The structures of higher boron halides B8X12(X = F, Cl, Br and I) by gas-phase electron diffraction and ab initio calculations

The structure of B8F12 has been shown by gas electron diffraction and computational methods (up to MP2/6-31+G*) to have the same highly asymmetric form observed in crystalline phases. The structure can be regarded as derived from a central B2 group, bridged by two BF2 groups to give a central B4 core that is folded, not planar, and with a very short bond [164.3 pm calculated, 164.2(19) pm experimental] along the fold line. There are also four terminal BF2 groups. One of the other four bonds in the core is consistently 20-30 pm longer than the others. This asymmetry has been attributed to many intra-molecular B...F interactions, particularly those between core boron atoms and fluorines of the terminal BF2 groups. Calculations for the chloro analogue lead to a structure similar to that for B8F12, but with the long core bond extended so that one of the bridging BCl2 groups may now be regarded as terminal. With bromine as the halogen the structure changes again, with one bromine atom taking up a bridging position. With iodine, this process continues further, and there are three bridging iodine atoms. However, in this case this is not the lowest energy structure, and instead a loosely associated dimer of B4I6 is preferred. In all these cases, and particularly with the heavier halogens, there are huge differences between the results obtained with different computational methods.     

Precision model independent determination of |Vub| from B --> pilnu

A precision method for determining |V(ub)| using the full range in q(2) of B --> pilnu data is presented. At large q(2) the form factor is taken from unquenched lattice QCD, at q(2) = 0 we impose a model independent constraint obtained from B --> pipi using the soft-collinear effective theory, and the shape is constrained using QCD dispersion relations. We find |V(ub)| = (3.54 +/- 0.170 +/- 0.44) x 10(-3). With 5% experimental error and 12% theory error, this is competitive with inclusive methods. Theory error is dominated by the input points, with negligible uncertainty from the dispersion relations.     

The structural and spectroscopic characterisation of three actinyl complexes with coordinated and uncoordinated perrhenate: [UO2(ReO4)2(TPPO)3], [[(UO2)(TPPO)3]2(mu2-O2)][ReO4]2 and [NpO2(TPPO)4][ReO4

The first structural characterization of an actinide complex with coordinated perrhenate is reported, [UO2(ReO4)2(TPPO)3] (1). In this [UO2]2+ complex two [ReO4]- anions and three TPPO (triphenylphosphine oxide) P=O donor ligands are coordinated in the equatorial plane in a cisoid arrangement. This bonding arrangement, and apparent strain observed in the equatorially bonded ligands, is attributed to the solid state packing in adjacent molecules in which hydrophobic TPPO ligands form an effective "shell" around a hydrophilic core of two UO2(ReO4)2 moieties. Solid state vibrational spectroscopy (infrared and Raman), 31P CP MAS NMR and elemental analysis are also consistent with the formula of 1. Solution state vibrational spectroscopy and 31P NMR measurements in EtOH indicate the lability of the TPPO and [ReO4]- groups. The photolytic generation of peroxide in EtOH solutions of 1 leads to the formation of trace quantities of [[(UO2)(TPPO)3]2(mu2-O2)][ReO4]2, 2, in which the coordinated [ReO4]- groups of 1 have been displaced by bridging O2(2-), derived from atmospheric O2. Finally, attempts to synthesise a [NpO2]+ analogue of have resulted only in the formation of [NpO2(TPPO)4][ReO4], 3, in which [ReO4]- acts solely as a counter anion. From these results it can be concluded that [ReO4]- will bond to [UO2]2+, but will be readily displaced by a more strongly coordinating ligand (e.g. peroxide) and will not coordinate to an actinyl cation with a lower charge, [NpO2]+, under the same reaction conditions.     

Fine structure in proton emission from 145Tm discovered with digital signal processing

Fine structure in proton emission from the 3.1(3) mus activity of 145Tm was discovered by using a novel technique of digital processing of overlapping recoil implantation and decay signals. Proton transitions to the ground state of 144Er and to its first excited 2(+) state at 0.33(1) MeV with a branching ratio I(p)(2(+))=9.6+/-1.5% were observed. The structure of the 145Tm wave function and the emission process were analyzed by using particle-core vibration coupling models.     

Two-photon microscopy of fura-2-loaded cardiac myocytes with an all-solid-state tunable and visible femtosecond laser source

We report a robust and reliable platform source for visible-wavelength multiphoton microscopy that is based on nonlinear optical methods. We demonstrate a synchronously pumped, singly resonant optical parametric oscillator with simultaneous intracavity third-order quasi-phase matching in a single crystal that generates continuously tunable, visible, and femtosecond-pulsed radiation. The application of the system is demonstrated by two-photon laser-scanning fluorescence microscopy of rabbit cardiac myocytes loaded with the fluorescent Ca2+ indicator fura-2.     

Dyad beads and the combinatorial discovery of catalysts

Dyad beads, bearing both a substrate and a catalyst, were prepared to enable direct split and mix bead based screening for catalysis.     

The preparation of hexasilsesquioxane (T6) cages by "non aqueous" hydrolysis of trichlorosilanes

Hexasilsesquioxane cages (T6) have been prepared from a range of alkyl and aryl trichlorosilanes using a "non aqueous" hydrolysis with dimethyl sulfoxide.     

An equivariant Brauer semigroup and the symmetric imprimitivity theorem

Suppose that is a second countable locally compact transformation group. We let denote the set of Morita equivalence classes of separable dynamical systems where is a -algebra and is compatible with the given -action on . We prove that is a commutative semigroup with identity with respect to the binary operation for an appropriately defined balanced tensor product on -algebras. If and act freely and properly on the left and right of a space , then we prove that and are isomorphic as semigroups. If the isomorphism maps the class of to the class of , then is Morita equivalent to .

     

Phonon screening in high-temperature superconductors

In good conductors optical phonons are usually screened, and therefore not observed. However, sharp features due to infrared-active modes in the copper-oxygen planes are observed in the optical conductivity of Pr1.85Ce0.15CuO4 and YBa2Cu3O6.95. Oscillator strengths indicate that the screening of these modes is poor or totally absent. These materials are compared with eta-Mo4O11, in which lattice modes appear suddenly below the charge-density wave transition. It is proposed that poor screening in the cuprates originates from fluctuating charge inhomogeneities in the copper-oxygen planes.