2026A&A...705A..50A

Chemical models are routinely used to predict the atmospheric composition of exoplanets and compare it with the composition retrieved from observations, but little is known about the reliability of the calculated composition. We carried out a sensitivity analysis to quantify the uncertainties in the abundances calculated by a state-of-the-art chemical atmosphere model of the widely observed planets WASP-33b, HD 209458b, HD 189733b, WASP-39b, GJ 436b, and GJ 1214b. We found that the abundance uncertainties in the observable atmosphere are relatively small, below one order of magnitude and in many cases below a factor of two, where vertical mixing is a comparable or even larger source of uncertainty than (photo)chemical kinetics. In general, planets with a composition close to chemical equilibrium have smaller abundance uncertainties than planets whose composition is dominated by photochemistry. Some molecules, such as H₂O, CO, CO₂, and SiO, show low abundance uncertainties, while others such as HCN, SO₂, PH₃, and TiO have more uncertain abundances. We identified several critical albeit poorly constrained processes involving S-, P-, Si-, and Ti-bearing species whose better characterization should lead to a global improvement in the accuracy of models. Some of these key processes are the three-body association reactions S + H₂, Si + O, NH + N, and N₂H₂ + H; the chemical reactions S + OH → SO + H, NS + NH₂ → H₂S + N₂, P + PH → P₂ + H, and N + NH₃ → N₂H + H₂; and the photodissociation of molecules such as P₂, PH₂, SiS, CH, and TiO.