Laboratory light-scattering measurements with Titan's aerosols analogues produced by a dusty plasma

The chemistry leading to the formation of solid aerosols (tholins) in Titan's atmosphere is simulated by a capacitively coupled plasma in a N₂-CH₄ gas mixture. The solid grains are produced in volume directly in the gas phase and studied ex-situ by SEM imaging and by light scattering on clouds of particles. The scattered light properties depend on the physical properties of the particles (morphologies, size distribution), as well as on the phase angle and the wavelength of the light. The particles may be aggregated or agglomerated grains. The grains size distribution is studied as a function of plasma parameters such as initial methane concentration introduced into the discharge, gas flow, absorbed RF power and plasma duration. The average grain size increases when the amount of CH₄ increases, when the gas flow decreases, and when the plasma duration increases up to a limit for each production condition.For all the samples, the absorption decreases with increasing wavelength in the visible domain. As usually found for irregular particles, the polarization phase curves have a bell-shaped positive branch and a shallow negative branch. The maximum of polarization (P_max) increases when the average grain size decreases (sub-μm-sized grains). To obtain P_max values within the range of those measured in Titan's atmosphere; the average grains diameter has to be smaller than 100 nm, in agreement with the space observations results. In the light-scattering experiment, the size of the agglomerates in the clouds is in the 40-80 μm range in equivalent diameter. As a consequence P_max increases with decreasing wavelength due to the increasing absorption, in agreement with observations of Titan from outside the atmosphere.     

Experimental simulation of Titan's atmosphere: Detection of ammonia and ethylene oxide

For several years now, an experimental simulation of Titan's atmosphere has been on going at LISA. A cold plasma is established in a gas mixture representative of the atmosphere of the satellite. In these experiments, more than 70 organic compounds have been identified, including the first identification in this type of experimental simulation of C₄N₂ already detected in its solid form on Titan, which suggests that the setup correctly mimics the chemistry of Titan's atmosphere.We have carried out the first experimental simulation including O-containing compounds in order to study the influence of the presence of CO on the chemical behavior of Titan's atmosphere. With the help of gas chromatography–mass spectrometry (GC–MS) and infrared spectroscopy (IRS) we can thus determine which minor species still undetected in Titan's atmosphere are likely to be present and understand the complex chemistry of the atmosphere of this satellite. Surprisingly we have identified unpredicted O-containing gaseous compounds, mainly ethylene oxide (also named oxirane, C₂H₄O). This molecule has been observed in the interstellar medium by observation in the millimeter region (Astrophys. J. 489 (1997) 553; Astron. Astrophys. 337 (1998) 275). On the contrary, the predicted O-compounds (formaldehyde and methanol) have not been identified in this experiment. Furthermore, we have identified NH₃ in the gaseous products with an initial mixture of N₂ (98%) and CH₄ (2%).The paper describes the experimental device used in this work, in particular the IRS and GC–MS techniques. We also comment the results related to the detection of the O-containing compounds and NH₃ and their implications on our knowledge of the chemistry of Titan's atmosphere and on the retrieval of the future Titan data expected from Cassini-Huygens.     

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.     

Titan’s atmosphere: An optimal gas mixture for aerosol production?

Here we present the first quantitative study of the gas to solid particle conversion in a Radio Frequency dusty plasma experiment simulating the complex atmospheric reactivity on Titan.Analogs of Titan’s aerosols have been produced in different N₂-CH₄ gas mixtures. Using in situ mass spectrometry, it has been found that, by varying the initial methane concentration, aerosols could be produced in methane steady state concentrations similar to Titan’s atmospheric conditions. In our experiment, an initial ∼5% methane concentration is necessary to ensure a ∼1.5% methane steady state concentration in the plasma.The tholin mass production rate has been quantified as a function of the initial methane concentration. A maximum was found for a steady state CH₄ concentration in agreement with Titan’s atmospheric CH₄ concentrations. At this maximum, the tholin C/N ratio is about 1.45 and the carbon gas to solid conversion yield is about 35%.We have modeled the mass production rate by a parabolic function, highlighting two competitive chemical regimes controlling the tholin production efficiency: an efficient growth process which is proportional to the methane consumption, and an inhibiting process which opposes the growth process and dominates it for initial methane concentrations higher than ∼5%. To explain these two opposite effects, we propose two mechanisms: one involving HCN patterns in the tholins for the growth process, and one involving the increasing amount of atomic hydrogen in the plasma as well as the increase in aliphatic contributions in the tholins for the inhibiting process. This study highlights new routes for understanding the chemical growth of the organic aerosols in Titan’s atmosphere.     

Experimental laboratory simulation of Titan’s atmosphere: aerosols and gas phase

The discovery that Titan, the largest satellite of Saturn, has an atmosphere and that methane is a significant constituent of it, was the starting point for a systematic study of Titan’s atmospheric organic chemistry. Since then, the results from numerous ground-based observations and two flybys of Titan, by Voyager I and II, have led to experimental laboratory simulation studies and photochemical and physical modeling. All these works have provided a more detailed picture of Titan. We report here a continuation of such a study performing an experimental laboratory simulation of Titan’s atmospheric chemistry, and considering the two physical phases involved: gases and aerosols. Concerning the gaseous phase, we report the first detection of C₄N₂ and we propose possible atmospheric abundances for 70 organic compounds on Titan’s upper atmosphere. Concerning the solid phase, we have characterized aerosol analogues synthesized in conditions close to those of Titan’s environment, using elemental analysis, pyrolysis, solubility studies and infrared spectroscopy.     

Carbon isotopic enrichment in Titan's tholins? Implications for Titan's aerosols

Since the discovery of the main composition of Titan's atmosphere, many laboratory experiments have been carried out to reproduce its chemical evolution, particularly the formation of organic haze particles found throughout this atmosphere. Some of these simulations have produced solid products—referred to as Titan's tholins—that are assumed to have properties similar to those of Titan's aerosols. In the present work, we focus on the possible isotopic fractionation of carbon during the processes involved in the formation of Titan's tholins. Initial ¹²C/¹³C isotopic ratios measured on tholins made in the laboratory using cold plasma discharges are presented. Measurements of isotopic enhancement in ¹³C (δ¹³C), both on tholins and on the initial gas mixture (N₂:CH₄ (98:2)) used to produce them do not show any clear deficit or enrichment in ¹³C relative to ¹²C in the lab-made tholins compared to the initial gas mixture. Preliminary data recovered from the Aerosol Collector Pyrolyzer (ACP) experiment of the Huygens probe suggests that Titan's aerosols may also be exempt of carbon isotopic enrichment. This observation creates possibilities for deeper analysis of ACP experiment data.     

Complex Refractive Index of Titan's Aerosol Analogues in the 200-900 nm Domain

The main gas-phase constituents of Titan's upper atmosphere, N₂ and CH₄, are photolyzed and radiolyzed by solar photons and magnetospheric electrons, respectively. The primary products of these chemical interactions evolve to heavier organic compounds that are likely to associate into the particles of haze layers that hide Titan's surface. The different theories and models that have been put forward to explain the characteristics and properties of the haze composites require a knowledge of their optical properties, which are determined by the complex refractive index. We present a new set of values for refractive index n and extinction coefficient k calculated directly from the transmittance and reflectance curves exhibited by a laboratory analogue of Titan's aerosols in the 200-900 nm range. Improvements in the aerosol analogue quality have been made. The effects of variables such as the uncertainty in sample thickness, aerosol porosity, and amount of scattered light on the final n and k values are assessed and discussed. Within the studied wavelength domain, n varies from 1.53 to 1.68 and k varies from 2.62×10⁻⁴ to 2.87×10⁻². These final n and k values should be considered as a new reference to modelers who compute the properties of Titan's aerosols in trying to explain the atmospheric dynamics and surface characteristics.     

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.     

Titan's atmospheric engine: an overview

Heating occurs in Titan's stratosphere from the absorption of incident solar radiation by methane and aerosols. About 10% of the incident sunlight reaches Titan's surface and causes heating there. Thermal radiation redistributes heat within the atmosphere and cools to space. The resulting vertical temperature profile is stable against convection and a state of radiative equilibrium is established. Equating theoretical and observed temperature profiles enables an empirical determination of the vertical distribution of thermal opacity. A uniformly mixed aerosol is responsible for most of the opacity in the stratosphere, whereas collision-induced absorption of gases is the main contributor in the troposphere. Occasional clouds are observed in the troposphere in spite of the large degrees of methane supersaturation found there. Photochemistry converts CH₄ and N₂ into more complex hydrocarbons and nitriles in the stratosphere and above. Thin ice clouds of trace organics are formed in the winter and early spring polar regions of the lower stratosphere. Precipitating ice particles serve as condensation sites for supersaturated methane vapor in the troposphere below, resulting in lowered methane degrees of supersaturation in the polar regions. Latitudinal variations of stratospheric temperature are seasonal, and lag instantaneous response to solar irradiation by about one season for two reasons: (1) an actual instantaneous thermal response to a latitudinal distribution of absorbing gases, themselves out of phase with the sun by about one season, and (2) a sluggish dynamical response of the stratosphere to the latitudinal transport of angular momentum, induced by radiative heating and cooling. Mean vertical abundances of stratospheric organics and aerosols are determined primarily by atmospheric chemistry and condensation, whereas latitudinal distributions are more influenced by meridional circulations. In addition to preferential scavenging by precipitating ice particles from above, the polar depletion of supersaturated methane results from periodic scavenging by short-lived tropospheric clouds, coupled with the steady poleward march of the continuously drying atmosphere due to meridional transport.     

Titan's corona: The contribution of exothermic chemistry

The contribution of exothermic ion and neutral chemistry to Titan's corona is studied. The production rates for fast neutrals N₂, CH₄, H, H₂, ³CH₂, CH₃, C₂H₄, C₂H₅, C₂H₆, N(⁴S), NH, and HCN are determined using a coupled ion and neutral model of Titan's upper atmosphere. After production, the formation of the suprathermal particles is modeled using a two-stream simulation, as they travel simultaneously through a thermal mixture of N₂, CH₄, and H₂. The resulting suprathermal fluxes, hot density profiles, and energy distributions are compared to the N₂ and CH₄ INMS exospheric data presented in [De La Haye, V., Waite Jr., J.H., Johnson, R.E., Yelle, R.V., Cravens, T.E., Luhmann, J.G., Kasprzak, W.T., Gell, D.A., Magee, B., Leblanc, F., Michael, M., Jurac, S., Robertson, I.P., 2007. J. Geophys. Res., doi:10.1029/2006JA012222, in press], and are found insufficient for producing the suprathermal populations measured. Global losses of nitrogen atoms and carbon atoms in all forms due to exothermic chemistry are estimated to be and .     

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.     

The role of organic haze in Titan's atmospheric chemistry: II. Effect of heterogeneous reaction to the hydrogen budget and chemical composition of the atmosphere

One of the key components controlling the chemical composition and climatology of Titan's atmosphere is the removal of reactive atomic hydrogen from the atmosphere. A proposed process of the removal of atomic hydrogen is the heterogeneous reaction with organic aerosol. In this study, we investigate the effect of heterogeneous reactions in Titan's atmospheric chemistry using new measurements of the heterogeneous reaction rate [Sekine, Y., Imanaka, H., Matsui, T., Khare, B.N., Bakes, E.L.O., McKay, C.P., Sugita, S., 2008. Icarus 194, 186-200] in a one-dimensional photochemical model. Our results indicate that 60-75% of the atomic hydrogen in the stratosphere and mesosphere are consumed by the heterogeneous reactions. This result implies that the heterogeneous reactions on the aerosol surface may predominantly remove atomic hydrogen in Titan's stratosphere and mesosphere. The results of our calculation also indicate that a low concentration of atomic hydrogen enhances the concentrations of unsaturated complex organics, such as C₄H₂ and phenyl radical, by more than two orders in magnitude around 400 km in altitude. Such an increase in unsaturated species may induce efficient haze production in Titan's mesosphere and upper stratosphere. These results imply a positive feedback mechanism in haze production in Titan's atmosphere. The increase in haze production would affect the chemical composition of the atmosphere, which might induce further haze production. Such a positive feedback could tend to dampen the loss and supply cycles of CH₄ due to an episodic CH₄ release into Titan's atmosphere.     

Coupling photochemistry with haze formation in Titan's atmosphere, Part II: Results and validation with Cassini/Huygens data

The new one-dimensional radiative-convective/photochemical/microphysical model described in Part I is applied to the study of Titan's atmospheric processes that lead to haze formation. Our model generates the haze structure from the gaseous species photochemistry. Model results are presented for the species vertical concentration profiles, haze formation and its radiative properties, vertical temperature/density profiles and geometric albedo. These are validated against Cassini/Huygens observations and other ground-based and space-borne measurements. The model reproduces well most of the latest measurements from the Cassini/Huygens instruments for the chemical composition of Titan's atmosphere and the vertical profiles of the observed species. For the haze production we have included pathways that are based on pure hydrocarbons, pure nitriles and hydrocarbon/nitrile copolymers. From these, the nitrile and copolymer pathways provide the stronger contribution, in agreement with the results from the ACP instrument, which support the incorporation of nitrogen in the pyrolized haze structures. Our haze model reveals a new second major peak in the vertical profile of haze production rate between 500 and 900 km. This peak is produced by the copolymer family used and has important ramifications for the vertical atmospheric temperature profile and geometric albedo. In particular, the existence of this second peak determines the vertical profile of haze extinction. Our model results have been compared with the DISR retrieved haze extinction profiles and are found to be in very good agreement. We have also incorporated in our model heterogeneous chemistry on the haze particles that converts atomic hydrogen to molecular hydrogen. The resultant H₂ profile is closer to the INMS measurements, while the vertical profile of the diacetylene formed is found to be closer to that of the CIRS profile when this heterogenous chemistry is included.     

Coupled ion and neutral rotating model of Titan's upper atmosphere

A one-dimensional composition model of Titan's upper atmosphere is constructed, coupling 36 neutral species and 47 ions. Energy inputs from the Sun and from Saturn's magnetosphere and updated temperature and eddy coefficient parameters are taken into account. A rotating technique at constant latitude and varying local-time is proposed to account for the diurnal variation of solar inputs. The contributions of photodissocation, neutral chemistry, ion-neutral chemistry, and electron recombination to neutral production are presented as a function of altitude and local time. Local time-dependent mixing ratio and density profiles are presented in the context of the TA and T₅ Cassini data and are compared in detail to previous models. An independent and simplified ion and neutral scheme (19-species) is also proposed for future 3D-purposes. The model results demonstrate that a complete understanding of the chemistry of Titan's upper atmosphere requires an understanding of the coupled ion and neutral chemistry. In particular, the ionospheric chemistry makes significant contributions to production rates of several important neutral species.     

Transition from Gaseous Compounds to Aerosols in Titan's Atmosphere

We investigate the chemical transition of simple molecules like C₂H₂ and HCN into aerosol particles in the context of Titan's atmosphere. Experiments that synthesize analogs (tholins) for these aerosols can help illuminate and constrain these polymerization mechanisms. Using information available from these experiments, we suggest chemical pathways that can link simple molecules to macromolecules, which will be the precursors to aerosol particles: polymers of acetylene and cyanoacetylene, polycyclic aromatics, polymers of HCN and other nitriles, and polyynes. Although our goal here is not to build a detailed kinetic model for this transition, we propose parameterizations to estimate the production rates of these macromolecules, their C/N and C/H ratios, and the loss of parent molecules (C₂H₂, HCN, HC₃N and other nitriles, and C₆H₆) from the gas phase to the haze. We use a one-dimensional photochemical model of Titan's atmosphere to estimate the formation rate of precursor macromolecules. We find a production zone slightly lower than 200 km altitude with a total production rate of 4×10⁻¹⁴ g cm⁻² s⁻¹ and a C/N?4. These results are compared with experimental data, and to microphysical model requirements. The Cassini/Huygens mission will bring a detailed picture of the haze distribution and properties, which will be a great challenge for our understanding of these chemical processes.     

The dust environment at Titan

To explain the observed abundances of CO₂ in Titan's atmosphere, a relatively high water deposition into the atmosphere needs to be invoked due to the importance of H₂O photolysis in CO₂ production. A likely source of H₂O is icy dust particles from space. This paper considers the direct dust input to Titan's atmosphere from the interplanetary environment, and also ejecta particles from micrometeoroid impacts with the icy satellites Hyperion, Iapetus and Phoebe. It is found that the likely mass influx to Titan is 10^–16 to 10^–15 kg m^–2 s^–1. This mass influx is an order of magnitude too low to explain the observed levels of CO₂ in Titan's atmosphere in the context of a recent photochemical model. This leads one to speculate as to the likelihood of one large impact to Titan in the recent past;i.e., that the atmosphere is not in equilibrium but is cnrrently losing CO₂.     

Laboratory studies of methane and ethane adsorption and nucleation onto organic particles: Application to Titan's clouds

Titan, Saturn's largest moon, has a thick nitrogen/methane atmosphere. The temperature and pressure conditions in Titan's atmosphere are such that the methane vapor should condense near the tropopause to form clouds. Several ground-based measurements have observed sparse cloud-like features in Titan's atmosphere, while the Cassini mission to Saturn has provided large scale images of the clouds. However, Titan's cloud formation conditions remain poorly constrained. Heterogeneous nucleation (from the vapor phase onto a solid or liquid aerosol surface) greatly enhances cloud formation relative to homogeneous nucleation. In order to elucidate the cloud formation mechanism near the tropopause, we have performed laboratory measurements of the adsorption of methane and ethane onto solid organic particles (tholins) representative of Titan's photochemical haze. We find that monolayers of methane adsorb onto tholin particles at saturation ratios less than unity. We also find that solid methane nucleates onto the adsorbed methane at a saturation ratio of S=1.07±0.008. This implies that Titan's methane clouds should form easily. This is consistent with recent measurements of the column of methane ruling out excessive methane supersaturation. In addition, we find ethane adsorbs onto tholin particles in a metastable phase prior to nucleation. However, ethane nucleation onto the adsorbed ethane occurs at a relatively high saturation ratio of S=1.36±0.08. These findings are consistent with the recent report of polar ethane clouds in Titan's lower stratosphere.     

Ejection of nitrogen from Titan's atmosphere by magnetospheric ions and pick-up ions

A 3-D Monte Carlo model is used to describe the ejection of N and N₂ from Titan due to the interaction of Saturn's magnetospheric N⁺ ions and molecular pick-up ions with its N₂ atmosphere. Based on estimates of the ion flux into Titan's corona, atmospheric sputtering is an important source of both atomic and molecular nitrogen for the neutral torus and plasma in Saturn's outer magnetosphere, a region now being studied by the Cassini spacecraft.     

Temperature dependence of HC3N,C6H2, and C4N2 mid-UV absorption coefficients. Application to the interpretation of Titan's atmospheric spectra

Three organic compounds (HC₃N, C₆H₂, and C₄N₂) relevant of Titan's atmosphere have been studied within the framework of the SIPAT (Spectroscopie UV d'Intérêt Prébiologique dans l'Atmosphère de Titan) program. Since this facility is still unable to reach the very low temperatures (170 K) of Titan's high atmosphere, spectra have to be obtained at several absorption-cell temperatures, and the data extrapolated towards lower temperatures. Previously published HC₃N and C₆H₂ absorption coefficient data are reviewed, while new spectroscopic data are presented on C₄N₂. Integrated intensity calculations over the vibrational bands are performed apart from the background continuum. Thus, only the band contrast is considered here. While, the temperature dependence of the hot-band integrated intensity follows a Boltzmann distribution, we have enhanced the fit through an empirical parametrisation to account for the observed temperature dependence of the C₄N₂ and HC₃N absorption coefficients, and to extrapolate those data to the low temperature conditions of Titan's high atmosphere. Finally, we discuss the implications of the results to possible detection by remote sensing observations of these minor compounds in Titan's atmosphere.     

Ion chemistry and N-containing molecules in Titan's upper atmosphere

High-energy photons, electrons, and ions initiate ion-neutral chemistry in Titan's upper atmosphere by ionizing the major neutral species (nitrogen and methane). The Ion and Neutral Mass Spectrometer (INMS) onboard the Cassini spacecraft performed the first composition measurements of Titan's ionosphere. INMS revealed that Titan has the most compositionally complex ionosphere in the Solar System, with roughly 50 ions at or above the detection threshold. Modeling of the ionospheric composition constrains the density of minor neutral constituents, most of which cannot be measured with any other technique. The species identified with this approach include the most complex molecules identified so far on Titan. This confirms the long-thought idea that a very rich chemistry is actually taking place in this atmosphere. However, it appears that much of the interesting chemistry occurs in the upper atmosphere rather than at lower altitudes. The species observed by INMS are probably the first intermediates in the formation of even larger molecules. As a consequence, they affect the composition of the bulk atmosphere, the composition and optical properties of the aerosols and the flux of condensable material to the surface. In this paper, we discuss the production and loss reactions for the ions and how this affects the neutral densities. We compare our results to neutral densities measured in the stratosphere by other instruments, to production yields obtained in laboratory experiments simulating Titan's chemistry and to predictions of photochemical models. We suggest neutral formation mechanisms and highlight needs for new experimental and theoretical data.