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.

Accurate Treatment of Large Supramolecular Complexes by Double-Hybrid Density Functionals Coupled with Nonlocal van der Waals Corrections

In this work, we present a thorough assessment of the performance of some representative double-hybrid density functionals (revPBE0-DH-NL and B2PLYP-NL) as well as their parent hybrid and GGA counterparts, in combination with the most modern version of the nonlocal (NL) van der Waals correction to describe very large weakly interacting molecular systems dominated by noncovalent interactions. Prior to the assessment, an accurate and homogeneous set of reference interaction energies was computed for the supramolecular complexes constituting the L7 and S12L data sets by using the novel, precise, and efficient DLPNO-CCSD(T) method at the complete basis set limit (CBS). The correction of the basis set superposition error and the inclusion of the deformation energies (for the S12L set) have been crucial for obtaining precise DLPNO-CCSD(T)/CBS interaction energies. Among the density functionals evaluated, the double-hybrid revPBE0-DH-NL and B2PLYP-NL with the three-body dispersion correction provide remarkably accurate association energies very close to the chemical accuracy. Overall, the NL van der Waals approach combined with proper density functionals can be seen as an accurate and affordable computational tool for the modeling of large weakly bonded supramolecular systems.

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.

Golf course irrigation and self-sufficiency water in Southern Spain

During the first decade of the 21st century, many golf courses were developed in the Southeast of Spain, which greatly increased the number of these facilities. Almost all of these golf courses have been accompanied by large residential developments composed of thousands of dwelling units. This article seeks to identify the factors that influence golf courses’ water consumption and estimate the number of dwelling units that an associated residential development needs to have to provide the effluent necessary to fully meet the irrigation needs of a golf course. The study indicates that private golf courses achieve greater levels of irrigation efficiency than public golf courses and that the golf courses associated with residential developments subject the irrigation needs of the grassland to the sale requirements of the real estate properties. The study also estimates that a golf course requires approximately 3000 dwelling units with an average annual occupancy of 33% to achieve self-sufficiency for irrigation.

Indium-Mediated Cleavage of the Trityl Group from Protected 1H-Tetrazoles

On treatment with indium metal in MeOH–THF, trityl groups undergo reductive removal from 1H-protected tetrazoles (including aliphatic, aromatic, and heteroaromatic substituents), affording the corresponding free tetrazoles in excellent yields, without any decomposition of the tetrazole ring or reduction of any other group.

The influence of organic amendments on soil aggregate stability from semiarid sites

Restoring the native vegetation is the most effective way to regenerate soil health. Under these conditions, vegetation cover in areas having degraded soils may be better sustained if the soil is amended with an external source of organic matter. The addition of organic materials to soils also increases infiltration rates and reduces erosion rates; these factors contribute to an available water increment and a successful and sustainable land management. The goal of this study was to analyze the effect of various organic amendments on the aggregate stability of soils in afforested plots. An experimental paired-plot layout was established in southern of Spain (homogeneous slope gradient: 7.5%; aspect: N170). Five amendments were applied in an experimental set of plots: straw mulching; mulch with chipped branches of Aleppo Pine (Pinus halepensis L.); TerraCotten hydroabsobent polymers; sewage sludge; sheep manure and control. Plots were afforested following the same spatial pattern, and amendments were mixed with the soil at the rate 10 Mg ha-1. The vegetation was planted in a grid pattern with 0.5 m between plants in each plot. During the afforestation process the soil was tilled to 25 cm depth from the surface. Soil from the afforested plots was sampled in: i) 6 months post-afforestation; ii) 12 months post-afforestation; iii) 18 months post-afforestation; and iv) 24 months post-afforestation. The sampling strategy for each plot involved collection of 4 disturbed soil samples taken from the surface (0–10 cm depth). The stability of aggregates was measured by wet-sieving. Regarding to soil aggregate stability, the percentage of stable aggregates has increased slightly in all the treatments in relation to control. Specifically, the differences were recorded in the fraction of macroaggregates (≥ 0.250 mm). The largest increases have been associated with straw mulch, pinus mulch and sludge. Similar results have been registered for the soil organic carbon content. Independent of the soil management, after six months, no significant differences in microaggregates were found regarding to the control plots. These results showed an increase in the stability of the macroaggregates when soil is amended with sludge, pinus mulch and straw much. This fact has been due to an increase in the number cementing agents due to: (i) the application of pinus, straw and sludge had resulted in the release of carbohydrates to the soil; and thus (ii) it has favored the development of a protective vegetation cover, which has increased the number of roots in the soil and the organic contribution to it.

Interaction and cooperative effort among scientific societies. Twelve years of COSCE

The evolution of knowledge and technology in recent decades has brought profound changes in science policy, not only in the countries but also in the supranational organizations. It has been necessary, therefore, to adapt the scientific institutions to new models in order to achieve a greater and better communication between them and the political counterparts responsible for defining the general framework of relations between science and society. The Federationon of Scientific Societies of Spain (COSCE, Confederación de Sociedades Científicas de España) was founded in October 2003 to respond to the urgent need to interact with the political institutions and foster a better orientation in the process of making decisions about the science policy. Currently COSCE consists of over 70 Spanish scientific societies and more than 40,000 scientists. During its twelve years of active life, COSCE has developed an intense work of awareness of the real situation of science in Spain by launching several initiatives (some of which have joined other organizations) or by joining initiatives proposed from other groups related to science both at the Spanish level and at the European and non-European scenarios.

Essays on internationalization in the context of heterogeneous firms

The significant increase in global trade flows in last decades has been one of the main features of the globalization process that started in the 1950s. In general, the main factors behind this increase were linked to (i) the significant reductions of trade costs and technical barriers; (ii) the improvements in transport infrastructure and telecommunications; (iii) the progress of the international financial system and the increasing legal certainty; and (iv) the development of a corporate culture that promotes the internationalization of firms as a strategic tool in order to survive and to grow. The remarkable increase of trade openness has also been observed in the Spanish economy. In this regard, it is clear that the entry into force of the Treaty of Accession of Spain to the European Economic Community (now the European Union) in 1986 played a main role in this dramatic increase. In addition, and because of the deep depression of domestic demand caused by the global financial and economic crisis that started in 2008, the external trade has become a key driver in the economic recovery of the Spanish economy...

Purity of Blood and the Curial Market in Iberian Cathedrals

This article analyses the dynamics of accessing cathedral chapters with purity of blood statutes in the Iberian Peninsula, from a comparative perspective, and the interaction with the phenomenon of commodification of ecclesiastical benefices. This phenomenon created a Curial market that was open to any applicant with sufficient economic capacity, regardless of their ancestry. What was the result of the clash between the Iberian concept of purity and the commodified Roman reality?

Relatório no âmbito da unidade curricular prática de ensino supervisionada relativo ao ano letivo 2015/2016, na Escola Secundária/3 Rainha Santa Isabel, Estremoz

O presente relatório refere-se à Prática de Ensino Supervisionada incluída no Mestrado em Ensino de Português no 3º Ciclo do Ensino Básico e Ensino Secundário e de Espanhol dos Ensinos Básico e Secundário, que decorreu na Escola Secundária/3 Rainha Santa Isabel, em Estremoz. Conscientes da complexidade do processo de ensino-aprendizagem, tal como da parte central que os alunos ocupam no mesmo, este relatório faz uma reflexão crítica sobre algumas das áreas determinantes referentes ao processo de ensino-aprendizagem e sobre a Prática de Ensino Supervisionada realizada durante o ano letivo 2015/2016. Assim, o relatório organiza-se em seis capítulos, nomeadamente: preparação científica, pedagógica e didática; planificação e condução de aulas e avaliação das aprendizagens; descrição e reflexão das aulas lecionadas; análise da prática de ensino; participação na escola; e desenvolvimento profissional; Abstract: Report in the scope of the curricular unit of Supervised Teaching Practice This report refers to the Supervised Teaching Practice included in the Masters in teaching Portuguese in the 3rd cycle of Basic Education and Secondary Education and of Spanish in the Basic and Secondary Education, developed in the Secondary/3 school Rainha Santa Isabel, in Estremoz. Aware of the complexity of the teaching-learning process, as well as the central part of the students in its development, this report makes a critical reflection of some of the main areas concerning the teaching-learning process as well as of the Supervised Teaching Practice that took place during the school year of 2015/2016. Therefore, the report is organized in six chapters, namely: scientific, pedagogical and didactic preparation; planning and teaching classes and learning evaluation; description and reflection on the classes; teaching practice analysis, school participation; and professional development.

“Y a medida que el trabajo de la muerte avanzaba, y el aire se volvía más calmado, los ruidos de la artillería pesada parecían sacudir los techos de las iglesias sobre las aterrorizadas gentes que se reunían en ellas” : la otra guerra de la independencia

La Guerra de la Independencia, según la denominación tradicional de la historiografía española o The Peninsular Wars, como se suele denominar ese acontecimiento por los historiadores de habla inglesa, se perfila como uno de esos momentos en que las relaciones hispano-británicas adquieren una intensidad especial. De esa colaboración, de ese acto de comunicación intensa entre combatientes de un mismo enemigo, surgen unas manifestaciones literarias y muchos más relatos y diarios escritos por oficiales e incluso simples soldados del ejército de su majestad que contienen todo un tesoro de anécdotas, descripciones, y, principalmente, valoraciones dignas de analizar y hasta de disfrutar. Se trata, en este caso, de una recopilación de vivencias muy personales, en la mayoría de las ocasiones muy dolorosas, como cabría esperar de una guerra, y que a menudo ofrecen juicios y opiniones de España y Portugal que revelan una actitud paternalista y crítica.

Historia caballeresca de Don Claridoro de España, libro de caballerías manuscrito

Integran este número de la revista ponencias presentadas en Studia Hispanica Medievalia VIII: Actas de las IX Jornadas Internacionales de Literatura Española Medieval, 2008, y de Homenaje al Quinto Centenario de Amadis de Gaula

El compromiso como variable mediadora para la predicción de las futuras intenciones de consumo en los servicios. Una aproximación empírica a los consumidores de artes escénicas en España

[ES] El presente trabajo de investigación trata de arrojar luz sobre las relaciones entre las variables Satisfacción, Compromiso, Confianza y Futuras Intenciones de compra. Con este fin, se propone un Modelo de Gestión de las Relaciones con Clientes de Servicios en el que se observa que la variable más importante en la consecución de resultados positivos en lo que respecta a intenciones de asistencia futura de los consumidores es el Compromiso.

Una historia de España audiovisual y joseantoniana

[EN] The paper analyses a very interesting documentary film about the ancient history of Spain from a franquist, more specifically, falangist point of view (“Nueva Visión de la Historia). It was based on a book about the history of Spain written by a member of Falange, the fascist group in Spain, Antonio Almagro, and was intended as a formative instrument for the youth in the late forties or early fifties. We know only the episodes dealing with Ancient Spain (probably the only ones shot), 25 minutes in all, and it represents an outstanding example of an hyper-nationalistic and hyper-catholic perspective of Spanish history. It also shows a very sympathetic image of José Antonio, the leader of Falange, but, remarkably enough, not of Franco. The film also includes a “theoretical” Introduction about the notion of History.

Plasma brain-derived neurotrophic factor levels, learning capacity and cognition in patients with first episode psychosis

Background: Cognitive impairments are seen in first psychotic episode (FEP) patients. The neurobiological underpinnings that might underlie these changes remain unknown. The aim of this study is to investigate whether Brain Derived Neurotrophic Factor (BDNF) levels are associated with cognitive impairment in FEP patients compared with healthy controls. Methods: 45 FEP patients and 45 healthy controls matched by age, gender and educational level were selected from the Basque Country area of Spain. Plasma BDNF levels were assessed in healthy controls and in patients. A battery of cognitive tests was applied to both groups, with the patients being assessed at 6 months after the acute episode and only in those with a clinical response to treatment. Results: Plasma BDNF levels were altered in patients compared with the control group. In FEP patients, we observed a positive association between BDNF levels at six months and five cognitive domains (learning ability,immediate and delayed memory, abstract thinking and processing speed) which persisted after controlling for medications prescribed, drug use, intelligence quotient (IQ) and negative symptoms. In the healthy control group, BDNF levels were not associated with cognitive test scores. Conclusion: Our results suggest that BDNF is associated with the cognitive impairment seen after a FEP. Further investigations of the role of this neurotrophin in the symptoms associated with psychosis onset are warranted.