We have developed a one-dimensional photochemical and thermochemical kinetics and diffusion model to study the effects of disequilibrium chemistry on the atmospheric composition of "hot Jupiter" exoplanets. Here we investigate the coupled chemistry of neutral carbon, hydrogen, oxygen, and nitrogen species on HD 189733b and HD 209458b, 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; however, the warmer stratospheric temperatures on HD 209458b help maintain thermochemical equilibrium and reduce the effects of disequilibrium chemistry. For both planets, the methane and ammonia mole fractions are found to be enhanced over their equilibrium values at pressures of a few bar to less than a mbar due to transport-induced quenching, but CH 4 and NH 3 are photochemically removed at higher altitudes. Disequilibrium chemistry also enhances atomic species, unsaturated hydrocarbons (particularly C 2 H 2 ), some nitriles (particularly HCN), and radicals like OH, CH 3 , and NH 2 . In contrast, CO, H 2 O, N 2 , and CO 2 more closely follow their equilibrium profiles, except at pressures ∼ < 1 microbar, where CO, H 2 O, and N 2 are photochemically destroyed and CO 2 is produced before its eventual high-altitude destruction. The enhanced abundances of CH 4 , NH 3 , and HCN are expected to affect the spectral signatures and thermal profiles of HD 189733b and other relatively cool, transiting exoplanets. We examine the sensitivity of our results to the assumed temperature structure and eddy diffusion coefficients and discuss further observational consequences of these models.

As brown dwarfs cool, a variety of species condense in their atmospheres, forming clouds. Iron and silicate clouds shape the emergent spectra of L dwarfs, but these clouds dissipate at the L/T transition. A variety of other condensates are expected to form in cooler T dwarf atmospheres. These include Cr, MnS, Na 2 S, ZnS, and KCl, but the opacity of these optically thinner clouds has not been included in previous atmosphere models. Here, we examine their effect on model T and Y dwarf atmospheres. The cloud structures and opacities are calculated using the Ackerman & Marley (2001) cloud model, which is coupled to an atmosphere model to produce atmospheric pressure-temperature profiles in radiative-convective equilibrium. We generate a suite of models between T eff = 400 and 1300 K, log g=4.0 and 5.5, and condensate sedimentation efficiencies from f sed =2 to 5. Model spectra are compared to two red T dwarfs, Ross 458C and UGPS 0722-05; models that include clouds are found to match observed spectra significantly better than cloudless models. The emergence of sulfide clouds in cool atmospheres, particularly Na 2 S, may be a more natural explanation for the "cloudy" spectra of these objects, rather than the re-emergence of silicate clouds that wane at the L-to-T transition. We find that sulfide clouds provide a mechanism to match the near-and mid-infrared colors of observed T dwarfs.Our results indicate that including the opacity of condensates in T dwarf atmospheres is necessary to accurately determine the physical characteristics of many of the observed objects.

Context.A new class of exoplanets has emerged: the ultra hot Jupiters, the hottest close-in gas giants. The majority of them have weaker-than-expected spectral features in the 1.1 − 1.7µm bandpass probed by HST/WFC3 but stronger spectral features at longer wavelengths probed by Spitzer. This led previous authors to puzzling conclusions about the thermal structures and chemical abundances of these planets. Aims. We investigate how thermal dissociation, ionization, H − opacity, and clouds shape the thermal structures and spectral properties of ultra hot Jupiters. Methods. We use the SPARC/MITgcm to model the atmospheres of four ultra hot Jupiters and discuss more thoroughly the case of WASP-121b. We expand our findings to the whole population of ultra hot Jupiters through analytical quantification of the thermal dissociation and its influence on the strength of spectral features. Results. We predict that most molecules are thermally dissociated and alkalies are ionized in the dayside photospheres of ultra hot Jupiters. This includes H 2 O, TiO, VO, and H 2 but not CO, which has a stronger molecular bond. The vertical molecular gradient created by the dissociation significantly weakens the spectral features from H 2 O while the 4.5µm CO feature remains unchanged. The water band in the HST/WFC3 bandpass is further weakened by the continuous opacity of the H − ions. Molecules are expected to recombine before reaching the limb, leading to order of magnitude variations of the chemical composition and cloud coverage between the limb and the dayside. Conclusions. Molecular dissociation provides a qualitative understanding of the lack of strong spectral features of water in the 1 − 2µm bandpass observed in most ultra hot Jupiters. Quantitatively, our model does not provide a satisfactory match to the WASP-121b emission spectrum. Together with WASP-33b and Kepler-33Ab, they seem the outliers among the population of ultra hot Jupiters, in need of a more thorough understanding.

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 H 2 O and CO 2 are much more abundant when C/O < 1, whereas CH 4 , HCN, and C 2 H 2 gain significantly in abundance when C/O > 1. Other notable species like N 2 and NH 3 that do not contain carbon or oxygen are relatively unaffected by the C/O ratio. Disequilibrium processes tend to enhance the abundance of CH 4 , NH 3 , HCN, and C 2 H 2 over a wide range of C/O ratios. We compare the results of our models with secondary-eclipse photometric data from the Spitzer Space Telescope and conclude that (1) disequilibrium models with C/O ∼ 1 are consistent with spectra of WASP-12b, XO-1b, and CoRoT-2b, confirming the possible carbon-rich nature of these planets, (2) spectra from HD 189733b are consistent with C/O ∼ < 1, but as the assumed metallicity is increased above solar, the required C/O ratio must increase toward 1 to prevent too much H 2 O absorption, (3) species like HCN can have a significant influence on spectral behavior in the 3.6 and 8.0 µm Spitzer channels, potentially providing even more opacity than CH 4 when C/O > 1, and (4) the very high CO 2 abundance inferred for HD 189733b from near-infrared observations cannot be explained through equilibrium or disequilibrium chemistry in a hydrogen-dominated atmosphere. We discuss possible formation mechanisms for carbon-rich hot Jupiters, including scenarios in which the accretion of CO-rich, H 2 O-poor gas dominates the atmospheric envelope, and scenarios in which the planets accrete carbon-rich solids while migrating through disk regions inward of the snow line. The C/O ratio and bulk atmospheric metallicity provide important clues regarding the formation and evolution of the giant planets. Subject headings: planetary systems -planets and satellites: atmospheres -planets and satellites:composition -planets and satellites: individual (HD 189733b, WASP-12b, XO-1b, CoRoT-2b) -stars: individual (HD 189733, WASP-12, XO-1, CoRoT-2)