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 accreti
on of nebular gas is expected produce hot Neptunes whose masses are dominated by elements heavier than hydrogen and helium. At high atmospheric metallicities of 10-10,000x 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 fit obtained from pure retrieval methods, the atmospheric composition predicted by these forward models is more physically and chemically plausible. High-metallicity atmospheres (orders of magnitude in excess of solar) should therefore be considered as a possibility for GJ 436b and other hot Neptunes.
In the giant impact theory for lunar origin, the Moon forms from material ejected by the impact into an Earth-orbiting disk. Here we report the initial results from a silicate melt-vapor equilibrium chemistry model for such impact-generated planetary
debris disks. In order to simulate the chemical behavior of a two-phase (melt+vapor) disk, we calculate the temperature-dependent pressure and chemical composition of vapor in equilibrium with molten silicate from 2000 to 4000 K. We consider the elements O, Na, K, Fe, Si, Mg, Ca, Al, Ti, and Zn for a range of bulk silicate compositions (Earth, Moon, Mars, eucrite parent body, angrites, and ureilites). In general, the disk atmosphere is dominated by Na, Zn, and O2 at lower temperatures (< 3000 K) and SiO, O2, and O at higher temperatures. The high-temperature chemistry is consistent for any silicate melt composition, and we thus expect abundant SiO, O2, and O to be a common feature of hot, impact-generated debris disks. In addition, the saturated silicate vapor is highly oxidizing, with oxygen fugacity (fO2) values (and hence H2O/H2 and CO2/CO ratios) several orders of magnitude higher than those in a solar-composition gas. High fO2 values in the disk atmosphere are found for any silicate composition because oxygen is the most abundant element in rock. We thus expect high oxygen fugacity to be a ubiquitous feature of any silicate melt-vapor disk produced via collisions between rocky planets.
Close-in exoplanets with highly eccentric orbits are subject to large variations in incoming stellar flux between periapse and apoapse. These variations may lead to large swings in atmospheric temperature, which in turn may cause changes in the chemi
stry of the atmosphere from higher CO abundances at periapse to higher CH4 abundances at apoapse. Here we examine chemical timescales for CO<->CH4 interconversion compared to orbital timescales and vertical mixing timescales for the highly eccentric exoplanets HAT-P-2b and CoRoT-10b. As exoplanet atmospheres cool, the chemical timescales for CO<->CH4 tend to exceed orbital and/or vertical mixing timescales, leading to quenching. The relative roles of orbit-induced thermal quenching and vertical quenching depend upon mixing timescales relative to orbital timescales. For both HAT-P-2b and CoRoT-10b, vertical quenching will determine disequilibrium CO<->CH4 chemistry at faster vertical mixing rates (Kzz > 10^7 cm^2 s^-1), whereas orbit-induced thermal quenching may play a significant role at slower mixing rates (Kzz < 10^7 cm^2 s^-1). The general abundance and chemical timescale results - calculated as a function of pressure, temperature, and metallicity - can be applied for different atmospheric profiles in order to estimate the quench level and disequilibrium abundances of CO and CH4 on hydrogen-dominated exoplanets. Observations of CO and CH4 on highly eccentric exoplanets may yield important clues to the chemical and dynamical properties of their atmospheres.
We use thermochemical equilibrium calculations to model iron, magnesium, and silicon chemistry in the atmospheres of giant planets, brown dwarfs, extrasolar giant planets (EGPs), and low-mass stars. The behavior of individual Fe-, Mg-, and Si-bearing
gases and condensates is determined as a function of temperature, pressure, and metallicity. Our results are thus independent of any particular model atmosphere. The condensation of Fe metal strongly affects iron chemistry by efficiently removing Fe-bearing species from the gas phase. Monatomic Fe is the most abundant Fe-bearing gas throughout the atmospheres of EGPs and L dwarfs and in the deep atmospheres of giant planets and T dwarfs. Mg- and Si-bearing gases are effectively removed from the atmosphere by forsterite (Mg2SiO4) and enstatite (MgSiO3) cloud formation. Monatomic Mg is the dominant magnesium gas throughout the atmospheres of EGPs and L dwarfs and in the deep atmospheres of giant planets and T dwarfs. Silicon monoxide (SiO) is the most abundant Si-bearing gas in the deep atmospheres of brown dwarfs and EGPs, whereas SiH4 is dominant in the deep atmosphere of Jupiter and other gas giant planets. Several other Fe-, Mg-, and Si-bearing gases become increasingly important with decreasing effective temperature. In principle, a number of Fe, Mg, and Si gases are potential tracers of weather or diagnostic of temperature in substellar atmospheres.
