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.     

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.     

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.     

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.     

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.     

Influence of neutral transport on ion chemistry uncertainties in Titan ionosphere

Models of Titan ionospheric chemistry have shown that ion densities depend strongly on the neutral composition. The turbulent diffusion transport conditions, as modeled by eddy coefficients, can spectacularly affect the uncertainty on predicted neutral densities. In order to evaluate the error budget on ion densities predicted by photochemical models, we perform uncertainty propagation of neutral densities by Monte Carlo sampling and assess their sensitivity to two turbulent diffusion profiles, corresponding to the extreme profiles at high altitudes described in the literature. A strong sensitivity of the ion density uncertainties to transport is observed, generally more important than to ion–molecule reaction parameters themselves. This highlights the necessity to constrain eddy diffusion profiles for Titan ionosphere, which should progressively be done thanks to the present and future measurements of the orbiter Cassini.     

Removal of Titan's noble gases by their trapping in its haze

Titan's haze, formed by photolysis of C₂H₂, C₂H₄ and HCN, was found experimentally to trap Ar, Kr and Xe with efficiencies of 3.5 × 10⁻⁴, 1.9 × 10⁻³ and 6.5 × 10⁻² [noble gas atom]/[carbon atom] in the polymer, respectively. The rate of aerosol formation and settling down of 3 × 10⁻¹³ kg m⁻² s⁻¹, as inferred from our experiments on CH₄ photolysis in the far UV [Podolak, M., Bar-Nun, A., 1979. Icarus 39, 272-276], is sufficient to reduce the mixing ratios of ³⁶Ar and ⁴⁰Ar to their low values of (2.8 ± 0.3) × 10⁻⁷ and (4.3 ± 0.1) × 10⁻³, respectively, and those of Kr and Xe to below the detection limit of 10⁻⁸.     

Chemical sources of haze formation in Titan's atmosphere

A prominent feature of Titan's atmosphere is a thick haze region that acts as the end product of hydrocarbon and nitrile chemistry. Using a one-dimensional photochemical model, an investigation into the chemical mechanisms responsible for the formation of this haze region is conducted. The model derives profiles for Titan's atmospheric constituents that are consistent with observations. Included is an updated benzene profile that matches more closely with—recent ISO observations (Icarus 161 (2003) 383), replacing the profile given in the benzene study of Wilson et al. (J. Geophys. Res. 108 (2003) 5014). Using these profiles, pathways from polyynes, aromatics, and nitriles are considered, as well as possible copolymerization among the pathways. The model demonstrates that the growth of polycyclic aromatic hydrocarbons throughout the lower stratosphere plays an important role in furnishing the main haze layer, with nitriles playing a secondary role. The peak chemical production of haze layer ranges from 140 to 300 km peaking at an altitude of 220 km, with a production rate of 3.2×10⁻¹⁴ gcm⁻² s⁻¹. Possible mechanisms for polymerization and copolymerization and suggestions for further kinetic study are discussed, along with the implications for the distribution of haze in Titan's atmosphere.     

Titan's atmospheric chemistry: Photolysis of gas mixtures containing hydrogen cyanide and carbon monoxide at 185 and 254 nm

The formation of organic compounds in the atmosphere of Titan is an ongoing process of the generation of complex organics from the simplest hydrocarbon, methane. Solar radiation and magnetosphere electrons are the main energy sources that drive the reactions in Titan's atmosphere. Since energy from solar radiation is 200 times greater than that from magnetosphere electrons, we have investigated the products formed by the action of UV radiation (185 and 254 nm) on a mixture of gases containing nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene, the basic gas mixture (BGM) that simulates aspects of Titan's atmosphere using a flow reactor [Tran, B.N., Ferris, J.P., Chera, J.J., 2003a. Icarus 162, 114-124; Tran, B.N., Joseph, J.C., Force, M., Briggs, R.G., Vuitton, V., Ferris, J.P., 2005. Icarus 177, 106-115]. The present research extends these studies by the addition of carbon monoxide and hydrogen cyanide to the BGM. Quantum yields for the loss of reactants and the formation of volatile products were determined and compared with those measured in the absence of the hydrogen cyanide and carbon monoxide. The GCMS analyses of the volatile photolysis products from the BGM, with added hydrogen cyanide, had a composition similar to that of the BGM while the photolysis products of the BGM with added carbon monoxide contained many oxygenated compounds. The infrared spectrum of the corresponding solid product revealed the absorption band of a ketone group, which was probably formed from the reaction of carbon monoxide with the free radicals generated by photolysis of acetylene and ethylene. Of particular interest was the observation that the addition of HCN to the gas mixture only resulted in a very small change in the C/N ratio and in the intensity of the CN frequency at 2210 cm⁻¹ in the infrared spectrum suggesting that little HCN is incorporated into the haze analog. The C/N ratio of the haze analogs was found to be in the 10-12 range. The UV spectra of the solid products formed when HCN or CO added to the BGM is similar to the UV absorption formed from the BGM alone. This result is consistent with absence of additional UV chromophores to the solid product when these mixtures are photolyzed. The following photoproducts, which were not starting materials in our photochemical studies, have been observed on Titan: acetonitrile, benzene, diacetylene, ethane, propene, propane, and propyne.     

Analysis of Titan's neutral upper atmosphere from Cassini Ion Neutral Mass Spectrometer measurements

In this paper we present an in-depth study of the distributions of various neutral species in Titan's upper atmosphere, between 950 and 1500 km for abundant species (N₂, CH₄, H₂) and between 950 and 1200 km for other minor species. Our analysis is based on a large sample of Cassini/INMS (Ion Neutral Mass Spectrometer) measurements in the CSN (Closed Source Neutral) mode, obtained during 15 close flybys of Titan. To untangle the overlapping cracking patterns, we adopt Singular Value Decomposition (SVD) to determine simultaneously the densities of different species. Except for N₂, CH₄, H₂ and ⁴⁰Ar (as well as their isotopes), all species present density enhancements measured during the outbound legs. This can be interpreted as a result of wall effects, which could be either adsorption/desorption of these molecules or heterogeneous surface chemistry of the associated radicals on the chamber walls. In this paper, we provide both direct inbound measurements assuming ram pressure enhancement only and abundances corrected for wall adsorption/desorption based on a simple model to reproduce the observed time behavior. Among all minor species of photochemical interest, we have firm detections of C₂H₂, C₂H₄, C₂H₆, CH₃C₂H, C₄H₂, C₆H₆, CH₃CN, HC₃N, C₂N₂ and NH₃ in Titan's upper atmosphere. Upper limits are given for other minor species.The globally averaged distributions of N₂, CH₄ and H₂ are each modeled with the diffusion approximation. The N₂ profile suggests an average thermospheric temperature of 151 K. The CH₄ and H₂ profiles constrain their fluxes to be and , referred to Titan's surface. Both fluxes are significantly higher than the Jeans escape values. The INMS data also suggest horizontal/diurnal variations of temperature and neutral gas distribution in Titan's thermosphere. The equatorial region, the ramside, as well as the nightside hemisphere of Titan appear to be warmer and present some evidence for the depletion of light species such as CH₄. Meridional variations of some heavy species are also observed, with a trend of depletion toward the north pole. Though some of the above variations might be interpreted by either the solar-driven models or auroral-driven models, a physical scenario that reconciles all the observed horizontal/diurnal variations in a consistent way is still missing. With a careful evaluation of the effect of restricted sampling, some of the features shown in the INMS data are more likely to be observational biases.     

Low temperature (39-298 K) kinetics study of the reactions of the C4H radical with various hydrocarbons observed in Titan's atmosphere

The reaction kinetics of the butadinyl radical, C₄H, with various hydrocarbons detected in the atmosphere of Titan (methane, ethane, propane, acetylene, ethene and methylacetylene) are studied over the temperature range of 39-298 K using the Rennes CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme) apparatus. Kinetic measurements were made using the pulsed laser photolysis—laser induced fluorescence technique. The rate coefficients, except for the reaction with methane, all show a negative temperature dependence and can be fitted with the following expressions over the temperature range of this study: ; ; , , . These expressions are not intended to be physically meaningful but rather to provide an easy way to introduce experimental results in photochemical models. They are only valid over the temperature range of the experiments. Possible channels of these reactions are discussed as well as possible consequences of these results for the production of large molecules and hazes in the atmosphere of Titan. These results should also be considered for the photochemistry of Giant Planets.     

Titan's hydrodynamically escaping atmosphere

The upper atmosphere of Titan is currently losing mass at a rate , by hydrodynamic escape as a high density, slow outward expansion driven principally by solar UV heating by CH₄ absorption. The hydrodynamic mass loss is essentially CH₄ and H₂ escape. Their combined escape rates are restricted by power limitations from attaining their limiting rates (and limiting fluxes). Hence they must exhibit gravitational diffusive separation in the upper atmosphere with increasing mixing ratios to eventually become major constituents in the exosphere. A theoretical model with solar EUV heating by N₂ absorption balanced by HCN rotational line cooling in the upper thermosphere yields densities and temperatures consistent with the Huygens Atmospheric Science Investigation (HASI) data [Fulchignoni, M., and 42 colleagues, 2005. Nature 438, 785-791], with a peak temperature of ∼185-190 K between 3500-3550 km. This model implies hydrodynamic escape rates of and , or some other combination with a higher H₂ escape flux, much closer to its limiting value, at the expense of a slightly lower CH₄ escape rate. Nonthermal escape processes are not required to account for the loss rates of CH₄ and H₂, inferred by the Cassini Ion Neutral Mass Spectrometer (INMS) measurements [Yelle, R.V., Borggren, N., de la Haye, V., Kasprzak, W.T., Niemann, H.B., Müller-Wodarg, I., Waite Jr., J.H., 2006. Icarus 182, 567-576].     

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 .     

In situ thermal conductivity measurements of Titan's lower atmosphere

Thermal conductivity measurements, presented in this paper (Fig. 3), were made during the descent of the Huygens probe through the atmosphere of Titan below the altitude of 30 km. The measurements are broadly consistent with reference values derived from the composition, pressure and temperature profiles of the atmosphere; except in narrow altitude regions around 19 km and 11 km, where the measured thermal conductivity is lower than the reference by 1% and 2%, respectively. Only single data point exists at each of the two altitudes mentioned above; if true however, the result supports the case for existence for molecules heavier than nitrogen in these regions (such as: ethane, other primordial noble gases, carbon dioxide, and other hydrocarbon derivatives). The increasing thermal conductivity observed below 7 km altitude could be due to some liquid deposition during the descent; either due to condensation and/or due to passing through layers of fog/cloud containing liquid nitrogen-methane. Thermal conductivity measurements do not allow conclusions to be drawn about how such liquid may have entered the sensor, but an estimate of the cumulative liquid content encountered in the last 7 km is 0.6% by volume of the Titan's atmosphere sampled during descent.     

Modeling chemical growth processes in Titan's atmosphere 2. Theoretical study of reactions between C2H and ethene, propene, 1-butene, 2-butene, isobutene, trimethylethene, and tetramethylethene

Barrierless reactions between unsaturated hydrocarbons and the ethynyl radical (C₂H) can contribute to the growth of organic particulates in the haze-forming regions of Titan's atmosphere as well as in the gas giants and in the interstellar medium. We employed a combination of quantum chemistry and statistical rate theories to characterize reactions between ground state C₂H and seven alkenes of the general structure R₁R₂C^′C^″R₃R₄ containing up to six carbons. The alkenes included ethene (C₂H₄); propene (C₃H₆); 1-butene, 2-butene, and isobutene (C₄H₈); trimethylethene (C₅H₁₀); and tetramethylethene (C₆H₁₂). Density functional theory calculations at the B3LYP/6-31 + G^∗∗ level were used to characterize the adducts, isomers, products, and the intervening transition states for the addition-elimination reactions of all seven species. A multiple-well treatment was then employed to determine the outcome distributions for the range of temperatures and pressures relevant to Titan's atmosphere, the interstellar medium, and the outer atmospheres of the gas giants. Finally, trajectory calculations using an ROMP2 potential energy surface were used to calculate kinetic rates for the ethene + C₂H reaction, where the agreement between the computed and measured values is very good. At low pressure and temperature, vinyl acetylene is a dominant product of several of the reactions, and all of the reactions yield at least one dominant product with both a double and a triple CC bond.     

Epistemic bimodality and kinetic hypersensitivity in photochemical models of Titan's atmosphere

We show that photochemical models of Titan's atmosphere can give rise to bimodal distributions in the abundances of some major compounds, like C₂H₂ and C₂H₄. Sensitivity analysis enabled us to identify the causes and conditions of this bimodality. We propose several methods to control this behavior in photochemical models. In particular, we point out the importance of two key reactions and the needs for a critical evaluation of the kinetic data. We also show that the abundances of some compounds are hypersensitive to the ratio [CH₄]/[H], suggesting that a time-dependent variation of this ratio might lead to a real bistability in the high atmosphere of Titan.     

The photochemical model of Titan’s atmosphere and ionosphere: A version without hydrodynamic escape

There are observational and theoretical evidences both in favor of and against hydrodynamic escape (HDE) on Titan, and the problem remains unsolved. A test presented here for a static thermosphere does not support HDE on Titan and Triton but favors HDE on Pluto. Cooling of the atmosphere by the HCN rotational lines is limited by rotational relaxation above 1100 km and self-absorption below 900 km on Titan. HDE can affect the structure and composition of the atmosphere and its evolution. Hydrocarbon, nitrile, and ion chemistries are strongly coupled on Titan, and attempts to calculate them separately may result in significant errors. Here we apply our photochemical model of Titan’s atmosphere and ionosphere to the case of no hydrodynamic escape. Our model is still the only after-Cassini self-consistent model of coupled neutral and ion chemistry. The lack of HDE is a distinct possibility, and comparing models with and without HDE is of practical interest. The mean difference between the models and the neutral and ion compositions observed by INMS are somewhat better for the model with HDE. A reaction of NH₂ with H₂CN suggested by Yelle et al. (2009) reduces but does not remove a significant difference between the ammonia abundances in the models and INMS observations. Losses of methane and nitrogen and production and deposition to the surface of hydrocarbons and nitriles are evaluated in the model, along with lifetimes and evolutionary aspects.     

Vertical profiles of HCN, HC3N, and C2H2 in Titan's atmosphere derived from Cassini/CIRS data

Mid-infrared limb spectra in the range 600-1400 cm⁻¹ taken with the Composite InfraRed Spectrometer (CIRS) on-board the Cassini spacecraft were used to determine vertical profiles of HCN, HC₃N, C₂H₂, and temperature in Titan's atmosphere. Both high (0.5 cm⁻¹) and low (13.5 cm⁻¹) spectral resolution data were used. The 0.5 cm⁻¹ data gave profiles at four latitudes and the 13.5 cm⁻¹ data gave almost complete latitudinal coverage of the atmosphere. Both datasets were found to be consistent with each other. High temperatures in the upper stratosphere and mesosphere were observed at Titan's northern winter pole and were attributed to adiabatic heating in the subsiding branch of a meridional circulation cell. On the other hand, the lower stratosphere was much colder in the north than at the equator, which can be explained by the lack of solar radiation and increased IR emission from volatile enriched air. HC₃N had a vertical profile consistent with previous ground based observations at southern and equatorial latitudes, but was massively enriched near the north pole. This can also be explained in terms of subsidence at the winter pole. A boundary observed at 60° N between enriched and un-enriched air is consistent with a confining polar vortex at 60° N and HC₃N's short lifetime. In the far north, layers were observed in the HC₃N profile that were reminiscent of haze layers observed by Cassini's imaging cameras. HCN was also enriched over the north pole, which gives further evidence for subsidence. However, the atmospheric cross section obtained from 13.5 cm⁻¹ data indicated a HCN enriched layer at 200-250 km, extending into the southern hemisphere. This could be interpreted as advection of polar enriched air towards the south by a meridional circulation cell. This is observed for HCN but not for HC₃N due to HCN's longer photochemical lifetime. C₂H₂ appears to have a uniform abundance with altitude and is not significantly enriched in the north. This is consistent with observations from previous CIRS analysis that show increased abundances of nitriles and hydrocarbons but not C₂H₂ towards the north pole.     

Carbon monoxide fluorescence from Titan's atmosphere

We report on the discovery of emissions due to carbon monoxide from Titan's atmosphere, from mid-infrared observations with the ISAAC spectrometer at the Very Large Telescope and covering the 4.50-4.85 μm range. We detected about 45 emission lines coinciding with CO ro-vibrational lines, including CO(1-0) (P18 to R11) and CO(2-1) (P11 to R11). We show that these emissions cannot be generated thermally but occur in non-LTE conditions, due to radiative de-excitation from the v=1 and v=2 CO levels after excitation at 4.7 and 2.3 μm by solar radiation. A complete fluorescence model is then developed, allowing to compute the state populations of the two most abundant CO isotopes and N₂(1). It includes absorption by CO and CH₄, and vibrational-thermal and vibrational-vibrational collisional exchanges with CO, N₂, CH₄, and H₂. Emerging radiances at the top of the atmosphere are evaluated with a line-by-line code and compared to observations. Contribution functions show that the CO emissions sound Titan's stratosphere: while the (1-0) lines generally probe two layers, located respectively at 100-250 km and 300-550 km, the (2-1) lines are sensitive to the intermediate layer at 150-300 km. A sensitivity study is performed to establish the effect of the main model parameters (temperature profile, collisional scenario, and CO stratospheric abundance) on the results. Models reproduce the essential structure of the observed emissions. The (1-0) fundamental band is generally well fit with a nominal CO mixing ratio of 32 ppm—as inferred in the troposphere from observations at 4.80-5.10 μm (Lellouch et al., 2003, Icarus 162, 126-143). However, this band is only weakly dependent on the CO abundance, and given temperature and collisional scenario uncertainties, it constrains the CO stratospheric mixing ratio only to within a factor of ∼3. In addition, the nominal model with 32 ppm CO underestimates the first hot (2-1) transition by approximately a factor of 2. This discrepancy can be resolved by a combined adjustment of collisional rates and an increased CO stratospheric ratio of 60 ppm, consistent with the determination of Gurwell and Muhleman (2000, Icarus 145, 653-656). In contrast, the CO vertical profile suggested by Hidayat et al. (1998, Icarus 133, 109-133), strongly depleted above 200 km, cannot match the data for any realistic collisional scenario, and is therefore not supported by our results.