Cluster measurement and benchmarking - A recent Welsh approach

Drawing on extensive academic research and theory on clusters and their analysis, the methodology employed in this pilot study (sponsored by the Welsh Assembly Government’s Economic Research Grants Assessment Board) seeks to create a framework for reviewing and monitoring clusters in Wales on an ongoing basis, and generate the information necessary for successful cluster development policy to occur. The multi-method framework developed and tested in the pilot study is designed to map existing Welsh sectors with cluster characteristics, uncover existing linkages, and better understand areas of strength and weakness. The approach adopted relies on synthesising both quantitative and qualitative evidence. Statistical measures, including the size of potential clusters, are united with other evidence on input-output derived inter-linkages within clusters and to other sectors in Wales and the UK, as well as the export and import intensity of the cluster. Multi Sector Qualitative Analysis is then designed for competencies/capacity, risk factors, markets, types and crucially, the perceived strengths of cluster structures and relationships. The approach outlined above can, with the refinements recommended through the review process, provide policy-makers with a valuable tool for reviewing and monitoring individual sectors and ameliorating problems in sectors likely to decline further.

How patchy can one get and still condense? The role of dissimilar patches in the interactions of colloidal particles

We investigate the influence of strong directional, or bonding, interactions on the phase diagram of complex fluids, and in particular on the liquid-vapour critical point. To this end we revisit a simple model and theory for associating fluids which consist of spherical particles having a hard-core repulsion, complemented by three short-ranged attractive sites on the surface (sticky spots). Two of the spots are of type A and one is of type B; the interactions between each pair of spots have strengths [image omitted], [image omitted] and [image omitted]. The theory is applied over the whole range of bonding strengths and results are interpreted in terms of the equilibrium cluster structures of the coexisting phases. In systems where unlike sites do not interact (i.e. where [image omitted]), the critical point exists all the way to [image omitted]. By contrast, when [image omitted], there is no critical point below a certain finite value of [image omitted]. These somewhat surprising results are rationalised in terms of the different network structures of the two systems: two long AA chains are linked by one BB bond (X-junction) in the former case, and by one AB bond (Y-junction) in the latter. The vapour-liquid transition may then be viewed as the condensation of these junctions and we find that X-junctions condense for any attractive [image omitted] (i.e. for any fraction of BB bonds), whereas condensation of the Y-junctions requires that [image omitted] be above a finite threshold (i.e. there must be a finite fraction of AB bonds).

Criticality of colloids with distinct interaction patches: The limits of linear chains, hyperbranched polymers, and dimers

We use a simple model of associating fluids which consists of spherical particles having a hard-core repulsion, complemented by three short-ranged attractive sites on the surface (sticky spots). Two of the spots are of type A and one is of type B; the bonding interactions between each pair of spots have strengths epsilon(AA), epsilon(BB), and epsilon(AB). The theory is applied over the whole range of bonding strengths and the results are interpreted in terms of the equilibrium cluster structures of the phases. In addition to our numerical results, we derive asymptotic expansions for the free energy in the limits for which there is no liquid-vapor critical point: linear chains (epsilon(AA)not equal 0, epsilon(AB)=epsilon(BB)=0), hyperbranched polymers (epsilon(AB)not equal 0, epsilon(AA)=epsilon(BB)=0), and dimers (epsilon(BB)not equal 0, epsilon(AA)=epsilon(AB)=0). These expansions also allow us to calculate the structure of the critical fluid by perturbing around the above limits, yielding three different types of condensation: of linear chains (AA clusters connected by a few AB or BB bonds); of hyperbranched polymers (AB clusters connected by AA bonds); or of dimers (BB clusters connected by AA bonds). Interestingly, there is no critical point when epsilon(AA) vanishes despite the fact that AA bonds alone cannot drive condensation.

A study on parallel versus sequential relational fuzzy clustering methods

Dissertação para obtenção do Grau de Mestre em Engenharia Informática

Computational modeling of the properties of TiO2 nanoparticles

In this study we discuss the electronic, structural, and optical properties of titanium dioxide nanoparticles, and also the properties of Ni(II) diimine dithiolato complexes as dyes in dye-sensitized TiO2 based solar cells. The abovementioned properties have been modeled by using computational codes based on the density functional theory. The results achieved show slight evidence on the structure-dependent band gap broadening, and clear blue-shifts in absorption spectra and refractive index functions of ultra-small TiO2 particles. It is also shown that these properties are strongly dependent on the shape of the nanoparticles. Regarding the Ni(II) diimine dithiolato complexes as dyes in dye-sensitized TiO2 based solar cells, it is shown that based on the experimental electrochemical investigation and DFT studies all studied diimine derivatives could serve as potential candidates for the light harvesting, but the e ciencies of the dyes studied are not very promising.

EXPLORING THE DEVELOPMENT AND PSYCHOSOCIAL CORRELATES OF SPIRITUALITY /RELIGIOSITY ACROSS ADOLESCENCE

The goal of the four studies that comprised this dissertation was to examine how spirituality/religiosity (SIR), as both an institutional and personal phenomenon, developed over time, and how its institutional (i.e., religious activity involvement) and personal (i.e., sense of connection with the sacred) components were uniquely linked with psychosocial adjustment. In Study 1, the differential longitudinal correlates of religious service attendance, as compared to involvement in other clubs, were evaluated with a sample of adolescents (n=1050) who completed a survey in grades 9, 11 and 12. Religious attendance and involvement in non-religious clubs were uniquely associated with positive adjustment in terms of lower substance use and better academic marks, particularly when involvement was sustained over time. In Study 2, the direction of effects was tested for the association between religious versus non-religious activities and both substance use and academic marks. Participants (n= 3993) were surveyed in grades 9 through 12. Higher religious attendance (but not non-religious club involvement) in one grade predicted lower levels of substance use in the next grade. Higher levels of nonreligious club involvement (but not religious service attendance) in one grade predicted higher academic achievement in the next grade, and higher academic achievement in one grade predicted more frequent non-religious club involvement in the next grade. The results suggest that different assets may be fostered in religious as compared to nonreligious activities, and, specifically, religious activity involvement may be important for the avoidance of substance use. The goal of Study 3 was to assess the unique associations between the institutional versus personal dimensions of SIR and a wide range of domains of psychosocial adjustment (namely, intrapersonal well-being, substance use, risk attitudes, parental relationship quality, academic orientation, and club involvement), and to examine the direction of effects in these associations. Participants (n=756) completed a survey in grades 11 and 12. Personal and institutional dimensions of SIR were differentially associated with adjustment, but it may only be in the domain of risk-taking (Le., risk attitudes, substance use) that SIR may predict positive adjustment over time. Finally, in Study 4, the goal was to examine how institutional and personal aspects of SIR developed within individual adolescents. Configurations of mUltiple dimensions of spirituality/religiosity were identified across 2 time points with an empirical classification procedure (cluster analysis), and sample- and individual-level development in these configurations were assessed. A five cluster-solution was optimal at both grades. Clusters were identified as aspirituallirreligious, disconnected wonderers, high institutional and personal, primarily personal, and meditators. With the exception of the high institutional and personal cluster, the cluster structures were stable over time. There also was significant intraindividual stability in all clusters over time; however, a significant proportion of individuals classified as high institutional and personal in Grade 11 moved into the primarily personal cluster in Grade 12. This program of research represented an important step towards addressing some of the limitations within the body of literature; namely, the uniqueness of religious activity involvement as a structured club, the differential link between institutional versus personal SIR and psychosocial adjustment, the direction of effects in the associations between institutional versus personal SIR and adjustment, and the way in which different dimensions of SIR may be configured and develop within individual adolescents over time.

Towards a Reconstruction of Thermal Properties of Light Nuclei from Fusion - Evaporation reactions

This thesis work has been developed in the framework of a new experimental campaign, proposed by the NUCL-EX Collaboration (INFN III Group), in order to progress in the understanding of the statistical properties of light nuclei, at excitation energies above particle emission threshold, by measuring exclusive data from fusion-evaporation reactions. The determination of the nuclear level density in the A~20 region, the understanding of the statistical behavior of light nuclei with excitation energies ~3 A.MeV, and the measurement of observables linked to the presence of cluster structures of nuclear excited levels are the main physics goals of this work. On the theory side, the contribution to this project given by this work lies in the development of a dedicated Monte-Carlo Hauser-Feshbach code for the evaporation of the compound nucleus. The experimental part of this thesis has consisted in the participation to the measurement 12C+12C at 95 MeV beam energy, at Laboratori Nazionali di Legnaro - INFN, using the GARFIELD+Ring Counter(RCo) set-up, from the beam-time request to the data taking, data reduction, detector calibrations and data analysis. Different results of the data analysis are presented in this thesis, together with a theoretical study of the system, performed with the new statistical decay code. As a result of this work, constraints on the nuclear level density at high excitation energy for light systems ranging from C up to Mg are given. Moreover, pre-equilibrium effects, tentatively interpreted as alpha-clustering effects, are put in evidence, both in the entrance channel of the reaction and in the dissipative dynamics on the path towards thermalisation.

Magnetic charachterization of surface sediments in the South Atlantic

Surface sediment samples representative for the tropical and subtropical South Atlantic (15°N to 40°S) were investigated by isothermal magnetic methods to delineate magnetic mineral distribution patterns and to identify their predominant Holocene climatic and oceanographic controls. Individual parameters reveal distinct, yet frequently overlapping, regional sedimentation characteristics. A probabilistic ('fuzzy c-means') cluster analysis was applied to five concentration independent magnetic properties assessing magnetite to hematite ratios and diagnostic of bulk and fine-particle magnetite grain size and coercivity spectra. The resultant 10 cluster structures establish an oceanwide magnetic sediment classification scheme tracing the major terrigenous eolian and fluvial fluxes, authigenic biogenic magnetite accumulation in high-productivity areas, transport by ocean current systems, and effects of bottom water velocity on depositional regimes. Distinct dissimilarities in magnetic mineral inventories between the eastern and western basins of the South Atlantic reflect prominent contrasts of both oceanic and continental influences.

The syntheses, structures and redox properties of phosphine-gold(I) and triruthenium-carbonyl cluster derivatives of tolans

The syntheses of several ethynyl-gold(I) phosphine substituted tolans (1,2-diaryl acetylenes) of general form [Au(C=CC6H4C=CC6H4X)(PPh3)] are described [X = Me (2a), OMe (2b), CO2Me (2c), NO2 (2d), CN (2e)]. These complexes react readily with [Ru-3(CO) 10(mu-dppm)] to give the heterometallic clusters [Ru3(mu-AuPPh3)(mu-eta(1), eta(2)-C2C6H4C, CC6H4X)(CO)(7)(mu-dppm)] (3a-e). The crystallographically determined molecular structures of 2b, 2d, 2e and 3a-e are reported here, that of 2a having been described on a previous occasion. Structural, spectroscopic and electrochemical studies were conducted and have revealed little electronic interaction between the remote substituent and the organometallic end-caps. (C) 2007 Elsevier B. V. All rights reserved.

Metal cluster expansion by addition of low valent group 14 reagents: III. Reaction of bis[bis(trimethylsilyl)methyl]tin with M3(CO)12 or its derivatives (M = Fe, Ru, or Os): the crystal and molecular structures of M3(μ-SnR2)2(CO)10(R = CH(SiMe3)2; M = Ru or Os)

The stannylene [SnR2] (R = CH(SiMe3)2) reacts in different ways with the three dodecacarbonyls of the iron triad: [Fe3(CO)12] gives [Fe2(CO)8(μ-SnR2)], [Ru3(CO)12] gives the planar pentametallic cluster [Ru3(CO)10(μ-SnR2)2], for which a full structural analysis is reported, while [Os3(CO)12] fails to react. Different products are also obtained from three nitrile derivatives: [Fe3-(CO)11(MeCN)] gives [Fe2(CO)6(μ-SnR2)2], which has a structure significantly different from that of known Fe2Sn2 clusters, [Ru3(CO)10(MeCN)2] gives the pentametallic cluster described above, while [Os3(CO)10(MeCN)2] gives the isostructural osmium analogue, which shows the unusual feature of a CO group bridging two osmium atoms.

Stepwise construction of [Os6(CO)18(μ6-P)]-, a hexanuclear osmium cluster monoanion with trigonal-prismatic co-ordination for phosphorus: X-ray crystal structures of [Os6(μ-H)2(CO)20(MeCN)(μ3-PH)] and [PPh3Me][Os6(CO)18(μ6-P)]

Treatment of the labile cluster [Os3(CO)11(MeCN)] with PH3 affords the substituted product [Os3(CO)11(PH3)](1) in high yield. Subsequent reaction of (1) with Na2CO3 in MeOH, followed by acidification, gives the hydrido phosphido cluster [Os3(µ-H)(CO)10(µ-PH2)](2). When (2) is heated to 45–60 °C in the presence of [Os3(CO)11(MeCN)] a hexanuclear complex with the formulation [Os6(µ-H)2(CO)21(µ3-PH)](3) is obtained. If this reaction is repeated using [Os3(CO)10(MeCN)2] instead of [Os3(CO)11(MeCN)], an acetonitrile-containing product, [Os6(µ-H)2(CO)20(MeCN)(µ3-PH)](4), is obtained. An X-ray analysis of (4) shows that two Os3 triangular units are linked by a µ3-phosphinidene ligand, which symmetrically bridges an Os–Os edge of one triangle and is terminally co-ordinated to one Os atom of the second triangle. When (3) is treated with a weak base, such as [N(PPh3)2]Cl or [PPh3Me] Br, deprotonation to the corresponding cluster monoanion [Os6(µ-H)(CO)21(µ3-PH)]–(5) occurs. Treatment of (5) with a weak acid regenerates (3) in quantitative yield. Thermolysis of (3) leads to a closing up of the metal framework, affording the cluster [Os6(µ-H)(CO)18(µ6-P)], which readily deprotonates to give the anion [Os6(CO)18(µ6-P)]–(7) in the presence of [N(PPh3)2] Cl or [PPh3Me]Br. The same anion (7) may also be obtained by direct thermolysis of (5). An X-ray analysis of the [PPh3Me]+ salt of (7) confirms that the phosphorus occupies an interstitial site in a trigonal-prismatic hexaosmium framework, and co-ordinates to all six metal atoms with an average Os–P distance of 2.31 (1)Å. Proton and 31P n.m.r. data on all the new clusters are presented, and the position of the phosphorus resonance in the 31P n.m.r. spectrum is related to the changes in the environment of the phosphorus atom.

Cooperative Effects of Electron Donors and Acceptors for the Stabilization of Elusive Metal Cluster Frameworks: Synthesis and Solid-State Structures of Pt-19(CO)(24)(mu(4)-AuPPh3)(3)](-) and Pt-19(CO)(24){mu(4)-Au-2(PPh3)(2)}(2)]

The anionic cluster Pt-19(CO)(22)](4-) (1), of pentagonal symmetry, reacts with CO and AuPPh3+ fragments. Upon increasing the Au:Pt-19, molar ratio, different species are sequentially formed, but only the last two members of the series could be characterized by X-ray diffraction, namely, Pt-19(CO)(24)(mu(4)-AuPPh3)(3)](-) (2) and Pt-19(CO)(24){mu(4)-Au-2(PPh3)(2)}(2)] (3).The metallic framework of the starting cluster is completely modified after the addition of CO and AuL+, and both products display the same platinum core of trigonal symmetry, with closely packed metal atoms. The three AuL+ units cap three different square faces in 2, whereas four AuL+ fragments are grouped in two independent bimetallic units in the neutral cluster 3. Electrochemical and spectroelectrochemical studies on 2 showed that its redox ability is comparable with that of the homometallic 1.