Transferability of some properties of localized molecular orbitals

The localized molecular orbitals of some related ten- and eighteen-electron systems have been studied. The transferability of the kinetic, self-interaction, Coulomb and exchange interaction energies on localized orbitals have been shown. The standard deviation of the kinetic and of the interaction energies (including exchange) are less than 2.5% except for lone pair orbitals of the oxygen atoms where the standard deviation is close to 4%.     

Nondiffusive spin dynamics in a two-dimensional electron gas

We describe measurements of spin dynamics in the two-dimensional electron gas in GaAs/GaAlAs quantum wells. Optical techniques, including transient spin-grating spectroscopy, are used to probe the relaxation rates of spin polarization waves in the wave vector range from zero to 6x10(4) cm-1. We find that the spin polarization lifetime is maximal at a nonzero wave vector, in contrast with expectations based on ordinary spin diffusion, but in quantitative agreement with recent theories that treat diffusion in the presence of spin-orbit coupling.     

Transition quadrupole moments of superdeformed states in194Pb

Lifetimes of superdeformed states in¹⁹⁴Pb were measured by the Doppler-shift attenuation method. Quadrupole moments around 20 eb, that are constant over the observed frequency range, are derived. The results rule out large centrifugal stretching effects.     

Diffusive flux of nanoparticles through chemically modified alumina membranes

Surface chemistry plays an important role in determining flux through porous media such as in the environment. In this paper diffusive flux of nanoparticles through alkylsilane modified porous alumina is measured as a model for understanding transport in porous media of differing surface chemistries. Experiments are performed as a function of particle size, pore diameter, attached hydrocarbon chain length and chain terminus, and solvent. Particle fluxes are monitored by the change in absorbance of the solution in the receiving side of a diffusion cell. In general, flux increases when the membranes are modified with alkylsilanes compared to untreated membranes, which is attributed to the hydrophobic nature of the porous membranes and differences in wettability. We find that flux decreases, in both hexane and aqueous solutions, when the hydrocarbon chain lining the interior pore wall increases in length. The rate and selectivity of transport across these membranes is related to the partition coefficient (K(p)) and the diffusion coefficient (D) of the permeating species. By conducting experiments as a function of initial particle concentration, we find that K(p)D increases with increasing particle size, is greater in alkylsilane-modified pores, and larger in hexane solution than water. The impact of the alkylsilane terminus (-CH(3), -Br, -NH(2), -COOH) on permeation in water is also examined. In water, the highest K(p)D is observed when the membranes are modified with carboxylic acid terminated silanes and lowest with amine terminated silanes as a result of electrostatic effects during translocation.     

The steady shear viscosity of filled polymeric liquids described by a linear superposition of two relaxation mechanisms

Filled polymeric liquids often exhibit apparent yielding and shear thinning in steady shear flow. Yielding results from non-hydrodynamic particle—particle interactions, while shear thinning results from the non-Newtonian behavior of the polymer melt. A simple equation, based on the linear superposition of two relaxation mechanisms, is proposed to describe the viscosity of filled polymer melts over a wide range of shear rates and filler volume fraction.The viscosity is written as the sum of two generalized Newtonian liquid models. The resulting equation can describe a wide range of shear-thinning viscosity curves, and a hierarchy of equations is obtained by simplifying the general case. Some of the parameters in the equation can be related to the properties of the unfilled liquid and the solid volume fraction. One adjustable parameter, a yield stress, is necessary to describe the viscosity at low rates where non-hydrodynamic particle—particle interaction dominate. At high shear rates, where particle—particle interactions are dominated by interparticle hydrodynamics, no adjustable parameters are necessary. A single equation describes both the high and low shear rate regimes. Predictions of the equation closely fit published viscosity data of filled polymer melts. n power-law index - n ₁,n ₂ power-law index of first (second) term - shear rate - steady shear viscosity - ₀ zero-shear rate viscosity - _{0, 1}, _{0, 2} zero-shear rate viscosity of first (second) term - time constant - ₁, ₂ time constant of first (second) term - µ _r relative viscosity of filled Newtonian liquid - ₀ yield stress - ø solid volume fraction - ø _m maximum solid volume fraction     

An intramolecular N‐arylation approach to 3‐functionalized 4,9‐dihydropyrrolo[2,1‐b]quinazolines

A series of 4,9‐dihydropyrrolo[2,1‐b]quinazolines containing electron withdrawing groups at the 3‐position have been prepared by the palladium‐catalyzed intramolecular N‐arylation of some 2‐aminopyrroles having a 2‐bromobenzyl group at the N‐1 position. Important for success of the reaction is the use of X‐phos, a biphenyl mono‐phosphine ligand, instead of xantphos, a more standard diphosphine ligand, and the use of t‐BuOH as reaction solvent. J. Heterocyclic Chem., (2011).