We present an open-source and validated chemical kinetics code for studying hot exoplanetary atmospheres, which we name VULCAN. It is constructed for gaseous chemistry from 500 to 2500 K, using a reduced C-H-O chemical network with about 300 reactions. It uses eddy diffusion to mimic atmospheric dynamics and excludes photochemistry. We have provided a full description of the rate coefficients and thermodynamic data used. We validate VULCAN by reproducing chemical equilibrium and by comparing its output versus the disequilibriumchemistry calculations of Moses et al. and Rimmer & Helling. It reproduces the models of HD 189733b and HD 209458b by Moses et al., which employ a network with nearly 1600 reactions. We also use VULCAN to examine the theoretical trends produced when the temperature-pressure profile and carbon-to-oxygen ratio are varied. Assisted by a sensitivity test designed to identify the key reactions responsible for producing a specific molecule, we revisit the quenching approximation and find that it is accurate for methane but breaks down for acetylene, because the disequilibrium abundance of acetylene is not directly determined by transport-induced quenching, but is rather indirectly controlled by the disequilibrium abundance of methane. Therefore we suggest that the quenching approximation should be used with caution and must always be checked against a chemical kinetics calculation. A one-dimensional model atmosphere with 100 layers, computed using VULCAN, typically takes several minutes to complete. VULCAN is part of the Exoclimes Simulation Platform (ESP; exoclime.net) and publicly available at https://github.com/exoclime/VULCAN.

We present the open-source radiative transfer code named HELIOS, which is constructed for studying exoplanetary atmospheres. In its initial version, the model atmospheres of HELIOS are one-dimensional and plane-parallel, and the equation of radiative transfer is solved in the two-stream approximation with non-isotropic scattering. A small set of the main infrared absorbers is employed, computed with the opacity calculator HELIOS-K and combined using a correlated-k approximation. The molecular abundances originate from validated analytical formulae for equilibrium chemistry. We compare HELIOS with the work of Miller-Ricci & Fortney using a model of GJ 1214b, and perform several tests, where we find: model atmospheres with single-temperature layers struggle to converge to radiative equilibrium; k-distribution tables constructed with 0.01 cm −1 resolution in the opacity function ( 10 3 points per wavenumber bin) may result in errors 1-10% in the synthetic spectra; and a diffusivity factor of 2 approximates well the exact radiative transfer solution in the limit of pure absorption. We construct "null-hypothesis" models (chemical equilibrium, radiative equilibrium and solar element abundances) for 6 hot Jupiters. We find that the dayside emission spectra of HD 189733b and WASP-43b are consistent with the null hypothesis, while it consistently under-predicts the observed fluxes of WASP-8b, WASP-12b, WASP-14b and WASP-33b. We demonstrate that our results are somewhat insensitive to the choice of stellar models (blackbody, Kurucz or PHOENIX) and metallicity, but are strongly affected by higher carbon-to-oxygen ratios. The code is publicly available as part of the Exoclimes Simulation Platform (ESP; exoclime.net).

We present results from a set of simulations using a fully coupled three-dimensional (3D) chemistry-radiationhydrodynamics model and investigate the effect of transport of chemical species by the large-scale atmospheric flow in hot Jupiter atmospheres. We couple a flexible chemical kinetics scheme to the Met Office Unified Model which enables the study of the interaction of chemistry, radiative transfer and fluid dynamics. We use a newly-released "reduced" chemical network comprising 30 chemical species that has been specifically developed for application in 3D atmosphere models. We simulate the atmospheres of the well-studied hot Jupiters HD 209458b and HD 189733b which both have dayside-nightside temperature contrasts of several hundred Kelvin and superrotating equatorial jets. We find qualitatively quite different chemical structures between the two planets, particularly for methane (CH4), when advection of chemical species is included. Our results show that consideration of 3D chemical transport is vital in understanding the chemical composition of hot Jupiter atmospheres. 3D mixing leads to significant changes in the abundances of absorbing gas-phase species compared with what would be expected by assuming local chemical equilibrium, or from models including 1D -and even 2D -chemical mixing. We find that CH4, carbon dioxide (CO2) and ammonia (NH3) are particularly interesting as 3D mixing of these species leads to prominent signatures of out-of-equilibrium chemistry in the transmission and emission spectra, detectable with near-future instruments.

Radiative-transfer (RT) is a fundamental part of modelling exoplanet atmospheres with general circulation models (GCMs). An accurate RT scheme is required for estimates of the atmospheric energy transport and for gaining physical insight from model spectra. We implement three RT schemes for Exo-FMS: semi-grey, non-grey ‘picket fence’, and real gas with correlated-k. We benchmark the Exo-FMS GCM using these RT schemes to hot Jupiter simulation results from the literature. We perform a HD 209458b-like simulation with the three schemes and compare their results. These simulations are then post-processed to compare their observable differences. The semi-grey scheme results show qualitative agreement with previous studies in line with variations seen between GCM models. The real gas model reproduces well the temperature and dynamical structures from other studies. After post-processing our non-grey picket fence scheme compares very favourably with the real gas model, producing similar transmission spectra, emission spectra and phase curve behaviours. Exo-FMS is able to reliably reproduce the essential features of contemporary GCM models in the hot gas giant regime. Our results suggest the picket fence approach offers a simple way to improve upon RT realism beyond semi-grey schemes.

Measuring the abundances of carbon and oxygen in exoplanet atmospheres is considered a crucial avenue for unlocking the formation and evolution of exoplanetary systems1,2. Access to the chemical inventory of an exoplanet requires high-precision observations, often inferred from individual molecular detections with low-resolution space-based3–5 and high-resolution ground-based6–8 facilities. Here we report the medium-resolution (R ≈ 600) transmission spectrum of an exoplanet atmosphere between 3 and 5 μm covering several absorption features for the Saturn-mass exoplanet WASP-39b (ref. 9), obtained with the Near Infrared Spectrograph (NIRSpec) G395H grating of JWST. Our observations achieve 1.46 times photon precision, providing an average transit depth uncertainty of 221 ppm per spectroscopic bin, and present minimal impacts from systematic effects. We detect significant absorption from CO2 (28.5σ) and H2O (21.5σ), and identify SO2 as the source of absorption at 4.1 μm (4.8σ). Best-fit atmospheric models range between 3 and 10 times solar metallicity, with sub-solar to solar C/O ratios. These results, including the detection of SO2, underscore the importance of characterizing the chemistry in exoplanet atmospheres and showcase NIRSpec G395H as an excellent mode for time-series observations over this critical wavelength range10.