A first-principles analysis of the magnetism of CuII polynuclear coordination complexes: the case of [Cu4(bpy)4(aspartate)2(H2O)3](ClO4)4·2.5H2O

The magnetic structure of the [Cu4(bpy)4(aspartate)2(H2O)3](ClO4)4·2.5 H2Ocrystal - using fractional coordinates determined at room-temperature ¿ has beenanalysed in detail. This analysis has been carried out by extending our first principlesbottom-up theoretical approach, which was initially designed to study through-spacemagnetic interactions, to handle through-bond magnetic interactions. The only input datarequired by this approach are the values of the computed JAB exchange parameters for allthe unique pairs of spin-containing centres. The results allow the magnetic structure ofthe crystal, which presents two types of isolated tetranuclear CuII clusters, to be definedin quantitative terms. Each of these clusters presents ferro and antiferromagneticinteractions, the former being stronger, although outnumbered by the latter. Thecomputed magnetic susceptibility curve shows the same qualitative features as theexperimental data. However, there are small differences that are presumed to beassociated with the use of room-temperature crystal coordinates.

A first-principles analysis of the magnetism of CuII polynuclear coordination complexes: the case of [Cu4(bpy)4(aspartate)2(H2O)3](ClO4)4·2.5H2O

The magnetic structure of the [Cu4(bpy)4(aspartate)2(H2O)3](ClO4)4·2.5 H2Ocrystal - using fractional coordinates determined at room-temperature ¿ has beenanalysed in detail. This analysis has been carried out by extending our first principlesbottom-up theoretical approach, which was initially designed to study through-spacemagnetic interactions, to handle through-bond magnetic interactions. The only input datarequired by this approach are the values of the computed JAB exchange parameters for allthe unique pairs of spin-containing centres. The results allow the magnetic structure ofthe crystal, which presents two types of isolated tetranuclear CuII clusters, to be definedin quantitative terms. Each of these clusters presents ferro and antiferromagneticinteractions, the former being stronger, although outnumbered by the latter. Thecomputed magnetic susceptibility curve shows the same qualitative features as theexperimental data. However, there are small differences that are presumed to beassociated with the use of room-temperature crystal coordinates.

Tax Coordination Between Regions in Spain. The Role of the Courts

Overview of the Tax Coordination of the Regions in Spain from the point of view of the role of the Courts in developing the present system

Tax Coordination Between Regions in Spain - Role of the Courts

Análisis de la jurisprudencia constitucional española sobre la distribución de competencias tributarias entre los distintos niveles de gobierno.

Assessment of the water chemistry and the macroinvertebrate community changes produced during the creation of the new Llobregat river mouth (Barcelona, NE Spain)

In 1999, a set of coordinated projects and investments whose principal objective was to transform Barcelona into one of the main distribution points of southern Europe resulted in the relocation of the Llobregat River mouth. The mouth was relocated by draining the old river mouth and constructing a new one. The aim of this study was to characterise the physico-chemical properties and the aquatic macroinvertebrate communities of the new river mouth and to monitor the changes experienced by the estuarine environment during its creation. A sampling point was established in the river 1.8 km upstream from its connection with the new mouth, and two sampling points were established in the new mouth. Samples of water and macroinvertebrates were collected every two months from May 2004 to June 2005, covering the periods before (from May to September 2004) and after (from September 2004 to June 2005) the new mouth was connected to the river and the sea. During the period before its connection to the river and the sea, the new mouth was functionally similar to a lagoon, with clear waters, charophytes and a rich invertebrate community. After the connection was completed, seawater penetrated the river mouth and extended to the connection point with the river (approximately 3.9 km upstream). An increase in conductivity from 4-6 mS cm 1 to 24-30 mS cm 1 caused important changes in the macroinvertebrate community of the new mouth. An initial defaunation was followed by a colonisation of the new mouth by brackish-water and marine invertebrate species. Due to its design (which allows the penetration of the sea) and the decreased discharge from the lower part of the Llobregat River, the new mouth has become an arm of the sea

The nature of the Cr-C bond: direct estimation of aromaticity in Fischer carbenes

Report for the scientific sojourn at the the Philipps-Universität Marburg, Germany, from september to december 2007. For the first, we employed the Energy-Decomposition Analysis (EDA) to investigate aromaticity on Fischer carbenes as it is related through all the reaction mechanisms studied in my PhD thesis. This powerful tool, compared with other well-known aromaticity indices in the literature like NICS, is useful not only for quantitative results but also to measure the degree of conjugation or hyperconjugation in molecules. Our results showed for the annelated benzenoid systems studied here, that electron density is more concentrated on the outer rings than in the central one. The strain-induced bond localization plays a major role as a driven force to keep the more substituted ring as the less aromatic. The discussion presented in this work was contrasted at different levels of theory to calibrate the method and ensure the consistency of our results. We think these conclusions can also be extended to arene chemistry for explaining aromaticity and regioselectivity reactions found in those systems.In the second work, we have employed the Turbomole program package and density-functionals of the best performance in the state of art, to explore reaction mechanisms in the noble gas chemistry. Particularly, we were interested in compounds of the form H--Ng--Ng--F (where Ng (Noble Gas) = Ar, Kr and Xe) and we investigated the relative stability of these species. Our quantum chemical calculations predict that the dixenon compound HXeXeF has an activation barrier for decomposition of 11 kcal/mol which should be large enough to identify the molecule in a low-temperature matrix. The other noble gases present lower activation barriers and therefore are more labile and difficult to be observable systems experimentally.