Two-dimensional interferogram of an exploding selenium foil using asoft X-ray laser interferometer

We have developed a soft X-ray interferometer capable of probing large high-density plasmas with micron spatial resolutions. A neon-like yttrium X-ray laser operating at 155 Å was combined with the Mach-Zehnder interferometer to obtain electron density profiles of a laser-produced exploding selenium foil plasma. The plasma was produced with one Nova laser beam using a 120-μm line focus, the same conditions used to create a selenium X-ray laser. The interferogram of the selenium plasma was obtained from an end-on perspective     

A model for the electron thermal conductivity of a two-component,strongly coupled plasma

An expression for the electron thermal conductivity in the two-component strongly coupled plasmas is derived. The new formulation is examined in the context of laser fusion plasmas, using static correlations derived from the hypernetted chain equations. The model yields results in good agreement with molecular dynamics simulations.     

Anion radical [2 + 2] cycloaddition as a mechanistic probe: stoichiometry- and concentration-dependent partitioning of electron-transfer and alkylation pathways in the reaction of the Gilman reagent Me2CuLi.LiI with bis(enones)

Exposure of easily reduced aromatic bis(enones) 1a-1e to the methyl Gilman reagent Me(2)CuLi.LiI at 0 degrees C in tetrahydrofuran solvent provides the products of tandem conjugate addition-Michael cyclization, 2a-2e, along with the products of [2 + 2] cycloaddition, 3a-3e. Complete partitioning of the Gilman alkylation and [2 + 2] cycloaddition pathways may be achieved by adjusting the loading of the Gilman reagent, the rate of addition of the Gilman reagent, and the concentration of the reaction mixture. The Gilman alkylation manifold is favored by the rapid addition of excess Gilman reagent at higher substrate concentrations, while the [2 + 2] cycloaddition manifold is favored by slow addition of the same Gilman reagent at lower concentrations and loadings. Notably, [2 + 2] cycloaddition to form 3a-3e is catalytic in Gilman reagent. Kinetic data reveal that the ratio of 2a and 3a changes such that the cycloaddition pathway becomes dominant upon increased consumption of Gilman reagent. These data suggest a concentration-dependent speciation of the Gilman reagent and differential reactivity of the aggregates present at higher and lower concentrations. While the species present at higher concentration induce Gilman alkylation en route to products 2a-2e, the species present at lower concentration provide products of catalytic [2 + 2] cycloaddition, 3a-3e. Moreover, upon electrochemical reduction of the bis(enones) 1a-1e, or chemically induced single-electron transfer from arene anion radicals, the very same [2 + 2] cycloadducts 3a-3e are formed. The collective data suggest that [2 + 2] cycloadducts 3a-3e arising under Gilman conditions may be products of anion radical chain cyclobutanation that derive via electron transfer (ET) from the Me(2)CuLi.LiI aggregate(s) present at low concentration. These observations provide a link between the Gilman alkylation reaction and related ET chemistry and suggest these reaction paths are mechanistically distinct. This analysis is made possible by the recent observation that easily reduced bis(enones) are subject to intramolecular [2 + 2] cycloaddition upon cathodic reduction or chemically induced ET from arene anion radicals, and is herewith showcased as a novel method of testing for the intermediacy of enone anion radicals.     

Shock-induced transformation of liquid deuterium into a metallic fluid

Simultaneous measurements of shock velocity and optical reflectance at 1064, 808, and 404 nm of a high pressure shock front propagating through liquid deuterium show a continuous increase in reflectance from below 10% and saturating at approximately (40-60)% in the range of shock velocities from 12 to 20 &mgr;m/ns (pressure range 17-50 GPa). The high optical reflectance is evidence that the shocked deuterium reaches a conducting state characteristic of a metallic fluid. Above 20 &mgr;m/ns shock velocity (50 GPa pressure) reflectance is constant indicating that the transformation is substantially complete.     

Studies on the enantioselective catalysis of photochemically promoted transformations: "sensitizing receptors" as chiral catalysts

A strategy for the enantioselective catalysis of photomediated reactions in solution is described, involving the use of chiral molecular receptors possessing appendant triplet-sensitizing moieties. Energy transfer is selectively directed to bound substrate as a consequence of the distance dependence of triplet-triplet energy transfer. This effect, which is equivalent to a binding-induced rate enhancement, enables substoichiometric chirality transfer from the receptor template to the substrate, as observed in the intramolecular enone-olefin photo[2 + 2]cycloaddition of a quinolone substrate.     

A model for the spectral line polarization shift in dense plasma

The plasma polarization shift (PPS) of spectral lines from hydrogenic ions immersed in a dense hydrogen plasma is examined by using an interaction model that includes the effects of perturbers exterior to the bound electron orbit. The semiclassical model is compared with (a) experimental shifts of Paschen lines in He⁺ at densities of 10¹⁶–10¹⁷ cm^?3 and temperatures of a few eV and (b) self-consistent potential calculations for Lyman α in Ne⁺⁹ and Ar⁺¹⁷ at densities of 10²⁴–10²⁵ cm^?3 and temperatures of 500–2000 eV.