In this work we study the effect of disequilibrium processes on mixing ratio profiles of neutral species and on the simulated spectra of a hot Jupiter exoplanet that orbits stars of different spectral types. We also address the impact of stellar activity that should be present to a different degree in all stars with convective envelopes. We used the VULCAN chemical kinetic code to compute number densities of species. The temperature-pressure profile of the atmosphere was computed with the HELIOS code. We also utilized the $τ$-ReX forward model to predict the spectra of planets in primary and secondary eclipses. In order to account for the stellar activity we made use of the observed solar XUV spectrum taken from Virtual Planetary Laboratory (VPL) as a proxy for an active sun-like star. We find large changes in mixing ratios of most chemical species in planets orbiting A-type stars that radiate strong XUV flux inducing a very effective photodissociation. For some species, these changes can propagate very deep into the planetary atmosphere to pressures of around 1 bar. To observe disequilibrium chemistry we favor hot Jupiters with temperatures Teq=1000 K and ultra-hot Jupiters with Teq=3000$ K that also have temperature inversion in their atmospheres. On the other hand, disequilibrium calculations predict little changes in spectra of planets with intermediate temperatures. We also show that stellar activity similar to the one of the modern Sun drives important changes in mixing ratio profiles of atmospheric species. However, these changes take place at very high atmospheric altitudes and thus do not affect predicted spectra. We estimate that the effect of disequilibrium chemistry in planets orbiting nearby bright stars could be robustly detected and studied with future missions with spectroscopic capabilities in infrared such as, e.g., JWST and ARIEL.
The retrieval approach is currently a standard method for deriving atmospheric properties from observed spectra of exoplanets. However, the approach ignores disequilibrium chemistry in most current retrieval codes, which can lead to misinterpretation of the metallicity or elemental abundance ratios of the atmosphere. We have implemented the disequilibrium effect of vertical mixing or quenching for the major species in hydrogen/helium-dominated atmospheres, namely $\mathrm{CH_4}$, $\mathrm{CO}$, $\mathrm{H_2O}$, $\mathrm{NH_3}$, $\mathrm{N_2}$, and $\mathrm{CO_2}$, for the spectral retrieval co…
Disequilibrium species have been used previously to probe the deep water abundances and the eddy diffusion coefficient for giant planets. In this paper, we present a diffusion-kinetics code that predicts the abundances of disequilibrium species in the tropospheres of Jupiter and Saturn with updated thermodynamic and kinetic data. The dependence on the deep water abundance and the eddy diffusion coefficient is investigated. We quantified the disagreements in CO kinetics that comes from using different reaction networks and identified C$_2$H$_6$ as a useful tracer for the eddy diffusion coeffici…
Cold brown dwarfs are excellent analogs of widely separated, gas giant exoplanets, and provide insight into the potential atmospheric chemistry and physics we may encounter in objects discovered by future direct imaging surveys. We present a low resolution R $\sim$ 300 $M$-band spectroscopic sequence of seven brown dwarfs with effective temperatures between 750 K and 250 K along with Jupiter. These spectra reveal disequilibrium abundances of carbon monoxide (CO) produced by atmospheric quenching. We use the eddy diffusion coefficient (K$_{zz}$) to estimate the strength of vertical mixing in ea…
The bulk water abundance on Jupiter potentially constrains the planet's formation conditions. We improve the chemical constraints on Jupiter's deep water abundance in this paper. The eddy diffusion coefficient is used to model vertical mixing in planetary atmosphere, and based on laboratory studies dedicated to turbulent rotating convection, we propose a new formulation of the eddy diffusion coefficient for the troposphere of giant planets. The new formulation predicts a smooth transition from the slow rotation regime (near the equator) to the rapid rotation regime (near the pole). We estimate…
Jupiter's tropospheric composition is studied using high resolution spatially-resolved 5-micron observation from the CRIRES instrument at the Very Large Telescope. The high resolving power (R=96,000) allows us to spectrally resolve the line shapes of individual molecular species in Jupiter's troposphere and, by aligning the slit north-south along Jupiter's central meridian, we are able to search for any latitudinal variability. Despite the high spectral resolution, we find that there are significant degeneracies between the cloud structure and aerosol scattering properties that complicate the …
On hot Jupiter exoplanets, strong horizontal and vertical winds should homogenize the abundances of the important absorbers CH$_4$ and CO much faster than chemical reactions restore chemical equilibrium. This effect, typically neglected in general circulation models (GCMs), has been suggested as explanation for discrepancies between observed infrared lightcurves and those predicted by GCMs: On the nightsides of several hot Jupiters, GCMs predict outgoing fluxes that are too large, especially in the Spitzer 4.5 $μ$m band. We modified the SPARC/MITgcm to include disequilibrium abundances of CH$_…
Motivated by recent spectroscopic evidence for carbon-rich atmospheres on some transiting exoplanets, we investigate the influence of the C/O ratio on the chemistry, composition, and spectra of extrasolar giant planets both from a thermochemical-equilibrium perspective and from consideration of disequilibrium processes like photochemistry and transport-induced quenching. We find that although CO is predicted to be a major atmospheric constituent on hot Jupiters for all C/O ratios, other oxygen-bearing molecules like H2O and CO2 are much more abundant when C/O < 1, whereas CH4, HCN, and C2H2 ga…
Exoplanet and brown dwarf atmospheres commonly show signs of disequilibrium chemistry. In the James Webb Space Telescope era high resolution spectra of directly imaged exoplanets will allow the characterization of their atmospheres in more detail, and allow systematic tests for the presence of chemical species that deviate from thermochemical equilibrium in these atmospheres. Constraining the presence of disequilibrium chemistry in these atmospheres as a function of parameters such as their effective temperature and surface gravity will allow us to place better constrains in the physics govern…
Evidence of disequilibrium chemistry due to vertical mixing in the atmospheres of many T and Y-dwarfs has been inferred due to enhanced mixing ratios of CO and reduced NH$_3$. Atmospheric models of planets and brown dwarfs typically parameterize this vertical mixing phenomenon with the vertical eddy diffusion coefficient, $K_{\rm zz}$. While $K_{\rm zz}$ can perhaps be approximated in the convective regions in the atmosphere with mixing length theory, in radiative regions the strength of vertical mixing is uncertain by many orders of magnitude. With a new grid of self-consistent 1D model atmos…
We aim to see if the difference between equilibrium and disequilibrium chemistry is observable in the atmospheres of transiting planets by the James Webb Space Telescope (JWST). We perform a case study comparing the dayside emission spectra of three planets like HD 189733b, WASP-80b, and GJ436b, in and out of chemical equilibrium at two metallicities each. These three planets were chosen because they span a large range of planetary masses and equilibrium temperatures, from hot and Jupiter-sized to warm and Neptune-sized. We link the one-dimensional disequilibrium chemistry model from Venot et …
The atmospheres of ultra-hot Jupiters are commonly considered to be at thermochemical equilibrium. We aim to provide disequilibrium chemistry maps for a global understanding of the chemistry in HAT-P-7b's atmosphere and assess the importance of disequilibrium chemistry on UHJs. We apply a hierarchical modelling approach utilising 97 1D atmospheric profiles from 3D GCM of HAT-P-7b. For each 1D profile, we evaluate our kinetic cloud formation model consistently with the local gas-phase composition in chemical equilibrium. We then evaluate quenching results from a zeroth-order approximation in co…
We have developed 1-D photochemical and thermochemical kinetics and diffusion models for the transiting exoplanets HD 189733b and HD 209458b to study the effects of disequilibrium chemistry on the atmospheric composition of "hot Jupiters." Here we investigate the coupled chemistry of neutral carbon, hydrogen, oxygen, and nitrogen species, and we compare the model results with existing transit and eclipse observations. We find that the vertical profiles of molecular constituents are significantly affected by transport-induced quenching and photochemistry, particularly on cooler HD 189733b; howe…
Disequilibrium chemical processes have a large effect upon the spectra of substellar objects. To study these effects, dynamical disequilibrium has been parameterized using the quench and eddy diffusion approximations, but little work has been done to explore how these approximations perform under realistic planetary conditions in different dynamical regimes. As a first step in addressing this problem, we study the localized, small scale convective dynamics of planetary atmospheres by direct numerical simulation of fully compressible hydrodynamics with reactive tracers using the Dedalus code. U…
[Abridged] Aims. We present a large atmospheric study of 49 gas giant exoplanets using infrared transmission photometry with Spitzer/IRAC at 3.6 and 4.5um. Methods. We uniformly analyze 70 photometric light curves of 33 transiting planets using our custom pipeline, which implements pixel level decorrelation. We use this survey to understand how infrared photometry traces changes in atmospheric chemical properties as a function of planetary temperature. We compare our measurements to a grid of 1D radiative-convective equilibrium forward atmospheric models which include disequilibrium chemistry.…
Spectral features in the observed spectra of exoplanets depend on the composition of their atmospheres. A good knowledge of the main atmospheric processes that drive the chemical distribution is therefore essential to interpret exoplanetary spectra. An atmosphere reaches chemical equilibrium if the rates of the forward and backward chemical reactions converge to the same value. However, there are atmospheric processes, such as atmospheric transport, that destabilize this equilibrium. In this work we study the changes in composition driven by a 3D wind field in WASP-43b using our Global Circula…
Clouds and Chemistry Across the Brown Dwarf T-Y Sequence: Insights from JWST Atmospheric Retrievals
Ludwig Maximilian University（路德维希-马克西米利安大学）；University of Bern（伯尔尼大学）；ARTORG Center for Biomedical Engineering Research, University of Bern（伯尔尼大学ARTORG生物医学工程研究中心）；University College London（伦敦大学学院）；University of Warwick（华威大学）
Hydrogen cyanide (HCN) is a critical reactive source of nitrogen for building key biomolecules relevant for the origin of life. Still, many HCN reactions remain uncharacterized by experiments and theory, and the complete picture of HCN production in planetary atmospheres is not fully understood. To improve this situation, we develop a novel technique making use of computational quantum chemistry, experimental data, and atmospheric numerical simulations. First, we use quantum chemistry simulations to explore the entire field of possible reactions for a list of primary species in N2-, CH4-, and …
The past decade has seen significant progress on the direct detection and characterization of young, self-luminous giant planets at wide orbital separations from their host stars. Some of these planets show evidence for disequilibrium processes like transport-induced quenching in their atmospheres; photochemistry may also be important, despite the large orbital distances. These disequilibrium chemical processes can alter the expected composition, spectral behavior, thermal structure, and cooling history of the planets, and can potentially confuse determinations of bulk elemental ratios, which …
Chemical disequilibrium has recently become a relevant topic in the study of the atmospheres of of transiting extrasolar planets, brown dwarfs, and directly imaged exoplanets. We present a new way of assessing whether or not a Jovian-like atmosphere is in chemical disequilibrium from observations of detectable or inferred gases such as H$_2$O, CH$_4$, CO, and H$_2$. Our hypothesis, based on previous kinetic modeling studies, is that cooler atmospheres will show stronger signs of disequilibrium than hotter atmospheres. We verify this with chemistry-transport models and show that planets with te…
Clouds are ubiquitous in exoplanet atmospheres and represent a challenge for the model interpretation of their spectra. Complex cloud models are too numerically costly for generating a large number of spectra, while more efficient models may be too strongly simplified. We aim to constrain the atmospheric properties of the directly imaged planet HR 8799e with a free retrieval approach. We use our radiative transfer code petitRADTRANS for generating spectra, which we couple to the PyMultiNest tool. We added the effect of multiple scattering which is important for treating clouds. Two cloud model…
Comparatively little is known about atmospheric chemistry on Uranus and Neptune, because remote spectral observations of these cold, distant ``Ice Giants'' are challenging, and each planet has only been visited by a single spacecraft during brief flybys in the 1980s. Thermochemical equilibrium is expected to control the composition in the deeper, hotter regions of the atmosphere on both planets, but disequilibrium chemical processes such as transport-induced quenching and photochemistry alter the composition in the upper atmospheric regions that can be probed remotely. Surprising disparities i…
Inferences of molecular compositions of exoplanetary atmospheres have generally focused on C, H, and O-bearing molecules. Recently, additional absorption in HST WFC3 transmission spectra around 1.55$μ$m has been attributed to nitrogen-bearing chemical species: NH$_3$ or HCN. These species, if present in significant abundance, would be strong indicators of disequilibrium chemical processes -- e.g. vertical mixing and photochemistry. The derived N abundance, in turn, could also place important constraints on planetary formation mechanisms. Here, we examine the detectability of nitrogen chemistry…
We use a 1D thermochemical and photochemical kinetics model to predict the disequilibrium stratospheric chemistries of warm and hot Jupiters (800 < T < 1200 K). Thermal chemistry and vertical mixing are generally more important than photochemistry. At 1200 K, methane is oxidized to CO and CO2 by OH radicals from thermal decomposition of water. At T < 1000 K, methane is reactive but stable enough to reach the stratosphere, while water is stable enough that OH levels are suppressed by reaction with H2. These trends raise the effective C/O ratio in the reacting gases above unity. Reduced products…
Secondary eclipse observations of hot Jupiters can reveal both their compositions and thermal structures. Previous observations have shown a diversity of hot Jupiter eclipse spectra, including absorption features, emission features, and featureless blackbody-like spectra. We present a secondary eclipse spectrum of the hot Jupiter WASP-77Ab observed between $1-5$ $μ$m with the Hubble Space Telescope (HST) and the Spitzer Space Telescope. The HST observations show signs of water absorption indicative of a non-inverted thermal structure. We fit the data with both a one-dimensional free retrieval …
Ultra-hot Jupiters have recently attracted interest from observers and theoreticians alike, as they provide observationally accessible test cases. We apply a hierarchical modelling approach as a virtual laboratory to study cloud formation and gas-phase chemistry. We utilise 97 vertical 1D profiles of a 3D GCM for HAT-P-7b to evaluate our kinetic cloud formation model consistently with the local equilibrium gas-phase composition. The day/night temperature difference on HAT-P-7b (~ 2500K) causes clouds to form on the nightside (dominated by H2/He) while the dayside (dominated by H/He) retains cl…
We present a study of photochemical hazes of exoplanet atmospheres based on a self-consistent model including haze microphysics, disequilibrium chemistry, and radiative feedbacks. We derive the haze properties required to match HST observations of ten hot-Jupiters. HAT-P-12b, HD-189733b, HD-209458b and WASP-6b require haze mass fluxes between 5x10$^{-15}$ and 9x10$^{-12} g.cm^{-2}.s^{-1}$ to match the observations. WASP-12b and WASP-19b with equilibrium temperatures above 2000 K are incompatible with the presence of haze and are better fitted by heavy metals. HAT-P-1b and WASP-31b do not show …
We present results from a set of simulations using a fully coupled three-dimensional (3D) chemistry-radiation-hydrodynamics 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 …
Contrasting C/O ratios in Uranus and Neptune from disequilibrium chemistry: A clue to distinct evolutionary pathways?
Aix-Marseille Université（艾克斯-马赛大学）；Southwest Research Institute（西南研究院）；Laboratoire d’Astrophysique de Bordeaux, Univ. Bordeaux（波尔多大学天体物理实验室）；Observatoire de Paris, Université PSL, CNRS, Sorbonne Université, Université Paris Cité（巴黎天文台、巴黎文理研究大学、法国国家科学研究中心、索邦大学、巴黎西岱大学）；University of Science and Technology of China（中国科学技术大学）；Dublin Institute for Advanced Studies（都柏林高等研究所）；Space Science Institute（空间科学研究所）
Aerosols appear to be ubiquitous in close-in gas giant atmospheres, and disequilibrium chemistry likely impacts the emergent spectra of these planets. Lofted aerosols and disequilibrium chemistry are caused by vigorous vertical transport in these heavily irradiated atmospheres. Here we numerically and analytically investigate how vertical transport should change over the parameter space of spin-synchronized gas giants. In order to understand how tracer transport depends on planetary parameters, we develop an analytic theory to predict vertical velocities and mixing rates ($K_\mathrm{zz}$) and …
University College London（伦敦大学学院）；European Space Agency, ESAC（欧洲空间局，欧洲空间天文中心）；King’s College London, University of London（伦敦国王学院，伦敦大学）；Université Paris Cité and Univ Paris Est Creteil, CNRS, LISA（巴黎西岱大学与巴黎东克雷泰伊大学，法国国家科学研究中心，天体物理和行星实验室）
We present the low-resolution transmission spectra of the puffy hot Jupiter HAT-P-65b (0.53 M$_\mathrm{Jup}$, 1.89 R$_\mathrm{Jup}$, $T_\mathrm{eq}=1930$ K), based on two transits observed using the OSIRIS spectrograph on the 10.4 m Gran Telescopio CANARIAS (GTC). The transmission spectra of the two nights are consistent, covering the wavelength range 517--938 nm and consisting of mostly 5 nm spectral bins. We perform equilibrium-chemistry spectral retrieval analyses on the jointly fitted transmission spectrum and obtain an equilibrium temperature of $1645^{+255}_{-244}$ K and a cloud coverage…
We present results from an atmospheric circulation study of nine hot Jupiters that comprise a large transmission spectral survey using the Hubble and Spitzer Space Telescopes. These observations exhibit a range of spectral behavior over optical and infrared wavelengths which suggest diverse cloud and haze properties in their atmospheres. By utilizing the specific system parameters for each planet, we naturally probe a wide phase space in planet radius, gravity, orbital period, and equilibrium temperature. First, we show that our model "grid" recovers trends shown in traditional parametric stud…
We have conducted laboratory experiments to study the chemistry in hot Jupiter atmospheres with C/O ratio of 0.35. We have compared our results with the ones obtained previously for atmospheres with a C/O ratio of 1 to investigate the influence of the C/O ratio on the chemistry and formation of photochemical organic aerosol. We found that the C/O ratio and the gas mixture compositions strongly influence the pathways responsible for the formation of CO2. Thermochemical reactions are primarily responsible for the formation of CO2 in low C/O ratio atmospheres, while photochemistry is the dominant…
The elemental ratios of carbon, nitrogen, and oxygen in the atmospheres of hot Jupiters may hold clues to their formation locations in the protostellar disc. In this work, we adopt gas phase chemical abundances of C, N and O from several locations in a disc chemical kinetics model as sources for the envelope of the hot Jupiter HD 209458b and evolve the planet's atmospheric composition using a 1D chemical kinetics model, treating both vertical mixing and photochemistry. We consider two atmospheric pressure-temperature profiles, one with and one without a thermal inversion. From each of the resu…
There is growing evidence suggesting the presence of aqueous environment on ancient Mars, raising the question of the possibility of life in such an environment. Subsequently, with the erosion of the Martian atmosphere resulting in drastic changes in its climate, surface water disappeared, shrinking habitable spaces on the planet, with only a limited amount of water remaining near the surface in form of brines and water-ice deposits. Life, if it ever existed, would have had to adapt to harsh modern conditions, which includes low temperatures and surface pressure, and high radiation dose. Prese…
Observations of ultra-hot Jupiters indicate the existence of thermal inversion in their atmospheres with day-side temperatures greater than 2200 K. Various physical mechanisms such as non-local thermal equilibrium, cloud formation, disequilibrium chemistry, ionisation, hydrodynamic waves and associated energy, have been omitted in previous spectral retrievals while they play an important role on the thermal structure of their upper atmospheres.We aim at exploring the atmospheric properties of WASP-19b to understand its largely featureless thermal spectra using a state-of-the-art atmosphere cod…
We present and validate a new network of atmospheric thermo-chemical and photo-chemical sulfur reactions. We use a 1-D chemical kinetics model to investigate these reactions as part of a broader HCNO chemical network in a series of hot and warm Jupiters. We find that temperatures approaching $1400\,\mathrm{K}$ are favourable for the production of H2S and HS around $\mathrm{10^{-3}\,bar}$, the atmospheric level where detection by transit spectroscopy may be possible, leading to mixing ratios of around $10^{-6}$. At lower temperatures, down to $1000\,\mathrm{K}$, the abundance of S2 can be up to…
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 disequilibrium-chemistry calculations of Moses et al. and Rimmer & Helling. It rep…
The atmosphere of K2-18 b: The role of hazes, clouds and photoelectrons
Université Reims Champagne Ardenne（兰斯香槟阿登大学）；Institut d’Astrophysique de Paris, UMR CNRS 7095（巴黎天体物理研究所）；University College London（伦敦大学学院）；King’s College London（伦敦国王学院）；Observatoire de Paris, Université PSL, Sorbonne Université, Université Paris Cité, CY Cergy Paris Université, CNRS（巴黎天文台）
We investigate the effects of atmospheric circulation on the chemistry of the hot Jupiter HD 209458b. We use a simplified dynamical model and a robust chemical network, as opposed to previous studies which have used a three dimensional circulation model coupled to a simple chemical kinetics scheme. The temperature structure and distribution of the main atmospheric constituents are calculated in the limit of an atmosphere that rotates as a solid body with an equatorial rotation rate of 1 km/s. Such motion mimics a uniform zonal wind which resembles the equatorial superrotation structure found b…
The radial-dependent positions of snowlines of abundant oxygen- and carbon-bearing molecules in protoplanetary discs will result in systematic radial variations in the C/O ratios in the gas and ice. This variation is proposed as a tracer of the formation location of gas-giant planets. However, disc chemistry can affect the C/O ratios in the gas and ice, thus potentially erasing the chemical fingerprint of snowlines in gas-giant atmospheres. We calculate the molecular composition of hot Jupiter atmospheres using elemental abundances extracted from a chemical kinetics model of a disc midplane wh…
The formation of clouds affects brown dwarf and planetary atmospheres of nearly all effective temperatures. Iron and silicate condense in L dwarf atmospheres and dissipate at the L/T transition. Minor species such as sulfides and salts condense in mid-late T dwarfs. For brown dwarfs below Teff=450 K, water condenses in the upper atmosphere to form ice clouds. Currently over a dozen objects in this temperature range have been discovered, and few previous theoretical studies have addressed the effect of water clouds on brown dwarf or exoplanetary spectra. Here we present a new grid of models tha…
