The Detection and Location of Hydrido Ligands in High Nuclearity Osmium and Ruthenium Carbonyl Clusters: A Critical Survey

Hydrido carbonyl clusters represent powerful molecular models for the co-adsorption of carbon monoxide and hydrogen on metal surfaces, a key step in several catalytic processes. Over the past two decades a considerable number of such species have been reported in the literature. In this paper, the structural chemistry of high nuclearity osmium and ruthenium hydrido carbonyl clusters is critically reviewed. Particular emphasis is placed on the limits of the various indirect methods of hydride location in clusters, and an alternative interpretation of the results of spectroscopic studies performed for samples of some Ru and Os clusters in solution is given

Unitary limit and quantum interference effect in disordered two-dimensional crystals with nearly half-filled bands

Based on the self-consistent $T$-matrix approximation, the quantum interference (QI) effect is studied with the diagrammatic technique in weakly-disordered two-dimensional crystals with nearly half-filled bands. In addition to the usual 0-mode cooperon and diffuson, there exist $\pi$-mode cooperon and diffuson in the unitary limit due to the particle-hole symmetry. The diffusive $\pi$-modes are gapped by the deviation from the exactly-nested Fermi surface. The conductivity diagrams with the gapped $\pi$-mode cooperon or diffuson are found to give rise to unconventional features of the QI effect. Besides the inelastic scattering, the thermal fluctuation is shown to be also an important dephasing mechanism in the QI processes related with the diffusive $\pi$-modes. In the proximity of the nesting case, a power-law anti-localization effect appears due to the $\pi$-mode diffuson. For large deviation from the nested Fermi surface, this anti-localization effect is suppressed, and the conductivity remains to have the usual logarithmic weak-localization correction contributed by the 0-mode cooperon. As a result, the dc conductivity in the unitary limit becomes a non-monotonic function of the temperature or the sample size, which is quite different from the prediction of the usual weak-localization theory.Comment: 21 pages, 4 figure

Coupled Maps on Trees

We study coupled maps on a Cayley tree, with local (nearest-neighbor) interactions, and with a variety of boundary conditions. The homogeneous state (where every lattice site has the same value) and the node-synchronized state (where sites of a given generation have the same value) are both shown to occur for particular values of the parameters and coupling constants. We study the stability of these states and their domains of attraction. As the number of sites that become synchronized is much higher compared to that on a regular lattice, control is easier to effect. A general procedure is given to deduce the eigenvalue spectrum for these states. Perturbations of the synchronized state lead to different spatio-temporal structures. We find that a mean-field like treatment is valid on this (effectively infinite dimensional) lattice.Comment: latex file (25 pages), 4 figures included. To be published in Phys. Rev.

Toward a Neutral Single-Component Amidinate Iodide Aluminum Catalyst for the CO₂ Fixation into Cyclic Carbonates

A new iodide aluminum complex ({AlI(κ⁴-naphbam)}, 3) supported by a tetradentate amidinate ligand derived from a naphthalene-1,8-bisamidine precursor (naphbamH, 1) was obtained in quantitative yield via reaction of the corresponding methyl aluminum complex ({AlMe(κ⁴-naphbam)}, 2) with 1 equiv of I₂ in CH₂Cl₂ at room temperature. Complexes 2 and 3 were tested and found to be active as catalysts for the cyclic carbonate formation from epoxides at 80 °C and 1 bar of CO₂ pressure. A first series of experiments were carried out with 1.5 mol % of the alkyl complex 2 and 1.5 mol % of tetrabutylammonium iodide (TBAI) as a cocatalyst; subsequently, the reactions were carried out with 1.5 mol % of iodide complex 3 as a single-component catalyst. Compound 3 is one of the first examples of a nonzwitterionic halide single-component aluminum catalyst producing cyclic carbonates. The full catalytic cycle with characterization of all minima and transition states was characterized by quantum chemistry calculations (QCCs) using density functional theory. QCCs on the reaction mechanism support a reaction pathway based on the exchange of the iodine contained in the catalyst by 1 equiv of epoxide, with subsequent attack of I⁻ to the epoxide moiety producing the ring opening of the epoxide. QCCs triggered new insights for the design of more active halide catalysts in future explorations of the field

Development of CIGS2 Thin Films on Ultralightweight Flexible Large Area Foil Sunstrates

The development of thin film solar cells is aimed at reducing the costs for photovoltaic systems. Use of thin film technology and thin foil substrate such as 5-mil thick stainless steel foil or 1-mil thick Ti would result in considerable costs savings. Another important aspect is manufacturing cost. Current single crystal technology for space power can cost more than $300 per watt at the array level and weigh more than 1 kg/sq m equivalent to specific power of approx. 65 W/kg. Thin film material such as CuIn1-xGaxS2 (CIGS2), CuIn(1-x)Ga(x)Se(2-y)S(y) (CIGSS) or amorphous hydrogenated silicon (a-Si:H) may be able to reduce both the cost and mass per unit area by an order of magnitude. Manufacturing costs for solar arrays are an important consideration for total spacecraft budget. For a medium sized 5kW satellite for example, the array manufacturing cost alone may exceed$ 2 million. Moving to thin film technology could reduce this expense to less than $ 500K. Earlier publications have demonstrated the potential of achieving higher efficiencies from CIGSS thin film solar cells on 5-mil thick stainless steel foil as well as initial stages of facility augmentation for depositing thin film solar cells on larger (6 in x 4 in) substrates. This paper presents the developmental study of achieving stress free Mo coating; uniform coatings of Mo back contact and metallic precursors. The paper also presents the development of sol gel process, refurbishment of selenization/sulfurization furnace, chemical bath deposition (CBD) for n-type CdS and scrubber for detoxification of H2S and H2Se gases

Synchronisation in Coupled Sine Circle Maps

We study the spatially synchronized and temporally periodic solutions of a 1-d lattice of coupled sine circle maps. We carry out an analytic stability analysis of this spatially synchronized and temporally periodic case and obtain the stability matrix in a neat block diagonal form. We find spatially synchronized behaviour over a substantial range of parameter space. We have also extended the analysis to higher spatial periods with similar results. Numerical simulations for various temporal periods of the synchronized solution, reveal that the entire structure of the Arnold tongues and the devil's staircase seen in the case of the single circle map can also be observed for the synchronized coupled sine circle map lattice. Our formalism should be useful in the study of spatially periodic behaviour in other coupled map lattices.Comment: uuencoded, 1 rextex file 14 pages, 3 postscript figure

Beta-delayed proton emission in the 100Sn region

Beta-delayed proton emission from nuclides in the neighborhood of 100Sn was studied at the National Superconducting Cyclotron Laboratory. The nuclei were produced by fragmentation of a 120 MeV/nucleon 112Sn primary beam on a Be target. Beam purification was provided by the A1900 Fragment Separator and the Radio Frequency Fragment Separator. The fragments of interest were identified and their decay was studied with the NSCL Beta Counting System (BCS) in conjunction with the Segmented Germanium Array (SeGA). The nuclei 96Cd, 98Ing, 98Inm and 99In were identified as beta-delayed proton emitters, with branching ratios bp = 5.5(40)%, 5.5+3 -2%, 19(2)% and 0.9(4)%, respectively. The bp for 89Ru, 91,92Rh, 93Pd and 95Ag were deduced for the first time with bp = 3+1.9 -1.7%, 1.3(5)%, 1.9(1)%, 7.5(5)% and 2.5(3)%, respectively. The bp = 22(1)% for 101Sn was deduced with higher precision than previously reported. The impact of the newly measured bp values on the composition of the type-I X-ray burst ashes was studied.Comment: 15 pages, 14 Figures, 4 Table

Observation of isotonic symmetry for enhanced quadrupole collectivity in neutron-rich 62,64,66Fe isotopes at N=40

The transition rates for the 2_{1}^{+} states in 62,64,66Fe were studied using the Recoil Distance Doppler-Shift technique applied to projectile Coulomb excitation reactions. The deduced E2 strengths illustrate the enhanced collectivity of the neutron-rich Fe isotopes up to N=40. The results are interpreted by the generalized concept of valence proton symmetry which describes the evolution of nuclear structure around N=40 as governed by the number of valence protons with respect to Z~30. The deformation suggested by the experimental data is reproduced by state-of-the-art shell calculations with a new effective interaction developed for the fpgd valence space.Comment: 4 pages, 2 figure