Hydrogen adsorption in the metal-organic frameworks Fe2(dobdc) and Fe2(O2)(dobdc)

The hydrogen storage properties of Fe(2)(dobdc) (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) and an oxidized analog, Fe(2)(O(2))(dobdc), have been examined using several complementary techniques, including low-pressure gas adsorption, neutron powder diffraction, and inelastic neutron scattering. These two metal-organic frameworks, which possess one-dimensional hexagonal channels decorated with unsaturated iron coordination sites, exhibit high initial isosteric heats of adsorption of -9.7(1) and -10.0(1) kJ mol(-1), respectively. Neutron powder diffraction has allowed the identification of three D(2) binding sites within the two frameworks, with the closest contacts corresponding to Fe-D(2) separations of 2.47(3) and 2.53(5) ?, respectively. Inelastic neutron scattering spectra, obtained from p-H(2) (para-H(2)) and D(2)-p-H(2) mixtures adsorbed in Fe(2)(dobdc), reveal weak interactions between two neighboring adsorption sites, a finding that is in opposition to a previous report of possible 'pairing' between neighboring H(2) molecules.     

Erratum to: The Asymptotic Distribution of Self-Normalized Triangular Arrays

We correct and clarify some ambiguous statements in D. M. Mason (2005): The asymptotic distribution of self-normalized triangular arrays. J. Theoret. Probab., 18, 853–870.     

Group invariant solution for a pre-existing fracture driven by a power-law fluid in impermeable rock

The effect of power-law rheology on hydraulic fracturing is investigated. The evolution of a two-dimensional fracture with non-zero initial length and driven by a power-law fluid is analyzed. Only fluid injection into the fracture is considered. The surrounding rock mass is impermeable. With the aid of lubrication theory and the PKN approximation a partial differential equation for the fracture half-width is derived. Using a linear combination of the Lie-point symmetry generators of the partial differential equation, the group invariant solution is obtained and the problem is reduced to a boundary value problem for an ordinary differential equation. Exact analytical solutions are derived for hydraulic fractures with constant volume and with constant propagation speed. The asymptotic solution near the fracture tip is found. The numerical solution for general working conditions is obtained by transforming the boundary value problem to a pair of initial value problems. Throughout the paper, hydraulic fracturing with shear thinning, Newtonian and shear thickening fluids are compared.     

Organic mass spectrometry and control of fragmentation using a fast flow glow discharge ion source

Representative organic vapors have been introduced into the flowing afterglow of a low power (<5 W) dc-glow discharge, coupled to a quadrupole mass spectrometer. When a positive bias was applied to the ion sampling orifice, the very surprising result was that molecular mass spectra were obtained with a high sensitivity. When a negative bias was applied to the ion sampling orifice, fragmentation of the analyte was observed with an increase in the extent of ion dissociation as the voltage was increased. The breakdown pattern is compound-specific and would be useful in confirming the identity of an unknown sample. When combined with chromatographic separation, the FFGD-MS technique could be used for chemical speciation studies at the sub-picogram level.     

Folding of viscous threads in diverging microchannels

We study the folding instability of a viscous thread surrounded by a less viscous miscible liquid flowing from a square to a diverging microchannel. Because of the change in the flow introduced by the diverging channel, the viscous thread minimizes viscous dissipation by oscillating to form bends rather than by simply dilating. The folding frequency and the thread diameter can be related to the volume flow rates and thus to the characteristic shear rate. Diffusive mixing at the boundary of the thread can significantly modify the folding flow morphologies. This microfluidic system enables us to control the bending of the thread and to enhance mixing between liquids having significantly different viscosities.     

Heating mechanisms in short-pulse laser-driven cone targets

The fast ignitor is a modern approach to laser fusion that uses a short-pulse laser to initiate thermonuclear burn. In its simplest form the laser launches relativistic electrons that carry its energy to a precompressed fusion target. Cones have been used to give the light access to the dense target core through the low-density ablative cloud surrounding it. Here the ANTHEM implicit hybrid simulation model shows that the peak ion temperatures measured in recent cone target experiments arose chiefly from return current joule heating, mildly supplemented by relativistic electron drag. Magnetic fields augment this heating only slightly, but capture hot electrons near the cone surface and force the hot electron stream into filaments.     

Dense cluster formation during aggregation and gelation of attractive slippery nanoemulsion droplets

Using time-resolved small angle neutron scattering, we have measured the wave-number-dependent structure factor S(q) of monodisperse nanoemulsions that aggregate and gel after we suddenly turn on a strong, short-range, slippery attraction between the droplets. At high q, peaks in S(q) appear as dense clusters of droplets form, and S(q) increases strongly toward low q, as these dense clusters become locked into a rigid gel network, despite the fluidity of the films between the droplets. The long-time high-q structure of nanoemulsion gels formed by slippery diffusion-limited cluster aggregation is universal in shape and remarkably independent of the droplet volume fraction, phi.     

VUV photoabsorption spectroscopy of sulfur dioxide ice

In this paper we present the first study of the VUV photoabsorption spectrum of condensed phase SO(2) recorded over the VUV region 120 to 320 nm (10.33 to 3.64 eV). Distinct spectral features were observed that can be used to distinguish between the formation of amorphous and crystalline ice structures. These signatures may then be used to probe the formation of different ice structures as a function of both deposition rate and substrate temperature.     

VUV electronic state spectroscopy of 1,1-difluoroethene and difluorochloromethane by high resolution synchrotron radiation

High resolution VUV photoabsorption spectra of 1,1-difluoroethene (C(2)H(2)F(2)) and difluorochloromethane (CF(2)HCl) are reported in the wavelength range 115-200 nm (10.8-6.2 eV). New photoabsorption features are observed in C(2)H(2)F(2) and some Rydberg and vibrational assignments are proposed for the first time. Evidence for a weak vibrational pattern in CF(2)HCl is discussed here for the first time. Absolute cross section values have been obtained allowing photolysis lifetimes to be derived in the Earth's troposphere and stratosphere.     

Photophysical properties of dioxolane-substituted pentacene derivatives dispersed in tris(quinolin-8-olato)aluminum(III)

Two novel dioxolane-substituted pentacene derivatives, namely, 6,14-bis-(triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m]pentacene (TP-5) and 2,2,10,10-tetraethyl-6,14-bis-(triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m]pentacene (EtTP-5), have been synthesized and spectroscopically characterized. Here, we examine the steady-state and time-resolved photoluminescence (PL) of solid-state composite films containing these pentacene derivatives dispersed in tris(quinolin-8-olato)aluminum(III) (Alq(3)). The films show narrow red emission and high absolute photoluminescence quantum yields (phi(PL) = 59% and 76% for films containing approximately 0.25 mol % TP-5 and EtTP-5, respectively). The F?rster transfer radius for both guest-host systems is estimated to be approximately 33 A. The TP-5/Alq(3) thin films show a marked decrease in phi(PL) with increasing guest molecule concentrations, accompanied by dramatic changes in the PL spectra, suggesting that intermolecular interactions between pentacene molecules result in the formation of weakly radiative aggregates. In contrast, a lesser degree of fluorescence quenching is observed for EtTP-5/Alq(3) films. The measured fluorescence lifetimes of TP-5 and EtTP-5 are similar (approximately 18 ns) at low concentrations but deviate at higher concentrations as aggregation begins to play a role in the TP-5/Alq(3) films. The onset of aggregation in EtTP-5/Alq(3) films occurs at higher guest molecule concentrations (>1.00 mol %). The addition of ethyl groups on the terminal dioxolane rings leads to an increase in the intermolecular spacing in the solid, thereby reducing the tendency for pi-pi molecular stacking and aggregation.