Inclusion of sulfur chemistry in a validated C/H/O/N chemical network: identification of key C/S coupling pathways

Abstract

The detection of SO2 in both WASP-39 b and WASP-107 b recently brought more attention to the modeling of photochemistry in exoplanets. However, sulfur kinetics data is lacking in the literature for the full C/H/O/N/S system. The networks used to model this chemistry neglect the coupling between sulfur and other C/H/O/N species. We aimed to integrate sulfur kinetics to our previously developed C_0-C_2/H/O/N chemical network, with the inclusion of its coupling to carbon and nitrogen chemistry, for conditions between 500 - 2500 K and 100 - 10^-6 bar, and any atomic composition. To achieve this reliability, we used a dual approach, deriving the network from other available combustion networks and from original ab initio calculations where data was lacking. This was performed together with an extensive validation of the network on 1606 experimental measurements from the literature on the combustion and pyrolysis of multiple sulfur compounds such as H2S, CH3SH, CS2 and OCS. To examine the consequences of this new chemical network on exoplanets atmospheric studies, we generated abundance profiles for GJ 436 b, GJ 1214 b, HD 189733 b, HD 209458 b, WASP-39 b and WASP-107 b using the 1D kinetic model FRECKLL, calculated the corresponding transmission spectra using TauREx 3.1 and compared these results with other chemical networks used in exoplanet modeling with sulfur. The coupling between carbon and sulfur chemistry is found to be impactful on both abundance profiles and observables, with CH2S being its key species. CS2 abundance is found to be probably much higher than anticipated in current kinetic networks for exoplanets. The detection of CS2 in TOI-270 d highlights the importance of using validated chemical networks to improve the reliability of our models, particularly in the JWST era. Combustion and pyrolysis data are largely available tools that reveal to be very useful for this task.