Simulating the density of organic species in the atmosphere of Titan with a coupled ion-neutral photochemical model

We present a one-dimensional coupled ion-neutral photochemical kinetics and diffusion model to study the atmospheric composition of Titan in light of new theoretical kinetics calculations and scientific findings from the Cassini-Huygens mission. The model extends from the surface to the exobase. The atmospheric background, boundary conditions, vertical transport and aerosol opacity are all constrained by the Cassini-Huygens observations. The chemical network includes reactions between hydrocarbons, nitrogen and oxygen bearing species. It takes into account neutrals and both positive and negative ions with masses extending up to 116 and 74u, respectively. We incorporate high-resolution isotopic photoabsorption and photodissociation cross sections for N-2 as well as new photodissociation branching ratios for CH4 and C2H2. Ab initio transition state theory calculations are performed in order to estimate the rate coefficients and products for critical reactions. Main reactions of production and loss for neutrals and ions are quantitatively assessed and thoroughly discussed. The vertical distributions of neutrals and ions predicted by the model generally reproduce observational data, suggesting that for the small species most chemical processes in Titan's atmosphere and ionosphere are adequately described and understood; some differences are highlighted. Notable remaining issues include (i) the total positive ion density (essentially HCNH+) in the upper ionosphere, (ii) the low mass negative ion densities (CN-, C3N-/C4H-) in the upper atmosphere, and (iii) the minor oxygen-bearing species (CO2, H2O) density in the stratosphere. Pathways towards complex molecules and the impact of aerosols (UV shielding, atomic and molecular hydrogen budget, nitriles heterogeneous chemistry and condensation) are evaluated in the model, along with lifetimes and solar cycle variations. (C) 2018 Elsevier Inc. All rights reserved.