An Analysis of Limited Maritime War

Limited maritime war is a promising area for investigation for two reasons. First, it is one of the two major nonstrategic-nuclear war scenarios upon which the naval planning of the United States is based

Long-Range Proton-Coupled Electron-Transfer Reactions of Bis(imidazole) Iron Tetraphenylporphyrins Linked to Benzoates

Concerted proton–electron transfer (CPET) reactions in iron carboxytetraphenylporphyrin complexes have been investigated using both experimental and theoretical methods. Synthetic heme models abstract H+ and e– from the hydroxylamine TEMPOH or an ascorbate derivative, and the kinetics of the TEMPOH reaction indicate concerted transfer of H+ and e–. Phenylene linker domains vary the electron donor/acceptor separation by approximately 4 Å. The rate data and extensive molecular simulations show that the electronic coupling decay constant (β) depends on conformational flexibility and solvation associated with the linker domain. Our best estimate of β is 0.23 ± 0.07 Å^(–1), a value that is near the low end of the range (0.2–0.5 Å^(–1)) established for electron-transfer reactions involving related linkers. This is the first analysis of β for a CPET reaction

Capabilities, Design, Construction and Commissioning of New Vibration, Acoustic, and Electromagnetic Capabilities Added to the World's Largest Thermal Vacuum Chamber at NASA's Space Power Facility

NASA s human space exploration plans developed under the Exploration System Architecture Studies in 2005 included a Crew Exploration Vehicle launched on an Ares I launch vehicle. The mass of the Crew Exploration Vehicle and trajectory of the Ares I coupled with the need to be able to abort across a large percentage of the trajectory generated unprecedented testing requirements. A future lunar lander added to projected test requirements. In 2006, the basic test plan for Orion was developed. It included several types of environment tests typical of spacecraft development programs. These included thermal-vacuum, electromagnetic interference, mechanical vibration, and acoustic tests. Because of the size of the vehicle and unprecedented acoustics, NASA conducted an extensive assessment of options for testing, and as result, chose to augment the Space Power Facility at NASA Plum Brook Station, of the John H. Glenn Research Center to provide the needed test capabilities. The augmentation included designing and building the World s highest mass capable vibration table, the highest power large acoustic chamber, and adaptation of the existing World s largest thermal vacuum chamber as a reverberant electromagnetic interference test chamber. These augmentations were accomplished from 2007 through early 2011. Acceptance testing began in Spring 2011 and will be completed in the Fall of 2011. This paper provides an overview of the capabilities, design, construction and acceptance of this extraordinary facility

High Aspect Ratio Silicon Wire Array Photoelectrochemical Cells

In an effort to develop low-cost solar energy conversion techniques, high uniformity vertically oriented silicon wire arrays have been fabricated. These arrays, which allow for radial diffusion of minority charge carriers, have been measured in a photoelectrochemical cell. Large photovoltages (∼400 mV) have been measured, and these values are significantly greater than those obtained from the substrate alone. Additionally, the wire array samples displayed much higher current densities than the underlying substrate, demonstrating that significant energy conversion was occurring due to the absorption and charge-carrier transport in the vertically aligned Si wires. This method therefore represents a step toward the use of collection-limited semiconductor materials in a wire array format in macroscopic solar cell devices

Proton–hydride tautomerism in hydrogen evolution catalysis

Efficient generation of hydrogen from renewable resources requires development of catalysts that avoid deep wells and high barriers. Information about the energy landscape for H_2 production can be obtained by chemical characterization of catalytic intermediates, but few have been observed to date. We have isolated and characterized a key intermediate in 2e^– + 2H^+ → H_2 catalysis. This intermediate, obtained by treatment of Cp*Rh(bpy) (Cp*, η^5-pentamethylcyclopentadienyl; bpy, κ^2-2,2′-bipyridyl) with acid, is not a hydride species but rather, bears [η^4-Cp*H] as a ligand. Delivery of a second proton to this species leads to evolution of H_2 and reformation of η^5-Cp* bound to rhodium(III). With suitable choices of acids and bases, the Cp*Rh(bpy) complex catalyzes facile and reversible interconversion of H^+ and H_2

Photoanodic behavior of vapor-liquid-solid–grown, lightly doped, crystalline Si microwire arrays

Arrays of n-Si microwires have to date exhibited low efficiencies when measured as photoanodes in contact with a 1-1′-dimethylferrocene (Me_2Fc^(+/0))–CH_3OH solution. Using high-purity Au or Cu catalysts, arrays of crystalline Si microwires were grown by a vapor-liquid-solid process without dopants, which produced wires with electronically active dopant concentrations of 1 × 10^(13) cm^(−3). When measured as photoanodes in contact with a Me_2Fc^(+/0)–CH_3OH solution, the lightly doped Si microwire arrays exhibited greatly increased fill factors and efficiencies as compared to n-Si microwires grown previously with a lower purity Au catalyst. In particular, the Cu-catalyzed Si microwire array photoanodes exhibited open-circuit voltages of ~0.44 V, carrier-collection efficiencies exceeding ~0.75, and an energy-conversion efficiency of 1.4% under simulated air mass 1.5 G illumination. Lightly doped Cu-catalyzed Si microwire array photoanodes have thus demonstrated performance that is comparable to that of optimally doped p-type Si microwire array photocathodes in photoelectrochemical cells

Characterization and petrologic interpretation of olivine-rich basalts at Gusev Crater, Mars

Rocks on the floor of Gusev crater are basalts of uniform composition and mineralogy. Olivine, the only mineral to have been identified or inferred from data by all instruments on the Spirit rover, is especially abundant in these rocks. These picritic basalts are similar in many respects to certain Martian meteorites (olivine-phyric shergottites). The olivine megacrysts in both have intermediate compositions, with modal abundances ranging up to 20–30%. Associated minerals in both include low-calcium and highcalcium pyroxenes, plagioclase of intermediate composition, iron-titanium-chromium oxides, and phosphate. These rocks also share minor element trends, reflected in their nickel-magnesium and chromium-magnesium ratios. Gusev basalts and shergottites appear to have formed from primitive magmas produced by melting an undepleted mantle at depth and erupted without significant fractionation. However, apparent differences between Gusev rocks and shergottites in their ages, plagioclase abundances, and volatile contents preclude direct correlation. Orbital determinations of global olivine distribution and compositions by thermal emission spectroscopy suggest that olivine-rich rocks may be widespread. Because weathering under acidic conditions preferentially attacks olivine and disguises such rocks beneath alteration rinds, picritic basalts formed from primitive magmas may even be a common component of the Martian crust formed during ancient and recent times.Additional co-authors: PR Christensen, BC Clark, JA Crisp, DJ DesMarais, T Economou, JD Farmer, W Farrand, A Ghosh, M Golombek, S Gorevan, R Greeley, VE Hamilton, JR Johnson, BL Joliff, G Klingelhöfer, AT Knudson, S McLennan, D Ming, JE Moersch, R Rieder, SW Ruff, PA de Souza Jr, SW Squyres, H Wnke, A Wang, A Yen, J Zipfe

Morphology and Composition of the Surface of Mars: Mars Odyssey THEMIS Results

The Thermal Emission Imaging System (THEMIS) on Mars Odyssey has produced infrared to visible wavelength images of the martian surface that show lithologically distinct layers with variable thickness, implying temporal changes in the processes or environments during or after their formation. Kilometer-scale exposures of bedrock are observed; elsewhere airfall dust completely mantles the surface over thousands of square kilometers. Mars has compositional variations at 100-meter scales, for example, an exposure of olivine-rich basalt in the walls of Ganges Chasma. Thermally distinct ejecta facies occur around some craters with variations associated with crater age. Polar observations have identified temporal patches of water frost in the north polar cap. No thermal signatures associated with endogenic heat sources have been identified