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Interstellar problems and matrix solutions.

The application of the matrix isolation technique, which is but one of the experimental techniques pioneered in George Pimentel's laboratories, to interstellar problems is described. Following a brief discussion of the interstellar medium (ISM) three areas are reviewed in which matrix experiments are particularly well-suited to contribute the information which is sorely needed to further our understanding of the ISM. The first involves the measurement of the spectroscopic properties of reactive species. The second is the determination of reaction rates and the elucidation of reaction pathways involving atoms, radicals and ions which are likely to interact on grain surfaces and in grain mantles. The third entails the determination of the spectroscopic, photochemical and photophysical properties of interstellar and cometary ice analogs. Significant, but limited, progress has been made in these three areas and a tremendous amount of work is required to fully address the variety of unique chemical and spectroscopic questions posed by the astronomical observations.

Astronomy↗

Results of TV imaging of Phobos (Experiment VSK-Fregat).

From February to March 1989 the Phobos 2 spacecraft took 37 TV images of Phobos at a distance of 190-1100 km. These images complement Mariner-9 and Viking data by providing higher-resolution coverage of a large region West of the crater Stickney (40-160 degrees W) and by providing disk-resolved measurements of surface brightness at a greater range of wavelengths and additional phase angles. These images have supported updated mapping and characterization of large craters and grooves, and have provided additional observations of craters' and grooves' bright rims. Variations in surface visible/near-infrared color ratio of almost a factor of 2 have been recognized; these variations appear to be associated with the ejecta of specific large impact craters. Updated determinations of satellite mass and volume allow calculation of a more accurate value of bulk density, 1.90 +/- 0.1 g cm-3. This is significantly lower than the density of meteoritic analogs to Phobos' surface, suggesting a porous interior perhaps containing interstitial ice.

Astronomy↗

Slope variations on the surface of Phobos.

It has been suggested that slope fluctuations on the scale of pixel dimensions could be determined by statistical photoclinometry. A closer study of the surface of Phobos reveals variations in the scattering properties of single particles and micro-structures formed by the particles. In the present context, the photoclinometric method of brightness moments is extended to account for these variations by allowing statistical fluctuations in the phase function of the assumed Lommel-Seeliger scattering law. The mean slope on the investigated regions of Phobos has been found to vary from approximately 12 degrees on a 61m scale to approximately 7 degrees on a 216-272m scale. On the same scales, a value of the order of 2% has been obtained for the standard deviation of the scattering phase function. Hints of a fractal-like scale-invariance have been noticed in the covariance function of brightness.

Astronomy↗

Interpretation of the surface brightness of Phobos.

Analysis of disk resolved images of Phobos obtained by the Phobos 2 spacecraft allows us to study the surface scattering law and albedo variations. From low phase angle images we find variations in local geometric albedo approximately 10%, with a correlation length approximately 1km. The scattering law is reasonably well matched by the recent proposed LPI (Lumme et al. 1990a) model, which allows us to deduce a small scale (approximately 1 mm) surface roughness (approximately 0.5), defined here as the rms. tangent of the local surface normal relative to the mean surface normal in the Duxbury (1991) model of Phobos. This value is very close to what has been found for Mercury and the Moon.

Astronomy↗

Fractionation of hydrogen and deuterium on Venus due to collisional ejection.

The fractionation factor f is important for interpreting the current escape fluxes of H and D on Venus and how the D/H ratio has evolved. The escape flux is currently governed by the two processes of charge exchange and collisional ejection by fast oxygen atoms. Using a best-fit parameterized equation for the O-H scattering angle phase function, more accurate branching ratios for the oxygen ion dissociation and including the effects of the initial energy and momentum of the ions and electrons, as well as for the hydrogen and deuterium gas, we have reanalyzed the collisional ejection process. Our analysis produces improved values for the efficiency of H and D escape as a function of the ionospheric temperature. From our results we propose the reduction of the hydrogen flux for collisional ejection from 8 to 3.5 x 10(6) cm-2 s-1. Assuming that collisions leading to escape occur mostly in the region between 200 and 400 km, the revised D/H fractionation factor due to collisional ejection is 0.47, where previously the process had been considered completely discriminating against deuterium escape (or f approximately 0.) The resulting deuterium flux is 3.1 x 10(4) cm-2 s-1, roughly 6 times the flux due to charge exchange, making collisional ejection the dominant escape mechanism for deuterium on Venus.

Atmosphere↗

Modelling the VUV emission spectrum of N2: preliminary results on the effects of rotational interactions on line intensities.

A theoretical model of the excited singlet ungerade electronic states of the nitrogen molecule is presented. This work is an extension of a previous study (D. Stahel, M. Leoni and K. Dressler, J. Chem. Phys. 79, 2541-2558, 1983) with the addition of rotational interactions between states of different symmetry. These rotational interactions together with the homogeneous couplings frequently lead to extreme mixing of the states. This model is being used to analyse the high resolution vacuum ultraviolet emission spectrum which is currently being recorded photoelectrically. The ultimate goal of this work is the reliable interpretation of the low resolution emission spectra observed from planetary atmospheres, notably that of Titan, and the transitions assigned as being important in the Voyager 1 spectra of Titan are discussed in detail.

Atmosphere↗

Techniques for the study of reaction kinetics at low temperatures: application to the atmospheric chemistry of Titan.

Data on the low-temperature (< 200 K) dependence of the kinetics of chemical reactions are of great importance for understanding the composition of planetary atmospheres (as well as interstellar clouds). To date such studies have been relatively rare but the situation is beginning to change. During the past 10 years a number of experimental instruments have been designed to address this problem. These instruments rely on either cryogenic or supersonic cooling, and both methods have been applied to the study of neutral-neutral or ion-neutral reactions. We briefly review these different techniques, with an emphasis on the CRESU method, and provide examples of the types of reactive systems that have been studied, with particular attention to those relevant to the atmosphere of Titan. The perspectives for future work are also evoked.

Atmosphere↗

Laboratory simulations of Titan's atmosphere: organic gases and aerosols.

Titan, the main satellite of Saturn, has been observed by remote sensing for many years, both from interplanetary probes (Pioneer and Voyager's flybys) and from the Earth. Its N2 atmosphere, containing a small fraction of CH4 (approximately 2%), with T approximately 90 K and P approximately 1.5 bar at the ground level, is irradiated by solar UV photons and deeply bombarded by energetic particles, i.e. Saturn mangetospheric electrons and protons, interplanetary electrons and cosmic rays. The resulting energy deposition, which takes place mainly below 1000 km, initiates chemical reactions which yield gaseous hydrocarbons and nitriles and, through polymerisation processes, solid aerosol particles which grow by coagulation and settle down to the ground. At the present time, photochemical models strongly require the results of specific laboratory studies. Chemical rate constants are not well known at low temperatures, charged-particle-induced reactions are difficult to model and laboratory simulations of atmospheric processes are therefore of great interest. Moreover, the synthesis of organic compounds which have not been detected to date provides valuable information for future observations. The origin and chemical composition of aerosols depend on the nature of chemical and energy sources. Their production from gaseous species may be monitored in laboratory chambers and their optical or microphysical properties compared to those deduced from the observations of Titan's atmosphere. The development of simulation chambers of Titan's extreme conditions is necessary for a better understanding of past and future observations. Space probes will sound Titan's atmosphere by remote sensing and in situ analysis in the near future (Cassini-Huygens mission). It appears necessary, as a preliminary step to test on-board experiments in such chambers, and as a final step, when new space data have been acquired, to use them for more general scientific purposes.

Aerosols↗

Two formation regions for Titan's hazes: indirect clues and possible synthesis mechanisms.

It is suggested that aerosol particles forming the detached and main haze layers of Titan's atmosphere do not originate in the same atmospheric levels. Particles present above approximately 350 km could be formed of polyacetylenes synthetized in the 500-800 km altitude range through successive insertion reactions involving the C2H radical under the action of solar ultraviolet photons (Yung et al., Astrophys. J. Suppl. 55, 465, 1984). They might contain C-N oligomers in comparable amounts, as well as C-H-N oligomers synthetized at high altitude (900-1000 km) by the action of suprathermal Saturn plasma electrons. Physically, they are expected to consist of fluffy aggregates of density approximately 0.01-0.1 g cm-3. Their mass production rate is small (10(-15)-10(-14) kg m-2 s-1), that is typically 10% or less of the main haze production rate. Due to their low fall velocity, they are very sensitive to large scale horizontal motions and one substantial part of them may be swept away by meridional circulation at the detached haze level. The altitude range where these aerosols are created is well above the range proposed by Cabane et al. (Planet. Space Sci. 41, 257, 1993) for aerosols of the main haze layer, on the basis of a new fractal microphysical modeling of Titan's aggregates, that is approximately 350-400 km. A natural outcome of this apparent discrepancy is to suppose that there is a second formation region, below approximately 400 km altitude, giving rise to the main haze layer. The aim of the present paper is to review the different possible formation mechanisms of this main haze layer and assess their ability to account for the observed characteristics of the haze. Several conditions are established. The first one, called "condition A", concerns the formation altitude range imposed by fractal modeling. Possible chemical and energy sources are examined. Two additional constraints, relative to the minimum gas mass ("condition B") and input energy ("condition C") required for efficient conversion of gas into aerosols, are defined. By comparing the production rates of the haze, as derived from microphysical models, and of gaseous chemical species, as derived from photochemical models, five possible source constituents are identified: N2, CH4, C2H2, C2H6 and HCN. Polymerization of C2H2 into (C2H2)n through action of solar ultraviolet photons is shown to be rather improbable (condition A is hardly satisfied). From both our current knowledge of the gaseous phase photochemistry, through modeling and laboratory experiments, and existing models of the interaction between Saturn magnetosphere and Titan atmosphere, the formation of C-H-N polymers through action of Saturn magnetospheric energetic particles (E approximately 100 keV), is proposed as the basic polymerization mechanism in the lower formation region (conditions A,B and C are jointly satisfied).

Acetylene↗

A study of chemical systems using signal flow graph theory: application to Neptune.

Photochemistry of giant planets and their satellites is characterized by numerous reactions involving many chemical species. In the present paper, chemical systems are modeled by signal flow graphs. Such a technique evaluates the transmission of any input into the system (solar flux, electrons...) and gives access to the identification of the most important mechanisms in the chemical system. For a given chemical system, we first evaluate rate coefficients. Then, in order to obtain concentrations of each compound, we integrate the set of continuity equations by Gear's method. Gear's method is chosen rather than another classical method because it is recommended for a system of stiff equations due to the existence of greatly differing time constants. Finally, the technique of signal flow graphs is used. This method is applied to the production of hydrocarbons in the atmospheres of giant planets. In particular, the production of C2H6 in the atmosphere of Neptune from the photodissociation of CH4 is investigated. Different paths of dissociation of CH4 are possible from L alpha radiations. A chemical system containing 14 species and 30 reactions including these different paths of dissociation is integrated. The main mechanism of production of C2H6 is identified and evaluated for each model of dissociation. The importance of various reaction paths as a function of time is discussed.

Atmosphere↗

Absolute absorption coefficient of C6H2 in the mid-UV range at low temperature; implications for the interpretation of Titan atmospheric spectra.

The interpretation of mid-UV albedo spectra of planetary atmospheres, especially that of Titan, is the main goal of the SIPAT (Spectroscopie uv d'Interet Prebiologique dans l'Atmosphere de Titan) research program. This laboratory experiment has been developed in order to systematically determine the absorption coefficients of molecular compounds which are potential absorbers of scattered sunlight in planetary atmospheres, with high spectral resolution, and at various temperatures below room temperature. From photochemical modelling and experimental simulations, we may expect triacetylene (C6H2) to be present in the atmosphere of Titan, even though it has not yet been detected. We present here the first determination of the absolute absorption coefficient of that compound in the 200-300 nm range and at two temperatures (296 K and 233 K). The temperature dependence of the C6H2 absorption coefficient in that wavelength range is compared to that previously observed in the case of cyanoacetylene (HC3N). We then discuss the implications of the present results for the interpretation of Titan UV spectra, where it appears that large uncertainities can be introduced either by the presence of trace impurities in laboratory samples or by the variations of absorption coefficients with temperature.

Acetylene↗

Measurements in N2-CH4(C2H2) discharges of reaction rates and thermochemical constants for Titan atmosphere study.

The kinetic reactions in N2-xCH4(C2H2) gas discharges with x less than 1% have been studied by emission spectroscopy in the afterglow of D.C. discharges and by mass spectroscopy from radiolysis ionization using alpha particles. The pressure range is from several Torr to 100 Torr. At the end of N2 D.C. discharges at room temperature, for a residence time of about 10(-2) s, the dominant active species are the N atoms with density of 10(14)-10(15) cm-3 for N2 density of about 10(17) cm-3 (3 Torr), the N2(X,V) vibrational molecules with for example [N2(X,V = 10)] approximately 10(14) cm-3 and the electronic metastable molecules N2(A 3 sigma u +) with a density of 10(12) cm-3. In such conditions, the following kinetic reactions have been studied: N2(A) + N2(A) --> N2(C,B,V') + N2(X), N2(A) + N2(X,V>5) --> N2(X) + N2(B,V') in pure N2 post-discharges and N2(A) + CH4 --> products, C + N + M2 --> CN(B,V') + M2, N2(X,V>4) + CN --> N2(X) + CN(B,A,V'), in N2-1% CH4 post-discharges. The clustering reactions of N2-(1-5%)CH4(C2H2) gas mixtures after radiolysis ionization have been studied for the H2CN+ nN2 ions and the equilibrium constants have been determined in the temperature range T = 140-300 K.

Acetylene↗

Germane photochemistry. Photolysis of gas mixtures of planetary interest.

Photolysis of germane (GeH4) in the presence of acetylene (C2H2), propyne (C3H4) or phosphine (PH3) with a 185 nm mercury lamp has been studied. The volatile products formed in these reactions are characterized by 1H, 31P and 13C NMR. Vinylgermanes are the first reaction products formed in the photolysis of GeH4 with alkynes. A reaction pathway is proposed. The initial step is the dissociation of germane 1 to hydrogen and GeH3 radicals. Addition of the germyl radical on alkyne is proposed as the next step. Vinyl-germanes are then formed by radical combination. Photolysis of ethenylgermane 2 gives diethenylgermane 3 in the presence of acetylene and digermaethane 4 in the presence of GeH4. The application of these findings to Jovian and Saturn atmospheric chemistry is discussed.

Acetylene↗

Mass spectrometric study of three-body ion-molecule clustering reactions of CpHq+ ions with N2 or CH4 in N2-CH4 mixtures.

Thermochemical data for several ion-molecule clustering of hydrocarbon ions with N2 or CH4 were obtained from clustering equilibria studies in gas mixtures irradiated by alpha-particles. High-pressure mass spectrometry was used to determine the enthalpy and entropy changes of clustering (delta H0 and delta S0, respectively) for the reactions X+(N2)n-1 + 2N2 <==> X(+)(N2)n + N2 with X = CH5, n = 1-2; X = C2H5, n = 1-4; and X = C3H7, n = 1. For X = CH5, the values (delta H0; delta S0) are found to be (-6.8 kcal mol-1; -19.7 cal mol-1 K-1) for n = 1, and (-5.3 kcal mol-1; -15.9 cal mol-1 K-1) for n = 2. For X = C2H5, (delta H0; delta S0) = (-6.9 kcal mol-1; -18.2 cal mol-1 K-1), for n = 1, and (-4.6 kcal mol-1; -20.8 cal mol-1 K-1) for n = 2. From the equilibrium measurements at 129 K, estimates of the thermochemical values could be obtained for n = 3-4. The results obtained for the free energy, delta G0, were -1.4 kcal mol-1 for n = 3, and -1.1 kcal mol-1 for n = 4. For X = C3H7 we found delta G0 = -0.7 kcal mol-1 at 213 K. The association reactions X+ + 2CH4 <==> X+(CH4) + CH4 with X = CH5, C2H5, C2H7, and C3H7 were also studied, resulting in free energy values at 206 K of -3.1, -1.9, -0.5 and -1.3 kcal mol-1, respectively. The results for CH5, C2H5 and C3H7 are compared with previously reported measurements.

Atmosphere↗

Inorganic chemistry of O2 in a dense primitive atmosphere

A simple steady-state photochemical model is developed in order to determine typical molecular oxygen concentrations for a comprehensive range of primitive abiotic atmospheres. Carbon dioxide is assumed to be the dominant constituent in these atmospheres since CO2 photodissociation may potentially result in the enhancement of the O2 partial pressure. The respective effects of the H2O content, temperature, eddy diffusion coefficient and UV flux on the results are investigated. It is shown that for any pressure at the surface, the partial pressure of molecular oxygen does not exceed 10 mbar. The peculiar case of a runaway greenhouse which has possibly taken place on Venus is qualitatively envisaged. Although O2 is basically absent in the present Venus atmosphere, a transient presence in a primitive stage cannot be ruled out. Possible mechanisms for O2 removal in such an atmosphere are reviewed. At the present stage, we think that the detection of large O2 amounts would be at least a good clue for the presence of life on an extrasolar planet.

Atmosphere↗

Plasma processing of interstellar PAHs into solar system kerogen.

Processes resulting in the formation of hydrocarbons of carbonaceous chondrites and the identity of the interstellar molecular precursors involved are an objective of investigations into the origin of the solar system and perhaps even life on earth. We have combined the resources and experience of an astronomer and physicists doing laboratory simulations with those of a chemical expert in the analysis of meteoritic hydrocarbons, in a project that investigated the conversion of polycyclic aromatic hydrocarbons (PAHs) formed in stellar atmospheres into alkanes found in meteorites. Plasma hydrogenation has been found in the University of Alabama at Birmingham Astrophysics Laboratory to produce from the precursor PAH naphthalene, a new material having an IR absorption spectrum (Lee, W. and Wdowiak, T.J., Astrophys. J. 417, L49-L51, 1993) remarkably similar to that obtained at Arizona State University of the benzene-methanol extract of the Murchison meteorite (Cronin, J.R. and Pizzarello, S., Geochim. Cosmochim. Acta 54, 2859-2868, 1990). There are astrophysical and meteoritic arguments for PAH species from extra-solar sources being incorporated into the solar nebula, where plasma hydrogenation is highly plausible. Conversion of PAHs into alkanes could also have occurred in the interstellar medium. The synthesis of laboratory analogs of meteoritic hydrocarbons through plasma hydrogenation of PAH species is underway, as is chemical analysis of those analogs. The objective is to clarify this heretofore uninvestigated process and to understand its role during the origin of the solar system as a mechanism of production of hydrocarbon species now found in meteorites. Results have been obtained in the form of time-of-flight spectroscopy and chemical analysis of the lab analog prepared from naphthalene.

Alkanes↗

Laboratory comparisons of organic materials to interstellar dust and the Murchison meteorite.

Spectra of objects which lie along several lines of sight through the diffuse interstellar medium (DISM) reveal an absorption feature near 3.4 micrometers, which has been attributed to saturated aliphatic hydrocarbons on interstellar grains. The similarity of the absorption bands near 3.4 micrometers (2950 cm-1) along different lines of sight indicates that the carrier of this band lies in the diffuse dust. Several materials have been proposed as "fits" to the 3.4 micrometers feature over the years. A comparison of these identifications is presented. These comparisons illustrate the need for high resolution, high signal-to-noise observational data as a means of distinguishing between laboratory organics as matches to the interstellar material. Although any material containing hydrocarbons will produce features in the 3.4 micrometers region, the proposed "matches" to the DISM do differ in detail. These differences may help in the analyses of the chemical composition and physical processes which led to the production of the DISM organics, although ISO Observations through the 5-8 micrometers spectral region are essential for a definitive identification. A remarkable similarity between the spectrum of the diffuse dust and an organic extract from the Murchison meteorite suggests that some of the interstellar organic material may be preserved in primitive solar system bodies. The 3.4 micrometers absorption feature (in the rest frame) has recently been detected in external galaxies, indicating the widespread availability of organic material for incorporation into planetary systems.

Astronomy↗

Human roles in future space operations.

Mankind has evolved in the biosphere from essentially another animal to the level that his industries and societies are powerful components of the life-cycles of Earth. Terrestrial industrial experience can be extended to the use of matter from the Moon and other non-terrestrial sources to create permanent habitats and industry in space. Space stations in low Earth orbit and small bases on the Moon can be the foci of early space industries for learning how to grow in space with local resources. Several near term and long range research topics appropriate to permanent human occupancy of space are reviewed.

Biological Evolution↗