Theory of nitride oxide adsorption on transition metal (111) surfaces: a first-principles investigation

In this work, we report a density functional theory study of nitric oxide (NO) adsorption on close-packed transition metal (TM) Rh(111), Ir(111), Pd(111) and Pt(111) surfaces in terms of adsorption sites, binding mechanism and charge transfer at a coverage of Theta(NO) = 0.25, 0.50, 0.75 monolayer (ML). Based on our study, an unified picture for the interaction between NO and TM(111) and site preference is established, and valuable insights are obtained. At low coverage (0.25 ML), we find that the interaction of NO/TM(111) is determined by an electron donation and back-donation process via the interplay between NO 5 sigma/2 pi* and TM d-bands. The extent of the donation and back-donation depends critically on the coordination number (adsorption sites) and TM d-band filling, and plays an essential role for NO adsorption on TM surfaces. DFT calculations shows that for TMs with high d-band filling such as Pd and Pt, hollow-site NO is energetically the most favorable, and top-site NO prefers to tilt away from the normal direction. While for TMs with low d-band filling (Rh and Ir), top-site NO perpendicular to the surfaces is energetically most favorable. Electronic structure analysis show that irrespective of the TM and adsorption site, there is a net charge transfer from the substrate to the adsorbate due to overwhelming back-donation from the TM substrate to the adsorbed NO molecules. The adsorption-induced change of the work function with respect to bare surfaces and dipole moment is however site dependent, and the work function increases for hollow-site NO, but decreases for top-site NO, because of differences in the charge redistribution. The interplay between the energetics, lateral interaction and charge transfer, which is element dependent, rationalizes the structural evolution of NO adsorption on TM(111) surfaces in the submonolayer regime.

Timoshenko versus Euler beam theory: Pitfalls of a deterministic approach

The selection criteria for Euler-Bernoulli or Timoshenko beam theories are generally given by means of some deterministic rule involving beam dimensions. The Euler-Bernoulli beam theory is used to model the behavior of flexure-dominated (or ""long"") beams. The Timoshenko theory applies for shear-dominated (or ""short"") beams. In the mid-length range, both theories should be equivalent, and some agreement between them would be expected. Indeed, it is shown in the paper that, for some mid-length beams, the deterministic displacement responses for the two theories agrees very well. However, the article points out that the behavior of the two beam models is radically different in terms of uncertainty propagation. In the paper, some beam parameters are modeled as parameterized stochastic processes. The two formulations are implemented and solved via a Monte Carlo-Galerkin scheme. It is shown that, for uncertain elasticity modulus, propagation of uncertainty to the displacement response is much larger for Timoshenko beams than for Euler-Bernoulli beams. On the other hand, propagation of the uncertainty for random beam height is much larger for Euler beam displacements. Hence, any reliability or risk analysis becomes completely dependent on the beam theory employed. The authors believe this is not widely acknowledged by the structural safety or stochastic mechanics communities. (C) 2010 Elsevier Ltd. All rights reserved.

Consolidation of elastic-plastic saturated porous media by the boundary element method

This paper presents a domain boundary element formulation for inelastic saturated porous media with rate-independent behavior for the solid skeleton. The formulation is then applied to elastic-plastic behavior for the solid. Biot`s consolidation theory, extended to include irreversible phenomena is considered and the direct boundary element technique is used for the numerical solution after time discretization by the implicit Euler backward algorithm. The associated nonlinear algebraic problem is solved by the Newton-Raphson procedure whereby the loading/unloading conditions are fully taken into account and the consistent tangent operator defined. Only domain nodes (nodes defined inside the domain) are used to represent all domain values and the corresponding integrals are computed by using an accurate sub-elementation scheme. The developments are illustrated through the Drucker-Prager elastic-plastic model for the solid skeleton and various examples are analyzed with the proposed algorithms. (c) 2008 Elsevier B.V. All rights reserved.

Verification of a mixed high-order accurate DNS code for laminar turbulent transition by the method of manufactured solutions

This paper presents results on a verification test of a Direct Numerical Simulation code of mixed high-order of accuracy using the method of manufactured solutions (MMS). This test is based on the formulation of an analytical solution for the Navier-Stokes equations modified by the addition of a source term. The present numerical code was aimed at simulating the temporal evolution of instability waves in a plane Poiseuille flow. The governing equations were solved in a vorticity-velocity formulation for a two-dimensional incompressible flow. The code employed two different numerical schemes. One used mixed high-order compact and non-compact finite-differences from fourth-order to sixth-order of accuracy. The other scheme used spectral methods instead of finite-difference methods for the streamwise direction, which was periodic. In the present test, particular attention was paid to the boundary conditions of the physical problem of interest. Indeed, the verification procedure using MMS can be more demanding than the often used comparison with Linear Stability Theory. That is particularly because in the latter test no attention is paid to the nonlinear terms. For the present verification test, it was possible to manufacture an analytical solution that reproduced some aspects of an instability wave in a nonlinear stage. Although the results of the verification by MMS for this mixed-order numerical scheme had to be interpreted with care, the test was very useful as it gave confidence that the code was free of programming errors. Copyright (C) 2009 John Wiley & Sons, Ltd.

DESIGN OF CONCRETE PLATFORMS OFFSHORE USING THE THREE-LAYER SHELL THEORY

The concrete offshore platforms, which are subjected a several loading combinations and, thus, requires an analysis more generic possible, can be designed using the concepts adopted to shell elements, but the resistance must be verify in particular cross-sections to shear forces. This work about design of shell elements will be make using the three-layer shell theory. The elements are subject to combined loading of membrane and plate, totalizing eight components of internal forces, which are three membrane forces, three moments (two out-of-plane bending moments and one in-plane, or torsion, moment) and two shear forces. The design method adopted, utilizing the iterative process proposed by Lourenco & Figueiras (1993) obtained from equations of equilibrium developed by Gupta (1896) , will be compared to results of experimentally tested shell elements found in the literature using the program DIANA.

An EFG method for the nonlinear analysis of plates undergoing arbitrarily large deformations

The applicability of a meshfree approximation method, namely the EFG method, on fully geometrically exact analysis of plates is investigated. Based on a unified nonlinear theory of plates, which allows for arbitrarily large rotations and displacements, a Galerkin approximation via MLS functions is settled. A hybrid method of analysis is proposed, where the solution is obtained by the independent approximation of the generalized internal displacement fields and the generalized boundary tractions. A consistent linearization procedure is performed, resulting in a semi-definite generalized tangent stiffness matrix which, for hyperelastic materials and conservative loadings, is always symmetric (even for configurations far from the generalized equilibrium trajectory). Besides the total Lagrangian formulation, an updated version is also presented, which enables the treatment of rotations beyond the parameterization limit. An extension of the arc-length method that includes the generalized domain displacement fields, the generalized boundary tractions and the load parameter in the constraint equation of the hyper-ellipsis is proposed to solve the resulting nonlinear problem. Extending the hybrid-displacement formulation, a multi-region decomposition is proposed to handle complex geometries. A criterium for the classification of the equilibrium`s stability, based on the Bordered-Hessian matrix analysis, is suggested. Several numerical examples are presented, illustrating the effectiveness of the method. Differently from the standard finite element methods (FEM), the resulting solutions are (arbitrary) smooth generalized displacement and stress fields. (c) 2007 Elsevier Ltd. All rights reserved.

Algebraic Bethe ansatz method for the exact calculation of energy spectra and form factors: applications to models of Bose-Einstein condensates and metallic nanograins

In this review we demonstrate how the algebraic Bethe ansatz is used for the calculation of the-energy spectra and form factors (operator matrix elements in the basis of Hamiltonian eigenstates) in exactly solvable quantum systems. As examples we apply the theory to several models of current interest in the study of Bose-Einstein condensates, which have been successfully created using ultracold dilute atomic gases. The first model we introduce describes Josephson tunnelling between two coupled Bose-Einstein condensates. It can be used not only for the study of tunnelling between condensates of atomic gases, but for solid state Josephson junctions and coupled Cooper pair boxes. The theory is also applicable to models of atomic-molecular Bose-Einstein condensates, with two examples given and analysed. Additionally, these same two models are relevant to studies in quantum optics; Finally, we discuss the model of Bardeen, Cooper and Schrieffer in this framework, which is appropriate for systems of ultracold fermionic atomic gases, as well as being applicable for the description of superconducting correlations in metallic grains with nanoscale dimensions.; In applying all the above models to. physical situations, the need for an exact analysis of small-scale systems is established due to large quantum fluctuations which render mean-field approaches inaccurate.

A hybrid planning method for transmission networks in a deregulated environment

The reconstruction of power industries has brought fundamental changes to both power system operation and planning. This paper presents a new planning method using multi-objective optimization (MOOP) technique, as well as human knowledge, to expand the transmission network in open access schemes. The method starts with a candidate pool of feasible expansion plans. Consequent selection of the best candidates is carried out through a MOOP approach, of which multiple objectives are tackled simultaneously, aiming at integrating the market operation and planning as one unified process in context of deregulated system. Human knowledge has been applied in both stages to ensure the selection with practical engineering and management concerns. The expansion plan from MOOP is assessed by reliability criteria before it is finalized. The proposed method has been tested with the IEEE 14-bus system and relevant analyses and discussions have been presented.

Theory manual to OctVCE – a cartesian cell CFD code with special application to blast wave problems, Department of Mechanical Engineering Report 2007/12

OctVCE is a cartesian cell CFD code produced especially for numerical simulations of shock and blast wave interactions with complex geometries, in particular, from explosions. Virtual Cell Embedding (VCE) was chosen as its cartesian cell kernel for its simplicity and sufficiency for practical engineering design problems. The code uses a finite-volume formulation of the unsteady Euler equations with a second order explicit Runge-Kutta Godonov (MUSCL) scheme. Gradients are calculated using a least-squares method with a minmod limiter. Flux solvers used are AUSM, AUSMDV and EFM. No fluid-structure coupling or chemical reactions are allowed, but gas models can be perfect gas and JWL or JWLB for the explosive products. This report also describes the code’s ‘octree’ mesh adaptive capability and point-inclusion query procedures for the VCE geometry engine. Finally, some space will also be devoted to describing code parallelization using the shared-memory OpenMP paradigm. The user manual to the code is to be found in the companion report 2007/13.

A director theory for visco-elastic folding instabilities in multilayered rock

A model for finely layered visco-elastic rock proposed by us in previous papers is revisited and generalized to include couple stresses. We begin with an outline of the governing equations for the standard continuum case and apply a computational simulation scheme suitable for problems involving very large deformations. We then consider buckling instabilities in a finite, rectangular domain. Embedded within this domain, parallel to the longer dimension we consider a stiff, layered beam under compression. We analyse folding up to 40% shortening. The standard continuum solution becomes unstable for extreme values of the shear/normal viscosity ratio. The instability is a consequence of the neglect of the bending stiffness/viscosity in the standard continuum model. We suggest considering these effects within the framework of a couple stress theory. Couple stress theories involve second order spatial derivatives of the velocities/displacements in the virtual work principle. To avoid C-1 continuity in the finite element formulation we introduce the spin of the cross sections of the individual layers as an independent variable and enforce equality to the spin of the unit normal vector to the layers (-the director of the layer system-) by means of a penalty method. We illustrate the convergence of the penalty method by means of numerical solutions of simple shears of an infinite layer for increasing values of the penalty parameter. For the shear problem we present solutions assuming that the internal layering is oriented orthogonal to the surfaces of the shear layer initially. For high values of the ratio of the normal-to the shear viscosity the deformation concentrates in thin bands around to the layer surfaces. The effect of couple stresses on the evolution of folds in layered structures is also investigated. (C) 2002 Elsevier Science Ltd. All rights reserved.

Is your vision consistent? A method for checking, based on scenario concepts

Common sense tells us that the future is an essential element in any strategy. In addition, there is a good deal of literature on scenario planning, which is an important tool in considering the future in terms of strategy. However, in many organizations there is serious resistance to the development of scenarios, and they are not broadly implemented by companies. But even organizations that do not rely heavily on the development of scenarios do, in fact, construct visions to guide their strategies. But it might be asked, what happens when this vision is not consistent with the future? To address this problem, the present article proposes a method for checking the content and consistency of an organization`s vision of the future, no matter how it was conceived. The proposed method is grounded on theoretical concepts from the field of future studies, which are described in this article. This study was motivated by the search for developing new ways of improving and using scenario techniques as a method for making strategic decisions. The method was then tested on a company in the field of information technology in order to check its operational feasibility. The test showed that the proposed method is, in fact, operationally feasible and was capable of analyzing the vision of the company being studied, indicating both its shortcomings and points of inconsistency. (C) 2007 Elsevier Ltd. All rights reserved.

Structure optimization combining soft-core interaction functions, the diffusion equation method, and molecular dynamics

Smoothing the potential energy surface for structure optimization is a general and commonly applied strategy. We propose a combination of soft-core potential energy functions and a variation of the diffusion equation method to smooth potential energy surfaces, which is applicable to complex systems such as protein structures; The performance of the method was demonstrated by comparison with simulated annealing using the refinement of the undecapeptide Cyclosporin A as a test case. Simulations were repeated many times using different initial conditions and structures since the methods are heuristic and results are only meaningful in a statistical sense.

ADHD in a representative sample of the Brazilian population: estimated prevalence and comparative adequacy of criteria between adolescents and adults according to the item response theory

Background: Attention deficit hyperactivity disorder (ADHD) is a clinically significant disorder in adulthood, but current diagnostic criteria and instruments do not seem to adequately capture the complexity of the disorder in this developmental phase. Accordingly, there are limited data on the proportion of adults affected by the disorder, specially in developing countries. Method: We assessed a representative household sample of the Brazilian population for ADHD with the Adult ADHD Self-report Scale (ASRS) Screener, and evaluated the instrument according to the Rasch model of item response theory. Results: The sample was comprised by 3007 individuals, and the overal prevalence of positive screeners for ADHD was 5.8% [95% confidence interval (CI), 4.8-7.0]. Rasch analyses revealed the misfitt of the overall sample to expectations of the model. The evaluation of the sample stratified by age revealed that data for adolescents showed a signficant fittnes to the model expectations, while items completed by adults were not adequated. Conclusions: The lack of fitness to the model for adult respondents challenges the possibility of a linear transformation of the ordinal data into interval measures and the utilization of parametric analyses of data. This result suggests that diagnostic criteria and instruments for adult ADHD must take into account a developmental perspective. Moreover, it calls for further evaluation of currently employed research methods in light of modern theories of psychometrics. Copyright (C) 2010 John Wiley & Sons, Ltd.

Theory of pseudomodes in quantum optical processes

This paper deals with non-Markovian behavior in atomic systems coupled to a structured reservoir of quantum electromagnetic field modes, with particular relevance to atoms interacting with the field in high-Q cavities or photonic band-gap materials. In cases such as the former, we show that the pseudomode theory for single-quantum reservoir excitations can be obtained by applying the Fano diagonalization method to a system in which the atomic transitions are coupled to a discrete set of (cavity) quasimodes, which in turn are coupled to a continuum set of (external) quasimodes with slowly varying coupling constants and continuum mode density. Each pseudomode can be identified with a discrete quasimode, which gives structure to the actual reservoir of true modes via the expressions for the equivalent atom-true mode coupling constants. The quasimode theory enables cases of multiple excitation of the reservoir to now be treated via Markovian master equations for the atom-discrete quasimode system. Applications of the theory to one, two, and many discrete quasimodes are made. For a simple photonic band-gap model, where the reservoir structure is associated with the true mode density rather than the coupling constants, the single quantum excitation case appears to be equivalent to a case with two discrete quasimodes.

Quasimode theory of quantum optical processes in photonic band gap materials

This paper deals with atomic systems coupled to a structured reservoir of quantum EM field modes, with particular relevance to atoms interacting with the field in photonic band gap materials. The case of high Q cavities has been treated elsewhere using Fano diagonalization based on a quasimode approach, showing that the cavity quasimodes are responsible for pseudomodes introduced to treat non-Markovian behaviour. The paper considers a simple model of a photonic band gap case, where the spatially dependent permittivity consists of a constant term plus a small spatially periodic term that leads to a narrow band gap in the spectrum of mode frequencies. Most treatments of photonic band gap materials are based on the true modes, obtained numerically by solving the Helmholtz equation for the actual spatially periodic permittivity. Here the field modes are first treated in terms of a simpler quasimode approach, in which the quasimodes are plane waves associated with the constant permittivity term. Couplings between the quasimodes occur owing to the small periodic term in the permittivity, with selection rules for the coupled modes being related to the reciprocal lattice vectors. This produces a field Hamiltonian in quasimode form. A matrix diagonalization method may be applied to relate true mode annihilation operators to those for quasimodes. The atomic transitions are coupled to all the quasimodes, and the true mode atom-EM field coupling constants (one-photon Rabi frequencies) are related to those for the quasimodes and also expressions are obtained for the true mode density. The results for the one-photon Rabi frequencies differ from those assumed in other work. Expressions for atomic decay rates are obtained using the Fermi Golden rule, although these are valid only well away from the band gaps.