Electron collisions with the HCOOH...(H2O)n (n=1, 2 and 3) complexes in liquid phase: the influence on the π* shape resonance of formic acid

In this conference we report cross sections for elastic collisions of low-energy electrons with the HCOOH…(H2O)n complexes, with n = 1, 2 and 3. The scattering cross sections were computed with the Schwinger multichannel method [K. Takatsuka and V. McKoy, Phys. Rev. A 24 , 2473 (1981); Phys. Rev. A 30 , 1734 (1984)] with pseudopotentials [M. H. F. Bettega, L. G. Ferreira, and M. A. P. Lima, Phys. Rev. A 47, 1111 (1993)] in the static-exchange and static-exchange plus polarization approximations, for energies from 0.5 eV to 6 eV. We considered some diÆerent hydrogen-bonded structures for the complexes that were generated with classical Monte Carlo simulations [K. Coutinho and S. Canuto, J. Chem. Phys. 113, 9132, (2000)]. The aim of this work is to investigate the effect of the surrounding water molecules on the π* shape resonance of the solute. Previous theoretical and experimental studies carried out in the gas phase reported a π* state for HCOOH at around 1.9 eV. For the n = 1 case and for all complexes, the stabilization of the resonance was observed (it appears at lower energy compared to the value obtained in the gas phase), as reported previously for the CH2O…H2O complexes [T. C. Freitas, M. A. P. Lima, S. Canuto, and M. H. F. Bettega, Phys. Rev. A 80, 062710 (2009)]. This result indicates that the presence of the solvent may affect the processes related to the π* state, such as the molecular dissociation by electron impact. For the n = 2 case we have observed both stabilization and destabilization of the π* resonance, that is associated with the hydrogen bond donor or acceptor role of the water molecules in the complexes. For the n = 3 case, preliminary static-exchange results show the stabilization of the π* state. We propose an explanation of the stabilization/destabilization of the π* state in terms of the polarization of the solute due to the surrounding water molecules and the net charge in the solute.

A theoretical study of the characterization and the absorption spectrum of Mg: Tetracycline complexes in aqueous environment.

The complex formed by the tetracycline (TC) molecule with the Mg ion is able to prevent the replication of the genetic material in the bacterial ribosome, making an excellent antibiotic. In general, the absorption and emission spectra of TC are very sensitive to the host ions and the pH of the solvent that the set is immersed. However, the theoretical absorption spectrum available in the literature is scarce and limited to simple models that do not consider the fluctuations of the liquid. Our aim is to obtain the electronic absorption spectrum of TC and the complex Mg:TC in the ratio 1:1 and 2:1. Moreover, we analyze the changes in intensity and shifts of the bands in the systems listed. We performed the simulation using the classical Monte Carlo technique with the Lennard-Jones plus Coulomb potential applied to each atom of the both TC molecule and the Mg:TC complexes in water. The electronic absorption spectrum was obtained from the time-dependent density functional theory using different solvent models. In general, we obtained a good qualitative description of the spectra when compared with the experimental results. The Mg atom shifts the first band by 4 nm in our models, in excellent agreement to the experimental result of 4 nm. The second absorption band is found here to be useful for the characterization of the position where the ion attaches to the TC.

Dissociative electron attachment to chloromethane.

A low energy electron may attach to a molecule, forming a metastable resonance, which may dissociate into a stable anion and a neutral radical. Chloromethane has been a good target for dissociative electron attachment studies, since it is a small molecule with a clear dissociative ‘sigma*’ shape resonance. We present potential energy curves for CH3Cl and its anion, as a function of the C-Cl distance. Due to the resonant nature of the anion, a correct description requires a treatment based on scattering calculations. In order to compute elastic cross sections and phase shifts we employed the Schwinger multichannel method, implemented with pseudopotentials of Bachelet, Hamann and Schlüter, at the static-exchange plus polarization approximation. At the equilibrium geometry, the resonance was found arround 3.3 eV, in accordance to experience. The incoming electron is captured by a ‘sigma*’ orbital located at the C-Cl bond, which will relax in the presence of this extra electron. We took this bond as the reaction coordinate, and performed several scattering calculations for a series of nuclear conformations. The phase shift obtained in each calculation was fitted by a two component function, consisting in the usual Breit-Wigner profile, which captures the resonant character, and a second order polynomial in the wave number, which accounts for the background contribution. That way, we obtained position and width of the resonance, which allowed us to build the potential energy curve. For larger distances, the anion becomes stable and usual electronic structure calculations suffice. Furthermore, the existence of a dipole-bound anion state is revealed when we employed a set of very diffuse functions. The knowledge on the behaviour of the neutral and anionic electronic states helps us in elucidating how the dissociation takes place.

Low energy elastic and electronically inelastic electron scattering from biomolecules.

Reactions initiated by collisions with low-energy secondary electrons has been found to be the prominent mechanism toward the radiation damage on living tissues through DNA strand breaks. Now it is widely accepted that during the interaction with these secondary species the selective breaking of chemical bonds is triggered by dissociative electron attachment (DEA), that is, the capture of the incident electron and the formation of temporary negative ion states [1,2,3]. One of the approaches largely used toward a deeper understanding of the radiation damage to DNA is through modeling of DEA with its basic constituents (nucleotide bases, sugar and other subunits). We have tried to simplify this approach and attempt to make it comprehensible at a more fundamental level by looking at even simple molecules. Studies involving organic systems such as carboxylic acids, alcohols and simple ¯ve-membered heterocyclic compounds are taken as starting points for these understanding. In the present study we investigate the role played by elastic scattering and electronic excitation of molecules on electron-driven chemical processes. Special attention is focused on the analysis of the in°uence of polarization and multichannel coupling e®ects on the magnitude of elastic and electronically inelastic cross-sections. Our aim is also to investigate the existence of resonances in the elastic and electronically inelastic channels as well as to characterize them with respect to its type (shape, core-excited or Feshbach), symmetry and position. The relevance of these issues is evaluated within the context of possible applications for the modeling of discharge environments and implications in the understanding of mutagenic rupture of DNA chains. The scattering calculations were carried out with the Schwinger multichannel method (SMC) [4] and its implementation with pseudopotentials (SMCPP) [5] at di®erent levels of approximation for impact energies ranging from 0.5 eV to 30 eV. References [1] B. Boudai®a, P. Cloutier, D. Hunting, M. A. Huels and L. Sanche, Science 287, 1658 (2000). [2] X. Pan, P. Cloutier, D. Hunting and L. Sanche, Phys. Rev. Lett. 90, 208102 (2003). [3] F. Martin, P. D. Burrow, Z. Cai, P. Cloutier, D. Hunting and L. Sanche, Phys. Rev. Lett. 93, 068101 (2004). [4] K. Takatsuka and V. McKoy, Phys. Rev. A 24, 2437 (1981); ibid. Phys. Rev. A 30, 1734 (1984). [5] M. H. F. Bettega, L. G. Ferreira and M. A. P. Lima, Phys. Rev. A 47, 1111 (1993).

Determinação de elementos traços em diques mesozoicos da Serra do Mar por meio de ativação com nêutrons

A análise de elementos traço, tais como terras raras, TH, U, Ta, Hf, Ba, Rb e Ba, é uma ferramenta muito importante para estudos petrogenéticos. No intuito de estudar tais processos em diques do Enxame Serra do Mar (litoral de São Paulo e Rio de Janeiro), pertencente à Provincia Magmática do Paraná (PMP), uma das províncias de basaltos continentais mais expressivas do mundo, foram realizadas análises por ativação com nêutrons nestes diques. A técnica, empregada no Centro de Reator de pesquisa do Instituto de Pesquisas Energéticas e Nucleares, forneceu concentrações de elementos traço com os níveis de precisão de 10% e exatidão 9% os quais são adequadas para estudos petrogenéticos. Devido as baixas concentrações dos elementos analisados, a rotina experimental de preparação das amostras abrangeu processos bastantes cuidadosos para evitar contaminação. As amostras investigadas podem ser divididas em quatro grupos: rochas básicas (SiO2<55%) com Ti/Y<500; rochas intermediárias (55%63%). Diques de composição intermediária e ácida só ocorrem na Ilha de São Sebastião e na região costeira adjacente. As concentrações de elementos maiores e menores, bem como os padrões de abundância de terras raras e de outros elementos incompatíveis dessas rochas mais diferenciadas, apresentaram semelhanças significativas com os das vulcânicas Chapecó do tipo Ourinhos, sugerindo gênese similar, ou seja, incluindo também processos de contaminação crustal .

Radiactividad natural y Medio Ambiente en las Islas Canarias

XX Jornadas Blascabrerianas, organizadas por la Academia de Ciencias e Ingenierías de Lanzarote y el Departamento de Física de la Universidad de Las Palmas de Gran Canaria

Assessing the identity of the variety 'Pedro Giménez' grown in Argentina through the use of microsatellite markers

Pedro Giménez' is a white criolla variety cropped in Argentina, mainly in Mendoza and San Juan, being the most planted white variety destined for wine making in the country. Its origin remains unknown, as well as its relationship with Spanish variety 'Pedro Ximénez', mostly grown in Jerez, Spain. Previous works have probed that most of Criollas varieties existing in America at the moment, are the offspring of 'Muscat of Alexandria' x 'Criolla Chica'. The aim of the present work was to compare 'Pedro Giménez' with the Spanish variety 'Pedro Ximénez', and to establish its degree of relatedness to 'Muscat of Alexandria' and 'Criolla Chica'. Therefore we used a set of 18 nuclear SSR loci and 3 chloroplast SSR loci. 'Pedro Giménez' shared only 38% of the alleles under analysis with 'Pedro Ximénez', indicating that they are indeed two different varieties. In all 18 polymorphic nuclear SSR loci 'Pedro Giménez' shared 50% of its alleles with 'Muscat of Alexandria', while the other 50% of the alleles present in 'Pedro Giménez' were also present in 'Criolla Chica'. This data, along with those from the chloroplast SSR analysis, strongly suggest that 'Pedro Giménez' is the progeny of 'Muscat of Alexandria' x 'Criolla Chica', being the latest one the most likely female progenitor.

Trabajo de investigación sobre la Comisión Nacional de Energía Atómica

Fil: Izura Bustos, Teresita Alicia.

Aplicación de métodos bibliométricos a la evaluación de colecciones : el caso de la Biblioteca del Instituto Argentino de Radioastronomía

La evaluación es una herramienta de gestión que permite a las instituciones obtener información fiable para la toma de decisiones de distinta naturaleza. En la última década los procesos evaluativos se han venido desarrollando en diferentes organizaciones públicas y privadas. Las bibliotecas no han sido ajenas a estas cuestiones y han debido llevar adelante la evaluación de su gestión con el objetivo de justificar su utilidad en las instituciones de las que dependen. En nuestro país las bibliotecas de los institutos de investigación han sido históricamente relegadas considerándoselas meros reservorios bibliográficos, por tal motivo la evaluación de la gestión en este ámbito puede constituirse en un punto de partida para mejorar la visión que tienen los gestores de las instituciones mayores con respecto a sus bibliotecas. Llevar adelante un plan de evaluación de la colección puede constituirse en una herramienta de análisis y diagnóstico que facilite la elaboración de políticas y que mejore la calidad de los servicios que brindan las bibliotecas científicas. La determinación del grupo de publicaciones nucleares a considerar en el desarrollo de la colección de la Biblioteca del Instituto Argentino de Radioastronomía (IAR) es un elemento de relevancia en los procesos anteriormente mencionados. Para ello se realiza un estudio bibliométrico de la producción y el consumo de literatura científica de los investigadores de la institución a partir del análisis de referencias. Se determinan los índices de obsolescencia y la utilidad para la literatura consultada. Se determinan los frentes de investigación del instituto a partir del análisis de co-ocurrencia de palabras y el análisis de redes sociales.

Tres construcciones de realce y un patrón entonativo

El enfoque cognitivo-prototípico sostiene que la intención comunicativa motiva otros aspectos del lenguaje: la sintaxis, la fonética y la fonología. En el marco de esa hipótesis, el presente trabajo, propone una síntesis evaluativa y comparativa de resultados obtenidos previamente con el fin de sugerir figuras entonativas que parecen funcionar con suficiente sistematicidad como para considerarlas patrones fonológicos. Estos emergen, precisamente, de una motivación semántico pragmática común que también motiva la sintaxis: la intención del hablante de realzar un aspecto de su mensaje. Se analizan ejemplos del español rioplatense que contienen segmentos con construcciones con tal/tan....que, cláusulas relativas con un(a)(s)...que, y construcciones hendidas propiamente dichas con esquema es...el/la/los/las que. Se confeccionaron corpora con un total de 1.028 oraciones que fueron grabadas en forma especial por 12 hablantes, seis mujeres y seis varones, cuatro por cada corpus, sin problemas de habla y con un nivel de formación educativa media y terciaria. Se caracterizaron los siguientes ítems prosódicos: a) Tonos de frontera (juntura) (Inicio y fin de la frase entonativa); b) Tonos nucleares (acentos más característicos); c) Duración de pausas; d) Frecuencia fundamental y e) Picos de energía. De la transcripción tonal alineada temporalmente surgen contornos entonativos que pueden considerarse por su sistematicidad como patrones fonológicos de estas estructuras. Los contornos tonales muestran una frase entonativa delimitada por un acento de juntura inicial alto y un acento de juntura final M (medio). El tono subyacente L+H* marca contrastivamente los constituyentes de la oración portadora del elemento de realce y emerge en todas las frases entonativas detectadas, con repetición del mismo tipo de acento tonal, como indicador de la modulación que el hablante ejerce sobre su frecuencia fundamental. Se observa en los tres casos la presencia fuerte de picos de F0. El efecto de las pausas previas al que se observa en todos los casos

Intransitividad, transitividad y bitransitividad en los verbos del ranquel

En el siguiente trabajo se pretende señalar la estructura sintáctica de la frase ranquel. Específicamente, el número y las características de los argumentos admitidos por los verbos de esta lengua. Antes de emprender el estudio de la construcción argumental, se definirán necesariamente algunos conceptos preliminares, como los elementos nucleares que intervienen en la noción predicativa del verbo. Para llevar a cabo este trabajo, nos basaremos en material teórico que explique el tema a desarrollar. Asimismo, reuniremos un corpus de oraciones de la lengua ranquel que nos sirva de ejemplo para dar mayor claridad sobre el tema a presentar