First principles based multiparadigm modeling of electronic structures and dynamics

Electronic structures and dynamics are the key to linking the material composition and structure to functionality and performance.

An essential issue in developing semiconductor devices for photovoltaics is to design materials with optimal band gaps and relative positioning of band levels. Approximate DFT methods have been justified to predict band gaps from KS/GKS eigenvalues, but the accuracy is decisively dependent on the choice of XC functionals. We show here for CuInSe₂ and CuGaSe₂, the parent compounds of the promising CIGS solar cells, conventional LDA and GGA obtain gaps of 0.0-0.01 and 0.02-0.24 eV (versus experimental values of 1.04 and 1.67 eV), while the historically first global hybrid functional, B3PW91, is surprisingly the best, with band gaps of 1.07 and 1.58 eV. Furthermore, we show that for 27 related binary and ternary semiconductors, B3PW91 predicts gaps with a MAD of only 0.09 eV, which is substantially better than all modern hybrid functionals, including B3LYP (MAD of 0.19 eV) and screened hybrid functional HSE06 (MAD of 0.18 eV).

The laboratory performance of CIGS solar cells (> 20% efficiency) makes them promising candidate photovoltaic devices. However, there remains little understanding of how defects at the CIGS/CdS interface affect the band offsets and interfacial energies, and hence the performance of manufactured devices. To determine these relationships, we use the B3PW91 hybrid functional of DFT with the AEP method that we validate to provide very accurate descriptions of both band gaps and band offsets. This confirms the weak dependence of band offsets on surface orientation observed experimentally. We predict that the CBO of perfect CuInSe₂/CdS interface is large, 0.79 eV, which would dramatically degrade performance. Moreover we show that band gap widening induced by Ga adjusts only the VBO, and we find that Cd impurities do not significantly affect the CBO. Thus we show that Cu vacancies at the interface play the key role in enabling the tunability of CBO. We predict that Na further improves the CBO through electrostatically elevating the valence levels to decrease the CBO, explaining the observed essential role of Na for high performance. Moreover we find that K leads to a dramatic decrease in the CBO to 0.05 eV, much better than Na. We suggest that the efficiency of CIGS devices might be improved substantially by tuning the ratio of Na to K, with the improved phase stability of Na balancing phase instability from K. All these defects reduce interfacial stability slightly, but not significantly.

A number of exotic structures have been formed through high pressure chemistry, but applications have been hindered by difficulties in recovering the high pressure phase to ambient conditions (i.e., one atmosphere and room temperature). Here we use dispersion-corrected DFT (PBE-ulg flavor) to predict that above 60 GPa the most stable form of N₂O (the laughing gas in its molecular form) is a 1D polymer with an all-nitrogen backbone analogous to cis-polyacetylene in which alternate N are bonded (ionic covalent) to O. The analogous trans-polymer is only 0.03-0.10 eV/molecular unit less stable. Upon relaxation to ambient conditions both polymers relax below 14 GPa to the same stable non-planar trans-polymer, accompanied by possible electronic structure transitions. The predicted phonon spectrum and dissociation kinetics validate the stability of this trans-poly-NNO at ambient conditions, which has potential applications as a new type of conducting polymer with all-nitrogen chains and as a high-energy oxidizer for rocket propulsion. This work illustrates in silico materials discovery particularly in the realm of extreme conditions.

Modeling non-adiabatic electron dynamics has been a long-standing challenge for computational chemistry and materials science, and the eFF method presents a cost-efficient alternative. However, due to the deficiency of FSG representation, eFF is limited to low-Z elements with electrons of predominant s-character. To overcome this, we introduce a formal set of ECP extensions that enable accurate description of p-block elements. The extensions consist of a model representing the core electrons with the nucleus as a single pseudo particle represented by FSG, interacting with valence electrons through ECPs. We demonstrate and validate the ECP extensions for complex bonding structures, geometries, and energetics of systems with p-block character (C, O, Al, Si) and apply them to study materials under extreme mechanical loading conditions.

Despite its success, the eFF framework has some limitations, originated from both the design of Pauli potentials and the FSG representation. To overcome these, we develop a new framework of two-level hierarchy that is a more rigorous and accurate successor to the eFF method. The fundamental level, GHA-QM, is based on a new set of Pauli potentials that renders exact QM level of accuracy for any FSG represented electron systems. To achieve this, we start with using exactly derived energy expressions for the same spin electron pair, and fitting a simple functional form, inspired by DFT, against open singlet electron pair curves (H₂ systems). Symmetric and asymmetric scaling factors are then introduced at this level to recover the QM total energies of multiple electron pair systems from the sum of local interactions. To complement the imperfect FSG representation, the AMPERE extension is implemented, and aims at embedding the interactions associated with both the cusp condition and explicit nodal structures. The whole GHA-QM+AMPERE framework is tested on H element, and the preliminary results are promising.

Caminhos contemporâneos Cortázar e outros destruidores de bússolas

A presente tese se ocupa de uma vertente da literatura e do cinema contemporâneos, especialmente do escritor Julio Cortázar e do cineasta David Lynch, que: busca um novo tratamento para a realidade, não esconde os artifícios discursivos das obras, joga com estratégias ilusionistas e antiilusionistas, debate a própria ficção por meio de recursos metaficcionais, que se utiliza da metáfora do teatro como espaço diferenciado e como palco de ilusões e que trabalha com a questão do fantástico (ou absurdo). Grande parte do trabalho é dedicada ao estudo da obra do escritor argentino Julio Cortázar. Estudo esse que se constrói a partir das correspondências entre as produções ficcionais e teóricas de Cortázar, além de suas próprias entrevistas. Cortázar é nosso foco principal e dele, acreditamos, brotou um veio dos mais significativos na narrativa contemporânea, que estabelece novos modos de se lidar com a representação e com as referências. É devido a esses aspectos, apontados anteriormente, que estabelecemos relações com outros autores, inclusive do cinema, como é o caso de David Lynch

Bacantes de Eurípides: Felicidad iniciática y furia salvaje en el cortejo femenino de Dioniso

404 p. E-mail de contacto del autor: jbreviatti@yahoo.es

A santa absolvição do crime: violência, revolta e religiosidade nas dramaturgias de Jean Genet e Plínio Marcos

A presente tese de doutorado analisa, em perspectiva comparada, as convergências e divergências entre as dramaturgias do francês Jean Genet e do brasileiro Plínio Marcos, sob o prisma de três tópicos inegavelmente presentes, nelas: a violência, a revolta e a religiosidade. As questões de margem, borda, periferia, ex-centricidade, dissenso etc são abordadas neste trabalho para situar a ideia de outro como o referencial ontológico que sustenta a obra teatral de ambos. As respectivas biografias dos autores em questão, direta ou indiretamente, tem relação com a aura de marginalidade artística atribuída (e até assumida por eles próprios) a sua produção em geral (seus romances, poemas, ensaios e contos). Pode-se dizer que muito da persona que ambos assumiram correspondia às expectativas que os círculos intelectuais engajados tinham em adotar uma figura que viesse a encarnar o papel de autêntico porta-voz do segmento marginalizado da sociedade na qual cada um deles se criou. Ambos gozam de certo status de vanguardistas no caso do metateatro de Genet, na sua atribuída vinculação ao Teatro do Absurdo, e, no caso do hipernaturalismo dramático de Plínio, na sua atribuída (e mesmo confessa) descendência da linhagem criativa de caracteres e motivos do teatro de Nelson Rodrigues. Outro aspecto comum à dramaturgia de Genet e Plínio que abordamos é a problematização de dois espaços alegóricos definidores por excelência do ethos dos tipos humanos que o habitam: a prisão e o prostíbulo. Para tanto, ganham destaque, aqui, Alta vigilância e O Balcão, de Genet, e Barrela e O abajur lilás, de Plínio. Nelas também se verifica a figuração de motivos de inspiração religiosa que, no autor francês, concorrem para uma espécie de sacralização ritual do crime (o que ecoa o ideário de Antonin Artaud) e, no brasileiro, funcionam como um exercício catártico de compaixão à sombra de uma cristandade de feição primitiva que se insinua no tratamento que dá à degradação dos párias sociais que compõem seu universo dramático. Por fim, analisamos comparativamente três peças brasileiras (Pedro Mico, de Antonio Callado; Gimba, o presidente dos valentes, de Gianfrancesco Guarnieri; e Oração para um pé de chinelo, de Plínio Marcos) tomando como ponto de partida uma situação dramática comum a elas para traçar, assim, as afinidades e distinções de cada qual quanto à abordagem da criminalidade. E, assim, também, poder apontar o tipo de projeto de teatro a que cada uma se vincula, trazendo à tona questões caras ao momento histórico-cultural no qual foram compostas, como a figuração do negro e do favelado na sociedade brasileira

Analytical Representation of Contours

The interpretation and recognition of noisy contours, such as silhouettes, have proven to be difficult. One obstacle to the solution of these problems has been the lack of a robust representation for contours. The contour is represented by a set of pairwise tangent circular arcs. The advantage of such an approach is that mathematical properties such as orientation and curvature are explicityly represented. We introduce a smoothing criterion for the contour tht optimizes the tradeoff between the complexity of the contour and proximity of the data points. The complexity measure is the number of extrema of curvature present in the contour. The smoothing criterion leads us to a true scale-space for contours. We describe the computation of the contour representation as well as the computation of relevant properties of the contour. We consider the potential application of the representation, the smoothing paradigm, and the scale-space to contour interpretation and recognition.

Neural Pattern Recognition on Multichannel Input Representation

This article presents a new neural pattern recognition architecture on multichannel data representation. The architecture emploies generalized ART modules as building blocks to construct a supervised learning system generating recognition codes on channels dynamically selected in context using serial and parallel match trackings led by inter-ART vigilance signals.

Multiple Dynamic Processes Contribute to the Complex Steady Shear Behavior of Cross-Linked Supramolecular Networks of Semidilute Entangled Polymer Solutions.

Molecular theories of shear thickening and shear thinning in associative polymer networks are typically united in that they involve a single kinetic parameter that describes the network -- a relaxation time that is related to the lifetime of the associative bonds. Here we report the steady-shear behavior of two structurally identical metallo-supramolecular polymer networks, for which single-relaxation parameter models break down in dramatic fashion. The networks are formed by the addition of reversible cross-linkers to semidilute entangled solutions of PVP in DMSO, and they differ only in the lifetime of the reversible cross-links. Shear thickening is observed for cross-linkers that have a slower dissociation rate (17 s(-1)), while shear thinning is observed for samples that have a faster dissociation rate (ca. 1400 s(-1)). The difference in the steady shear behavior of the unentangled vs. entangled regime reveals an unexpected, additional competing relaxation, ascribed to topological disentanglement in the semidilute entangled regime that contributes to the rheological properties.

The Development of Piano Variations in the Romantic Era

The purpose of this study is to illustrate the development of piano variations as a genre during the Romantic era. In order to facilitate this examination of piano variations techniques, a brief look at the types of variation procedures used by composers of previous eras will assist in understanding developments that later occurred in the Romantic period. Throughout the Baroque era, composers preferred the fured-bass, fixed-melody, and harmonic forms of variation. The crowning achievement of Baroque keyboard music, Bach's Goldberg Variations (1725), contains examples of the "constantharmonic" method in its collection of 30 variations, each of which maintains both the bass and harmonic structure of the themes. While most composers of the classical period favored the "melodic-outline" form of variation, Haydn developed hybrid variation procedure that exhibits recurrence of material rather than repetition, alternating variation (ABABA), rondo variation (ABACA), and ternary variation (ABA). Haydn, Mozart and early Beethoven variations also exhibit simpler textures than do their Baroque predecessors. The nineteenth century produced numerous compositions that display variation techniques, some based on such older, classical models as melodic-outline variation and hybrid variation, others in the style of the character variation or fiee variation. At the beginning of the nineteenth century, Beethoven and Schubert used such classical variation techmques as melodic-outline variations and hybrid variations. Beethoven's late sonatas displayed such new means of expression as variation, fugue, and dramatic recitatives. The third movement of the Sonata in E major, Op. 109 (1820) has a theme and six variations of the melodic-outline type. Johannes Brahms was particularly fond of composing variations for piano. Among the best known examples of formal-outline variations are those found in the Variations and Fugue on a Theme of Handel, Op. 24 (1861). Character variations, in which styles are characterized by the retention and variability of particular elements, also flourished during the Romantic period. Cesar Franck's Variations Symphoniques (1885) are, perhaps, among the most important examples of free variations. This composition is a one-movement work consisting of three sections, Introduction, Variations, and Finale (all movements played "attaca"). This work combines two independent classical formal structures, the concerto and the variation.

Long-Term Oceanographic and Ecological Research in the Western English Channel

Long-term research in the western English Channel, undertaken by the marine laboratories in Plymouth, is described and details of survey methods, sites, and time series given in this chapter. Major findings are summarized and their limitations outlined. Current research, with recent reestablishment and expansion of many sampling programmes, is presented, and possible future approaches are indicated. These unique long-term data sets provide an environmental baseline for predicting complex ecological responses to local, regional, and global environmental change. Between 1888 and the present, investigations have been carried out into the physical, chemical, and biological components (ranging from plankton and fish to benthic and intertidal assemblages) of the western English Channel ecosystem. The Marine Biological Association of the United Kingdom has performed the main body of these observations. More recent contributions come from the Continuous Plankton Recorder Survey, now the Sir Alister Hardy Foundation for Ocean Science, dating from 1957; the Institute for Marine Environmental Research, from 1974 to 1987; and the Plymouth Marine Laboratory, which was formed by amalgamation of the Institute for Marine Environmental Research and part of the Marine Biological Association, from 1988. Together, these contributions constitute a unique data series; one of the longest and most comprehensive samplings of environmental and marine biological variables in the world. Since the termination of many of these time series in 1987-1988 during a reorganisation of UK marine research, there has been a resurgence of interest in long-term environmental change. Many programmes have been restarted and expanded with support from several agencies. The observations span significant periods of warming (1921-1961; 1985-present) and cooling (1962-1980). During these periods of change, the abundance of key species underwent dramatic shifts. The first period of warming saw changes in zooplankton, pelagic fish, and larval fish, including the collapse of an important herring fishery. During later periods of change, shifts in species abundances have been reflected in other assemblages, such as the intertidal zone and the benthic fauna. Many of these changes appear to be related to climate, manifested as temperature changes, acting directly or indirectly. The hypothesis that climate is a forcing factor is widely supported today and has been reinforced by recent studies that show responses of marine organisms to climatic attributes such as the strength of the North Atlantic Oscillation. The long-term data also yield important insights into the effects of anthropogenic disturbances such as fisheries exploitation and pollution. Comparison of demersal fish hauls over time highlights fisheries effects not only on commercially important species but also on the entire demersal community. The effects of acute ("Torrey Canyon" oil spill) and chronic (tributyltin [TBT] antifoulants) pollution are clearly seen in the intertidal records. Significant advances in diverse scientific disciplines have been generated from research undertaken alongside the long-term data series.

The European Convention on Human Rights after Enlargement

The Council of Europe has dramatically enlarged its membership over the past decade, encompassing the vast majority of the formerly Communist states of Central and Eastern Europe. With this dramatic enlargement, the Council has sought to secure its place in the complex institutional architecture of post-Cold War Europe, building on its traditional strengths in the promotion of democratic governance and human rights. Yet, both inside and outside the organisation, voices have been raised to suggest that the Council has lowered its admission standards in a manner which risks compromising the legitimacy of the European Convention on Human Rights. Against the background of these ongoing controversies, this article assesses the impact of enlargement on the European human rights system. Focusing on the composition of the European Court of Human Rights and the initial pattern of cases from the Central and East European member states, it is demonstrated that the short-term impact of enlargement has been quite limited. Nevertheless, it is clear that the Court will face major new challenges over the coming years. In part, the Court will have to assume the role of an adjudicator of transition. More generally, there will also be mounting pressures for it to (re)cast itself more clearly as a European constitutional court.

‘Glimpses into the unmentionable: Montserrat, tourism and anthropological readings of “subordinate exotic” and “comic exotic” travel writing’

This article explores the relationship between anthropology and identity through the process of travel writing and reading. Specifically, the article examines a range of travel writing about the British Caribbean colony Montserrat to read into the culture of the writer. These deconstructive ‘glimpses into the unmentionable’ reveal an implicit racism. The travel writing texts are also found to divide into two types of representation – the ‘subordinate exotic’ and the ‘comic exotic’.

An Absence of Ghosts: cultural and theatrical translation in the British Reception of The Mysteries-Yiimimangaliso

Mark Dornford-May’s widely-acclaimed adaptation of the medieval English Chester “mystery” plays, The Mysteries-Yiimimangaliso, reveal the extent to which theatrical translation, if it is to be intelligible to audiences, risks trading in cultural stereotypes belonging to both source and target cultures. As a South African production of a medieval English theatrical tradition which subsequently plays to an English audience, The Mysteries-Yiimimangaliso enacts a number of disorientating forms of cultural translation. Rather than facilitating the transmission of challenging literary and dramatic traditions, The Mysteries-Yiimimangaliso reveals the extent to which translation, as a politically correct - and thus politically anaemic - act, can become an end in itself in a globalised Anglophone theatrical culture.

Liouville-space R-matrix-Floquet description of atomic radiative processes involving autoionizing states in the presence of intense electromagnetic fields

A reduced-density-operator description is developed for coherent optical phenomena in many-electron atomic systems, utilizing a Liouville-space, multiple-mode Floquet–Fourier representation. The Liouville-space formulation provides a natural generalization of the ordinary Hilbert-space (Hamiltonian) R-matrix-Floquet method, which has been developed for multi-photon transitions and laser-assisted electron–atom collision processes. In these applications, the R-matrix-Floquet method has been demonstrated to be capable of providing an accurate representation of the complex, multi-level structure of many-electron atomic systems in bound, continuum, and autoionizing states. The ordinary Hilbert-space (Hamiltonian) formulation of the R-matrix-Floquet method has been implemented in highly developed computer programs, which can provide a non-perturbative treatment of the interaction of a classical, multiple-mode electromagnetic field with a quantum system. This quantum system may correspond to a many-electron, bound atomic system and a single continuum electron. However, including pseudo-states in the expansion of the many-electron atomic wave function can provide a representation of multiple continuum electrons. The 'dressed' many-electron atomic states thereby obtained can be used in a realistic non-perturbative evaluation of the transition probabilities for an extensive class of atomic collision and radiation processes in the presence of intense electromagnetic fields. In order to incorporate environmental relaxation and decoherence phenomena, we propose to utilize the ordinary Hilbert-space (Hamiltonian) R-matrix-Floquet method as a starting-point for a Liouville-space (reduced-density-operator) formulation. To illustrate how the Liouville-space R-matrix-Floquet formulation can be implemented for coherent atomic radiative processes, we discuss applications to electromagnetically induced transparency, as well as to related pump–probe optical phenomena, and also to the unified description of radiative and dielectronic recombination in electron–ion beam interactions and high-temperature plasmas.

Representações gráficas da dinâmica do corpo : Desenho, 12º ano

Relatório da Prática de Ensino Supervisionada, Ensino das Artes Visuais no 3º Ciclo do Ensino Básico e no Ensino Secundário, Universidade de Lisboa, 2013

The wars of the gulls; : an historical romance in three chapters; chap. I, Shewing how and why and with whom the gulls went to war: chap. II, Shewing how the gulls make the deep to boil like a pot: chap. III, Shewing how a certain doughty general of the gulls goes forth to play the game of hull-gull in Upper Canada.

Transcribed on front paste-down: W.G. Phelps Oct. 29 1890.