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 provide important insights into planet-formation mechanisms. Using a thermo/photochemical kinetics and transport model, we investigate the extent to which disequilibrium chemistry affects the composition and spectra of directly imaged giant exoplanets. Results for specific "young Jupiters" such as HR 8799 b and 51 Eri b are presented, as are general trends as a function of planetary effective temperature, surface gravity, incident ultraviolet flux, and strength of deep atmospheric convection. We find that quenching is very important on young Jupiters, leading to CO/CH4 and N2/NH3 ratios much greater than, and H2O mixing ratios a factor of a few less than, chemical-equilibrium predictions. Photochemistry can also be important on such planets, with CO2 and HCN being key photochemical products. Carbon dioxide becomes a major constituent when stratospheric temperatures are low and recycling of water via the H2 + OH reaction becomes kinetically stifled. Young Jupiters with effective temperatures ≲700 K are in a particularly interesting photochemical regime that differs from both transiting hot Jupiters and our own solar-system giant planets.

Neptune-sized extrasolar planets that orbit relatively close to their host stars - often called "hot Neptunes" - are common within the known population of exoplanets and planetary candidates. Similar to our own Uranus and Neptune, inefficient accretion of nebular gas is expected produce hot Neptunes whose masses are dominated by elements heavier than hydrogen and helium. At high atmospheric metallicities of 10-10,000× solar, hot Neptunes will exhibit an interesting continuum of atmospheric compositions, ranging from more Neptune-like, H2-dominated atmospheres to more Venus-like, CO2-dominated atmospheres. We explore the predicted equilibrium and disequilibrium chemistry of generic hot Neptunes and find that the atmospheric composition varies strongly as a function of temperature and bulk atmospheric properties such as metallicity and the C/O ratio. Relatively exotic H2O, CO, CO2, and even O2-dominated atmospheres are possible for hot Neptunes. We apply our models to the case of GJ 436b, where we find that a CO-rich, CH4-poor atmosphere can be a natural consequence of a very high atmospheric metallicity. From comparisons of our results with Spitzer eclipse data for GJ 436b, we conclude that although the spectral fit from the high-metallicity forward models is not quite as good as the best fit obtained from pure retrieval methods, the atmospheric composition predicted by these forward models is more physically and chemically plausible in terms of the relative abundance of major constituents. High-metallicity atmospheres (orders of magnitude in excess of solar) should therefore be considered as a possibility for GJ 436b and other hot Neptunes.