Barrier for the reaction X20+ + X20+ -> X402+ in alkali-metal clusters related to electron density at the bond midpoint of the supermolecule (X20+)2

Using the extended Thomas-Fermi version of density-functional theory (DFT), calculations are presented for the barrier for the reaction Na20++Na20+¿Na402+. The deviation from the simple Coulomb barrier is shown to be proportional to the electron density at the bond midpoint of the supermolecule (Na20+)2. An extension of conventional quantum-chemical studies of homonuclear diatomic molecular ions is then effected to apply to the supermolecular ions of the alkali metals. This then allows the Na results to be utilized to make semiquantitative predictions of position and height of the maximum of the fusion barrier for other alkali clusters. These predictions are confirmed by means of similar DFT calculations for the K clusters.

Avalanches in a fluctuationless first-order phase transition in a random-bond Ising model

We study the behavior of the random-bond Ising model at zero temperature by numerical simulations for a variable amount of disorder. The model is an example of systems exhibiting a fluctuationless first-order phase transition similar to some field-induced phase transitions in ferromagnetic systems and the martensitic phase transition appearing in a number of metallic alloys. We focus on the study of the hysteresis cycles appearing when the external field is swept from positive to negative values. By using a finite-size scaling hypothesis, we analyze the disorder-induced phase transition between the phase exhibiting a discontinuity in the hysteresis cycle and the phase with the continuous hysteresis cycle. Critical exponents characterizing the transition are obtained. We also analyze the size and duration distributions of the magnetization jumps (avalanches).

Resonating-valence-bond theory for the square-planar lattice

The short-range resonating-valence-bond (RVB) wave function with nearest-neighbor (NN) spin pairings only is investigated as a possible description for the Heisenberg model on a square-planar lattice. A type of long-range order associated to this RVB Ansatz is identified along with some qualitative consequences involving lattice distortions, excitations, and their coupling.

Valence-bond treatment of distortions in polyacene polymers

Distortions of polyacene polymers are studied within a many-body valence-bond framework using a powerful transfer-matrix technique for the valence-bond (or Heisenberg) model of the system. The computations suggest that the ground-state geometry is either totally symmetric or possibly exhibits a slight (A2 or B2 symmetry) bond-alternation distortion. The lowest-energy (nonsymmetric, in-plane) distortions are the A2 and B2 modes, which, within our approximations, are degenerate.

Evidence for oxygen-island formation on Al(111): Cluster-model theory and x-ray photoelectron spectroscopy

The O 1s x-ray photoelectron spectroscopy spectrum for Al(111)/O at 300 K shows two components whose behavior as a function of time and variation of detection angle are consistent with either (a) a surface species represented by the higher binding-energy (BE) component and a subsurface species represented by the lower BE component, or (b) small close-packed oxygen islands with the interior atoms represented by the lower BE component and the perimeter atoms by the higher BE component. We have modeled both situations using ab initio Hartree-Fock wave functions for clusters of Al and O atoms. For an O atom in a threefold site, it was found that a below-surface position gave a higher O 1s BE than an above-surface position, incompatible with interpretation (a). This change in the O 1s BE could arise because the bond for O to Al may have a more covalent character when the O is below the surface than when it is above the surface. We present evidence consistent with this view. An O adatom island with all the O atoms in threefold sites gives calculated O 1s BE's which are significantly higher for the perimeter O atoms. Further, the results for an isolated O island without the Al substrate present also give higher BE¿s for the perimeter atoms. Both these results are consistent with interpretation (b). Published scanning-tunneling-microscopy data supports the suggestion that the chemisorbed state consists of small, close-packed islands, whereas the presence of two vibrational modes in high-resolution electron-energy-loss spectroscopy data has been interpreted as representing surface and subsurface oxygen atoms. In light of the present results, we suggest that a vibrational interpretation in terms of interior and perimeter adatoms should be considered.

Ab initio valence-bond cluster model for ionic solids: Alkaline-earth oxides

A linear M-O-M (M=metal, O=oxygen) cluster embedded in a Madelung field, and also including the quantum effects of the neighboring ions, is used to represent the alkaline-earth oxides. For this model an ab initio wave function is constructed as a linear combination of Slater determinants written in an atomic orbital basis set, i.e., a valence-bond wave function. Each valence-bond determinant (or group of determinants) corresponds to a resonating valence-bond structure. We have obtained ab initio valence-bond cluster-model wave functions for the electronic ground state and the excited states involved in the optical-gap transitions. Numerical results are reasonably close to the experimental values. Moreover, the model contains the ionic model as a limiting case and can be readily extended and improved.

Ground and excited states of KNiF3: An ab initio cluster-model approach

Finite cluster models and a variety of ab initio wave functions have been used to study the electronic structure of bulk KNiF3. Several electronic states, including the ground state and some charge-transfer excited states, have been considered. The study of the cluster-model wave functions has permitted an understanding of the nature of the chemical bond in the electronic ground state. This is found to be highly ionic and the different ionic and covalent contributions to the bonding have been identified and quantified. Finally, we have studied the charge-transfer excited states leading to the optical gap and have found that calculated and experimental values are in good agreement. The wave functions corresponding to these excited states have also been analyzed and show that although KNiF3 may be described as a ligand-to-metal charge-transfer insulator there is a strong configuration mixing with the metal-to-metal charge-transfer states.

Bond strength of orthodontic brackets using different light and self-curing cements

The purpose of the study was to evaluate the shear bond strength of stainless steel orthodontic brackets directly bonded to extracted human premolar teeth. Fifty teeth were randomly divided into ¿ve groups: (1) System One (chemically cured composite resin), (2) Light Bond (light-cured composite resin), (3) Vivaglass Cem (self-curing glass ionomer cement), (4) Fuji Ortho LC (light-cured glass ionomer cement) used after 37% orthophosphoric acid¿etching of enamel (5) Fuji Ortho LC without orthophosphoric acid¿etching. The brackets were placed on the buccal and lingual surfaces of each tooth, and the specimens were stored in distilled water (24 hours) at 378C and thermocycled. Teeth were mounted on acrylic block frames, and brackets were debonded using an Instron machine. Shear bond strength values at fracture (Nw)were recorded. ANOVA and Student-Newman-Keuls multiple comparison tests were performed (P , .05). Bonding failure site was recorded by stereomicroscope and analyzed by Chi-square test, selected specimens of each group were observed by scanning electron microscope. System One attained the highest bond strength. Light Bond and Fuji Ortho LC, when using an acid-etching technique, obtained bond strengths that were within the range of estimated bond strength values for successful clinical bonding. Fuji Ortho LC and Vivaglass Cem left an almost clean enamel surface after debracketing.

Effect of water contamination on the shear bond strength of five orthodontic adhesives

Objectives: To evaluate the shear bond strength and site of failure of brackets bonded to dry and wet enamel. Study design: 50 teeth were divided into ten groups of 5 teeth each (10 surfaces). In half the groups enamel was kept dry before bonding, and in the other half distilled water was applied to wet the surface after etching. The following groups were established: 1)Acid/Transbond-XT (dry/wet) XT; 2) Transbond Plus Self Etching Primer (TSEP)/Transbond-XT paste (dry/wet); 3) Concise (dry), Transbond MIP/Concise (wet), 4) FujiOrtho-LC (dry/wet); 5) SmartBond (dry/wet). Brackets were bonded to both buccal and lingual surfaces. Specimens were stored in distilled water (24 hours at 37ºC) and thermocycled. Brackets were debonded using a Universal testing machine (cross-head speed 1 mm/min). Failure sites were classified using a stereomicroscope. Results: No significant differences in bond strength were detected between the adhesives under wet and dry conditions except for Smart- Bond, whose bond strength was significantly lower under dry conditions. For all the adhesives most bond failures were of mixed site location except for Smartbond, which failed at the adhesive-bracket interface. Conclusions: Under wet conditions the bonding capacity of the adhesives tested was similar than under dry conditions, with the exception of SmartBond which improved under wet conditions

A synthetic approach to palmerolides via Negishi cross coupling. The challenge of the C15-C16 bond formation

The esterification of fragment C1-C8 (2) with fragment C16-C23 (3) to give iodo derivative 4, followed by a Pd-catalysed coupling with a C9-C15 fragment (7 or 8), may provide a common precursor of most palmerolides. Ligands and reaction conditions were exhaustively examined to perform the C15-C16 bond formation via Negishi reaction. With simple models, pre-activated Pd-Xantphos and Pd-DPEphos complexes were the most efficient catalysts at RT. Zincation of the C9-C15 fragment (8) and cross coupling with 4 required 3 equiv of t-BuLi, 10 mol % of Pd-Xantphos and 60 °C.

Financial stress transmission in EMU sovereign bond market volatility: a connectedness analysis

This paper measures the connectedness in EMU sovereign market volatility between April 1999 and January 2014, in order to monitor stress transmission and to identify episodes of intensive spillovers from one country to the others. To this end, we first perform a static and dynamic analysis to measure the total volatility connectedness in the entire period (the system-wide approach) using a framework recently proposed by Diebold and Yılmaz (2014). Second, we make use of a dynamic analysis to evaluate the net directional connectedness for each country and apply panel model techniques to investigate its determinants. Finally, to gain further insights, we examine the timevarying behaviour of net pair-wise directional connectedness at different stages of the recent sovereign debt crisis.

Volatility spillovers in EMU sovereign bond markets

We analyse volatility spillovers in EMU sovereign bond markets. First, we examine the unconditional patterns during the full sample (April 1999-January 2014) using a measure recently proposed by Diebold and Yılmaz (2012). Second, we make use of a dynamic analysis to evaluate net directional volatility spillovers for each of the eleven countries under study, and to determine whether core and peripheral markets present differences. Finally, we apply a panel analysis to empirically investigate the determinants of net directional spillovers of this kind.

Quantification of the bond-angle dispersion by Raman spectroscopy and the strain energy of amorphous silicon

A thorough critical analysis of the theoretical relationships between the bond-angle dispersion in a-Si, Δθ, and the width of the transverse optical Raman peak, Γ, is presented. It is shown that the discrepancies between them are drastically reduced when unified definitions for Δθ and Γ are used. This reduced dispersion in the predicted values of Δθ together with the broad agreement with the scarce direct determinations of Δθ is then used to analyze the strain energy in partially relaxed pure a-Si. It is concluded that defect annihilation does not contribute appreciably to the reduction of the a-Si energy during structural relaxation. In contrast, it can account for half of the crystallization energy, which can be as low as 7 kJ/mol in defect-free a-Si