Double Hybrid Functionals and the Π-System Bond Length Alternation Challenge: Rivaling Accuracy of Post-HF Methods

Predicting accurate bond length alternations (BLAs) in long conjugated oligomers has been a significant challenge for electronic-structure methods for many decades, made particularly important by the close relationships between BLA and the rich optoelectronic properties of π-delocalized systems. Here, we test the accuracy of recently developed, and increasingly popular, double hybrid (DH) functionals, positioned at the top of Jacobs Ladder of DFT methods of increasing sophistication, computational cost, and accuracy, due to incorporation of MP2 correlation energy. Our test systems comprise oligomeric series of polyacetylene, polymethineimine, and polysilaacetylene up to six units long. MP2 calculations reveal a pronounced shift in BLAs between the 6-31G(d) basis set used in many studies of BLA to date and the larger cc-pVTZ basis set, but only modest shifts between cc-pVTZ and aug-cc-pVQZ results. We hence perform new reference CCSD(T)/cc-pVTZ calculations for all three series of oligomers against which we assess the performance of several families of DH functionals based on BLYP, PBE, and TPSS, along with lower-rung relatives including global- and range-separated hybrids. Our results show that DH functionals systematically improve the accuracy of BLAs relative to single hybrid functionals. xDH-PBE0 (N4 scaling using SOS-MP2) emerges as a DH functional rivaling the BLA accuracy of SCS-MP2 (N5 scaling), which was found to offer the best compromise between computational cost and accuracy the last time the BLA accuracy of DFT- and wave function-based methods was systematically investigated. Interestingly, xDH-PBE0 (XYG3), which differs to other DHs in that its MP2 term uses PBE0 (B3LYP) orbitals that are not self-consistent with the DH functional, is an outlier of trends of decreasing average BLA errors with increasing fractions of MP2 correlation and HF exchange.

Systematic Improvement of Density Functionals through Parameter-Free Hybridization Schemes

It is suggested here that the ultimate accuracy of DFT methods arises from the type of hybridization scheme followed. This idea can be cast into a mathematical formulation utilizing an integrand connecting the noninteracting and the interacting particle system. We consider two previously developed models for it, dubbed as HYB0 and QIDH, and assess a large number of exchange-correlation functionals against the AE6, G2/148, and S22 reference data sets. An interesting consequence of these hybridization schemes is that the error bars, including the standard deviation, are found to markedly decrease with respect to the density-based (nonhybrid) case. This improvement is substantially better than variations due to the underlying density functional used. We thus finally hypothesize about the universal character of the HYB0 and QIDH models.

Utilisation of maternal health services in Ethiopia: a key informant research project

This article explores the application of key informant research to examine barriers and facilitators to maternal health services in rural and pastoralist Ethiopia. The key informants were health extension workers (HEWs) who assist women with birth preparedness and facilitate timely referral to health centres for birth. While women encounter many barriers to giving birth in health facilities, where HEWs are supported by their communities and health centre staff, they can effectively encourage women to travel to health centres to give birth with skilled birth attendants rather than at home with unskilled relatives or traditional birth attendants.

New Haitian social movements: Alternative modernities, (trans)local nationalisms, and solidarity economies

My dissertation is the first project on the Haitian Platform for Advocacy for an Alternative Development- PAPDA, a nation-building coalition founded by activists from varying sectors to coordinate one comprehensive nationalist movement against what they are calling an Occupation. My work not only provides information on this under-theorized popular movement but also situates it within the broader literature on the postcolonial nation-state as well as Latin American and Caribbean social movements. The dissertation analyzes the contentious relationship between local and global discourses and practices of citizenship. Furthermore, the research draws on transnational feminist theory to underline the scattered hegemonies that intersect to produce varied spaces and practices of sovereignty within the Haitian postcolonial nation-state. The dissertation highlights how race and class, gender and sexuality, education and language, and religion have been imagined and co-constituted by Haitian social movements in constructing ‘new’ collective identities that collapse the private and the public, the rural and the urban, the traditional and the modern. My project complements the scholarship on social movements and the postcolonial nation-state and pushes it forward by emphasizing its spatial dimensions. Moreover, the dissertation de-centers the state to underline the movement of capital, goods, resources, and populations that shape the postcolonial experience. I re-define the postcolonial nation-state as a network of local, regional, international, and transnational arrangements between different political agents, including social movement actors. To conduct this interdisciplinary research project, I employed ethnographic methods, discourse and textual analysis, as well as basic mapping and statistical descriptions in order to present a historically-rooted interpretation of individual and organizational negotiations for community-based autonomy and regional development. ^

Potential Mechanisms Underlying Response to Effects of the Fungicide Pyrimethanil from Gene Expression Profiling inSaccharomyces cerevisiae

Pyrimethanil is a fungicide mostly applied in vineyards. When misused, residue levels detected in grape must or in the environment may be of concern. The present work aimed to analyze mechanisms underlying response to deleterious effects of pyrimethanil in the eukaryotic model Saccharomyces cerevisiae. Pyrimethanil concentration-dependent effects at phenotypic (inhibition of growth) and transcriptomic levels were examined. For transcriptional profiling, analysis focused on two sublethal exposure conditions that inhibited yeast growth by 20% or 50% compared with control cells not exposed to the fungicide. Gene expression modifications increased with the magnitude of growth inhibition, in numbers and fold-change of differentially expressed genes and in diversity of over-represented functional categories. These included mostly biosynthesis of arginine and sulfur amino acids metabolism, as well as energy conservation, antioxidant response, and multidrug transport. Several pyrimethanil-responsive genes encoded proteins sharing significant homology with proteins from phytopathogenic fungi and ecologically relevant higher eukaryotes.

New invertebrate vectors of Okadaic acid from the North Atlantic Waters - Portugal (Azores and Madeira) and Morocco

Okadaic acid and its analogues are potent phosphatase inhibitors that cause Diarrheic Shellfish Poisoning (DSP) through the ingestion of contaminated shellfish by humans. This group of toxins is transmitted worldwide but the number of poisoning incidents has declined over the last 20 years due to legislation and monitoring programs that were implemented for bivalves. In the summer of 2012 and 2013, we collected a total of 101 samples of 22 different species that were made up of benthic and subtidal organisms such echinoderms, crustaceans, bivalves and gastropods from Madeira, São Miguel Island (Azores archipelago) and the northwestern coast of Morocco. The samples were analyzed by UPLC-MS/MS. Our main objective was to detect new vectors for these biotoxins. We can report nine new vectors for these toxins in the North Atlantic: Astropecten aranciacus, Arbacia lixula, Echinaster sepositus, Holothuria sanctori, Ophidiaster ophidianus, Onchidella celtica, Aplysia depilans, Patella spp., and Stramonita haemostoma. Differences in toxin contents among the species were found. Even though low concentrations were detected, the levels of toxins that were present, especially in edible species, indicate the importance of these types of studies. Routine monitoring should be extended to comprise a wider number of vectors other than for bivalves of okadaic acid and its analogues.

Creativity, Clusters and the Competitive Advantage of Cities

Purpose – This paper aims to marry Michael Porter’s industrial cluster theory of traded and local clusters to Richard Florida’s occupational approach of creative and routine workers to gain a better understanding of the process of economic development. Design/methodology/approach – Combining these two approaches, four major industrial-occupational categories are identified. The shares of US employment in each – creative-in-traded, creative-in-local, routine-in-traded and routine-in-local – are calculated, and a correlation analysis is used to examine the relationship of each to regional economic development indicators. Findings – Economic growth and development is positively related to employment in the creative-in-traded category. While metros with a higher share of creative-in-traded employment enjoy higher wages and incomes overall, these benefits are not experienced by all worker categories. The share of creative-in-traded employment is also positively and significantly associated with higher inequality. After accounting for higher median housing costs, routine workers in both traded and local industries are found to be relatively worse off in metros with high shares of creative-in-traded employment, on average. Social implications – This work points to the imperative for the US Government and industry to upgrade routine jobs, which make up the majority of all employment, by increasing the creative content of this work. Originality/value – The research is among the first to systematically marry the industry and occupational approaches to clusters and economic development.

A stakeholder perspective on heritage branding and digital communication

How does an archaeological museum understand its function in a digital environment? Consumer expectations are rapidly shifting, from what used to be a passive relationship with exhibition contents, towards a different one, in which interaction, individuality and proactivity define the visitor experience. This consumer paradigm is much studied in fast moving markets, where it provokes immediately measurable impacts. In other fields, such as tourism and regional development, the very heterogeneous nature of the product to be branded makes it near to impossible for only one player to engage successfully. This systemic feature implies that museums, acting as major stakeholders, often anchor a regional brand around which SME tend to cluster, and thus assume responsibilities in constructing marketable identities. As such, the archaeological element becomes a very useful trademark. On the other hand, it also emerges erratically on the Internet, in personal blogs, commercial websites, and social networks. This forces museums to enter as a mediator, authenticating contents and providing credibility. What might be called the digital pull factor poses specific challenges to museum management: what is to be promoted, and how, in order to create and maintain a coherent presence in social media? The underlying issue this paper tries to address is how museums perceive their current and future role in digital communication.

Using multivariate sequential patterns to improve survival prediction in intensive care burn unit

Resuscitation and stabilization are key issues in Intensive Care Burn Units and early survival predictions help to decide the best clinical action during these phases. Current survival scores of burns focus on clinical variables such as age or the body surface area. However, the evolution of other parameters (e.g. diuresis or fluid balance) during the first days is also valuable knowledge. In this work we suggest a methodology and we propose a Temporal Data Mining algorithm to estimate the survival condition from the patient’s evolution. Experiments conducted on 480 patients show the improvement of survival prediction.

Nordic policy lessons for Australia

This report considers public debate on Scandinavian and Finnish policy ideas of possible relevance to Australia since the publication in November 2014 by an Australian university press of Andrew Scott’s book Northern Lights: The Positive Policy Example of Sweden, Finland, Denmark and Norway. Two years on from the book’s publication, the report considers the varying reception in Australia of propositions advanced in Northern Lights for: expansion of public early childhood education and care and extension of paid parental leave, as well as properly enshrining children’s rights and other actions to reduce child poverty and improve children’s wellbeing (learning from Sweden); more equitable schools funding, better valuing of a quality teaching profession and more effective provision of vocational education in schools (learning from Finland); enhancement of support and skills retraining for mature-age workers displaced by job losses (learning from Denmark); and increasing revenue including through greater taxation and regulation of natural resource wealth (learning from Norway). The report then considers the main priority areas of Nordic achievement nominated by policy actors for additional consideration for Australia to now learn from. These are: better, healthier and more natural urban design, together with more balanced regional development; better workplace design – specifically the importance of taking into account aesthetics, ergonomics and nature in people’s workplace environments; and greater emphasis on both the prevention of crime and the rehabilitation of persons convicted of crimes. Sweden and Norway’s continuing leadership in the provision of quality foreign aid and other foreign policy initiatives such as Sweden's current “feminist foreign policy” are also discussed. Objections raised to the book’s premises, including to the possibility of policy transfer to Australia from nations presumed to be less multicultural, are evaluated.

New invertebrate vectors of Okadaic acid from the North Atlantic Waters - Portugal (Azores and Madeira) and Morocco

Okadaic acid and its analogues are potent phosphatase inhibitors that cause Diarrheic Shellfish Poisoning (DSP) through the ingestion of contaminated shellfish by humans. This group of toxins is transmitted worldwide but the number of poisoning incidents has declined over the last 20 years due to legislation and monitoring programs that were implemented for bivalves. In the summer of 2012 and 2013, we collected a total of 101 samples of 22 different species that were made up of benthic and subtidal organisms such echinoderms, crustaceans, bivalves and gastropods from Madeira, São Miguel Island (Azores archipelago) and the northwestern coast of Morocco. The samples were analyzed by UPLC-MS/MS. Our main objective was to detect new vectors for these biotoxins. We can report nine new vectors for these toxins in the North Atlantic: Astropecten aranciacus, Arbacia lixula, Echinaster sepositus, Holothuria sanctori, Ophidiaster ophidianus, Onchidella celtica, Aplysia depilans, Patella spp., and Stramonita haemostoma. Differences in toxin contents among the species were found. Even though low concentrations were detected, the levels of toxins that were present, especially in edible species, indicate the importance of these types of studies. Routine monitoring should be extended to comprise a wider number of vectors other than for bivalves of okadaic acid and its analogues.

Entrepreneurship: a long way to go

Entrepreneurship education has emerged as one popular research domain in academic fields given its aim at enhancing and developing certain entrepreneurial qualities of undergraduates that change their state of behavior, even their entrepreneurial inclination and finally may result in the formation of new businesses as well as new job opportunities. This study attempts to investigate the Colombian student´s entrepreneurial qualities and the influence of entrepreneurial education during their studies.

Análisis de la estrategia de política exterior del Desarrollo Pacífico china en la construcción de su identidad dentro del grupo BRICS (2003-2014)

El interés de esta monografía es interpretar la manera en la que un Estado tiene la capacidad para transformar su identidad y proyectarla satisfactoriamente hacia otros actores. En el caso de China, esto sucede gracias a su estrategia de política exterior conocida como Desarrollo Pacífico, la cual forma parte de su relación con los miembros del grupo BRICS y ha ayudado a consolidar una tendencia hacia la cooperación. Para poder realizar una buena interpretación de la construcción de identidad china dentro del foro internacional BRICS es primordial realizar un acercamiento teórico constructivista que permite un entendimiento del proceso histórico que le ha permitido a China configurar su identidad en el marco de los BRICS, a partir de un proceso constante de interacción e identificación.

Inteligencia territorial para la recuperación de las dinámicas socio-productivas en la subregión de Lengupá (Boyacá, Colombia)

Este documento corresponde al ejercicio preliminar de la línea de investigación en dinámicas territoriales, y es uno de los artículos científicos propuestos como resultado del Proyecto de investigación “Inteligencia territorial para la recuperación de las dinámicas socio-productivas de la subregión de Lengupá”. Por lo tanto, presenta los resultados de la fase exploratoria, correspondiente al diagnóstico regional en el marco de los enfoques teóricos desde los cuales la región es estudiada. A continuación, se presentarán los dos pilares fundamentales de ésta investigación: el territorio y la Inteligencia Territorial. En el caso del territorio, este proceso de investigación parte de un diferenciación previa respecto al lugar y al espacio, debido a que en el territorio se dan relaciones históricas y de poder en una relación dialéctica, entre los atributos ecológicos y culturales, teniendo en cuenta el planteamiento de Sasquet, (2015) cuando menciona que para comprender el territorio es necesario comprender el espacio geográfico, territorialidad humana, en escala subregional y a través del tiempo.

Modelling and studies of the spectral response of some optoelectronic components

Solar radiation takes in today's world, an increasing importance. Different devices are used to carry out spectral and integrated measurements of solar radiation. Thus the sensors can be divided into the fallow types: Calorimetric, Thermomechanical, Thermoelectric and Photoelectric. The first three categories are based on components converting the radiation to temperature (or heat) and then into electrical quantity. On the other hand, the photoelectric sensors are based on semiconductor or optoelectronic elements that when irradiated change their impedance or generate a measurable electric signal. The response function of the sensor element depends not only on the intensity of the radiation but also on its wavelengths. The radiation sensors most widely used fit in the first categories, but thanks to the reduction in manufacturing costs and to the increased integration of electronic systems, the use of the photoelectric-type sensors became more interesting. In this work we present a study of the behavior of different optoelectronic sensor elements. It is intended to verify the static response of the elements to the incident radiation. We study the optoelectronic elements using mathematical models that best fit their response as a function of wavelength. As an input to the model, the solar radiation values are generated with a radiative transfer model. We present a modeling of the spectral response sensors of other types in order to compare the behavior of optoelectronic elements with other sensors currently in use.