Probing high-barrier pathways of surface reactions by scanning tunneling microscopy

The ability of scanning tunneling microscopy to probe the pathways of thermally activated high-barrier surface processes is frequently limited by competing low-barrier processes that can confuse measurement of the true initial and final configuration. We introduce an approach to circumvent this difficulty by driving the surface process with nanosecond laser heating. The method is applied to determine the pathway of recombinative desorption in the H/Si(001) system. The observed configuration of dangling bonds after laser heating reveals that the desorbed hydrogen molecules are not formed on single dimers, but rather from neighboring silicon dimers via an interdimer reaction pathway.     

The Breakdown of Olivine to Perovskite and Magnesiowustite

San Carlos olivine crystals under laboratory conditions of 26 gigapascals and 973 to 1473 kelvin (conditions typical of subducted slabs at a depth of 720 kilometers) for periods of a few minutes to 19 hours transformed to the phase assemblage of perovskite and magnesiowustite in two stages: (i) the oxygen sublattice transformed into a cubic close-packed lattice, forming a metastable spinelloid, and (ii) at higher temperatures or longer run durations, this spinelloid broke down to perovskite and magnesiowustite by redistributing silicon and magnesium while maintaining the general oxygen framework. The breakdown was characterized by a blocking temperature of 1000 kelvin, below which olivine remained metastable, and by rapid kinetics once the reaction was activated.     

Importance of surface morphology in interstellar H2 formation

Detailed laboratory experiments on the formation of HD from atom recombination on amorphous solid water films show that this process is extremely efficient in a temperature range of 8 to 20 kelvin, temperatures relevant for H2 formation on dust grain surfaces in the interstellar medium (ISM). The fate of the 4.5 electron volt recombination energy is highly dependent on film morphology. These results suggest that grain morphology, rather than the detailed chemical nature of the grain surface, is most important in determining the energy content of the H2 as it is released from the grain into the ISM.     

Melting of (Mg, Fe)SiO3-Perovskite to 625 Kilobars: Indication of a High Melting Temperature in the Lower Mantle

The melting curves of two compositions of (Mg,Fe) SiO3-perovskite, the likely dominant mineral phase in the lower mantle, have been measured in a C02 laser-heated diamond cell with direct temperature measurements and in situ detection of melting. At 625 kilobars, the melting temperature is 5000 +/- 200 kelvin, independent of composition. Extrapolation to the core-mantle boundary pressure of 1.35 megabar with three different melting relations yields melting temperatures between 7000 and 8500 kelvin. Thus, the temperature at the base of the lower mantle, accepted to lie between 2550 and 2750 kelvin, is only at about one-third of the melting temperature. The large difference between mantle temperature and corresponding melting temperature has several important implications; particularly the temperature sensitivity of the viscosity is reduced thus allowing large lateral temperature variations inferred from seismic tomographic velocity anomalies and systematics found in measured velocity-density functions. Extensive melting of the lower mantle can be ruled out throughout the history of the Earth.     

Evidence suggesting superconductivity at 250 k in a sequentially deposited cuprate film

An artificial cuprate compound belonging to the BiSrCaCuO family with eight adjacent sequetially imposed layer epitaxy. This compound undergoes a five order of magnitude resistivity drop with an onset near 280 kelvin and an offset at 250 kelvin. It exhibits a diamagnetic variation of susceptibility and magnetization below 290 kelvin. Additional observed features, such as strongly nonlinear conductivity, suggests superconductivity as a plausible explanation of the properties of this compound.     

Body-centered cubic iron-nickel alloy in Earth's core

Cosmochemical, geochemical, and geophysical studies provide evidence that Earth's core contains iron with substantial (5 to 15%) amounts of nickel. The iron-nickel alloy Fe(0.9)Ni(0.1) has been studied in situ by means of angle-dispersive x-ray diffraction in internally heated diamond anvil cells (DACs), and its resistance has been measured as a function of pressure and temperature. At pressures above 225 gigapascals and temperatures over 3400 kelvin, Fe(0.9)Ni(0.1) adopts a body-centered cubic structure. Our experimental and theoretical results not only support the interpretation of shockwave data on pure iron as showing a solid-solid phase transition above about 200 gigapascals, but also suggest that iron alloys with geochemically reasonable compositions (that is, with substantial nickel, sulfur, or silicon content) adopt the bcc structure in Earth's inner core.     

Spin transition zone in Earth's lower mantle

Mineral properties in Earth's lower mantle are affected by iron electronic states, but representative pressures and temperatures have not yet been probed. Spin states of iron in lower-mantle ferropericlase have been measured up to 95 gigapascals and 2000 kelvin with x-ray emission in a laser-heated diamond cell. A gradual spin transition of iron occurs over a pressure-temperature range extending from about 1000 kilometers in depth and 1900 kelvin to 2200 kilometers and 2300 kelvin in the lower mantle. Because low-spin ferropericlase exhibits higher density and faster sound velocities relative to the high-spin ferropericlase, the observed increase in low-spin (Mg,Fe)O at mid-lower mantle conditions would manifest seismically as a lower-mantle spin transition zone characterized by a steeper-than-normal density gradient.     

Organic globules in the Tagish Lake meteorite: remnants of the protosolar disk

Coordinated transmission electron microscopy and isotopic measurements of organic globules in the Tagish Lake meteorite shows that they have elevated ratios of nitrogen-15 to nitrogen-14 (1.2 to 2 times terrestrial) and of deuterium to hydrogen (2.5 to 9 times terrestrial). These isotopic anomalies are indicative of mass fractionation during chemical reactions at extremely low temperatures (10 to 20 kelvin), characteristic of cold molecular clouds and the outer protosolar disk. The globules probably originated as organic ice coatings on preexisting grains that were photochemically processed into refractory organic matter. The globules resemble cometary carbon, hydrogen, oxygen, and nitrogen (CHON) particles, suggesting that such grains were important constituents of the solar system starting materials.     

Retention of xenon in quartz and Earth's missing xenon

The reactivity of xenon with terrestrial oxides was investigated by in situ synchrotron x-ray diffraction. At high temperature (T > 500 kelvin), some silicon was reduced, and the pressure stability of quartz was expanded, attesting to the substitution of some xenon for silicon. When the quartz was quenched, xenon diffused out and only a few weight percent remained trapped in samples. These results show that xenon can be covalently bonded to oxygen in quartz in the lower continental crust, providing an answer to the missing xenon problem; synthesis paths of rare gas compounds are also opened.     

Molecular dynamics of adsorption and segregation from an alkane mixture

Adsorption and segregation of n-hexadecane molecules from an equal by weight mixture of n-hexadecane and n-hexane to an Au(001) surface at 315 kelvin are studied with the use of molecular dynamics simulations. Preferential adsorption of n-hexadecane at the solid-to-liquid interface together with subsequent layer-by-layer growth of an ordered, wetting interface were observed. The long chains penetrate and adsorb at the interfacial layer by means of a sequential segmental mechanism involving end-segment anchoring and displacive desorption of preadsorbed n-hexane molecules.     

Pressure-induced enhancement of tc above 150 k in hg-1223

The recently discovered homologous series HgBa(2)Can-1 Cun O2n+2+delta possesses remarkable properties. A superconducting transition temperature, T(c), as high as 133 kelvin has been measured in a multiphase Hg-Ba-Ca-Cu-O sample and found to be attributable to the Hg-1223 compound. Temperature-dependent electrical resistivity measurements under pressure on a (> 95%) pure Hg-1223 phase are reported. These data show that T(c) increases steadily with pressure at a rate of about 1 kelvin per gigapascal up to 15 gigapascals, then more slowly and reaches a T(c) = 150 kelvin, with the onset of the transition at 157 kelvin, for 23.5 gigapascals. This large pressure variation (as compared to the small effects observed in similar compounds with the optimal T(c)) strongly suggests that higher critical temperatures could be obtained at atmospheric pressure.     

Titan's atmospheric temperatures, winds, and composition

Temperatures obtained from early Cassini infrared observations of Titan show a stratopause at an altitude of 310 kilometers (and 186 kelvin at 15 degrees S). Stratospheric temperatures are coldest in the winter northern hemisphere, with zonal winds reaching 160 meters per second. The concentrations of several stratospheric organic compounds are enhanced at mid- and high northern latitudes, and the strong zonal winds may inhibit mixing between these latitudes and the rest of Titan. Above the south pole, temperatures in the stratosphere are 4 to 5 kelvin cooler than at the equator. The stratospheric mole fractions of methane and carbon monoxide are (1.6 +/- 0.5) x 10(-2) and (4.5 +/- 1.5) x 10(-5), respectively.     

Direct Radiometric Observations of the Water Vapor Greenhouse Effect Over the Equatorial Pacific Ocean

Airborne radiometric measurements were used to determine tropospheric profiles of the clear sky greenhouse effect. At sea surface temperatures (SSTs) larger than 300 kelvin, the clear sky water vapor greenhouse effect was found to increase with SST at a rate of 13 to 15 watts per square meter per kelvin. Satellite measurements of infrared radiances and SSTs indicate that almost 52 percent of the tropical oceans between 20°N and 20°S are affected during all seasons. Current general circulation models suggest that the increase in the clear sky water vapor greenhouse effect with SST may have climatic effects on a planetary scale.     

Water diffusion and clustering on Pd(111)

The adsorption, diffusion, and clustering of water molecules on a Pd(111) surface were studied by scanning tunneling microscopy. At 40 kelvin, low-coverage water adsorbs in the form of isolated molecules, which diffuse by hopping to nearest neighbor sites. Upon collision, they form first dimers, then trimers, tetramers, and so on. The mobility of these species increased by several orders of magnitude when dimers, trimers, and tetramers formed, and decreased again when the cluster contained five or more molecules. Cyclic hexamers were found to be particularly stable. They grow with further exposure to form a commensurate hexagonal honeycomb structure relative to the Pd(111) substrate. These observations illustrate the change in relative strength between intermolecular hydrogen bonds and molecule-substrate bonds as a function of water cluster size, the key property that determines the wetting properties of materials.     

Mercury-Based Cuprate High-Transition Temperature Grain-Boundary Junctions and SQUIDs Operating Above 110 Kelvin

The superconducting transport characteristics of HgBa(2) CaCu(2)O(6+delta) (Hg-1212) films and grain-boundary junctions grown on (100)-oriented SrTiO(3) bicrystal substrates have been investigated. The films exhibit a zero-resistance temperature of approximately 120 kelvin and sustain large critical current densities, with values as high as 10(6) amperes per square centimeter at around 100 kelvin. On the other hand, the grain boundaries behave as weak links, with substantially lower critical currents, as is observed for other cuprate superconductors. A reduction of three orders of magnitude in critical current was observed for transport across a 36.8 degrees grain boundary. The current-voltage characteristics of bridges across such a grain boundary show weak-link behavior qualitatively resembling that of a resistively shunted junction. Single-level direct-current superconducting quantum interference devices (SQUIDs) have been fabricated with such bicrystal junctions. These SQUIDs show clear periodic voltage modulations when subjected to applied magnetic fields. The SQUIDs operate at temperatures as high as 111.8 kelvin, which makes them attractive for operation in portable sensors and devices that utilize nonconventional cooling methods.     

Melting of (Mg,Fe)2SiO4 at the Core-Mantle Boundary of the Earth

The lower mantle of the Earth is believed to be largely composed of (Mg,Fe)O (magnesiowustite) and (Mg,Fe)SiO3 (perovskite). Radiative temperatures of single-crystal olivine [(Mg0.9,Fe0.1)2SiO4] decreased abruptly from 7040 +/- 315 to 4300 +/- 270 kelvin upon shock compression above 80 gigapascals. The data indicate that an upper bound to the solidus of the magnesiowustite and perovskite assemblage at 4300 +/- 270 kelvin is 130 +/- 3 gigapascals. These conditions correspond to those for partial melting at the base of the mantle, as has been suggested occurs within the ultralow-velocity zone beneath the central Pacific.     

Solidus of Earth's deep mantle

The solidus of a pyrolite-like composition, approximating that of the lower mantle, was measured up to 59 gigapascals by using CO2 laser heating in a diamond anvil cell. The solidus temperatures are at least 700 kelvin below the melting temperatures of magnesiowustite, which in the deep mantle has the lowest melting temperatures of the three major components-magnesiowustite, Mg-Si-perovskite, and Ca-Si-perovskite. The solidus in the deep mantle is more than 1500 kelvin above the average present-day geotherm, but at the core-mantle boundary it is near the core temperature. Thus, partial melting of the mantle is possible at the core-mantle boundary.     

Io's thermal emission from the Galileo photopolarimeter-radiometer

Galileo's photopolarimeter-radiometer instrument mapped Io's thermal emission during the I24, I25, and I27 flybys with a spatial resolution of 2.2 to 300 kilometers. Mapping of Loki in I24 shows uniform temperatures for most of Loki Patera and high temperatures in the southwest corner, probably resulting from an eruption that began 1 month before the observation. Most of Loki Patera was resurfaced before I27. Pele's caldera floor has a low temperature of 160 kelvin, whereas flows at Pillan and Zamama have temperatures of up to 200 kelvin. Global maps of nighttime temperatures provide a means for estimating global heat flow.     

A low-operating-temperature solid oxide fuel cell in hydrocarbon-Air mixtures

The performance of a single-chamber solid oxide fuel cell was studied using a ceria-based solid electrolyte at temperatures below 773 kelvin. Electromotive forces of approximately 900 millivolts were generated from the cell in a flowing mixture of ethane or propane and air, where the solid electrolyte functioned as a purely ionic conductor. The electrode-reaction resistance was negligibly small in the total internal resistances of the cell. The resulting peak power density reached 403 and 101 milliwatts per square centimeter at 773 and 623 kelvin, respectively.     

Large-scale thermal events in the solar nebula: evidence from Fe,Ni metal grains in primitive meteorites

Chemical zoning patterns in some iron, nickel metal grains from CH carbonaceous chondrites imply formation at temperatures from 1370 to 1270 kelvin by condensation from a solar nebular gas cooling at a rate of approximately 0.2 kelvin per hour. This cooling rate requires a large-scale thermal event in the nebula, in contrast to the localized, transient heating events inferred for chondrule formation. In our model, mass accretion through the protoplanetary disk caused large-scale evaporation of precursor dust near its midplane inside of a few astronomical units. Gas convectively moved from the midplane to cooler regions above it, and the metal grains condensed in these parcels of rising gas.