Brian J.; Havenith, Remco W. A.

    2016-01-01

    The use of larger basis sets to approach the complete basis limit, now common in quantum chemistry, is applied for the first time to a range of valence bond functions for the simplest case of molecular hydrogen. Good convergence of the energy is slow due to difficulty in getting a correct cusp near

  20. Electric and Magnetic properties Computed for Valence Bond Structures: Is There a Link between Pauling Resonance Energy and Ring Current?

    NARCIS (Netherlands)

    Havenith, R.W.A.

    2006-01-01

    To establish the link between the aromaticity descriptors based on the Pauling resonance energy and the molecular properties, the electric (polarizability) and magnetic (magnetizability) field response properties haven been calculated using the valence bond approach for various molecules and their i

  1. 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

    2009-10-13

    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 S(N)2 nucleophilic substitution reactions, the hybrid functional B3LYP severely underestimates the barrier heights, while the approximate two-state VBDFT method overcomes the self-interaction error, and overestimates the barrier heights. Inclusion of the ionic state in a three

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

    Science.gov (United States)

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

    2014-10-07

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

  3. Reactive force field simulation of proton diffusion in BaZrO{sub 3} using an empirical valence bond approach

    Energy Technology Data Exchange (ETDEWEB)

    Raiteri, Paolo; Gale, Julian D [Nanochemistry Research Institute, Department of Chemistry, Curtin University, GPO Box 1987, Perth, WA 6845 (Australia); Bussi, Giovanni, E-mail: paolo@ivec.org, E-mail: julian@ivec.org [Scuola Internazionale Superiore di Studi Avanzati (SISSA), Via Bonomea 265, 34136 Trieste (Italy)

    2011-08-24

    A new reactive force field to describe proton diffusion within the solid oxide fuel cell material BaZrO{sub 3} has been derived. Using a quantum mechanical potential energy surface, the parameters of an interatomic potential model to describe hydroxyl groups within both pure and yttrium-doped BaZrO{sub 3} have been determined. Reactivity is then incorporated through the use of the empirical valence bond model. Molecular dynamics simulations (EVB-MD) have been performed to explore the diffusion of hydrogen using a stochastic thermostat and barostat whose equations are extended to the isostress-isothermal ensemble. In the low concentration limit, the presence of yttrium is found not to significantly influence the diffusivity of hydrogen, despite the proton having a longer residence time at oxygen adjacent to the dopant. This lack of influence is due to the fact that trapping occurs infrequently, even when the proton diffuses through octahedra adjacent to the dopant. The activation energy for diffusion is found to be 0.42 eV, in good agreement with experimental values, though the prefactor is slightly underestimated.

  4. Intramolecular hydrogen bond: Can it be part of the basis set of valence internal coordinates in normal mode analysis?

    Indian Academy of Sciences (India)

    Sarvesh Kumar Pandey; Prasanta Das; Puspendu K Das; Elangannan Arunan; Sadasivam Manogaran

    2015-06-01

    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. Sometimes, it is possible to have a complete VIC basis that does not contain the intramolecular hydrogen bond (IMHB) as part of the basis. This means the RFC of IMHB is not necessarily a measure of bond strength. However, we know that IMHB is a weak bond and hence its RFC has to be a measure of bond strength. We resolve this problem of IMHB not being part of the complete basis by postulating `equivalent’ basis sets where IMHB is part of the basis at least in one of the equivalent sets of VIC. As long as a given IMHB appears in one of the equivalent complete VIC basis sets, its RFC could be used as a measure of bond strength parameter.

  5. Ab initio determination of bond length dependence of the correlated valence shell Hamiltonian of CH: Comparison with semiempirical theories

    Science.gov (United States)

    Sun, Hosung; Freed, Karl F.

    1984-01-01

    The exact ab initio effective valence shell Hamiltonian, which is mimicked by semiempirical theories of valence, is calculated for CH at 11 bond lengths using quasidegenerate many-body perturbation theory to incorporate extensive correlation contributions. Least squares fits of the bond length dependence of the calculated CH matrix elements provide simple formulas which are compared with the intuitive forms introduced into semiempirical theories. Some of the semiempirical formulas, e.g., one-center, one-electron integrals and two-center, two-electron integrals, are in good agreement with our correlated ab initio calculations, while others display substantial departures. For example, the bond length dependence of one-center, two-electron integrals, which are assumed to be independent of bond length in semiempirical theories, is substantial but physically understandable. Corrections are found to the assumed proportionality of resonance and overlap integrals. The bond length dependence of nonclassical three-electron integrals is presented along with the hybrid and exchange integrals that are ignored in zero differential overlap methods.

  6. 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.

  7. Delocalized mixed-valence bi- and trinuclear complexes with short Cu-Cu bonds.

    Science.gov (United States)

    Yang, Lei; Powell, Douglas R; Klein, Eric L; Grohmann, Andreas; Houser, Robert P

    2007-08-20

    Two mixed-valence copper complexes were synthesized with ligands N-(2-pyridylmethyl)acetamide (Hpmac) and N,N'-(2-methyl-2-pyridylpropan-1,3-diyl)bis(acetamide) (H2pp(ac)2). Dimer [Cu2(pmac)2]OTf and trimer [Cu3(pp(ac)2)2].NaOTf both contain fully delocalized, mixed-valence Cu(1.5)Cu(1.5) moieties.

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

    Science.gov (United States)

    Song, Lingchun; Mo, Yirong; Gao, Jiali

    2009-01-01

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

  9. Electronic structure and bond length dependence of the effective valence shell Hamiltonian of S2 as studied by quasidegenerate many-body perturbation theory

    Science.gov (United States)

    Wang, Xiao-Chuan; Freed, Karl F.

    1987-03-01

    The effective valence shell Hamiltonian (Hv) of S2 is calculated as a function of internuclear distance using quasidegenerate many-body perturbation theory with the full valence space spanned by eight valence orbitals. Calculated potential curves and excitation energies for several valence states are in good agreement with experiment and are compared with configuration interaction calculations using the same primitive basis. In order to test assumptions of semiempirical theories, we also perform a more approximate calculation of Hv in which the valence space is constructed as the union of the atomic valence spaces with the atomic orbitals taken from atomic SCF calculations. A new and important feature of this approximate, correlated Hv is the use of optimized valence and excited orbitals as determined from a constrained SCF procedure. The matrix elements of this approximate, correlated Hv are transformed to the original nonorthogonal atomic valence basis, and their bond length dependences are fit with simple analytical functions. Some calculated Hv matrix elements agree with the forms commonly postulated for semiempirical integrals, while others display quite different behavior. An example of the latter are the one-center, two-electron integrals which depend significantly on bond length in marked contrast to semiempirical theories which assume them to be bond length independent.

  10. Electric and magnetic properties computed for valence bond structures: is there a link between pauling resonance energy and ring current?

    Science.gov (United States)

    Havenith, Remco W A

    2006-04-28

    To establish the link between the aromaticity descriptors based on the Pauling resonance energy and the molecular properties, the electric (polarizability) and magnetic (magnetizability) field response properties have been calculated using the valence bond approach for various molecules and their individual Kekulé resonance structures. The results show that there is no direct relationship between the Pauling resonance energy and the properties; the response properties are weighted averages of the properties of the individual structures. According to the aromaticity criteria based on molecular properties, one-structure benzene would be aromatic; thus, concerning molecular properties, spin-coupled bonds do not behave like localized bonds in Lewis structures, with which they are usually associated.

  11. Valence electron structure and bonding features of RuB2 and OSB2: The empirical electron theory calculations

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The valence electron structure (VES) of RuB2 and OsB2 were calculated by the empirical electron theory (EET) of solids and molecules and compared with the results derived from the first-principles calculations. The distributions of covalent electrons in different bonds indicate that B-B and B-Me have remarkably covalent bonding characters. Lattice electrons cruising around Me-Me layers are found to have great influences on electronic conductivity and high temperature plasticity. The ultra-high values of elastic constant Cn in the two compounds originate from close-packed covalent bonding along the c axis. Uneven bond strengths and distributions of covalent bonds, especially for B-Afe bonds, yield significant anisotropy. Low ratios of lattice electrons to covalent electrons suggest the intrinsic embrittlement in crystals. The fact that the calculated cohesive energies well agree with experimental results demonstrates the good suitability of the EET calculations in estimating cohesive energy for transition-metal borides.

  12. In-Medium Pion Valence Distributions in a Light-Front Model

    CERN Document Server

    de Melo, J P B C; Ahmed, I

    2016-01-01

    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.

  13. A Valence Bond Description of the Prefulvene Extended Conical Intersection Seam of Benzene.

    Science.gov (United States)

    Blancafort, Lluís; Robb, Michael A

    2012-12-11

    The permutational isomers of the prefulvene-like minimum energy conical intersection lie on an extended conical intersection seam, where they are connected by higher symmetry structures. Here, we present a VB analysis of the electronic states involved along this extended seam. The VB method produces a spin-exchange density (ie. a bonding pattern) that provides the basis to assign resonance structures to the states. The results show that in the high symmetry region of the seam, the character of the states is dominated by the positive and negative combination of the Kekulé structures, (A+B) and (A-B). The low energy parts of the seam, comprised of lower symmetry conical intersection structures, are stabilized by mixing with the Dewar resonance structures. This feature is responsible for the stability of the benzvalene-like conical intersections. The validity of the VB model is confirmed by calculating the branching space vectors at this level of theory, which are in good agreement with the CASSCF calculated vectors. The VB analysis has also allowed us to complete our picture of the global seam, since it has provided the clue to locate a conical intersection saddle point that interconverts two minima of the prefulvene conical intersection where the carbon bent out of the plane is inverted and rotated by 60°. This saddle point has a benzvalene-like geometry, in agreement with the VB picture.

  14. Optical conductivity of visons in Z2 spin liquids close to a valence bond solid transition on the kagome lattice

    Science.gov (United States)

    Huh, Yejin; Punk, Matthias; Sachdev, Subir

    2013-06-01

    We consider Z2 spin liquids on the kagome lattice on the verge of a valence bond solid (VBS) transition, where vortex excitations carrying Z2 magnetic flux—so-called visons—condense. We show that these vison excitations can couple directly to the external electromagnetic field, even though they carry neither spin nor charge. This is possible via a magnetoelastic coupling mechanism recently identified. [Potter, Senthil, and Lee, arXiv:1301.3495; Hao, Phys. Rev. BPRBMDO1098-012110.1103/PhysRevB.85.174432 85, 174432 (2012)] For the case of transitions to a 36-site unit cell VBS state, the corresponding finite ac conductivity has a specific power-law frequency dependence, which is related to the crossover exponent of the quantum critical point. The visons’ contribution to the optical conductivity at transitions to VBS states with a 12-site unit cell vanishes, however.

  15. 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.

  16. 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 algori

  17. Modelling longevity bonds: Analysing the Swiss Re Kortis bond

    OpenAIRE

    2015-01-01

    A key contribution to the development of the traded market for longevity risk was the issuance of the Kortis bond, the world's first longevity trend bond, by Swiss Re in 2010. We analyse the design of the Kortis bond, develop suitable mortality models to analyse its payoff and discuss the key risk factors for the bond. We also investigate how the design of the Kortis bond can be adapted and extended to further develop the market for longevity risk.

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

    Science.gov (United States)

    D'Emidio, Jonathan; Kaul, Ribhu K.

    2016-02-01

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

  19. A bottom-up valence bond derivation of excitation energies in 1D-like delocalized systems.

    Science.gov (United States)

    Kepenekian, Mikaël; Robert, Vincent; Boilleau, Corentin; Malrieu, Jean-Paul

    2012-01-28

    Using the chemically relevant parameters hopping integral t(0) and on-site repulsion energy U, the charge gap (lowest dipolarly allowed transition energy) in 1D systems is examined through a bottom-up strategy. The method is based on the locally ionized states, the energies of which are corrected using short-range delocalization effects. In a valence bond framework, these states interact to produce an excitonic matrix which accounts for the delocalized character of excited states. The treatment, which gives access to the correlated spectrum of ionization potentials, is entirely analytical and valid whatever the U/|t(0)| ratio for such systems ruled by Peierls-Hubbard Hamiltonians. This second-order analytical derivation is finally confronted to numerical results of a renormalized excitonic treatment using larger blocks as functions of the U/|t(0)| ratio. The method is applied to dimerized chains and to fused polybenzenic 1D lattices. Such approaches complement the traditional Bloch-function based picture and deliver a conceptual understanding of the charge gap opening process based on a chemical intuitive picture.

  20. Reduced form models of bond portfolios

    OpenAIRE

    Matti Koivu; Teemu Pennanen

    2010-01-01

    We derive simple return models for several classes of bond portfolios. With only one or two risk factors our models are able to explain most of the return variations in portfolios of fixed rate government bonds, inflation linked government bonds and investment grade corporate bonds. The underlying risk factors have natural interpretations which make the models well suited for risk management and portfolio design.

  1. Valence space electron momentum spectroscopy of diborane

    Energy Technology Data Exchange (ETDEWEB)

    Wang Feng [Centre for Molecular Simulation, Swinburne University of Technology, P.O. Box 218, Hawthorn, Melbourne, Vic. 3122 (Australia)]. E-mail: fwang@swin.edu.au; Pang Wenning [Department of Physics, Polarization Physics Laboratory, Tsinghua University, Beijing 100084 (China); Huang Ming [Department of Physics, Polarization Physics Laboratory, Tsinghua University, Beijing 100084 (China)

    2006-05-15

    A non-classical mechanism of binding in diborane (B{sub 2} H{sub 6}) is derived quantum-mechanically (B3LYP/6-311++G**) using a dual-space analysis. High-resolution binding-energy spectra of diborane, generated using an outer-valence Green's-function and density-functional theory with a statistical average of model orbital potentials (SAOP), agree satisfactorily with experiment. Electron-correlation energies of diborane produce orbital-based variations in ionization energy in the valence space, but with negligible impact on the shape of only a{sub g} symmetry orbitals as indicated in momentum space. The present work indicates quantitatively that (a) the pair of three-centre banana-shaped B-H{sub b}-B bonds are more accurately described as one diamond-shaped bond with B-H{sub b}-B-H{sub b}, (b) all bonds in diborane are electron-deficient including the four equivalent B-H{sub t} bonds, (c) there is no pure B?B bond but contributions from all valence orbitals form an unconventional electron-deficient B-B bond, and (d) only two innermost valence orbitals - 2a{sub g} and 2b{sub 1u} - are sp{sup 2}-hybridized and no evidence indicates other valence orbitals of diborane to be hybridized.

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

    Science.gov (United States)

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

    2016-06-01

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

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

    Science.gov (United States)

    Higa, Ryota; Asano, Kenichi

    2016-06-01

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

  4. Bond—Valence Sum and Distortion of Coordination Polyhedra

    Institute of Scientific and Technical Information of China (English)

    章礼明

    1993-01-01

    By using the Lagrange's intermediate value theorem,it is derived mathematically that the structur-al distortion of a coordination polyhedron may lead to an increase in bond-valence sum of the cen-tral atom of ion .The applicabilities of the bond-valence model are discussed in the following two cases:the modeling of crystal structure ,and the indication of distortion degree of a coordination polyhedron.Also it is shown that a distorted polyhedron should be in favor of a longer average bond length or a smaller coordination number.

  5. 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

  6. Classification model of arousal and valence mental states by EEG signals analysis and Brodmann correlations

    Directory of Open Access Journals (Sweden)

    Adrian Rodriguez Aguinaga

    2015-06-01

    Full Text Available This paper proposes a methodology to perform emotional states classification by the analysis of EEG signals, wavelet decomposition and an electrode discrimination process, that associates electrodes of a 10/20 model to Brodmann regions and reduce computational burden. The classification process were performed by a Support Vector Machines Classification process, achieving a 81.46 percent of classification rate for a multi-class problem and the emotions modeling are based in an adjusted space from the Russell Arousal Valence Space and the Geneva model.

  7. The Total Position Spread in mixed-valence compounds: A study on the H4+ model system.

    Science.gov (United States)

    Bendazzoli, Gian Luigi; El Khatib, Muammar; Evangelisti, Stefano; Leininger, Thierry

    2014-04-15

    The behavior of the Total Position Spread (TPS) tensor, which is the second moment cumulant of the total position operator, is investigated in the case of a mixed-valence model system. The system consists of two H2 molecules placed at a distance D. If D is larger than about 4 bohr, the singly ionized system shows a mixed-valence character. It is shown that the magnitude of the TPS has a strong peak in the region of the avoided crossing. We believe that the TPS can be a powerful tool to characterize the behavior of the electrons in realistic mixed-valence compounds.

  8. Bond diluted anisotropic quantum Heisenberg model

    Energy Technology Data Exchange (ETDEWEB)

    Akıncı, Ümit, E-mail: umit.akinci@deu.edu.tr

    2013-10-15

    Effects of the bond dilution on the critical temperatures, phase diagrams and the magnetization behaviors of the isotropic and anisotropic quantum Heisenberg model have been investigated in detail. For the isotropic case, bond percolation threshold values have been determined for several numbers of two (2D) and three (3D) dimensional lattices. In order to investigate the effect of the anisotropy in the exchange interaction on the results obtained for the isotropic model, a detailed investigation has been made on a honeycomb lattice. Some interesting results, such as second order reentrant phenomena in the phase diagrams have been found. - Highlights: • Anisotropic quantum Heisenberg model with bond dilution investigated. • Bond percolation threshold values given for 2D and 3D lattices in isotropic case. • Phase diagrams and ground state magnetizations investigated in detail. • Variation of the bond percolation threshold values with anisotropy determined.

  9. 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)

  10. Combining quantum wavepacket ab initio molecular dynamics with QM/MM and QM/QM techniques: Implementation blending ONIOM and empirical valence bond theory.

    Science.gov (United States)

    Sumner, Isaiah; Iyengar, Srinivasan S

    2008-08-07

    We discuss hybrid quantum-mechanics/molecular-mechanics (QM/MM) and quantum mechanics/quantum mechanics (QM/QM) generalizations to our recently developed quantum wavepacket ab initio molecular dynamics methodology for simultaneous dynamics of electrons and nuclei. The approach is a synergy between a quantum wavepacket dynamics, ab initio molecular dynamics, and the ONIOM scheme. We utilize this method to include nuclear quantum effects arising from a portion of the system along with a simultaneous description of the electronic structure. The generalizations provided here make the approach a potentially viable alternative for large systems. The quantum wavepacket dynamics is performed on a grid using a banded, sparse, and Toeplitz representation of the discrete free propagator, known as the "distributed approximating functional." Grid-based potential surfaces for wavepacket dynamics are constructed using an empirical valence bond generalization of ONIOM and further computational gains are achieved through the use of our recently introduced time-dependent deterministic sampling technique. The ab initio molecular dynamics is achieved using Born-Oppenheimer dynamics. All components of the methodology, namely, quantum dynamics and ONIOM molecular dynamics, are harnessed together using a time-dependent Hartree-like procedure. We benchmark the approach through the study of structural and vibrational properties of molecular, hydrogen bonded clusters inclusive of electronic, dynamical, temperature, and critical quantum nuclear effects. The vibrational properties are constructed through a velocity/flux correlation function formalism introduced by us in an earlier publication.

  11. Valence electron theory of graphite spheroidizing in primary crystallization

    Institute of Scientific and Technical Information of China (English)

    刘志林; 孙振国; 李志林

    1995-01-01

    Bond-length-difference (BLD) analysis results show that austenrte and cementite containing Mg, Zr. S have very different valence electron structures from Fe -C austenite and cementite. We find that this difference is the tie of absorption hypothesis, surface tension hypothesis, undercooling hypothesis in graphite spheroidizing theory. By using "the model of valence electron theory of drag-like effect" in our previous paper in crystallization theory, the spheroidizing effect of Mg and Zr and the anti-spheroidizing effect of S can be explained with the valence electron structure data of phases. Therefore, electron theory of graphite spheroidizing can be advanced.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ponou, Simeon [Centre for Analysis and Synthesis, Lund University; Lidin, Sven [Centre for Analysis and Synthesis, Lund University; Zhang, Yuemei [Ames Laboratory; Miller, Gordon J. [Ames Laboratory

    2014-04-18

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

  13. Bond diluted Ising model in 2D

    Directory of Open Access Journals (Sweden)

    Bouamrane Rachid

    2013-03-01

    Full Text Available The bond diluted Ising model is studied by Monte Carlo method. The simulation is carried out on a two dimensional square lattice with missing bonds and free boundary conditions. The aim of this work is to investigate the thermodynamical properties of this model for different disorder degree parameter σ. The critical temperature is determined from the Binder cumulant and is shown to decreases as the disorder parameter σ increases linearly.

  14. 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.

  15. Mechatronic modeling and simulation using bond graphs

    CERN Document Server

    Das, Shuvra

    2009-01-01

    Bond graphs are especially well-suited for mechatronic systems, as engineering system modeling is best handled using a multidisciplinary approach. Bond graphing permits one to see the separate components of an engineering system as a unified whole, and allows these components to be categorized under a few generalized elements, even when they come from different disciplines. In addition to those advantages, the bond graph offers a visual representation of a system from which derivation of the governing equations is algorithmic. This makes the design process accessible to beginning readers, prov

  16. Molecular model with quantum mechanical bonding information.

    Science.gov (United States)

    Bohórquez, Hugo J; Boyd, Russell J; Matta, Chérif F

    2011-11-17

    The molecular structure can be defined quantum mechanically thanks to the theory of atoms in molecules. Here, we report a new molecular model that reflects quantum mechanical properties of the chemical bonds. This graphical representation of molecules is based on the topology of the electron density at the critical points. The eigenvalues of the Hessian are used for depicting the critical points three-dimensionally. The bond path linking two atoms has a thickness that is proportional to the electron density at the bond critical point. The nuclei are represented according to the experimentally determined atomic radii. The resulting molecular structures are similar to the traditional ball and stick ones, with the difference that in this model each object included in the plot provides topological information about the atoms and bonding interactions. As a result, the character and intensity of any given interatomic interaction can be identified by visual inspection, including the noncovalent ones. Because similar bonding interactions have similar plots, this tool permits the visualization of chemical bond transferability, revealing the presence of functional groups in large molecules.

  17. Modeling the Hydrogen Bond within Molecular Dynamics

    Science.gov (United States)

    Lykos, Peter

    2004-01-01

    The structure of a hydrogen bond is elucidated within the framework of molecular dynamics based on the model of Rahman and Stillinger (R-S) liquid water treatment. Thus, undergraduates are exposed to the powerful but simple use of classical mechanics to solid objects from a molecular viewpoint.

  18. Polysulfide anions II: structure and vibrational spectra of the S4(2-) and S5(2-) anions. Influence of the cations on bond length, valence, and torsion angle.

    Science.gov (United States)

    el Jaroudi, O; Picquenard, E; Demortier, A; Lelieur, J P; Corset, J

    2000-06-12

    The influence of the cations on bond length, valence, and torsion angle of S4(2-) and S5(2-) anions was examined in a series of solid alkali tetra- and pentasulfides by relating their Raman spectra to their known X-ray structures through a force-field analysis. The IR and Raman spectra of BaS4.H2O and the Raman spectra of (NH4)2S4.nNH3, gamma-Na2S4, and delta-Na2S5 are presented. The similarity of spectra of gamma-Na2S4 with those of BaS4.H2O suggests similar structures of the S4(2-) anions in these two compounds with a torsion angle smaller than 90 degrees. The variations of SS bond length, SSS valence angle, and dihedral angle of Sn2- anions are related to the polarization of the lone pair and electronic charge of the anion by the electric field of the cations. A correlation between the torsion angle and the SSS valence angle is shown as that previously reported between the length of the bond around which the torsion takes place and the dihedral angle value. These geometry changes are explained by the hyperconjugation concept and the electron long-pair repulsion.

  19. Vibrational progressions in the valence ionizations of transition metal hydrides: evaluation of metal-hydride bonding and vibrations in (eta(5)-C(5)R(5))Re(NO)(CO)H [R = H, CH(3)].

    Science.gov (United States)

    Lichtenberger, Dennis L; Gruhn, Nadine E; Rai-Chaudhuri, Anjana; Renshaw, Sharon K; Gladysz, John A; Jiao, Haijun; Seyler, Jeff; Igau, Alain

    2002-02-20

    The first examples of vibrational structure in metal-ligand sigma-bond ionizations are observed in the gas-phase photoelectron spectra of CpRe(NO)(CO)H and CpRe(NO)(CO)H [Cp = eta(5)-C(5)H(5), Cp = eta(5)-C(5)(CH(3))(5)]. The vibrational progressions are due to the Re-H stretch in the ion states formed by removal of an electron from the predominantly Re-H sigma-bonding orbitals. A vibrational progression is also observed in the corresponding ionization of the deuterium analogue, CpRe(NO)(CO)D, but with lower vibrational energy spacing as expected from the reduced mass effect. The vibrational progressions in these valence ionizations are directly informative about the nature of the metal-hydride bonding and electronic structure in these molecules. Franck-Condon analysis shows that for these molecules the Re-H or Re-D bond lengthens by 0.25(1) A when an electron is removed from the Re-H or Re-D sigma-bond orbital. This bond lengthening is comparable to that of H(2) upon ionization. Removal of an electron from the Re-H or Re-D bonds leads to a quantum-mechanical inner sphere reorganization energy (lambda(QM)) of 0.34(1) eV. These observations suggest that even in these low symmetry molecules the orbital corresponding to the Re-H sigma bond and the Re-H vibrational mode is very localized. Theoretical calculations of the electronic structure and normal vibrational modes of CpRe(NO)(CO)H support a localized two-electron valence bond description of the Re-H interaction.

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

    Science.gov (United States)

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

    2016-07-21

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

  1. Bonded-cell model for particle fracture

    OpenAIRE

    Nguyen, Duc-Hanh; Azéma, Émilien; Sornay, Philippe; Radjaï, Farhang

    2015-01-01

    International audience; Particle degradation and fracture play an important role in natural granular flows and in many applications of granular materials. We analyze the fracture properties of two-dimensional disklike particles modeled as aggregates of rigid cells bonded along their sides by a cohesive Mohr-Coulomb law and simulated by the contact dynamics method. We show that the compressive strength scales with tensile strength between cells but depends also on the friction coefficient and ...

  2. Alteration of Expected Hemispheric Asymmetries: Valence and Arousal Effects in Neuropsychological Models of Emotion

    Science.gov (United States)

    Alfano, Keith M.; Cimino, Cynthia R.

    2008-01-01

    The relative advantage of the left (LH) over the right hemisphere (RH) in processing of verbal material for most individuals is well established. Nevertheless, several studies have reported the ability of positively and negatively valenced stimuli to enhance and reverse, respectively, the usual LH greater than RH asymmetry. These studies, however,…

  3. Valence electron structure of the(ZrTi)B2 solid solutions calculated by the three models

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The Zr-rich(Zr0.8Ti0.2)B2 and the Ti-rich(Ti0.8Zr0.2)B2 solid solutions are formed when TiB2 and ZrB2 are hot-pressed.To forecast the properties of the two solid solutions,their valence electron structure was analyzed based on the empirical electron theory(EET) of solids and molecules.We used three different models,the average atom model,the average cell model and the real cell model,and compared with the calculation results from the three models.In the real cell model,the lattice constants of the solid solu-tions were supposed to be changed or unchanged.The results showed that different models could only result in slight change in the hybridization levels of the metal atoms in the two solid solutions and little difference between the calculation values.However,they can not change the variant trend of the va-lence electron structure nor the properties of the solid solutions.Thus,the three models and the methods are appropriate and the calculation results are reasonable and consistent.

  4. Bonded-cell model for particle fracture.

    Science.gov (United States)

    Nguyen, Duc-Hanh; Azéma, Emilien; Sornay, Philippe; Radjai, Farhang

    2015-02-01

    Particle degradation and fracture play an important role in natural granular flows and in many applications of granular materials. We analyze the fracture properties of two-dimensional disklike particles modeled as aggregates of rigid cells bonded along their sides by a cohesive Mohr-Coulomb law and simulated by the contact dynamics method. We show that the compressive strength scales with tensile strength between cells but depends also on the friction coefficient and a parameter describing cell shape distribution. The statistical scatter of compressive strength is well described by the Weibull distribution function with a shape parameter varying from 6 to 10 depending on cell shape distribution. We show that this distribution may be understood in terms of percolating critical intercellular contacts. We propose a random-walk model of critical contacts that leads to particle size dependence of the compressive strength in good agreement with our simulation data.

  5. Valence electron structure of the (ZrTi)B2 solid solutions calculated by the three models

    Institute of Scientific and Technical Information of China (English)

    LI JinPing; HAN JieCai; MENG SongHe; WANG BaoLin

    2009-01-01

    The Zr-rich (Zr0.8Ti0.2)B2 and the Ti-rich Zr0.8Ti0.2)B2 solid solutions are formed when TiB2 and ZrB2 are hot-pressed. To forecast the properties of the two solid solutions, their valence electron structure was analyzed based on the empirical electron theory (EET) of solids and molecules. We used three differen tmodels, the average atom model, the average cell model and the real cell model, and compared with the calculation results from the three models. In the real cell model, the lattice constants of the solid solu-tions were supposed to be changed or unchanged. The results showed that different models could only result in slight change in the hybridization levels of the metal atoms in the two solid solutions and little difference between the calculation values. However, they can not change the variant trend of the va-lence electron structure nor the properties of the solid solutions. Thus, the three models and the methods are appropriate and the calculation results are reasonable and consistent.

  6. Dynamic force spectroscopy on multiple bonds: experiments and model

    CERN Document Server

    Erdmann, T; Nassoy, P; Schwarz, U S

    2007-01-01

    We probe the dynamic strength of multiple biotin-streptavidin adhesion bonds under linear loading using the biomembrane force probe setup for dynamic force spectroscopy. Measured rupture force histograms are compared to results from a master equation model for the stochastic dynamics of bond rupture under load. This allows us to extract the distribution of the number of initially closed bonds. We also extract the molecular parameters of the adhesion bonds, in good agreement with earlier results from single bond experiments. Our analysis shows that the peaks in the measured histograms are not simple multiples of the single bond values, but follow from a superposition procedure which generates different peak positions.

  7. High Valence, Normal Valence and Unknown Valence

    DEFF Research Database (Denmark)

    Morsing, Thorbjørn Juul

    quality of single crystal multi frequency EPR is used to make a new model which is more physically accurate and which better describes the observed experimental behaviour. This has implications not just for the investigated chromium systems, but for exchange coupled systems in general. Chapter 3 details...... that the coordination of Ag(I) has no perceivable eect on the Ir ligand eld. Chapter 6 details the synthesis of new terminal ruthenium carbide complexes by ligand substitution on the Ru center. This approach to new, rationally tuned carbide complexes is virtually unexplored. The reaction of the known carbide complex...... [RuC(Cl)2(PCy3)2] with cyanide aords the cyanide analogue [RuC(CN)2(PCy3)2]. The reaction kinetics are studied with NMR. It is also possible to exchange only one of the chloride ligands, with the intermediate [RuC(Cl)(NCCH3)(PCy3)2]+ and this control of the ligand environment opens up the possibility...

  8. DSE inspired model for the pion's valence dressed-quark GPD

    CERN Document Server

    Chang, L; Moutarde, H; Roberts, C D; Rodríguez-Quintero, J; Sabatié, F

    2015-01-01

    We sketch here an approach to the computation of generalised parton distributions (GPDs), based upon a rainbow-ladder (RL) truncation of QCD's Dyson-Schwinger equations and exemplified via the pion's valence dressed-quark GPD, $H_\\pi^{\\rm v}(x,\\xi,t)$. Our analysis focuses on the case of zero skewness, $\\xi=0$, and underlines 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 $H_\\pi^{\\rm v}(x,0,t)$, expressed as the Radon transform of a single amplitude. Therewith we obtain results for $H_\\pi^{\\rm v}(x,0,t)$ and the associated impact-parameter dependent distribution, $q_\\pi^{\\rm v}(x,|\\vec{b}_\\perp|)$, which provide a qualitatively sound picture of the pion's dressed-quark structure at an hadronic scale.

  9. 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.

  10. [2.2]paracyclophane-bridged mixed-valence compounds: application of a generalized Mulliken-Hush three-level model.

    Science.gov (United States)

    Amthor, Stephan; Lambert, Christoph

    2006-01-26

    A series of [2.2]paracylophane-bridged bis-triarylamine mixed-valence (MV) radical cations were analyzed by a generalized Mulliken-Hush (GMH) three-level model which takes two transitions into account: the intervalence charge transfer (IV-CT) band which is assigned to an optically induced hole transfer (HT) from one triarylamine unit to the second one and a second band associated with a triarylamine radical cation to bridge (in particular, the [2.2]paracyclophane bridge) hole transfer. From the GMH analysis, we conclude that the [2.2]paracyclophane moiety is not the limiting factor which governs the intramolecular charge transfer. AM1-CISD calculations reveal that both through-bond as well as through-space interactions of the [2.2]paracyclophane bridge play an important role for hole transfer processes. These electronic interactions are of course smaller than direct pi-conjugation, but from the order of magnitude of the couplings of the [2.2]paracyclophane MV species, we assume that this bridge is able to mediate significant through-space and through-bond interactions and that the cyclophane bridge acts more like an unsaturated spacer rather than a saturated one. From the exponential dependence of the electronic coupling V between the two triarylamine localized states on the distance r between the two redox centers, we infer that the hole transfer occurs via a superexchange mechanism. Our analysis reveals that even significantly longer pi-conjugated bridges should still mediate significant electronic interactions because the decay constant beta of a series of pi-conjugated MV species is small.

  11. Pricing for Catastrophe Bonds Based on Expected-value Model

    Directory of Open Access Journals (Sweden)

    Junfei Chen

    2013-02-01

    Full Text Available As the catastrophes cannot be avoided and result in huge economic losses, therefore the compensation issue for catastrophe losses become an important research topic. Catastrophe bonds can effectively disperse the catastrophe risks which mainly undertaken by the government and the insurance companies currently and focus on capital more effectively in broad capital market, therefore to be an ideal catastrophe securities product. This study adopts Expectancy Theory to supplement and improve the pricing of catastrophe bonds based on Value Theory. A model of expected utility is established to determine the conditions of the expected revenue R of catastrophe bonds. The pricing model of the value function is used to get the psychological value of R,U (R-R‾, for catastrophe bonds. Finally, the psychological value is improved by the value according to expected utility and this can more accurately evaluate catastrophe bonds at a reasonable price. This research can provide decision-making for the pricing of catastrophe bonds.

  12. Theoretical Model of Transformation Superlastic Diffusion Bonding for Eutectoid Steel

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Based on current theories of diffusion and creep cavity closure at high temperature, a theoretical analysis of phase transformation diffusion bonding for T8/T8 eutectoid steel is carried out. The diffusion bonding is mainly described as two-stage process: Ⅰ The interfacial cavity with shape change from diamond to cylinder.Ⅱ The radius of the cylindrical cavity are reduced and eliminated gradually. A new theoretical model is established for the process of transformation superplastic diffusion bonding (TSDB) ...

  13. Valence-state Model of Strain-dependent Mn L2,3 X-ray Magnetic Circular Dichroism from Ferromagnetic Semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    van der Laan, G.; Edmonds, K. W.; Arenholz, E.; Farley, N. R. S.; Gallagher, B. L.

    2010-03-30

    We present a valence-state model to explain the characteristics of a recently observed pre-edge feature in Mn L{sub 3} x-ray magnetic circular dichroism (XMCD) of ferromagnetic (Ga,Mn)As and (Al,Ga,Mn)As thin films. The prepeak XMCD shows a uniaxial anisotropy, contrary to the cubic symmetry of the main structures induced by the crystalline electric field. Reversing the strain in the host lattice reverses the sign of the uniaxial anisotropy. With increasing carrier localization, the prepeak height increases, indicating an increasing 3d character of the hybridized holes. Hence, the feature is ascribed to transitions from the Mn 2p core level to unoccupied p-d hybridized valence states. The characteristics of the prepeak are readily reproduced by the model calculation taking into account the symmetry of the strain-, spin-orbit-, and exchange-split valence states around the zone center.

  14. 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…

  15. Modelling of the Through-air Bonding Process

    Directory of Open Access Journals (Sweden)

    M. Hossain

    2009-06-01

    Full Text Available A computational fluid dynamics (CFD modelling ofthe through-air bonding process of nonwoven fabricproduction is reported in this article. In the throughairprocess, hot air is passed through the fibrous webto heat and melt polymer fibers. Molten polymersubsequently flows to the point of contact betweenany two fibers to produce a bond. Two differentmodelling strategies are adapted to produce acomprehensive understanding of the through-airbonding process. In macroscale modelling, a CFDmodel is developed treating the whole web as aporous media in order to investigate the effect ofprocess parameters. Results reveal that the timerequired to heat and melt the fibers decreases with theincreasing porosity of the web and the velocity of hotair. The CFD modelling technique is then used toanalyze the bonding process at a more fundamentallevel by considering the bonding of individual fibersat microscale. The effects of the fiber diameter,bonding temperature and contact angle between twofibers on the bonding time are investigated. Resultsshow that the time required to bond fibers is weaklyrelated to bonding temperature and fiber diameter.Fiber orientation angle, on the other hand, hassignificant effect on the progression of bondformation.

  16. 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...

  17. Small cluster models of the surface electronic structure and bonding properties of titanium carbide, vanadium carbide, and titanium nitride.

    Science.gov (United States)

    Didziulis, Stephen V; Butcher, Kristine D; Perry, Scott S

    2003-12-01

    Density functional theory (DFT) calculations on stoichiometric, high-symmetry clusters have been performed to model the (100) and (111) surface electronic structure and bonding properties of titanium carbide (TiC), vanadium carbide (VC), and titanium nitride (TiN). The interactions of ideal surface sites on these clusters with three adsorbates, carbon monoxide, ammonia, and the oxygen atom, have been pursued theoretically to compare with experimental studies. New experimental results using valence band photoemission of the interaction of O(2) with TiC and VC are presented, and comparisons to previously published experimental studies of CO and NH(3) chemistry are provided. In general, we find that the electronic structure of the bare clusters is entirely consistent with published valence band photoemission work and with straightforward molecular orbital theory. Specifically, V(9)C(9) and Ti(9)N(9) clusters used to model the nonpolar (100) surface possess nine electrons in virtually pure metal 3d orbitals, while Ti(9)C(9) has no occupation of similar orbitals. The covalent mixing of the valence bonding levels for both VC and TiC is very high, containing virtually 50% carbon and 50% metal character. As expected, the predicted mixing for the Ti(9)N(9) cluster is somewhat less. The Ti(8)C(8) and Ti(13)C(13) clusters used to model the TiC(111) surface accurately predict the presence of Ti 3d-based surface states in the region of the highest occupied levels. The bonding of the adsorbate species depends critically on the unique electronic structure features present in the three different materials. CO bonds more strongly with the V(9)C(9) and Ti(9)N(9) clusters than with Ti(9)C(9) as the added metal electron density enables an important pi-back-bonding interaction, as has been observed experimentally. NH(3) bonding with Ti(9)N(9) is predicted to be somewhat enhanced relative to VC and TiC due to greater Coulombic interactions on the nitride. Finally, the interaction with

  18. 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

  19. Minimal model for dynamic bonding in colloidal transient networks

    Science.gov (United States)

    Krinninger, Philip; Fortini, Andrea; Schmidt, Matthias

    2016-04-01

    We investigate a model for colloidal network formation using Brownian dynamics computer simulations. Hysteretic springs establish transient bonds between particles with repulsive cores. If a bonded pair of particles is separated by a cutoff distance, the spring vanishes and reappears only if the two particles contact each other. We present results for the bond lifetime distribution and investigate the properties of the van Hove dynamical two-body correlation function. The model displays crossover from fluidlike dynamics, via transient network formation, to arrested quasistatic network behavior.

  20. 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.

  1. News from the Periodic Table: An Introduction to "Periodicity Symbols, Tables, and Models for Higher-Order Valency and Donor-Acceptor Kinships"

    Science.gov (United States)

    Bent, Henry A.; Weinhold, Frank

    2007-01-01

    The study presents and explains the various periodicity symbols, tables and models for the higher-order valency and donor-acceptor kinships used in chemistry. The described alternative tables are expected to improve the pedagogical consistency of the chemical periodicity patterns with better electronic behavior.

  2. 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.

  3. In-Medium Pion Valence Distribution Amplitude

    CERN Document Server

    Tsushima, K

    2016-01-01

    After a brief review of the quark-based model for nuclear matter, and some pion properties in medium presented in our previous works, we report new results for the pion valence wave function as well as the valence distribution amplitude in medium, which are presented in our recent article. We find that both the in-medium pion valence distribution and the in-medium pion valence wave function, are substantially modified at normal nuclear matter density, due to the reduction in the pion decay constant.

  4. In-Medium Pion Valence Distribution Amplitude

    Science.gov (United States)

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

    2017-03-01

    After a brief review of the quark-based model for nuclear matter, and some pion properties in medium presented in our previous works, we report new results for the pion valence wave function as well as the valence distribution amplitude in medium, which are presented in our recent article. We find that both the in-medium pion valence distribution and the in-medium pion valence wave function, are substantially modified at normal nuclear matter density, due to the reduction in the pion decay constant.

  5. 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.

  6. Bayesian parameter estimation in the Expectancy Valence model of the Iowa gamblling task

    NARCIS (Netherlands)

    Wetzels, R.; Vandekerckhove, J.; Tuerlinckx, F.; Wagenmakers, E.-J.

    2010-01-01

    The purpose of the popular Iowa gambling task is to study decision making deficits in clinical populations by mimicking real-life decision making in an experimental context. Busemeyer and Stout [Busemeyer, J. R., & Stout, J. C. (2002). A contribution of cognitive decision models to clinical assessme

  7. Modelling of spreading process: effect from hydrogen bonds

    Institute of Scientific and Technical Information of China (English)

    Li Xin; Hu Yuan-Zhong; Jiang Lan

    2008-01-01

    Lubricant spreading on solid substrates has drawn considerable attention not only for the microscopic wetting theory but also for the dramatic application in head-disk interface of magnetic storage drive systems. Molecular dynamic simulation based on a coarse-grained bead-spring model has been used to study such a spreading process.The spreading profiles indicate that the hydrogen bonds among lubricant molecules and the hydrogen bonds between lubricant molecules and polar atoms of solid substrates will complicate the spreading process in a tremendous degree.The hydrogen bonds among lubricant molecules will strengthen the lubricant combination intensity, which may hinder most molecules from flowing down to the substrates and diffusing along the substrates. And the hydrogen bonds between lubricant molecules and polar atoms of solid substrates will confine the lubricant molecules around polar atoms, which may hinder the molecules from diffusing along the substrates and cause precursor film to vanish.

  8. 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.

  9. Valence electronic structure of tantalum carbide and nitride

    Institute of Scientific and Technical Information of China (English)

    FAN; ChangZeng

    2007-01-01

    The valence electronic structures of tantalum carbide (TaC) and tantalum nitride (TaN) are studied by using the empirical electronic theory (EET). The results reveal that the bonds of these compounds have covalent, metallic and ionic characters. For a quantitative analysis of the relative strength of these components, their ionicities have been calculated by implanting the results of EET to the PVL model. It has been found that the ionicity of tantalum carbide is smaller than that of tantalum nitride. The EET results also reveal that the covalent electronic number of the strongest bond in the former is larger than that of the latter. All these suggest that the covalent bond of TaC is stronger than that of TaN, which coincides to that deduced from the first-principles method.……

  10. Valence electronic structure of tantalum carbide and nitride

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    @@ The valence electronic structures of tantalum carbide (TaC) and tantalum nitride (TaN) are studied by using the empirical electronic theory (EET). The results reveal that the bonds of these compounds have covalent, metallic and ionic characters. For a quantitative analysis of the relative strength of these components, their ionicities have been calculated by implanting the results of EET to the PVL model. It has been found that the ionicity of tantalum carbide is smaller than that of tantalum nitride. The EET results also reveal that the covalent electronic number of the strongest bond in the former is larger than that of the latter. All these suggest that the covalent bond of TaC is stronger than that of TaN, which coincides to that deduced from the first-principles method.

  11. 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 asymmet

  12. Pairing preferences of the model mono-valence mono-atomic ions investigated by molecular simulation.

    Science.gov (United States)

    Zhang, Qiang; Zhang, Ruiting; Zhao, Ying; Li, HuanHuan; Gao, Yi Qin; Zhuang, Wei

    2014-05-14

    We carried out a series of potential of mean force calculations to study the pairing preferences of a series of model mono-atomic 1:1 ions with evenly varied sizes. The probabilities of forming the contact ion pair (CIP) and the single water separate ion pair (SIP) were presented in the two-dimensional plots with respect to the ion sizes. The pairing preferences reflected in these plots largely agree with the empirical rule of matching ion sizes in the small and big size regions. In the region that the ion sizes are close to the size of the water molecule; however, a significant deviation from this conventional rule is observed. Our further analysis indicated that this deviation originates from the competition between CIP and the water bridging SIP state. The competition is mainly an enthalpy modulated phenomenon in which the existing of the water bridging plays a significant role.

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

    Science.gov (United States)

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

    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 science. However, many studies have determined that the use of models in science education can contribute to students' difficulties understanding the topic, and that students generally find chemical bonding a challenging topic. The aim of this study is to investigate teachers' knowledge of teaching chemical bonding. The study focuses on three essential components of pedagogical content knowledge (PCK): (1) the students' understanding, (2) representations, and (3) instructional strategies. We analyzed lesson plans about chemical bonding generated by 10 chemistry teachers with whom we also conducted semi-structured interviews about their teaching. Our results revealed that the teachers were generally unaware of how the representations of models they used affected student comprehension. The teachers had trouble specifying students' difficulties in understanding. Moreover, most of the instructional strategies described were generic and insufficient for promoting student understanding. Additionally, the teachers' rationale for choosing a specific representation or activity was seldom directed at addressing students' understanding. Our results indicate that both PCK components require improvement, and suggest that the two components should be connected. Implications for the professional development of pre-service and in-service teachers are discussed.

  14. 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.

  15. 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

  16. 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

  17. 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...

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

    Directory of Open Access Journals (Sweden)

    Stefanie Krysiak

    2015-05-01

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

  19. Confining Bond Rearrangement in the Random Center Vortex Model

    CERN Document Server

    Altarawneh, Derar; Engelhardt, Michael

    2015-01-01

    We present static meson-meson and baryon--anti-baryon potentials in Z(2) and Z(3) random center vortex models for the infrared sector of Yang-Mills theory, i.e., hypercubic lattice models of random vortex world-surfaces. In particular, we calculate Polyakov loop correlators of two static mesons resp. (anti-)baryons in a center vortex background and observe that their expectation values follow the minimal area law and show bond rearrangement behavior. The static meson-meson and baryon--anti-baryon potentials are compared with theoretical predictions and lattice QCD simulations.

  20. Everyone Wants to Be a Model Teacher: Part III: Extensions to Atomic Structures and Bonding.

    Science.gov (United States)

    Schrader, C. L.

    1985-01-01

    Describes activities in which students: (1) propose creative atomic models that account for observed properties and predict additional experimental data; (2) calculate empirical formulas for 27 binary compounds; (3) propose a model to explain why certain elements have certain valences; and (4) arrange hypothetical elements into a periodic chart.…

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. Monetary Policy and Bond Option Pricing in an Analytical RBC Model

    OpenAIRE

    Söderlind, Paul

    2003-01-01

    This paper analyzes how bond option prices are affected by different types of monetary policy. Analytical results from a general equilibrium model with sticky wages show that employment or output targeting typically give lower bond option prices than inflation targeting.

  6. The Fluctuating Bond Model, a Glue for Cuprate Superconductivity?

    Science.gov (United States)

    Newns, Dennis

    2008-03-01

    Twenty years of research have yet to produce a consensus on the origin of high temperature superconductivity (HTS). The mechanism of HTS - which originates in the CuO2 plane, common to all HTS families - can be constrained by some key experimental facts regarding superconducting and pseudogap behaviors. Superconductivity, involving a Tc of order 100 K, exhibits an unusual d-wave superconducting gap, with Fermi liquid nodal excitations, and an anomalous doping- dependent oxygen isotope shift. A ``pseudogap,'' also with d-symmetry, leads to a dip in the density of states below a characteristic temperature scale T^*, which has a negative isotope shift; we associate the pseudogap with the recently observed spatially inhomogeneous (nanometer- scale) C4 symmetry breaking. The isotope shifts and other evidence imply a key role for oxygen vibrations, but conventional BCS single-phonon coupling is essentially forbidden by symmetry and by the on-site Coulomb interaction U. In a novel approach, we introduce a model based on a strong, local, nonlinear interaction between electrons within the Cu-O-Cu bond in the CuO2 plane, and the oxygen vibrational degrees of freedom, termed the Fluctuating Bond Model (FBM) [D.M. Newns and C.C. Tsuei, Nature Physics 3, 184 (2007)]. In mean field the model predicts a phase manifesting broken C4 symmetry, with a d-type pseudogap, and an upper phase boundary in temperature, with a negative isotope shift, which we identify with T^*. An intrinsic d-wave pairing tendency is found, leading to a transition temperature dome and an anomalous isotope shift similar to that found experimentally. The softening in the oxygen vibrational frequency below Tc, seen in Raman and neutron spectra, has a natural explanation in the FBM. Recent ab initio calculations have been implemented which provide microscopic support for the model.

  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. Double site-bond percolation model for biomaterial implants

    CERN Document Server

    Mely, H

    2011-01-01

    We present a double site-bond percolation model to account, on the one hand, for the vascularization and/or resorption of biomaterial implant in bones and, on the other hand, for its mechanical continuity. The transformation of the implant into osseous material, and the dynamical formation/destruction of this osseous material is accounted for by creation and destruction of links and sites in two, entangled, networks. We identify the relevant parameters to describe the implant and its evolution, and separate their biological or chemical origin from their physical one. We classify the various phenomena in the two regimes, percolating or non-percolating, of the networks. We present first numerical results in two dimensions.

  10. Vector-based model of elastic bonds for simulation of granular solids.

    Science.gov (United States)

    Kuzkin, Vitaly A; Asonov, Igor E

    2012-11-01

    A model (further referred to as the V model) for the simulation of granular solids, such as rocks, ceramics, concrete, nanocomposites, and agglomerates, composed of bonded particles (rigid bodies), is proposed. It is assumed that the bonds, usually representing some additional gluelike material connecting particles, cause both forces and torques acting on the particles. Vectors rigidly connected with the particles are used to describe the deformation of a single bond. The expression for potential energy of the bond and corresponding expressions for forces and torques are derived. Formulas connecting parameters of the model with longitudinal, shear, bending, and torsional stiffnesses of the bond are obtained. It is shown that the model makes it possible to describe any values of the bond stiffnesses exactly; that is, the model is applicable for the bonds with arbitrary length/thickness ratio. Two different calibration procedures depending on bond length/thickness ratio are proposed. It is shown that parameters of the model can be chosen so that under small deformations the bond is equivalent to either a Bernoulli-Euler beam or a Timoshenko beam or short cylinder connecting particles. Simple analytical expressions, relating parameters of the V model with geometrical and mechanical characteristics of the bond, are derived. Two simple examples of computer simulation of thin granular structures using the V model are given.

  11. Modelling the Loss of Steel-Concrete Bonds in Corroded Reinforced Concrete Beams

    DEFF Research Database (Denmark)

    Thoft-Christensen, Palle

    2007-01-01

    The existing stochastic models for deterioration of reinforced concrete structures is extended by adding modelling of "loss of bond" due to corrosion between the reinforcement bars and the surrounding concrete.......The existing stochastic models for deterioration of reinforced concrete structures is extended by adding modelling of "loss of bond" due to corrosion between the reinforcement bars and the surrounding concrete....

  12. Physical Nature of Hydrogen Bond

    CERN Document Server

    Zhyganiuk, I V

    2015-01-01

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

  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. Critical behavior of the random-bond clock model

    Science.gov (United States)

    Wu, Raymond P. H.; Lo, Veng-cheong; Huang, Haitao

    2012-09-01

    The critical behavior of the clock model in two-dimensional square lattice is studied numerically using Monte Carlo method with Wolff algorithm. The Kosterlitz-Thouless (KT) transition is observed in the 8-state clock model, where an intermediate phase exists between the low-temperature ordered phase and the high-temperature disordered phase. The bond randomness is introduced to the system by assuming a Gaussian distribution for the coupling coefficients with the mean μ = 1 and different values of variance: from σ2 = 0.1 to σ2 = 3.0. An abrupt jump in the helicity modulus at the transition, which is the key characteristic of the KT transition, is verified with a stability argument. Our results show that, a small amount of disorder (small σ) reduces the critical temperature of the system, without altering the nature of transition. However, a larger amount of disorder changes the transition from the KT-type into that of non-KT-type.

  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. Developing A Laser Shockwave Model For Characterizing Diffusion Bonded Interfaces

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-07-01

    12. Other advances in QNDE and related topics: Preferred Session Laser-ultrasonics Developing A Laser Shockwave Model For Characterizing Diffusion Bonded Interfaces 41st Annual Review of Progress in Quantitative Nondestructive Evaluation Conference QNDE Conference July 20-25, 2014 Boise Centre 850 West Front Street Boise, Idaho 83702 James A. Smith, Jeffrey M. Lacy, Barry H. Rabin, Idaho National Laboratory, Idaho Falls, ID ABSTRACT: The US National Nuclear Security Agency has a Global Threat Reduction Initiative (GTRI) which is assigned with 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. The new LEU fuel is based on a monolithic fuel made from a U-Mo alloy foil encapsulated in Al-6061 cladding. In order to complete the fuel qualification process, the laser shock technique is being developed to characterize the clad-clad and fuel-clad interface strengths in fresh and irradiated fuel plates. The Laser Shockwave Technique (LST) is being investigated to characterize interface strength in 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 the deposition of laser energy into the containment layer on specimen’s surface is intractably complex. The shock wave energy is inferred from the velocity on the backside and the depth of the impression left on the surface from the high pressure plasma pulse created by the shock laser. To help quantify the stresses and strengths at the interface, a finite element model is being developed and validated by comparing numerical and experimental results for back face velocities and front face depressions with experimental results. This paper will report on initial efforts to develop a finite element model for laser

  17. Energetics of hydrogen bonding in proteins: a model compound study.

    OpenAIRE

    1996-01-01

    Differences in the energetics of amide-amide and amide-hydroxyl hydrogen bonds in proteins have been explored from the effect of hydroxyl groups on the structure and dissolution energetics of a series of crystalline cyclic dipeptides. The calorimetrically determined energetics are interpreted in light of the crystal structures of the studied compounds. Our results indicate that the amide-amide and amide-hydroxyl hydrogen bonds both provide considerable enthalpic stability, but that the amide-...

  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. 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…

  20. 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

  1. Gradient Bundle Analysis: A Full Topological Approach to Chemical Bonding

    CERN Document Server

    Morgenstern, Amanda

    2016-01-01

    The "chemical bond" is a central concept in molecular sciences, but there is no consensus as to what a bond actually is. Therefore, a variety of bonding models have been developed, each defining the structure of molecules in a different manner with the goal of explaining and predicting chemical properties. This thesis describes the initial development of gradient bundle analysis (GBA), a chemical bonding model that creates a high resolution picture of chemical interactions within the charge density framework. GBA is based on concepts from the quantum theory of atoms in molecules (QTAIM), but uses a more complete picture of the topology and geometry of the electron charge density to understand and predict bonding interactions. Gradient bundles are defined as volumes bounded by zero-flux surfaces (ZFSs) in the gradient of the charge density with well-defined energies. The structure of gradient bundles provides an avenue for detecting the locations of valence electrons, which correspond to reactive regions in a ...

  2. Critical behavior of the random-bond Ashkin-Teller model: A Monte Carlo study

    Science.gov (United States)

    Wiseman, Shai; Domany, Eytan

    1995-04-01

    The critical behavior of a bond-disordered Ashkin-Teller model on a square lattice is investigated by intensive Monte Carlo simulations. A duality transformation is used to locate a critical plane of the disordered model. This critical plane corresponds to the line of critical points of the pure model, along which critical exponents vary continuously. Along this line the scaling exponent corresponding to randomness φ=(α/ν) varies continuously and is positive so that the randomness is relevant, and different critical behavior is expected for the disordered model. We use a cluster algorithm for the Monte Carlo simulations based on the Wolff embedding idea, and perform a finite size scaling study of several critical models, extrapolating between the critical bond-disordered Ising and bond-disordered four-state Potts models. The critical behavior of the disordered model is compared with the critical behavior of an anisotropic Ashkin-Teller model, which is used as a reference pure model. We find no essential change in the order parameters' critical exponents with respect to those of the pure model. The divergence of the specific heat C is changed dramatically. Our results favor a logarithmic type divergence at Tc, C~lnL for the random-bond Ashkin-Teller and four-state Potts models and C~ln lnL for the random-bond Ising model.

  3. Virtual multi-dimensional internal bonds model and its application in simulation of rock mass

    Institute of Scientific and Technical Information of China (English)

    ZHANG ZhenNan; GE XiuRun

    2008-01-01

    VMIB (virtual multi-dimensional internal bonds) is a multiscale mechanical model developed from the VIB (virtual internal bond) theory. In VIB theory, the solid material is considered to consist of random-distributed material particles in microscale. These particles are connected with normal bonds. The macro constitutive relation is derived from the cohesive law between particles. However, in VMIB, the micro particles are connected with both normal and shear bonds. The macro constitutive relation is derived in terms of bond stiffness coefficients. It has been theoretically certified that there exists a corresponding relationship between the two bond stiffness coefficients and the two macro material constants, i.e. the Young's modulus and Poisson ratio. This corresponding relationship suggests that it should be necessary and sufficient to simultaneously account for the normal and shear interactions between particles. Due to the fact that the fracture criterion is directly incorporated into the constitutive relation, both VIB and VMIB present many advantages in simulating fractures of materials. In the damage model of rock mass, a damage tensor is usually defined to describe the distribution of cracks. The damage value in one direction determines the relative stiffness of rock mass in this direction. In VMIB solid, the relative distribution density of micro bonds in one direction determines the relative macro stiffness of the material in this direction. The effects of the damage value and the relative distribution density of bonds are consistent. To simulate the failure behavior of rock mass with VMIB, the presented paper sets up a quantitative relationship between the damage tensor and the relative distribution density of bonds. Comparison of the theoretical and the experimental results shows that VMIB model can represent the effect of distributed cracks on rock mass with this relationship. The presented work provides a foundation for further simulating fracture

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

    OpenAIRE

    LUBNA MOIN; VALI UDDIN

    2016-01-01

    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 Wigge...

  5. The bond graph model of planar flexible multibody mechanical systems and its dynamic principle

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    In order to increase the efficiency and reliability of the dynamic analysis for flexible planar linkage containing the coupling of multi-energy domains, a method based on bond graph is introduced. From the viewpoint of power conservation, the peculiar property of bond graph multiport element MTF is discussed. The procedure of modeling planar flexible multibody mechanical systems by bond graphs and its dynamic principle are described. To overcome the algebraic difficulty brought by differential causality and nonlinear junction structure, the constraint forces at joints can be considered as unknown effort sources and added to the corresponding O-junctions of system bond graph model. As a result, the automatic modeling on a computer is realized. The validity of the procedure is illustrated by a practical example.

  6. Janus Nematic Colloids with Designable Valence

    Directory of Open Access Journals (Sweden)

    Simon Čopar

    2014-05-01

    Full Text Available Generalized Janus nematic colloids based on various morphologies of particle surface patches imposing homeotropic and planar surface anchoring are demonstrated. By using mesoscopic numerical modeling, multiple types of Janus particles are explored, demonstrating a variety of novel complex colloidal structures. We also show binding of Janus particles to a fixed Janus post in the nematic cell, which acts as a seed and a micro-anchor for the colloidal structure. Janus colloidal structures reveal diverse topological defect configurations, which are effectively combinations of surface boojum and bulk defects. Topological analysis is applied to defects, importantly showing that topological charge is not a well determined topological invariant in such patchy nematic Janus colloids. Finally, this work demonstrates colloidal structures with designable valence, which could allow for targeted and valence-conditioned self-assembly at micro- and nano-scale.

  7. 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

  8. On the relation between hydrogen bonds, tetrahedral order and molecular mobility in model water

    CERN Document Server

    Pereyra, R G; Malaspina, D C; Carignano, M A

    2013-01-01

    We studied by molecular dynamics simulations the relation existing between the lifetime of hydrogen bonds, the tetrahedral order and the diffusion coefficient of model water. We tested four different models: SPC/E, TIP4P-Ew, TIP5P-Ew and Six-site, these last two having sites explicitly resembling the water lone pairs. While all the models perform reasonably well at ambient conditions, their behavior is significantly different for temperatures below 270 K. The models with explicit lone-pairs have a longer hydrogen bond lifetime, a better tetrahedral order and a smaller diffusion coefficient than the models without them.

  9. Theoretical and experimental research on nonlinear spring models of a bonding interface%Theoretical and experimental research on nonlinear spring models of a bonding interface

    Institute of Scientific and Technical Information of China (English)

    AN Zhiwu; WANG Xiaomin; MAO Jie; LI Mingxuan; DENG Mingxi

    2012-01-01

    The nonlinear boundary conditions on a bonding interface between two solids of a longitudinal or shear horizontal (SH) wave under normal incidence were explored. By applying the second-order perturbation method, the nonlinear spring models are rigorously developed in the limit of small thickness to wavelength ratio. Numerical results agree well with the exact solutions obtained by continuous boundary conditions. The nonlinear spring model for longitudinal wave is verified by measuring the nonlinearity of a wedge-shaped bonding structure of steel or aluminum substrates. The experimental results reveal that the above model is rather accurate and as the impedance ratio of adherend to adhesive increases, the model becomes more accurate.

  10. 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...

  11. 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.

  12. Bonding Energy and Growth Habit of Lithium Niobate Single Crystals

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    On the basis of crystallographic structure of lithium niobate (LN), the bonding energy was quantitatively calculated by the bond valence sum model, which was employed to investigate the crystal growth. A possible relationship between the crystal growth habit and chemical bonding energy of LN crystals are found. It is found that the higher the bond energy, the slower the growth rate, and the more important the plane. The analytical results indicate that (012) plane is the most influential face for the LN crystal growth, which consists well with the standard card (JCPDS Card: 20-0631) and our previous experimental observation. The current work shows that the chemical bond analysis of LN crystals allows us to predict its growth habit and thus to obtain the expected morphology during the spontaneous growth.

  13. A discrete-time two-factor model for pricing bonds and interest rate derivatives under random volatility

    OpenAIRE

    Heston, Steven L.; Nandi, Saikat

    1999-01-01

    This paper develops a discrete-time two-factor model of interest rates with analytical solutions for bonds and many interest rate derivatives when the volatility of the short rate follows a GARCH process that can be correlated with the level of the short rate itself. Besides bond and bond futures, the model yields analytical solutions for prices of European options on discount bonds (and futures) as well as other interest rate derivatives such as caps, floors, average rate options, yield curv...

  14. Static and Dynamical Valence-Charge-Density Properties of GaAs

    Science.gov (United States)

    Pietsch, Ullrich

    1993-02-01

    Owing to the close neighbourhood of Ga and As in Mendeleev's table, GaAs shows two fundamental classes of X-ray structure amplitudes distinguished by their extremely different scattering power. They are differently sensitive to the valence electron density (VED) redistribution caused by the chemical bond and must be measured by different experimental methods. Using such data, both the VED and the difference electron densities (DED) are calculated here. Comparison with theoret-ical densities shows that the VED is characterized by covalent, ionic and metallic contributions. The DED constructed from GaAs and Ge data demonstrates the electronic response caused by a "protonic" charge transfer between both f.c.c. sublattices as well as the transition from a purely covalent to a mixed covalent-ionic bond. Especially the charge-density accumulation between nearest neighbours (bond charge (BC)) depends on the distance between the bonding atoms and changes under the influence of any lattice deformation. This phenomenon is described by a BC-transfer model. Its direct experimental proof is given by measuring the variation of the scattering power of weak reflections under the influence of an external electric field. This experiment demonstrates that the ionicity of the bond changes in addition to the BC variation.

  15. Applications of the Local Mode Model to CH Bond Length Changes, Molecular Conformations and Vibrational Dynamics

    OpenAIRE

    Henry, Bryan R.; Gough, Kathleen M.

    1983-01-01

    The theoretical basis for the local mode model is reviewed. The model is applied to gas phase overtone spectra of aromatic molecules to investigate both substituent induced CH bond length changes and conformationally inequivalent hydrogens. The dynamic implications of the local mode model are discussed.

  16. 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…

  17. 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

    2007-11-16

    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 Xtransition 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.

  18. Bond graph modeling, simulation, and reflex control of the Mars planetary automatic vehicle

    Science.gov (United States)

    Amara, Maher; Friconneau, Jean Pierre; Micaelli, Alain

    1993-01-01

    The bond graph modeling, simulation, and reflex control study of the Planetary Automatic Vehicle are considered. A simulator derived from a complete bond graph model of the vehicle is presented. This model includes both knowledge and representation models of the mechanical structure, the floor contact, and the Mars site. The MACSYMEN (French acronym for aided design method of multi-energetic systems) is used and applied to study the input-output power transfers. The reflex control is then considered. Controller architecture and locomotion specificity are described. A numerical stage highlights some interesting results of the robot and the controller capabilities.

  19. Quenched bond randomness in marginal and non-marginal Ising spin models in 2D

    Science.gov (United States)

    Fytas, N. G.; Malakis, A.; Hadjiagapiou, I. A.

    2008-11-01

    We investigate and contrast, via entropic sampling based on the Wang-Landau algorithm, the effects of quenched bond randomness on the critical behavior of two Ising spin models in 2D. The random bond version of the superantiferromagnetic (SAF) square model with nearest- and next-nearest-neighbor competing interactions and the corresponding version of the simple Ising model are studied, and their general universality aspects are inspected by means of a detailed finite size scaling (FSS) analysis. We find that the random bond SAF model obeys weak universality, hyperscaling, and exhibits a strong saturating behavior of the specific heat due to the competing nature of interactions. On the other hand, for the random Ising model we encounter some difficulties as regards a definite discrimination between the two well-known scenarios of the logarithmic corrections versus the weak universality. However, a careful FSS analysis of our data favors the field theoretically predicted logarithmic corrections.

  20. Computational Study of Bond Dissociation Enthalpies for Lignin Model Compounds. Substituent Effects in Phenethyl Phenyl Ethers

    Energy Technology Data Exchange (ETDEWEB)

    Beste, Ariana [ORNL; Buchanan III, A C [ORNL

    2009-01-01

    Lignin is an abundant natural resource that is a potential source of valuable chemicals. Improved understanding of the pyrolysis of lignin occurs through the study of model compounds for which phenethyl phenyl ether (PhCH2CH2OPh, PPE) is the simplest example representing the dominant -O-4 ether linkage. The initial step in the thermal decomposition of PPE is the homolytic cleavage of the oxygen-carbon bond. The rate of this key step will depend on the bond dissociation enthalpy, which in turn will depend on the nature and location of relevant substituents. We used modern density functional methods to calculate the oxygen-carbon bond dissociation enthalpies for PPE and several oxygen substituted derivatives. Since carbon-carbon bond cleavage in PPE could be a competitive initial reaction under high temperature pyrolysis conditions, we also calculated substituent effects on these bond dissociation enthalpies. We found that the oxygen-carbon bond dissociation enthalpy is substantially lowered by oxygen substituents situated at the phenyl ring adjacent to the ether oxygen. On the other hand, the carbon-carbon bond dissociation enthalpy shows little variation with different substitution patterns on either phenyl ring.

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

    Science.gov (United States)

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

    2016-09-01

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

  2. New T=1 effective interactions for the f5/2 p3/2 p1/2 g9/2 model space; Implications for valence-mirror symmetry and seniority isomers

    CERN Document Server

    Lisetskiy, A F; Horoi, M; Grawe, H

    2004-01-01

    New shell model Hamiltonians are derived for the T=1 part of the residual interaction in the f5/2 p3/2 p1/2 g9/2 model space based on the analysis and fit of the available experimental data for 57Ni-78Ni isotopes and 77Cu-100Sn isotones. The fit procedure, properties of the determined effective interaction as well as new results for valence-mirror symmetry and seniority isomers for nuclei near 78Ni and 100Sn are discussed.

  3. Bond Graph Modeling and Validation of an Energy Regenerative System for Emulsion Pump Tests

    Directory of Open Access Journals (Sweden)

    Yilei Li

    2014-01-01

    Full Text Available The test system for emulsion pump is facing serious challenges due to its huge energy consumption and waste nowadays. To settle this energy issue, a novel energy regenerative system (ERS for emulsion pump tests is briefly introduced at first. Modeling such an ERS of multienergy domains needs a unified and systematic approach. Bond graph modeling is well suited for this task. The bond graph model of this ERS is developed by first considering the separate components before assembling them together and so is the state-space equation. Both numerical simulation and experiments are carried out to validate the bond graph model of this ERS. Moreover the simulation and experiments results show that this ERS not only satisfies the test requirements, but also could save at least 25% of energy consumption as compared to the original test system, demonstrating that it is a promising method of energy regeneration for emulsion pump tests.

  4. On the valence fluctuation in the early actinide metals

    Energy Technology Data Exchange (ETDEWEB)

    Söderlind, P., E-mail: soderlind@llnl.gov [Lawrence Livermore National Laboratory, Livermore, CA 94550 (United States); Landa, A.; Tobin, J.G.; Allen, P. [Lawrence Livermore National Laboratory, Livermore, CA 94550 (United States); Medling, S.; Booth, C.H. [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Bauer, E.D.; Cooley, J.C. [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Sokaras, D.; Weng, T.-C.; Nordlund, D. [Stanford Synchrotron Radiation Lightsource, SLAC National Laboratory, Menlo Park, CA 94025 (United States)

    2016-02-15

    Highlights: • We make a connection between experimentally observed valence fluctuations and density functional theory. • We present a new model for valence fluctuations. • We present new experimental data for uranium and valence fluctuations. - Abstract: Recent X-ray measurements suggest a degree of valence fluctuation in plutonium and uranium intermetallics. We are applying a novel scheme, in conjunction with density functional theory, to predict 5f configuration fractions of states with valence fluctuations for the early actinide metals. For this purpose we perform constrained integer f-occupation calculations for the α phases of uranium, neptunium, and plutonium metals. For plutonium we also investigate the δ phase. The model predicts uranium and neptunium to be dominated by the f{sup 3} and f{sup 4} configurations, respectively, with only minor contributions from other configurations. For plutonium (both α and δ phase) the scenario is dramatically different. Here, the calculations predict a relatively even distribution between three valence configurations. The δ phase has a greater configuration fraction of f{sup 6} compared to that of the α phase. The theory is consistent with the interpretations of modern X-ray experiments and we present resonant X-ray emission spectroscopy results for α-uranium.

  5. 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.

  6. 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…

  7. 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 c...

  8. Thermal-hydraulic modeling and analysis of hydraulic system by pseudo-bond graph

    Institute of Scientific and Technical Information of China (English)

    胡均平; 李科军

    2015-01-01

    To increase the efficiency and reliability of the thermodynamics analysis of the hydraulic system, the method based on pseudo-bond graph is introduced. According to the working mechanism of hydraulic components, they can be separated into two categories: capacitive components and resistive components. Then, the thermal-hydraulic pseudo-bond graphs of capacitive C element and resistance R element were developed, based on the conservation of mass and energy. Subsequently, the connection rule for the pseudo-bond graph elements and the method to construct the complete thermal-hydraulic system model were proposed. On the basis of heat transfer analysis of a typical hydraulic circuit containing a piston pump, the lumped parameter mathematical model of the system was given. The good agreement between the simulation results and experimental data demonstrates the validity of the modeling method.

  9. 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

  10. Creep simulation of adhesively bonded joints using modified generalized time hardening model

    Energy Technology Data Exchange (ETDEWEB)

    Sadigh, Mohammad Ali Saeimi [Azarbaijan Shahid Madani University, Tabriz (Iran, Islamic Republic of)

    2016-04-15

    Creep behavior of double lap adhesively bonded joints was investigated using experimental tests and numerical analysis. Firstly, uniaxial creep tests were carried out to obtain the creep characteristics and constitutive parameters of the adhesive at different stress and temperature levels. Generalized time hardening model was used to predict the creep behavior of the adhesive. This model was modified to simulate the creep behavior at different stress and temperature levels. Secondly, the developed model was used to simulate the creep behavior of bonded joints using finite element based numerical analysis. Creep deformations of the joints were measured experimentally and good agreement was observed in comparison with the results obtained using numerical simulation. Afterward, stress redistribution due to the creep along the adhesively bonded joint was obtained numerically. It was observed that temperature level had a significant effect on the stress redistribution along the adhesive thickness.

  11. Virtual multi-dimensional internal bonds model and its application in simulation of rock mass

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    VMIB (virtual multi-dimensional internal bonds) is a multiscale mechanical model developed from the VIB (virtual internal bond) theory. In VIB theory,the solid mate-rial is considered to consist of random-distributed material particles in microscale. These particles are connected with normal bonds. The macro constitutive relation is derived from the cohesive law between particles. However,in VMIB,the micro particles are connected with both normal and shear bonds. The macro constitutive relation is derived in terms of bond stiffness coefficients. It has been theoretically certified that there exists a corresponding relationship between the two bond stiffness coefficients and the two macro material constants,i.e. the Young’s modulus and Poisson ratio. This corresponding relationship suggests that it should be necessary and sufficient to simultaneously account for the normal and shear interactions between particles. Due to the fact that the fracture criterion is directly incorporated into the constitutive relation,both VIB and VMIB present many advantages in simulating fractures of materials. In the damage model of rock mass,a damage tensor is usually defined to describe the distribution of cracks. The damage value in one direction determines the relative stiffness of rock mass in this direction. In VMIB solid,the relative distribution density of micro bonds in one direction determines the relative macro stiffness of the material in this direction. The effects of the damage value and the relative distribution density of bonds are consistent. To simulate the failure behavior of rock mass with VMIB,the presented paper sets up a quantitative relationship between the damage tensor and the rela-tive distribution density of bonds. Comparison of the theoretical and the experi-mental results shows that VMIB model can represent the effect of distributed cracks on rock mass with this relationship. The presented work provides a founda-tion for further simulating fracture

  12. 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.

  13. Prediction of peptide bonding affinity: kernel methods for nonlinear modeling

    CERN Document Server

    Bergeron, Charles; Sundling, C Matthew; Krein, Michael; Katt, Bill; Sukumar, Nagamani; Breneman, Curt M; Bennett, Kristin P

    2011-01-01

    This paper presents regression models obtained from a process of blind prediction of peptide binding affinity from provided descriptors for several distinct datasets as part of the 2006 Comparative Evaluation of Prediction Algorithms (COEPRA) contest. This paper finds that kernel partial least squares, a nonlinear partial least squares (PLS) algorithm, outperforms PLS, and that the incorporation of transferable atom equivalent features improves predictive capability.

  14. Investigation of Highly Designable Dented Structures in HP Model with Hydrogen Bond Energy

    Institute of Scientific and Technical Information of China (English)

    ZHANG Wei; HUANG Shengyou; YU Tao; ZOU Xianwu

    2007-01-01

    Some highly designable protein structures have dented on the surface of their native structures, and are not full compactly folded. According to hydrophobic-polar (HP) model the most designable structures are full compactly folded. To investigate the designability of the dented structures, we introduce the hydrogen bond energy in the secondary structures by using the secondary-structure-favored HP model proposed by Ou-yang etc. The result shows that the average designability increases with the strength of the hydrogen bond. The designabilities of the structures with same dented shape increase exponentially with the number of secondary structure sites. The dented structures can have the highest designabilities for a certain value of hydrogen bond energy density.

  15. Thermal Recombination: Beyond the Valence Quark Approximation

    CERN Document Server

    Müller, B; Bass, S A

    2005-01-01

    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.

  16. 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...

  17. Critical Interfaces in the Random-Bond Potts Model

    Science.gov (United States)

    Jacobsen, Jesper L.; Le Doussal, Pierre; Picco, Marco; Santachiara, Raoul; Wiese, Kay Jörg

    2009-02-01

    We study geometrical properties of interfaces in the random-temperature q-states Potts model as an example of a conformal field theory weakly perturbed by quenched disorder. Using conformal perturbation theory in q-2 we compute the fractal dimension of Fortuin-Kasteleyn (FK) domain walls. We also compute it numerically both via the Wolff cluster algorithm for q=3 and via transfer-matrix evaluations. We also obtain numerical results for the fractal dimension of spin clusters interfaces for q=3. These are found numerically consistent with the duality κspinκFK=16 as expressed in putative SLE parameters.

  18. 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.

  19. A MULTISCALE MECHANICAL MODEL FOR MATERIALS BASED ON VIRTUAL INTERNAL BOND THEORY

    Institute of Scientific and Technical Information of China (English)

    Zhang Zhennan; Ge Xiurun; Li Yonghe

    2006-01-01

    Only two macroscopic parameters are needed to describe the mechanical properties of linear elastic solids, I.e. The Poisson's ratio and Young's modulus. Correspondingly, there should be two microscopic parameters to determine the mechanical properties of material if the macroscopic mechanical properties of linear elastic solids are derived from the microscopic level.Enlightened by this idea, a multiscale mechanical model for material, the virtual multi-dimensional internal bonds (VMIB) model, is proposed by incorporating a shear bond into the virtual internal bond (VIB) model. By this modification, the VMIB model associates the macro mechanical properties of material with the microscopic mechanical properties of discrete structure and the corresponding relationship between micro and macro parameters is derived. The tensor quality of the energy density function, which contains coordinate vector, is mathematically proved. From the point of view of VMIB, the macroscopic nonlinear behaviors of material could be attributed to the evolution of virtual bond distribution density induced by the imposed deformation. With this theoretical hypothesis, as an application example, a uniaxial compressive failure of brittle material is simulated. Good agreement between the experimental results and the simulated ones is found.

  20. Effect of Bond-Diluted on Spin-3/2 Transverse Ising Model with Crystal Field

    Institute of Scientific and Technical Information of China (English)

    JIANG Wei; LU Zhan-Hong; WEI Guo-Zhu; DU An

    2002-01-01

    The magnetic properties of the bond-diluted spin-3/2 transverse Ising model with the presence of a crystalfield on the honeycomb lattice are studied within the framework of the effective field theory with correlations. Theinteractions Jij are assumed to be independent random variables with distribution P(Jij) = pδ(Jij - J) + (1 - P)δ(Jij).

  1. Critical Dynamics Behavior of the Wolff Algorithm in the Site-Bond-Correlated Ising Model

    Science.gov (United States)

    Campos, P. R. A.; Onody, R. N.

    Here we apply the Wolff single-cluster algorithm to the site-bond-correlated Ising model and study its critical dynamical behavior. We have verified that the autocorrelation time diminishes in the presence of dilution and correlation, showing that the Wolff algorithm performs even better in such situations. The critical dynamical exponents are also estimated.

  2. An S-N2-model for proton transfer in hydrogen-bonded systems

    DEFF Research Database (Denmark)

    Kuznetsov, A.M.; Ulstrup, Jens

    2004-01-01

    A new mechanism of proton transfer in donor-acceptor complexes with long hydrogen bonds is suggested. The transition is regarded as totally adiabatic. Two closest water molecules that move synchronously by hindered translation to and from the reaction complex are crucial. The water molecules induce...... a shift of the proton from the donor to the acceptor with simultaneous breaking/formation of hydrogen bonds between these molecules and the proton donor and acceptor. Expressions for the activation barrier and kinetic hydrogen isotope effect are derived. The general scheme is illustrated with the use...... of model molecular potentials, and with reference to the excess proton conductivity in aqueous solution....

  3. 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, even...... 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....

  4. 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.

  5. Generalization of Weber's adiabatic bond charge model to amorphous group IV semiconductors

    Science.gov (United States)

    Winer, K.; Wooten, F.

    1984-11-01

    The generalization of Weber's adiabatic bond charge model to amorphous group IV semiconductors is described. Methods of relaxing the coordinates to their equilibrium configuration and of calculating the dynamical matrix for the phonon spectra are given. Particular emphasis is given to the optimization of the Coulomb subroutines required in this model. Estimates of computation time are included for the calculation of equilibrium configuration on a Cray computer.

  6. Discrete-Element bonded-particle Sea Ice model DESIgn, version 1.3a - model description and implementation

    Science.gov (United States)

    Herman, Agnieszka

    2016-04-01

    This paper presents theoretical foundations, numerical implementation and examples of application of the two-dimensional Discrete-Element bonded-particle Sea Ice model - DESIgn. In the model, sea ice is represented as an assemblage of objects of two types: disk-shaped "grains" and semi-elastic bonds connecting them. Grains move on the sea surface under the influence of forces from the atmosphere and the ocean, as well as interactions with surrounding grains through direct contact (Hertzian contact mechanics) and/or through bonds. The model has an experimental option of taking into account quasi-three-dimensional effects related to the space- and time-varying curvature of the sea surface, thus enabling simulation of ice breaking due to stresses resulting from bending moments associated with surface waves. Examples of the model's application to simple sea ice deformation and breaking problems are presented, with an analysis of the influence of the basic model parameters ("microscopic" properties of grains and bonds) on the large-scale response of the modeled material. The model is written as a toolbox suitable for usage with the open-source numerical library LIGGGHTS. The code, together with full technical documentation and example input files, is freely available with this paper and on the Internet.

  7. Discrete-Element bonded particle Sea Ice model DESIgn, version 1.3 – model description and implementation

    Directory of Open Access Journals (Sweden)

    A. Herman

    2015-07-01

    Full Text Available This paper presents theoretical foundations, numerical implementation and examples of application of a two-dimensional Discrete-Element bonded-particle Sea Ice model DESIgn. In the model, sea ice is represented as an assemblage of objects of two types: disk-shaped "grains", and semi-elastic bonds connecting them. Grains move on the sea surface under the influence of forces from the atmosphere and the ocean, as well as interactions with surrounding grains through a direct contact (Hertzian contact mechanics and/or through bonds. The model has an option of taking into account quasi-threedimensional effects related to space- and time-varying curvature of the sea surface, thus enabling simulation of ice breaking due to stresses resulting from bending moments associated with surface waves. Examples of the model's application to simple sea ice deformation and breaking problems are presented, with an analysis of the influence of the basic model parameters ("microscopic" properties of grains and bonds on the large-scale response of the modeled material. The model is written as a toolbox suitable for usage with the open-source numerical library LIGGGHTS. The code, together with a full technical documentation and example input files, is freely available with this paper and on the Internet.

  8. A Non-Perturbative Approach to the Random-Bond Ising Model

    CERN Document Server

    Cabra, D C; Mussardo, G; Pujol, P

    1997-01-01

    We study the N -> 0 limit of the O(N) Gross-Neveu model in the framework of the massless form-factor approach. This model is related to the continuum limit of the Ising model with random bonds via the replica method. We discuss how this method may be useful in calculating correlation functions of physical operators. The identification of non-perturbative fixed points of the O(N) Gross-Neveu model is pursued by its mapping to a WZW model.

  9. Optimized resonating valence bond state in square lattice: correlations & excitations

    Directory of Open Access Journals (Sweden)

    Z Nourbakhsh

    2009-09-01

    Full Text Available We consider RVB state as a variational estimate for the ground state of Heisenberg antiferromagnet in square lattice. We present numerical calculation of energy, spin-spin correlation function and spin excitation spectrum. We show, that the quantum flactuations reduce of magnetization respect to Neel order. Our results are in good agreement with other methods such as spin-wave calculation and series expansions.

  10. Sufficient minimal model for DNA denaturation: Integration of harmonic scalar elasticity and bond energies.

    Science.gov (United States)

    Singh, Amit Raj; Granek, Rony

    2016-10-14

    We study DNA denaturation by integrating elasticity - as described by the Gaussian network model - with bond binding energies, distinguishing between different base pairs and stacking energies. We use exact calculation, within the model, of the Helmholtz free-energy of any partial denaturation state, which implies that the entropy of all formed "bubbles" ("loops") is accounted for. Considering base pair bond removal single events, the bond designated for opening is chosen by minimizing the free-energy difference for the process, over all remaining base pair bonds. Despite of its great simplicity, for several known DNA sequences our results are in accord with available theoretical and experimental studies. Moreover, we report free-energy profiles along the denaturation pathway, which allow to detect stable or meta-stable partial denaturation states, composed of bubble, as local free-energy minima separated by barriers. Our approach allows to study very long DNA strands with commonly available computational power, as we demonstrate for a few random sequences in the range 200-800 base-pairs. For the latter, we also elucidate the self-averaging property of the system. Implications for the well known breathing dynamics of DNA are elucidated.

  11. Sufficient minimal model for DNA denaturation: Integration of harmonic scalar elasticity and bond energies

    Science.gov (United States)

    Singh, Amit Raj; Granek, Rony

    2016-10-01

    We study DNA denaturation by integrating elasticity — as described by the Gaussian network model — with bond binding energies, distinguishing between different base pairs and stacking energies. We use exact calculation, within the model, of the Helmholtz free-energy of any partial denaturation state, which implies that the entropy of all formed "bubbles" ("loops") is accounted for. Considering base pair bond removal single events, the bond designated for opening is chosen by minimizing the free-energy difference for the process, over all remaining base pair bonds. Despite of its great simplicity, for several known DNA sequences our results are in accord with available theoretical and experimental studies. Moreover, we report free-energy profiles along the denaturation pathway, which allow to detect stable or meta-stable partial denaturation states, composed of bubble, as local free-energy minima separated by barriers. Our approach allows to study very long DNA strands with commonly available computational power, as we demonstrate for a few random sequences in the range 200-800 base-pairs. For the latter, we also elucidate the self-averaging property of the system. Implications for the well known breathing dynamics of DNA are elucidated.

  12. War Bonds in the Second World War: A Model for a New Iraq/Afghanistan War Bond

    Science.gov (United States)

    2010-03-01

    Afghanistan War Bond? James M. Bickley Specialist in Public Finance March 1, 2010 Congressional Research Service 7-5700 www.crs.gov R41087 Report...James M. Bickley Specialist in Public Finance jbickley@crs.loc.gov, 7-7794 11 U.S

  13. The sudden vector projection model for reactivity: mode specificity and bond selectivity made simple.

    Science.gov (United States)

    Guo, Hua; Jiang, Bin

    2014-12-16

    CONSPECTUS: Mode specificity is defined by the differences in reactivity due to excitations in various reactant modes, while bond selectivity refers to selective bond breaking in a reaction. These phenomena not only shed light on reaction dynamics but also open the door for laser control of reactions. The existence of mode specificity and bond selectivity in a reaction indicates that not all forms of energy are equivalent in promoting the reactivity, thus defying a statistical treatment. They also allow the enhancement of reactivity and control product branching ratio. As a result, they are of central importance in chemistry. This Account discusses recent advances in our understanding of these nonstatistical phenomena. In particular, the newly proposed sudden vector projection (SVP) model and its applications are reviewed. The SVP model is based on the premise that the collision in many direct reactions is much faster than intramolecular vibrational energy redistribution in the reactants. In such a sudden limit, the coupling of a reactant mode with the reaction coordinate at the transition state, which dictates its ability to promote the reaction, is approximately quantified by the projection of the former onto the latter. The SVP model can be considered as a generalization of the venerable Polanyi's rules, which are based on the location of the barrier. The SVP model is instead based on properties of the saddle point and as a result capable of treating the translational, rotational, and multiple vibrational modes in reactions involving polyatomic reactants. In case of surface reactions, the involvement of surface atoms can also be examined. Taking advantage of microscopic reversibility, the SVP model has also been used to predict product energy disposal in reactions. This simple yet powerful rule of thumb has been successfully demonstrated in many reactions including uni- and bimolecular reactions in the gas phase and gas-surface reactions. The success of the SVP

  14. Equilibrium CO bond lengths

    Science.gov (United States)

    Demaison, Jean; Császár, Attila G.

    2012-09-01

    Based on a sample of 38 molecules, 47 accurate equilibrium CO bond lengths have been collected and analyzed. These ultimate experimental (reEX), semiexperimental (reSE), and Born-Oppenheimer (reBO) equilibrium structures are compared to reBO estimates from two lower-level techniques of electronic structure theory, MP2(FC)/cc-pVQZ and B3LYP/6-311+G(3df,2pd). A linear relationship is found between the best equilibrium bond lengths and their MP2 or B3LYP estimates. These (and similar) linear relationships permit to estimate the CO bond length with an accuracy of 0.002 Å within the full range of 1.10-1.43 Å, corresponding to single, double, and triple CO bonds, for a large number of molecules. The variation of the CO bond length is qualitatively explained using the Atoms in Molecules method. In particular, a nice correlation is found between the CO bond length and the bond critical point density and it appears that the CO bond is at the same time covalent and ionic. Conditions which permit the computation of an accurate ab initio Born-Oppenheimer equilibrium structure are discussed. In particular, the core-core and core-valence correlation is investigated and it is shown to roughly increase with the bond length.

  15. The acoustic correlates of valence depend on emotion family.

    Science.gov (United States)

    Belyk, Michel; Brown, Steven

    2014-07-01

    The voice expresses a wide range of emotions through modulations of acoustic parameters such as frequency and amplitude. Although the acoustics of individual emotions are well understood, attempts to describe the acoustic correlates of broad emotional categories such as valence have yielded mixed results. In the present study, we analyzed the acoustics of emotional valence for different families of emotion. We divided emotional vocalizations into "motivational," "moral," and "aesthetic" families as defined by the OCC (Ortony, Clore, and Collins) model of emotion. Subjects viewed emotional scenarios and were cued to vocalize congruent exclamations in response to them, for example, "Yay!" and "Damn!". Positive valence was weakly associated with high-pitched and loud vocalizations. However, valence interacted with emotion family for both pitch and amplitude. A general acoustic code for valence does not hold across families of emotion, whereas family-specific codes provide a more accurate description of vocal emotions. These findings are consolidated into a set of "rules of expression" relating vocal dimensions to emotion dimensions.

  16. Social learning modulates the lateralization of emotional valence.

    Science.gov (United States)

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

    2008-08-01

    Although neuropsychological studies of lateralization of emotion have emphasized valence (positive vs. negative) or type (basic vs. complex) dimensions, the interaction between the two dimensions has yet to be elucidated. The purpose of the current study was to test the hypothesis that recognition of basic emotions is processed preferentially by the right prefrontal cortex (PFC), whereas recognition of complex social emotions is processed preferentially by the left PFC. Experiment 1 assessed the ability of healthy controls and patients with right and left PFC lesions to recognize basic and complex emotions. Experiment 2 modeled the patient's data of Experiment 1 on healthy participants under lateralized displays of the emotional stimuli. Both experiments support the Type as well as the Valence Hypotheses. However, our findings indicate that the Valence Hypothesis holds for basic but less so for complex emotions. It is suggested that, since social learning overrules the basic preference of valence in the hemispheres, the processing of complex emotions in the hemispheres is less affected by valence.

  17. Evidence for chemical bond formation at rubber-brass interface: Photoelectron spectroscopy study of bonding interaction between copper sulfide and model molecules of natural rubber

    Science.gov (United States)

    Ozawa, Kenichi; Mase, Kazuhiko

    2016-12-01

    Strong adhesion between rubber and brass has been considered to arise mainly from the mechanical interaction, which is characterized by dendritic interlocking at the interface. In order to examine a possible contribution of the chemical interaction, chemical state analysis was carried out for model molecules of natural rubber (2-methyl-2-butene and isoprene) adsorbed on Cu2S, a key chemical species for adhesion, by means of photoelectron spectroscopy (PES). Absence of a C 1s PES component associated with C=C bonds and the appearance of adsorption-induced components in the S 2p region indicate that the molecules interact with the Cu2S surface via the C=C bond to form C-S covalent bonds. This proves that the chemical interaction certainly plays a role in rubber-brass adhesion along with the mechanical interaction.

  18. 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.

  19. A bond graph approach to modeling the anuran vocal production system.

    Science.gov (United States)

    Kime, Nicole M; Ryan, Michael J; Wilson, Preston S

    2013-06-01

    Air-driven vocal production systems such as those found in mammals, birds, and anurans (frogs and toads) combine pneumatic and mechanical elements in species-specific ways to produce a diversity of communication signals. This study uses bond graphs to model a generalized anuran vocal production system. Bond graphs allow an incremental approach to modeling dynamic physical systems involving different domains. Anurans provide an example of how signal diversity results from variation in the structure and behavior of vocal system elements. This paper first proposes a bond graph model of the integrated anuran vocal system as a framework for future study. It then presents a simulated submodel of the anuran sound source that produces sustained oscillations in vocal fold displacement and air flow through the larynx. The modeling approach illustrated here should prove of general applicability to other biological sound production systems, and will allow researchers to study the biomechanics of vocal production as well as the functional congruence and evolution of groups of traits within integrated vocal systems.

  20. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Kozyukhin, S., E-mail: sergkoz@igic.ras.ru [Russian Academy of Science, Institute of General and Inorganic Chemistry (Russian Federation); Golovchak, R. [Lviv Scientific Research Institute of Materials of SRC ' Carat' (Ukraine); Kovalskiy, A. [Lehigh University, Department of Materials Science and Engineering (United States); Shpotyuk, O. [Lviv Scientific Research Institute of Materials of SRC ' Carat' (Ukraine); Jain, H. [Lehigh University, Department of Materials Science and Engineering (United States)

    2011-04-15

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

  2. Ferrimagnetic Properties of Bond Dilution Mixed Blume-Capel Model with Random Single-Ion Anisotropy

    Institute of Scientific and Technical Information of China (English)

    LIU Lei; YAN Shi-Lei

    2005-01-01

    We study the ferrimagnetic properties of spin 1/2 and spin-1 systems by means of the effective field theory.The system is considered in the framework of bond dilution mixed Blume-Capel model (BCM) with random single-ion anisotropy. The investigation of phase diagrams and magnetization curves indicates the existence of induced magnetic ordering and single or multi-compensation points. Special emphasis is placed on the influence of bond dilution and random single-ion anisotropy on normal or induced magnetic ordering states and single or multi-compensation points.Normal magnetic ordering states take on new phase diagrams with increasing randomness (bond and anisotropy), while anisotropy induced magnetic ordering states are always occurrence no matter whether concentration of anisotropy is large or small. Existence and disappearance of compensation points rely strongly on bond dilution and random single-ion anisotropy.Some results have not been revealed in Previous papers and predicted by Néel theory of ferrimagnetism.

  3. 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.

  4. Ion channel stability and hydrogen bonding. Molecular modelling of channels formed by synthetic alamethicin analogues.

    Science.gov (United States)

    Breed, J; Kerr, I D; Molle, G; Duclohier, H; Sansom, M S

    1997-12-04

    Several analogues of the channel-forming peptaibol alamethicin have been demonstrated to exhibit faster switching between channel substates than does unmodified alamethicin. Molecular modelling studies are used to explore the possible molecular basis of these differences. Models of channels formed by alamethicin analogues were generated by restrained molecular dynamics in vacuo and refined by short molecular dynamics simulations with water molecules within and at either mouth of the channel. A decrease in backbone solvation was found to correlate with a decrease in open channel stability between alamethicin and an analogue in which all alpha-amino-isobutyric acid residues of alamethicin were replaced by leucine. A decrease in the extent of hydrogen-bonding at residue 7 correlates with lower open channel stabilities of analogues in which the glutamine at position 7 was replaced by smaller polar sidechains. These two observations indicate the importance of alamethicin/water H-bonds in stabilizing the open channel.

  5. Bayesian Network Based Fault Prognosis via Bond Graph Modeling of High-Speed Railway Traction Device

    Directory of Open Access Journals (Sweden)

    Yunkai Wu

    2015-01-01

    component-level faults accurately for a high-speed railway traction system, a fault prognosis approach via Bayesian network and bond graph modeling techniques is proposed. The inherent structure of a railway traction system is represented by bond graph model, based on which a multilayer Bayesian network is developed for fault propagation analysis and fault prediction. For complete and incomplete data sets, two different parameter learning algorithms such as Bayesian estimation and expectation maximization (EM algorithm are adopted to determine the conditional probability table of the Bayesian network. The proposed prognosis approach using Pearl’s polytree propagation algorithm for joint probability reasoning can predict the failure probabilities of leaf nodes based on the current status of root nodes. Verification results in a high-speed railway traction simulation system can demonstrate the effectiveness of the proposed approach.

  6. 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.

  7. Single-cluster algorithm for the site-bond-correlated Ising model

    Science.gov (United States)

    Campos, P. R. A.; Onody, R. N.

    1997-12-01

    We extend the Wolff algorithm to include correlated spin interactions in diluted magnetic systems. This algorithm is applied to study the site-bond-correlated Ising model on a two-dimensional square lattice. We use a finite-size scaling procedure to obtain the phase diagram in the temperature-concentration space. We also have verified that the autocorrelation time diminishes in the presence of dilution and correlation, showing that the Wolff algorithm performs even better in such situations.

  8. 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.

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

    Science.gov (United States)

    Braïda, Benoît; Hiberty, Philippe C.

    2013-05-01

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

  10. Valence Induction with a Head-Lexicalized PCFG

    CERN Document Server

    Carroll, G; Carroll, Glenn; Rooth, Mats

    1998-01-01

    This paper presents an experiment in learning valences (subcategorization frames) from a 50 million word text corpus, based on a lexicalized probabilistic context free grammar. Distributions are estimated using a modified EM algorithm. We evaluate the acquired lexicon both by comparison with a dictionary and by entropy measures. Results show that our model produces highly accurate frame distributions.

  11. SPIN POLARIZATION AND MAGNETIC DICHROISM IN PHOTOEMISSION FROM CORE AND VALENCE STATES IN LOCALIZED MAGNETIC SYSTEMS

    NARCIS (Netherlands)

    THOLE, BT; VANDERLAAN, G

    1991-01-01

    Using group theory we derive a general model for spin polarization and magnetic dichroism in photo-emission in the presence of atomic interactions between the hole created and the valence holes. We predict strong effects in the photoemission from core levels and localized valence levels of transitio

  12. 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.

  13. 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...... the complexity of the examined systems....

  14. About bond model of S-type negative differential resistance in GaP LEDs

    Science.gov (United States)

    Gaydar, G.; Konoreva, O.; Maliy, Ye.; Olikh, Ya.; Petrenko, I.; Pinkovska, M.; Radkevych, O.; Tartachnyk, V.

    2017-04-01

    The bond models are presented that explain the S-type anomaly of GaP LEDs' electrical characteristics at temperatures Т ≤ 120 K. A possible mechanism of negative differential resistance appearing in current-voltage characteristics is proposed, based on the features of the gallium phosphide complex band structure. The conductive zone absolute minimum in this crystal is near the Brillouin zone end. Due to the positive internal bond, controlled by the current, intervalley electron transfer occurs from the side valley to the higher one with the smaller effective electron mass. While the applied voltage is increased, electrons move from the lateral valley to the direct conductive zone bottom and an S-type negative differential resistance region appears.

  15. Predicting bond strength from a single Hartree-Fock ground state using the localized pair model.

    Science.gov (United States)

    Hennessey, Dylan C; Sheppard, Brendan J H; Mackenzie, Dalton E C K; Pearson, Jason K

    2014-12-14

    We present an application of the recently introduced Localized Pair Model (LPM) [Z. A. Zielinksi and J. K. Pearson, Comput. Theor. Chem., 2013, 1003, 7990] to characterize and quantify properties of the chemical bond in a series of substituted benzoic acid molecules. By computing interelectronic distribution functions for doubly-occupied Edmiston-Ruedenberg localized molecular orbitals (LMOs), we show that chemically intuitive electron pairs may be uniquely classified and bond strength may be predicted with remarkable accuracy. Specifically, the HF/u6-311G(d,p) level (where u denotes a complete uncontraction of the basis set) is used to generate the relevant LMOs and their respective interelectronic distribution functions can be linearly correlated to the well-known Hammett σp or σm parameters with near-unity correlation coefficients.

  16. Numerical Simulation of Rock Fracturing under Uniaxial Compression Using Virtual Internal Bond Model

    Institute of Scientific and Technical Information of China (English)

    KE Chang-ren; JIANG Jun-ling; GE Xiu-run

    2009-01-01

    A multi-scale virtual internal bond (VIB) model for the isotropic materials has been recently proposed to describe the material deformation and fracturing. During the simulation process of material fracturing using VIB, the fracture criterion is directly built into the constitutive formulation of the material using the cohesive force law. Enlightened by the similarity of the damage constitutive model of rock under uniaxial compression and the cohesive force law of VIB, a VIB density function of rock under uniaxial compression is suggested. The elastic modulus tensor is formulated on the basis of the density function. Thus the complete deformation process of rock under the uniaxial compression is simulated.

  17. A simple and realistic model system for studying hydrogen bonds in beta-sheets

    DEFF Research Database (Denmark)

    Rossmeisl, Jan; Hinnemann, Berit; Jacobsen, Karsten Wedel

    2003-01-01

    We investigate the interaction between peptide chains at the level of state-of-the-art ab initio density functional theory. We propose an interacting periodic polypeptide model for studying the interactions in beta-sheets and apply this to glycine and alanine peptide chains in both parallel...... and antiparallel structures. The calculated structures of alanine are compared to x-ray structures of beta-sheets and the model is found to reproduce the geometry of the hydrogen bonds very well both concerning parallel and antiparallel beta-sheets. We investigate the structures of both the N-H...O=C and the C...

  18. Characterization and Modeling of the Collision Induced Dissociation Patterns of Deprotonated Glycosphingolipids: Cleavage of the Glycosidic Bond

    Science.gov (United States)

    Rožman, Marko

    2016-01-01

    Glycosphingolipid fragmentation behavior was investigated by combining results from analysis of a series of negative ion tandem mass spectra and molecular modeling. Fragmentation patterns extracted from 75 tandem mass spectra of mainly acidic glycosphingolipid species (gangliosides) suggest prominent cleavage of the glycosidic bonds with retention of the glycosidic oxygen atom by the species formed from the reducing end (B and Y ion formation). Dominant product ions arise from dissociation of sialic acids glycosidic bonds whereas product ions resulting from cleavage of other glycosidic bonds are less abundant. Potential energy surfaces and unimolecular reaction rates of several low-energy fragmentation pathways leading to cleavage of glycosidic bonds were estimated in order to explain observed dissociation patterns. Glycosidic bond cleavage in both neutral (unsubstituted glycosyl group) and acidic glycosphingolipids was the outcome of the charge-directed intramolecular nucleophilic substitution (SN2) mechanism. According to the suggested mechanism, the nucleophile in a form of carboxylate or oxyanion attacks the carbon at position one of the sugar ring, simultaneously breaking the glycosidic bond and yielding an epoxide. For gangliosides, unimolecular reaction rates suggest that dominant product ions related to the cleavage of sialic acid glycosidic bonds are formed via direct dissociation channels. On the other hand, low abundant product ions related to the dissociation of other glycosidic bonds are more likely to be the result of sequential dissociation. Although results from this study mainly contribute to the understanding of glycosphingolipid fragmentation chemistry, some mechanistic findings regarding cleavage of the glycosidic bond may be applicable to other glycoconjugates.

  19. The Pauling 3-Electron Bond: A Recommendation for the Use of the Linnett Structure.

    Science.gov (United States)

    Harcourt, Richard D.

    1985-01-01

    Recommends the Linnett structure IV (as in VIII for molecular oxygen) for future use when a valence-bond structure for a Pauling 3-electron bond is required. Examples are provided to illustrate why this recommendation is made. (JN)

  20. A model ternary heparin conjugate by direct covalent bond strategy applied to drug delivery system.

    Science.gov (United States)

    Wang, Ying; Xin, Dingcheng; Hu, Jiawen; Liu, Kaijian; Pan, Jiangao; Xiang, Jiannan

    2009-01-01

    A model ternary heparin conjugate by direct covalent bond strategy has been developed, in which modified heparin using active mix anhydride as intermediate conjugates with model drug molecule and model specific ligand, respectively. Designed ester bonds between model drug and heparin facilitate hydrolysis kinetics research. The strategy can be extended to design and synthesize a targeted drug delivery system. The key point is to use mixed anhydride groups as activating intermediates to mediate the synthesis of the ternary heparin conjugate. Formation of mixed anhydride is detected by the conductimetry experiment. The ternary heparin conjugate is characterized by (13)C NMR, FT-IR and GPC, respectively. The decreased trend on degree of substitution (DS) is consistent with that of introduced anticancer drug and specific ligand in drug delivery system. Moreover, their anticoagulant activity is evaluated by measuring activated partial thromboplastin time (APTT) and anti-factor Xa activity. The results show that model ternary heparin conjugate with reduced anticoagulant activity may avoid the risk of severe hemorrhagic complication during the administration and is potential to develop a safe and effective drug delivery system on anticancer research.

  1. Effects of Nb and Si on densities of valence electrons in bulk and defects of Fe3Al alloys

    Institute of Scientific and Technical Information of China (English)

    邓文; 钟夏平; 黄宇阳; 熊良钺; 王淑荷; 郭建亭; 龙期威

    1999-01-01

    Positron lifetime measurements have been performed in binary Fe3Al and Fe3Al doping with Nb or Si alloys. The densities of valence electrons of the bulk and microdefects in all tested samples have been calculated by using the positron lifetime parameters. Density of valence electron is low in the bulk of Fe3Al alloy. It indicates that, the 3d electrons in a Fe atom have strong-localized properties and tend to form covalent bonds with Al atoms, and the bonding nature in Fe3Al is a mixture of metallic and covalent bonds. The density of valence electron is very low in the defects of Fe3Al grain boundary, which makes the bonding cohesion in grain boundary quite weak. The addition of Si to Fe3Al gives rise to the decrease of the densities of valence electrons in the bulk and the grain boundary thus the metallic bonding cohesion. This makes the alloy more brittle. The addition of Nb to Fe3Al results in the decrease of the ordering energy of the alloy and increases the density of valence electron and th

  2. 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.

  3. Discrete kink dynamics in hydrogen-bonded chains: the one-component model.

    Science.gov (United States)

    Karpan, V M; Zolotaryuk, Y; Christiansen, P L; Zolotaryuk, A V

    2002-12-01

    We study topological solitary waves (kinks and antikinks) in a nonlinear one-dimensional Klein-Gordon chain with the on-site potential of a double-Morse type. This chain is used to describe the collective proton dynamics in quasi-one-dimensional networks of hydrogen bonds, where the on-site potential plays the role of the proton potential in the hydrogen bond. The system supports a rich variety of stationary kink solutions with different symmetry properties. We study the stability and bifurcation structure of all these stationary kink states. An exactly solvable model with a piecewise "parabola-constant" approximation of the double-Morse potential is suggested and studied analytically. The dependence of the Peierls-Nabarro potential on the system parameters is studied. Discrete traveling-wave solutions of a narrow permanent profile are shown to exist, depending on the anharmonicity of the Morse potential and the cooperativity of the hydrogen bond (the coupling constant of the interaction between nearest-neighbor protons).

  4. Structural model for covalent adhesion of the Streptococcus pyogenes pilus through a thioester bond.

    Science.gov (United States)

    Linke-Winnebeck, Christian; Paterson, Neil G; Young, Paul G; Middleditch, Martin J; Greenwood, David R; Witte, Gregor; Baker, Edward N

    2014-01-03

    The human pathogen Streptococcus pyogenes produces pili that are essential for adhesion to host surface receptors. Cpa, the adhesin at the pilus tip, was recently shown to have a thioester-containing domain. The thioester bond is believed to be important in adhesion, implying a mechanism of covalent attachment analogous to that used by human complement factors. Here, we have characterized a second active thioester-containing domain on Cpa, the N-terminal domain of Cpa (CpaN). Expression of CpaN in Escherichia coli gave covalently linked dimers. These were shown by x-ray crystallography and mass spectrometry to comprise two CpaN molecules cross-linked by the polyamine spermidine following reaction with the thioester bonds. This cross-linked CpaN dimer provides a model for the covalent attachment of Cpa to target receptors and thus the streptococcal pilus to host cells. Similar thioester domains were identified in cell wall proteins of other Gram-positive pathogens, suggesting that thioester domains are more widely used and provide a mechanism of adhesion by covalent bonding to target molecules on host cells that mimics that used by the human complement system to eliminate pathogens.

  5. Quantum phase diagram of the half filled Hubbard model with bond-charge interaction

    Energy Technology Data Exchange (ETDEWEB)

    Dobry, A.O., E-mail: dobry@ifir-conicet.gov.a [Facultad de Ciencias Exactas Ingenieria y Agrimensura, Universidad Nacional de Rosario and Instituto de Fisica Rosario, Bv. 27 de Febrero 210 bis, 2000 Rosario (Argentina); Aligia, A.A. [Centro Atomico Bariloche and Instituto Balseiro, Comision Nacional de Energia Atomica, 8400 Bariloche (Argentina)

    2011-02-21

    Using quantum field theory and bosonization, 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 at half-filling, for small values of the interactions. We show that it is essential to take into account formally irrelevant terms of order X. They generate relevant terms proportional to X{sup 2} in the flow of the renormalization group (RG). These terms are calculated using operator product expansions. The model shows three phases separated by a charge transition at U=U{sub c} and a spin transition at U=U{sub s}>U{sub c}. For UU{sub s}, the system is in the spin-density wave phase as in the usual Hubbard model. For intermediate values U{sub c}bond-ordered wave phase, which is absent in the ordinary Hubbard model with X=0. We obtain that the charge transition remains at U{sub c}=0 for X{ne}0. Solving the RG equations for the spin sector, we provide an analytical expression for U{sub s}(X). The results, with only one adjustable parameter, are in excellent agreement with numerical ones for X

  6. Red-bond exponents of the critical and the tricritical Ising model in three dimensions

    Science.gov (United States)

    Deng, Youjin; Blöte, Henk W. J.

    2004-11-01

    Using the Wolff and geometric cluster algorithms and finite-size scaling analysis, we investigate the critical Ising and the tricritical Blume-Capel models with nearest-neighbor interactions on the simple-cubic lattice. The sampling procedure involves the decomposition of the Ising configuration into geometric clusters, each of which consists of a set of nearest-neighboring spins of the same sign connected with bond probability p . These clusters include the well-known Kasteleyn-Fortuin clusters as a special case for p=1-exp(-2K) , where K is the Ising spin-spin coupling. Along the critical line K=Kc , the size distribution of geometric clusters is investigated as a function of p . We observe that, unlike in the case of two-dimensional tricriticality, the percolation threshold in both models lies at pc=1-exp(-2Kc) . Further, we determine the corresponding red-bond exponents as yr=0.757(2) and 0.501(5) for the critical Ising and the tricritical Blume-Capel models, respectively. On this basis, we conjecture yr=1/2 for the latter model.

  7. Rare beryllium icosahedra in the intermediate valence compound CeBe13.

    Science.gov (United States)

    Wilson, Zakiya S; Macaluso, Robin T; Bauer, E D; Smith, J L; Thompson, J D; Fisk, Z; Stanley, George G; Chan, Julia Y

    2004-11-01

    Single-crystal X-ray diffraction experiments show that the Be atoms in CeBe13 form a Be12 icosahedra, which is a very unusual structural feature due, in part, to the remarkably low valence electron count of Be. Magnetization studies show that CeBe13 displays intermediate valence behavior, in which valence fluctuations between the Ce 4f0 and 4f1 states give rise to enhanced electronic specific heat and magnetic susceptibility. Calculations using ab initio theory were used to determine the electronic structure and bonding and to give insight into the relationship between the crystal structure, the bonding, and the intermediate valence behavior of CeBe13. The hybridization between the localized f electrons and the conduction electrons is responsible for the large values of the electronic specific heat coefficient (gamma approximately 100 mJ/mol K2) and magnetic susceptibility (chi approximately 1 x 10-3 emu/mol), which is in marked contrast to those of ordinary metals that have gamma approximately 1 mJ/mol K2 and chi approximately 1 x 10-5 emu/mol values. The magnetic susceptibility, chi = M/H versus T, of a single crystal of CeBe13 exhibits a broad maximum at Tmax approximately 130 K and is typical of intermediate valence systems with an unusually large energy scale (Kondo), TK approximately 500 K.

  8. Lie-Algebraic Approach for Pricing Zero-Coupon Bonds in Single-Factor Interest Rate Models

    Directory of Open Access Journals (Sweden)

    C. F. Lo

    2013-01-01

    Full Text Available The Lie-algebraic approach has been applied to solve the bond pricing problem in single-factor interest rate models. Four of the popular single-factor models, namely, the Vasicek model, Cox-Ingersoll-Ross model, double square-root model, and Ahn-Gao model, are investigated. By exploiting the dynamical symmetry of their bond pricing equations, analytical closed-form pricing formulae can be derived in a straightfoward manner. Time-varying model parameters could also be incorporated into the derivation of the bond price formulae, and this has the added advantage of allowing yield curves to be fitted. Furthermore, the Lie-algebraic approach can be easily extended to formulate new analytically tractable single-factor interest rate models.

  9. Structural bonding-breakage constitutive model for natural unsaturated clayey soils

    Science.gov (United States)

    Cai, Guo-Qing; Zhao, Cheng-Gang; Qin, Xiao-Ming

    2010-12-01

    The natural clayey soils are usually structural and unsaturated, which makes their mechanical properties quite different from the remolded saturated soils. A structural constitutive model is proposed to simulate the bonding-breakage micro-mechanism. In this model, the unsaturated soil element is divided into a cementation element and a friction element according to the binary medium theory, and the stress-strain coordination for these two elements is obtained. The cementation element is regarded as elastic, whereas the friction element is regarded as elastoplastic which can be described with the Gallipoli's model. The theoretical formulation is verified with the comparative experiments of isotropic compressions on the saturated and unsaturated structural soils. Parametric analyses of the effects of damage variables on the model predictions are further carried out, which show that breakage deformation of natural clayey soils increases with the rising amount of initial defects.

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

    Energy Technology Data Exchange (ETDEWEB)

    Dunning, Thom H., E-mail: thdjr@uw.edu; Xu, Lu T.; Takeshita, Tyler Y. [Department of Chemistry, University of Illinois at Urbana-Champaign, 600 S. Mathews Avenue, Urbana, Illinois 61801 (United States)

    2015-01-21

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

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

    Science.gov (United States)

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

    2016-07-01

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

  12. Monte Carlos studies of critical and dynamic phenomena in mixed bond Ising model

    Science.gov (United States)

    Santos-Filho, J. B.; Moreno, N. O.; de Albuquerque, Douglas F.

    2010-11-01

    The phase transition of a random mixed-bond Ising ferromagnet on a cubic lattice model is studied both numerically and analytically. In this work, we use the Metropolis and Wolff algorithm with histogram technique and finite size scaling theory to simulate the dynamics of the system. We obtained the thermodynamic quantities such as magnetization, susceptibility, and specific heat. Our results were compared with those obtained using a new technique in effective field theory that employs similar probability distribution within the framework of two-site clusters.

  13. 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.

  14. 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.

  15. Adiabatic bond charge model for lattice dynamics of ternary chalcopyrite semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Guerel, T.; Eryigit, R. [Department of Physics, Abant Izzet Baysal University, Bolu, 14280 (Turkey)

    2006-01-01

    The adiabatic bond charge model of Rustagi and Weber is extended to study lattice dynamical properties of ternary chalcopyrite semiconductors AgGaS{sub 2}, AgGaSe{sub 2}, CuInS{sub 2}, CuInSe{sub 2}, CuGaS{sub 2}, CuGaSe{sub 2}, CuAlS{sub 2} and CuAlSe{sub 2}. The new model calculations agree well with the results of Raman/IR and neutron measurements of Brillouin zone center phonon frequencies for both low and high frequency modes which was difficult for other phenomenological lattice dynamical models. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  16. Definition and Application of Topological Index Based on Bond Connectivity

    Institute of Scientific and Technical Information of China (English)

    WANG Zhen-dong; YANG Feng; YANG Hai-lang; LUO Ming-dao; QU Song-sheng

    2003-01-01

    Bond connectivity topological index Si based on chemical bonds was defined by using a matrix method.And Si is formed by atomic parameters such as the number of valence electrons,the number of the highest main quantum of atoms and the bonding electrons and bond parameters such as the length of bonds,the electronegativity difference of bonding atoms.The molecular bond connectivity topological index S is composed of Si.The thermodynamic properties of saturated hydrocarbons,unsaturated hydrocarbons,oxygen organic,methane halide and transitional element compounds and the molecular bond connectivity topological index S have an optimal correlative relationship.

  17. Ferromagnetic Properties of Bond-Dilution and Random Positive or Negative Uniaxial Anisotropy Blume-Capel Model

    Institute of Scientific and Technical Information of China (English)

    ZHU Hai-Xia; YAN Shi-Lei

    2004-01-01

    We study the ferromagnetic properties of spin-1 system, which is considered in the frame of the bond dilution and random positive or negative anisotropy Blume-Capel model in the effective field theory and a cutting approximation. The investigation of phase diagrams displays some rich properties of the trajectory of tricritical point, reentrant henomena at low temperatures. Under certain both bond concentrations and random negative anisotropy, there are new transition lines of double tricritical points. So special emphasis is placed on the influence of the bond dilution and random anisotropy on phase diagrams. The magnetizations of the system are also discussed. Some results have not been evealed in previous reports.

  18. Experimental Characterisation and Multi-Physic Modelling of Direct Bonding Mechanical Behaviour: Application to Spatial Optical Systems

    Science.gov (United States)

    Cocheteau, N.; Maurel-Pantel, A.; Lebon, F.; Rosu, I.; Ait-Zaid, S.; Savin de Larclause, I.; Salaun, Y.

    2014-06-01

    Direct bonding is a well-known process. However in order to use this process in spatial instrument fabrication the mechanical resistance needs to be quantified precisely. In order to improve bonded strength, optimal parameters of the process are found by studying the influence of annealing time, temperature and roughness which are studied using three experimental methods: double shear, cleavage and wedge tests. Those parameters are chosen thanks to the appearance of time/temperature equivalence. All results brought out the implementation of a multi-physic model to predict the mechanical behavior of direct bonding interface.

  19. Valence electron structure of cast iron and graphltization behaviour criterion of elements

    Institute of Scientific and Technical Information of China (English)

    刘志林; 李志林; 孙振国; 杨晓平; 陈敏

    1995-01-01

    The valence electron structure of common alloy elements in phases of cast iron is calculated- The relationship between the electron structure of alloy elements and equilibrium, non-equilibrium solidification and graphitization is revealed by defining the bond energy of the strongest bond in a phase as structure formation factor S. A criterion of graphitization behaviour of elements is advanced with the critical value of the structure formation factor of graphite and the n of the strongest covalent bond in cementite. It is found that this theory conforms to practice very well when the criterion is applied to the common alloy elements.

  20. A constitutive model for bonded geomaterials subject to mechanical and/or chemical degradation

    Science.gov (United States)

    Nova, R.; Castellanza, R.; Tamagnini, C.

    2003-08-01

    The mechanical behaviour of bonded geomaterials is described by means of an elastoplastic strain-hardening model. The internal variables, taking into account the history of the material, depend on the plastic strains experienced and on a conveniently defined scalar measure of damage induced by weathering and/or chemical degradation.For the sake of simplicity, it is assumed that only internal variables are affected by mechanical and chemical history of the material. Despite this simplifying assumption, it can be shown that many interesting phenomena exhibited by weathered bonded geomaterials can be successfully described. For instance, (i) the transition from brittle to ductile behaviour with increasing pressure of a calcarenite with collapsing internal structure, (ii) the complex behaviour of chalk and other calcareous materials in oedometric tests, (iii) the chemically induced variation of the stress and strain state of such kind of materials, are all phenomena that can be qualitatively reproduced. Several comparisons with experimental data show that the model can capture the observed behaviour also quantitatively.

  1. Bond percolation in films

    Science.gov (United States)

    Korneta, W.; Pytel, Z.

    1988-04-01

    Bond percolation in films with simple cubic structure is considered. It is assumed that the probability of a bond being present between nearest-neighbor sites depends on the distances to surfaces. Based on the relation between the Potts model and the bond percolation model, and using the mean-field approximation, the phase diagram and profiles of the percolation probability have been obtained.

  2. Development of Remote Plutonium Valence State Analyzer

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    <正>In the Purex process of spent fuel reprocessing, the separation of uranium and plutonium depends on the capability extracting state plutonium ions with various valence by TBP. The separate degree of

  3. Lattice Thermal Conductivity of Superlattices from an Adiabatic Bond Charge Model

    Science.gov (United States)

    Ward, Alistair; Broido, David

    2007-03-01

    The adiabatic bond charge model (ABCM) has successfully rendered phonon dispersions of a host of bulk semiconductors [1,2] and has also been used to calculate the phonon dispersions in quantum well superlattices [3]. We have developed an ABCM for superlattices and combined it with a symmetry-based representation of the anharmonic interatomic forces to calculate the lattice thermal conductivity of short-period superlattices, using an iterative solution to the Boltzmann-Peierls equation [4]. We compare our ABCM results with those obtained from some commonly used models for the interatomic forces in semiconductors to assess the importance of accurate descriptions of the phonon dispersions in thermal conductivity calculations. [1] W. Weber, Physical Review B 15, 4789 (1977). [2] K. C. Rustagi and W. Weber, Solid State Communications 18, 673 (1976). [3] S. K. Yip and Y. C. Chang, Physical Review B 30 7037 (1984). [4] D. A. Broido, A. Ward, and N. Mingo, Physical Review B 72, 014308 (2005).

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

    Institute of Scientific and Technical Information of China (English)

    Zhenming Shi; Tao Jiang; Mingjing Jiang; Fang Liu; Ning Zhang

    2015-01-01

    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 para-metric simulations. In addition, weathering has a significant impact on both stressestrain relationship and failure pattern of rocks.

  5. Thermodynamic properties, decomposition kinetics and reaction models of BCHMX and its Formex bonded explosive

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Qi-Long, E-mail: terry.well@163.com [Institute of Energetic Materials, Faculty of Chemical technology, University of Pardubice, 532 10 Pardubice (Czech Republic); Zeman, Svatopluk, E-mail: svatopluk.zeman@upce.cz [Institute of Energetic Materials, Faculty of Chemical technology, University of Pardubice, 532 10 Pardubice (Czech Republic); Svoboda, Roman [Department of Physical Chemistry, Faculty of Chemical technology, University of Pardubice, 532 10 Pardubice (Czech Republic); Elbeih, Ahmed [Military Technical College, Cairo (Egypt)

    2012-11-10

    As an attractive new energetic material, cis-1,3,4,6-tetranitrooctahydroimidazo-[4,5-d]imidazole (BCHMX) and its polymer bonded explosive (PBX) with styrene-butadiene rubber (SBR) binder (Formex type) have been investigated with regard to its thermal decomposition kinetics and reaction models by using DSC, TG and SEM techniques. It was found that the decomposition of BCHMX in dynamic nitrogen could be divided into two steps, while there is only one step for its Formex bonded explosive. The activation energy for decomposition of BCHMX/Formex was obtained to be 221.7 {+-} 4.99 kJ mol{sup -1} by modified KAS method, while the mean activation energies for pure BCHMX are calculated as 233.0 {+-} 2.1 kJ mol{sup -1} for first step and 186.0 {+-} 0.92 kJ mol{sup -1} for the second step. It was further proved that the first decomposition step of BCHMX is autocatalytic, during which the crystal of BCHMX could dissolve in the liquid phase of its thermolysis products on the surface. Besides, the JMA and AC models were found to be appropriate to interpret the two-step decomposition of pure BCHMX and JMA model for BCHMX/Formex, the parameterized reaction models for BCHMX could be established as f({alpha}) = {alpha}{sup 0.45}(1 - {alpha}){sup 1.51} and f({alpha}) = 2.33 Multiplication-Sign (1 - {alpha})[-ln(1 - {alpha})]{sup 0.57}, while for BCHMX/Formex as f({alpha}) = 2 Multiplication-Sign (1 - {alpha})[-ln(1 - {alpha})]{sup 1/2}.

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

    Science.gov (United States)

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

    2014-09-05

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

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

    Science.gov (United States)

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

    2013-10-01

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

  8. 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.

  9. Spontaneous alignment of frustrated bonds in an anisotropic, three-dimensional Ising model

    Science.gov (United States)

    Jalabert, Rodolfo A.; Sachdev, Subir

    1991-07-01

    The Ising model on a three-dimensional cubic lattice with all plaquettes in the x-y frustrated plane is studied by use of a Monte Carlo technique; the exchange constants are of equal magnitude, but have varying signs. At zero temperature, the model has a finite entropy and no long-range order. The low-temperature phase is characterized by an order parameter measuring the openZ4 symmetry of lattice rotations which is invariant under Mattis gauge transformation; fluctuations lead to the alignment of frustrated bonds into columns and a fourfold degeneracy. An additional factor-of-2 degeneracy is obtained from a global spin flip. The order vanishes at a critical temperature by a transition that appears to be in the universality class of the D=3, XY model. These results are consistent with the theoretical predictions of Blankschtein et al. This Ising model is related by duality to phenomenological models of two-dimensional frustrated quantum antiferromagnets.

  10. Global dynamic modeling of electro-hydraulic 3-UPS/S parallel stabilized platform by bond graph

    Science.gov (United States)

    Zhang, Lijie; Guo, Fei; Li, Yongquan; Lu, Wenjuan

    2016-08-01

    Dynamic modeling of a parallel manipulator(PM) is an important issue. A complete PM system is actually composed of multiple physical domains. As PMs are widely used in various fields, the importance of modeling the global dynamic model of the PM system becomes increasingly prominent. Currently there lacks further research in global dynamic modeling. A unified modeling approach for the multi-energy domains PM system is proposed based on bond graph and a global dynamic model of the 3-UPS/S parallel stabilized platform involving mechanical and electrical-hydraulic elements is built. Firstly, the screw bond graph theory is improved based on the screw theory, the modular joint model is modeled and the normalized dynamic model of the mechanism is established. Secondly, combined with the electro-hydraulic servo system model built by traditional bond graph, the global dynamic model of the system is obtained, and then the motion, force and power of any element can be obtained directly. Lastly, the experiments and simulations of the driving forces, pressure and flow are performed, and the results show that, the theoretical calculation results of the driving forces are in accord with the experimental ones, and the pressure and flow of the first limb and the third limb are symmetry with each other. The results are reasonable and verify the correctness and effectiveness of the model and the method. The proposed dynamic modeling method provides a reference for modeling of other multi-energy domains system which contains complex PM.

  11. A Corpuscular Picture of Electrons in Chemical Bond

    CERN Document Server

    Ando, Koji

    2015-01-01

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

  12. MESOSCALE MODELING OF DEFLAGRATION-INDUCED DECONSOLIDATION IN POLYMER-BONDED EXPLOSIVES

    Energy Technology Data Exchange (ETDEWEB)

    Springer, H K; Glascoe, E A; Reaugh, J E; Kercher, J R; Maienschein, J L

    2011-08-01

    Initially undamaged polymer-bonded explosives can transition from conductive burning to more violent convective burning via rapid deconsolidation at higher pressures. The pressure-dependent infiltration of cracks and pores, i.e., damage, by product gases at the burn-front is a key step in the transition to convective burning. However, the relative influence of pre-existing damage and the evolution of deflagration-induced damage during the transition to convective burning is not well understood. The objective of this study is to investigate the role of microstructure and initial pressurization on deconsolidation. We performed simulations using the multi-physics hydrocode, ALE3D. HMX-Viton A served as our model explosive. A Prout-Tompkins chemical kinetic model, Vielle's Law pressure-dependent burning, Gruneisen equation-of-state, and simplified strength model were used for the HMX. The propensity for deconsolidation increased with increasing defect size and decreasing initial pressurization, as measured by the increase in burning surface area. These studies are important because they enable the development of continuum-scale damage models and the design of inherently safer explosives.

  13. Adaptive Shape Functions and Internal Mesh Adaptation for Modelling Progressive Failure in Adhesively Bonded Joints

    Science.gov (United States)

    Stapleton, Scott; Gries, Thomas; Waas, Anthony M.; Pineda, Evan J.

    2014-01-01

    Enhanced finite elements are elements with an embedded analytical solution that can capture detailed local fields, enabling more efficient, mesh independent finite element analysis. The shape functions are determined based on the analytical model rather than prescribed. This method was applied to adhesively bonded joints to model joint behavior with one element through the thickness. This study demonstrates two methods of maintaining the fidelity of such elements during adhesive non-linearity and cracking without increasing the mesh needed for an accurate solution. The first method uses adaptive shape functions, where the shape functions are recalculated at each load step based on the softening of the adhesive. The second method is internal mesh adaption, where cracking of the adhesive within an element is captured by further discretizing the element internally to represent the partially cracked geometry. By keeping mesh adaptations within an element, a finer mesh can be used during the analysis without affecting the global finite element model mesh. Examples are shown which highlight when each method is most effective in reducing the number of elements needed to capture adhesive nonlinearity and cracking. These methods are validated against analogous finite element models utilizing cohesive zone elements.

  14. On valence electron density, energy dissipation and plasticity of bulk metallic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Pang, J.J.; Tan, M.J. [School of Mechanical and Aerospace Engineering, Nanyang Technological University, 639798 Singapore (Singapore); Liew, K.M., E-mail: kmliew@cityu.edu.hk [Department of Civil and Architectural Engineering, City University of Hong Kong, Kowloon (Hong Kong)

    2013-11-15

    Highlights: ► Relationship between valence electron density and plasticity of metallic glasses. ► Poisson's ratio increases as electron density decreases. ► Energy dissipation proposed to understand plasticity. ► Low electron density indicates small activation energy. -- Abstract: In conventional crystalline alloys, valence electron density (VED) is one of the most significant factors in determining their phase stability and mechanical properties. Extending the concept to metallic glasses (MGs), it is found, not totally surprisingly, that their mechanical properties are VED-dependent as in crystalline alloys. Interestingly, the whole VED region can be separated into two zones: Zone 1 consists of Mg-, Ca-, and RE-based (RE for rare earth) alloys; Zone 2 consists of the rest of MGs. In either zone, for each type of MGs, Poisson's ratio generally decreases as VED increases. From the energy dissipation viewpoint proposed recently, the amorphous plasticity is closely related to the activation energy for the operation of shear-transformation-zones (STZs). Smaller STZ activation energy suggests higher ductility because STZs with lower activation energy are able to convert deformation work more efficiently into configurational energy rather than heat, which yields mechanical softening and advances the growth of shear bands (SBs). Following this model, it is revealed that the activation energies for STZ operation and crystallization are certainly proportional to VED. Thus, it is understood that, in Zone 2, MGs have a smaller VED and hence lower activation energies which are favorable for ductility and Poisson's ratio. In Zone 1, MGs have the lowest VED but apparent brittleness because either of low glass transition temperature and poor resistance to oxidation or of a large fraction of covalent bonds.

  15. 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.

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

    Directory of Open Access Journals (Sweden)

    Lei Chang

    2014-10-01

    Full Text Available The impulse-approximation expression used hitherto to define the pion's valence-quark distribution function is flawed because it omits contributions from the gluons which bind quarks into the pion. A corrected leading-order expression produces the model-independent result that quarks dressed via the rainbow–ladder truncation, or any practical analogue, carry all the pion's light-front momentum at a characteristic hadronic scale. Corrections to the leading contribution may be divided into two classes, responsible for shifting dressed-quark momentum into glue and sea-quarks. Working with available empirical information, we use an algebraic model to express the principal impact of both classes of corrections. This enables a realistic comparison with experiment that allows us to highlight the basic features of the pion's measurable valence-quark distribution, qπ(x; namely, at a characteristic hadronic scale, qπ(x∼(1−x2 for x≳0.85; and the valence-quarks carry approximately two-thirds of the pion's light-front momentum.

  17. Nature of the Frequency Shift of Hydrogen Valence Vibrations

    CERN Document Server

    Zhyganiuk, I V

    2015-01-01

    The physical nature of a frequency shift of hydrogen valence vibrations in a water molecule due to its interaction with neighbor molecules has been studied. Electrostatic forces connected with the multipole moments of molecules are supposed to give a dominating contribution to the intermolecular interaction. The frequency shift was calculated in the case where two neighbor molecules form a dimer. The obtained result is in qualitative agreement with the frequency shifts observed for water vapor, hexagonal ice, and liquid water, as well as for aqueous solutions of alcohols. This fact testifies to the electrostatic nature of H-bonds used to describe both the specific features of the intermolecular interaction in water and the macroscopic properties of the latter.

  18. Emotional stocks and bonds: a metaphorical model for conceptualizing and treating codependency and other forms of emotional overinvesting.

    Science.gov (United States)

    Daire, Andrew P; Jacobson, Lamerial; Carlson, Ryan G

    2012-01-01

    Codependent behaviors are associated with an unhealthy reliance on others for meeting emotional needs. This over-reliance on others often leads to dysfunctional interpersonal relationships. This article presents emotional stocks and bonds (ESB), a metaphorical model for use with clients who display codependent behaviors. Emotional stocks and bonds incorporates theoretical tenets from Bowen family systems and attachment theory and aids clients in understanding and changing unhealthy relationship behavior patterns. In addition to an overview of the model's key concepts and its use in clinical practice, we provide a case illustration and a discussion of practice implications and limitations.

  19. 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.

  20. 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

  1. Hückel-Hubbard-Ohno modeling of π-bonds in ethene and ethyne with application to trans-polyacetylene

    Science.gov (United States)

    Timár, Máté; Barcza, Gergely; Gebhard, Florian; Veis, Libor; Legeza, Örs

    Quantum chemistry calculations provide the potential energy between two carbon atoms in ethane (H$_3$C$-$CH$_3$), ethene (H$_2$C$=$CH$_2$), and ethyne (HC$\\equiv$CH) as a function of the atomic distance. Based on the energy function for the $\\sigma$-bond in ethane, $V_{\\sigma}(r)$, we use the H\\"uckel model with Hubbard--Ohno interaction for the $\\pi$~electrons to describe the energies $V_{\\sigma\\pi}(r)$ and $V_{\\sigma\\pi\\pi}(r)$ for the $\\sigma\\pi$ double bond in ethene and the $\\sigma\\pi\\pi$ triple bond in ethyne, respectively. The fit of the force functions shows that the Peierls coupling can be estimated with some precision whereas the Hubbard-Ohno parameters are insignificant at the distances under consideration. We apply the H\\"uckel-Hubbard-Ohno model to describe the bond lengths and the energies of elementary electronic excitations of trans-polyacetylene, (CH)$_n$, and adjust the $\\sigma$-bond potential for conjugated polymers.

  2. 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.

  3. Nucleus-Dependent Valence-Space Approach to Nuclear Structure

    Science.gov (United States)

    Stroberg, S. R.; Calci, A.; Hergert, H.; Holt, J. D.; Bogner, S. K.; Roth, R.; Schwenk, A.

    2017-01-01

    We present a nucleus-dependent valence-space approach for calculating ground and excited states of nuclei, which generalizes the shell-model in-medium similarity renormalization group to an ensemble reference with fractionally filled orbitals. Because the ensemble is used only as a reference, and not to represent physical states, no symmetry restoration is required. This allows us to capture three-nucleon (3 N ) forces among valence nucleons with a valence-space Hamiltonian specifically targeted to each nucleus of interest. Predicted ground-state energies from carbon through nickel agree with results of other large-space ab initio methods, generally to the 1% level. In addition, we show that this new approach is required in order to obtain convergence for nuclei in the upper p and s d shells. Finally, we address the 1+/3+ inversion problem in 22Na and 46V. This approach extends the reach of ab initio nuclear structure calculations to essentially all light- and medium-mass nuclei.

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

    CERN Document Server

    Mezrag, C; Moutarde, H; Roberts, C D; Rodriguez-Quintero, J; Sabatie, F; Schmidt, S M

    2014-01-01

    In order to learn effectively from measurements of generalised parton distributions (GPDs), it is desirable to compute them using a framework that can potentially connect empirical information with basic features of the Standard Model. We sketch an approach to such computations, based upon a rainbow-ladder (RL) truncation of QCD's Dyson-Schwinger equations and exemplified via the pion's valence dressed-quark GPD, $H_\\pi^{\\rm v}(x,\\xi,t)$. Our analysis focuses primarily on $\\xi=0$, although we also capitalise on the symmetry-preserving nature of the RL truncation by connecting $H_\\pi^{\\rm v}(x,\\xi=\\pm 1,t)$ 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 $H_\\pi^{\\rm v}(x,0,t)$, expressed as th...

  5. Comparative computational study of model halogen-bonded complexes of FKrCl.

    Science.gov (United States)

    Joseph, Jerelle A; McDowell, Sean A C

    2015-03-19

    Quantum chemical calculations for the FKrCl molecule at various levels of theory were performed and suggest that this molecule is metastable and may be amenable to experimental synthesis under cryogenic conditions. The FKrCl molecule forms weak halogen-bonded complexes FKrCl···Y with small molecules like FH and H2O and its computed properties were compared with those for analogous complexes of its precursor, FCl, and its rare gas hydride counterpart, FKrH. The cooperative effect of additional noncovalent interactions introduced at the F atom in the FKrCl···Y dimer (to give Z···FKrCl···Y trimers) showed a general strengthening of the intermolecular interactions in the order halogen bond < hydrogen bond < beryllium bond < lithium bond.

  6. Strength Modeling of Reinforced Concrete Beam with Externally Bonded FRP Reinforcement

    Directory of Open Access Journals (Sweden)

    N. Pannirselvam

    2008-01-01

    Full Text Available This research study presents the evaluation of the structural behaviour of reinforced concrete beams with externally bonded Fibre Reinforced Polymer (FRP reinforcements. Three different steel ratios with two different Glass Fibre Reinforced Polymer (GFRP types and two different thicknesses in each type of GFRP were used. Totally fifteen rectangular beams of 3 m length were cast. Three rectangular beams were used as reference beam (Control Beams and the remaining were fixed with GFRP laminates on the soffit of the rectangular beam. The variables considered for the study includes longitudinal steel ratio, type of GFRP laminates, thickness of GFRP laminates and composite ratios. Flexural test, using simple beam with third-point loading was adopted to study the performance of FRP plated beams interms flexural strength, deflection, ductility and was compared with the unplated beams. The test results show that the beams strengthened with GFRP laminates exhibit better performance. The flexural strength and ductility increase with increase in thickness of GFRP plate. The increase in first crack loads was up to 88.89% for 3 mm thick WRGFRP plates and 100.00% for 5 mm WRGFRP plated beams and increase in ductility interms of energy and deflection was found to be 56.01 and 64.69% respectively with 5 mm thick GFRP plated beam. Strength models were developed for predicting the flexural strength (ultimate load, service load and ductility of FRP beams. The strength model developed give prediction matching the measurements.

  7. Nuclear magnetic resonance and molecular modeling study of exocyclic carbon-carbon double bond polarization in benzylidene barbiturates

    Science.gov (United States)

    Figueroa-Villar, J. Daniel; Vieira, Andreia A.

    2013-02-01

    Benzylidene barbiturates are important materials for the synthesis of heterocyclic compounds with potential for the development of new drugs. The reactivity of benzylidene barbiturates is mainly controlled by their exocyclic carbon-carbon double bond. In this work, the exocyclic double bond polarization was estimated experimentally by NMR and correlated with the Hammett σ values of the aromatic ring substituents and the molecular modeling calculated atomic charge difference. It is demonstrated that carbon chemical shift differences and NBO charge differences can be used to predict their reactivity.

  8. Valence electron structure analysis of refining mecha-nism of Sc and Ti additions on aluminum

    Institute of Scientific and Technical Information of China (English)

    LI PieJie; YE YiCong; HE LiangJu

    2009-01-01

    The mechanism of the difference of refining effect between Sc and Ti adding to aluminum can not be explained substantially with traditional theory. Valence electron structures of AI-Ti and Al-Sc alloys have been studied by using the empirical electron theory of solids and molecules (EET). The covalent bond electron numbers and interfacial electron density differences are calculated. The conclusion is that, in the two alloys, different covalent bond electron numbers of nucleation particles, and different electron densities on the interface between the second phase particles and the matrix, fundamentally lead to the difference of refining effect between Sc and Ti adding to aluminum.

  9. 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…

  10. Masked emotional priming beyond global valence activations

    NARCIS (Netherlands)

    Rohr, M.; Degner, J.; Wentura, D.

    2012-01-01

    An immense body of research demonstrates that emotional facial expressions can be processed unconsciously. However, it has been assumed that such processing takes place solely on a global valence-based level, allowing individuals to disentangle positive from negative emotions but not the specific em

  11. FTIR and molecular mechanics studies of H-bonds in aliphatic polyurethane and polyamide-66 model molecules

    Science.gov (United States)

    Wang, Guoqing; Zhang, Chunxia; Guo, Xiaohe; Ren, Zhiyong

    2008-02-01

    Model aliphatic polyurethane (APU) hard segment based on 1,6-hexamethylene diisocyanate (HDI) and 1,4-butanediol (BDO) were prepared. FTIR and molecular mechanics (MM) simulation were used to conduct the systematic studies on APU and polyamide-66 (PA-66) whose sole difference lies in the alkoxyl oxygen. It was found that the introduction of the alkoxyl not only increases the conformations in APU, makes it a possible H-bond acceptor, but also weakens the H-bond between NH and O dbnd C in APU. There are two conformers stably existed in APU with lowest energy, leading to eight H-bond complexes based on NH as donor and (1) O dbnd C as acceptor, and another two complexes based on (2) alkoxyl O and (3) urethane N as acceptors, whereas there is only one stable conformer in PA-66, leading to one H-bond complex. One predominant H-bond complex has been found in APU with probability of about 95%. The simulated results are consistent with the νNH and νC dbnd O band shifting in FTIR.

  12. Modeling and analysis of the electromechanical behavior of surface-bonded piezoelectric actuators using finite element method

    CERN Document Server

    Yu, Huangchao

    2016-01-01

    Piezoelectric actuators have been widely used to form a self-monitoring smart system to do Structural health monitoring (SHM). One of the most fundamental issues in using actuators is to determine the actuation effects being transferred from the actuators to the host structure. This report summaries the state of the art of modeling techniques for piezoelectric actuators and provides a numerical analysis of the static and dynamic electromechanical behavior of piezoelectric actuators surface-bonded to an elastic medium under in-plane mechanical and electric loads using finite element method. Also case study is conducted to study the effect of material properties, bonding layer and loading frequency using static and harmonic analysis of ANSYS. Finally, stresses and displacements are determined, and singularity behavior at the tips of the actuator is proved. The results indicate that material properties, bonding layers and frequency have a significant influence on the stresses transferred to the host structure.

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

    Energy Technology Data Exchange (ETDEWEB)

    Reena Philip, Rachel [Solid State Physics Laboratory, Department of Physics, Cochin University of Science and Technology, Kochi-682022 Kerala (India)]. E-mail: reenatara@cusat.ac.in; Pradeep, B. [Solid State Physics Laboratory, Department of Physics, Cochin University of Science and Technology, Kochi-682022 Kerala (India)

    2005-01-24

    Polycrystalline thin films of ternary chalcopyrite CuInSe{sub 2} and defect compounds CuIn{sub 3}Se{sub 5} and CuIn{sub 5}Se{sub 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{sub 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.

  14. Valence Topological Charge-Transfer Indices for Dipole Moments: Percutaneous Enhancers

    Directory of Open Access Journals (Sweden)

    Francisco Torrens

    2004-12-01

    Full Text Available Valence topological charge-transfer (CT indices are applied to the calculationof dipole moments. The algebraic and vector semisum CT indices are defined. Thecombination of CT indices allows the estimation of the dipole moments. The model isgeneralized for molecules with heteroatoms. The ability of the indices for the descriptionof the molecular charge distribution is established by comparing them with the dipolemoments of homologous series of percutaneous enhancers (phenyl alcohols and4-alkylanilines. Linear and quadratic correlation models are obtained. CT indicesimprove the multivariable quadratic regression equations for the dipole moment. Thevariance decreases 97% (4-alkylanilines. No superposition of the corresponding Gk–Jkand GkV–JkV pairs is observed in the fits, which diminishes the risk of co-linearity. Theinclusion of the heteroatom in the π-electron system is beneficial for the description ofthe dipole moment, owing to either the role of the additional p orbitals provided by theheteroatom or the role of steric factors in the π-electron conjugation. Inclusion of aconjugated double bond in the alkyl chain lends to more rigid structures with dipolemoment variations lower than1%.

  15. Testing and modeling of diffusion bonded prototype optical windows under ITER conditions

    Energy Technology Data Exchange (ETDEWEB)

    Jacobs, M. [Flemish Inst. for Technological Research, Mol (Belgium); Van Oost, G. [Dept. of Applied Physics, Ghent Univ., Ghent (Belgium); Degrieck, J.; De Baere, I. [Dept. of Materials Science and Engineering, Ghent Univ., Ghent (Belgium); Gusarov, A. [Belgian Nuclear Research Center, Mol (Belgium); Gubbels, F. [TNO, Eindhoven (Netherlands); Massaut, V. [Belgian Nuclear Research Center, Mol (Belgium)

    2011-07-01

    Glass-metal joints are a part of ITER optical diagnostics windows. These joints must be leak tight for the safety (presence of tritium in ITER) and to preserve the vacuum. They must also withstand the ITER environment: temperatures up to 220 deg.C and fast neutron fluxes of {approx}3.10{sup 9} n/cm{sup 2}.s. At the moment, little information is available about glass-metal joints suitable for ITER. Therefore, we performed mechanical and thermal tests on some prototypes of an aluminium diffusion bonded optical window. Finite element modeling with Abaqus code was used to understand the experimental results. The prototypes were helium leaking probably due to very tiny cracks in the interaction layer between the steel and the aluminium. However, they were all able to withstand a thermal cycling test up to 200 deg. C; no damage could be seen after the tests by visual inspection. The prototypes successfully passed push-out test with a 500 N load. During the destructive push-out tests the prototypes broke at a 6-12 kN load between the aluminium layer and the steel or the glass, depending on the surface quality of the glass. The microanalysis of the joints has also been performed. The finite element modeling of the push-out tests is in a reasonable agreement with the experiments. According to the model, the highest thermal stress is created in the aluminium layer. Thus, the aluminium joint seems to be the weakest part of the prototypes. If this layer is improved, it will probably make the prototype helium leak tight and as such, a good ITER window candidate. (authors)

  16. Study of vibrational spectra and hydrogen bonding network in dimeric and tetrameric model of ampicillin using DFT and AIM approach

    Science.gov (United States)

    Shukla, Anuradha; Khan, Eram; Tandon, Poonam; Sinha, Kirti

    2017-03-01

    Ampicillin is a β-lactam antibiotic that is active against both gram-positive and gram-negative bacteria and is widely used for the treatment of infections. In this work, molecular properties of ampicillin are calculated on the basis of calculations on its dimeric and tetrameric models using DFT/B3LYP/6-311G(d,p). HOMO-LUMO energy gap shows that chemical reactivity of tetrameric model of ampicillin is higher than the dimeric and monomeric model of ampicillin. To get a better understanding of intra and intermolecular bonding and interactions among bonds, NBO analysis is carried out with tetrameric model of ampicillin, and is further finalized with an 'quantum theory of atoms-in-molecules' (QTAIM) analysis. The binding energy of dimeric model of ampicillin is calculated as -26.84 kcal/mol and -29.34 kcal/mol using AIM and DFT calculations respectively. The global electrophilicity index (ω = 2.8118 eV) of tetrameric model of ampicillin shows that this behaves as a strong electrophile in comparison to dimeric and monomeric model of ampicillin. The FT-Raman and FT-IR spectra were recorded in the solid phase, and interpreted in terms of potential energy distribution analysis. A collective theoretical and experimental vibrational analysis approves the presence of hydrogen bonds in the ampicillin molecule.

  17. Detailed modeling of sloshing in satellites tank at low Bond numbers

    Science.gov (United States)

    Lepilliez, Mathieu; Tanguy, Sebastien; Interface Team

    2015-11-01

    Consumption of ergols is a critical issue regarding the whole lifetime of a satellite. During maneuvers in mission phases, the Helium bubble used to pressurize the tank can move freely inside, thus generating movement of the center of mass, and sloshing which can disrupt the control of the satellite. In this study we present numerical results obtained from CFD computation, using an Immersed Interface Method to model the tank with a level-set approach for both liquid-gas interface and solid-fluid interface. A parametric study is proposed to observe the influence of the Bond number on resulting forces and torques generated on the tank. One can observe different steps during the maneuvers under microgravity: the first part is dominated by accelerations and volume forces, which flatten the bubble on the hydrophilic tank wall. When the forcing stops, the bubble bounces back, generating sloshing by moving under the influence of inertia and capillary effects. Finally viscous effects damp the sloshing by dissipating the kinetic energy of the bubble. Those results are compared to actual in-flight data for different typical maneuvers on forces and torques, allowing us to characterize the period and damping of the sloshing. CNES/ Airbus Defence & Space funding.

  18. Electron states in a quantum dot in an effective-bond-orbital model

    Science.gov (United States)

    Nair, Selvakumar V.; Ramaniah, Lavanya M.; Rustagi, Kailash C.

    1992-03-01

    The electronic-level structure in semiconductor quantum dots is investigated in a tight-binding framework. The energy levels and wave functions of GaAs and CdS crystallites containing up to ~4000 atoms are calculated using an effective-bond-orbital model. The results obtained for GaAs crystallites by using parameters that accurately reproduce the band structure near the Γ point are compared with those obtained by calculations based on a multiband effective-mass theory. The effective-mass approximation (EMA) is found to correctly describe the qualitative features of the level structure, such as the bunching of levels and the spatial dependence of the wave functions. However, for very small particles the EMA grossly overestimates the confinement energies mainly because of the deviation of the bulk band structure from parabolic dispersion at high energies. For CdS crystallites we use a parametrization scheme that reproduces the main features of the bulk band structure throughout the Brillouin zone, and compare the results with those obtained by the multiband EMA, as well as with experimental data on interband transitions.

  19. Thermal-hydraulic modeling and analysis of spool valve with sloping U-shape notch by bond graph

    Institute of Scientific and Technical Information of China (English)

    娄磊; 吴万荣; 王兆强; 梁向京

    2015-01-01

    To increase the efficiency and reliability of the thermodynamics analysis of the spool valve, the precise function expression of the flow area for the sloping U-shape notch orifice versus the spool stroke and thermal-hydraulic bond graph based on the conservation of mass and energy were introduced. Subsequently, the connection rule for the bond graph elements and the method to construct the complete thermal-hydraulic system model were proposed. On the basis of heat transfer analysis of a typical hydraulic circuit containing the spool valve, the lumped parameter for mathematical model of the system was given. At last, the reliability of the mathematical model of the flow area and the thermal-hydraulic system for the sloping U-shape notch orifice on the spool were demonstrated by the test. The good agreement between the simulation results and experimental data demonstrates the validity of the modeling method.

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

    Directory of Open Access Journals (Sweden)

    Putz Mihai V

    2012-11-01

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

  1. Scaling of Entanglement Entropy for the Heisenberg Model on Clusters Joined by Point Contacts

    Science.gov (United States)

    Friedman, B. A.; Levine, G. C.

    2016-11-01

    The scaling of entanglement entropy for the nearest neighbor antiferromagnetic Heisenberg spin model is studied computationally for clusters joined by a single bond. Bisecting the balanced three legged Bethe cluster, gives a second Renyi entropy and the valence bond entropy which scales as the number of sites in the cluster. For the analogous situation with square clusters, i.e. two L × L clusters joined by a single bond, numerical results suggest that the second Renyi entropy and the valence bond entropy scales as L. For both systems, the environment and the system are connected by the single bond and interaction is short range. The entropy is not constant with system size as suggested by the area law.

  2. 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.

  3. Entropically patchy particles: engineering valence through shape entropy.

    Science.gov (United States)

    van Anders, Greg; Ahmed, N Khalid; Smith, Ross; Engel, Michael; Glotzer, Sharon C

    2014-01-28

    Patchy particles are a popular paradigm for the design and synthesis of nanoparticles and colloids for self-assembly. In "traditional" patchy particles, anisotropic interactions arising from patterned coatings, functionalized molecules, DNA, and other enthalpic means create the possibility for directional binding of particles into higher-ordered structures. Although the anisotropic geometry of nonspherical particles contributes to the interaction patchiness through van der Waals, electrostatic, and other interactions, how particle shape contributes entropically to self-assembly is only now beginning to be understood. The directional nature of entropic forces has recently been elucidated. A recently proposed theoretical framework that defines and quantifies directional entropic forces demonstrates the anisotropic-that is, patchy-nature of these emergent, attractive forces. Here we introduce the notion of entropically patchy particles as the entropic counterpart to enthalpically patchy particles. Using three example "families" of shapes, we show how to modify entropic patchiness by introducing geometric features to the particles via shape operations so as to target specific crystal structures assembled here with Monte Carlo simulations. We quantify the emergent entropic valence via a potential of mean force and torque. We show that these forces are on the order of a few kBT at intermediate densities below the onset of crystallization. We generalize these shape operations to shape anisotropy dimensions, in analogy with the anisotropy dimensions introduced for enthalpically patchy particles. Our findings demonstrate that entropic patchiness and emergent valence provide a way of engineering directional bonding into nanoparticle systems, whether in the presence or absence of additional, non-entropic forces.

  4. Pion valence-quark parton distribution function

    Directory of Open Access Journals (Sweden)

    Lei Chang

    2015-10-01

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

  5. 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.

  6. Masked emotional priming beyond global valence activations.

    Science.gov (United States)

    Rohr, Michaela; Degner, Juliane; Wentura, Dirk

    2012-01-01

    An immense body of research demonstrates that emotional facial expressions can be processed unconsciously. However, it has been assumed that such processing takes place solely on a global valence-based level, allowing individuals to disentangle positive from negative emotions but not the specific emotion. In three studies, we investigated the specificity of emotion processing under conditions of limited awareness using a modified variant of an affective priming task. Faces with happy, angry, sad, fearful, and neutral expressions were presented as masked primes for 33 ms (Study 1) or 14 ms (Studies 2 and 3) followed by emotional target faces (Studies 1 and 2) or emotional adjectives (Study 3). Participants' task was to categorise the target emotion. In all three studies, discrimination of targets was significantly affected by the emotional primes beyond a simple positive versus negative distinction. Results indicate that specific aspects of emotions might be automatically disentangled in addition to valence, even under conditions of subjective unawareness.

  7. Chemical bond properties and Mossbauer spectroscopy in (La1-xMx)2CuO4 (M=Ba, Sr)

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    By using the average band-gap model, the chemical bond properties of (La1-x Mx)2CuO4(M=Ba, Sr) were calculated . The calculated covalencies for Cu(O and La(O bond in the compounds are 0.3 and 0.03 respectively. M?ssbauer isomer shifts of 57Fe doped in La2CuO4 and 119Sn doped in La2CuO4 were calculated by using the chemical surrounding factor defined by covalency and electronic polarizability. Four valence state tin and three valence iron sites were identified in 57Fe and 119Sn doped La2CuO4.

  8. Effects of Bond Alternation on the Ground-State Phase Diagram of One-Dimensional XXZ Model

    Institute of Scientific and Technical Information of China (English)

    QIANG Ling; LIU Guang-Hua; TIAN Guang-Shan

    2013-01-01

    The ground-state properties and quantum phase transitions (QPTs) of the one-dimensional bond-alternative XXZ model are investigated by the infinite time-evolving block decimation (iTEBD) method.The bond-alternative effects on its ground-state phase diagram are discussed in detail.Once the bond alternation is taken into account,the antiferromagnetic phase (△ > 1) will be destroyed at a given critical point and change into a disordered phase without nonlocal string order.The QPT is shown to be second-order,and the whole phase diagram is provided.For the ferromagnetic phase region (△ <-1),the critical point rc always equals 1 (independent of △),and the QPT for this case is shown to be first-order.The dimerized Heisenberg model is also discussed,and two disordered phases can be distinguished by with or without nonlocal string orders.Both the bipartite entanglement and the fidelity per site,as two kinds of model-independent measures,are capable of describing all the QPTs in such a quantum model.

  9. 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...

  10. Stark spectroscopy of mixed-valence systems.

    Science.gov (United States)

    Silverman, Lisa N; Kanchanawong, Pakorn; Treynor, Thomas P; Boxer, Steven G

    2008-01-13

    Many mixed-valence systems involve two or more states with different electric dipole moments whose magnitudes depend upon the charge transfer distance and the degree of delocalization; these systems can be interconverted by excitation of an intervalence charge transfer transition. Stark spectroscopy involves the interaction between the change in dipole moment of a transition and an electric field, so the Stark spectra of mixed-valence systems are expected to provide quantitative information on the degree of delocalization. In limiting cases, a classical Stark analysis can be used, but in intermediate cases the analysis is much more complex because the field affects not only the band position but also the intrinsic bandshape. Such non-classical Stark effects lead to widely different bandshapes. Several examples of both classes are discussed. Because electric fields are applied to immobilized samples, complications arise from inhomogeneous broadening, along with other effects that limit our ability to extract unique parameters in some cases. In the case of the radical cation of the special pair in photosynthetic reaction centres, where the mixed-valence system is in a very complex but structurally well-defined environment, a detailed analysis can be performed.

  11. Constructing a gapless spin-liquid state for the spin-1/2 J(1)-J(2) Heisenberg model on a square lattice.

    Science.gov (United States)

    Wang, Ling; Poilblanc, Didier; Gu, Zheng-Cheng; Wen, Xiao-Gang; Verstraete, Frank

    2013-07-19

    We construct a class of projected entangled pair states which is exactly the resonating valence bond wave functions endowed with both short range and long range valence bonds. With an energetically preferred resonating valence bond pattern, the wave function is simplified to live in a one-parameter variational space. We tune this variational parameter to minimize the energy for the frustrated spin-1/2 J(1)-J(2) antiferromagnetic Heisenberg model on the square lattice. Taking a cylindrical geometry, we are able to construct four topological sectors with an even or odd number of fluxes penetrating the cylinder and an even or odd number of spinons on the boundary. The energy splitting in different topological sectors is exponentially small with the cylinder perimeter. We find a power law decay of the dimer correlation function on a torus, and a lnL correction to the entanglement entropy, indicating a gapless spin-liquid phase at the optimum parameter.

  12. Discrete kink dynamics in hydrogen-bonded chains: The one-component model

    DEFF Research Database (Denmark)

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

    2002-01-01

    We study topological solitary waves (kinks and antikinks) in a nonlinear one-dimensional Klein-Gordon chain with the on-site potential of a double-Morse type. This chain is used to describe the collective proton dynamics in quasi-one-dimensional networks of hydrogen bonds, where the on-site poten......We study topological solitary waves (kinks and antikinks) in a nonlinear one-dimensional Klein-Gordon chain with the on-site potential of a double-Morse type. This chain is used to describe the collective proton dynamics in quasi-one-dimensional networks of hydrogen bonds, where the on...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-01-18

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

  14. 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......, accurate correlations were obtained. The prediction ability of the approach was evaluated against predictions from the COSMO-RS model. A thorough discussion is made for the appropriate modeling of solid solubility considering the effect of the difference of the heat capacities of the solute in liquid...

  15. Bond Issues.

    Science.gov (United States)

    Pollack, Rachel H.

    2000-01-01

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

  16. "I Owe Her So Much; Without Her I Would Be Dead": Developing a Model of Mother-Infant Bonding Following a Maternal Antenatal HIV Diagnosis.

    Science.gov (United States)

    Willcocks, Kate; Evangeli, Michael; Anderson, Jane; Zetler, Sarah; Scourse, Rosalind

    2016-01-01

    Women can face a period of psychological vulnerability following antenatal HIV diagnosis, affecting feelings about both the pregnancy and motherhood. Our study explored the impact of being diagnosed with HIV during pregnancy on mother-infant bonding. Grounded Theory was used to assess perceived challenges and facilitating factors for mother-infant bonding for 10 mothers given an HIV diagnosis during pregnancy. Data analysis led to a model of mother-infant bonding composed of four theoretical codes: (a) facing barriers to bonding, (b) feeling disconnected from the baby, (c) developing a special bond, and (d) strengthening and moving on. Challenges with bonding emerged primarily during early stages after diagnosis and birth, with maternal resilience and positivity about the future developing as the infant HIV testing process progressed. Study recommendations include more timely information regarding vertical transmission and more targeted psychological support along with greater promotion of services to support women diagnosed with HIV antenatally.

  17. Fracture model for predicting concrete cover-cracking induced by steel corrosion based on interface bond state

    Institute of Scientific and Technical Information of China (English)

    WANG Xian-li; ZHENG Jian-jun; WU Zhi-min

    2009-01-01

    Time-to-cracking of the concrete cover induced by the steel corrosion is one of the critical problems faced by engineers, operators and asset managers in making strategies for the maintenance and repairs of reinforced concrete (RC)structures affected by corrosion. In this paper, a theoretical model for predicting the time-to-cracking is derived by assuming the bond between the steel bar and the concrete as a linear combination of perfectly smooth and bonded. The model takes into account the characteristics of existing exiguous flaws and initial cracks in the concrete before the load acting on RC structures. The validity of the proposed model is preliminarily verified by comparing the obtained results with the available experimental results. A remarkable advantage of the proposed method is its application to the prediction of the service life of RC structures, made of the deformed steel bars as well as the round bars. By determining an experimental constant α, which is related to the interface bond state between the steel bar and the concrete, the service life of RC structures can be predicted using the proposed scheme. Analysis of major factors affecting the time-to-cracking demonstrates that the length of the initial crack affects the service life of RC structures significantly. Moreover, the larger cover thickness and the smaller diameter of the steel bar within a certain range are beneficial to prolonging the time-to-cracking.

  18. Solubility of block copolymer surfactants in compressed CO{sub 2} using a lattice fluid hydrogen-bonding model

    Energy Technology Data Exchange (ETDEWEB)

    Takishima, Shigeki; O`Neill, M.L.; Johnston, K.P. [Univ. of Texas, Austin, TX (United States). Dept. of Chemical Engineering

    1997-07-01

    Supercritical carbon dioxide (CO{sub 2}) is an environmentally benign alternative to organic solvents in chemical processing. The solubilities of the homopolymers poly(ethylene glycol), poly(ethylene glycol) dimethyl ether (PEGDME), and poly(propylene glycol) (PPG) in CO{sub 2} were correlated with a lattice fluid hydrogen-bonding (LFHB) model, which was then used to predict solubilities of Pluronic L (PEG-PPG-PEG) and Pluronic R (PPG-PEG-PPG) triblock copolymers. Simple averaging rules were developed to evaluate the physical properties of the copolymers without introducing any adjustable parameters. For a given average molecular weight, the predictions of the model were quite reasonable and in some cases perhaps more accurate than the data, due to the large polydispersity of the samples. The model predicts the effects of total molecular weight, PEG/PPG ratio, terminal functional groups, temperature, and density on solubility. The much higher solubility of PPG versus PEG is due primarily to steric hindrance from the methyl branch, which weakens segment-segment interactions, and to a lesser extent to the stronger hydrogen bond donor strength of a primary (in the case of PEG) versus a secondary (in the case of PPG) alcohol terminal group. Consequently, the predicted solubilities of Pluronic L surfactants, which have stronger hydrogen bond donors on the terminal groups, are not much smaller than those of Pluronic R surfactants for given molecular weights of the blocks.

  19. AddRemove : A new link model for use in QM/MM studies

    NARCIS (Netherlands)

    Swart, M

    2003-01-01

    The division of a system under study in a quantum mechanical (QM) and a classical system in QM/MM molecular mechanical calculations is sometimes very natural, but a problem arises in the case of bonds crossing the QM/MM boundary. A new link model that uses a capping (link) atom to satisfy the valenc

  20. Modeling and Simulation of the Vibration Characteristics of the In-Wheel Motor Driving Vehicle Based on Bond Graph

    Directory of Open Access Journals (Sweden)

    Di Tan

    2016-01-01

    Full Text Available Bond graph theory is applied to the modeling and analysis of the vibration characteristics of the in-wheel motor driving vehicle. First, an 11-degree-of-freedom vibration model of the in-wheel motor driving vehicle is established based on bond graph, and then the correctness of the model is verified. Second, under the driving condition of class B road excitations and a speed of 50 Km/h, the vibration characteristics of the in-wheel motor driving vehicle are simulated and analyzed, and the activity of each part in the system is then calculated. Third, these parts that have less of an effect on the vibration characteristics of an in-wheel motor driving vehicle are identified according to the magnitude of the activity, and then the model is simplified by removing these parts. Finally, the reliability of the simplified model is verified by comparing the vibration characteristics of the model before and after simplification. This study can provide a method for the modeling and simulation of the vibration characteristics of the in-wheel motor driving vehicle.

  1. 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

    2017-03-02

    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.

  2. Linear and Non-linear Modeling of Cement-bonded Moulding Sand System Using Conventional Statistical Regression Analysis

    Science.gov (United States)

    Parappagoudar, Mahesh B.; Pratihar, Dilip K.; Datta, Gouranga L.

    2008-08-01

    A cement-bonded moulding sand system takes a fairly long time to attain the required strength. Hence, the moulds prepared with cement as a bonding material will have to wait a long time for the metal to be poured. In this work, an accelerator was used to accelerate the process of developing the bonding strength. Regression analysis was carried out on the experimental data collected as per statistical design of experiments (DOE) to establish input-output relationships of the process. The experiments were conducted to measure compression strength and hardness (output parameters) by varying the input variables, namely amount of cement, amount of accelerator, water in the form of cement-to-water ratio, and testing time. A two-level full-factorial design was used for linear regression model, whereas a three-level central composite design (CCD) had been utilized to develop non-linear regression model. Surface plots and main effects plots were used to study the effects of amount of cement, amount of accelerator, water and testing time on compression strength, and mould hardness. It was observed from both the linear as well as non-linear models that amount of cement, accelerator, and testing time have some positive contributions, whereas cement-to-water ratio has negative contribution to both the above responses. Compression strength was found to have linear relationship with the amount of cement and accelerator, and non-linear relationship with the remaining process parameters. Mould hardness was seen to vary linearly with testing time and non-linearly with the other parameters. Analysis of variance (ANOVA) was performed to test statistical adequacy of the models. Twenty random test cases were considered to test and compare their performances. Non-linear regression models were found to perform better than the linear models for both the responses. An attempt was also made to express compression strength of the moulding sand system as a function of mould hardness.

  3. 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.

  4. Evaluation of bond strength of silorane and methacrylate based restorative systems to dentin using different cavity models

    Directory of Open Access Journals (Sweden)

    Stephano Zerlottini Isaac

    2013-09-01

    Full Text Available OBJECTIVE: The aim of this in vitro study was to evaluate the microtensile bond strength (µTBS to dentin of two different restorative systems: silorane-based (P90, and methacrylate-based (P60, using two cavity models. MATERIAL AND METHODS: Occlusal enamel of 40 human third molars was removed to expose flat dentin surface. Class I cavities with 4 mm mesial-distal width, 3 mm buccal-lingual width and 3 mm depth (C-factor=4.5 were prepared in 20 teeth, which were divided into two groups (n=10 restored with P60 and P90, bulk-filled after dentin treatment according to manufacturer's instructions. Flat buccal dentin surfaces were prepared in the 20 remaining teeth (C-factor=0.2 and restored with resin blocks measuring 4x3x3 mm using the two restorative systems (n=10. The teeth were sectioned into samples with area between 0.85 and 1.25 mm2 that were submitted to µTBS testing, using a universal testing machine (EMIC at speed of 0.5 mm/min. Fractured specimens were analyzed under stereomicroscope and categorized according to fracture pattern. Data were analyzed using ANOVA and Tukey Kramer tests. RESULTS: For flat surfaces, P60 obtained higher bond strength values compared with P90. However, for Class I cavities, P60 showed significant reduction in bond strength (p0.05, or between Class I Cavity and Flat Surface group, considering P90 restorative system (p>0.05. Regarding fracture pattern, there was no statistical difference among groups (p=0.0713 and 56.3% of the fractures were adhesive. CONCLUSION: It was concluded that methacrylate-based composite µTBS was influenced by cavity models, and the use of silorane-based composite led to similar bond strength values compared to the methacrylate-based composite in cavities with high C-factor.

  5. Barrier-free proton transfer in the valence anion of 2'-deoxyadenosine-5'-monophosphate. II. A computational study.

    Science.gov (United States)

    Kobyłecka, Monika; Gu, Jiande; Rak, Janusz; Leszczynski, Jerzy

    2008-01-28

    The propensity of four representative conformations of 2(')-deoxyadenosine-5(')-monophosphate (5(')-dAMPH) to bind an excess electron has been studied at the B3LYP6-31++G(d,p) level. While isolated canonical adenine does not support stable valence anions in the gas phase, all considered neutral conformations of 5(')-dAMPH form adiabatically stable anions. The type of an anionic 5(')-dAMPH state, i.e., the valence, dipole bound, or mixed (valence/dipole bound), depends on the internal hydrogen bond(s) pattern exhibited by a particular tautomer. The most stable anion results from an electron attachment to the neutral syn-south conformer. The formation of this anion is associated with a barrier-free proton transfer triggered by electron attachment and the internal rotation around the C4(')-C5(') bond. The adiabatic electron affinity of the a_south-syn anion is 1.19 eV, while its vertical detachment energy is 1.89 eV. Our results are compared with the photoelectron spectrum (PES) of 5(')-dAMPH(-) measured recently by Stokes et al., [J. Chem. Phys. 128, 044314 (2008)]. The computational VDE obtained for the most stable anionic structure matches well with the experimental electron binding energy region of maximum intensity. A further understanding of DNA damage might require experimental and computational studies on the systems in which purine nucleotides are engaged in hydrogen bonding.

  6. 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

  7. Bond-length analysis of the omega structure in Ti,Zr,Hf and their alloys: experimental data, new correlations and implications for chemical bonding models

    Energy Technology Data Exchange (ETDEWEB)

    Grad, G.B.; Benites, G.M. [Comision Nacional de Energia Atomica, San Carlos de Bariloche (Argentina). Centro Atomico Bariloche; Aurelio, G. [Departamento de Fisica, Universidad del Comahue, 8300, Neuquen (Argentina); Fernandez Guillermet, A. [Centro Atomico Bariloche, 8400, San Carlos de Bariloche (Argentina)

    1999-12-15

    An analysis is performed of the experimental information on the key interatomic distances (IDs) of the AlB{sub 2} type structure, the so-called omega ({omega}) phase in Ti and Zr, as well as in Ti-V and Zr-Nb alloys. Various remarkable correlations are found between these IDs and standard measures of the atomic size, and with Pauling's bond-lengths. These observations are discussed in the light of the phenomenological bonding pictures of the {omega} structure, and with our recent ab initio calculations of the electronic structure of this phase. (orig.)

  8. Aggression proneness: Transdiagnostic processes involving negative valence and cognitive systems.

    Science.gov (United States)

    Verona, Edelyn; Bresin, Konrad

    2015-11-01

    Aggressive behavior is observed in persons with various mental health problems and has been studied from the perspectives of neuroscience and psychophysiology. The present research reviews some of the extant experimental literature to help clarify the interplay between domains of functioning implicated in aggression proneness. We then convey a process-oriented model that elucidates how the interplay of the Negative Valence and Cognitive System domains of NIMH's Research Domain Criteria (RDoC) helps explain aggression proneness, particularly reactive aggression. Finally, we report on a study involving event-related potential (ERP) indices of emotional and inhibitory control processing during an emotional-linguistic go/no-go task among 67 individuals with histories of violence and criminal offending (30% female, 44% African-American) who reported on their aggressive tendencies using the Buss-Perry Aggression Questionnaire. Results provide evidence that tendencies toward angry and aggressive behavior relate to reduced inhibitory control processing (no-go P3) specifically during relevant threat-word blocks, suggesting deterioration of cognitive control by acute or sustained threat sensitivity. These findings highlight the value of ERP methodologies for clarifying the interplay of Negative Valence and Cognitive System processes in aggression proneness.

  9. 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

  10. DFT modeling and spectroscopic study of metal ligand bonding in La(III) complex of coumarin-3-carboxylic acid

    Science.gov (United States)

    Mihaylov, Tz.; Trendafilova, N.; Kostova, I.; Georgieva, I.; Bauer, G.

    2006-09-01

    The binding mode of coumarin-3-carboxylic acid (HCCA) to La(III) is elucidated at experimental and theoretical level. The complexation ability of the deprotonated ligand (CCA -) to La(III) is studied using elemental analysis, DTA and TGA data as well as FTIR, 1H NMR and 13C NMR spectra. The experimental data suggest the complex formula La(CCA) 2(NO 3)(H 2O) 2. B3LYP, BHLYP, B3P86, B3PW91, PW91P86 and MPW1PW91 functionals are tested for geometry and frequency calculations of the neutral ligand and all of them show bond length deviations bellow 1%. B3LYP/6-31G(d) level combined with large quasi-relativistic effective core potential for lanthanum is selected to describe the molecular, electronic and vibrational structures as well as the conformational behavior of HCCA, CCA - and La-CCA complex. The metal-ligand binding mode is predicted through molecular modeling and energy estimation of different La-CCA structures. The calculated atomic charges and the bonding orbital polarizations point to strong ionic metal-ligand bonding in La-CCA complex and insignificant donor acceptor interaction. Detailed vibrational analysis of HCCA, CCA - and La(CCA) 2(NO 3)(H 2O) 2 systems based on both calculated and experimental frequencies confirms the suggested metal-ligand binding mode.

  11. Force modulating dynamic disorder: A physical model of catch-slip bond transitions in receptor-ligand forced dissociation experiments

    Science.gov (United States)

    Liu, Fei; Ou-Yang, Zhong-Can

    2006-11-01

    Recent experiments found that some adhesive receptor-ligand complexes have counterintuitive catch-slip transition behaviors: the mean lifetimes of these complexes first increase (catch) with initial application of a small external force, and then decrease (slip) when the force is beyond some threshold. In this work we suggest that the forced dissociation of these complexes might be a typical rate process with dynamic disorder. The one-dimensional force modulating Agmon-Hopfield model is used to describe the transitions in the single-bond P-selectin glycoprotein ligand 1-P-selectin forced dissociation experiments, which were respectively performed in the constant force [Marshall , Nature (Landon) 423, 190 (2003)] and the ramping force [Evans , Proc. Natl. Acad. Sci. U.S.A 98, 11281 (2004)] modes. We find that, an external force can not only accelerate the bond dissociation, but also modulate the complex from the lower-energy barrier to the higher one; the catch-slip bond transition can arise from a particular energy barrier shape. The agreement between our calculation and the experimental data is satisfactory.

  12. 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 ne

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

    Science.gov (United States)

    Gunardi, Setiawan, Ezra Putranda

    2015-12-01

    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.

  14. 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...

  15. 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.

  16. The structure and bonding of iron-acceptor pairs in silicon

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, S.; Assali, L.V.C.; Kimerling, L.C. [Massachusetts Inst. of Technology, Cambridge, MA (United States)

    1995-08-01

    The highly mobile interstitial iron and Group III impurities (B, Al, Ga, In) form iron-acceptor pairs in silicon. Based on the migration kinetics and taking host silicon as a dielectric medium, we have simulated the pairing process in a static silicon lattice. Different from the conventional point charge ionic model, our phenomenological calculations include (1) a correction that takes into account valence electron cloud polarization which adds a short range, attractive interaction in the iron-acceptor pair bonding; and (2) silicon lattice relaxation due to the atomic size difference which causes a local strain field. Our model explains qualitatively (1) trends among the iron-acceptor pairs revealing an increase of the electronic state hole emission energy with increasing principal quantum number of acceptor and decreasing pair separation distance; and (2) the stable and metastable sites and configurational symmetries of the iron-acceptor pairs. The iron-acceptor pairing and bonding mechanism is also discussed.

  17. Simulating Valence-to-Core X-ray Emission Spectroscopy of Transition Metal Complexes with Time-Dependent Density Functional Theory

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yu; Mukamel, Shaul; Khalil, Munira; Govind, Niranjan

    2015-11-09

    Valence-to-core (VtC) X-ray emission spectroscopy (XES) has emerged as a power- ful technique for the structural characterization of complex organometallic compounds in realistic environments. Since the spectrum represents electronic transitions from the ligand molecular orbitals to the core holes of the metal centers, the approach is more chemically sensitive to the metal-ligand bonding character compared with con- ventional X-ray absorption techniques. In this paper we study how linear-response time-dependent density functional theory (LR-TDDFT) can be harnessed to simulate K-edge VtC X-ray emission spectra reliably. LR-TDDFT allows one to go beyond the single-particle picture that has been extensively used to simulate VtC-XES. We con- sider seven low- and high-spin model complexes involving chromium, manganese and iron transition metal centers. Our results are in good agreement with experiment.

  18. A Model of Thermal Energy Storage According to the Convention of Bond Graphs (Bg and State Equations (Se

    Directory of Open Access Journals (Sweden)

    Cichy Marian

    2015-12-01

    Full Text Available The main advantage of the use of the Bond Graphs method and State Equations for modeling energy systems with a complex structure (marine power plants, hybrid vehicles, etc. is the ability to model the system components of different physical nature using identical theoretical basis. The paper presents a method of modeling thermal energy storage, which is in line with basic BG theory. Critical comments have been put forward concerning multiport energy storage introduced by other authors or the so-called C-field. In suggested approach, the decision not to use pseudo Bond Graphs has been justified as not being in line with basic BG theory. On the basis of molecular physics it was considered that the state variable, in physical and mathematical sense, should be temperature rather than entropy. Examples of the application of the proposed approach to thermodynamic processes and heat exchange have been presented. The application of a single graph as a model for thermal energy storage has been illustrated by a way of numerical simulation examples.

  19. Emotion perception and functional outcome in schizophrenia: the importance of negative valence and fear.

    Science.gov (United States)

    Brittain, Philip J; Ffytche, Dominic H; Surguladze, Simon A

    2012-12-30

    A substantial body of work has demonstrated that persons with schizophrenia have a deficit in the perception of emotional stimuli. More recently this deficit has been linked to poor functional outcomes (FO) in this group. The current research investigated the perception of emotional stimuli in a group of 64 schizophrenia patients and 65 matched healthy controls. In the patient group, across two different emotion perception tasks and a social perception task, small deficits were found in the perception of negative, positive and neutrally valenced stimuli. Only the ability to perceive negative and neutrally valenced stimuli significantly correlated with a set of FO measures in the patients, with one task indicating these associations were strongest for the perception of fear. Subsequent regression modelling, controlling for the effects of symptomatology, demonstrated that for each of the three tasks, the measure of negative valence perception accounted for a similar but small amount (4%) of the variance seen in the functional status of the patients.

  20. 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).

  1. Monte Carlo studies of the cubic lattice mixed-bond Ising model

    Science.gov (United States)

    Santos-Filho, J. B.; Moreno, N. O.; de Albuquerque, D. F.; de Arruda, A. S.

    2007-09-01

    In this work, we used the Cluster Wolff algorithms to simulate the dynamics of the system. We obtained the thermodynamic quantities such as magnetization and susceptibility. Critical temperatures were estimated at the maximum of the susceptibility and with these values we made the phase diagram, TC versus p (the concentration of magnetic bonds) for different α values, being α the competition parameter. Our results were compared to those obtained by using a new technique in the effective field theory which employs similar probability distribution within the framework of two-site clusters.

  2. Mechanism of gold solvent extraction from aurocyanide solution by quaternary amines: models of extracting species based on hydrogen bonding

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The mechanism of gold solvent extraction from KAu(CN)2 solution was investigated by means of FTIR, EXAFS, ICP and radioactive tracer methods. Two extraction systems were studied, namely N263-tributyl phosphate(TBP)-n-dodecane and N263-iso-octanol-n-dodecane. High-reso- lution FT IR spectroscopy indicated that the CN stretching vibrations of the two extraction systems differred greatly. In order to interpret the significant difference in CN stretching vibrations, two extracting species models are proposed supramolecular structures based on the formation of hydrogen bonds between Au(CN)2- and modifiers such as TBP and iso-octanol.

  3. Mechanism of gold solvent extraction from aurocyanide solution by quaternary amines: models of extracting species based on hydrogen bonding

    Institute of Scientific and Technical Information of China (English)

    马刚; 闫文飞; 陈景; 严纯华; 高宏成; 周维金; 施鼐; 吴谨光; 徐光宪; 黄昆; 余建民; 崔宁

    2000-01-01

    The mechanism of gold solvent extraction from KAu(CN)2 solution was investigated by means of FTIR, EXAFS, ICP and radioactive tracer methods. Two extraction systems were studied, namely N263-tributyl phosphate(TBP)-n-dodecane and N263-iso-octanol-n-dodecane. High-resolution FT IR spectroscopy indicated that the CN stretching vibrations of the two extraction systems differred greatly. In order to interpret the significant difference in CN stretching vibrations, twoextracting species models are proposed——supramolecular structures based on the formation ofhydrogen bonds between Au(CN)2- and modifiers such as TBP and iso-octanol.

  4. Molecular orbital study of coordinated dioxygen. I. Structure and bonding of model monomeric Co(II) complexes

    Science.gov (United States)

    Boča, R.

    1980-08-01

    The CNDO—UHF type of MO—LCAO—SCP calculation is carried out for model systems of dioxygen fixation: O 2 CoCl 4L 2- complexes in which L = none and L = NH 3. A geometry variation is performed with respect to 5 internal coordinates describing the degrees of freedom of the Co—O 2 group. The calculated geometry, spin densities and atomic charges agree with available data based on X-ray and ESR measurements of real dioxygen carriers. Structure and bonding of complexes are discussed in more detail.

  5. The valence electron structure and property analysis of TiC

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The valence electron structure of TiC was calculated by using the empirical electron theory of solids and molecules. The calculated results show that with the increase of temperature the number of common electrons of TiC increases, which indicates that TiC has a good thermal sta-bility; and there exists a close relationship between hardness and brittleness of TiC. According to the number of lattice electrons, the differences among the crystals with different structures can be explained qualitatively. Using the "bond- strengthening factor", the differences of hardness among the crystals with different structures can also be qualitatively explained to some extent.

  6. Pion's valence-quark GPD and its extension beyond DGLAP region

    CERN Document Server

    Mezrag, C; Rodríguez-Quintero, J

    2015-01-01

    We briefly report on a recent computation, with the help of a fruitful algebraic model, sketching the pion valence dressed-quark generalized parton distribution and, very preliminary, discuss on a possible avenue to get reliable results in both Dokshitzer-Gribov-Lipatov-Altarelli-Parisi (DGLAP) and Efremov-Radyushkin-Brodsky-Lepage (ERBL) kinematial regions.

  7. Determining binding energies of valence-band electrons in insulators and semiconductors via lanthanide spectroscopy

    NARCIS (Netherlands)

    Dorenbos, P.

    2013-01-01

    Models and methods to determine the absolute binding energy of 4f-shell electrons in lanthanide dopants will be combined with data on the energy of electron transfer from the valence band to a lanthanide dopant. This work will show that it provides a powerful tool to determine the absolute binding e

  8. Metallic bond effects on mean excitation energies for stopping powers

    Science.gov (United States)

    Wilson, J. W.; Xu, Y. J.

    1982-01-01

    Mean excitation energies for first row metals are evaluated by means of the local plasma approximation. Particle corrections based on Pines' (1953) procedure and the Wigner Seitz (1934) model of the metallic state are included. The agreement with experimental values is remarkably good. In contrast to previous work, the calculations given here estimate shifts in the plasma frequency according to the theory for plane wave states in an extended plasma as calculated by Pines. It is demonstrated that the effects of the metallic bond in lithium and beryllium are quite large and that they appear mainly as a result of collective oscillations in the 'free' electron gas formed from the valence electrons. The usefulness of the plasma frequency shift derived for a degenerate electron gas in predicting the plasma frequency shift within the ion core is considered surprising.

  9. Hydrogen bond and halogen bond inside the carbon nanotube

    Science.gov (United States)

    Wang, Weizhou; Wang, Donglai; Zhang, Yu; Ji, Baoming; Tian, Anmin

    2011-02-01

    The hydrogen bond and halogen bond inside the open-ended single-walled carbon nanotubes have been investigated theoretically employing the newly developed density functional M06 with the suitable basis set and the natural bond orbital analysis. Comparing with the hydrogen or halogen bond in the gas phase, we find that the strength of the hydrogen or halogen bond inside the carbon nanotube will become weaker if there is a larger intramolecular electron-density transfer from the electron-rich region of the hydrogen or halogen atom donor to the antibonding orbital of the X-H or X-Hal bond involved in the formation of the hydrogen or halogen bond and will become stronger if there is a larger intermolecular electron-density transfer from the electron-rich region of the hydrogen or halogen atom acceptor to the antibonding orbital of the X-H or X-Hal bond. According to the analysis of the molecular electrostatic potential of the carbon nanotube, the driving force for the electron-density transfer is found to be the negative electric field formed in the carbon nanotube inner phase. Our results also show that the X-H bond involved in the formation of the hydrogen bond and the X-Hal bond involved in the formation of the halogen bond are all elongated when encapsulating the hydrogen bond and halogen bond within the carbon nanotube, so the carbon nanotube confinement may change the blue-shifting hydrogen bond and the blue-shifting halogen bond into the red-shifting hydrogen bond and the red-shifting halogen bond. The possibility to replace the all electron nanotube-confined calculation by the simple polarizable continuum model is also evaluated.

  10. Néel to spin-Peierls transition in a quasi-one-dimensional Heisenberg model coupled to bond phonons

    Science.gov (United States)

    Pillay, Jason Cornelius; Wierschem, Keola; Sengupta, Pinaki

    2013-08-01

    The zero and finite temperature spin-Peierls transitions in a quasi-one-dimensional spin-(1)/(2) Heisenberg model coupled to adiabatic bond phonons is investigated using the stochastic series expansion (SSE) quantum Monte Carlo (QMC) method. The quantum phase transition from a gapless Néel state to a spin-gapped Peierls state is studied in the parameter space spanned by spatial anisotropy, interchain coupling strength, and spin-lattice coupling strength. It is found that for any finite interchain coupling, the transition to a dimerized Peierls ground state only occurs when the spin-lattice coupling exceeds a finite, nonzero critical value. This is in contrast to the pure 1D model (zero interchain coupling), where adiabatic/classical phonons lead to a dimerized ground state for any nonzero spin-phonon interaction. The phase diagram in the parameter space shows that for a strong interchain coupling, the relation between the interchain coupling and the critical value of the spin-phonon interaction is linear whereas for weak interchain coupling, this behavior is found to have a natural logarithmlike relation. No region was found to have a long range magnetic order and dimerization occurring simultaneously. Instead, the Néel state order vanishes simultaneously with the setting in of the spin-Peierls state. For the thermal phase transition, a continuous heat capacity with a peak at the critical temperature Tc shows a second order phase transition. The variation of the equilibrium bond length distortion δeq with temperature showed a power law relation which decayed to zero as the temperature was increased to Tc, indicating a continuous transition from the dimerized phase to a paramagnetic phase with uniform bond length and zero antiferromagnetic susceptibility.

  11. 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

  12. Activation of a Carbon-Oxygen Bond of Benzofuran by Precoordination of Manganese to the Carbocyclic Ring: A Model for Hydrodeoxygenation.

    Science.gov (United States)

    Zhang; Watson; Dullaghan; Gorun; Sweigart

    1999-08-01

    Stable unsaturated heterocycles such as benzofuran are difficult to remove from petroleum by conventional catalytic hydrotreating. However, in a model system, coordination of Mn(CO)(3)(+) to the aromatic ring of benzofuran activates the C-O bond towards insertion of [Pt(PPh(3))(2)] [Eq. (1)]. The insertion is preceded by precoordination to the furan C=C bond; thus, the 2,3-dihydro analogue of 1, which lacks this double bond, does not undergo insertion of the Pt moiety.

  13. Valence framing of political preferences and resistance to persuasion

    Directory of Open Access Journals (Sweden)

    Žeželj Iris

    2007-01-01

    Full Text Available This study tested the "valence framing effect": an assumption that negatively conceptualized attitudes (as opposing the non-preferred alternative are more resistant to later persuasion attempts. In the experiment we created choice between two political candidates and experimental subjects were led to conceptualize their political preferences in one of two possible ways: either as supporting the preferred candidate or as opposing the non-preferred candidate. The data indicate that negative preferences show less overall change when exposed to counterarguments. This finding can be incorporated in two theoretical frameworks: dual process theories of attitude change (Elaboration likelihood model and descriptive decision making theories (Prospect theory. Results are discussed for their implications for the efficacy of political communication. .

  14. How do attachment dimensions affect bereavement adjustment? A mediation model of continuing bonds.

    Science.gov (United States)

    Yu, Wei; He, Li; Xu, Wei; Wang, Jianping; Prigerson, Holly G

    2016-04-30

    The current study aims to examine mechanisms underlying the impact of attachment dimensions on bereavement adjustment. Bereaved mainland Chinese participants (N=247) completed anonymous, retrospective, self-report surveys assessing attachment dimensions, continuing bonds (CB), grief symptoms and posttraumatic growth (PTG). Results demonstrated that attachment anxiety predicted grief symptoms via externalized CB and predicted PTG via internalized CB at the same time, whereas attachment avoidance positively predicted grief symptoms via externalized CB but negatively predicted PTG directly. Findings suggested that individuals with a high level of attachment anxiety could both suffer from grief and obtain posttraumatic growth after loss, but it depended on which kind of CB they used. By contrast, attachment avoidance was associated with a heightened risk of maladaptive bereavement adjustment. Future grief therapy may encourage the bereaved to establish CB with the deceased and gradually shift from externalized CB to internalized CB.

  15. Mulliken-Hush analysis of a bis(triarylamine) mixed-valence system with a N...N distance of 28.7 A.

    Science.gov (United States)

    Heckmann, Alexander; Amthor, Stephan; Lambert, Christoph

    2006-07-28

    An organic mixed valence compound with a spacer length of 25 unsaturated bonds separating two amine redox centres was synthesised and the electron transfer behaviour was investigated in the context of a Mulliken-Hush analysis in order to estimate the longest redox centre separation for which an intervalence charge transfer band can be observed.

  16. 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.

  17. 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.

  18. Mathematical Simulation of Graphene With Modified c-c Bond Length and Transfer Energy

    Directory of Open Access Journals (Sweden)

    P.A. Alvi

    2011-01-01

    Full Text Available In nanotechnology research, allotropes of carbon like Graphene, Fullerene (Buckyball and Carbon nanotubes are widely used due to their remarkable properties. Electrical and mechanical properties of those allotropes vary with their molecular geometry. This paper is specially based on modeling and simulation of graphene in order to calculate energy band structure in k space with varying the C-C bond length and C-C transfer energy. Significant changes have been observed in the energy band structure of graphene due to variation in C-C bond length and C-C transfer energy. In particular, this paper focuses over the electronic structure of graphene within the frame work of tight binding approximation. It has been reported that conduction and valence states in graphene only meet at two points in k-space and that dispersion around these special points is conical.

  19. Prediction of valence and arousal from music features

    NARCIS (Netherlands)

    Den Brinker, A.C.; Van Dinther, C.H.B.A.; Skowronek, J.

    2011-01-01

    Mood is an important attribute of music and knowledge on mood can beused as a basic ingredient in music recommender and retrieval systems. Moods are assumed to be dominantly determined by two dimensions:valence and arousal. An experiment was conducted to attain data forsong-based ratings of valence

  20. Valency, Secondary Frequency, and Lexical Access: A Japanese Study.

    Science.gov (United States)

    Yamada, Jun; Kayamoto, Yuriko

    1998-01-01

    A study examined the effects of valency (associative value representing the number of two-kanji words containing the first-positional kanji of the word) on recognition of two-kanji words in Japanese. Frequency and valency of the first constituent kanji were significant factors for word recognition, and frequency of the first constituent kanji was…

  1. DFT modeling and spectroscopic study of metal-ligand bonding in La(III) complex of coumarin-3-carboxylic acid

    Energy Technology Data Exchange (ETDEWEB)

    Mihaylov, Tz. [Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Trendafilova, N. [Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria)], E-mail: ntrend@svr.igic.bas.bg; Kostova, I. [Department of Chemistry, Faculty of Pharmacy, Medical University, Sofia 1000 (Bulgaria); Georgieva, I. [Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Bauer, G. [Institute of Chemical Technologies and Analytics, Technical University of Vienna, Vienna A-1060 (Austria)

    2006-09-11

    The binding mode of coumarin-3-carboxylic acid (HCCA) to La(III) is elucidated at experimental and theoretical level. The complexation ability of the deprotonated ligand (CCA{sup -}) to La(III) is studied using elemental analysis, DTA and TGA data as well as FTIR, {sup 1}H NMR and {sup 13}C NMR spectra. The experimental data suggest the complex formula La(CCA){sub 2}(NO{sub 3})(H{sub 2}O){sub 2}. B3LYP, BHLYP, B3P86, B3PW91, PW91P86 and MPW1PW91 functionals are tested for geometry and frequency calculations of the neutral ligand and all of them show bond length deviations bellow 1%. B3LYP/6-31G(d) level combined with large quasi-relativistic effective core potential for lanthanum is selected to describe the molecular, electronic and vibrational structures as well as the conformational behavior of HCCA, CCA{sup -} and La-CCA complex. The metal-ligand binding mode is predicted through molecular modeling and energy estimation of different La-CCA structures. The calculated atomic charges and the bonding orbital polarizations point to strong ionic metal-ligand bonding in La-CCA complex and insignificant donor acceptor interaction. Detailed vibrational analysis of HCCA, CCA{sup -} and La(CCA){sub 2}(NO{sub 3})(H{sub 2}O){sub 2} systems based on both calculated and experimental frequencies confirms the suggested metal-ligand binding mode.

  2. 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....

  3. Exploring the Strength of the H-Bond in Synthetic Models for Heme Proteins: The Importance of the N-H Acidity of the Distal Base.

    Science.gov (United States)

    Alberti, Mariza N; Polyhach, Yevhen; Tzirakis, Manolis D; Tödtli, Laura; Jeschke, Gunnar; Diederich, François

    2016-07-11

    The distal hydrogen bond (H-bond) in dioxygen-binding proteins is crucial for the discrimination of O2 with respect to CO or NO. We report the preparation and characterization of a series of Zn(II) porphyrins, with one of three meso-phenyl rings bearing both an alkyl-tethered proximal imidazole ligand and a heterocyclic distal H-bond donor connected by a rigid acetylene spacer. Previously, we had validated the corresponding Co(II) complexes as synthetic model systems for dioxygen-binding heme proteins and demonstrated the structural requirements for proper distal H-bonding to Co(II) -bound dioxygen. Here, we systematically vary the H-bond donor ability of the distal heterocycles, as predicted based on pKa values. The H-bond in the dioxygen adducts of the Co(II) porphyrins was directly measured by Q-band Davies-ENDOR spectroscopy. It was shown that the strength of the hyperfine coupling between the dioxygen radical and the distal H-atom increases with enhanced acidity of the H-bond donor.

  4. Bond Boom

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen,and Zhejiang and Guangdong provinces to issue bonds for the first time.How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the Shanghai Securities Journal.Edited excerpts follow.

  5. Bond Boom

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen, and Zhejiang and Guangdong provinces to issue bonds for the first time. How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the ShanghaiSecuritiesJournal. Edited excerpts follow:

  6. Structure and Bonding Investigation of Plutonium Peroxocarbonate Complexes Using Cerium Surrogates and Electronic Structure Modeling

    Energy Technology Data Exchange (ETDEWEB)

    Sweet, Lucas E.; Corbey, Jordan F.; Gendron, Frédéric; Autschbach, Jochen; McNamara, Bruce K.; Ziegelgruber, Kate L.; Arrigo, Leah M.; Peper, Shane M.; Schwantes, Jon M.

    2017-12-29

    Herein, we report the synthesis and structural characterization of K8[(CO3)3Pu]2(µ-η2-η2-O2)2•12H2O. This is the second plutonium-containing addition to the previously studied alkali metal peroxo-carbonate series M8[(CO3)3A]2(µ-η2-η2-O2)2•xH2O (M = alkali metal; A = Ce or Pu; x = 8, 10, 12 or 18), for which only the M = Na analog has been previously reported when A = Pu. The previously reported crystal structure for Na8[(CO3)3Pu]2(µ-η2-η2-O2)2•12H2O is not isomorphous with its known Ce analogue. However, a new synthetic route to these M8[(CO3)3A]2(µ-η2-η2-O2)2•12H2O complexes, described below, has produced crystals of Na8[(CO3)3Ce]2(µ-η2-η2-O2)2•12H2O that are isomorphous with the previously reported Pu analogue. Via this synthetic method, the M = Na, K, Rb, and Cs salts of M8[(CO3)3Ce]2(µ-η2-η2-O2)2•xH2O have also been synthesized for systematic structural comparison with each other and the available Pu analogues using single-crystal X-ray diffraction, Raman spectroscopy and density functional theory (DFT) calculations. The cerium salts in particular demonstrate subtle differences in the peroxide bond lengths which correlate to Raman shifts for the peroxide Op–Op stretch (Op = the oxygen atoms of the peroxide bridges) with each of the cations studied: Na+ (1.492(3) Å /847 cm-1), Rb+ (1.471(1) Å /854 cm-1), Cs+ (1.474(1) Å /859 cm-1), and K+ (1.468(6) Å, 870 cm-1). The trends observed in the M–Op and Op–Op bond distances appear to relate to supermolecular interactions between the neighboring cations.

  7. Atomic volume, atomic distances and chemical bonding in solid metallic elements; Atomvolumen, Atomabstaende und chemische Bindung in festen metallischen Elementen

    Energy Technology Data Exchange (ETDEWEB)

    Troemel, M.; Huebner, S. [Frankfurt Univ. (Germany). Inst. fuer Anorganische Chemie

    2001-05-01

    Relationships between bond lengths and bond numbers and also between atomic volumes and valencies are derived and parameters for their calculation are given for the s-block, p-block, and d-block metals. From the atomic volumes under pressure, the valencies of three solid lanthanoids have been confirmed or redetermined: La 3; Ce 2, 3, and 4; Yb 2 and 3. (orig.)

  8. Silver- and gold-mediated nucleobase bonding.

    Science.gov (United States)

    Acioli, Paulo H; Srinivas, Sudha

    2014-08-01

    We report the results of a density functional theory investigation of the bonding of nucleobases mediated by silver and gold atoms in the gas phase. Our calculations use the Becke exchange and Perdew-Wang correlation functional (BPW91) combined with the Stuttgart effective core potentials to represent the valence electrons of gold, silver, and platinum, and the all-electron DGTZVP basis set for C, H, N, and O. This combination was chosen based on tests on the metal atoms and tautomers of adenine, cytosine, and guanine. To establish a benchmark to understand the metal-mediated bonding, we calculated the binding energy of each of the base pairs in their canonical forms. Our calculations show rather strong bonds between the Watson-Crick base pairs when compared with typical values for N-H-N and N-H-O hydrogen bonds. The neutral metal atoms tend to bond near the nitrogen atoms. The effect of the metal atoms on the bonding of nucleobases differs depending on whether or not the metal atoms bond to one of the hydrogen-bonding sites. When the silver or gold atoms bond to a non-hydrogen-bonding site, the effect is a slight enhancement of the cytosine-guanine bonding, but there is almost no effect on the adenine-thymine pairing. The metal atoms can block one of the hydrogen-bonding sites, thus preventing the normal cytosine-guanine and adenine-thymine pairings. We also find that both silver and gold can bond to consecutive guanines in a similar fashion to platinum, albeit with a significantly lower binding energy.

  9. FT-IR and computer modeling study of hydrogen bonding in N-alkyl acrylamide-toluene binary mixtures

    Science.gov (United States)

    Rumyantsev, Misha; Kazantsev, Oleg A.; Kamorina, Sofia I.; Kamorin, Denis M.; Sivokhin, Alexey P.

    2016-10-01

    Degree of hydrogen bonding driven self-association of N-(n-butyl)acrylamide, N-(n-octyl)acrylamide, N-(sec-octyl)acrylamide and N-(tert-octyl)acrylamide in toluene was investigated using IR spectroscopy and computer modeling methods. Consistent results were demonstrated in the treatment of the Amide-I (νC=O), Amide-II (δN-H and νC-N) and Amide-A (νN-H) absorption bands in IR spectra. Thus, the content of non-bonded (free) amide groups decreases from 83-98% to 8-20% and the content of linear polyassociates increases to 80-90% with an increase in monomer concentration from 0.5 wt% to 50 wt%. The content of cyclic dimers was equal to the value between 5 and 10% regardless of the initial monomer concentration. Dependences of the association degree and the content of the linear polyassociates on the concentration were found to be similar for all of the studied amides.

  10. A Molecular Perspective of Inter-filament Bonding in Fused Deposition Modeling 3-D Printing

    Science.gov (United States)

    Duranty, Edward; Spradlin, Brandon; Dadmun, Mark

    2015-03-01

    Fused deposition 3D printing is an important tool for low-cost and rapid prototyping of objects with complex geometries. 3D printed materials are composed of many filaments deposited on a heated substrate, requiring the bonding of neighboring filaments during the deposition process. Filament deposition often creates voids between filaments, which requires necking between them to create a robust sample. Therefore the amount of interfacial contact and interdiffusion between filaments become important parameters that control the macroscopic physical properties of the printed prototype. Our research focuses on quantifying the interfacial adhesion between ABS filaments and its impact on structural properties. The time evolution of the temperature profile near the heated substrate demonstrates that the deposited filaments are repeatedly heated above the Tg of ABS allowing interpenetration of the polymer chains between adjacent filaments. Results of DMA experiments on samples of different geometries have been correlated to microphotography that monitors the degree of necking between filaments and the thermal history. Results indicate that interfacial contact area between filaments and increased thermal energy are crucial to their mechanical properties.

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

    Science.gov (United States)

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

    2009-03-01

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

  13. Modeling the conformational preference of the carbon-bonded covalent adduct formed upon exposure of 2'-deoxyguanosine to ochratoxin A.

    Science.gov (United States)

    Sharma, Purshotam; Manderville, Richard A; Wetmore, Stacey D

    2013-05-20

    The conformational flexibility of the C8-linked guanine adduct formed from attachment of ochratoxin A (OTA) was analyzed using a systematic computational approach and models ranging from the nucleobase to the adducted DNA helix. A focus was placed on the influence of the C8-modification of 2'-deoxyguanosine (dG) on the preferred relative arrangement of the nucleobase and the C8-substituent and, more importantly, the anti/syn conformational preference with respect to the glycosidic bond. Although OTA is twisted with respect to the base in the nucleobase model, addition of the deoxyribose sugar induces a further twist and restricts rotation about the C-C linkage due to close contacts between OTA and the sugar. The nucleoside model preferentially adpots a syn orientation (by 10-20 kJ mol(-1) depending on the OTA conformation) due to the presence of an O5'-H···N3 interaction. However, when this hydrogen bond is eliminated, which better mimics the DNA environment, a small (simulations and free energy analysis predict that both syn- and anti-conformations of OTB-dG are equally stable in helices when paired opposite cytosine. These results indicate that the adduct will likely adopt a syn conformation in an isolated nucleoside and nucleotide, while a mixture of syn and anti conformations will be observed in DNA duplexes. Since the syn conformation could stabilize base mismatches upon DNA replication or Z-DNA structures with varied biological outcomes, future computational and experimental work should elucidate the consequences of the conformational preference of this potentially harmful DNA lesion.

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

    Science.gov (United States)

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

    2016-08-01

    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 in full depletion. In a first step, Synopsys Sentaurus TCAD is used to evaluate the soundness of this technique for interface traps characterization such as it may happen in bonded interfaces. Next, an analytical model is developed in details to give a better insight into the physics behind the TCT for interface layers. Further, this can be used as a simple tool to evidence what are the relevant parameters influencing the TCT signal and to set the basis for preliminary characterizations.

  15. Theoretical study on O$\\cdots$Br and O$\\cdots$Cl halogen bonds in some small model molecular systems

    Indian Academy of Sciences (India)

    Damanjit Kaur; Rajinder Kaur

    2014-11-01

    Halogen bonding interactions of type X$\\cdots$O=C are important in various fields including biological 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$\\cdots$X halogen bonds between CH2O andCH3CHO as halogen bond acceptor with X-Y (X = Cl, Br; Y = CF3, CF2 H, CFH2, CN, CCH, CCCN) as halogen bond donors. The strength of interaction energy for O$\\cdots$Br halogen-bonded complexes varies from −2.16 to −5.26 kcal/mol while for O$\\cdots$Cl complexes, it is between −1.65 to −3.67 kcal/mol, which indicate the O$\\cdots$Br bond to be stronger in comparison to O$\\cdots$Cl bond. SAPT analysis suggests that the strength of halogen bonding arises from the electrostatic and induction forces while dispersion is playing a comparatively smaller role. The halogen-bonded interaction energies were found to correlate well with positive electrostatic potential VS,max, halogen bonded distances, and the change in s-character of C-X bond. The halogen-bonded interaction energies were also evaluated for O$\\cdots$I bonded complexes and thus these complexes were found to be stronger than O$\\cdots$Br and O$\\cdots$Cl bonded complexes.

  16. Schwinger boson approach to the fully screened Kondo model.

    Science.gov (United States)

    Rech, J; Coleman, P; Zarand, G; Parcollet, O

    2006-01-13

    We apply the Schwinger boson scheme to the fully screened Kondo model and generalize the method to include antiferromagnetic interactions between ions. Our approach captures the Kondo crossover from local moment behavior to a Fermi liquid with a nontrivial Wilson ratio. When applied to the two-impurity model, the mean-field theory describes the "Varma-Jones" quantum phase transition between a valence bond state and a heavy Fermi liquid.

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

    Energy Technology Data Exchange (ETDEWEB)

    Oeiras, R. Y.; Silva, E. Z. da [Institute of Physics “Gleb Wataghin”, University of Campinas-Unicamp, 13083-859 Campinas, SP (Brazil)

    2014-04-07

    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.

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

    Science.gov (United States)

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

    2014-04-01

    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.

  19. Temperature dependency of the silicon heterojunction lifetime model based on the amphoteric nature of dangling bonds

    Science.gov (United States)

    Vasudevan, R.; Poli, I.; Deligiannis, D.; Zeman, M.; Smets, A. H. M.

    2016-11-01

    This work adapts a model to simulate the carrier injection dependent minority carrier lifetime of crystalline silicon passivated with hydrogenated amorphous silicon at elevated temperatures. Two existing models that respectively calculate the bulk lifetime and surface recombination velocity are used and the full temperature dependency of these models are explored. After a thorough description of these temperature dependencies, experimental results using this model show that the minority carrier lifetime changes upon annealing of silicon heterojunction structures are not universal. Furthermore, comparisons of the temperature dependent model to using the room temperature model at elevated temperatures is given and significant differences are observed when using temperatures above 100 °C. This shows the necessity of taking temperature effects into account during in-situ annealing experiments.

  20. Positron annihilation with core and valence electrons

    CERN Document Server

    Green, D G

    2015-01-01

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

  1. 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...

  2. One Way to Design a Valence-Skip Compound

    Science.gov (United States)

    Hase, I.; Yanagisawa, T.; Kawashima, K.

    2017-02-01

    Valence-skip compound is a good candidate with high T c and low anisotropy because it has a large attractive interaction at the site of valence-skip atom. However, it is not easy to synthesize such compound because of (i) the instability of the skipping valence state, (ii) the competing charge order, and (iii) that formal valence may not be true in some compounds. In the present study, we show several examples of the valence-skip compounds and discuss how we can design them by first principles calculations. Furthermore, we calculated the electronic structure of a promising candidate of valence skipping compound RbTlCl3 from first principles. We confirmed that the charge-density wave (CDW) is formed in this compound, and the Tl atoms in two crystallographic different sites take the valence Tl1+ and Tl3+. Structure optimization study reveals that this CDW is stable at the ambient pressure, while this CDW gap can be collapsed when we apply pressure with several gigapascals. In this metallic phase, we can expect a large charge fluctuation and a large electron-phonon interaction.

  3. 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.

  4. Valence electron structure and properties of the ZrO2

    Institute of Scientific and Technical Information of China (English)

    LI JinPing; MENG SongHe; HAN JieCai; ZHANG XingHong

    2008-01-01

    To reveal the properties of ZrO2 at the atom and electron levels, the valence elec-tron structures of three ZrO2 phases were analyzed on the basis of the empirical electron theory of solids and molecules. The results showed that the hybridization levels of Zr and O atoms in the m-ZrO2 were the same as those in the t-ZrO2, while those in the c-ZrO2 rose markedly. The electron numbers and bond energies on the strongest covalent bonds in the m-ZrO2 phase were the greatest, the values were 0.901106 and 157.5933 kJ/mol, respectively. Those in the t-ZrO2 phase took second place, which were 0.722182 and 123.9304 kJ/mol, and those in the c-ZrO2 phase were the smallest, which were 0.469323 and 79.0289 kJ/mol. According to the product of the bond energy on the strongest covalent bond and equivalent bond number (this value reflected the crystal cohesive energy), the order from the greatness to smallness was the c-ZrO2 t-ZrO2 m-ZrO2. This showed that the m-phase bonds were the tightest, their energy was the smallest, the crystal cohe-sive energy of the m-phase was the largest, and the m-phase existed most stably at room temperature. So it must need energy or higher temperature to take apart the stronger covalent bonds to form a new phase.

  5. Chemical Bond Parameters in Sr3MRhO6 (M=Rare earth)

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Chemical bond parameters, that is, bond covalency, bond valence, macroscopic linear susceptibility, and oxidation states of elements in Sr3MRhO6 (M=Sm, Eu, Tb, Dy, Ho, Er, Yb) have been calculated. The results indicate that the bond covalency of M-O decreases sharply with the decrease of ionic radius of M3+ from Sm to Yb, while no obvious trend has been found for Rh-O and Sr-O bonds. The global instability index indicates that the crystal structures of Sr3MrhO6 (M = Sm, Eu, Tb, Dy, Ho) have strained bonds.

  6. Port-Based Modeling of Dynamic Systems in Terms of Bond Graphs

    NARCIS (Netherlands)

    Breedveld, Peter C.; Troch, I.; Breitenecker, F.

    2006-01-01

    Port-based modeling of dynamic systems is the topic of the first chapter of the book that will be one of the main results of the European project ‘Geometric Network Modeling and Control of Complex Physical Systems’ (GEOPLEX, IST-2001-34166, Key Action, Action line KAIV: Essential Technologies and In

  7. A novel diffusion model considering curvature radius at the bonding interface in a titanium/steel explosive clad plate

    Institute of Scientific and Technical Information of China (English)

    Hai-tao Jiang; Qiang Kang; Xiao-qian Yan

    2015-01-01

    This article introduces an element diffusion behavior model for a titanium/steel explosive clad plate characterized by a typical curved interface during the heat-treatment process. A series of heat-treatment experiments were conducted in the temperature range from 750°C to 950°C, and the effects of heat-treatment parameters on the microstructural evolution and diffusion behavior were investigated by optical microscopy, scanning electron microscopy, X-ray diffraction analysis, and electron-probe microanalysis. Carbon atoms within the steel matrix were observed to diffuse toward the titanium matrix and to aggregate at the bonding interface at 850°C or lower;in contrast, when the temperature exceeded 850°C, the mutual diffusion of Ti and Fe occurred, along with the diffusion of C atoms, resulting in the for-mation of Ti–Fe intermetallics (Fe2Ti/FeTi). The diffusion distances of C, Ti, and Fe atoms increased with increasing heating temperature and/or holding time. On the basis of this diffusion behavior, a novel diffusion model was proposed. This model considers the effects of vari-ous factors, including the curvature radius of the curved interface, the diffusion coefficient, the heating temperature, and the holding time. The experimental results show good agreement with the calculated values. The proposed model could clearly provide a general prediction of the elements’ diffusion at both straight and curved interfaces.

  8. Thermal-mechanical-chemical responses of polymer-bonded explosives using a mesoscopic reactive model under impact loading.

    Science.gov (United States)

    Wang, XinJie; Wu, YanQing; Huang, FengLei

    2017-01-05

    A mesoscopic framework is developed to quantify the thermal-mechanical-chemical responses of polymer-bonded explosive (PBX) samples under impact loading. A mesoscopic reactive model is developed for the cyclotetramethylenetetranitramine (HMX) crystal, which incorporates nonlinear elasticity, crystal plasticity, and temperature-dependent chemical reaction. The proposed model was implemented in the finite element code ABAQUS by the user subroutine VUMAT. A series of three-dimensional mesoscale models were constructed and calculated under low-strength impact loading scenarios from 100m/s to 600m/s where only the first wave transit is studied. Crystal anisotropy and microstructural heterogeneity are responsible for the nonuniform stress field and fluctuations of the stress wave front. At a critical impact velocity (≥300m/s), a chemical reaction is triggered because the temperature contributed by the volumetric and plastic works is sufficiently high. Physical quantities, including stress, temperature, and extent of reaction, are homogenized from those across the microstructure at the mesoscale to compare with macroscale measurements, which will advance the continuum-level models. The framework presented in this study has important implications in understanding hot spot ignition processes and improving predictive capabilities in energetic materials.

  9. Valence Parity Renders z•-Type Ions Chemically Distinct

    OpenAIRE

    Hubler, Shane L.; Jue, April; Keith, Jason; McAlister, Graeme C.; Craciun, Gheorghe; Coon, Joshua J.

    2008-01-01

    Here we report that the odd electron z•-type ions formed by the electron-based peptide dissociation methods (electron capture or transfer, ECD or ETD) have distinctive chemical compositions from other common product ion types. Specifically, b-, c-, and y-type ions have an odd number of atoms with an odd valence (e.g., N and H), while z•-type ions contain an even number of atoms with an odd valence. This tenet, referred to as the valence parity rule, mandates that no c-type ion shall have the ...

  10. 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.

  11. 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

    are fixed) and two-component models. The effect of stability switchings, discovered previously for a class of one-component kink-bearing models, is shown to exist in these two-component models as well. However, the presence of the second component, i.e., the softness of the heavy-ion sublattice, brings...... principal differences, like a significant difference in the stability switchings behavior for the kinks and the antikinks. Water-filled carbon nanotubes are briefly discussed as possible realistic systems, where topological discrete (anti)kink states might exist....

  12. 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. .

  13. A finite element modelling methodology for the non-linear stiffness evaluation of adhesively bonded single lap-joints. Part 2, Novel shell mesh to minimise analysis time

    OpenAIRE

    Pearson, Ian T.; Mottram, J. Toby

    2012-01-01

    A new modelling methodology is presented that enables the stiffness of adhesively bonded single lap-joints to be included in the finite element analysis of whole vehicle bodies. This work was driven by the need to significantly reduce computing resources for vehicle analysis. To achieve this goal the adhesive bond line and adherends are modelled by a relatively ‘small’ number of shell elements to replace the usual solid element mesh for a reliable analysis. Previous work in Part 1 has provide...

  14. 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.

  15. Dynamic modeling and analysis of the PZT-bonded composite Timoshenko beams: Spectral element method

    Science.gov (United States)

    Lee, Usik; Kim, Daehwan; Park, Ilwook

    2013-03-01

    The health of thin laminated composite beams is often monitored using the ultrasonic guided waves excited by wafer-type piezoelectric transducers (PZTs). Thus, for the smart composite beams which consist of a laminated composite base beam and PZT layers, it is very important to develop a very reliable mathematical model and to use a very accurate computational method to predict accurate dynamic characteristics at very high ultrasonic frequency. In this paper, the axial-bending-shear-lateral contraction coupled differential equations of motion are derived first by the Hamilton's principle with Lagrange multipliers. The smart composite beam is represented by a Timoshenko beam model by adopting the first-order shear deformation theory (FSDT) for the laminated composite base beam. The axial deformation of smart composite beam is improved by taking into account the effects of lateral contraction by adopting the concept of Mindlin-Herrmann rod theory. The spectral element model is then formulated by the variation approach from coupled differential equations of motion transformed into the frequency domain via the discrete Fourier transform. The high accuracy of the present spectral element model is verified by comparing with other solution methods: the finite element model developed in this paper and the commercial FEA package ANSYS. Finally the dynamics and wave characteristics of some example smart composite beams are investigated through the numerical studies.

  16. Analysis of the valence electronic structures and calculation of the physical properties of Fe,Co,and Ni

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The valence electronic structures of Fe, Co and Ni have been investigated with Empirical Electron Theory of Solids and Molecules. The magnetic moments, Curie temperature, cohesive energy and melting point have been calculated according to the valence electronic structure. These calculations fit the experimental data very well. Based on the calculations, the magnetic moments are proportional to the number of 3d magnetic electrons. Curie temperatures are related to the magnetic electrons and the bond lengths between magnetic atoms. Cohesive energies increase with the increase of the number of covalent electrons, and the decrease of the number of magnetic and dumb pair electrons. The melting point is mainly related to the number of covalent electron pairs distributed in the strongest bond. The contribution from the lattice electrons is very small, the dumb pair electrons weaken the melting point; however, the contribution to melting point of the magnetic electrons can be neglected. It reveals that the magnetic and thermal properties are closely related to the valence electronic structures, and the changes or transitions between the electrons obviously affect the physical properties.

  17. Analysis of the valence electronic structures and calculation of the physical properties of Fe, Co, and Ni

    Institute of Scientific and Technical Information of China (English)

    WU WenXia; XUE ZhiYong; HONG Xing; LI XiuMei; GUO YongQuan

    2009-01-01

    The valence electronic structures of Fe, Co and Ni have been investigated with Empirical Electron Theory of Solids and Molecules. The magnetic moments, Curie temperature, cohesive energy and melting point have been calculated according to the valence electronic structure. These calculations fit the experimental data very well. Based on the calculations, the magnetic moments are proportional to the number of 3d magnetic electrons. Curie temperatures are related to the magnetic electrons and the bond lengths between magnetic atoms. Cohesive energies increase with the increase of the number of covalent electrons, and the decrease of the number of magnetic and dumb pair electrons. The melting point is mainly related to the number of covalent electron pairs distributed in the strongest bond. The contribution from the lattice electrons is very small, the dumb pair electrons weaken the melting point; however, the contribution to melting point of the magnetic electrons can be neglected. It reveals that the magnetic and thermal properties are closely related to the valence electronic structures, and the changes or transitions between the electrons obviously affect the physical properties.

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

    Science.gov (United States)

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

    2016-05-01

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

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

    Science.gov (United States)

    Gagné, Olivier Charles; Hawthorne, Frank Christopher

    2016-08-01

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

  20. A New Optimum Frequency Controller of Hybrid Pumping System: Bond Graph Modeling-Simulation and Practice with ARDUINO Board

    Directory of Open Access Journals (Sweden)

    MEZGHANI Dhafer

    2017-01-01

    Full Text Available The strategy of rural development in Tunisia needs to include as one of its priorities: the control of water. In seeking solutions for the energy control dedicated to pumping, it seems interesting to know the benefits of a new technique based on the complementarities of two renewable energy sources such as solar and wind power. The climate’s dependence requires a complex modelling and more optimization methods for controlling of hybrid system. Moreover, in recent years, technological progression at hardware and software enables researchers to process these optimization problems using embedded platforms. For this paper, we apply the approach bond graph to model a complex system. Our hybrid pumping installation contains a photovoltaic generator, a wind source, converters and an induction motor-pump group. The numerical closed-loop simulation of the complete model in an appropriate environment allows us to generate an optimisation control whose the appropriate frequency depends on meteorological conditions (wind speed, insulation and temperature. The implementation of this control and the experimental measurements validate the optimum efficiency and verify operation reliability of our hybrid structure.

  1. 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.

  2. A New Lease of Life for Thomson's Bonds Model of Intelligence

    Science.gov (United States)

    Bartholomew, David J.; Deary, Ian J.; Lawn, Martin

    2009-01-01

    Modern factor analysis is the outgrowth of Spearman's original "2-factor" model of intelligence, according to which a mental test score is regarded as the sum of a general factor and a specific factor. As early as 1914, Godfrey Thomson realized that the data did not require this interpretation and he demonstrated this by proposing what became…

  3. 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

  4. 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…

  5. Trait valence and the better-than-average effect.

    Science.gov (United States)

    Gold, Ron S; Brown, Mark G

    2011-12-01

    People tend to regard themselves as having superior personality traits compared to their average peer. To test whether this "better-than-average effect" varies with trait valence, participants (N = 154 students) rated both themselves and the average student on traits constituting either positive or negative poles of five trait dimensions. In each case, the better-than-average effect was found, but trait valence had no effect. Results were discussed in terms of Kahneman and Tversky's prospect theory.

  6. Bond Growth under Temperature Gradient.

    Directory of Open Access Journals (Sweden)

    P.K. Satyawali

    1999-12-01

    Full Text Available Grain and bond growth for dry snow are determined by the distribution of temperature andtemperature gradient in the snow matrix. From the standpoint of particle approach and based oncubic packing structure, a bond growth model has been developed for TG metamorphism. The paper.highlights the importance of bond formation and its effect on snow viscosity and finally on the rateof settlement. This is very important for developing a numerical snow pack model if microstructureis considered to be a basic parameter. A few experiments have been carried out to validate bond formation under temperature gradient.

  7. The random-bond Ising model in 2.01 and 3 dimensions

    Science.gov (United States)

    Komargodski, Zohar; Simmons-Duffin, David

    2017-04-01

    We consider the Ising model between 2 and 4 dimensions perturbed by quenched disorder in the strength of the interaction between nearby spins. In the interval 2  group. At d  =  2 such disorder is marginally irrelevant and can be studied using conformal perturbation theory. Combining conformal perturbation theory with recent results from the conformal bootstrap we compute some scaling exponents in an expansion around d  =  2. If one trusts these computations also in d  =  3, one finds results consistent with experimental data and Monte Carlo simulations. In addition, we perform a direct uncontrolled computation in d  =  3 using new results for low-lying operator dimensions and OPE coefficients in the 3d Ising model. We compare these new methods with previous studies. Finally, we comment about the O(2) model in d  =  3, where we predict a large logarithmic correction to the infrared scaling of disorder.

  8. 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.

  9. The Random-Bond Ising Model in 2.01 and 3 Dimensions

    CERN Document Server

    Komargodski, Zohar

    2016-01-01

    We consider the Ising model between 2 and 4 dimensions perturbed by quenched disorder in the strength of the interaction between nearby spins. In the interval 2model. We compare these new methods with previous studies. Finally, we comment about the $O(2)$ model in d=3, where we predict a large logarithmic correction to the infrared scaling of disorder.

  10. 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.

  11. Emotional valence and the free-energy principle.

    Science.gov (United States)

    Joffily, Mateus; Coricelli, Giorgio

    2013-01-01

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

  12. 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.

  13. Localization of the valence electron of endohedrally confined hydrogen, lithium and sodium in fullerene cages

    CERN Document Server

    Cuestas, Eloisa

    2016-01-01

    The localization of the valence electron of $H$, $Li$ and $Na$ atoms enclosed by three different fullerene molecules is studied. The structure of the fullerene molecules is used to calculate the equilibrium position of the endohedrally atom as the minimum of the classical $(N+1)$-body Lennard-Jones potential. Once the position of the guest atom is determined, the fullerene cavity is modeled by a short range attractive shell according to molecule symmetry, and the enclosed atom is modeled by an effective one-electron potential. In order to examine whether the endohedral compound is formed by a neutral atom inside a neutral fullerene molecule $X@C_{N}$ or if the valence electron of the encapsulated atom localizes in the fullerene giving rise to a state with the form $X^{+}@C_{N}^{-}$, we analyze the electronic density, the projections onto free atomic states, and the weights of partial angular waves.

  14. Critical behavior of two-dimensional spin systems under the random-bond six-state clock model

    Science.gov (United States)

    Wu, Raymond P. H.; Lo, Veng-cheong; Huang, Haitao

    2012-09-01

    The critical behavior of the clock model in two-dimensional square lattice is studied numerically using Monte Carlo method with Wolff algorithm. The Kosterlitz-Thouless (KT) transition is observed in the six-state clock model, where an intermediate phase exists between the low-temperature ordered phase and the high-temperature disordered phase. The bond randomness is introduced to the system by assuming a Gaussian distribution for the coupling coefficients with the mean μ =1 and different values of variance, from σ2=0.1 to σ2=3.0. An abrupt jump in the helicity modulus at the transition, which is the key characteristic of the KT transition, is verified with a stability argument. The critical temperature Tc for both pure and disordered systems is determined from the critical exponent η(Tc)=1/4. The results showed that a small amount of disorder (small σ) reduces the critical temperature of the system, without altering the nature of transition. However, a larger amount of disorder changes the transition from the KT-type into that of non-KT-type.

  15. Modelling of ‘sub-atomic’ contrast resulting from back-bonding on Si(111-7×7

    Directory of Open Access Journals (Sweden)

    Adam Sweetman

    2016-06-01

    Full Text Available It has recently been shown that ‘sub-atomic’ contrast can be observed during NC-AFM imaging of the Si(111-7×7 substrate with a passivated tip, resulting in triangular shaped atoms [Sweetman et al. Nano Lett. 2014, 14, 2265]. The symmetry of the features, and the well-established nature of the dangling bond structure of the silicon adatom means that in this instance the contrast cannot arise from the orbital structure of the atoms, and it was suggested by simple symmetry arguments that the contrast could only arise from the backbonding symmetry of the surface adatoms. However, no modelling of the system has been performed in order to understand the precise origin of the contrast. In this paper we provide a detailed explanation for ‘sub-atomic’ contrast observed on Si(111-7×7 using a simple model based on Lennard-Jones potentials, coupled with a flexible tip, as proposed by Hapala et al. [Phys. Rev. B 2014, 90, 085421] in the context of interpreting sub-molecular contrast. Our results show a striking similarity to experimental results, and demonstrate how ‘sub-atomic’ contrast can arise from a flexible tip exploring an asymmetric potential created due to the positioning of the surrounding surface atoms.

  16. Plant G-proteins come of age: Breaking the bond with animal models

    Science.gov (United States)

    Botella, Jimmy; Trusov, Yuri

    2016-05-01

    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 fromthe accepted animal paradigm.

  17. Salience, valence, context, and integration: conceptualizing the needs of sexually and gender diverse youth in P-12 schools.

    Science.gov (United States)

    Moe, Jeffry L; Perera-Diltz, Dilani; Sepulveda, Victoria; Finnerty, Peter

    2014-01-01

    A framework for conceptualizing the needs of lesbian, gay male, bisexual, transgender, questioning, and other sexually and gender diverse youth is essential for guiding service delivery throughout educational settings. Review and synthesis of the literature reveals that integrating assessment of the salience, valence, and context of issues related to sexual and gender diversity facilitates affirmative practice at the individual student, group, and school-wide levels. The authors describe the components of the salience, valence, context, and integration (SVCI) model with emphasis on practical application. The theoretical and empirical support for each component of the model is also discussed.

  18. 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.

    1985-01-01

    Determined the effects of reasoning, use of models during testing, and sex type on posttest achievement in chemical bonding under controlled instruction. Indicates that chemistry students' (N=84) reasoning capabilities influenced performance; other variables were not significant. Other conclusions are noted and discussed. (DH)

  19. High-pressure synchrotron Mössbauer and X-ray diffraction studies: Exploring the structure-related valence fluctuation in EuNi2P2

    Science.gov (United States)

    Li, Chunyu; Yu, Zhenhai; Bi, Wenli; Zhao, Jiyong; Hu, Michael Y.; Zhao, Jinggeng; Wu, Wei; Luo, Jianlin; Yan, Hao; Alp, Esen E.; Liu, Haozhe

    2016-11-01

    The high-pressure effect on valence fluctuation of the ThCr2Si2-type intermetallic compound EuNi2P2 has been investigated using in situ synchrotron Mössbauer spectroscopy (SMS). The isomer shift of 151Eu in EuNi2P2 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 EuNi2P2 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.

  20. 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

  1. Critical behaviours and magnetic properties of three-dimensional bond and anisotropy dilution Blume-Capel model in the presence of an applied field

    Institute of Scientific and Technical Information of China (English)

    Yan Shi-Lei; Zhu Hai-Xia

    2006-01-01

    This paper studies the critical behaviours and magnetic properties of three-dimensional bond and anisotropy dilution Blume-Capel model (BCM) in the presence of an applied field within the effective field theory. The trajectory of tricritical point, reentrant transitions and degenerate patterns of anisotropy are obtained both for the bond and the anisotropy dilutions. The global phase diagrams demonstrate unusually reentrant phenomena. The temperature dependences of magnetization curves undergo remarkable spin glass behaviour at low temperatures, and transform from ferromagnetism to paramagnetism at high temperature in applied fields. Temperature dependence of magnetic susceptibility curve is in qualitative agreement with experimental result.

  2. Dynamic force spectroscopy of parallel individual mucin1-antibody bonds

    Energy Technology Data Exchange (ETDEWEB)

    Sulchek, T A; Friddle, R W; Langry, K; Lau, E; Albrecht, H; Ratto, T; DeNardo, S; Colvin, M E; Noy, A

    2005-05-02

    We used atomic force microscopy (AFM) to measure the binding forces between Mucin1 (MUC1) peptide and a single chain antibody fragment (scFv) selected from a scFv library screened against MUC1. This binding interaction is central to the design of the molecules for targeted delivery of radioimmunotherapeutic agents for prostate and breast cancer treatment. Our experiments separated the specific binding interaction from non-specific interactions by tethering the antibody and MUC1 molecules to the AFM tip and sample surface with flexible polymer spacers. Rupture force magnitude and elastic characteristics of the spacers allowed identification of the bond rupture events corresponding to different number of interacting proteins. We used dynamic force spectroscopy to estimate the intermolecular potential widths and equivalent thermodynamic off rates for mono-, bi-, and tri-valent interactions. Measured interaction potential parameters agree with the results of molecular docking simulation. Our results demonstrate that an increase of the interaction valency leads to a precipitous decline in the dissociation rate. Binding forces measured for mono and multivalent interactions match the predictions of a Markovian model for the strength of multiple uncorrelated bonds in parallel configuration. Our approach is promising for comparison of the specific effects of molecular modifications as well as for determination of the best configuration of antibody-based multivalent targeting agents.

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

    Science.gov (United States)

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

    2009-01-01

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

  5. Identification of Possible Pathways for C-C Bond Formation during Electrochemical Reduction of CO2: New Theoretical Insights from an Improved Electrochemical Model.

    Science.gov (United States)

    Goodpaster, Jason D; Bell, Alexis T; Head-Gordon, Martin

    2016-04-21

    We have carried out a periodic Kohn-Sham density functional theory investigation of the pathways by which carbon-carbon bonds could be formed during the electrochemical reduction of CO2 on Cu(100) using a model that includes the effects of the electrochemical potential, solvent, and electrolyte. The electrochemical potential was set by relating the applied potential to the Fermi energy and then calculating the number of electrons required by the simulation cell for that specific Fermi energy. The solvent was included as a continuum dielectric, and the electrolyte was described using a linearized Poisson-Boltzmann model. The calculated potential of zero charge for a variety of surfaces agrees with experiment to within a mean average error of 0.09 V, thereby validating the assumptions of the model. Analysis of the mechanism for C-C bond formation revealed that at low-applied potential, C-C bond formation occurs through a CO dimer. However, at high applied potentials, a large activation barrier blocks this pathway; therefore, C-C bond formation occurs through reaction of adsorbed CHO and CO. Rate parameters determined from our calculations were used to simulate the kinetics of ethene formation during the electrochemical reduction of CO over a Cu(100) surface. An excellent match was observed between previously reported measurements of the partial current for ethene formation as a function of applied voltage and the variation in the partial current for C-C bond formation predicted by our microkinetic model. The electrochemical model reported here is simple, fairly easy to implement, and involves only a small increase in computational cost over calculations neglecting the effects of the electrolyte and the applied field. Therefore, it can be used to study the effects of applied potential and electrolyte composition on the energetics of surface reactions for a wide variety of electrochemical reactions.

  6. Dissociable effects of valence and arousal in adaptive executive control.

    Directory of Open Access Journals (Sweden)

    Christof Kuhbandner

    Full Text Available BACKGROUND: Based on introspectionist, semantic, and psychophysiological experimental frameworks, it has long been assumed that all affective states derive from two independent basic dimensions, valence and arousal. However, until now, no study has investigated whether valence and arousal are also dissociable at the level of affect-related changes in cognitive processing. METHODOLOGY/PRINCIPAL FINDINGS: We examined how changes in both valence (negative vs. positive and arousal (low vs. high influence performance in tasks requiring executive control because recent research indicates that two dissociable cognitive components are involved in the regulation of task performance: amount of current control (i.e., strength of filtering goal-irrelevant signals and control adaptation (i.e., strength of maintaining current goals over time. Using a visual pop-out distractor task, we found that control is exclusively modulated by arousal because interference by goal-irrelevant signals was largest in high arousal states, independently of valence. By contrast, control adaptation is exclusively modulated by valence because the increase in control after trials in which goal-irrelevant signals were present was largest in negative states, independent of arousal. A Monte Carlo simulation revealed that differential effects of two experimental factors on control and control adaptation can be dissociated if there is no correlation between empirical interference and conflict-driven modulation of interference, which was the case in the present data. Consequently, the observed effects of valence and arousal on adaptive executive control are indeed dissociable. CONCLUSIONS/SIGNIFICANCE: These findings indicate that affective influences on cognitive processes can be driven by independent effects of variations in valence and arousal, which may resolve several heterogeneous findings observed in previous studies on affect-cognition interactions.

  7. 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.

  8. Zero-Coupon bond pricing模型的最优系统与群不变解%An optimal system and group-invariant solutions of the Zero-Coupon bond pricing models

    Institute of Scientific and Technical Information of China (English)

    张颖; 高雯

    2009-01-01

    Lie group theory is applied to differential equations occurring as mathematical models in financial problems. The Zero-Coupon bond pricing models are studied. Its one-parameter Lie point symmetries and corresponding group of adjoint representations are obtained. An optimal system of one-dimensional subalgebra is derived and used to construct distinct families of special closed-form solutions of the equation.%将李群理论用于金融问题中出现的数学模型的微分方程,研究了Zero-Coupon bond pricing模型.求出了该模型的单参数李点对称及它相应的群伴随表达式,由此求得该模型允许的一维李群的子代数的最优系统并且利用最优系统构造该模型相应的微分方程的一些特殊的不同类的闭解.

  9. Effects of valence, geometry and electronic correlations on transport in transition metal benzene sandwich molecules

    Science.gov (United States)

    Karolak, M.; Jacob, D.

    2016-11-01

    We study the impact of the valence and the geometry on the electronic structure and transport properties of different transition metal-benzene sandwich molecules bridging the tips of a Cu nanocontact. Our density-functional calculations show that the electronic transport properties of the molecules depend strongly on the molecular geometry which can be controlled by the nanocontact tips. Depending on the valence of the transition metal center certain molecules can be tuned in and out of half-metallic behaviour facilitating potential spintronics applications. We also discuss our results in the framework of an Anderson impurity model, indicating cases where the inclusion of local correlations alters the ground state qualitatively. For Co and V centered molecules we find indications of an orbital Kondo effect.

  10. 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...... of eight different cases shows that bond utility scores can explain variation in relationship outcome, and that the pattern of explanation differs across the eight cases in a meaningful way....

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

    Indian Academy of Sciences (India)

    G Gangadhar Reddy; A Ramakanth; S K Ghatak

    2002-05-01

    The magnetic-field-induced valence transition in rare-earth systems has been investigated using the periodic Anderson model supplemented by the Falicov–Kimball term. This model has been solved by first decoupling the Falicov–Kimball term as proposed by Khomskii and Koharjan and then taking the limit of infinite intra-site Coulomb repulsion. The valence transition both in the absence and in the presence of magnetic field as a function of temperature is studied. It has been found that the system makes transition from non-magnetic to magnetic state when the magnetic field increases beyond a critical value c. The phase boundary defined in terms of reduced field c()/c(0) and reduced temperature /v (v being the valence transition temperature in the absence of field) is almost independent of the position of the localized level. The results are in qualitative agreement with experimental observations in Yb- and Eu-compounds.

  12. 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.

  13. Hard-Core Bosons on the Kagome Lattice: Valence-Bond Solids and Their Quantum Melting

    Science.gov (United States)

    Isakov, S. V.; Wessel, S.; Melko, R. G.; Sengupta, K.; Kim, Yong Baek

    2006-10-01

    Using large scale quantum Monte Carlo simulations and dual vortex theory, we analyze the ground state phase diagram of hard-core bosons on the kagome lattice with nearest-neighbor repulsion. In contrast with the case of a triangular lattice, no supersolid emerges for strong interactions. While a uniform superfluid prevails at half filling, two novel solid phases emerge at densities ρ=1/3 and ρ=2/3. These solids exhibit an only partial ordering of the bosonic density, allowing for local resonances on a subset of hexagons of the kagome lattice. We provide evidence for a weakly first-order phase transition at the quantum melting point between these solid phases and the superfluid.

  14. Local Bonding Analysis of the Valence and Conduction Band Features of TiO2

    Science.gov (United States)

    2007-01-01

    anatase than with rutile .33 The shape of the L3 spectrum in Fig. 2 is also more qualitatively similar to XAS spectra of anatase surfaces shown in the...annealed TiO2 surfaces of anatase and rutile at photon ener- gies of 40–80 eV would appear to reveal a stronger similarity to the resonance behavior...of the anatase surfaces than to rutile , for which the Ti 3p→4sp resonance at 54 eV is dominant.7 However, it is clear from the same study that the CIS

  15. 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.

  16. 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.

  17. Circulant Double Coverings of a Circulant Graph of Valency Five

    Institute of Scientific and Technical Information of China (English)

    Rong Quan FENG; Jin Ho KWAK

    2007-01-01

    Enumerating the isomorphism classes of several types of graph covering projections is one of the central research topics in enumerative topological graph theory. A covering of G is called circulant if its covering graph is circulant. Recently, the authors [Discrete Math., 277, 73-85 (2004)]enumerated the isomorphism classes of circulant double coverings of a certain type, called a typicalcovering, and showed that no double covering of a circulant graph of valency three is circulant. Also, in [Graphs and Combinatorics, 21, 386-400 (2005)], the isomorphism classes of circulant double coverings of a circulant graph of valency four are enumerated. In this paper, the isomorphism classes of circulant double coverings of a circulant graph of valency five are enumerated.

  18. Recognizing the emotional valence of names: an ERP study.

    Science.gov (United States)

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

    2013-04-01

    Unlike common nouns, person names refer to unique entities and generally have a referring function. We used event-related potentials to investigate the time course of identifying the emotional meaning of nouns and names. The emotional valence of names and nouns were manipulated separately. The results show early N1 effects in response to emotional valence only for nouns. This might reflect automatic attention directed towards emotional stimuli. The absence of such an effect for names supports the notion that the emotional meaning carried by names is accessed after word recognition and person identification. In addition, both names with negative valence and emotional nouns elicited late positive effects, which have been associated with evaluation of emotional significance. This positive effect started earlier for nouns than for names, but with similar durations. Our results suggest that distinct neural systems are involved in the retrieval of names' and nouns' emotional meaning.

  19. 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

  20. Role of valence states of adsorbates in inelastic electron tunneling spectroscopy: A study of nitric oxide on Cu(110) and Cu(001)

    Science.gov (United States)

    Shiotari, Akitoshi; Okuyama, Hiroshi; Hatta, Shinichiro; Aruga, Tetsuya; Alducin, Maite; Frederiksen, Thomas

    2016-08-01

    We studied nitric oxide (NO) molecules on Cu(110) and Cu(001) surfaces with low-temperature scanning tunneling microscopy (STM) and density functional theory (DFT). NO monomers on the surfaces are characterized by STM images reflecting 2 π* resonance states located at the Fermi level. NO is bonded vertically to the twofold short-bridge site on Cu(110) and to the fourfold hollow site on Cu(001). When NO molecules form dimers on the surfaces, the valence orbitals are modified due to the covalent bonding. We measured inelastic electron tunneling spectroscopy (IETS) for both NO monomers and dimers on the two surfaces, and detected characteristic structures assigned to frustrated rotation and translation modes by density functional theory simulations. Considering symmetries of valence orbitals and vibrational modes, we explain the intensity of the observed IETS signals in a qualitative manner.

  1. 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...

  2. Valence quark contributions for the gamma N -> P11(1440) transition

    Energy Technology Data Exchange (ETDEWEB)

    G. Ramalho, K. Tsushima

    2011-03-01

    A covariant spectator quark model is applied to estimate the valence quark contributions to the$ F1*(Q2) and F2*(Q2) transition form factors for the gamma N -> P11(1440) reaction. The Roper resonance, P11(1440), is assumed to be the first radial excitation of the nucleon. The model requires no extra parameters except for those already fixed by the previous studies for the nucleon. The results are consistent with the experimental data in the high Q2 region, and those from the lattice QCD. Finally the model is also applied to estimate the meson cloud contributions from the CLAS and MAID analysis.

  3. Valence quark contributions for the gamma N -> P11(1440) transition

    CERN Document Server

    Ramalho, G

    2010-01-01

    A covariant spectator quark model is applied to estimate the valence quark contributions to the$ F1*(Q2) and F2*(Q2) transition form factors for the gamma N -> P11(1440) reaction. The Roper resonance, P11(1440), is assumed to be the first radial excitation of the nucleon. The model requires no extra parameters except for those already fixed by the previous studies for the nucleon. The results are consistent with the experimental data in the high Q2 region, and those from the lattice QCD. Finally the model is also applied to estimate the meson cloud contributions from the CLAS and MAID analysis.

  4. Relation between plasmons and the valence-band density-of-states in polymethylmethacrylate - influence of ion irradiation on damage selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Moliton, J.P. [Limoges Univ., 87 (France); Jussiaux, C.; Trigaud, T.; Lazzaroni, R. [Mons Univ. (Belgium); Lhost, O.; Bredas, J.L.; Kihn, Y.; Sevely, J. [Centre National de la Recherche Scientifique (CNRS), 31 - Toulouse (France)

    1996-05-01

    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).

  5. Lattice anomalies in CeNi unstable valence compound

    Energy Technology Data Exchange (ETDEWEB)

    Lazukov, V.N.; Nefeodova, E.V.; Alekseev, P.A.; Nemkovski, K.S.; Sadikov, I.P.; Tiden, N.N. [RRC ' ' Kurchatov Institute' ' , 123182 Moscow (Russian Federation); Sikolenko, V.V. [JINR, 141980 Dubna, Moscow region (Russian Federation); Staub, U.; Pradervand, C. [SLS, PSI, 5232 Villigen PSI (Switzerland); Braden, M. [LLB, CEA/Saclay, 91191 Gif sur Yvette Cedex (France); INFP Postfach 3640, 76021 Karlsruhe (Germany); Soderholm, L. [Chemistry Division, Argonne National Laboratory, Argonne Il-60439 (United States)

    2002-07-01

    Neutron diffraction and X-ray absorption measurements have been performed to study the changes in the structure and the Ce valence between 10 K and 295 K. No evidence for a phase transition was obtained, but some nearest-neighbour distances have clear peculiarities in the temperature range of 100 K to 150 K. The valence of Ce increases continuously with decreasing temperature, which can explain neither the lattice anomalies nor the previously observed temperature dependence of the phonon frequencies. A correlation between the gap-like magnetic excitation spectrum formed at low temperatures and observed lattice anomalies is discussed. (orig.)

  6. Hydrogen bonds of 2-aminothiazoles in intermolecular complexes (1:1 and 1:2) with proton acceptors in solutions

    Science.gov (United States)

    Borisenko, V. E.; Koll, A.; Kolmakov, E. E.; Rjasnyi, A. G.

    2006-02-01

    IR spectra of the free molecules of 2-aminothiazole and 2-aminobenzothiazole and their H-bonded complexes of 1:1 composition with acetonitrile, dioxane, tetrahydrofourane, dimethylformamide, dimethylsulfoxide and hexamethyl-phosphoramide in CCl 4 were studied in the range of stretching and deformational vibrations of the amino group. The complexes of 1:2 compositions were studied in undiluted aprotic solvents. The absorption band spectral characteristics of monomers and complexes were determined: M (0)—zero spectral moment (integrated band intensity B), M(1)—first spectral moment (band gravity center) and effective half-width (Δ ν1/2) eff which is related to the second central moment M(2): (Δ ν1/2) eff=2( M(2)) 1/2. The temperature influence on the absorption band spectral characteristics of the amino group stretching vibrations for monomers and 1:1 complexes were studied in the interval 283-323 K. It was shown that within the range mentioned above, spectral characteristics have practically linear dependence on temperature. Parameters of the linear regression equation Y= aT+ b ( Y= B, M(1), 2( M(2)) 1/2) were determined. It was stated that the temperature sensitivity a= ∂Y/ ∂T of spectral characteristics for 1:1 complexes of 2-aminothiazoles with proton acceptors is approximately 10 times higher than for monomers. The monomer-complex equilibrium constants K( T) (1:1) were calculated and the thermodynamical characteristics -Δ H and Δ S were determined, based on Vant-Hoff equation. For free (R-NH 2, R-NHD, R-ND 2) and H-bonded (1:1 and 1:2, with various proton acceptors) molecules of 2-aminothiazoles, the vibrational and electro optic problems were solved in the approximation of the six-coordinate valence force field model. The valence angles γ(HNH), force constants K(NH), electro optic parameters ∂μ/ ∂q (derivative of the dipole moment by the length of NH-bond) and ∂μ/ ∂q' (derivative of the dipole moment by the length of the neighboring NH-bond

  7. Numerical evidence of hyperscaling violation in wetting transitions of the random-bond Ising model in d =2 dimensions

    Science.gov (United States)

    Albano, Ezequiel V.; Luque, Luciana; Trobo, Marta L.; Binder, Kurt

    2017-02-01

    We performed extensive simulations of the random-bond Ising model confined between walls where competitive surface fields act. By properly taking the thermodynamic limit we unambiguously determined wetting transition points of the system, as extrapolation of localization-delocalization transitions of the interface between domains of different orientation driven by the respective fields. The finite-size scaling theory for wetting with short-range fields [E. V. Albano and K. Binder, Phys. Rev. Lett. 109, 036101 (2012), 10.1103/PhysRevLett.109.036101] establishes that the average magnetization of the sample, with critical exponent β , is the proper order parameter for the study of wetting. While the hyperscaling relationship given by γ +2 β =ν∥+ν⊥ requires β =1 /2 (γ =4 , ν∥=3 , and ν⊥=2 ), the thermodynamic scaling establishes that Δs=γ +β , which in contrast requires β =0 (Δs=4 ), where γ , ν∥, ν⊥, and Δs are the critical exponents of the susceptibility, the correlation lengths parallel and perpendicular to the interface, and the gap exponent, respectively. So, we formulate a finite-size scaling theory for wetting without hyperscaling and perform numerical simulations that provide strong evidence of hyperscaling violation (i.e., β =0 ) and a direct measurement of the susceptibility critical exponent γ /ν⊥=2.0 ±0.2 , in agreement with theoretical results for the strong fluctuation regime of wetting transitions with quenched noise.

  8. Data-Driven Contextual Valence Shifter Quantification for Multi-Theme Sentiment Analysis

    Science.gov (United States)

    Yu, Hongkun; Shang, Jingbo; Hsu, Meichun; Castellanos, Malú; Han, Jiawei

    2017-01-01

    Users often write reviews on different themes involving linguistic structures with complex sentiments. The sentiment polarity of a word can be different across themes. Moreover, contextual valence shifters may change sentiment polarity depending on the contexts that they appear in. Both challenges cannot be modeled effectively and explicitly in traditional sentiment analysis. Studying both phenomena requires multi-theme sentiment analysis at the word level, which is very interesting but significantly more challenging than overall polarity classification. To simultaneously resolve the multi-theme and sentiment shifting problems, we propose a data-driven framework to enable both capabilities: (1) polarity predictions of the same word in reviews of different themes, and (2) discovery and quantification of contextual valence shifters. The framework formulates multi-theme sentiment by factorizing the review sentiments with theme/word embeddings and then derives the shifter effect learning problem as a logistic regression. The improvement of sentiment polarity classification accuracy demonstrates not only the importance of multi-theme and sentiment shifting, but also effectiveness of our framework. Human evaluations and case studies further show the success of multi-theme word sentiment predictions and automatic effect quantification of contextual valence shifters. PMID:28232874

  9. 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.

  10. 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.

  11. A nucleus-dependent valence-space approach to nuclear structure

    CERN Document Server

    Stroberg, S R; Hergert, H; Holt, J D; Bogner, S K; Roth, R; Schwenk, A

    2016-01-01

    We present a nucleus-dependent valence-space approach for calculating ground and excited states of nuclei, which generalizes the shell-model in-medium similarity renormalization group to an ensemble reference with fractionally filled orbitals. Because the ensemble is used only as a reference, and not to represent physical states, no symmetry restoration is required. This allows us to capture 3N forces among valence nucleons with a valence-space Hamiltonian specifically targeted to each nucleus of interest. Predicted ground-state energies from carbon through nickel agree with results of other large-space ab initio methods, generally to the 1\\% level. In addition, we show that this new approach is required in order to obtain convergence for nuclei in the upper $p$ and $sd$ shells. Finally, we address the $1^+$/$3^+$ ground-state inversion problem in $^{22}\\text{Na}$ and $^{46}\\text{V}$. This approach extends the reach of ab initio nuclear structure calculations to essentially all light- and medium-mass nuclei.

  12. Transition-metal dopants in tetrahedrally bonded semiconductors: Symmetry and exchange interactions from tight-binding models

    Science.gov (United States)

    Kortan, Victoria Ramaker

    It has become increasingly apparent that the future of electronic devices can and will rely on the functionality provided by single or few dopant atoms. The most scalable physical system for quantum technologies, i.e. sensing, communication and computation, are spins in crystal lattices. Diamond is an excellent host crystal offering long room temperature spin coherence times and there has been exceptional experimental work done with the nitrogen vacancy center in diamond demonstrating many forms of spin control. Transition metal dopants have additional advantages, large spin-orbit interaction and internal core levels, that are not present in the nitrogen vacancy center. This work explores the implications of the internal degrees of freedom associated with the core d levels using a tight-binding model and the Koster-Slater technique. The core d levels split into two separate symmetry states in tetrahedral bonding environments and result in two levels with different wavefunction spatial extents. For 4 d semiconductors, e.g. GaAs, this is reproduced in the tight-binding model by adding a set of d orbitals on the location of the transition metal impurity and modifying the hopping parameters from impurity to its nearest neighbors. This model does not work in the case of 3d semiconductors, e.g. diamond, where there is no physical reason to drastically alter the hopping from 3 d dopant to host and the difference in wavefunction extent is not as pronounced. In the case of iron dopants in gallium arsenide the split symmetry levels in the band gap are responsible for a decrease in tunneling current when measured with a scanning tunneling microscope due to interference between two elastic tunneling paths and comparison between wavefunction measurements and tight-binding calculations provides information regarding material parameters. In the case of transition metal dopants in diamond there is less distinction between the symmetry split d levels. When considering pairs of

  13. Solvent effect on intramolecular electron transfer rates of mixed-valence biferrocene monocation derivatives.

    Science.gov (United States)

    Masuda, Y; Shimizu, C

    2006-06-01

    Intramolecular electron transfer (ET) rates in various solvents of mixed-valence biferrocene monocation (Fe(II), Fe(III)) and the 1',1' ''-diiodo and 1',1' ''-diethyl derivatives (respectively abbreviated as BFC(+), I(2)BFC(+), and Et(2)BFC(+)) were determined by means of the spin-lattice relaxation times of the protons, taking into account the local magnetic field fluctuation caused by the electron hopping between the two ferrocene units. We also determined the ET rates of a mixed-valence diferrocenylacetylene monocation (DFA(+)) in order to examine the effect of the insertion of an acetylene bridge between the two ferrocene units. The insertion of the bridge decreased the ET rate, while the effect of substitution on the cyclopentadienyl rings on the rate was minor. The observed rates for each mixed-valence monocation in various solvents did not correlate with the reorganization energies, but we did find a significant contribution of the solvent dynamics. The observed rates were considerably higher than those expected on the basis of the Sumi-Marcus-Nalder model in which the solvents were regarded as dielectric continua. The slope of the logarithm plot of the pre-exponential factors in various solvents for each mixed-valence monocation versus the inverse of the longitudinal dielectric relaxation times of the solvents was significantly smaller than unity, and the slope for DFA(+) was larger than those for BFC(+), I(2)BFC(+), and Et(2)BFC(+). These results were ascribed to a partial contribution of the dielectric friction to the dynamics along the solvent coordinate; the extent of the contribution decreased with a reduction in the ET distance. For the dynamics along the solvent coordinate of the ET reactions in methanol, the observed rates indicated an important contribution by the minor dielectric relaxation components with faster relaxation times, rather than the major component with an extraordinarily long relaxation time.

  14. 改进的股票债券时期模型及动态分析%Improved Stock-bond-period Model and Dynamic Analysis

    Institute of Scientific and Technical Information of China (English)

    张雯婷; 李仁安

    2013-01-01

    证券投资组合的根本目的在于获利最大化和风险最小化,通过构建股票债券的混合投资组合,可以在保证收益的情况下分散风险.在股票债券模型中加入时间维度,提出了股票债券时期模型,用一种比较简便的方法对传统模型进行了动态分析.最后通过对2010-2012年一组股票和债券的实际交易利率进行了实证分析,验证了该模型的有效性.%The fundamental purpose of portfolio investment lies in the maximizing of benefits and minimizing of risks.Through the construction of mixed portfolio investment among stocks and bonds,risks can be largely reduced while the profits are guaranteed.A new stock-bond-period model was proposed when the dimension of time was added to the model.Relevant dynamic analysis of the classic model was conducted under using a relatively easy method to facilitate.At last,empirical analysis was done by using a group of actual exchange rate of stocks and bonds during 2010 and 2012.The validity of the new model was proved.

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

    Science.gov (United States)

    Valero, Rosendo; Truhlar, Donald G

    2007-09-06

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

  16. 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.

  17. Voice and Valency in San Luis Potosi Huasteco

    Science.gov (United States)

    Munoz Ledo Yanez, Veronica

    2014-01-01

    This thesis presents an analysis of the system of transitivity, voice and valency alternations in Huasteco of San Luis Potosi (Mayan) within a functional-typological framework. The study is based on spoken discourse and elicited data collected in the municipalities of Aquismon and Tancanhuitz de Santos in the state of San Luis Potosi, Mexico. The…

  18. Raman Sideband Cooling of Two-Valence-Electron Fermionic Atoms

    Institute of Scientific and Technical Information of China (English)

    LI Guo-Hui; XU Xin-Ye

    2011-01-01

    We propose a method for laser cooling two-valence-electron fermionic atoms. Our protocol employs resolved-sideband cooling on the stimulated Raman transition between the two magnetic sublevels (m = F and m = F - 1) of the ground state with total anguiar momentum F. The optical pumping from m = F - 1 to 1 Pi are used to decouple atoms in the m = F - 1 state. We calculate the Raman coupling generated by an engineered optical lattice. The result shows that it is possible to laser cool the two-valence-electron fermionic atoms to the ground state. The atoms in the ground state provide a new system for quantum optics.%@@ We propose a method for laser cooling two-valence-electron fermionic atoms.Our protocol employs resolved- sideband cooling on the stimulated Raman transition between the two magnetic sublevels (m=F and m = F- 1) of the ground state with total angular momentum F.The optical pumping from m = F - 1 to p are used to decouple atoms in the m = F - 1 state.We calculate the Raman coupling generated by an engineered optical lattice.The result shows that it is possible to laser cool the two-valence-electron fermionic atoms to the ground state.The atoms in the ground state provide a new system for quantum optics.

  19. Contrastive Verb Valency and Conceptual Structures in the Verbal Lexicon.

    Science.gov (United States)

    Devos, Filip; And Others

    1996-01-01

    Reports on research consisting of compiling a contrastive verb valency dictionary of Dutch, French, and English whose main strength lies in depicting semantic differences between its entries and conceptual differences between languages. Using these analyses, one can start to discern nuclear and peripheral meanings, analyze possible meaning…

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

    Science.gov (United States)

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

    2014-08-20

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

  1. 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 ...

  2. Photochemical properties of carotenoids: what can we get from the VB model?

    Institute of Scientific and Technical Information of China (English)

    GAO; Yi; (高嶷); LIU; Chungen; (刘春根); JIANG; Yuansheng; (江元生)

    2003-01-01

    The empirical valence bond model, solved by the DMRG technique, is applied to the systematical study of the photochemical processes of carotenoids. The polyenes with five up to one hundred of C=C bonds are investigated. The probability of the state arrangement for the conjugated bond, Pij, is evaluated. It is a parameter to correlate the bond lengths, and could also be applied to rationalizing the quantum yields of the photo-isomerization and the reaction constantof the quenching of singlet-oxygen happened to the external C=C bond of the carotenoids. The maximum reaction constant in long chain limit is determined as about 2.92×1010 L·mol-1·s-1.

  3. Valence quark contributions for the gamma N -> P11(1440) form factors

    CERN Document Server

    Ramalho, G

    2010-01-01

    Using a covariant spectator quark model we estimate valence quark contributions to the F1*(Q2) and F2*(Q2) transition form factors for the gamma N -> P11(1440) reaction. The Roper resonance, P11(1440), is assumed to be the first radial excitation of the nucleon. The present model requires no extra parameters except for those already fixed by the previous studies for the nucleon. Our results are consistent with the experimental data in the high Q2 region, and those from lattice QCD. We also estimate the meson cloud contributions, focusing on the low Q2 region, where they are expected to be dominant.

  4. Improper hydrogen bonded cyclohexane C-Hax···Yax contacts: theoretical predictions and experimental evidence from 1H NMR spectroscopy of suitable axial cyclohexane models.

    Science.gov (United States)

    Kolocouris, Antonios; Zervos, Nikolaos; De Proft, Frank; Koch, Andreas

    2011-06-03

    C-H(ax)···Y(ax) contacts are a textbook prototype of steric hindrance in organic chemistry. The nature of these contacts is investigated in this work. MP2/6-31+G(d,p) calculations predicted the presence of improper hydrogen bonded C-H(ax)···Y(ax) contacts of different strength in substituted cyclohexane rings. To support the theoretical predictions with experimental evidence, several synthetic 2-substituted adamantane analogues (1-24) with suitable improper H-bonded C-H(ax)···Y(ax) contacts of different strength were used as models of a substituted cyclohexane ring. The (1)H NMR signal separation, Δδ(γ-CH(2)), within the cyclohexane ring γ-CH(2)s is raised when the MP2/6-31+G(d,p) calculated parameters, reflecting the strength of the H-bonded C-H(ax)···Y(ax) contact, are increased. In molecules with enhanced improper H-bonded contacts C-H(ax)···Y(ax), like those having sterically crowded contacts (Y(ax) = t-Bu) or contacts including considerable electrostatic attractions (Y(ax) = O-C or O═C) the calculated DFT steric energies of the γ-axial hydrogens are considerably reduced reflecting their electron cloud compression. The results suggest that the proton H(ax) electron cloud compression, caused by the C-H(ax)···Y(ax) contacts, and the resulting increase in Δδ(γ-CH(2)) value can be effected not just from van der Waals spheres compression, but more generally from electrostatic attraction forces and van der Waals repulsion, both of which are improper H-bonding components.

  5. π-Electron ring-currents and bond-currents in [10,5]-Coronene and related structures conforming to the 'Annulene-Within-an-Annulene' model.

    Science.gov (United States)

    Dickens, T K; Mallion, R B

    2013-06-01

    A series of hypothetical conjugated structures is defined; the series is called the p-Coronenes and the first four members of it are shown to respect the 'Annulene-Within-an-Annulene' (AWA) model when tested by means of Hückel-London-Pople-McWeeny (HLPM) π-electron ring-current and bond-current calculations. The first member of this series, 5-Coronene, is also a member of the regular [r,s]-Coronene series, where it is known as [10,5]-Coronene. It is shown that, as p is varied (with p always odd, and with p > 3) through the values 5, 7, 9, 11, etc., the resulting structures alternate between a '[4n + 2]-Annulene-Within-a-[4m]-Annulene' (if (p- 1) is divisible by 4) and a '[4n]-Annulene-Within-a-[4m + 2]-Annulene' (if (p- 1) is not divisible by 4). It is therefore claimed that the p-Coronenes constitute an ideal series for testing the AWA model. It is also remarked that each member of the p-Coronene series has only four Kekulé structures, and that the 'spokes' or 'transverse' bonds connecting the central [p(p- 3)]-membered ring to the outer [p(p- 1)]-membered periphery always have a Pauling bond-order of zero, ensuring that the outer and inner rings are 'decoupled'; such bonds also bear zero bond-current, by symmetry. It is argued that the former property of these transverse bonds, rather than the latter, determines that the p-Coronenes obey the AWA rule-which is in fact an exception, rather than a 'rule'per se. The paper concludes by explicitly stating our philosophy that a conceptually simple model depending on no subjective (or any other) parameters whatsoever can give intuitive chemical insight for certain systems equal to that available from far-more complex methods such as ab initio calculations-what Coulson once famously called 'primitive patterns of understanding'.

  6. First-principles analysis of the C-N bond scission of methylamine on Mo-based model catalysts

    Science.gov (United States)

    Lv, Cun-Qin; Li, Jun; Tao, Shu-Xia; Ling, Kai-Cheng; Wang, Gui-Chang

    2010-01-01

    The C-N bond breaking of methylamine on clean, carbon (nitrogen, oxygen)-modified Mo(100) [denoted as Mo(100) and Mo(100)-C(N,O), respectively], Mo2C(100), MoN(100), and Pt(100) surfaces has been investigated by the first-principles density functional theory (DFT) calculations. The results show that the reaction barriers of the C-N bond breaking in CH3NH2 on Mo(100)-C(N,O) are higher than that on clean Mo(100). The calculated energy barrier can be correlated linearly with the density of Mo 4d states at the Fermi level after the adsorption of CH3NH2 for those surfaces. Moreover, the DFT results show that the subsurface atom, e.g., carbon, can reduce the reaction barrier. In addition, We noticed that the activation energies for the C-N bond breaking on Mo2C(100) and MoN(100) are similar to that on Pt(100), suggesting that the catalytic properties of the transition metal carbides and nitrides for C-N bond scission of CH3NH2 might be very similar to the expensive Pt-group metals.

  7. Annealing effects on recombinative activity of nickel at direct silicon bonded interface

    Energy Technology Data Exchange (ETDEWEB)

    Kojima, Takuto, E-mail: tkojima@toyota-ti.ac.jp; Ohshita, Yoshio; Yamaguchi, Masafumi [Toyota Technological Institute, 2-12-1 Hisakata, Tempaku-ku, Nagoya, 468-8511 (Japan)

    2015-09-15

    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{sub 2}.

  8. VB studies on bonding features of HNC(←→)HCN

    Institute of Scientific and Technical Information of China (English)

    廖新丽; 吴玮; 莫亦荣; 张乾二

    2003-01-01

    Within the bonded tableau unitary group approach (BTUGA), a scheme, combined with Pauling's resonance theory to select the predominant valence bond structures for VB calculations, is proposed. This scheme ensures a reliable and illustrative bonding picture in the description of chemical reactions, as exemplified by the isomerization reaction HNCHCN. The computation results account for important bonding features about this isomerization at the ab initio level and explore the mechanism of phenomena such as (i) HCN is more stable than HNC; (ii) the C-N bond first lengthens and then shortens in the vicinity of the transition state; (iii) only H-atom migration is observed in the isomerization process, without the breaking of the CN bond. Our results demonstrate that only a few bonded tableau functions are sufficient enough to provide a visual and reliable bonding picture.

  9. First-principle study on bonding mechanism of ZnO by LDA+U method

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, G.C. [Key Laboratory of Low Dimensional Materials and Application Technology (Xiangtan University), Ministry of Education, Institute of Modern Physics, Xiangtan University, Xiangtan 411105 (China); Sun, L.Z. [Key Laboratory of Low Dimensional Materials and Application Technology (Xiangtan University), Ministry of Education, Institute of Modern Physics, Xiangtan University, Xiangtan 411105 (China) and National Laboratory for Infrared Physics, Shanghai Institute of Technical Physics, Chinese Academy of Science, 200083 Shanghai (China)]. E-mail: lzsun@xtu.edu.cn; Zhong, X.L. [Key Laboratory of Low Dimensional Materials and Application Technology (Xiangtan University), Ministry of Education, Institute of Modern Physics, Xiangtan University, Xiangtan 411105 (China); Chen Xiaoshuang [National Laboratory for Infrared Physics, Shanghai Institute of Technical Physics, Chinese Academy of Science, 200083 Shanghai (China)]. E-mail: xschen@mail.sitp.ac.cn; Wei Lu [National Laboratory for Infrared Physics, Shanghai Institute of Technical Physics, Chinese Academy of Science, 200083 Shanghai (China); Wang, J.B. [Key Laboratory of Low Dimensional Materials and Application Technology (Xiangtan University), Ministry of Education, Institute of Modern Physics, Xiangtan University, Xiangtan 411105 (China)]. E-mail: jbwang@xtu.edu.cn

    2007-08-13

    The electronic structure and the bonding mechanism of ZnO have been studied by using the Full-Potential Linear Augmented Plane Wave (FP-LAPW) method within the density-functional theory (DFT) based on LDA+U exchange correlation potential. The valence and the bonding charge density are calculated and compared with those derived from LDA and GGA to describe the bonding mechanism. The charge transfer along with the bonding process is analyzed by using the theory of Atoms in Molecules (AIM). The bonding, the topological characteristics and the p-d coupling effects on the bonding mechanism of ZnO are shown quantitatively with the critical points (CPs) along the bonding trajectory and the charge in the atomic basins. Meanwhile, the bonding characteristics for wurtzite, zinc blende and rocksalt phase of ZnO are discussed systematically in the present paper.

  10. Implicit Hamiltonian formulation of bond graphs

    NARCIS (Netherlands)

    Golo, G.; Schaft, A.J. van der; Breedveld, P.C.; Maschke, B.M.

    2003-01-01

    This paper deals with mathematical formulation of bond graphs. It is proven that the power continuous part of bond graphs, the junction structure, can be associated with a Dirac structure and that equations describing a bond graph model correspond to an implicit port-controlled Hamiltonian system wi

  11. Comparison of Sarns 3M heparin bonded to Duraflo II and control circuits in a porcine model: macro- and microanalysis of thrombi accumulation in circuit arterial filters.

    Science.gov (United States)

    Larson, D F; Arzouman, D; Kleinert, L; Patula, V; Williams, S

    2000-01-01

    Heparin-bonded perfusion circuits have been reported to reduce the thrombus formation during various levels of systemic heparinization. The goal of this study was to compare the efficacy of thrombo-resistance of the Sarns 3M heparin-bonded circuit to Baxter Duraflo II and untreated control in a porcine model. Fifteen Yorkshire pigs (60-65 kg) were anesthetized, heparinized with 3000 IU, intravenously (i.v.) and surgically cannulated with an internal jugular outflow and a femoral vein inflow. All circuits consisted of a 22-Fr venous cannula, centrifugal pump, arterial filter, an 18-Fr cannula for return and connected with equal lengths of 3/8" polyvinyl chloride tubing. The flows were maintained at 2.0 l/min for 4 h. Thrombus formation in filter samples were morphometrically analyzed through macro-densitometry, light microscopy, and scanning electron microscopy (SEM). Our findings revealed that the 3M circuit had significantly less gross thrombus (p < 0.001), 66% and 84% less microscopic thrombi and fivefold less SEM-measured aggregates (p = 0.03) compared to the Duraflo II and uncoated groups. This study demonstrated that the 3M heparin-bonded circuit had significantly reduced the formation of micro- and macro-thrombi in the minimally heparinized pig model compared to the Duraflo II and untreated control circuits.

  12. 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.

  13. 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......-aversion (CRRA) model. In addition, we compare the pricing errors of the different models using Hansen and Jagannathan's specification error measure. The main result is that for Denmark the Campbell-Cochrane model does not seem to perform markedly better than the CRRA model. For the long annual sample period...... covering more than 80 years there is absolutely no evidence of superior performance of the Campbell-Cochrane model. For the shorter and more recent quarterly data over a 20-30 year period, there is some evidence of counter-cyclical time-variation in the degree of risk-aversion, in accordance...

  14. 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....... In addition, we compare the pricing errors of the different models using Hansen and Jagannathan's (1997) specification error measure. The main result is that for Denmark the Campbell-Cochrane model does not seem to perform markedly better than the CRRA model. For the long annual sample period covering more...... than 80 years there is absolutely no evidence of superior performance of the Campbell-Cochrane model. For the shorter and more recent quarterly data over a 20-30 year period, there is some evidence of counter-cyclical time-variation in the degree of risk-aversion, in accordance with the Campbell...

  15. Ground-state energy and entropy of the two-dimensional Edwards-Anderson spin-glass model with different bond distributions

    Science.gov (United States)

    Perez-Morelo, D. J.; Ramirez-Pastor, A. J.; Romá, F.

    2012-02-01

    We study the two-dimensional Edwards-Anderson spin-glass model using a parallel tempering Monte Carlo algorithm. The ground-state energy and entropy are calculated for different bond distributions. In particular, the entropy is obtained by using a thermodynamic integration technique and an appropriate reference state, which is determined with the method of high-temperature expansion. This strategy provides accurate values of this quantity for finite-size lattices. By extrapolating to the thermodynamic limit, the ground-state energy and entropy of the different versions of the spin-glass model are determined.

  16. Organometallic Modeling of the Hydrodesulfurization (HDS) Process: Rhenium Carbonyl-promoted C-S Bond Cleavage and Hydrogenation of Thiophenes and Benozothiophenes

    Energy Technology Data Exchange (ETDEWEB)

    Reynolds, Michael A. [Iowa State Univ., Ames, IA (United States)

    2000-09-21

    Organometallic modeling of the HDS process at single or multiple metal centers is one approach to better understanding the mechanism that govern commercial HDS. Therefore, we have currently been investigating the use of Re2(CO)10 as a potential model system for catalytic HDS with respect to S-binding, ring-opening, and hydrogenation of thiophenes andbenzothiophenes. We have also been investigating the use of UV-light as a method for activating thiophenic molecules towards C-S and C-H bond cleavage.

  17. Bonding and Moessbauer Isomer Shifts in (Hg,Pb)—1223 Cuprate

    Institute of Scientific and Technical Information of China (English)

    高发明; 田永君; 谌岩; 李东春; 董海峰; 张思远

    2003-01-01

    By using the chemical bond theory of dielectric description,the chemical bond parameters of(Hg,Pb)-1223 were calculated.The results show that the(Ba,Sr)-O and Ca-0 types of bond have higher ionic character,while the Cu-O and(Hg,Pb)-0 types of bond have more covalent character.Moessbauer isomer shifts of 57Fe and 119Sn doped in(Hg,Pb)-1223 were calculated by using the chemical environmental factor,he,defined by covalency and electronic polarizability.Four valence state tin and three valence iron sites were identified in 57Fe and 119Sn doped(Hg,Pb)-1223 superconductor.It can be concluded that all of the Fe atoms substitute the Cu at square planar Cu(1) site,Whereas Sn prefers to substitute the square pyramidal Cu(2) site.

  18. Bonding and M?ssbauer Isomer Shifts in (Tl,Pb) - 1223 Cuprate

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    By using the chemical bond theory of dielectric description,the chemical bond parameters of (Tl,Pb) - 1223 was calculated.The results show that the Sr-O,Tl-O,and Ca-O types of bond have higher ionic character and the Cu-O types of bond have more covalent character.M?ssbauer isomer shifts of 57Fe and 119Sn doped in (Tl,Pb) -1223 were calculated by using the chemical environmental factor,he,defined by covalency and electronic polarizability.Four valence state tin and three valence iron sites were identified in 57Fe,and 119Sn doped (Tl,Pb) -1223 superconductor.We conclude that all of the Fe atoms substitute the Cu at square planar Cu (1) site,whereas Sn prefers to substitute the square pyramidal Cu (2) site.

  19. 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...

  20. Interaction of O-acylated chitosans with biomembrane models: probing the effects from hydrophobic interactions and hydrogen bonding.

    Science.gov (United States)

    Pavinatto, Adriana; Souza, Adriano L; Delezuk, Jorge A M; Pavinatto, Felippe J; Campana-Filho, Sérgio P; Oliveira, Osvaldo N

    2014-02-01

    One of the major challenges in establishing the mechanisms responsible for the chitosan action in biomedical applications lies in the determination of the molecular-level interactions with the cell membrane. In this study, we probed hydrophobic interactions and H-bonding in experiments with O,O'-diacetylchitosan (DACT) and O,O'-dipropionylchitosan (DPPCT) incorporated into monolayers of distinct phospholipids, the zwitterionic dipalmitoyl phosphatidyl choline (DPPC), and the negatively charged dipalmitoyl phosphatidyl glycerol (DPPG) and dimyristoyl phosphatidic acid (DMPA). The importance of hydrophobic interactions was confirmed with the larger effects observed for DACT and DPPCT than for parent chitosan (Chi), particularly for the more hydrophobic DPPCT. Such larger effects were noted in surface pressure isotherms and elasticity of the monolayers. Since H-bonding is hampered for the chitosan derivatives, which have part of their hydroxyl groups shielded by O-acylation, these effects indicate that H-bonding does not play an important role in the chitosan-membrane interactions. Using polarization-modulated infrared reflection absorption (PM-IRRAS) spectroscopy, we found that the chitosan derivatives were incorporated into the hydrophobic chain of the phospholipids, even at high surface pressures comparable to those in a real cell membrane. Taken together, these results indicate that the chitosan derivatives containing hydrophobic moieties would probably be more efficient than parent chitosan as antimicrobial agents, where interaction with the cell membrane is crucial.

  1. Magnetic and thermoelectric properties of a heterogeneous mixed-valence system, Yb sub 2 Pt sub 3 Sn sub 5

    CERN Document Server

    Muro, Y; Kim, M S; Takabatake, T; Godart, C; Rogl, P

    2003-01-01

    We have studied the valence states and thermoelectric properties of Yb sub 2 T sub 3 Sn sub 5 (T=Pt and Pd) with two inequivalent Yb sites. For Yb sub 2 Pt sub 3 Sn sub 5 , the 4 f-hole occupation number n sub f is estimated to be 0.4 at 300 K from the magnetic susceptibility and L sub I sub I sub I -edge absorption spectrum. Intermediate-valence behaviors manifest themselves in a largely negative value of the paramagnetic Curie temperature, -216 K, a broad peak at 300 K in the magnetic part of the resistivity, and a large minimum in the thermopower, -38 mu V/K at 60 K. The specific heat shows no transition down to 0.6 K. These results are explained by a model in which Yb ions in one site are divalent and those in the other site are in a valence fluctuating state with a Kondo temperature of 200 K. Thus, Yb sub 2 Pt sub 3 Sn sub 5 is a rare example of the heterogeneous mixed-valence system. An isostructural compound Yb sub 2 Pd sub 3 Sn sub 5 has a larger unit-cell volume by 2.4%, which allows the Yb ions in b...

  2. Cross Shear Roll Bonding

    DEFF Research Database (Denmark)

    Bay, Niels; Bjerregaard, Henrik; Petersen, Søren. B;

    1994-01-01

    The present paper describes an investigation of roll bonding an AlZn alloy to mild steel. Application of cross shear roll bonding, where the two equal sized rolls run with different peripheral speed, is shown to give better bond strength than conventional roll bonding. Improvements of up to 20......-23% in bond strength are found and full bond strength is obtained at a reduction of 50% whereas 65% is required in case of conventional roll bonding. Pseudo cross shear roll bonding, where the cross shear effect is obtained by running two equal sized rolls with different speed, gives the same results....

  3. Electronic parameters of Sr2Nb2O7 and chemical bonding

    DEFF Research Database (Denmark)

    Atuchin, V.V.; Grivel, Jean-Claude; Korotkov, A.S.

    2008-01-01

    /2)) and Delta(O-Sr) = BE(O 1s)-BE(Sr 3d(5/2)), were used to characterize the valence electron transfer on the formation of the Nb-O and Sr-O bonds. The chemical bonding effects were considered on the basis of our XPS results for Sr2Nb2O7 and earlier published structural and XPS data for other Sr- or Nb...

  4. 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…

  5. Correlation effects in the valence bands of ferromagnetic semiconductor EuS

    OpenAIRE

    Sharma, A; Nolting, W.

    2005-01-01

    We present a many body analysis of the multi-band Kondo lattice model. The study is then combined with the first principles TB-LMTO band structure calculations, in order to investigate the temperature dependent correlation effects in the 3$\\textit{p}$ valence bands of the ferromagnetic semiconductor EuS. Some of the physical properties of interest like the quasi-particle density of states (Q-DOS), spectral density (SD) and quasi-particle band structure (Q-BS) are calculated and discussed. The...

  6. Configuration of the valence neutrons of 17B

    Institute of Scientific and Technical Information of China (English)

    WANG Meng; MAO Rui-Shi; ZHANG Hong-Bin; ZHAO Tie-Cheng; XU Zhi-Guo; WANG Yue; CHEN Ruo-Fu; HUANG Tian-Heng; GAO Hui; JIA Fei; FU Fen; HU Zheng-Guo; GAO Qi; HAN Jian-Long; ZHANG Xue-Heng; ZHENG Chuan; YU Yu-Hong; FAN Rui-Rui; LI Bo; GUO Zhong-Yan; XU Hu-Shan; SUN Zhi-Yu; WANG Jian-Song; XIAO Guo-Qing; ZHAN Wen-Long; ZHANG Xue-Ying; LI Chen

    2008-01-01

    The reaction cross section of 17B on 12C target at (43.7±2.4) MeV/u has been measured at the Radioactive Ion Beam Line in Lanzhou (RIBLL). The root-mean-square matter radius (Rrms) was deduced to be (2.92±0.10) fm, while the Rrms of the core and the valence neutron distribution are 2.28 fm and 5.98 fm respectively. Assuming a "core plus 2n" structure in 17B, the mixed configuration of (2s1/2) and (1d5/2) of the valence neutrons is studied and the s-wave spectroscopic factor is found to be (80±21)%.

  7. Realistic estimate of valence transversity from dihadron production

    CERN Document Server

    Radici, Marco

    2015-01-01

    We have updated our extraction of the transversity parton distribution based on the analysis of pion-pair production in deep-inelastic scattering off transversely polarized targets in collinear factorization. The most recent COMPASS data for proton and deuteron targets, complemented by previous HERMES data on the proton, make it possible to perform a flavor separation of the valence components of the transversity distribution, using di-hadron fragmentation functions taken from the semi-inclusive production of two pion pairs in back-to-back jets in $e^+ e^-$ annihilation. The $e^+ e^-$ data from BELLE have been reanalyzed to reach a more realistic estimate of the uncertainties on the chiral-odd interference fragmentation function. Our results represent the most accurate estimate of the uncertainties on the valence components of the transversity distribution currently available.

  8. Verbal pragmatics following unilateral stroke: emotional content and valence.

    Science.gov (United States)

    Borod, J C; Rorie, K D; Pick, L H; Bloom, R L; Andelman, F; Campbell, A L; Obler, L K; Tweedy, J R; Welkowitz, J; Sliwinski, M

    2000-01-01

    Verbal pragmatic aspects of discourse production were examined in 16 right brain-damaged (RBD), 16 left brain-damaged (LBD), and 16 normal control right-handed adults. The facilitation effect of emotional content, valence hypothesis, and relationship between pragmatics and emotion were evaluated. Participants produced monologues while recollecting emotional and nonemotional experiences. Transcribed monologues were rated for appropriateness on 6 pragmatic features: conciseness, lexical selection, quantity, relevancy, specificity, and topic maintenance. Overall, brain-damaged groups were rated as significantly less appropriate than normals. Consistent with the facilitation effect, emotional content enhanced pragmatic performance of LBD aphasic participants yet suppressed performance of RBD participants. Contrary to the valence hypothesis, RBD participants were more impaired for positive emotions and LBD participants for negative emotions. Pragmatic appropriateness was not strongly correlated with a measure of emotional intensity.

  9. Covert face recognition relies on affective valence in congenital prosopagnosia.

    Science.gov (United States)

    Bate, Sarah; Haslam, Catherine; Jansari, Ashok; Hodgson, Timothy L

    2009-06-01

    Dominant accounts of covert recognition in prosopagnosia assume subthreshold activation of face representations created prior to onset of the disorder. Yet, such accounts cannot explain covert recognition in congenital prosopagnosia, where the impairment is present from birth. Alternatively, covert recognition may rely on affective valence, yet no study has explored this possibility. The current study addressed this issue in 3 individuals with congenital prosopagnosia, using measures of the scanpath to indicate recognition. Participants were asked to memorize 30 faces paired with descriptions of aggressive, nice, or neutral behaviours. In a later recognition test, eye movements were monitored while participants discriminated studied from novel faces. Sampling was reduced for studied--nice compared to studied--aggressive faces, and performance for studied--neutral and novel faces fell between these two conditions. This pattern of findings suggests that (a) positive emotion can facilitate processing in prosopagnosia, and (b) covert recognition may rely on emotional valence rather than familiarity.

  10. Realistic estimate of valence transversity distributions from inclusive dihadron production

    CERN Document Server

    Radici, Marco; Bacchetta, Alessandro; Guagnelli, Marco

    2015-01-01

    We present an updated extraction of the transversity parton distribution based on the analysis of pion-pair production in deep-inelastic scattering off transversely polarized targets in collinear factorization. Data for proton and deuteron targets make it possible to perform a flavor separation of the valence components of the transversity distribution, using di-hadron fragmentation functions taken from the semi-inclusive production of two pion pairs in back-to-back jets in e+e- annihilation. The e+e- data from Belle have been reanalyzed using the replica method and a more realistic estimate of the uncertainties on the chiral-odd interference fragmentation function has been obtained. Then, the transversity distribution has been extracted by using the most recent and more precise COMPASS data for deep-inelastic scattering off proton targets. Our results represent the most accurate estimate of the uncertainties on the valence components of the transversity distribution currently available.

  11. Valence, Implicated Actor, and Children's Acquiescence to False Suggestions.

    Science.gov (United States)

    Cleveland, Kyndra C; Quas, Jodi A; Lyon, Thomas D

    2016-01-01

    Although adverse effects of suggestive interviewing on children's accuracy are well documented, it remains unclear as to whether these effects vary depending on the valence of and the actor implicated in suggestions. In this study, 124 3-8-year-olds participated in a classroom activity and were later questioned about positive and negative false details. The interviewer provided positive reinforcement when children acquiesced to suggestions and negative feedback when they did not. Following reinforcement or feedback, young children were comparably suggestible for positive and negative details. With age, resistance to suggestions about negative details emerged first, followed by resistance to suggestions about positive details. Across age, more negative feedback was required to induce acquiescence to negative than positive false details. Finally, children were less willing to acquiesce when they (versus the confederate) were implicated. Findings highlight the interactive effects of valence and children's age on their eyewitness performance in suggestive contexts.

  12. 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...

  13. Valence electron structure and properties of stabilized ZrO2

    Institute of Scientific and Technical Information of China (English)

    LI JinPing; HAN JieOai; MENG SongHe; ZHANG XingHong

    2008-01-01

    To reveal the properties of stabilizers in ZrO2 on nanoscopic levels,the valence elec-tron structures of four stable ZrO2 phases and c-ZrO2 were analyzed on the basis of the empirical electron theory of solids and molecules.The results showed that the hybridization levels of Zr atoms in c-ZrO2 doped with Ca and Mg dropped from B17 to B13,the hybridization levels of Zr atoms in c-ZrO2 doped with Y and Ce dropped from B17 to B15,and that the four stabilizing atoms all made the hybridization levels of O atoms drop from level 4 to level 2.The numbers of covalent electrons in the strongest covalent bond in the descending order are c-ZrO2>ZrCeO2>ZrYOZrMgO>ZrCaO.The bond energies of the strongest covalent bond and the melting points of the solid solutions in the descending order are ZrCeO2>c-ZrO2>ZrYO>ZrMgO>ZrCaO.The percent-ages of the total number of covalent electrons in the descending order arec-ZrO2>ZrYO> ZrCeO2>ZrMgO> ZrCaO.From the above analysis,it can be concluded that the stabilizing degrees of the four stabilizers in the descending order are CaO> MgO>Y2O3>CeO2.

  14. Mineralogical Changes and Fe Valence State During Antigorite Breakdown in Subduction Settings

    Science.gov (United States)

    Merkulova, M.; Munoz, M.; Vidal, O.; Brunet, F.

    2014-12-01

    Mineralogical and petrological changes in subduction zones include transition from altered hydrated rocks (mostly serpentinites) to anhydrous peridotites with the release of fluid. Changes in the valence of iron and other ions capable for electron-exchanges remain poorly constrained during this transition. The approach of this work comprises thermodynamic modeling and experiments based on the use of a piston-cylinder apparatus. We show a series of experiments with the range of temperatures from 550 to 850oC at pressure of 2 GPa, which perform the antigorite dehydration reaction using Fe-bearing antigorite and magnetite as starting material. The experimentally produced mineral phases have been characterized by X-ray diffraction, electron microprobe and X-ray absorption spectroscopy (XANES at the iron K-edge). At each step of serpentinite dehydration reaction we provide the modal abundance of minerals, the amount of releasing water, the chemical compositions of phases and the Fe-oxidation state. The modal abundance of experimental product assemblage changes gradually. Thus, antigorite dominates untill 650 oC and it fully dehydrates after 700 oC. Olivine and enstatite are the most prevailing phases at higher temperatures. However, chlorite, diopside and tremolite are observed during the reaction. Furthermore, olivine and antigorite have been found to change their iron content depending on temperature, which is in consistent with thermodynamic modeling accomplished in the present study. As the reaction progress with the increase of temperature, evolution of iron oxidation state changes. Antigorite containing mostly Fe3+ releases water and breaks down into olivine and enstatite containing Fe2+. The bulk Fe3+/Fetotal ratio decreases rapidly during first steps of the reaction and continue decreasing after antigorite disappearance. In our results we have showed the analyses of Fe valence state in both bulk rocks and separate minerals. Characterizing the evolution of

  15. Valence holes observed in nanodiamonds dispersed in water.

    Science.gov (United States)

    Petit, Tristan; Pflüger, Mika; Tolksdorf, Daniel; Xiao, Jie; Aziz, Emad F

    2015-02-21

    Colloidal dispersion is essential for most nanodiamond applications, but its influence on nanodiamond electronic properties remains unknown. Here we have probed the electronic structure of oxidized detonation nanodiamonds dispersed in water by using soft X-ray absorption and emission spectroscopies at the carbon and oxygen K edges. Upon dispersion in water, the π* transitions from sp(2)-hybridized carbon disappear, and holes in the valence band are observed.

  16. Characterization of the valence and conduction bands in Si nanocrystals

    Science.gov (United States)

    van Buuren, T.; Terminello, L.; Chase, L.; Callcott, T.; Grush, M.

    1998-03-01

    Silicon nanocrystals with a mean diameter between 1 and 4 nm were produced by thermal evaporation of Si in Ar buffer gas and deposited on a substrate. The size-distribution and diameter of the clusters were characterized by atomic force microscopy. The valence and conduction band edges of the Si nanocrystals were measured in-situ using soft x-ray emission (SXE) and absorption (XAS) spectroscopies. The valence band of the smallest Si nanocrystals is shifted by much as 0.7 eV relative to bulk Si. Significant changes in the shape of the spectra are also observed between the Si nanocrytals and bulk Si. We interpret the shift and changes in the spectra of the valence band as resulting from an altered electronic band structure in the confined Si structures. A smaller but proportional shift of the conduction band to higher energy is also observed in the XAS spectra of the silicon nanostructures. We compare the experimentally measured bandgap to recent electronic structure calculations and find, that the experimentally measured bandgap is smaller than that predicted by theory. Work supported by the U.S. Department of Energy, BES-Materials Sciences, under Contract W-7405-ENG-48.

  17. Valence parity renders z(*)-type ions chemically distinct.

    Science.gov (United States)

    Hubler, Shane L; Jue, April; Keith, Jason; McAlister, Graeme C; Craciun, Gheorghe; Coon, Joshua J

    2008-05-21

    Here we report that the odd electron z (*) -type ions formed by the electron-based peptide dissociation methods (electron capture or transfer, ECD or ETD) have distinctive chemical compositions from other common product ion types. Specifically, b-, c-, and y-type ions have an odd number of atoms with an odd valence (e.g., N and H), while z (*)-type ions contain an even number of atoms with an odd valence. This tenet, referred to as the valence parity rule, mandates that no c-type ion shall have the same chemical composition, and by extension mass, as a z (*) -type ion. By experiment we demonstrate that nearly half of all observed c- and z (*) -type product ions resulting from 226 ETD product ion spectra can be assigned to a single, correct, chemical composition and ion type by simple inspection of the m/ z peaks. The assignments provide (1) a platform to directly determine amino acid composition, (2) an input for database search algorithms, or (3) a basis for de novo sequence analysis.

  18. The valence and spectral properties of rare-earth clusters

    CERN Document Server

    Peters, L; Litsarev, M S; Katsnelson, A Delin M I; Kirilyuk, A; Johansson, B; Sanyal, B; Eriksson, O

    2016-01-01

    The rare-earths are known to have intriguing changes of the valence, depending on chemical surrounding or geometry. Here we make predictions from theory that combines density functional theory with atomic multiplet-theory, on the transition of valence when transferring from the atomic divalent limit to the trivalent bulk, passing through different sized clusters, of selected rare-earths. We predict that Tm clusters show an abrupt change from pure divalent to pure trivalent at a size of 6 atoms, while Sm and Tb clusters are respectively pure divalent and trivalent up to 8 atoms. Larger Sm clusters are argued to likely make a transition to a mixed valent, or trivalent, configuration. The valence of all rare-earth clusters, as a function of size, is predicted from interpolation of our calculated results. We argue that the here predicted behavior is best analyzed by spectroscopic measurements, and provide theoretical spectra, based on dynamical mean field theory, in the Hubbard-I approximation, to ease experiment...

  19. Hydrogen bonding in oxalic acid and its complexes: A database study of neutron structures

    Indian Academy of Sciences (India)

    R Chitra; Amit Das; R R Choudhury; M Ramanadham; R Chidambaram

    2004-08-01

    The basic result of carboxylic group that the oxygen atom of the –OH never seems to be a hydrogen bond acceptor is violated in the cases, namely urea oxalic acid and bis urea oxalic acid complexes, where the hydroxyl oxygen atom is an acceptor of a weak N–H... O hydrogen bond. The parameters of this hydrogen bond, respectively in these structures are: hydrogen acceptor distance 2.110 Å and 2.127 Å and the bending angle at hydrogen, 165.6° and 165.8°. The bond strength around the hydroxyl oxygen is close to 1.91 valence units, indicating that it has hardly any strength left to form hydrogen bonds. These two structures being highly planar, force the formation of this hydrogen bond. As oxalic acid is the common moiety, the structures of the two polymorphs, -oxalic acid and -oxalic acid, also were looked into in terms of hydrogen bonding and packing.

  20. Structure-property relationships in cubic cuprous iodide: A novel view on stability, chemical bonding, and electronic properties.

    Science.gov (United States)

    Pishtshev, A; Karazhanov, S Zh

    2017-02-14

    Based on the combination of density functional theory and theory-group methods, we performed systematic modeling of γ-CuI structural design at the atomistic level. Being started from the metallic copper lattice, we treated a crystal assembly as a stepwise iodination process characterized in terms of a sequence of intermediate lattice geometries. These geometries were selected and validated via screening of possible structural transformations. The genesis of chemical bonding was studied for three structural transformations by analyzing the relevant changes in the topology of valence electron densities. We determined structural trends driven by metal-ligand coupling. This allowed us to suggest the improved scenario of chemical bonding in γ-CuI. In particular, the unconventional effect of spatial separation of metallic and covalent interactions was found to be very important with respect to the preferred arrangements of valence electrons in the iodination process. We rigorously showed that useful electronic and optical properties of γ-CuI originate from the combination of two separated bonding patterns-strong covalency established in I-Cu tetrahedral connections and noncovalent interactions of copper cores is caused by the 3d(10) closed-shell electron configurations. The other finding of ours is that the self-consistency of the GW calculations is crucial for correctly determining the dynamic electronic correlations in γ-CuI. Detail reinvestigation of the quasi-particle energy structure by means of the self-consistent GW approach allowed us to explain how p-type electrical conductivity can be engineered in the material.