Semiclassical relativistic fluid theory for electrostatic envelope modes in dense electron-positron-ion plasmas:Modulational instability and rogue waves

A fluid model is used to describe the propagation of envelope structures in an ion plasma under the influence of the action of weakly relativistic electrons and positrons. A multiscale perturbative method is used to derive a nonlinear Schrödinger equation for the envelope amplitude. Criteria for modulational instability, which occurs for small values of the carrier wavenumber (long carrier wavelengths), are derived. The occurrence of rogue waves is briefly discussed. © Cambridge University Press 2013.

Re-examining the Cairns-Tsallis model for ion acoustic solitons

Recently, a hybrid distribution function was proposed to describe a plasma species with an enhanced superthermal component. This combines a Cairns-type "nonthermal" form with the Tsallis theory for nonextensive thermodynamics. Using this alternative model, the propagation of arbitrary amplitude ion acoustic solitary waves in a two-component plasma is investigated. From a careful study of the distribution function it is found that the model itself is valid only for a very restricted range in the q-nonextensive parameter and the nonthermality parameter, a. Solitary waves, the amplitude and nature of which depend sensitively on both q and a, can exist within a narrow range of allowable Mach numbers. Both positive and negative potential structures are found, and coexistence may occur. © 2013 American Physical Society.

Influence of surface structures, subsurface carbon and hydrogen, and surface alloying on the activity and selectivity of acetylene hydrogenation on Pd surfaces: A density functional theory study

The selective hydrogenation of acetylene to ethylene on several Pd surfaces (Pd(111), Pd(100), Pd(211), and Pd(211)-defect) and Pd surfaces with subsurface species (carbon and hydrogen) as well as a number of Pd-based alloys (Pd-M/Pd(111) and Pd-M/Pd(211) (M = Cu, Ag and Au)) are investigated using density functional theory calculations to understand both the acetylene hydrogenation activity and the selectivity of ethylene formation. All the hydrogenation barriers are calculated, and the reaction rates on these surfaces are obtained using a two-step model. Pd(211) is found to have the highest activity for acetylene hydrogenation while Pd(100) gives rise to the lowest activity. In addition, more open surfaces result in over-hydrogenation to form ethane, while the close-packed surface (Pd(111)) is the most selective. However, we also find that the presence of subsurface carbon and hydrogen significantly changes the reactivity and selectivity of acetylene toward hydrogenation on Pd surfaces. On forming surface alloys of Pd with Cu, Ag and Au, the selectivity for ethylene is also found to be changed. A new energy decomposition method is used to quantitatively analyze the factors in determining the changes in selectivity. These surface modifiers are found to block low coordination unselective sites, leading to a decreased ethane production. (C) 2013 The Authors. Published by Elsevier Inc. All rights reserved.

Assessing parenting capacity in child protection: towards a knowledge-based model

The assessment of parenting capacity continues to engender public concern in cases of suspected harm to children. This paper outlines a model for approaching this task based on the application of three key domains of knowledge in social work relating to facts, theory and practice wisdom. The McMaster Model of Family Assessment is identified out of this process and reworked to give it a sharper focus on parenting roles and responsibilities. Seven formative dimensions of parenting are then elicited and combined with an analytical process of identifying strengths, concerns, prospects for growth and impact on child outcomes. The resulting assessment framework, it is argued, adds rigour to professional judgements about parenting capacity and enhances formulations on risk in child protection.

The changing university business model: a stakeholder perspective

Universities are in a current state of transition, whereby they are expected to develop a wide range of relationships with stakeholders in order to enhance regional innovation systems. However, despite external environmental pressures commonly regarded as one of the main drivers of business model evolution, there is a lack of studies that explore business model innovation as a result of multiple stakeholder influences. Accordingly, the aim of this paper is to examine the changing university business model within a region of the United Kingdom, using a stakeholder perspective that will aid theoretical development and refinement in both the business model and stakeholder fields. This examination is aided by consideration of the university business model as an activity system. Repeat interviews, combined with stakeholder theory, have been used to show how the changing university business model–stakeholder relationship has progressed through different stakeholder stages with resultant changes in content, structure and governance. Furthermore, conflicting objectives between each of the stakeholder groups (i.e. academics, industry liaison staff, technology transfer office staff and government support agency representatives) have led to the university business model evolving not as a process of co-creation but rather in a series of transitions whereby multiple stakeholders are continually shaping the university business model through strategies that are dependent upon their salience. Finally, this paper contributes to the development and refinement of business model innovation research, in that the use of stakeholder constructs can illustrate the impact of multiple stakeholders' power and influence on business model innovation.

Optimization through quantum annealing: theory and some applications

Quantum annealing is a promising tool for solving optimization problems, similar in some ways to the traditional ( classical) simulated annealing of Kirkpatrick et al. Simulated annealing takes advantage of thermal fluctuations in order to explore the optimization landscape of the problem at hand, whereas quantum annealing employs quantum fluctuations. Intriguingly, quantum annealing has been proved to be more effective than its classical counterpart in many applications. We illustrate the theory and the practical implementation of both classical and quantum annealing - highlighting the crucial differences between these two methods - by means of results recently obtained in experiments, in simple toy-models, and more challenging combinatorial optimization problems ( namely, Random Ising model and Travelling Salesman Problem). The techniques used to implement quantum and classical annealing are either deterministic evolutions, for the simplest models, or Monte Carlo approaches, for harder optimization tasks. We discuss the pro and cons of these approaches and their possible connections to the landscape of the problem addressed.

Theory of phonon dissipation in the conduction of stressed Au nanowires

Recent experiments on Au break junctions [Phys. Rev. Lett. 88 (2002) 216803] have characterized the nonlinear conductance of stretched short Au nanowires. They reveal in the voltage range 10-20 meV the signatures of dissipation effects, likely due to phonons in the nanowire, reducing the conductance below the quantized value of 2e(2)/h. We present here a theory, based on a model tight-binding Hamiltonian and on non-equilibrium Green's function techniques, which accounts for the main features of the experiment. The theory helps in revealing details of the experiment which need to be addressed with a more realistic, less idealized, theoretical framework. (C) 2004 Elsevier B.V. All rights reserved.

Universal tight binding model for chemical reactions in solution and at surfaces. II. Water

A revised water model intended for use in condensed phase simulations in the framework of the self consistent polarizable ion tight binding theory is constructed. The model is applied to water monomer, dimer, hexamers, ice, and liquid, where it demonstrates good agreement with theoretical results obtained by more accurate methods, such as DFT and CCSD(T), and with experiment. In particular, the temperature dependence of the self diffusion coefficient in liquid water predicted by the model, closely reproduces experimental curves in the temperature interval between 230 K and 350 K. In addition, and in contrast to standard DFT, the model properly orders the relative densities of liquid water and ice. A notable, but inevitable, shortcoming of the model is underestimation of the static dielectric constant by a factor of two. We demonstrate that the description of inter and intramolecular forces embodied in the tight binding approximation in quantum mechanics leads to a number of valuable insights which can be missing from ab initio quantum chemistry and classical force fields. These include a discussion of the origin of the enhanced molecular electric dipole moment in the condensed phases, and a detailed explanation for the increase of coordination number in liquid water as a function of temperature and compared with ice-leading to insights into the anomalous expansion on freezing. The theory holds out the prospect of an understanding of the currently unexplained density maximum of water near the freezing point. 

Universal tight binding model for chemical reactions in solution and at surfaces. III. Stoichiometric and reduced surfaces of titania and the adsorption of water

We demonstrate a model for stoichiometric and reduced titanium dioxide intended for use in molecular dynamics and other atomistic simulations and based in the polarizable ion tight binding theory. This extends the model introduced in two previous papers from molecular and liquid applications into the solid state, thus completing the task of providing a comprehensive and unified scheme for studying chemical reactions, particularly aimed at problems in catalysis and electrochemistry. As before, experimental results are given priority over theoretical ones in selecting targets for model fitting, for which we used crystal parameters and band gaps of titania bulk polymorphs, rutile and anatase. The model is applied to six low index titania surfaces, with and without oxygen vacancies and adsorbed water molecules, both in dissociated and non-dissociated states. Finally, we present the results of molecular dynamics simulation of an anatase cluster with a number of adsorbed water molecules and discuss the role of edge and corner atoms of the cluster. (C) 2014 AIP Publishing LLC.

Universal tight binding model for chemical reactions in solution and at surfaces. I. Organic molecules

As is now well established, a first order expansion of the Hohenberg-Kohn total energy density functional about a trial input density, namely, the Harris-Foulkes functional, can be used to rationalize a non self consistent tight binding model. If the expansion is taken to second order then the energy and electron density matrix need to be calculated self consistently and from this functional one can derive a charge self consistent tight binding theory. In this paper we have used this to describe a polarizable ion tight binding model which has the benefit of treating charge transfer in point multipoles. This admits a ready description of ionic polarizability and crystal field splitting. It is necessary in constructing such a model to find a number of parameters that mimic their more exact counterparts in the density functional theory. We describe in detail how this is done using a combination of intuition, exact analytical fitting, and a genetic optimization algorithm. Having obtained model parameters we show that this constitutes a transferable scheme that can be applied rather universally to small and medium sized organic molecules. We have shown that the model gives a good account of static structural and dynamic vibrational properties of a library of molecules, and finally we demonstrate the model's capability by showing a real time simulation of an enolization reaction in aqueous solution. In two subsequent papers, we show that the model is a great deal more general in that it will describe solvents and solid substrates and that therefore we have created a self consistent quantum mechanical scheme that may be applied to simulations in heterogeneous catalysis.

Relativistic theory for localized electrostatic excitations in degenerate electron-ion plasmas

A self-consistent relativistic two-fluid model is proposed for electron-ion plasma dynamics. A one-dimensional geometry is adopted. Electrons are treated as a relativistically degenerate fluid, governed by an appropriate equation of state. The ion fluid is also allowed to be relativistic, but is cold, nondegenerate, and subject only to an electrostatic potential. Exact stationary-profile solutions are sought, at the ionic scale, via the Sagdeev pseudopotential method. The analysis provides the pulse existence region, in terms of characteristic relativistic parameters, associated with the (ultrahigh) particle density.

Application of Asymmetric Marcus-Hush Theory to Voltammetry in Room-Temperature Ionic Liquids

Asymmetric MarcusHush (AMH) theory is applied for the first time in ionic solvents to model the voltammetric reduction of oxygen in 1-butyl-1-methylpyrrolidinium bis-(trifluoromethylsulfonyl)-imide and of 2-nitrotoluene (2-NT), nitrocyclopentane (NCP), and 1-nitro-butane (BuN) in trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate on a gold microdisc electrode. An asymmetry parameter, gamma, was estimated for all systems as -0.4 for the reduction of oxygen and -0.05, 0.25, and 0 +/- 0.05 for the reductions of 2-NT, NCP, and BuN, respectively, which suggests equal force constants of reactants and products in the case of 2-NT and BuN and unequal force constants for oxygen and NCP where the force constants of the oxidized species are greater than the reduced species in the case of oxygen and less than the reduced species in the case of NCP. Previously measured values for a, the Butler-Volmer transfer coefficient, reflect this in each case. Where appreciable asymmetry occurs, AMH theory was seen to parametrize the experimental data better than either Butler-Volmer or symmetric Marcus-Hush theory, allowing additionally the extraction of reorganization energy. This is the first study to provide key physical insights into electrochemical systems in room-temperature ionic liquids using AMH theory, allowing elucidation of the reorganization energies and the relative force constants of the reactants and products in each reaction.

Identifying the trend of reactivity for sp2 materials: an electron delocalization model from first principles calculations

The reactivity of sp² carbon materials is studied using the adsorption and dissociation of O₂ on graphene and graphene oxide as model systems. The reactions on the basal plane, zigzag and armchair edges of graphene and graphene oxide with different oxygen-containing groups are calculated using first principles calculations. Two Brønsted-Evans- Polanyi relationships are identified and an electron delocalization model is suggested to understand the general trend of reactivity for sp² carbon materials.

Acrolein hydrogenation on Pt(211) and Au(211) surfaces:a density functional theory study

Partial hydrogenation of acrolein, the simplest alpha, beta-unsaturated aldehyde, is not only a model system to understand the selectivity in heterogeneous catalysis, but also technologically an important reaction. In this work, the reaction on Pt(211) and Au(211) surfaces is thoroughly investigated using density functional theory calculations. The formation routes of three partial hydrogenation products, namely propenol, propanal and enol, on both metals are studied. It is found that the pathway to produce enol is kinetically favoured on Pt while on Au the route of forming propenol is preferred. Our calculations also show that the propanal formation follows an indirect pathway on Pt(211). An energy decomposition method to analyze the barrier is utilized to understand the selectivities at Pt(211) and Au(211), which reveals that the interaction energies between the reactants involved in the transition states play a key role in determining the selectivity difference.