Modeling of phase equilibrium and vapor adsorption on carbon black based on a combination of a lattice theory and equation of state

A thermodynamic approach is developed in this paper to describe the behavior of a subcritical fluid in the neighborhood of vapor-liquid interface and close to a graphite surface. The fluid is modeled as a system of parallel molecular layers. The Helmholtz free energy of the fluid is expressed as the sum of the intrinsic Helmholtz free energies of separate layers and the potential energy of their mutual interactions calculated by the 10-4 potential. This Helmholtz free energy is described by an equation of state (such as the Bender or Peng-Robinson equation), which allows us a convenient means to obtain the intrinsic Helmholtz free energy of each molecular layer as a function of its two-dimensional density. All molecular layers of the bulk fluid are in mechanical equilibrium corresponding to the minimum of the total potential energy. In the case of adsorption the external potential exerted by the graphite layers is added to the free energy. The state of the interface zone between the liquid and the vapor phases or the state of the adsorbed phase is determined by the minimum of the grand potential. In the case of phase equilibrium the approach leads to the distribution of density and pressure over the transition zone. The interrelation between the collision diameter and the potential well depth was determined by the surface tension. It was shown that the distance between neighboring molecular layers substantially changes in the vapor-liquid transition zone and in the adsorbed phase with loading. The approach is considered in this paper for the case of adsorption of argon and nitrogen on carbon black. In both cases an excellent agreement with the experimental data was achieved without additional assumptions and fitting parameters, except for the fluid-solid potential well depth. The approach has far-reaching consequences and can be readily extended to the model of adsorption in slit pores of carbonaceous materials and to the analysis of multicomponent adsorption systems. (C) 2002 Elsevier Science (USA).

Phase equilibria and surface tension of pure fluids using a molecular layer structure theory (MLST) model

This paper presents a new model based on thermodynamic and molecular interaction between molecules to describe the vapour-liquid phase equilibria and surface tension of pure component. The model assumes that the bulk fluid can be characterised as set of parallel layers. Because of this molecular structure, we coin the model as the molecular layer structure theory (MLST). Each layer has two energetic components. One is the interaction energy of one molecule of that layer with all surrounding layers. The other component is the intra-layer Helmholtz free energy, which accounts for the internal energy and the entropy of that layer. The equilibrium between two separating phases is derived from the minimum of the grand potential, and the surface tension is calculated as the excess of the Helmholtz energy of the system. We test this model with a number of components, argon, krypton, ethane, n-butane, iso-butane, ethylene and sulphur hexafluoride, and the results are very satisfactory. (C) 2002 Elsevier Science B.V. All rights reserved.

Simulation and theory of hybrid aligned liquid crystal films

We present a study of the effects of nanoconfinement on a system of hard Gaussian overlap particles interacting with planar substrates through the hard-needle-wall potential, extending earlier work by two of us [D. J. Cleaver and P. I. C. Teixeira, Chem. Phys. Lett. 338, 1 (2001)]. Here, we consider the case of hybrid films, where one of the substrates induces strongly homeotropic anchoring, while the other favors either weakly homeotropic or planar anchoring. These systems are investigated using both Monte Carlo simulation and density-functional theory, the latter implemented at the level of Onsager's second-virial approximation with Parsons-Lee rescaling. The orientational structure is found to change either continuously or discontinuously depending on substrate separation, in agreement with earlier predictions by others. The theory is seen to perform well in spite of its simplicity, predicting the positional and orientational structure seen in simulations even for small particle elongations.

Strategic bidding in electricity markets: an agent-based simulator with game theory for scenario analysis

Electricity markets are complex environments, involving a large number of different entities, with specific characteristics and objectives, making their decisions and interacting in a dynamic scene. Game-theory has been widely used to support decisions in competitive environments; therefore its application in electricity markets can prove to be a high potential tool. This paper proposes a new scenario analysis algorithm, which includes the application of game-theory, to evaluate and preview different scenarios and provide players with the ability to strategically react in order to exhibit the behavior that better fits their objectives. This model includes forecasts of competitor players’ actions, to build models of their behavior, in order to define the most probable expected scenarios. Once the scenarios are defined, game theory is applied to support the choice of the action to be performed. Our use of game theory is intended for supporting one specific agent and not for achieving the equilibrium in the market. MASCEM (Multi-Agent System for Competitive Electricity Markets) is a multi-agent electricity market simulator that models market players and simulates their operation in the market. The scenario analysis algorithm has been tested within MASCEM and our experimental findings with a case study based on real data from the Iberian Electricity Market are presented and discussed.

Implementation of fractional-order electromagnetic potential through a genetic algorithm

Several phenomena present in electrical systems motivated the development of comprehensive models based on the theory of fractional calculus (FC). Bearing these ideas in mind, in this work are applied the FC concepts to define, and to evaluate, the electrical potential of fractional order, based in a genetic algorithm optimization scheme. The feasibility and the convergence of the proposed method are evaluated.

Theory and phenomenology of two-higgs-doublet models

We discuss theoretical and phenomenological aspects of two-Higgs-doublet extensions of the Standard Model. In general, these extensions have scalar mediated flavour changing neutral currents which are strongly constrained by experiment. Various strategies are discussed to control these flavour changing scalar currents and their phenomenological consequences are analysed. In particular, scenarios with natural flavour conservation are investigated, including the so-called type I and type II models as well as lepton-specific and inert models. Type III models are then discussed, where scalar flavour changing neutral currents are present at tree level, but are suppressed by either a specific ansatz for the Yukawa couplings or by the introduction of family symmetries leading to a natural suppression mechanism. We also consider the phenomenology of charged scalars in these models. Next we turn to the role of symmetries in the scalar sector. We discuss the six symmetry-constrained scalar potentials and their extension into the fermion sector. The vacuum structure of the scalar potential is analysed, including a study of the vacuum stability conditions on the potential and the renormalization-group improvement of these conditions is also presented. The stability of the tree level minimum of the scalar potential in connection with electric charge conservation and its behaviour under CP is analysed. The question of CP violation is addressed in detail, including the cases of explicit CP violation and spontaneous CP violation. We present a detailed study of weak basis invariants which are odd under CP. These invariants allow for the possibility of studying the CP properties of any two-Higgs-doublet model in an arbitrary Higgs basis. A careful study of spontaneous CP violation is presented, including an analysis of the conditions which have to be satisfied in order for a vacuum to violate CP. We present minimal models of CP violation where the vacuum phase is sufficient to generate a complex CKM matrix, which is at present a requirement for any realistic model of spontaneous CP violation.

Riesz potential versus fractional Laplacian

This paper starts by introducing the Grünwald–Letnikov derivative, the Riesz potential and the problem of generalizing the Laplacian. Based on these ideas, the generalizations of the Laplacian for 1D and 2D cases are studied. It is presented as a fractional version of the Cauchy–Riemann conditions and, finally, it is discussed with the n-dimensional Laplacian.

Strategic Bidding in Electricity Markets: An agent-based simulator with game theory for scenario analysis

Electricity markets are complex environments, involving a large number of different entities, with specific characteristics and objectives, making their decisions and interacting in a dynamic scene. Game-theory has been widely used to support decisions in competitive environments; therefore its application in electricity markets can prove to be a high potential tool. This paper proposes a new scenario analysis algorithm, which includes the application of game-theory, to evaluate and preview different scenarios and provide players with the ability to strategically react in order to exhibit the behavior that better fits their objectives. This model includes forecasts of competitor players’ actions, to build models of their behavior, in order to define the most probable expected scenarios. Once the scenarios are defined, game theory is applied to support the choice of the action to be performed. Our use of game theory is intended for supporting one specific agent and not for achieving the equilibrium in the market. MASCEM (Multi-Agent System for Competitive Electricity Markets) is a multi-agent electricity market simulator that models market players and simulates their operation in the market. The scenario analysis algorithm has been tested within MASCEM and our experimental findings with a case study based on real data from the Iberian Electricity Market are presented and discussed.

Riesz potential versus fractional Laplacian

This paper starts by introducing the Grünwald–Letnikov derivative, the Riesz potential and the problem of generalizing the Laplacian. Based on these ideas, the generalizations of the Laplacian for 1D and 2D cases are studied. It is presented as a fractional version of the Cauchy–Riemann conditions and, finally, it is discussed with the n-dimensional Laplacian.

Exploring the bioavailability of (poly)phenols from berries and their potential activities in humans

(Poly)phenols are the most widely distributed secondary metabolites, in plants, and, therefore, are regular constituents of human food products. The regular ingestion of (poly)phenol-containing foods has been associated with a reduced risk of acquiring chronic diseases and many studies are currently trying to corroborate this theory. However, the precise contribution of (poly)phenols to disease prevention is still unknown.(...)

A conspiracy theory for clefts : the syntax and interpretation of cleft constructions

O objetivo final deste estudo é contribuir para a discussão sobre qual a medida em que conceitos semânticos e discursivos estão sintaticamente codificados. Mais especificamente, investiga-se se existe alguma correlação consistente entre alguns aspetos interpretativos e sintáticos de quatro construções clivadas do Português Europeu, e como se deve dar conta teoricamente destas potenciais correlações. As clivadas consideradas são as clivadas canónicas, as pseudoclivadas, as clivadas de é que e as clivadas de SER. Sintaticamente podemos distinguir dois tipos: clivadas bioracionais (canónicas e pseudoclivadas) e clivadas mono-oracionais (clivadas de é que e de SER). Todas as estruturas têm um constituinte clivado focalizado que pode constituir tanto um foco informacional como um foco contrastivo, e uma oração clivada que introduz uma pressuposição existencial. Adicionalmente, o constituinte clivado identifica exaustivamente uma posição vazia na oração clivada. Adota-se a semântica alternativa para o foco (Rooth 1985), segundo a qual o foco entoacional contribui uniformemente um conjunto de alternativas na Forma Lógica. Regras pragmáticas operando neste conjunto dão origem a duas implicaturas que podem ser suspensas: pressuposição existencial e exaustividade. Dado que as clivadas de é que e as de SER têm a mesma interpretação que orações não-clivadas, conclui-se que a sua estrutura sintática particular não contribui para estas propriedades interpretativas. Em contrapartida, as clivadas bioracionais, que são orações copulativas especificacionais, têm uma presuposição existencial e uma interpretação exaustiva que não pode ser suspensa, tal como as orações especificacionais não-clivadas. Argumenta-se que isto se deve ao facto de o constituinte clivado identificar uma variável introduzida por uma descrição definida. Demonstra-se que a oração clivada, uma relativa em posição de complemento de um determinador definido nas clivadas canónicas e uma relativa livre nas pseudoclivadas, tem a mesma denotação que um DP definido, e portanto tem uma pressuposição existencial inerente. A interpretação exaustiva deve-se à relação identificacional entre o constituinte clivado e a descrição definida. Além disso, defende-se que em Português Europeu um traço de foco não desencadeia movimento-A’ para um FocP especializado. Os constituintes focalizados movem-se antes por razões independentes do foco. Isto é confirmado pelo facto de apenas o constituinte clivado das clivadas de é que ter propriedades de movimento A’, os outros parecem estar in situ. Propõe-se que o constituinte clivado das clivadas de é que é um tópico com um traço de foco que se move para um TopP. Esta análise dá conta da existência de restrições discursivas semelhantes para tópicos não focalizados e para o constituinte clivado das clivadas de é que. O traço quantificacional de foco arrastado pela topicalização dá origem a efeitos de intervenção, causando a não-recursividade do foco na periferia esquerda e a sua incompatibilidade com movimento de outros constituintes com traços quantificacionais. A análise prediz as restrições de encaixe observadas para as clivadas de é que. Finalmente, desenvolve-se uma análise sintática das clivadas de SER que aproxima estas estruturas das estruturas com partículas de foco. Propõe-se que a cópula é um operador sensível ao foco que é merged juntamente com o constituinte clivado. As restrições distribucionais da cópula devem-se a requisitos selecionais de núcleos.

Improving the risk concept: a revision of Arrow-Pratt theory in the context of controlled dynamic stochastic environments

In the literature on risk, one generally assume that uncertainty is uniformly distributed over the entire working horizon, when the absolute risk-aversion index is negative and constant. From this perspective, the risk is totally exogenous, and thus independent of endogenous risks. The classic procedure is "myopic" with regard to potential changes in the future behavior of the agent due to inherent random fluctuations of the system. The agent's attitude to risk is rigid. Although often criticized, the most widely used hypothesis for the analysis of economic behavior is risk-neutrality. This borderline case must be envisaged with prudence in a dynamic stochastic context. The traditional measures of risk-aversion are generally too weak for making comparisons between risky situations, given the dynamic �complexity of the environment. This can be highlighted in concrete problems in finance and insurance, context for which the Arrow-Pratt measures (in the small) give ambiguous.

A well-posedness theory in measures for some kinetic models of collective motion

We present existence, uniqueness and continuous dependence results for some kinetic equations motivated by models for the collective behavior of large groups of individuals. Models of this kind have been recently proposed to study the behavior of large groups of animals, such as flocks of birds, swarms, or schools of fish. Our aim is to give a well-posedness theory for general models which possibly include a variety of effects: an interaction through a potential, such as a short-range repulsion and long-range attraction; a velocity-averaging effect where individuals try to adapt their own velocity to that of other individuals in their surroundings; and self-propulsion effects, which take into account effects on one individual that are independent of the others. We develop our theory in a space of measures, using mass transportation distances. As consequences of our theory we show also the convergence of particle systems to their corresponding kinetic equations, and the local-in-time convergence to the hydrodynamic limit for one of the models.

A cognitive attempt to understanding female entrepreneurial potential: the role of social norms and culture

This article analyzes the different perceptions of both male and female potential entrepreneurs from three European regions differing in their respective level of economic development and entrepreneurial culture. We use an extended cognitive model of entrepreneurial intentions based on the theory of planned behaviour, the theory of normative social behaviour and social capital literature. Results show females have lower self-efficacy and entrepreneurial attraction than males, thus leading to lower entrepreneurial intention. Differences between the three subsamples are small when males are studied. However, female entrepreneurial intentions and perceptions are more affected by the cultural context.

Basis set superposition error-counterpoise corrected potential energy surfaces : application to hydrogen peroxide ... X (X=F-, Cl-, Br-, Li+, Na+) complexes

Møller-Plesset (MP2) and Becke-3-Lee-Yang-Parr (B3LYP) calculations have been used to compare the geometrical parameters, hydrogen-bonding properties, vibrational frequencies and relative energies for several X- and X+ hydrogen peroxide complexes. The geometries and interaction energies were corrected for the basis set superposition error (BSSE) in all the complexes (1-5), using the full counterpoise method, yielding small BSSE values for the 6-311 + G(3df,2p) basis set used. The interaction energies calculated ranged from medium to strong hydrogen-bonding systems (1-3) and strong electrostatic interactions (4 and 5). The molecular interactions have been characterized using the atoms in molecules theory (AIM), and by the analysis of the vibrational frequencies. The minima on the BSSE-counterpoise corrected potential-energy surface (PES) have been determined as described by S. Simón, M. Duran, and J. J. Dannenberg, and the results were compared with the uncorrected PES