Hybrid density functional theory description of N- and C-doping of NiO

The large intrinsic bandgap of NiO hinders its potential application as a photocatalyst under visible-light irradiation. In this study, we have performed first-principles screened exchange hybrid density functional theory with the HSE06 functional calculations of N- and C-doped NiO to investigate the effect of doping on the electronic structure of NiO. C-doping at an oxygen site induces gap states due to the dopant, the positions of which suggest that the top of the valence band is made up primarily of C 2p-derived states with some Ni 3d contributions, and the lowest-energy empty state is in the middle of the gap. This leads to an effective bandgap of 1.7 eV, which is of potential interest for photocatalytic applications. N-doping induces comparatively little dopant-Ni 3d interactions, but results in similar positions of dopant-induced states, i.e., the top of the valence band is made up of dopant 2p states and the lowest unoccupied state is the empty gap state derived from the dopant, leading to bandgap narrowing. With the hybrid density functional theory (DFT) results available, we discuss issues with the DFT corrected for on-site Coulomb description of these systems.

A first principles analysis of the effect of hydrogen concentration in hydrogenated amorphous silicon on the formation of strained Si-Si bonds and the optical and mobility gaps

In this paper, we use a model of hydrogenated amorphous silicon generated from molecular dynamics with density functional theory calculations to examine how the atomic geometry and the optical and mobility gaps are influenced by mild hydrogen oversaturation. The optical and mobility gaps show a volcano curve as the hydrogen content varies from undersaturation to mild oversaturation, with largest gaps obtained at the saturation hydrogen concentration. At the same time, mid-gap states associated with dangling bonds and strained Si-Si bonds disappear at saturation but reappear at mild oversaturation, which is consistent with the evolution of optical gap. The distribution of Si-Si bond distances provides the key to the change in electronic properties. In the undersaturation regime, the new electronic states in the gap arise from the presence of dangling bonds and strained Si-Si bonds, which are longer than the equilibrium Si-Si distance. Increasing hydrogen concentration up to saturation reduces the strained bonds and removes dangling bonds. In the case of mild oversaturation, the mid-gap states arise exclusively from an increase in the density of strained Si-Si bonds. Analysis of our structure shows that the extra hydrogen atoms form a bridge between neighbouring silicon atoms, thus increasing the Si-Si distance and increasing disorder in the sample.

New pairing scheme to overhaul BCS theory

In a superconductor pair occupancy probabilities are doubly defined with conflicting values when normal and umklapp scattering coexist with the same destination momentum. To resolve this issue a new pairing scheme is introduced to assert normal–umklapp frustration under such circumstances. Superconductivity then arises solely from residual umklapp scattering to destination momenta not reached by normal scattering. Consequent Tc calculations from first principles for niobium, tantalum, lead and aluminum turn out to be accurate within a few percent. A new perspective is revealed to support Matthias׳ rule. New light is also shed relevant to the future study of metallic hydrogen.

The Design and Development of Educational Immersive Environments: From Theory to Classroom Deployment

Computer game technology is poised to make a significant impact on the way our youngsters will learn. Our youngsters are ‘Digital Natives’, immersed in digital technologies, especially computer games. They expect to utilize these technologies in learning contexts. This expectation, and our response as educators, may change classroom practice and inform curriculum developments. This chapter approaches these issues ‘head on’. Starting from a review of the current educational issues, an evaluation of educational theory and instructional design principles, a new theoretical approach to the construction of “Educational Immersive Environments” (EIEs) is proposed. Elements of this approach are applied to development of an EIE to support Literacy Education in UK Primary Schools. An evaluation of a trial within a UK Primary School is discussed. Conclusions from both the theoretical development and the evaluation suggest how future teacher-practitioners may embrace both the technology and our approach to develop their own learning resources.

Creating Educational Immersive Environments Using a Computer Game Engine: Case Studies and Design Theory

This paper aims to crystallize recent research performed at the University of Worcester to investigate the feasibility of using the commercial game engine ‘Unreal Tournament 2004’ (UT2004) to produce ‘Educational Immersive Environments’ (EIEs) suitable for education and training. Our research has been supported by the UK Higher Education Academy. We discuss both practical and theoretical aspects of EIEs. The practical aspects include the production of EIEs to support high school physics education, the education of architects, and the learning of literacy by primary school children. This research is based on the development of our novel instructional medium, ‘UnrealPowerPoint’. Our fundamental guiding principles are that, first, pedagogy must inform technology, and second, that both teachers and pupils should be empowered to produce educational materials. Our work is informed by current educational theories such as constructivism, experiential learning and socio-cultural approaches as well as elements of instructional design and game principles.

The Danger Theory and Its Application to Artificial Immune Systems

Over the last decade, a new idea challenging the classical self-non-self viewpoint has become popular amongst immunologists. It is called the Danger Theory. In this conceptual paper, we look at this theory from the perspective of Artificial Immune System practitioners. An overview of the Danger Theory is presented with particular emphasis on analogies in the Artificial Immune Systems world. A number of potential application areas are then used to provide a framing for a critical assessment of the concept, and its relevance for Artificial Immune Systems.

The Danger Theory and Its Application to Artificial Immune Systems

Over the last decade, a new idea challenging the classical self-non-self viewpoint has become popular amongst immunologists. It is called the Danger Theory. In this conceptual paper, we look at this theory from the perspective of Artificial Immune System practitioners. An overview of the Danger Theory is presented with particular emphasis on analogies in the Artificial Immune Systems world. A number of potential application areas are then used to provide a framing for a critical assessment of the concept, and its relevance for Artificial Immune Systems.

Relatório de Estágio

O presente relatório de estágio insere-se na etapa final da Unidade Curricular de Integração Curricular: Prática Educativa e Relatório de Estágio, requisito para a conclusão do mestrado profissionalizante em Ensino do 1.º e 2.º Ciclos do Ensino Básico. Assim, o objetivo último deste documento prende-se com uma reflexão fundamentada de toda a prática educativa desenvolvida em dois ciclos distintos. Uma vez que este momento de intervenção educativa decorreu numa fase final da formação da mestranda, permite relacionar toda a prática com a teoria até então estudada. Desta forma, torna-se importante construir um enquadramento académico e profissional para que os princípios generalistas de ação de um docente sejam seguidos, assim como a revisão de pressupostos teóricos generalistas, transversais e específicos às diferentes áreas do saber. Concomitantemente com a revisão referida, são descritas algumas das experiências educativas vivenciadas nos contextos em questão, valorizando os momentos elencados no ciclo do professor reflexivo e em princípios defendidos pelo professor investigador, em que se acrescenta ainda a importância do trabalho colaborativo. Em suma, toda a prática educativa foi baseada em pressupostos teóricos, no contexto educativo e no próprio perfil docente, com o objetivo maior de criar aprendizagens significativas, tanto para os estudantes como para a professora estagiária

Emotional Theory of Rationality

In recent decades, it has been definitely established the existence of a close relationship between the emotional phenomena and rational processes, but we still do not have a unified definition, or effective models to describe any of them well. To advance our understanding of the mechanisms governing the behavior of living beings we must integrate multiple theories, experiments and models from both fields. In this paper we propose a new theoretical framework that allows integrating and understanding, from a functional point of view, the emotion-cognition duality. Our reasoning, based on evolutionary principles, add to the definition and understanding of emotion, justifying its origin, explaining its mission and dynamics, and linking it to higher cognitive processes, mainly with attention, cognition, decision-making and consciousness. According to our theory, emotions are the mechanism for brain function optimization, besides being the contingency and stimuli prioritization system. As a result of this approach, we have developed a dynamic systems-level model capable of providing plausible explanations for some psychological and behavioral phenomena, and establish a new framework for scientific definition of some fundamental psychological terms.

First-Principles Calculations of the Electronic and Structural Properties of GaSb

In this paper, we carried out first-principles calculations in order to investigate the structural and electronic properties of the binary compound gallium antimonide (GaSb). This theoretical study was carried out using the Density Functional Theory within the plane-wave pseudopotential method. The effects ofexchange and correlation (XC) were treated using the functional Local Density Approximation (LDA), generalized gradient approximation (GGA): Perdew–Burke–Ernzerhof (PBE), Perdew-Burke-Ernzerhof revised for solids (PBEsol), Perdew-Wang91 (PW91), revised Perdew–Burke–Ernzerhof (rPBE), Armiento–Mattson 2005 (AM05) and meta-generalized gradient approximation (meta-GGA): Tao–Perdew– Staroverov–Scuseria (TPSS) and revised Tao–Perdew–Staroverov–Scuseria (RTPSS) and modified Becke-Johnson (MBJ). We calculated the densities of state (DOS) and band structure with different XC potentials identified and compared them with the theoretical and experimental results reported in the literature. It was discovered that functional: LDA, PBEsol, AM05 and RTPSS provide the best results to calculate the lattice parameters (a) and bulk modulus (B0); while for the cohesive energy (Ecoh), functional: AM05, RTPSS and PW91 are closer to the values obtained experimentally. The MBJ, Rtpss and AM05 values found for the band gap energy is slightly underestimated with those values reported experimentally.

AD-HOC principles of minimum energy expenditure as corollaries of the constructal law the cases of river basins and human vascular systems

In a recent paper [1] Reis showed that both the principles of extremum of entropy production rate, which are often used in the study of complex systems, are corollaries of the Constructal Law. In fact, both follow from the maximization of overall system conductivities, under appropriate constraints. In this way, the maximum rate of entropy production (MEP) occurs when all the forces in the system are kept constant. On the other hand, the minimum rate of entropy production (mEP) occurs when all the currents that cross the system are kept constant. In this paper it is shown how the so-called principle of "minimum energy expenditure" which is often used as the basis for explaining many morphologic features in biologic systems, and also in inanimate systems, is also a corollary of Bejan's Constructal Law [2]. Following the general proof some cases namely, the scaling laws of human vascular systems and river basins are discussed as illustrations from the side of life, and inanimate systems, respectively.

Computing the structural and vibrational properties of polymorphic organic molecular crystals through van der Waals corrected density functional theory and the electronic properties of organic thin films through microelectrostatic calculations.

The present Thesis reports on the various research projects to which I have contributed during my PhD period, working with several research groups, and whose results have been communicated in a number of scientific publications. The main focus of my research activity was to learn, test, exploit and extend the recently developed vdW-DFT (van der Waals corrected Density Functional Theory) methods for computing the structural, vibrational and electronic properties of ordered molecular crystals from first principles. A secondary, and more recent, research activity has been the analysis with microelectrostatic methods of Molecular Dynamics (MD) simulations of disordered molecular systems. While only very unreliable methods based on empirical models were practically usable until a few years ago, accurate calculations of the crystal energy are now possible, thanks to very fast modern computers and to the excellent performance of the best vdW-DFT methods. Accurate energies are particularly important for describing organic molecular solids, since they often exhibit several alternative crystal structures (polymorphs), with very different packing arrangements but very small energy differences. Standard DFT methods do not describe the long-range electron correlations which give rise to the vdW interactions. Although weak, these interactions are extremely sensitive to the packing arrangement, and neglecting them used to be a problem. The calculations of reliable crystal structures and vibrational frequencies has been made possible only recently, thanks to development of some good representations of the vdW contribution to the energy (known as “vdW corrections”).

[the Teaching Of Social Sciences In Health: Between Practice And Theory].

The models of teaching social sciences and clinical practice are insufficient for the needs of practical-reflective teaching of social sciences applied to health. The scope of this article is to reflect on the challenges and perspectives of social science education for health professionals. In the 1950s the important movement bringing together social sciences and the field of health began, however weak credentials still prevail. This is due to the low professional status of social scientists in health and the ill-defined position of the social sciences professionals in the health field. It is also due to the scant importance attributed by students to the social sciences, the small number of professionals and the colonization of the social sciences by the biomedical culture in the health field. Thus, the professionals of social sciences applied to health are also faced with the need to build an identity, even after six decades of their presence in the field of health. This is because their ambivalent status has established them as a partial, incomplete and virtual presence, requiring a complex survival strategy in the nebulous area between social sciences and health.

[principles Of Universality, Comprehensiveness And Equity In A Hearing Health Care Service].

This article analyzed whether the practices of hearing health care were consistent with the principles of universality, comprehensiveness and equity from the standpoint of professionals. It involved qualitative research conducted at a Medium Complexity Hearing Health Care Center. A social worker, three speech therapists, a physician and a psychologist constituted the study subjects. Interviews were conducted as well as observation registered in a field diary. The thematic analysis technique was used in the analysis of the material. The analysis of interviews resulted in the construction of the following themes: Universality and access to hearing health, Comprehensive Hearing Health Care and Hearing Health and Equity. The study identified issues that interfere with the quality of service and run counter to the principles of Brazilian Unified Health System. The conclusion reached was that a relatively simple investment in training and professional qualification can bring about significant changes in order to promote a more universal, comprehensive and equitable health service.

Atomic Charge Transfer-counter Polarization Effects Determine Infrared Ch Intensities Of Hydrocarbons: A Quantum Theory Of Atoms In Molecules Model.

Atomic charge transfer-counter polarization effects determine most of the infrared fundamental CH intensities of simple hydrocarbons, methane, ethylene, ethane, propyne, cyclopropane and allene. The quantum theory of atoms in molecules/charge-charge flux-dipole flux model predicted the values of 30 CH intensities ranging from 0 to 123 km mol(-1) with a root mean square (rms) error of only 4.2 km mol(-1) without including a specific equilibrium atomic charge term. Sums of the contributions from terms involving charge flux and/or dipole flux averaged 20.3 km mol(-1), about ten times larger than the average charge contribution of 2.0 km mol(-1). The only notable exceptions are the CH stretching and bending intensities of acetylene and two of the propyne vibrations for hydrogens bound to sp hybridized carbon atoms. Calculations were carried out at four quantum levels, MP2/6-311++G(3d,3p), MP2/cc-pVTZ, QCISD/6-311++G(3d,3p) and QCISD/cc-pVTZ. The results calculated at the QCISD level are the most accurate among the four with root mean square errors of 4.7 and 5.0 km mol(-1) for the 6-311++G(3d,3p) and cc-pVTZ basis sets. These values are close to the estimated aggregate experimental error of the hydrocarbon intensities, 4.0 km mol(-1). The atomic charge transfer-counter polarization effect is much larger than the charge effect for the results of all four quantum levels. Charge transfer-counter polarization effects are expected to also be important in vibrations of more polar molecules for which equilibrium charge contributions can be large.