Predictions of the electrical conductivity and charging of the aerosols in Titan's atmosphere

The electrical conductivity and electrical charge on the aerosols in atmosphere of Titan are computed for altitudes between 0 and 400 km. Ionization of methane and nitrogen due to galactic cosmic rays (GCR) is important at night where these ions are converted to ion clusters such as CH⁺₅CH₄, C₇H⁺₇, C₄H⁺₇, and H₄C₇N⁺. The ubiquitous aerosols observed also play an important role in determining the charge distribution in the atmosphere. Because polycyclic aromatic hydrocarbons (PAHs) are expected in Titan's atmosphere and have been observed in the laboratory and found to be electrophilic, we consider the formation of negative ions. During the night, the very smallest molecular complexes accept free electrons to form negative ions. This results in a large reduction of the electron abundance both in the region between 150 and 350 km over that predicted when such aerosols are not considered. During the day time, ionization by photoemission from aerosols irradiated by solar ultraviolet (UV) radiation overwhelms the GCR-produced ionization. The presence of hydrocarbon and nitrile minor constituents substantially reduces the UV flux in the wavelength band from the cutoff of CH₄ at 155 to 200 nm. These aerosols have such a low ionization potential that the bulk of the solar radiation at longer wavelengths is energetic enough to produce a photoionization rate sufficient to create an ionosphere even without galactic cosmic ray (GCR) bombardment. At altitudes below 60 km, the electron and positive ion abundances are influenced by the three-body recombination of ions and electrons. The addition of this reaction significantly reduces the predicted electron abundance over that previously predicted. Our calculations for the dayside show that the peaks of the charge distributions move to larger values as the altitude increases. This variation is the result of the increased UV flux present at the highest altitudes. Clearly, the situation is quite different than that for the night where the peak of the distribution for a particular size is nearly constant with altitude when negative ions are not present. The presence of very small aerosol particles (embryos) may cause the peak of the distribution to decrease from about 8 negative charges to as little as one negative charge or even zero charge. This dependence on altitude will require models of the aerosol formation to change their algorithms to better represent the effect of charged aerosols as a function of altitude. In particular, the charge state will be much higher than previously predicted and it will not be constant with altitude during the day time. Charging of aerosol particles, whether on the dayside or nightside, has a major influence on both the electron abundance and electrical conductivity. The predicted conductivities are within the measurement range of the HASI PWA instrument over most but not all, of the altitude range sampled.     

Heavy ion formation in Titan's ionosphere: Magnetospheric introduction of free oxygen and a source of Titan's aerosols?

Discovery by Cassini's plasma instrument of heavy positive and negative ions within Titan's upper atmosphere and ionosphere has advanced our understanding of ion neutral chemistry within Titan's upper atmosphere, primarily composed of molecular nitrogen, with ~2.5% methane. The external energy flux transforms Titan's upper atmosphere and ionosphere into a medium rich in complex hydrocarbons, nitriles and haze particles extending from the surface to 1200 km altitudes. The energy sources are solar UV, solar X-rays, Saturn's magnetospheric ions and electrons, solar wind and shocked magnetosheath ions and electrons, galactic cosmic rays (GCR) and the ablation of incident meteoritic dust from Enceladus’ E-ring and interplanetary medium. Here it is proposed that the heavy atmospheric ions detected in situ by Cassini for heights >950 km, are the likely seed particles for aerosols detected by the Huygens probe for altitudes <100 km. These seed particles may be in the form of polycyclic aromatic hydrocarbons (PAH) containing both carbon and hydrogen atoms C_nH_x. There could also be hollow shells of carbon atoms, such as C₆₀, called fullerenes which contain no hydrogen. The fullerenes may compose a significant fraction of the seed particles with PAHs contributing the rest. As shown by Cassini, the upper atmosphere is bombarded by magnetospheric plasma composed of protons, H₂⁺ and water group ions. The latter provide keV oxygen, hydroxyl and water ions to Titan's upper atmosphere and can become trapped within the fullerene molecules and ions. Pickup keV N₂⁺, N⁺ and CH₄⁺ can also be implanted inside of fullerenes. Attachment of oxygen ions to PAH molecules is uncertain, but following thermalization O+ can interact with abundant CH₄ contributing to the CO and CO₂ observed in Titan's atmosphere. If an exogenic keV O+ ion is implanted into the haze particles, it could become free oxygen within those aerosols that eventually fall onto Titan's surface. The process of freeing oxygen within aerosols could be driven by cosmic ray interactions with aerosols at all heights. This process could drive pre-biotic chemistry within the descending aerosols. Cosmic ray interactions with grains at the surface, including water frost depositing on grains from cryovolcanism, would further add to abundance of trapped free oxygen. Pre-biotic chemistry could arise within surface microcosms of the composite organic-ice grains, in part driven by free oxygen in the presence of organics and any heat sources, thereby raising the astrobiological potential for microscopic equivalents of Darwin's “warm ponds” on Titan.     

High-altitude charged aerosols in the atmosphere of Titan

Observations by several instruments onboard the Cassini spacecraft revealed the existence of heavy hydrocarbon and nitrile species with masses of several thousand atomic mass units in the ionosphere of Titan. These very large molecules are in fact aerosols. The goal of this paper is to compute the concentrations of the charged aerosols in the upper atmosphere (950-1200 km) of Titan. The charging of these aerosols has been studied using the charge balance equations, where positive ions, negative ions, electrons, neutral and charged aerosols are included. Number concentrations of charged aerosols are compared with those observed by the Cassini instruments. The present work estimates the aerosol mass density as 1-10 kg/m³, which is within the predicted range. The results show that the aerosols must be smaller than 10 nm in order to have reasonable agreement with observations by the Cassini Plasma Spectrometer.     

Photoelectric Charging of Submicron Aerosols and Macromolecules in the Titan Haze

We quantify the charge states of submicrometer aerosols and aromatic macromolecules in Titan's organic haze. The aerosol charge is balanced between the recombination of positive ions with the aerosol plus the ejection of electrons from the aerosol via the UV-driven photoelectric effect and the recombination of electrons with the aerosol. During the day, the dominant charge state for submicro-meter aerosols is positive. Macromolecules composed of fewer than 32 carbon atoms with low electron affinities (<1.0 eV) are neutral, while the rest are mainly neutral and negatively charged with a small fraction (∼10%) becoming positively charged at higher (≥300 km) altitudes. At night, Titan's aerosol population becomes uniformly neutral and negatively charged. The time taken for a nighttime aerosol to change from being negatively charged to its most probable daytime positive charge is on the order of a few seconds for the largest submicrometer aerosols, while macromolecules tend to persist in an anionic charge state for one to several Earth days. Charging strongly influences aerosol agglomeration via Coulomb attraction and may account for the seasonal variations in the albedo of the Titan haze at midrange (∼200-250 km) altitudes. Enhanced agglomeration may also efficiently produce a source of condensation nuclei for the daily rainout of methane. In addition, the difference in aerosol charge between Titan's day and night (or summer and winter) phases will produce dramatically different chemistries which must be accounted for in future photochemical models. Finally, if there are PAH-like macromolecules in the Titan haze, Cassini Huygens should be able to observe these charge differences, with neutral macromolecules emitting strongly at 3.3 and 11.2 μm, cationic macromolecules emitting between 6.2 and 8.6 μm, and anionic macromolecules emitting in both infrared spectral regions.     

Model-data comparisons for Titan's nightside ionosphere

Solar and X-ray radiation and energetic plasma from Saturn's magnetosphere interact with the upper atmosphere producing an ionosphere at Titan. The highly coupled ionosphere and upper atmosphere system mediates the interaction between Titan and the external environment. A model of Titan's nightside ionosphere will be described and the results compared with data from the Ion and Neutral Mass Spectrometer (INMS) and the Langmuir probe (LP) part of the Radio and Plasma Wave (RPWS) experiment for the T5 and T21 nightside encounters of the Cassini Orbiter with Titan. Electron impact ionization associated with the precipitation of magnetospheric electrons into the upper atmosphere is assumed to be the source of the nightside ionosphere, at least for altitudes above 1000 km. Magnetospheric electron fluxes measured by the Cassini electron spectrometer (CAPS ELS) are used as an input for the model. The model is used to interpret the observed composition and structure of the T5 and T21 ionospheres. The densities of many ion species (e.g., CH⁺₅ and C₂H⁺₅) measured during T5 exhibit temporal and/or spatial variations apparently associated with variations in the fluxes of energetic electrons that precipitate into the atmosphere from Saturn's magnetosphere.     

The role of organic haze in Titan's atmospheric chemistry: I. Laboratory investigation on heterogeneous reaction of atomic hydrogen with Titan tholin

In Titan's atmosphere consisting of N₂ and CH₄, large amounts of atomic hydrogen are produced by photochemical reactions during the formation of complex organics. This atomic hydrogen may undergo heterogeneous reactions with organic aerosol in the stratosphere and mesosphere of Titan. In order to investigate both the mechanisms and kinetics of the heterogeneous reactions, atomic deuterium is irradiated onto Titan tholin formed from N₂ and CH₄ gas mixtures at various surface-temperatures of the tholin ranging from 160 to 310 K. The combined analyses of the gas species and the exposed tholin indicate that the interaction mechanisms of atomic deuterium with the tholin are composed of three reactions; (a) abstraction of hydrogen from tholin resulting in gaseous HD formation (HD recombination), (b) addition of D atom into tholin (hydrogenation), and (c) removal of carbon and/or nitrogen (chemical erosion). The reaction probabilities of HD recombination and hydrogenation are obtained as ηabst=1.9(±0.6)×¹⁰⁻³×exp(−300/T) and ηhydro=2.08(±0.64)×exp(−1000/T), respectively. The chemical erosion process is very inefficient under the conditions of temperature range of Titan's stratosphere and mesosphere. Under Titan conditions, the rates of hydrogenation > HD recombination ? chemical erosion. Our measured HD recombination rate is about 10 times (with an uncertainty of a factor of 3-5) the prediction of previous theoretical model. These results imply that organic aerosol can remove atomic hydrogen efficiently from Titan's atmosphere through the heterogeneous reactions and that the presence of aerosol may affect the subsequent organic chemistry.     

The upper ionosphere of Titan

Photoionization of the upper atmosphere of Titan by sunlight is expected to produce a substantial ionospheric layer. We have solved one-dimensional forms of the mass, momentum, and energy conservation equations for ions and electrons and have obtained electron number densities of about 10³ cm^?3, using various model atmospheres. The significant ions in a CH₄H₂ atmosphere are H⁺, H₃⁺, CH₅⁺, CH₅⁺, CH₃⁺, and C₂H₅⁺. Electron temperatures may be as high as 1000°K, depending on the abundance of hydrogen in the high atmosphere. Interaction of the solar wind with the ionosphere is also discussed.     

Ion composition and chemistry in the coma of Comet 1P/Halley—A comparison between Giotto's Ion Mass Spectrometer and our ion-chemical network

In order to understand the cometary plasma environment it is important to track the closely linked chemical reactions that dominate ion evolution. We used a coupled MHD ion-chemistry model to analyze previously unpublished Giotto High Intensity Ion Mass Spectrometer (HIS-IMS) data. In this way we study the major species, but we also try to match some minor species like the CH_x and the NH_x groups. Crucial for this match is the model used for the electrons since they are important for ion-electron recombination. To further improve our results we included an enhanced density of supersonic electrons in the ion pile-up region which increases the local electron impact ionization. In this paper we discuss the results for the following important ions: C⁺, CH⁺, CH⁺₂, CH⁺₃, N⁺, NH⁺, NH⁺₂, NH⁺₃, NH⁺₄, O⁺, OH⁺, H₂O⁺, H₃O⁺, CO⁺, HCO⁺, H₃CO⁺, and CH₃OH⁺₂. We also address the inner shock which is very distinctive in our MHD model as well as in the IMS data. It is located just inside the contact surface at approximately 4550 km. Comparisons of the ion bulk flow directions and velocities from our MHD model with the data measured by the HIS-IMS give indication for a solar wind magnetic field direction different from the standard Parker angle at Halley's position. Our ion-chemical network model results are in a good agreement with the experimental data. In order to achieve the presented results we included an additional short lived inner source for the C⁺, CH⁺, and CH⁺₂ ions. Furthermore we performed our simulations with two different production rates to better match the measurements which is an indication for a change and/or an asymmetric pattern (e.g. jets) in the production rate during Giotto's fly-by at Halley's comet.     

Negative ion chemistry in Titan's upper atmosphere

The Electron Spectrometer (ELS), one of the sensors making up the Cassini Plasma Spectrometer (CAPS) revealed the existence of numerous negative ions in Titan's upper atmosphere. The observations at closest approach (∼1000 km) show evidence for negatively charged ions up to ∼10,000 amu/q, as well as two distinct peaks at 22±4 and 44±8 amu/q, and maybe a third one at 82±14 amu/q. We present the first ionospheric model of Titan including negative ion chemistry. We find that dissociative electron attachment to neutral molecules (mostly HCN) initiates the formation of negative ions. The negative charge is then transferred to more acidic molecules such as HC₃N, HC₅N or C₄H₂. Loss occurs through associative detachment with radicals (H and CH₃). We attribute the three low mass peaks observed by ELS to CN⁻, C₃N⁻/C₄H⁻ and C₅N⁻. These species are the first intermediates in the formation of the even larger negative ions observed by ELS, which are most likely the precursors to the aerosols observed at lower altitudes.     

Saturn's magnetospheric interaction with Titan as defined by Cassini encounters T9 and T18: New results

We present new results of Cassini's T9 flyby with complementary observations from T18. Based on Cassini plasma spectrometer (CAPS) and Cassini magnetometer (MAG), compositional evidence shows the upstream flow for both T9 and T18 appears composed of light ions (H⁺ and H₂⁺), with external pressures ∼30 times lower than that for the earlier TA flyby where heavy ions dominated the magnetospheric plasma. When describing the plasma heating and sputtering of Titan's atmosphere, T9 and T18 can be considered interactions of low magnetospheric energy input. On the other hand, T5, when heavy ion fluxes are observed to be higher than typical (i.e., TA), represents the limiting case of high magnetospheric energy input to Titan's upper atmosphere. Anisotropy estimates of the upstream flow are 1<T_⊥/T_‖<3 and the flow is perpendicular to B, indicative of local picked up ions from Titan's H and H₂ coronae extending to Titan's Hill sphere radius. Beyond this distance the corona forms a neutral torus that surrounds Saturn. The T9 flyby unexpectedly resulted in observation of two “wake” crossings referred to as Events 1 and 2. Event 2 was evidently caused by draped magnetosphere field lines, which are scavenging pickup ions from Titan's induced magnetopause boundary with outward flux ∼2×10⁶ ions/cm²/s. The composition of this out flow is dominated by H₂⁺ and H⁺ ions. Ionospheric flow away from Titan with ion flux ∼7×10⁶ ion/cm²/s is observed for Event 1. In between Events 1 and 2 are high energy field aligned flows of magnetosphere protons that may have been accelerated by the convective electric field across Titan's topside ionosphere. T18 observations are much closer to Titan than T9, allowing one to probe this type of interaction down to altitudes ∼950 km. Comparisons with previously reported hybrid simulations are made.     

Silicon ion chemistry in the ionosphere

Loss processes which remove Si⁺ ions selectively relative to other meteor-derived atomic ions in the E- and D-regions of the ionosphere have been identified and measured in the laboratory. The major Si⁺ loss in the E-region is the reaction Si⁺ + H₂O → HSiO⁺ + H (1) with a rate constant 2.3 ± 0.9 × 10^?10 cm³s^?1 at 300 K. The corresponding reactions with Fe⁺, Mg⁺ and other metallic meteor ions are endothermic. Presumably (1) is followed by a fast dissociative-recombination with electrons to produce neutral SiO or Si. At lower altitudes Si⁺ ions associate in a three-body reaction with O₂ with a much larger rate constant than the corresponding associations of Fe⁺ and Mg⁺ with O₂.     

Decrease of ozone and atomic oxygen in the lower mesosphere during a PCA event

It is argued that ozone measurements made by Weeks et al. (1972) can be interpreted in terms of the enhanced ionization present. The conversion of O₂⁺ ions to oxonium, H₃O⁺ · (H₂O)_n, ions plus the dissociative recombination of these ions provides for an increased OH and/or H formation rate. The resulting enhanced OH and HO₂ concentrations reduce the ambient atomic oxygen and hence ozone populations. The net excess H + OH formation rate is found to lie between one and two times the ionization production rate at altitudes where oxonium ions are the dominant positive ion species.     

Ion chemistry in the cometary atmosphere

Dirty ice of a second kind (major components, H₂O, CO, and N₂; minor components less than several percents, NH₃, CH₄, and other organic substances such as HCN, CH₃CN etc.) is assumed for the composition of volatiles in the cometary nucleus. The consistency with the observations of molecular ions and daughter molecules in the cometary atmosphere is argued by taking into account various ion-molecular reactions and dissociative recombinations. There is a satisfactory agreement for the second kind of dirty-ice model, but the presence of large amounts of CH₄ and NH₃ is found to be rather in contradiction with observational evidence. A velocity of 8 km s^?1 for the hydrogen atoms, derived from analysis of the hydrogen Lyman-alpha corona around comets, is found from the dissociative recombination of H₃O⁺, the dominant constituent of cometary ionosphere, in accordance with H₃O⁺+e ^?→OH+H+H.     

Ion-ion recombination rates in the earth's atmosphere

The temperature dependence of the binary recombination coefficient, α₂, for the reaction NO⁺+NO₂^? → products has been obtained over the range 185–530 K. It is found that the corresponding mean cross section $\text{σ}$ is described by the power law $\text{σ}\text{? A · T}{}^{\mathrm{?0.9}}$, and that α₂ ? B · T^?0.4. Data has also been obtained for two cluster ion recombination reactions which indicate that their recombination cross sections are only about 40% larger than for the parent ions at a given temperature, the cross sections for these reactions also apparently increasing with decreasing temperature. In the light of this data and by considering the most probable positive and negative ions existing at various altitudes up to 90km in the atmosphere, the most appropriate ionic recombination coefficients in various altitude ranges are deduced. Thus, between 30 and 90 km, where the recombination process is two-body, the coefficient varies over the narrow range 5–9 × 10^?8 cm³s^?1, while below 30 km the process is predominantly three-body with an effective two-body rate increasing rapidly to a maximum value ≈3 × 10^?6 cm³s^?1 in the troposphere, these deductions being based on published laboratory determinations of three-body recombination coefficients.     

The role of photochemical processes in evolution of the isotopic composition of the atmosphere of Titan

Molecular nitrogen, the main component of the modern atmosphere of Titan, may have formed without significant changes in the nitrogen and hydrogen isotopic composition from the clathrate hydrate of ammonia NH₃ · H₂O_SLD, which is the main accreted form of nitrogen. The most preferable transformation mechanism of NH₃ · H₂O_SLD into atmospheric N₂ is its thermal decomposition in the interior of Titan rather than the photochemical decomposition of ammonia in the upper atmosphere of early Titan. The photolysis of ammonia does not lead to a change in the isotopic composition of nitrogen, as all the nitrogen remains in Titan’s atmosphere. The photolysis of NH does not lead to a change in the isotopic composition of nitrogen in Titan’s atmosphere. Fractionation of hydrogen and nitrogen isotopes during the impacts of comets with Titan does not seem to be significant either. It will be possible to determine the dissociative fractionation factor, the original ratio ¹⁴N/¹⁵N, and the mass of Titan’s original atmosphere when fractionation of nitrogen isotopes in Titan’s atmosphere is examined in additional theoretical and experimental studies that take into account processes occurring during the formation of a system of Saturn’s satellites.     

Radial distribution of production rates, loss rates and densities corresponding to ion masses ?40 amu in the inner coma of Comet Halley: Composition and chemistry

In this paper we have studied the chemistry of C, H, N, O, and S compounds corresponding to ions of masses ?40 amu in the inner coma of the Comet 1P/Halley. The production rates, loss rates, and ion mass densities are calculated using the Analytical Yield Spectrum approach and solving coupled continuity equation controlled by the steady state photochemical equilibrium condition. The primary ionization sources in the model are solar EUV photons, photoelectrons, and auroral electrons of the solar wind origin. The chemical model couples ion-neutral, electron-neutral, photon-neutral and electron-ion reactions among ions, neutrals, electrons, and photons through over 600 chemical reactions. Of the 46 ions considered in the model the chemistry of 24 important ions (viz., CH₃OH⁺₂, H₃CO⁺, NH⁺₄, H₃S⁺, H₂CN⁺, H₂O⁺, NH⁺₃, CO⁺, C₃H⁺₃, OH⁺, H₃O⁺, CH₃OH⁺, C₃H⁺₄, C₂H⁺₂, C₂H⁺, HCO⁺, S⁺, CH⁺₃, H₂S⁺, O⁺, C⁺, CH⁺₄, C⁺₂, and O⁺₂) are discussed in this paper. At radial distances <1000 km, the electron density is mainly controlled by 6 ions, viz., NH⁺₄, H₃O⁺, CH₃OH⁺₂, H₃S⁺, H₂CN⁺, and H₂O⁺, in the decreasing order of their relative contribution. However, at distances >1000 km, the 6 major ions are H₃O⁺, CH₃OH⁺₂, H₂O⁺, H₃CO⁺, C₂H⁺₂, and NH⁺₄; along with ions CO⁺, OH⁺, and HCO⁺, whose importance increases with further increase in the radial distance. It is found that at radial distances greater than ∼1000 km (±500 km) the major chemical processes that govern the production and loss of several of the important ions in the inner coma are different from those that dominate at distances below this value. The importance of photoelectron impact ionization, and the relative contributions of solar EUV, and auroral and photoelectron ionization sources in the inner coma are clearly revealed by the present study. The calculated ion mass densities are compared with the Giotto Ion Mass Spectrometer (IMS) and Neutral Mass Spectrometer (NMS) data at radial distances 1500, 3500, and 6000 km. There is a reasonable agreement between the model calculation and the Giotto measurements. The nine major peaks in the IMS spectra between masses 10 and 40 amu are reproduced fairly well by the model within a factor of two inside the ionopause. We have presented simple formulae for calculating densities of the nine major ions, which contribute to the nine major peaks in the IMS spectra, throughout the inner coma that will be useful in estimating their densities without running the complex chemical models.     

Calculations of the thermochemistry of six reactions leading to ammonia formation in Titan's atmosphere

The thermochemical properties of the six reactions: (1) N₂+hν (solar EUV) → N⁺ + N(⁴S) + e⁻, (2) N⁺ + H₂ → NH⁺ + H, (3) NH⁺ + H₂ → NH⁺₂ + H, (4) NH⁺₂ + H₂ → NH⁺₃ + H, (5) NH⁺₃ + H₂ → NH⁺₄ + H, and (6) NH⁺₄ + e⁻ → NH₃ + H, were theoretically proposed by Atreya in 1986 and were cited in 2003 by Bernard who assumed that this chain reaction would lead to ammonia formation in Titan's atmosphere. The thermochemical properties of these six reactions have been calculated by means of the coupled cluster singles and doubles (CCSD) at the CCSD/cc-pvdz level, and the CCSD/6-311++g(3df,3pd) level, and G2 method. The geometries of the reactants and products of reactions have been optimized, the energies of reactions have been computed. The analysis of the results shows that: (I) The free energies of four reactions among these six reactions are negative. It means that these reactions, namely reactions (1)-(6) except reaction (2), can react spontaneously in Titan's low temperature environment. The converted temperatures of reactions (3) and (5) are 11881.7 and 4596.9 K, respectively. (II) Reaction (2) is an endothermic reaction, its converted temperature is 1797.6 K. When T<1797.6 K, reaction (2) cannot react forward spontaneously. The barrier of reaction (2) is 26.154 kcal mol⁻¹, which is probably too high to allow it to occur in the atmosphere of Titan. The rate for this reaction at 300 K has been calculated, and the value is k=4.16×¹⁰⁻⁷ s⁻¹. (III) The results of the three methods are more or less the same. So it is concluded that this chain reaction cannot be a pathway to lead to ammonia (gas phase) formation in Titan's atmosphere.     

A model of Titan's aerosols based on measurements made inside the atmosphere

The descent imager/spectral radiometer (DISR) instrument aboard the Huygens probe into the atmosphere of Titan measured the brightness of sunlight using a complement of spectrometers, photometers, and cameras that covered the spectral range from 350 to 1600 nm, looked both upward and downward, and made measurements at altitudes from 150 km to the surface. Measurements from the upward-looking visible and infrared spectrometers are described in Tomasko et al. [2008a. Measurements of methane absorption by the descent imager/spectral radiometer (DISR) during its descent through Titan's atmosphere. Planet. Space Sci., this volume]. Here, we very briefly review the measurements by the violet photometers, the downward-looking visible and infrared spectrometers, and the upward-looking solar aureole (SA) camera. Taken together, the DISR measurements constrain the vertical distribution and wavelength dependence of opacity, single-scattering albedo, and phase function of the aerosols in Titan's atmosphere.Comparison of the inferred aerosol properties with computations of scattering from fractal aggregate particles indicates the size and shape of the aerosols. We find that the aggregates require monomers of radius 0.05 μm or smaller and that the number of monomers in the loose aggregates is roughly 3000 above 60 km. The single-scattering albedo of the aerosols above 140 km altitude is similar to that predicted for some tholins measured in laboratory experiments, although we find that the single-scattering albedo of the aerosols increases with depth into the atmosphere between 140 and 80 km altitude, possibly due to condensation of other gases on the haze particles. The number density of aerosols is about 5/cm³ at 80 km altitude, and decreases with a scale height of 65 km to higher altitudes. The aerosol opacity above 80 km varies as the wavelength to the −2.34 power between 350 and 1600 nm.Between 80 and 30 km the cumulative aerosol opacity increases linearly with increasing depth in the atmosphere. The total aerosol opacity in this altitude range varies as the wavelength to the −1.41 power. The single-scattering phase function of the aerosols in this region is also consistent with the fractal particles found above 60 km.In the lower 30 km of the atmosphere, the wavelength dependence of the aerosol opacity varies as the wavelength to the −0.97 power, much less than at higher altitudes. This suggests that the aerosols here grow to still larger sizes, possibly by incorporation of methane into the aerosols. Here the cumulative opacity also increases linearly with depth, but at some wavelengths the rate is slightly different than above 30 km altitude.For purely fractal particles in the lowest few km, the intensity looking upward opposite to the azimuth of the sun decreases with increasing zenith angle faster than the observations in red light if the single-scattering albedo is assumed constant with altitude at these low altitudes. This discrepancy can be decreased if the single-scattering albedo decreases with altitude in this region. A possible explanation is that the brightest aerosols near 30 km altitude contain significant amounts of methane, and that the decreasing albedo at lower altitudes may reflect the evaporation of some of the methane as the aerosols fall into dryer layers of the atmosphere. An alternative explanation is that there may be spherical particles in the bottom few kilometers of the atmosphere.     

Anion chemistry on Titan: A possible route to large N-bearing hydrocarbons

The reaction of CN^? with cyanoacetylene (HC₃N), has been studied as a function of the HC₃N pressure in a quadrupole tandem mass spectrometer. The mass spectra revealed the fast depletion of the CN^? parent ion and formation of larger anions of rapidly growing size. Most of the ions observed were found to belong to two series of products: (HC₃N)_x·C_2p+1N^? and (HC₃N)_x·C_2pN^? resulting from the sequential additions of HC₃N molecules and loss of HCN or HCCN molecules. The mechanism and energetics of the first two reaction steps are briefly discussed. The laboratory data are compared with those from the Cassini CAPS-ELS spectrometer. It is believed that the reactions observed could account for the growth of anions in Titan’s ionosphere.     

The role of hydrocarbons in the lonospheres of the outer planets

The role of hydrocarbons as a possible sink for H⁺ and H₃⁺ ions in the lower ionosphere of the outer planets is examined. Calculations indicate that H⁺ and H₃⁺ are efficiently converted to hydrocarbon ions on reaction with methane. The terminal ions, CH₅⁺ and C₂H₅⁺ are rapidly neutralized in dissociative recombination with electrons. Extreme ultraviolet photolysis of hydrocarbons as a potential additional source of lower elevation ions in investigated.