Técnicas de análise do perfil de execução e otimização de programas em química computacional

In this paper we review the basic techniques of performance analysis within the UNIX environment that are relevant in computational chemistry, with particular emphasis on the execution profile using the gprof tool. Two case studies (in ab initio and molecular dynamics calculations) are presented in order to illustrate how execution profiling can be used to effectively identify bottlenecks and to guide source code optimization. Using these profiling and optimization techniques it was possible to obtain significant speedups (of up to 30%) in both cases.

Estudi i simulació aerodinàmica amb programari de dinàmica de fluids computacional (CFD) en un model bàsic de vehicle de competició de la categoria CM (curses de muntanya)

Aquest projecte té com a objectiu la simulació numérica de la carrosseria d’ un vehicle de curses de muntanya de categoria CM

Qual o sítio de reação? Um experimento computacional

A computational quantum chemistry experiment is described on the determination of the most reactive atom in a molecule for a reaction. The reaction studied was the S N2 of 4-(dimethylamino)pyridine and methyl iodide. Several indexes (HOMO coefficent, (c), charges, (q), nucleophilic softness, (s+), and Fukui index, (f+)) were employed to verify which correctly describe what nitrogen will react. The calculations were made by AM1 and HF/STO-3G methods. The correct reactivity order is only reproduced by s+ and f+. The lack of agreement of FMO based indexes was discussed.

Avaliação de contaminação ambiental causada por poluentes orgânicos persistentes utilizando simulação computacional

Environmental concern is growing in the current days and there is global agreement to banish production and use of persistent organic pollutants (POP). The synthetic insecticides chlordecone and mirex, classified as POPs, have similar structures and they are potentially toxic. This work uses properties and physicochemical constants related to the pesticides and computational simulation to evaluate the leach phenomenon and persistency in soil. The largest tendency of persistence of the compound is found to be in the surface of soil, but even low concentration in water represents a high risk due to bioaccumulation in adipose tissue.

Reatividade em reações de Diels-Alder: uma prática computacional

A computational quantum chemistry experiment is described of Diels-Alder reactions between 2-cycloenones and cyclopentadiene. The effects of FMO-Frontier Molecular Orbitals (HOMO-LUMO) and of the withdrawing nature of substituents at the C=C bond of cycloenones were evaluated. The calculations were made using HF/STO-3G and B3LYP/6-31+G(d,p) methods. The FMO based indexes are in agreement with the experimentally observed reactivity order. NBO - Natural Bond Orbitals - analysis was used to ascertain the effect of C=C substituents on the dienophile reactivity.

Anàlisi d'imatges estereoscòpiques utilitzant mètodes de baixa càrrega computacional

Mitjançant imatges estereoscòpiques es poden detectar la posició respecte de la càmera dels objectes que apareixen en una escena. A partir de les diferències entre les imatges captades pels dos objectius es pot determinar la profunditat dels objectes. Existeixen diversitat de tècniques de visió artificial que permeten calcular la localització dels objectes, habitualment amb l’objectiu de reconstruir l’escena en 3D. Aquestes tècniques necessiten una gran càrrega computacional, ja que utilitzen mètodes de comparació bidimensionals, i per tant, no es poden utilitzar per aplicacions en temps real. En aquest treball proposem un nou mètode d’anàlisi de les imatges estereoscòpiques que ens permeti obtenir la profunditat dels objectes d’una escena amb uns resultats acceptables. Aquest nou mètode es basa en transformar la informació bidimensional de la imatge en una informació unidimensional per tal de poder fer la comparació de les imatges amb un baix cost computacional, i dels resultats de la comparació extreure’n la profunditat dels objectes dins l’escena. Això ha de permetre, per exemple, que aquest mètode es pugui implementar en un dispositiu autònom i li permeti realitzar operacions de guiatge a través d’espais interiors i exteriors.

Uma perspectiva computacional sobre catálise enzimática

Enzymes are extremely efficient catalysts. Here, part of the mechanisms proposed to explain this catalytic power will be compared to quantitative experimental results and computer simulations. Influence of the enzymatic environment over species along the reaction coordinate will be analysed. Concepts of transition state stabilisation and reactant destabilisation will be confronted. Divided site model and near-attack conformation hypotheses will also be discussed. Molecular interactions such as covalent catalysis, general acid-base catalysis, electrostatics, entropic effects, steric hindrance, quantum and dynamical effects will also be analysed as sources of catalysis. Reaction mechanisms, in particular that catalysed by protein tyrosine phosphatases, illustrate the concepts.

Aplicação da química quântica computacional no estudo de processos químicos envolvidos em espectrometria de massas

The field of application of mass spectrometry (MS) has increased considerably due to the development of ionization techniques. Other factors that have stimulated the use of MS are the tandem mass spectrometry (MS/MS) and sequential mass spectrometry (MSn) techniques. However, the interpretation of the MS/MS and MSn data may lead to speculative conclusions. Thus, various quantum chemical methods have been applied for obtaining high quality thermochemical data in gas phase. In this review, we show some applications of computational quantum chemistry to understand the formation and fragmentation of gaseous ions of organic compounds in a MS analysis.

Avaliação do destino e bioacumulação de benzo(a)pireno através de simulação computacional

The objective of this work was to evaluate the environmental distribution of benzo(a)pirene, a polycyclic aromatic hydrocarbon, by the EQC model. The modeling of the contaminant distribution was accomplished by means of the fugacity model applied to a hypothetical scenario constituted by air, water, soil and sediment. The modeling and simulations revealed that the soil is the preferential compartment. We also discuss the implications of the results about fate and ecological risks associated with benzo(a)pirene. We concluded that the emissions of HPAs can not be ignored and bioaccumulation among others risks can be induced.

O ensino de reações orgânicas usando química computacional: I. reações de adição eletrofílica a alquenos

Basic concepts that play an important role in some organic reactions are revisited in this paper, which reports a pedagogical experience involving undergraduate and graduate students. A systematic procedure has been applied in order to use widespread available computational tools. This paper aims to discuss the use of computers in teaching electrophilic addition reactions to alkenes. Two classical examples have been investigated: addition to non-conjugated alkenes and addition to conjugated dienes. The results were compared with those normally discussed in organic textbooks. Several important concepts, such as conformational analysis and energy control (kinetic and thermodynamic) involved in reaction mechanisms can be taught more efficiently if one connects theoretical and practical tools.

La convergència lingüística: possible retardador del procés de gramaticalització?

En diferents zones d"Hispanoamèrica, la substitució del futur sintètic en -rá (cantaré, lloverá) per la construcció Ir a + Infinitiu (voy a cantar, va a llover) resulta cada vegada més evident (Bauhr, 1989; Troya, 1998; Almeida y Díaz, 1998; Blas Arroyo, 2005; Sedano, 2006). Si bé en les zones peninsulars monolingües aquesta substitució també es percep, sembla que en les zones bilingües on el castellà està en contacte amb el català la tendència és justament la contrària. En aquest article es pretén verificar aquesta tendència tot partint de la hipòtesi que la construcció Ir a + Infinitiu per expressar valors temporals prospectius es fa servir en menor grau, sobretot en els parlants amb el català como a L1. La justificació cal trobar-la en la influència del català sobre el castellà; concretament, en el paradigma verbal particular del català confusió amb el pretèrit perfet perifràstic (vaig cantar) i esforç articulatori i en el fet que Anar a + Infinitiu no ha gramaticalitzat els mateixos valors que el castellà a Ir a + Infinitiu manté els valors etimològics. Per comprovar-ho, ens valdrem del corpus RESOL; un corpus de dades orals constituït per 94 entrevistes semidirigides realitzades a nens de 6º de primària, i novament quan cursaven 1º de la ESO, a escoles de Mataró i de Manlleu. Un cop analitzat el corpus, les dades revelen que, efectivament, en les zones bilingües, els informants amb el català com a L1 tendeixen a utilitzar la forma sintètica en major grau que la forma analítica. En canvi, els parlants que tenen el castellà com a L1 fan servir majoritàriament la perífrasi Ir a + Infinitiu, tot i que aquest ús no es tan profús como en la resta de zones monolingües peninsulars. En definitiva, el fet de tenir el català como a L1 sembla ser un dels factor que condiciona o determina la proliferació de la construcció Ir a + Infinitiu en el castellà parlat a Catalunya, però, alhora, la convergència de diferents factors lingüístics és el que condiciona l"ús particular d"aquesta perífrasi verbal en la zona analitzada.

La expresión de futuro en el español de Cataluña. Un posible caso de confluencia lingüística

La incursión de nuevas disciplinas en la lingüística, tales como la sociología, el cognitivismo, la antropología, etc., han permitido encontrar diversos puntos de unión entre las investigaciones realizadas desde cada una de estas disciplinas. Ello resulta de gran interés para los estudios de variación y contacto de lenguas en los que, aparte de los factores lingüísticos tradicionales, intervienen significativamente otros de índole cognitiva, sociocultural y pragmático-discursiva.Partiendo de este marco teórico plural, y desde la perspectiva del contacto de lenguas, en las siguientes páginas se analizan las expresiones prospectivas del español. Concretamente, se pretende aseverar la hipótesis de la influencia del catalán sobre el español en la expresión formal del futuro,1 pues parece que en las zonas catalanohablantes la frecuencia de uso del futuro sintético (FS) y del futuro analítico (FA) para hablar de eventos venideros es opuesta al empleo que de estas mismas formas suele hacerse en el resto de zonas hispanohablantes.2 La idea parte del hecho de que, pese a que en catalán también alternan las dos estructuras —el FS y la perífrasis prospectiva «ANAR A+Infinitivo»—, el menor rendimiento de la perífrasis en catalán y, por tanto, su menor grado de gramaticalización, parece incidir en la frecuencia de uso de la perífrasis en español «IR A+Infinitivo».

Repensando la formación inicial del profesorado para abordar el tratamiento a la diversidad cultural y lingüística en el aula = Rethinking initial teacher education for linguistic and cvltural diversity in the classroom

In recent decades, European educational systems are facing many challenges related to the treatment of cultural and linguistic diversity. The need to address this diversity requires new approaches to education; this in turn requires changes in the way we prepare teachers for the new reality they face in their classrooms. In this article we highlight some of the major problems that initial teacher training has to address in order to enable teachers to deal effectively, respectfully, and fairly with students whose linguistic and cultural background is different from their own. We also present several models for teacher education from Europe and North America based on clearly identified teacher competences for linguistic and cultural diversity

Implementação computacional do modelo carga-fluxo de carga-fluxo de dipolo para cálculo e interpretação das intensidades do espectro infravermelho

The first computational implementation that automates the procedures involved in the calculation of infrared intensities using the charge-charge flux-dipole flux model is presented. The atomic charges and dipoles from the Quantum Theory of Atoms in Molecules (QTAIM) model was programmed for Morphy98, Gaussian98 and Gaussian03 programs outputs, but for the ChelpG parameters only the Gaussian programs are supported. Results of illustrative but new calculations for the water, ammonia and methane molecules at the MP2/6-311++G(3d,3p) theoretical level, using the ChelpG and QTAIM/Morphy charges and dipoles are presented. These results showed excellent agreement with analytical results obtained directly at the MP2/6-311++G(3d,3p) level of theory.

Modelagem da combustão da dinitramida de amônio por simulação computacional

In this work, the combustion process of ammonium dinitramide, ADN, has been modeled in two different situations: decomposition in open environment, with abundant air and decomposition in a rocket motor internal environmental conditions. The profiles of the two processes were achieved, based on molar fractions of the species that compose the products of ADN combustion. The velocity of formation and quantity of species in the open environment was bigger than the ones in the rocket motor environment, showing the effect of the different atmosphere in the reactions kinetics.