Mode-specific chemisorption of CH4 on Pt{110}-(1 x 2) explored by first-principles molecular dynamics

The chemisorption of CH4 on Pt{110}-(1 x 2) has been studied by vibrational analysis of the reaction pathway defined by the potential energy surface and, in time reversal, by first-principles molecular dynamics simulations of CH4 associative desorption, with the electronic structure treated explicitly using density functional theory. We find that the symmetric stretch vibration ν1 is strongly coupled to the reaction coordinate; our results therefore provide a firm theoretical basis for recently reported state-resolved reactivity measurements, which show that excitation of the ν1 normal mode is the most efficient way to enhance the reaction probability

The interaction of iron pyrite with oxygen, nitrogen and nitrogen oxides: a first-principles study

Sulphide materials, in particular MoS2, have recently received great attention from the surface science community due to their extraordinary catalytic properties. Interestingly, the chemical activity of iron pyrite (FeS2) (the most common sulphide mineral on Earth), and in particular its potential for catalytic applications, has not been investigated so thoroughly. In this study, we use density functional theory (DFT) to investigate the surface interactions of fundamental atmospheric components such as oxygen and nitrogen, and we have explored the adsorption and dissociation of nitrogen monoxide (NO) and nitrogen dioxide (NO2) on the FeS2(100) surface. Our results show that both those environmentally important NOx species chemisorb on the surface Fe sites, while the S sites are basically unreactive for all the molecular species considered in this study and even prevent NO2 adsorption onto one of the non-equivalent Fe–Fe bridge sites of the (1 1)–FeS2(100) surface. From the calculated high barrier for NO and NO2 direct dissociation on this surface, we can deduce that both nitrogen oxides species are adsorbed molecularly on pyrite surfaces.

Shared authority: courts and legislatures in legal theory

This book advances a fresh philosophical account of the relationship between the legislature and courts, opposing the common conception of law, in which it is legislatures that primarily create the law, and courts that primarily apply it. This conception has eclectic affinities with legal positivism, and although it may have been a helpful intellectual tool in the past, it now increasingly generates more problems than it solves. For this reason, the author argues, legal philosophers are better off abandoning it. At the same time they are asked to dismantle the philosophical and doctrinal infrastructure that has been based on it and which has been hitherto largely unquestioned. In its place the book offers an alternative framework for understanding the role of courts and the legislature; a framework which is distinctly anti-positivist and which builds on Ronald Dworkin’s interpretive theory of law. But, contrary to Dworkin, it insists that legal duty is sensitive to the position one occupies in the project of governing; legal interpretation is not the solitary task of one super-judge, but a collaborative task structured by principles of institutional morality such as separation of powers which impose a moral duty on participants to respect each other's contributions. Moreover this collaborative task will often involve citizens taking an active role in their interaction with the law.

First-principles study of the inversion thermodynamics and electronic structure of FeM2X4 (thio)spinels (M = Cr, Mn, Co, Ni; X = O, S)

FeM2X4 spinels, where M is a transition metal and X is oxygen or sulfur, are candidate materials for spin filters, one of the key devices in spintronics. We present here a computational study of the inversion thermodynamics and the electronic structure of these (thio)spinels for M = Cr, Mn, Co, Ni, using calculations based on the density functional theory with on-site Hubbard corrections (DFT+U). The analysis of the configurational free energies shows that different behaviour is expected for the equilibrium cation distributions in these structures: FeCr2X4 and FeMn2S4 are fully normal, FeNi2X4 and FeCo2S4 are intermediate, and FeCo2O4 and FeMn2O4 are fully inverted. We have analyzed the role played by the size of the ions and by the crystal field stabilization effects in determining the equilibrium inversion degree. We also discuss how the electronic and magnetic structure of these spinels is modified by the degree of inversion, assuming that this could be varied from the equilibrium value. We have obtained electronic densities of states for the completely normal and completely inverse cation distribution of each compound. FeCr2X4, FeMn2X4, FeCo2O4 and FeNi2O4 are half-metals in the ferrimagnetic state when Fe is in tetrahedral positions. When M is filling the tetrahedral positions, the Cr-containing compounds and FeMn2O4 are half-metallic systems, while the Co and Ni spinels are insulators. The Co and Ni sulfide counterparts are metallic for any inversion degree together with the inverse FeMn2S4. Our calculations suggest that the spin filtering properties of the FeM2X4 (thio)spinels could be modified via the control of the cation distribution through variations in the synthesis conditions.

Magnetism of Co overlayers and nanostructures on W(001): A first-principles study

The magnetic properties of Co nanostructures and a Co monolayer on W(001) have been studied in the framework of density functional theory. Different geometries such as planar and three-dimensional clusters have been considered, with cluster sizes varying between 2 and 13 atoms. The calculations were performed using the real-space linear muffin-tin orbital method (RS-LMTO-ASA). With respect to the stability of the magnetic state, we predict an antiferromagnetic (AFM) structure for the ground state of the planar Co clusters and a ferromagnetic (FM) state for the three-dimensional clusters. For the three-dimensional clusters, one of the AFM arrangements leads to frustration due to the competing FM and AFM exchange interactions between different atoms in the cluster, and gives rise to a non-collinear state with energy close to that of the FM ground state. The relative role of the Co-Co and Co-W exchange interactions is also investigated. (C) 2007 Elsevier B.V. All rights reserved.

First-principles calculation of the AlAs/GaAs interface band structure using a self-energy-corrected local density approximation

We apply a self-energy-corrected local density approximation (LDA) to obtain corrected bulk band gaps and to study the band offsets of AlAs grown on GaAs (AlAs/GaAs). We also investigate the Al(x)Ga(1-x)As/GaAs alloy interface, commonly employed in band gap engineering. The calculations are fully ab initio, with no adjustable parameters or experimental input, and at a computational cost comparable to traditional LDA. Our results are in good agreement with experimental values and other theoretical studies. Copyright (C) EPLA, 2011

Furan interaction with the Si(001)-(2 x 2) surface: structural, energetics, and vibrational spectra from first-principles

In this work we employ the state of the art pseudopotential method, within a generalized gradient approximation to the density functional theory, to investigate the adsorption process of furan on the silicon (001) surface. A direct comparison of different adsorption structures with x-ray photoelectron spectroscopy (XPS), ultra-violet photoelectron spectroscopy (UPS), high resolution electron energy loss spectroscopy (HREELS), near edge x-ray absorption fine structure (NEXAFS), and high resolution spectroscopy experimental data allows us to identify the [4 + 2] cycloaddition reaction as the most probable adsorbate. In addition, theoretical scanning tunnelling microscopy (STM) images are presented, with a view to contributing to further experimental investigations.

The electronic and optical properties of sodalite (Na(8)Al(6)Si(6)O(24)Cl(2)) from first principles

This study reports the results of ab initio electronic and optical calculations for pure socialite crystal using the linear augmented plane wave (LAPW) method within density functional theory (DFT). The calculated electronic structure revealed predominantly orbital characters of the valence band and the conduction band, and enabled us to determine the type and the value of the fundamental gap of the compound. The imaginary part of the dielectric tensor, extinction coefficient and refraction index were calculated as functions of the incident radiation wavelength. It is shown that the O 2p states and Na 3s states play the major role in optical transitions as initial and final states, respectively. The absorption spectrum is localized in the ultraviolet range between 40 and 250 nm. Furthermore, we concluded that the material does not absorb radiation in the visible range. (C) 2009 Elsevier Ltd. All rights reserved.

Parameter estimation of Poisson generalized linear mixed models based on three different statistical principles : a simulation study

Generalized linear mixed models are flexible tools for modeling non-normal data and are useful for accommodating overdispersion in Poisson regression models with random effects. Their main difficulty resides in the parameter estimation because there is no analytic solution for the maximization of the marginal likelihood. Many methods have been proposed for this purpose and many of them are implemented in software packages. The purpose of this study is to compare the performance of three different statistical principles - marginal likelihood, extended likelihood, Bayesian analysis-via simulation studies. Real data on contact wrestling are used for illustration.

Three principles of competitive nonlinear pricing

We make three contributions to the theory of contracting under asymmetric information. First, we establish a competitive analog to the revelation principIe which we call the implementation principIe. This principIe provides a complete characterization of all incentive compatible, indirect contracting mechanisms in terms of contract catalogs (or menus), and allows us to conclude that in competi tive contracting situations, firms in choosing their contracting strategies can restrict attention, without loss of generality, to contract catalogs. Second, we establish a competi tive taxation principIe. This principIe, a refinement of the implementation principIe, provides a complete characterization of all implementable nonlinear pricing schedules in terms of product-price catalogs and allows us to reduce any game played over nonlinear pricing schedules to a strategically equivalent game played over product-price catalogs. Third, using the competitive taxation principIe and a recent result due to Reny (1999) on the existence of Nash equilibria in discontinuous games, we demonstrate the existence of a N ash equilibrium for the mixed extension of the nonlinear pricing game.

Sustainable silvopastoral systems: theory and a practical case

Muitas transformações são esperadas por causa das mudanças do clima, especialmente das atividades agrícolas realizadas nos trópicos. Esta tese centra-se em dois aspectos. O primeiro deles é o de reunir o conhecimento de sistemas silvipastoris; este ponto de vista estabelece a importância de solos tropicais e sua gestão adequada de acordo com as normas ambientais e sustentáveis. A segunda parte da tese é a aplicação desses princípios em um caso específico: a fazenda "El Paraíso". O objetivo central ou problema a resolver da segunda parte é propor um projeto para melhorar as atividades de produção de carne e, ao mesmo tempo, ajudar a preservar e melhorar o meio ambiente e especialmente os ecossistemas tropicais. A metodologia utilizada na tese foi buscar e analisar informações sobre o assunto. Depois disso, a investigação experimental e de campo foi realizada para levantar o projeto que combinaria as duas partes da obra. No final, com a informação recolhida uma proposta de projeto foi feita. O objetivo era propor a transformação dos processos de produção na fazenda selecionada. Logo de desenvolver e apresentar o projeto, foram analisadas as possibilidades de implementação do projeto. A conclusão do estudo foi o de apresentar e discutir três cenários possíveis após a implementação. Finalmente, a conclusão geral apresenta as realizações, as oportunidades e possíveis expansões futuras do projeto.

Effective theory for trapped few-fermion systems

We apply the general principles of effective field theories to the construction of effective interactions suitable for few- and many-body calculations in a no-core shell model framework. We calculate the spectrum of systems with three and four two-component fermions in a harmonic trap. In the unitary limit, we find that three-particle results are within 10% of known semianalytical values even in small model spaces. The method is very general, and can be readily extended to other regimes, more particles, different species (e.g., protons and neutrons in nuclear physics), or more-component fermions (as well as bosons). As an illustration, we present calculations of the lowest-energy three-fermion states away from the unitary limit and find a possible inversion of parity in the ground state in the limit of trap size large compared to the scattering length. Furthermore, we investigate the lowest positive-parity states for four fermions, although we are limited by the dimensions we can currently handle in this case.

Understanding the origin of photoluminescence in disordered Ca0.60Sr0.40WO4: An experimental and first-principles study

Visible photoluminescence (PL) was observed for the first time at room temperature in structurally disordered calcium strontium tungstate powder, Ca0.60Sr0.40WO4 (CSW), obtained by the polymeric precursor method. The PL behavior of CSW powders has been analyzed as a function of the disorder rate, based on experimental and theoretical studies. Quantum mechanical theory based on density functional theory at the B3LYP level has been employed to study the electronic structure of two periodic models representing both crystalline and disordered powders. Their electronic structures have been analyzed in terms of density of states, band dispersion and charge densities. The calculations indicate a break in symmetry when passing from crystalline to disordered models, creating localized electronic levels above the valence band. Moreover, a negative charge transfer process takes place from the [WO3] cluster to the [WO4] cluster. The polarization induced by the break in symmetry and the existence of localized levels favors the creation of trapped holes and electrons, originating the PL phenomenon. (c) 2007 Elsevier B.V. All rights reserved.

Pattern recognition theory in nonlinear signal processing

A body of research has developed within the context of nonlinear signal and image processing that deals with the automatic, statistical design of digital window-based filters. Based on pairs of ideal and observed signals, a filter is designed in an effort to minimize the error between the ideal and filtered signals. The goodness of an optimal filter depends on the relation between the ideal and observed signals, but the goodness of a designed filter also depends on the amount of sample data from which it is designed. In order to lessen the design cost, a filter is often chosen from a given class of filters, thereby constraining the optimization and increasing the error of the optimal filter. To a great extent, the problem of filter design concerns striking the correct balance between the degree of constraint and the design cost. From a different perspective and in a different context, the problem of constraint versus sample size has been a major focus of study within the theory of pattern recognition. This paper discusses the design problem for nonlinear signal processing, shows how the issue naturally transitions into pattern recognition, and then provides a review of salient related pattern-recognition theory. In particular, it discusses classification rules, constrained classification, the Vapnik-Chervonenkis theory, and implications of that theory for morphological classifiers and neural networks. The paper closes by discussing some design approaches developed for nonlinear signal processing, and how the nature of these naturally lead to a decomposition of the error of a designed filter into a sum of the following components: the Bayes error of the unconstrained optimal filter, the cost of constraint, the cost of reducing complexity by compressing the original signal distribution, the design cost, and the contribution of prior knowledge to a decrease in the error. The main purpose of the paper is to present fundamental principles of pattern recognition theory within the framework of active research in nonlinear signal processing.

Density functional theory calculation of the electronic structure of Ba0.5Sr0.5TiO3: Photoluminescent properties and structural disorder

First-principles quantum-mechanical techniques, based on density functional theory (B3LYP level) were employed to study the electronic structure of ordered and deformed asymmetric models for Ba0.5Sr 0.5TiO3. Electronic properties are analyzed and the relevance of the present theoretical and experimental results on the photoluminescence behavior is discussed. The presence of localized electronic levels in the band gap, due to the symmetry break, would be responsible for the visible photoluminescence of the amorphous state at room temperature. Thin films were synthesized following a soft chemical processing. Their structure was confirmed by x-ray data and the corresponding photoluminescence properties measured.