Variations in the copper(I)-copper(I) distances in multinuclear clusters with identical coordination geometries. Short metal-metal contacts induced by oligomerization

Factors contributing to the variations in the Cu(I)-Cu(I) distances in two clusters with identical ligand and coordination geometries have been analyzed. While the hexamer, 4, exhibits metal-metal distances in the range 2.81-3.25 Angstrom, shorter contacts are found in the corresponding tetramer, 3 (2.60-2.77 Angstrom). EHT calculations reveal relatively little attractive interactions in the corresponding Cu-4(4+) and Cu-6(6+) cores. Introduction of the ligands lowers the reduced overlap populations between the metals further. MNDO calculations with model electrophiles have been carried out to determine the bite angle requirements of the ligands. These are satisfactorily met in the structures of both 3 and 4. The key geometric feature distinguishing 3 and 4 is the Cu-S-Cu angle involving the bridging S- unit. In 4, the corresponding angles are about 90 degrees, while the values in 3 are smaller (70-73 degrees). Wider angles are computed to be energetically favored and are characterized by an open three-center bond and a long Cu-Cu distance. The bridging angles are suggested to be primarily constrained by the mode of oligomerization. Implications of these results for the stability and reactivity of these clusters and for short metal-metal distances in d(10) systems in general are discussed.

Structure and Bonding in Stannadiphospholes and their Dianions SnC(2)P(2)R(2)(m) (R=H, tBu m=0,-2): A Comparative Study with C(5)H(5)(+) and C(5)H(5)(-) Analogues

The potential energy surfaces of both neutral and dianionic SnC(2)P(2)R(2) (R=H, tBu) ring systems have been explored at the B3PW91/LANL2DZ (Sn) and 6-311 + G* (other atoms) level. In the neutral isomers the global minimum is a nido structure in which a 1,2-diphosphocyclobutadiene ring (1,2-DPCB) is capped by the Sn. Interestingly, the structure established by Xray diffraction analysis, for R=tBu, is a 1,3-DPCB ring capped by Sn and it is 2.4 kcal mol(-1) higher in energy than the 1,2-DPCB ring isomer. This is possibly related to the kinetic stability of the 1,3-DPCB ring, which might originate from the synthetic precursor ZrCp(2)tBu(2)C(2)P(2). In the case of the dianionic isomers we observe only a 6 pi-electron aromatic structure as the global minimum, similarly to the cases of our previously reported results with other types of heterodiphospholes.([1,4,19]) The existence of large numbers of cluster-type isomers in neutral and 6 pi-planar structures in the dianions SnC(2)P(2)R(2)(2-) (R=H, tBu) is due to 3D aromaticity in neutral clusters and to 2D pi aromaticity of the dianionic rings. Relative energies of positional isomers mainly depend on: 1) the valency and coordination number of the Sn centre, 2) individual bond strengths, and 3) the steric effect of tBu groups. A comparison of neutral stannadiphospholes with other structurally related C(5)H(5)(+) analogues indicates that Sn might be a better isolobal analogue to P(+) than to BH or CH(+). The variation in global minima in these C(5)H(5)(+) analogues is due to characteristic features such as 1) the different valencies of C, B, P and Sn, 2) the electron deficiency of B, 3) weaker p pi-p pi bonding by P and Sn atoms, and 4) the tendency of electropositive elements to donate electrons to nido clusters. Unlike the C5H5+ systems, all C(5)H(5)(-) analogues have 6 pi-planar aromatic structures as global minima. The differences in the relative ordering of the positional isomers and ligating properties are significant and depend on 1) the nature of the pi orbitals involved, and 2) effective overlap of orbitals.

Thermal instability and the feedback regulation of hot haloes in clusters, groups and galaxies

We present global multidimensional numerical simulations of the plasma that pervades the dark matter haloes of clusters, groups and massive galaxies (the intracluster medium; ICM). Observations of clusters and groups imply that such haloes are roughly in global thermal equilibrium, with heating balancing cooling when averaged over sufficiently long time- and length-scales; the ICM is, however, very likely to be locally thermally unstable. Using simple observationally motivated heating prescriptions, we show that local thermal instability (TI) can produce a multiphase medium with similar to 104 K cold filaments condensing out of the hot ICM only when the ratio of the TI time-scale in the hot plasma (tTI) to the free-fall time-scale (tff) satisfies tTI/tff? 10. This criterion quantitatively explains why cold gas and star formation are preferentially observed in low-entropy clusters and groups. In addition, the interplay among heating, cooling and TI reduces the net cooling rate and the mass accretion rate at small radii by factors of similar to 100 relative to cooling-flow models. This dramatic reduction is in line with observations. The feedback efficiency required to prevent a cooling flow is similar to 10-3 for clusters and decreases for lower mass haloes; supernova heating may be energetically sufficient to balance cooling in galactic haloes. We further argue that the ICM self-adjusts so that tTI/tff? 10 at all radii. When this criterion is not satisfied, cold filaments condense out of the hot phase and reduce the density of the ICM. These cold filaments can power the black hole and/or stellar feedback required for global thermal balance, which drives tTI/tff? 10. In comparison to clusters, groups have central cores with lower densities and larger radii. This can account for the deviations from self-similarity in the X-ray luminositytemperature () relation. The high-velocity clouds observed in the Galactic halo can be due to local TI producing multiphase gas close to the virial radius if the density of the hot plasma in the Galactic halo is >rsim 10-5 cm-3 at large radii.

Organization of Mn-Clusters in pcu and bcu Networks: Synthesis, Structure, and Properties

Two new anionic inorganic-organic hybrid compounds H3O]Mn-3(mu(3)-OH)(C14H8O6S)(3)(H2O)](DMF)(5), I, and H3O](2)Mn-7(mu(3)-OH)(4)(C14H8O6S)(6)(H2O)(4)](H2O)(2)(DMF)(8), II have been prepared by employing mild solvothennal methods. Both the compounds have three-dimensionally extended structures formed by Mn-6 and Mn-7 clusters, respectively. The connectivity between Mn-6 and Mn-7 clusters and 4,4'-sulfonyldibenzoic acid anions (SDBA(2-)) results in a six connected pcu network in I and an eight connected bcu network in II. The presence of hydronium ion (H-3(O+)) along with the solvent molecules in the channels of both the compounds suggested proton conduction in the solids. Proton conductivity studies gave values of similar to 3 x 10(-4) Omega(-1) cm(-1) 98% relative humidity in both the compounds. The high activation energies indicate a vehicle mechanism in the compounds I and II. Magnetic studies indicate antiferromagnetic behavior in both the compounds.

A Reactive Intermediate, Ni-5(C6H4N3)(6)(CO)(4)], in the Formation of Nonameric Clusters of Nickel, Ni-9(C6H4N3)(12)(CO)(6)] and Ni-9(C6H4N3)(12)(CO)(6)].2(C3H7NO)

Three new molecular compounds, Ni-5(bta)(6)(CO)(4)], I, Ni-9(bta)(12)(CO)(6)], II, Ni-9(bta)(12)(CO)(6)]. 2(C3H7NO), III, (bta = benzotriazole) were prepared employing solvothermal reactions. Of these, I have pentanuclear nickel, whereas II and III have nonanuclear nickel species. The structures are formed by the connectivity between the nickel and benzotriazole giving rise to the 5- and 9-membered nickel clusters. The structures are stabilised by extensive pi aEuro broken vertical bar pi and C-H... pi interactions. Compound II and III are solvotamorphs as they have the same 9-membered nickel clusters and have different solvent molecules. To the best of our knowledge, the compounds I-III represent the first examples of the same transition element existing in two distinct coordination environment in this class of compounds. The studies reveal that compound I is reactive and could be an intermediate in the preparation of II and III. Thermal studies indicate that the compounds are stable upto 350(a similar to)C and at higher temperatures (similar to 800(a similar to)C) the compounds decompose into NiO. Magnetic studies reveal that II is anti-ferromagnetic.

Individual and combined additions of calcium and antimony on microstructure and mechanical properties of squeeze-cast AZ91D magnesium alloy

The effects of combined additions of Ca and Sb on the microstructure and tensile properties of AZ91D alloy fabricated by squeeze-casting have been investigated. For comparison, the same has also been studied with and without individual additions of Ca and Sb. The results indicate that both individual and combined additions refine the grain size and beta-Mg17Al12 phase, which is more pronounced with combined additions. Besides alpha-Mg and beta-Mg17Al12 phases, a new reticular Al2Ca and rod-shaped Mg3Sb2 phases are formed following individual additions of Ca and Sb in the AZ91D alloy. With combined additions, an additional Ca2Sb phase is formed suppressing Mg3Sb2 phase. Additions of both Ca and Sb increase yield strength (YS) at both ambient and elevated temperatures up to 200 degrees C. However, both ductility and ultimate tensile strength (UTS) decrease first up to 150 degrees C and then increase at 200 degrees C. The increase in YS is attributed to the refinement of grain size, whereas, ductility and UTS are deteriorated by the presence of brittle Al2Ca, Mg3Sb2 and Ca2Sb phases. The best tensile properties are obtained in the AZXY9110 alloy owing to the presence of lesser amount of brittle Al2Ca and Ca2Sb phases resulted from the optimum content of 1.0Ca and 0.3Sb (wt%). The fracture surface of the tensile specimen tested at ambient temperature reveals cleavage failure that changes to quasi-cleavage at 200 degrees C. The squeeze-cast alloys exhibited better tensile properties as compared to that of the gravity-cast alloys nullifying the detrimental effects of Ca and/or Sb additions. (C) 2014 Elsevier B.V. All rights reserved.

Emerging technologies for reef fisheries research and management [held during the 56th annual Gulf and Caribbean Fisheries Institute meeting in Tortola, British Virgin Islands, November 2003]

This publication of the NOAA Professional Paper NMFS Series is the product of a special symposium on “Emerging Technologies for Reef Fisheries Research and Management” held during the 56th annual Gulf and Caribbean Fisheries Institute meeting in Tortola, British Virgin Islands, November 2003. The purpose of this collection is to highlight the diversity of questions and issues in reef fisheries management that are benefiting from applications of technology. Topics cover a wide variety of questions and issues from the study of individual behavior, distribution and abundance of groups and populations, and associations between habitats and fish and shellfish species.(PDF files contains 124 pages.)

Emerging technologies for reef fisheries research and management

This publication of the NOAA Professional Paper NMFS Series is the product of a special symposium on “Emerging Technologies for Reef Fisheries Research and Management” held during the 56th annual Gulf and Caribbean Fisheries Institute meeting in Tortola, British Virgin Islands, November 2003. The purpose of this collection is to highlight the diversity of questions and issues in reef fisheries management that are benefiting from applications of technology. Topics cover a wide variety of questions and issues from the study of individual behavior, distribution and abundance of groups and populations, and associations between habitats and fish and shellfish species.

Experimental chemical physics of droplets and clusters

Time-of-flight measurements of energetic He atoms, field ionization of cryogenic liquid helium clusters, and time-of-flight and REMPI spectroscopy of radical salt clusters were investigated experimentally. The excited He atoms were generated in a corona discharge. Two strong neutral peaks were observed, accompanied by a prompt photon peak and a charged peak. All peaks were correlated with the pulsing of the discharge. The neutral hyperthermal and metastable atoms were formed by different mechanisms at different stages of the corona discharge. Positively charged helium droplets were produced by ionization of liquid helium in an electrostatic spraying experiment. The fluid emerging from a thin glass capillary was ionized by a high voltage applied to a needle inside the capillary. Fine droplets (less than 10 µm in diameter) were produced in showers with currents as high as 0.4 µA at 2-4 kV. The high currents resulting from field ionization in helium and the low surface tension of He I, led to charge densities that greatly exceeded the Rayleigh limit, thus resulting in coulombic explosion of the liquid. In contrast, liquid nitrogen formed a well-defined Taylor cone with droplets having diameters comparable to the jet (≈100 µm) at lower currents (10 nA) and higher voltages (8 kV). The metal-halide clusters of calcium and chlorine were generated by laser ablation of calcium metal in a Ar/CCl₄ expansion. A visible spectrum of the Ca₂Cl₃ cluster was observed from 651 to 630 nm by 1 +1' REMPI. The spectra were composed of a strong origin band at 15 350.8 cm^-1 and several weak vibronic bands. Density functional calculations predicted three minimum energy isomers. The spectrum was assigned to the ²B₂ ← X ²A₁ transition of a planar C_2V structure having a ring of two Cl and two Ca atoms and a terminal Cl atom. The ring isomer of Ca₂Cl₃ has the unpaired electron localized on one Ca²⁺ ion to form a Ca⁺ chromophore. A second electronic band of Ca₂Cl₃ was observed at 720 nm. The band is sharply different from the 650 nm band and likely due to a different isomer.

Social structure and underwater behavior of harbor seals in southern Monterey Bay, California

To understand harbor seal social and mating strategies, I examined site fidelity, seasonal abundance and distribution, herd integrity, and underwater behavior of individual harbor seals in southern Monterey Bay. Individual harbor seals (n = 444) were identified by natural markings and represented greater than 80% of an estimated 520 seals within this community. Year to year fidelity of individual harbor seals to southern Monterey Bay coastline was 84% (n = 388), and long-term associations (>2 yrs) among individuals were common (>40%). Consistent with these long-term associations, harbor seals were highly social underwater throughout the year. Underwater social behavior included three primary types: (1) visual and acoustic displays, such as vocalizing, surface splashing, and bubble-blowing; (2) playful or agonistic social behavior such as rolling, mounting, attending, and biting; and (3) signal gestures such as head-thrusting, fore-flipper scratch~ng, and growling. Frequency of these types of behavior was related to seal age, gender, season, and resource availability. Underwater behavior had a variety of functions, including promotion of learning and social development, reduction of aggression and preservation of social bonds by maintaining social hierarchy, and facilitation of mate selection during breeding season. Social behavior among adult males was significantly correlated with vocalization characteristics (r = 0.99, X2 = 37.7, p = 0.00087), indicating that seals may assess their competition based on underwater vocalization displays and adopt individual strategies for attracting females during breeding season based on social status. Individual mating strategies may include defending underwater territories, using scramble tactics, and developing social alliances. (PDF contains 105 pages)

An enactive and dynamical systems theory account of dyadic relationships

Many social relationships are a locus of struggle and suffering, either at the individual or interactional level. In this paper we explore why this is the case and suggest a modeling approach for dyadic interactions and the well-being of the participants. To this end we bring together an enactive approach to self with dynamical systems theory. Our basic assumption is that the quality of any social interaction or relationship fundamentally depends on the nature and constitution of the individuals engaged in these interactions. From an enactive perspective the self is conceived as an embodied and socially enacted autonomous system striving to maintain an identity. This striving involves a basic two-fold goal: the ability to exist as an individual in one's own right, while also being open to and affected by others. In terms of dynamical systems theory one can thus consider the individual self as a self-other organized system represented by a phase space spanned by the dimensions of distinction and participation, where attractors can be defined. Based on two everyday examples of dyadic relationship we propose a simple model of relationship dynamics, in which struggle or well-being in the dyad is analyzed in terms of movements of dyadic states that are in tension or in harmony with individually developed attractors. Our model predicts that relationships can be sustained when the dyad develops a new joint attractor toward which dyadic states tend to move, and well-being when this attractor is in balance with the individuals' attractors. We outline how this can inspire research on psychotherapy. The psychotherapy process itself provides a setting that supports clients to become aware how they fare with regards to the two-fold norm of distinction and participation and develop, through active engagement between client (or couple) and therapist, strategies to co-negotiate their self-organization.

Diet shifts of juvenile red snapper (Lutjanus campechanus) with changes in habitat and fish size

We examined the diets and habitat shift of juvenile red snapper (Lutjanus campechanus) in the northeast Gulf of Mexico. Fish were collected from open sand-mud habitat (little to no relief), and artificial reef habitat (1-m3 concrete or PVC blocks), from June 1993 through December 1994. In 1994, fish settled over open habitat from June to September, as shown by trawl collections, then began shifting to reef habitat — a shift that was almost completed by December as observed by SCUBA visual surveys. Stomachs were examined from 1639 red snapper that ranged in size from 18.0 to 280.0 mm SL. Of these, 850 fish had empty stomachs, and 346 fish from open habitat and 443 fish from reef habitat contained prey. Prey were identified to the lowest possible taxon and quantified by volumetric measurement. Specific volume of particular prey taxa were calculated by dividing prey volume by individual fish weight. Red snapper shifted diets with increasing size. Small red snapper (<60 mm SL) fed mostly on chaetognaths, copepods, shrimp, and squid. Large red snapper (60–280 mm SL) shifted feeding to fish prey, greater amounts of squid and crabs, and continued feeding on shrimp. We compared red snapper diets for overlapping size classes (70–160 mm SL) of fish that were collected from both habitats (Bray-Curtis dissimilarity index and multidimensional scaling analysis). Red snapper diets separated by habitat type rather than fish size for the size ranges that overlapped habitats. These diet shifts were attributed to feeding more on reef prey than on open-water prey. Thus, the shift in habitat shown by juvenile red snapper was reflected in their diet and suggested differential habitat values based not just on predation refuge but food resources as well.

Correlation between Er3+ emission and Si clusters in Erbium-doped a-SiOx : H films

Erbium-doped hydrogenated amorphous silicon suboxide films containing silicon clusters (a-SiOx:H) were prepared. The samples exhibited photoluminescence (PL) peaks at around 750nm and 1.54 mu m, which could be assigned to the electron-hole recombination in silicon clusters and the intra-4f transition in Er3+, respectively. We compared annealing behaviors of Si clusters and Er3+ emission and found that Si clusters emission depends strongly upon crystallinity of Si clusters, whereas Er3+ emission is not sensitive to whether it is Si nanocrystals (nc-Si) or amorphous Si (a-Si) clusters. The erbium-doped a-SiOx:H films containing either a-Si clusters or nc-Si have the same kind of Er3+ -emitting centers. Based on these results, it is concluded that a-Si clusters can play the same role on Er3+ excitation as nc-Si. (c) 2004 Elsevier B.V. All rights reserved.

Absorption and Raman spectra of Se-8-ring clusters in zeolite 5A

Samples with different weight ratio of Se to zeolite 5A (Se composition) have been prepared by loading Se into the cages of zeolite 5A and the measurements of the absorption and Raman spectra have been carried out for the prepared samples. The measured absorption edges of the samples close and blue shifted to the value for monoclinic Se containing Se-8-ring, suggesting the formation of Se-8-ring clusters dagger in the cages. The continuous and broadening features of the absorption spectra are interpreted by the strong electron-phonon coupling in Se-8-ring clusters. The sample with high Se composition has a red shift of the absorption band edge relative to the samples with less Se composition. It is tentatively attributed to the reason that with different Se composition, single Se-8-ring clusters and double Se-8-ring clusters are formed in the cages of zeolite 5A. A single broad band at about 262 cm(-1) is observed in the Raman spectra, that gives the further support of the formation of Se-8-ring clusters. Copyright (C) 1996 Elsevier Science Ltd

Templated assembly of mu(5)-CO32- decanuclear praseodymium and neodymium clusters through spontaneous fixation of atmospheric carbon dioxide

Reactions of Ln(III) acetate (Ln = Pr and Nd) and a polydentate Schiff-base in a mixture of methanol and acetonitrile resulted in the unprecedented assembly of novel Ln(10) aggregates containing two Ln(5) pentagons templated by mu(5)-CO32-, introduced via spontaneous fixation of atmospheric carbon dioxide. Magnetic analysis using an expression including the ligand field effects and molecular field approximation indicates weak antiferromagnetic coupling between the metal ions. This synthetic approach may represent a promising new route toward the design of new lanthanide clusters and novel multifunctional materials.