Relation between effective atomic charge and chemical shifts in X-ray absorption spectra of transition-metal compounds

Chemical shifts of K absorption discontinuities, Delta E, of several manganese, iron and cobalt oxides with the metal in the formal oxidation states between +2 and +4, have been measured. These data, together with data in the literature on other compounds of these metals, can be fitted into the expression Delta E=aq+bq2, where q is the effective atomic charge on the metal. Theoretical considerations also support this functional relationship between Delta E and q.

Space-charge-limited current in fast neutron irradiated silicon

DC and transient measurements of space-charge-limited currents through alloyed and symmetrical n^+ν n^+ structures made of nominally 75 kΩcm ν-type silicon are studied before and after the introduction of defects by 14 MeV neutron radiation. In the transient measurements, the current response to a large turn-on voltage step is analyzed. Right after the voltage step is applied, the current transient reaches a value which we shall call "initial current" value. At longer times, the transient current decays from the initial current value if traps are present.

Before the irradiation, the initial current density-voltage characteristics J(V) agree quantitatively with the theory of trap-free space-charge-limited current in solids. We obtain for the electron mobility a temperature dependence which indicates that scattering due to impurities is weak. This is expected for the high purity silicon used. The drift velocity-field relationships for electrons at room temperature and 77°K, derived from the initial current density-voltage characteristics, are shown to fit the relationships obtained with other methods by other workers. The transient current response for t > 0 remains practically constant at the initial value, thus indicating negligible trapping.

Measurement of the initial (trap-free) current density-voltage characteristics after the irradiation indicates that the drift velocity-field relationship of electrons in silicon is affected by the radiation only at low temperature in the low field range. The effect is not sufficiently pronounced to be readily analyzed and no formal description of it is offered. In the transient response after irradiation for t > 0, the current decays from its initial value, thus revealing the presence of traps. To study these traps, in addition to transient measurements, the DC current characteristics were measured and shown to follow the theory of trap-dominated space-charge-limited current in solids. This theory was applied to a model consisting of two discrete levels in the forbidden band gap. Calculations and experiments agreed and the capture cross-sections of the trapping levels were obtained. This is the first experimental case known to us through which the flow of space-charge-limited current is so simply representable.

These results demonstrate the sensitivity of space-charge-limited current flow as a tool to detect traps and changes in the drift velocity-field relationship of carriers caused by radiation. They also establish that devices based on the mode of space-charge-limited current flow will be affected considerably by any type of radiation capable of introducing traps. This point has generally been overlooked so far, but is obviously quite significant.

Studies of electron-transfer and charge-transfer coupling processes at a liquid/liquid interface by double-barrel micropipet technique

Investigation of a heterogeneous electron-transfer (ET) reaction at the water/1,2-dichloroethane interface employing a double-barrel micropipet technique is reported. The chosen system was the reaction between Fe(CN)(6)(3-) in the aqueous phase (W) and ferrocene in 1,2-dichloroethane (DCE). According to the generation and the collection currents as well as collection efficiency, the ET-ion-transfer (IT) coupling process at such an interface and competing reactions with the organic supporting electrolyte in the organic phase can be studied. In addition, this technique has been found to be an efficient method to distinguish and measure the charge-transfer coupling reaction between two ions (IT-IT) processes occurring simultaneously at a liquid/liquid interface. On this basis, the formal Gibbs energies of transfer of some ions across the W/DCE interface, such as NO3-, NO2-, Cl-, COO-, TBA(+), IPAs+, Cs+, Rb+, K+, Na+, and Li+, for which their direct transfers are usually difficult to obtain because of the IT-IT coupling processes, were quantitatively evaluated.

Charge transfer across the water/nitrobenzene interface by three-electrode system

A droplet of aqueous solution containing a certain molar ratio of redox couple is first attached onto a platinum electrode surface, then the resulting drop electrode is immersed into the organic solution containing very hydrophobic electrolyte. Combined with reference and counter electrodes, a classical three-electrode system has been constructed, Ion transfer (IT) and electron transfer (ET) are investigated systematically using three-electrode voltammetry. Potassium ion transfer and electron transfer between potassium ferricyanide in the aqueous phase and ferrocene in nitrobenzene are observed with potassium ferricyanide/potassium ferrocyanide as the redox couple. Meanwhile, the transfer reactions of lithium, sodium, potassium, proton and ammonium ions are obtained with ferric sulfate/ferrous sulfate as the redox couple. The formal transfer potentials and the standard Gibbs transfer energy of these ions are evaluated and consistent with the results obtained by a four-electrode system and other methods.

Formal Multilevel Hierarchical Verification of Synchronous MOS Circuits

I have designed and implemented a system for the multilevel verification of synchronous MOS VLSI circuits. The system, called Silica Pithecus, accepts the schematic of an MOS circuit and a specification of the circuit's intended digital behavior. Silica Pithecus determines if the circuit meets its specification. If the circuit fails to meet its specification Silica Pithecus returns to the designer the reason for the failure. Unlike earlier verifiers which modelled primitives (e.g., transistors) as unidirectional digital devices, Silica Pithecus models primitives more realistically. Transistors are modelled as bidirectional devices of varying resistances, and nodes are modelled as capacitors. Silica Pithecus operates hierarchically, interactively, and incrementally. Major contributions of this research include a formal understanding of the relationship between different behavioral descriptions (e.g., signal, boolean, and arithmetic descriptions) of the same device, and a formalization of the relationship between the structure, behavior, and context of device. Given these formal structures my methods find sufficient conditions on the inputs of circuits which guarantee the correct operation of the circuit in the desired descriptive domain. These methods are algorithmic and complete. They also handle complex phenomena such as races and charge sharing. Informal notions such as races and hazards are shown to be derivable from the correctness conditions used by my methods.

Avaliação comparativa entre a estimativa do impacto gerado por efluentes domésticos de assentamentos espontâneos e de ocupação formal na bacia do Tucunduba em Belém - Pará

A presente pesquisa apresenta avaliação comparativa do impacto ambiental gerado por contextos habitacionais diferentes dentro do mesmo espaço urbano, no caso o bairro do Guamá, município de Belém, o contexto formal corresponde à ocupação da Av. José Bonifácio e o contexto de produção informal corresponde à comunidade do Riacho Doce. Na referida avaliação foram levados em consideração para investigação os seguintes aspectos: Consumo per capita de água, consumo per capita de esgoto, universalidade e equidade do fornecimento dos serviços de saneamento (abastecimento de água e esgotamento sanitário), tarifação de abastecimento de água, qualidade e acessibilidade dos serviços, contexto habitacional, aspectos socioambientais, com objetivo de caracterizar a população residente nessas áreas e finalmente estimar a carga orgânica (Kg de DBO/dia) e a vazão (m3/d) de efluentes domésticos gerados de assentamentos espontâneos e em uma área urbana consolidada, com o intuito de identificar qual contexto habitacional apresenta maior potencial de impacto em termos de geração de vazão e carga orgânica sobre a bacia receptora de efluentes, neste caso a Bacia do Tucunduba. Apesar dos resultados serem valores relativamente próximos, na área de Assentamento Espontâneo, a vazão de esgotos estimada 44,38 m3/dia e Carga Orgânica de 13,31 Kg de DBO/dia, e na área de Ocupação Formal a vazão de esgotos estimada 43,06 m3/dia e Carga Orgânica de 12,91 Kg de DBO/dia, foi possível observar neste trabalho que existe diferenciação do impacto ambiental gerado pelas duas áreas na bacia receptora no Igarapé Tucunduba, sendo maior no Riacho Doce onde a população permanece em contato com os efluentes e sob maior vulnerabilidade sanitária, pois, os efluentes da José Bonifácio são encaminhados pela rede de drenagem e sua carga orgânica é diluída pela vazão de águas pluviais ao chegarem ao Igarapé (distanciando a contaminação de sua fonte) e os efluentes do Riacho Doce são lançados in natura diretamente sob as casas e no Igarapé.

La Esgrima como enseñanza formal en las instituciones educativas públicas de Madrid. Del Real Seminario de Nobles al Instituto de Segunda Enseñanza Cardenal Cisneros (1725-1950).

En el presente trabajo de investigación se ha analizado la presencia de la Esgrima como materia de enseñanza dentro de diversas Instituciones educativas formales de Madrid, abarcando un rango temporal de 225 años (1725-1950). Para la realización de la investigación se elaboró un esquema de trabajo basado en la metodología de la investigación histórica, la historiografía. La búsqueda de la información se llevó a cabo, fundamentalmente en el Archivo Histórico Nacional el Archivo General de la Administración, el Archivo Regional de Madrid, el Archivo General de la Universidad Complutense de Madrid, el Archivo del Real Conservatorio Superior de Música de Madrid, el Archivo General de Palacio, el Archivo de la Villa y la Biblioteca Nacional. La investigación presentada abarca cinco Instituciones educativas en las que se estudia la presencia de la Esgrima como enseñanza formal, siendo estas el Real Seminario de Nobles de Madrid, la Escuela Central de Profesores y Profesoras de Gimnástica, el Real Conservatorio de Música y Declamación y los Institutos de Segunda Enseñanza del Cardenal Cisneros y de San Isidro. Se analizaron las diferentes Constituciones de formación, Planes de Estudios, Reglamentos Interinos de funcionamiento, Leyes de fundación, libros, Programas de asignaturas y todos aquellos documentos, tanto oficiales como internos de cada uno de los Centros tratados. Así mismo, se estudiaron las figuras de los Maestros encargados de impartir la Esgrima como materia formal en las diversas Instituciones, alcanzando la mayor relevancia D. Manuel Antonio de Brea, D. Francisco de la Macorra y Guijeño, D. Ángel Lancho Martín de la Fuente, D. Afrodisio Aparicio Aparicio y D. José Carbonell. De la investigación realizada se concluye la presencia de la Esgrima como una materia perfectamente sistematizada en cada uno de las Instituciones analizadas así como la importancia que alcanzaba la figura del Maestro de Esgrima en todas ellas, siendo en algunos casos “Maestro Mayor del Reyno” y en otros convirtiéndose en Catedráticos de Esgrima, al tiempo que todos ellos contaban con una titulación que les capacitaba para el ejercicio de su profesión. Así mismo encontramos la presencia de la mujer en una de las Instituciones, el Real Conservatorio de Música y Declamación, con los mismos derechos que sus compañeros varones para matricularse y estudiar la Esgrima. Los Maestros estudiados, fundamentalmente D. Ángel Lancho, D. Afrodisio Aparicio y D. José Carbonell, contribuyeron a popularizar la Esgrima y a su desarrollo como deporte, organizando torneos para sus alumnos y compitiendo ellos mismos en multitud de asaltos. A lo largo de los 225 años que abarca esta investigación, la Esgrima evolucionó de Destreza a Habilidad y más tarde a Deporte, sin perder en ningún momento su importancia, extendiéndose a sectores de la sociedad a los que nunca habría llegado de no ser por la labor de los Maestros de Esgrima encargados de su formación. ABSTRACT. In this research work, the presence of Fencing as an educational subject within different formal educational Institutions in Madrid, over a period of 225 years (1725-1950), has been analysed. In order to carry out this research, a work schedule was drawn up, based on the methods of the historical research, historiography. The search for the information was primarily carried out in the Archivo Historico Nacional, the Archivo General de la Administración, the Archivo Regional of Madrid, the Archivo General de la Universidad Complutense de Madrid, the Archivo del Real Conservatorio Superior de Música of Madrid, the Archivo General de Palacio, the Archivo de la Villa and the Biblioteca Nacional. The research presented covers five educational Institutions, where the presence of Fencing as a formal education is studied. These Institutions are: the Real Seminario de Nobles de Madrid, the Escuela Central de Profesores y Profesoras de Gimnástica, the Real Conservatorio de Música y Declamación and the Cardenal Cisneros and the San Isidro Secondary Schools. The different Academic formation, Syllabuses, Temporary working Regulations, founding Law, books, subject Plans and all the documents, official or internal, of each of the Centres dealt with, were analysed. Moreover, the roles of the Masters in charge of teaching Fencing as a formal subject in different Institutions were studied, and Mr. Manuel Antonio de Brea, Mr. Francisco de la Macorra y Guijeño, Mr. Ángel Lancho Martín de la Fuente, Mr. Afrodisio Aparicio Aparicio and Mr. José Carbonell were the most prominent. The conclusion of the research carried out, is that the presence of Fencing is a subject perfectly organised in each one of the Institutions analysed, as well as the importance that the role of the Fencing Master reached in every Institution, in some cases being “Maestro Mayor del Reyno” and in others becoming Fencing Professors, while all of them had a qualification that enabled them to practice their profession. Similarly, we can find the presence of women in one of the Institutions, the Real Conservatorio de Música y Declamación, where they had the same rights as her male classmates to enrol and study Fencing. The Fencing Masters who were studied, principally Mr. Ángel Lancho, Mr. Afrodisio Aparicio and Mr. José Carbonell, all contributed to making Fencing popular and also towards its development as a sport, by organising tournaments for their students and by competing themselves in a number of assaults. Over the 225 years which the research covers, Fencing evolved from Skill to Ability and later on to a Sport, without, at any moment, losing its importance, spreading to parts of society that it would never have reached if it were not for the work of the Fencing Masters in charge of teaching it.

Zwitterionic and charge-balanced (polyampholyte) copolymer hydrogels

Zwitterionic compounds, or zwitterions, are electrically neutral compounds having an equal number of formal unit charges of opposite sign. In common polyzwitterions the zwitterionic groups are usually located in pendent groups rather than the backbone of the macromolecule. Polyzwitterions contain both the anion and cation in the same monomeric unit, unlike polyampholytes which can contain the anion and cation in different monomeric units. The use of cationic and anionic monomers (or monomers capable of becoming charged) in stoichiometric equivalent proportions produces charge-balanced polyampholyte copolymers. Hydrogel materials produced from zwitterionic monomers have been proposed for use and are used in many biomaterial applications but synthetic charge-balanced polyampholyte are less common. Certain properties of hydrogels which are important for their successful use as biomaterials, these include the equilibrium water content, mechanical, surface energy, oxygen permeability, swelling and the coefficient of friction. The zwitterionic monomer N,N-dimethyl-N-(2-acryloylethyl)-N-(3-sulfopropyl) ammonium betaine (SPDA) was synthesized with 2-hydroxyethly acrylate (HEMA) as the comonomer to produce a series of polyzwitterion hydrogels. To produce charged-balanced copolymer hydrogels two “cationic” monomers were selected; 2-(diethylamino) ethyl methacrylate (DMAEMA) and 3-(dimethylamino) propyl methacrylamide (DMAPMA) and an anionic monomer; 2-acrylamido 2,2 methylpropane sulphonic acid (AMPS). Two series’ of charge-balanced copolymers were synthesized from stoichiometric equivalent ratios of DMAEMA or DMAPMA and AMPS with HEMA as a terpolymer. The zwitterionic copolymer and both charge-balanced copolymers produced clear, cohesive hydrogels. The zwitterionic and charge-balanced copolymers displayed similar EWC’s along with similar mechanical and surface energy properties. The swelling of the zwitterionic copolymer displayed antipolyelectrolyte behavior whereas the charge-balanced copolymers displayed behaviour somewhere between this and a typical polyelectrolyte. This work describes some aspects of the polymerisation and properties of SPDA copolymers and charge-balanced (polyampholyte) copolymers relevant to their potential as biomedical / bioresponsive materials. The biomimetic nature of SPDA together with its compatibility with other monomers makes it a useful and complimentary addition to the building blocks of biomaterials.

Low valence cation doping of bulk Cr2O3: Charge compensation and oxygen vacancy formation

The different oxidation states of chromium allow its bulk oxide form to be reducible, facilitating the oxygen vacancy formation process, which is a key property in applications such as catalysis. Similar to other useful oxides such as TiO2, and CeO2, the effect of substitutional metal dopants in bulk Cr2O3 and its effect on the electronic structure and oxygen vacancy formation are of interest, particularly in enhancing the latter. In this paper, density functional theory (DFT) calculations with a Hubbard + U correction (DFT+U) applied to the Cr 3d and O 2p states, are carried out on pure and metal-doped bulk Cr2O3 to examine the effect of doping on the electronic and geometric structure. The role of dopants in enhancing the reducibility of Cr2O3 is examined to promote oxygen vacancy formation. The dopants are Mg, Cu, Ni, and Zn, which have a formal +2 oxidation state in their bulk oxides. Given this difference in host and, dopant oxidation states, we show that to predict the correct ground state two metal dopants charge compensated with an oxygen vacancy are required. The second oxygen atom removed is termed "the active" oxygen vacancy and it is the energy required to remove this atom that is related to the reduction process. In all cases, we find that substitutional doping improves the oxygen vacancy formation of bulk Cr2O3 by lowering the energy cost.

Who is in charge? An L2 Discourse Intonation Study on Four Prosodic Parameters to Exert the Pragmatic Function of Dominance and Control in the Context of L2 Non-specialist Public Speaking

This paper reports the findings from a study of the learning of English intonation by Spanish speakers within the discourse mode of L2 oral presentation. The purpose of this experiment is, firstly, to compare four prosodic parameters before and after an L2 discourse intonation training programme and, secondly, to confirm whether subjects, after the aforementioned L2 discourse intonation training, are able to match the form of these four prosodic parameters to the discourse-pragmatic function of dominance and control. The study designed the instructions and tasks to create the oral and written corpora and Brazil’s Pronunciation for Advanced Learners of English was adapted for the pedagogical aims of the present study. The learners’ pre- and post-tasks were acoustically analysed and a pre / post- questionnaire design was applied to interpret the acoustic analysis. Results indicate most of the subjects acquired a wider choice of the four prosodic parameters partly due to the prosodically-annotated transcripts that were developed throughout the L2 discourse intonation course. Conversely, qualitative and quantitative data reveal most subjects failed to match the forms to their appropriate pragmatic functions to express dominance and control in an L2 oral presentation.