Energetic neutral atom emissions from Titan interaction with Saturn's magnetosphere

The Cassini Magnetospheric Imaging Instrument (MIMI) observed the interaction of Saturn's largest moon, Titan, with Saturn's magnetosphere during two close flybys of Titan on 26 October and 13 December 2004. The MIMI Ion and Neutral Camera (INCA) continuously imaged the energetic neutral atoms (ENAs) generated by charge exchange reactions between the energetic, singly ionized trapped magnetospheric ions and the outer atmosphere, or exosphere, of Titan. The images reveal a halo of variable ENA emission about Titan's nearly collisionless outer atmosphere that fades at larger distances as the exospheric density decays exponentially. The altitude of the emissions varies, and they are not symmetrical about the moon, reflecting the complexity of the interactions between Titan's upper atmosphere and Saturn's space environment.     

Contact electrification and adhesion between dissimilar materials

Simultaneous measurements of surface force and surface charge demonstrate strong attraction due to the spontaneous transfer of electrical charge from one smooth insulator (mica) to another (silica) as a result of simple, nonsliding contact in dry nitrogen. The measured surface charge densities are 5 to 20 millicoulombs per square meter after contact. The work required to separate the charged surfaces is typically 6 to 9 joules per square meter, comparable to the fracture energies of ionic-covalent materials. Observation of partial gas discharges when the surfaces are approximately 1 micrometer apart gives valuable insight into the charge separation processes underlying static electrical phenomena in general.     

Extreme ultraviolet observations from voyager 1 encounter with saturn

The global hydrogen Lyman alpha, helium (584 angstroms), and molecular hydrogen band emissions from Saturn are qualitatively similar to those of Jupiter, but the Saturn observations emphasize that the H(2) band excitation mechanism is closely related to the solar flux. Auroras occur near 80 degrees latitude, suggesting Earth-like magnetotail activity, quite different from the dominant Io plasma torus mechanism at Jupiter. No ion emissions have been detected from the magnetosphere of Saturn, but the rings have a hydrogen atmosphere; atomic hydrogen is also present in a torus between 8 and 25 Saturn radii. Nitrogen emission excited by particles has been detected in the Titan dayglow and bright limb scans. Enhancement of the nitrogen emission is observed in the region of interaction between Titan's atmosphere and the corotating plasma in Saturn's plasmasphere. No particle-excited emission has been detected from the dark atmosphere of Titan. The absorption profile of the atmosphere determined by the solar occultation experiment, combined with constraints from the dayglow observations and temperature information, indicate that N(2) is the dominant species. A double layer structure has been detected above Titan's limb. One of the layers may be related to visible layers in the images of Titan.     

Selective bond dissociation and rearrangement with optimally tailored, strong-field laser pulses

We used strong-field laser pulses that were tailored with closed-loop optimal control to govern specified chemical dissociation and reactivity channels in a series of organic molecules. Selective cleavage and rearrangement of chemical bonds having dissociation energies up to approximately 100 kilocalories per mole (about 4 electron volts) are reported for polyatomic molecules, including (CH3)2CO (acetone), CH3COCF3 (trifluoroacetone), and C6H5COCH3 (acetophenone). Control over the formation of CH(3)CO from (CH3)2CO, CF3 (or CH3) from CH3COCF3, and C6H5CH3 (toluene) from C6H5COCH3 was observed with high selectivity. Strong-field control appears to have generic applicability for manipulating molecular reactivity because the tailored intense laser fields (about 10(13) watts per square centimeter) can dynamically Stark shift many excited states into resonance, and consequently, the method is not confined by resonant spectral restrictions found in the perturbative (weak-field) regime.     

Hot Plasma and Energetic Particles in Neptune's Magnetosphere

The low-energy charged particle (LECP) instrument on Voyager 2 measured within the magnetosphere of Neptune energetic electrons (22 kiloelectron volts /=0.5 MeV per nucleon) energies, using an array of solid-state detectors in various configurations. The results obtained so far may be summarized as follows: (i) A variety of intensity, spectral, and anisotropy features suggest that the satellite Triton is important in controlling the outer regions of the Neptunian magnetosphere. These features include the absence of higher energy (>/=150 keV) ions or electrons outside 14.4 R(N) (where R(N) = radius of Neptune), a relative peak in the spectral index of low-energy electrons at Triton's radial distance, and a change of the proton spectrum from a power law with gamma >/= 3.8 outside, to a hot Maxwellian (kT [unknown] 55 keV) inside the satellite's orbit. (ii) Intensities decrease sharply at all energies near the time of closest approach, the decreases being most extended in time at the highest energies, reminiscent of a spacecraft's traversal of Earth's polar regions at low altitudes; simultaneously, several spikes of spectrally soft electrons and protons were seen (power input approximately 5 x 10(-4) ergs cm(-2) s(-1)) suggestive of auroral processes at Neptune. (iii) Composition measurements revealed the presence of H, H(2), and He(4), with relative abundances of 1300:1:0.1, suggesting a Neptunian ionospheric source for the trapped particle population. (iv) Plasma pressures at E >/= 28 keV are maximum at the magnetic equator with beta approximately 0.2, suggestive of a relatively empty magnetosphere, similar to that of Uranus. (v) A potential signature of satellite 1989N1 was seen, both inbound and outbound; other possible signatures of the moons and rings are evident in the data but cannot be positively identified in the absence of an accurate magnetic-field model close to the planet. Other results indude the absence of upstream ion increases or energetic neutrals [particle intensity (j) < 2.8 x 10(-3) cm(-2) s(-1) keV(-1) near 35 keV, at approximately 40 R(N)] implying an upper limit to the volume-averaged atomic H density at R 22 keV) input on Neptune is approximately 3 x 10(7) W, surprisingly small when compared to energy input into the atmosphere of Jupiter, Saturn, and Uranus.     

Isotopic composition of nitrogen: implications for the past history of mars' atmosphere

Models are presented for the past history of nitrogen on Mars based on Viking measurements showing that the atmosphere is enriched in (15)N. The enrichment is attributed to selective escape, with fast atoms formed in the exosphere by electron impact dissociation of N(2) and by dissociative recombination of N(2)(+). The initial partial pressure of N(2) should have been at least as large as several millibars and could have been as large as 30 millibars if surface processes were to represent an important sink for atmospheric HNO(2) and HNO(3).     

Extreme ultraviolet observations from the voyager 2 encounter with saturn

Combined analysis of helium (584 angstroms) airglow and the atmospheric occultations of the star delta Scorpii imply a vertical mixing parameter in Saturn's upper atmosphere of K (eddy diffusion coefficient) approximately 8 x 10(7) square centimeters per second, an order of magnitude more vigorous than mixing in Jupiter's upper atmosphere. Atmospheric H(2) band absorption of starlight yields a preliminary temperature of 400 K in the exosphere and a temperature near the homopause of approximately 200 K. The energy source for the mid-latitude H(2) band emission still remains a puzzle. Certain auroral emissions can be fully explained in terms of electron impact on H(2), and auroral morphology suggests a link between the aurora and the Saturn kilometric radiation. Absolute optical depths have been determined for the entire C ring andparts of the A and B rings. A new eccentric ringlet has been detected in the C ring. The extreme ultraviolet reflectance of the rings is fairly uniform at 3.5 to 5 percent. Collisions may control the distribution of H in Titan's H torus, which has a total vertical extent of approximately 14 Saturn radii normal to the orbit plane.     

Electrochemistry and electrogenerated chemiluminescence from silicon nanocrystal quantum dots

Reversible electrochemical injection of discrete numbers of electrons into sterically stabilized silicon nanocrystals (NCs) (approximately 2 to 4 nanometers in diameter) was observed by differential pulse voltammetry (DPV) in N,N'-dimethylformamide and acetonitrile. The electrochemical gap between the onset of electron injection and hole injection-related to the highest occupied and lowest unoccupied molecular orbitals-grew with decreasing nanocrystal size, and the DPV peak potentials above the onset for electron injection roughly correspond to expected Coulomb blockade or quantized double-layer charging energies. Electron transfer reactions between positively and negatively charged nanocrystals (or between charged nanocrystals and molecular redox-active coreactants) occurred that led to electron and hole annihilation, producing visible light. The electrogenerated chemiluminescence spectra exhibited a peak maximum at 640 nanometers, a significant red shift from the photoluminescence maximum (420 nanometers) of the same silicon NC solution. These results demonstrate that the chemical stability of silicon NCs could enable their use as redox-active macromolecular species with the combined optical and charging properties of semiconductor quantum dots.     

Internal mixture of sea salt, silicates, and excess sulfate in marine aerosols

Individual aerosol particles from the remote marine atmosphere were investigated by scanning electron microscopy and electron microprobe analysis. A large fraction of the silicate mineral component of the aerosol was found to be internally mixed with sea-salt aerosol particles. This observation explains the unexpected similarity in the size distributions of silicates and sea salt that has been observed in remote marine aerosols. Reentrainment of dust particles previously deposited onto the sea surface and collision between aerosol particles can be excluded as possible source mechanisms for these internally mixed aerosols. The internal mixing could be produced by processes within clouds, including droplet coalescence. Cloud processes may also be responsible for the observed enrichment of excess (nonsea-salt) sulfate on sea-salt particles.     

Activation of alkanes with organotransition metal complexes

Alkanes, although plentiful enough to be considered for use as feedstocks in large-scale chemical processes, are so unreactive that relatively few chemical reagents have been developed to convert them to molecules having useful functional groups. However, a recently synthesized iridium (lr) complex successfully converts alkanes into hydridoalkylmetal complexes (M + R-H --> R-M-H). This is a dihydride having the formula Cp(*)(L)lrH(2), where Cp(*) and L are abbreviations for the ligands (CH(3))(5)C(5) and (CH(3))(3)P, respectively. Irradiation with ultraviolet light causes the dihydride to lose H(2), generating the reactive intermediate Cp(*)lrL. This intermediate reacts rapidly with C-H bonds in every molecule so far tested (including alkanes) and leads to hydridoalkyliridium complexes Cp(*)(L)lr(R)(H). Evidence has been obtained that this C-H insertion, or oxidative addition, reaction proceeds through a simple three-center transition state and does not involve organic free radicals as intermediates. Thus the intermediate Cp(*)lrL reacts most rapidly with C-H bonds having relatively high bond energies, such as those at primary carbon centers, in small organic rings, and in aromatic rings. This contrasts directly with the type of hydrogen-abstraction selectivity that is characteristic of organic radicals. The hydridoalkyliridium products of the insertion reactions can be converted into functionalized organic molecules-alkyl halides-by treatment with mercuric chloride followed by halogens. Expulsion (reductive elimination) of the hydrocarbon from the hydridoalkyliridium complexes can be induced by Lewis acids or heat, regenerating the reactive intermediate Cp(*)lrL. Oxidative addition of the corresponding rhodium complexes Cp(*)RhL to alkane C-H bonds has also been observed, although the products formed in this case are much less stable and undergo reductive elimination at -20 degrees C. These and other recent observations provide an incentive for reexamining the factors that have been assumed to control the rate of reaction of transition metal complexes with C-H bonds-notably the need for electron-rich metals and the proximity of reacting centers.     

Greenhouse Effects due to Man-Mad Perturbations of Trace Gases

Nitrous oxide, methane, ammonia, and a number of other trace constituents in the earth's atmosphere have infrared absorption bands in the spectral region 7 to 14 microm and contribute to the atmospheric greenhouse effect. The concentrations of these trace gases may undergo substantial changes because of man's activities. Extensive use of chemical fertilizers and combustion of fossil fuels may perturb the nitrogen cycle, leading to increases in atmospheric N(2)O, and the same perturbing processes may increase the amounts of atmospheric CH(4) and NH(3). We use a one-dimensional radiative-convective model for the atmospheric thermal structure to compute the change in the surface temperature of the earth for large assumed increases in the trace gas concentrations; doubling the N(2)O, CH(4), and NH(3) concentrations is found to cause additive increases in the surface temperature of 0.7 degrees , 0.3 degrees , and 0.1 degrees K, respectively. These systematic effects on the earth's radiation budget would have substantial climatic significance. It is therefore important that the abundances of these trace gases be accurately monitored to determine the actual trends of their concentrations.     

Prebiotic synthesis of methionine

Methionine has been shown to be a product of the action of a spark discharge on a simulated primitive earth atmosphere containing CH(4), N(2), NH(3), H(2)O, and H(2)S or CH(3)SH. Acrolein has also been shown to be a product of the discharge and is proposed as an intermediate in the prebiotic synthesis of methionine and of glutamic acid, homocysteine, homoserine, and alpha,gamma-diaminobutyric acid.     

A sulfur dioxide climate feedback on early Mars

Ancient Mars had liquid water on its surface and a CO2-rich atmosphere. Despite the implication that massive carbonate deposits should have formed, these have not been detected. On the basis of fundamental chemical and physical principles, we propose that climatic conditions enabling the existence of liquid water were maintained by appreciable atmospheric concentrations of volcanically degassed SO2 and H2S. The geochemistry resulting from equilibration of this atmosphere with the hydrological cycle is shown to inhibit the formation of carbonates. We propose an early martian climate feedback involving SO2, much like that maintained by CO2 on Earth.     

Catalytic reduction of dinitrogen to ammonia at a single molybdenum center

Dinitrogen (N2) was reduced to ammonia at room temperature and 1 atmosphere with molybdenum catalysts that contain tetradentate [HIPTN3N]3- triamidoamine ligands (such as [HIPTN3N]Mo(N2), where [HIPTN3N]3- is [(3,5-(2,4,6-i-Pr3C6H2)2C6H3NCH2CH2)3N]3-) in heptane. Slow addition of the proton source [(2,6-lutidinium)(BAr'4), where Ar' is 3,5-(CF3)2C6H3]and reductant (decamethyl chromocene) was critical for achieving high efficiency ( approximately 66% in four turnovers). Numerous x-ray studies, along with isolation and characterization of six proposed intermediates in the catalytic reaction under noncatalytic conditions, suggest that N2 was reduced at a sterically protected, single molybdenum center that cycled from Mo(III) through Mo(VI) states.     

Venus: density of upper atmosphere from measurements of drag on pioneer orbiter

Measurements of the changes in orbital period of the Pioneer Venus orbiter have yielded estimates of the density of the upper atmosphere of Venus at altitudes in the range from 150 to 200 kilometers. At the lower limit of this range, the density on the dayside of the terminator exhibits a temporal variation of amplitude near 4 x 10(-14) gram per cubic centimeter aboult a mean of approximately 1.4 x 10(-13) gram per cubic centimeter. The variation appears oscillatory, with a 4- to 5-day period, but barely one cycle was observed. The density on the nightside of the terminator, sampled inthe same 150-kilometer altitude range, fluctuates about a smaller mean of approximately 4 x 10(-14) gram per cubic centimeter. The density between the altitudes of 150 and 200 kilometers, sampled only on the dayside of the terminator, imply a scale height of between 15 and 20 kilometers. The interpretation of this estimate is uncertain, however, in view of the measurements at the different altitudes having been made at different times and, hence, at different values of solar phase.     

Biogenic methane, hydrogen escape, and the irreversible oxidation of early Earth

The low O2 content of the Archean atmosphere implies that methane should have been present at levels approximately 10(2) to 10(3) parts per million volume (ppmv) (compared with 1.7 ppmv today) given a plausible biogenic source. CH4 is favored as the greenhouse gas that countered the lower luminosity of the early Sun. But abundant CH4 implies that hydrogen escapes to space (upward arrow space) orders of magnitude faster than today. Such reductant loss oxidizes the Earth. Photosynthesis splits water into O2 and H, and methanogenesis transfers the H into CH4. Hydrogen escape after CH4 photolysis, therefore, causes a net gain of oxygen [CO2 + 2H2O --> CH4 + 2O2 --> CO2 + O2 + 4H(upward arrow space)]. Expected irreversible oxidation (approximately 10(12) to 10(13) moles oxygen per year) may help explain how Earth's surface environment became irreversibly oxidized.     

Ice record of delta13C for atmospheric CH4 across the Younger Dryas-Preboreal transition

We report atmospheric methane carbon isotope ratios (delta13CH4) from the Western Greenland ice margin spanning the Younger Dryas-to-Preboreal (YD-PB) transition. Over the recorded approximately 800 years, delta13CH4 was around -46 per mil (per thousand); that is, approximately 1 per thousand higher than in the modern atmosphere and approximately 5.5 per thousand higher than would be expected from budgets without 13C-rich anthropogenic emissions. This requires higher natural 13C-rich emissions or stronger sink fractionation than conventionally assumed. Constant delta13CH4 during the rise in methane concentration at the YD-PB transition is consistent with additional emissions from tropical wetlands, or aerobic plant CH4 production, or with a multisource scenario. A marine clathrate source is unlikely.     

Terrestrial atmospheric composition from stellar occultations

Stellar ultraviolet light transmitted through the earth's upper atmosphere is strongly absorbed by ozone and molecular oxygen. The stellar ultraviolet photometers aboard the Orbiting Astronomical Observatory (OAO-2) satellite have measured the intensity changes of several stars during occultation of the star by the earth's atmosphere. From the occultation data the nighttime vertical number density profiles of molecular oxygen at altitudes from 120 to 200 kilometers and of ozone at altitudes from 60 to 100 kilometers have been obtained.     

Studies of unusual simple molecules by neutralization-reionization mass spectrometry

Reactive or unstable molecules are key intermediates in many important reactions, but can be difficult to prepare for experimental studies. Species with missing (:CH-OH) or extra (H3) substituents can often be formed conveniently in the gas phase by neutralizing a beam of a more stable ionic counterpart (CH = O+H, H3+). Reionization of the neutral after approximately 10(-6) seconds tests its stability, whereas its unimolecular chemistry can be probed by preparing it with different amounts of internal energy. The resulting neutral products are reionized and mass analyzed. Isomers are then characterized by ion dissociation and a third mass-analysis step. Many unusual molecules have been characterized with this technique, which can also be used to probe complex unimolecular chemistry, such as that of cyclobutadiene and ethylene oxide.     

New perspectives on ancient Mars

Mars was most active during its first billion years. The core, mantle, and crust formed within approximately 50 million years of solar system formation. A magnetic dynamo in a convecting fluid core magnetized the crust, and the global field shielded a more massive early atmosphere against solar wind stripping. The Tharsis province became a focus for volcanism, deformation, and outgassing of water and carbon dioxide in quantities possibly sufficient to induce episodes of climate warming. Surficial and near-surface water contributed to regionally extensive erosion, sediment transport, and chemical alteration. Deep hydrothermal circulation accelerated crustal cooling, preserved variations in crustal thickness, and modified patterns of crustal magnetization.