Theoretical investigations on low energy surfaces and nanowires of MgH(2)

The phase stability, chemical bonding, and electronic structure of MgH(2) nanowires and possible low energy surfaces of α-MgH(2) thin films have been investigated using the ab initio projected augmented plane-wave method. Structural optimizations based on total energy calculations predicted that, for the α-MgH(2) phase, the (101) surface is more stable among the possible low energy surfaces. The electronic structure study reveals that the nanowires also have nonmetallic character similar to that of the bulk and thin film phases. Bonding analysis shows that the character of chemical bonding in nanowires has been considerably changed compared with that in bulk phases. Similarly, the bond distances in the surfaces of nanowires are found to be higher than in the bulk material, suggesting that it is possible to remove hydrogen from the nanowires considerably more easily than from bulk crystals.     

A Monte Carlo simulation of silicon nitride thin film microstructure in ultraviolet localized-chemical vapor deposition

Microstructural changes of surfaces and bulk of a SiN: H were investigated at the atomic level by a simulator. The simulator is based on a solid-on-solid type model for ultraviolet localized-chemical vapor deposition. The calculations consider the well-defined photolysis products adsorbed at atomic sites. Incorporation of main species is enabled by a Monte Carlo-Metropolis simulation technique. Photodeposition rates are obtained using bond dissociation energies. In this manner, the dependence of root-mean-square deviation of surface roughness and bulk porosity on operating conditions can be predicted. Photonucleation and photodeposition with a UV low pressure mercury lamp at low pressure and temperature were simulated onto indium phosphide substrate.     

Further study on structural and electronic properties of silicon phosphide compounds with 3:4 stoichiometry

Si₃N₄ has been extensively studied, due to its potential applications in electronic devices. Substitution of N by P results in Si₃P₄ which is a relatively unknown material. In this study, we carried out further investigation on the structural and electronic properties of Si₃P₄ using first principles total energy method based on the density functional theory and the generalized gradient approximation. Our calculations show that pseudocubic-Si₃P₄ is energetically favored. However, the present study based on the generalized gradient approximation predicts that the phase is more stable than the γ phase which was predicted to be more energetically stable in an earlier study based on the local density approximation. Other properties such as bulk modulus, band structure, of Si₃P₄ calculated using GGA are consistent with the LDA results.     

Structure and formation energy of steps on the GaAs(001)-2 × 4 surface

The energies of various steps on the As-terminated GaAs(001)-2 × 4 surface are evaluated using a novel, approximate method of “linear combination of structural motifs”. It is based on the observation that previous total energy minimizations of semiconductor surfaces produced invariably equilibrium structures made of the same recurring local structural motifs, e.g. tetrahedral fourfold Ga, pyramidal threefold As, etc. Furthermore, such surface structures were found to obey consistently the octet rules as applied to the local motifs. We thus express the total energy of a given semiconductor surface as a sum of (i) the energies _M of the local structural motifs appearing in the surface under consideration and (ii) an electrostatic term representing the Madelung energy of point charges resulting from application of the octet rule. The motif energies are derived from a set of pseudopotential total energy calculations for flat GaAs(001) surfaces and for point defects in bulk GaAs. This set of parameters suffices to reproduce the energies of other (001) surfaces, calculated using the same pseudopotential total energy approach. Application to GaAs(001)-2 × 4 surfaces with steps reveals the following. (i) “Primitive steps”, defined solely according to their geometries (i.e. step heights, widths and orientations) are often unstable. (ii) Additional, non-geometric factors beyond step geometries such as addition of surface adatoms, creation of vacancies and atomic rebonding at step edges are important to lower step energies. So is step-step interaction. (iii) The formation of steps is generally endothermic. (iv) The formation of steps with edges parallel to the direction of surface As dimers (A steps) is energetically favored over the formation of steps whose edges are perpendicular to the As dimers (B steps).     

A nonlinear model of piezoelectric polycrystalline ceramics under quasi-static electromechanical loading

Nonlinear characteristics of tetragonal perovskite type polycrystalline piezoelectric ceramics under electromechanical loading are theoretically simulated using a threedimensional micromechanical model. The model consists of many differently oriented grains which form the bulk material. Uni-axial, quasi-static loading is applied in the simulations. The calculations which are based on a linear constitutive and nonlinear domain switching model are performed at each grain. All grains are assumed to be statistically random oriented at the virgin state.The behavior of piezoelectric ceramics under constant compressive stress which is applied in the same direction of the cyclic electric field is investigated. The macroscopic response of the bulk ceramics to the applied loading is predicted by averaging the response of individual grains. It is assumed that a domain or a microstructure switches if the reduction in potential energy of the polycrystal exceeds a threshold of critical energy per unit volume of the material. Due to intergranular effects domain switching may occur in reality even for those grains, for which the critical energy level is not reached. This effect is modeled by introducing a probability for domain switching as a function of the actual energy level related to the critical energy level. By use of the probability functions, it is possible to model the nonlinearity even in a small electromechanical loading range. The effect of different probability functions, and material parameters are also analysed. The results of simulations have been compared with experimental data from literature.     

Zinc-blende GaN: ab initio calculations

The purpose of this paper is to contribute, on a theoretical basis, an understanding of future wide-gap device concepts and applications based on III–V nitride semiconductors. The electronic properties of zinc-blende structure GaN and their (110), (100) and (111) surfaces are investigated using ab initio calculations based on the full potential linear augmented plane-wave (FPLAPW) method within the large unit cell approach, and on the molecular Gaussian-92 code. Lattice constant, cohesive energy, bulk modulus are obtained from total energy calculations. Light-hole and heavy-hole effective masses along (100), (111) and (110) directions and electron masses at Γ point are extracted from band structure calculations and compared with previous ones based on pseudopotential methods. The hydrostatic pressure dependence of the ΓΓ, ΓX and ΓL energy gaps are also obtained. Comparing our band structure and ‘molecular cluster' calculations, the relaxations of the surfaces are found to be mostly determined by local rehybridization or valence effects and are basically independent of energy band features.     

Bonding to aged surfaces: A thermally-aged epoxy

It is common experience that aged surfaces are often difficult to bond to. We report an examination of bonding to thermally-aged epoxy surfaces, using as the adhesive the same epoxy as that of the aged surface. The cured and postcured epoxy was aged at 200 ° C, with the ageing time varying from 2 to 8 h. The fracture energy of the bond line was measured by mode I cleavage under conditions of relatively slow crack growth. The bondline fracture energy was found to decrease logarithmically with ageing time. The fracture energies for bonds to surfaces aged for 2, 4, and 8 h at 200 ° C were 0.077, 0.059, and 0.050 kJ M^–2, respectively. These compare to 0.13 kJ M^–2 for a bond to an unaged surface and 0.21 kJ m^–2 for bulk fracture. Fracture surfaces resulting from both slow and rapid fracture were examined by optical and scanning electron microscopy. Fracture features different from those arising from bulk fracture were found. Areas with good adhesion occurred amidst fields of featureless fracture surface; the frequency and size of these areas decreased with increased ageing time. Evidence of plastic deformation was found, always occurring on the new side of the bond: ridges parallel with crack propagation at high crack speeds and subsurface undulations perpendicular to crack propagation at low speeds. The bond has the effect of channelling the crack along the bondline, but fracture does not always remain exactly at the interface. Fracture often occurred a relatively constant distance away from the interface, suggesting that the presence of the interface was felt for some distance.     

新型三元层状硼化物Cr4AlB4的物相稳定性和力学行为分析

Cr₄AlB₄是一种近期发现的三元层状硼化物MAB相陶瓷。该材料可形成具有保护性的氧化膜, 在高温结构材料领域有巨大应用潜力。本工作采用基于第一性原理的“线性优化法”和“键刚度”理论模型分别研究了Cr₄AlB₄的物相稳定性和力学行为。声子谱中没有虚频出现, 表明Cr₄AlB₄具有本征稳定性。而与其它Cr-Al-B系内的竞争相相比, Cr₄AlB₄具有最低的能量, 表明其在热力学上也是稳定的。采用“键刚度”模型对化学键刚度的定量计算显示, Cr₄AlB₄中Cr和B以及B和B原子之间形成了强共价键, 而Cr和Al原子则形成相对较弱的Cr-Al(625 GPa)和 B-Al(574 GPa)键。Cr₄AlB₄可以看成是由强共价键紧密连接在一起的Cr-B结构单元, 被弱Cr(B)-Al键分割而成的层状结构, 与MAX相结构类似。Cr₄AlB₄具有类似于MAX相的高损伤容限和断裂韧性。     

Quantum chemical, ballistic and explosivity calculations on 2,4,6,8-tetranitro-1,3,5,7-tetraaza cyclooctatetraene: a new high energy molecule

Ab initio molecular orbital calculations have been carried out on 2,4,6,8-tetranitro-1,3,5,7-tetraazacyclooctatetraene, the tetramer of the series (NO(2)CN)(n) where n=1-4, using the Hartree-Fock theory with the 6-31 G(d) basis set. These calculations yield three conformers for the tetramer with D(4h), C(4h) and C(2) symmetries. The nonplanar conformer with the C(2) symmetry turns out to be 99.0 and 164.4kJmol(-1), respectively, lower in energy than the C(4h) and D(4h) conformers. The electron density topography - the density at the bond critical point - has been used as a measure of the CNO(2) strengths. Based on these bond strengths, heats of formation [obtained from the parametric model 3 (PM3) method] and specific decomposition energies, it may be concluded that (NO(2)CN)(4) is a promising candidate in the class of high energy molecules. Theoretically computed explosive (velocity of detonation, detonation pressure, etc.) and ballistic (characteristic velocity, specific impulse, etc.) parameters support these conclusions.     

Polyhedral 30‐Faceted BiVO4 Microcrystals Predominantly Enclosed by High‐Index Planes Promoting Photocatalytic Water‐Splitting Activity

Unprecedented 30‐faceted BiVO₄ polyhedra predominantly surrounded by {132}, {321}, and {121} high‐index facets are fabricated through the engineering of high‐index surfaces by a trace amount of Au nanoparticles. The growth of high‐index facets results in a 3–5 fold enhancement of O₂ evolution from photocatalytic water splitting by the BiVO₄ polyhedron, relative to its low‐index counterparts. Theory calculations reveal that water dissociation is more energetically favorable on the high‐index surfaces than on the low‐index (010), (110), and (101) surfaces, which is accompanied by a notable reduction in the overpotential (0.77–1.14 V) for the oxygen evolution reaction. The apparent quantum efficiency of O₂ generation without an external electron supply reaches 18.3% under 430 nm light irradiation, which is an order of magnitude higher than that of the catalysts reported hitherto.     

Modelling of critical fibre length and interfacial debonding in the fragmentation testing of polymer composites

Micro-mechanical models based on a unidimensional load transfer approximation are used to predict the critical fibre length as a function of applied strain in the fragmentation testing of polymer matrix composites. Conditions of perfect adhesion, partial debonding, and total debonding are considered in turn. Situations are identified where the critical length cannot be viewed as a material constant, i.e. where it remains strain dependent as the applied strain increases. Numerical results based on the partial debonding model are given for the critical fibre length and the extent of the debonding zone as a function of applied strain. The prediction of the total debonding model is recovered asymptotically for large strains. We find, however, that the critical length predicted by the partial debonding model can be lower than the one predicted by the total debonding model if the interfacial bond strength is sufficiently larger than the frictional shear stress. These theoretical results show that both bond strength and frictional shear stress must be taken into account in the interpretation of the fragmentation test data.     

Coordination-dependent surface atomic contraction in nanocrystals revealed by coherent diffraction

Surface atoms have fewer interatomic bonds than those in the bulk that they often relax and reconstruct on extended two-dimensional surfaces. Far less is known about the surface structures of nanocrystals. Here, we show that coherent diffraction patterns recorded from individual nanocrystals are very sensitive to the atomic structure of nanocrystal surfaces. Nanocrystals of Au of 3-5 nm in diameter were studied by examining diffraction intensity oscillations around the Bragg peaks. Both results obtained from modelling the experimental data and molecular dynamics simulations strongly suggest inhomogeneous relaxations, involving large out-of-plane bond length contractions for the edge atoms (approximately 0.2 A); a significant contraction (approximately 0.13 A) for {100} surface atoms; and a much smaller contraction (approximately 0.05 A) for atoms in the middle of the {111} facets. These results denote a coordination/facet dependence that markedly differentiates the structural dynamics of nanocrystals from bulk crystalline surfaces.     

Chlorine adsorption on Mg,Ca, and MgCa surfaces

The surface energies and work functions of Mg, Ca, and MgCa surfaces are derived by means of first principles calculation, and it is found that the Ca-terminated B2 MgCa surfaces have much lower surface energies than corresponding Mg-terminated surfaces. Moreover, calculations reveal that the adsorption energy of Cl atom on Ca (111) surface is much lower than that on Mg (0001) surface due to a stronger CaCl bond than MgCl, and that for MgCa (110) surface, various possible adsorption of Cl atoms are investigated and the most energetically preferred site is found. In addition, the magnitude of adsorption energies suggest that the corrosion resistance of MgCa (110) surface against Cl atom would be located between those of Mg (0001) and Ca (111) surfaces. The relative stability of various adsorption sites is discussed by means of electronic structures, and the present calculated results are in good agreement with experimental results in the literature.     

Atomistic design of thermoelectric properties of silicon nanowires

We present predictions of the thermoelectric figure of merit ( ZT) of Si nanowires with diameter up to 3 nm, based upon the Boltzman transport equation and ab initio electronic structure calculations. We find that ZT depends significantly on the wire growth direction and surface reconstruction, and we discuss how these properties can be tuned to select silicon based nanostructures with combined n-type and p-type optimal ZT. Our calculations show that only by reducing the ionic thermal conductivity by about 2 or 3 orders of magnitudes with respect to bulk values, one may attain ZT larger than 1, for 1 or 3 nm wires, respectively. We also find that ZT of p-doped wires is considerably smaller than that of their n-doped counterparts with the same size and geometry.     

Ab initio study of antiferroelectric PbZrO<Subscript>3</Subscript> (001) surfaces

We have carried out first-principles total-energy calculations of bulk and (001) surfaces of PbZrO₃. The ground state for bulk PbZrO₃ is determined to be the antiferroelectric orthorhombic phase, with the ferroelectric rhombohedral and paraelectric cubic phases being 0.14 and 0.39 eV per formula unit higher in energy, respectively. PbO- and ZrO₂-terminated (001) surfaces, either clean or when hydroxyl species were adsorbed were considered. Surface relaxations, in-plane antiferroelectric distortions and modifications to the electronic structure due to the surfaces, and hydroxyl adsorbates on the surfaces were investigated. We find that while clean surfaces retained bulk-like behavior, hydroxyl adsorbates induce significant changes to the surface geometry as well as introduce electronic states in the band gap possibly rendering the surfaces metallic.     

Computational studies on nitratoethylnitramine (NENA), its tautomers and charged forms

An energetic material, nitratoethylnitramine (NENA), its tautomers and also its charged forms are considered quantum chemically, using various basis sets at the levels of ab initio and density functional theories (DFT). NENA has been found to be sensitive to negative charge development, resulting in rupture of ONO(2) bond. Also conformational and molecular dynamics (MD) studies have been performed on NENA. Various geometrical parameters, energies and infrared spectra have been obtained and discussed. Also, calculations indicate that s-cis conformation of NENA is slightly more stable than the s-trans and the tautomers of it have very comparable total energy values to NENA. On the other hand, on the basis of homolytic bond dissociation energies (BDE) for ONO(2) bond in the structures, it is clear that the presence of the tautomers in the bulk of NENA somewhat should decrease its sensitivity.     

A cluster approach to hydrogen chemisorption on the GaAs(1 0 0) surface

Chemisorption properties of atomic hydrogen on the Ga-rich GaAs(1 0 0), (2×1) and β(4×2) surfaces are investigated using ab initio self-consistent restricted open shell Hartree–Fock (ROHF) total energy calculations with Hay–Wadt (HW) effective core potentials. The effects of electron correlation have been included using many-body perturbation theory through second order with the exception of β(4×2) symmetry due to computational limitations. The semiconductor surface is modeled by finite sized hydrogen saturated clusters. The effects of surface reconstruction have been investigated in detail. We report on the energetics of chemisorption on the (1 0 0) surface layer, including adsorption beneath the surface layer at an interstitial site, and also report on the possible dimer bond breaking at the bridge site. Chemisorption energies, bond lengths, and charge population analysis are reported for all considered sites of chemisorption.     

Hydrothermal synthesis and luminescent properties of microtubes constructed by fluffy Zns:Mn2+ with nanostructures

Tubular micrometer-sized ZnS:Mn2+ constructed by fluffy nanostructures were fabricated in the mixed solutions of water and ethanol in a fixed volume ratio with the aid of ethylenediamine. In the X-ray diffraction pattern, the products obtained in the presence and absence of ethylenediamine show the wurtzite and sphalerite phases, respectively. Field-emission scanning electron microscopic images reveal the evolution process from nanowires to fluffy ZnS:Mn2+ to microtubes with the reaction times of 2, 4, and 8 hours at 100 degrees C, and the basal nanowires are below 10 nm in diameter. Photoluminescence and photoluminescence excitation spectra were investigated. The results suggest that the wurtzite phase, instead of the sphalerite phase ZnS:Mn2+ is luminescence-active for the 4T1 -6A1 transition of the Mn2+ in the ZnS host. The excitation spectra monitored at orange emission bands exhibit sharp peaks at 320, 326 and 327 nm with increasing reaction times of 2, 4, and 8 hours, respectively, indicating the energy transfer from ZnS host to Mn2+ ions, and the blue-shifts compared with the band gap absorption of the bulk counterpart (344 nm) are also observed due to the quantum confinement effects. The formation mechanism of the wurtzite one-dimensional nanostructures at such a low temperature is proposed based on a molecular template mechanism involving the bidentate coordinating ligand, ethylenediamine, and the possible formation mechanism of novel tubular structure are also discussed.     

Two-dimensional cadmium selenide electronic and optical properties: first principles studies

Structural, electronic and optical properties of two-dimensional (2D) cadmium selenide (CdSe) structures with \(2\times 2\) periodicities are investigated. First principles total energy calculations are performed within the periodic density functional theory. Initially, the structural properties are determined using the local density approximation as implemented in the PWscf code of quantum ESPRESSO package. To investigate the electronic properties, the GW method is applied to determine the energy gap within the plasmon pole and the random phase approximations. Optical properties are investigated to determine the dielectric constant and the Bethe–Salpeter theory is used to calculate the exciton binding energies. Zinc blende and wurtzite phases are considered to calculate the bulk energy gaps, which are compared to the experimental values, finding good agreement. The 2D structure exhibits an energy gap larger than that of the bulk, indicating the effects of reduction in dimensionality; these changes can be attributed to the dangling bonds that are present in the 2D layer.     

Stability and Half-Metallicity of the (001) and (111) Surfaces of RbN with Cesium Chloride Structure

Using the full-potential local orbital minimum-basis method, we study the electronic and magnetic properties of relaxed (001) and (111) surfaces of the bulk RbN within the framework of density functional theory. It is shown that the Rb(N)-terminated (001) surfaces as well as the N-terminated (111) surface are the half-metallicity, while the Rb-terminated (111) surface loses the half-metallicity. The atomic magnetic moments at the N-terminated (001) and Rb(N)-terminated (111) surfaces increase considerably with respect to the corresponding bulk values. In addition, calculations reveal the half-metallicity of the N-terminated (111) surface is more robust than the bulk RbN due to its larger half-metallic gap. Finally, we discuss the stability of the surface. The positive formation energy in the bulk RbN indicates the surfaces unstable, and non-equilibrium growth techniques may be required for the realization of RbN thin films.