Electronic structure of porphyrin-based metal– organic frameworks and their suitability for solar fuel production photocatalysis

Metal–organic frameworks (MOFs) can be exceptionally good catalytic materials thanks to the presence of active metal centres and a porous structure that is advantageous for molecular adsorption and confinement. We present here a first-principles investigation of the electronic structure of a family of MOFs based on porphyrins connected through phenyl-carboxyl ligands and AlOH species, in order to assess their suitability for the photocatalysis of fuel production reactions using sunlight. We consider structures with protonated porphyrins and those with the protons exchanged with late 3d metal cations (Fe2+, Co2+, Ni2+, Cu2+, Zn2+), a process that we find to be thermodynamically favorable from aqueous solution for all these metals. Our band structure calculations, based on an accurate screened hybrid functional, reveal that the bandgaps are in a favorable range (2.0 to 2.6 eV) for efficient adsorption of solar light. Furthermore, by approximating the vacuum level to the pore centre potential, we provide the alignment of the MOFs' band edges with the redox potentials for water splitting and carbon dioxide reduction, and show that the structures studied here have band edges positions suitable for these reactions at neutral pH.Royal Society for an International Exchange Scheme grantVia our membership of the UK's HPC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202), this work made use of the facilities of ARCHER, the UK's national high-performance computing services, which are funded by the Office of Science and Technology through EPSRC's High End Computing ProgrammeEuropean Research Council through an ERC Starting Grant (ERC2011-StG-279520-RASPA)MINECO (CTQ2013-48396-P)Andalucía Region (FQM-1851)University of Granad

Dimensional hyper-reduction of nonlinear finite element models via empirical cubature

We present a general framework for the dimensional reduction, in terms of number of degrees of freedom as well as number of integration points (“hyper-reduction”), of nonlinear parameterized finite element (FE) models. The reduction process is divided into two sequential stages. The first stage consists in a common Galerkin projection onto a reduced-order space, as well as in the condensation of boundary conditions and external forces. For the second stage (reduction in number of integration points), we present a novel cubature scheme that efficiently determines optimal points and associated positive weights so that the error in integrating reduced internal forces is minimized. The distinguishing features of the proposed method are: (1) The minimization problem is posed in terms of orthogonal basis vector (obtained via a partitioned Singular Value Decomposition) rather that in terms of snapshots of the integrand. (2) The volume of the domain is exactly integrated. (3) The selection algorithm need not solve in all iterations a nonnegative least-squares problem to force the positiveness of the weights. Furthermore, we show that the proposed method converges to the absolute minimum (zero integration error) when the number of selected points is equal to the number of internal force modes included in the objective function. We illustrate this model reduction methodology by two nonlinear, structural examples (quasi-static bending and resonant vibration of elastoplastic composite plates). In both examples, the number of integration points is reduced three order of magnitudes (with respect to FE analyses) without significantly sacrificing accurac

Does Money Help Elections? Analysis of the Impact of Campaign Spending and Incumbency in Ecuador

Restricting policies on electoral spending are intended to equalize the conditions of participation of candidates for a seat in a popular election. However, does the application of these restrictions generate equity in the electoral contest, or the opposite? There is much evidence about the advantage of the candidate who is reelected (incumbent) against his contender (challenger), which questions whether the budget restriction on electoral spending is effective in itself. For this research, we used a multiple linear regression method that measures the effects of the effectiveness of campaign spending in attracting votes from candidates for mayor of Ecuador, resulting in incumbency providing a degree of advantage over challengers. much more than the efficiency of spending, all in a highly restrictive scenario in electoral budgets and political campaign time

La corrupción y la moralidad pública y administrativa en Colombia

This paper addresses the necessity to include public and administrative morality in the legal regulation of the activity of public servants in order to establish legitimate social expectations and prevent acts of corruption. This research is qualitative in nature and its scope is exploratory: a documentary analysis is carried out that privileges official data while making use of the static analysis of the case law of the higher courts. To achieve our purpose, a presentation is made of the scope of corruption in Colombia; then, the concepts of public and administrative morality are analyzed as a legitimate normative expectation and, finally, it is shown that, due to the sanctioning and punitive approach of the anti- corruption regulations, the contribution of public and administrative morality in the prevention of corruption has been ignored.El presente trabajo analiza la necesidad de incluir la moralidad pública y administrativa en la regulación jurídica de la actividad de los servidores públicos con el fin de establecer expectativas sociales legitimas y prevenir actos de corrupción. Esta investigación es de carácter cualitativo y su alcance es exploratorio, se realiza un análisis documental que privilegia datos oficiales al tiempo que hace uso del análisis estático de la jurisprudencia de las altas cortes. Para lograr el objetivo se realiza una presentación del alcance de la corrupción en Colombia, posteriormente se analizan los conceptos de moralidad pública y administrativa como una expectativa normativa legítima y por último se muestra que debido al enfoque sancionatorio y punitivo de la normatividad anticorrupción se ha soslayado el aporte de la moralidad pública y administrativa en la prevención de la corrupción

Una propuesta de reconversión territorial en la microcuenca del Río Moro, comuna de Puyehue, Décima Región, Chile

The Moro River basin, Comuna de Puyehue, Osorno, is analyzed. Currently, cattle use grasslands replace the native forests. Deforestation has produced imbalances in the hydrological cycle eventually affecting the city of Osorno in the form of pollution and reduced flow rates. The main goal of this work is to convert the territory of the watershed, by increasing forest area, in a setting conducive to development through the identification of technically suitable forest and socially acceptable alternatives. Economic attractions for owners of land, by changing land use on the river bank are shown. Is planed reforest river edges Moro River system considering the incentives offered by the market and forest legislation, according to Decree Law No. 701 of 1974. As methodology applies the technique of costbenefit analysis of deforestation alternatives, with information up on an inquiry of residents about their background demographic, legal, technical, commercial, economic, environmental expectations and their acceptance to the project. The results show that in general there is willingness to accept the project. Consequently, it is proposed reforestation with native species suited to the climate and soil, especially from family Mirtaceae, and melliferous species, which can develop various production systems such as agroforestry and exploitation of beehives, and with the exotic Castanea sativa, wood, lumber or firewood, and his marketable fruit . This would produce positive externalities, such as economic benefits (increased income into the household) and social improvements (better quality of life and status) to the resident population, adding also environmental benefits such as regulation of the hydrological balance of the watershed, increasing forest area as natural habitat and biodiversity benefits involved.    Se analiza la rnicrocuenca del Río Moro, Comuna de Puyehue, Osomo. Actualmente, praderas de uso ganadero reemplazan al bosque nativo, deforestación que ha producido desequilibrios en el ciclo hidrológico afectando finalmente a la ciudad de Osorno en forma de contaminación y disminución de los caudales. Se trata de reconvertir el territorio de la Microcuenca mediante el aumento de la superficie forestal, en un escenario propicio para el desarrollo, a través de la determinación de alternativas forestales técnicamente adecuadas y socialmente aceptables. Se demuestran atractivos económicos para los propietarios de los terrenos, por la modificación del uso del suelo sobre la ribera del río. Se plantea reforestar los bordes fluviales del sistema río Moro considerando los incentivos que ofrecen el mercado y la legislación forestal, según el Decreto Ley N° 701 de 1974. Como metodología se aplica la técnica de análisis costo-beneficio a distintas alternativas de forestación, con información levantada en una encuesta a los habitantes sobre sus antecedentes demográficos, legales, técnicos, comerciales, económicos, expectativas ambientales y su aceptación al proyecto. Los resultados muestran que en general existe disposición a aceptar el proyecto. En consecuencia, se propone reforestar con especies nativas adaptadas al clima y suelo, especialmente de la familia Mirtaceae y especies melíferas, que permitan desarrollar diversos sistemas productivos, tales como agroforestería y explotación de apiarios, y con especies exóticas maderables, comerciables como metro ruma, madera aserrable o leña, como Castanea sativa, de fruto comerciable. Ello produciría extemalidades positivas, tales como beneficios económicos (mayores ingresos al grupo familiar) y mejorías sociales (mejoría de la calidad de vida y del status) a la población habitante, agregando también beneficios ambientales tales como la regulación del equilibrio hidrológico de la microcuenca, el aumento del área forestada como hábitat natural y los beneficios a la biodiversidad implícitos.  

Two-scale topology optimization in computational material design: an integrated approach

The Domain Interface Method (DIM) is extended in this contribution for the case of mixed fields as encountered in multiphysics problems. The essence of the non-conforming domain decomposition technique consists in a discretization of a fictitious zero-thickness interface as in the original methodology and continuity of the solution fields across the domains is satisfied by incorporating the corresponding Lagrange Multipliers. The multifield DIM inherits the advantages of its irreducible version in the sense that the connections between non-matching meshes, with possible geometrically non-conforming interfaces, is accounted by the automatic Delaunay interface discretization without considering master and slave surfaces or intermediate surface projections as done in many established techniques, e.g. mortar methods. The multifield enhancement identifies the Lagrange multiplier field and incorporates its contribution in the weak variational form accounting for the corresponding consistent stabilization term based on a Nitsche method. This type of constraint enforcement circumvents the appearance of instabilities when the Ladyzhenskaya–Babuška–Brezzi (LBB) condition is not fulfilled by the chosen discretization. The domain decomposition framework is assessed in a large deformation setting for mixed displacement/pressure formulations and coupled thermomechanical problems. The continuity of the mixed field is studied in well selected benchmark problems for both mixed formulations and the objectivity of the response is compared to reference monolithic solutions. Results suggest that the presented strategy shows sufficient potential to be a valuable tool in situations where the evolving physics at particular domains require the use of different spatial discretizations or field interpolations

La información como instrumento de erradicación del delito fiscal

[ES]En el Capítulo Primero, se comienza por expresar que esta investigación tiene como fin primordial, demostrar que la información como instituto de las ciencias sociales, al ser cubierta por el ordenamiento jurídico, se inviste de poderes especiales para en el caso de la actividad impositiva, permitirse difundir hechos de trascendencia tributaria, convirtiéndose de esta manera en un instrumento de erradicación del delito fiscal