Kanani K. M. Lee

The recent JWST detections of carbon-bearing molecules in a habitable-zone sub-Neptune have opened a new era in the study of low-mass exoplanets. The sub-Neptune regime spans a wide diversity of planetary interiors and atmospheres not witnessed in the solar system, including mini-Neptunes, super-Earths, and water worlds. Recent works have investigated the possibility of gas dwarfs, with rocky interiors and thick H₂-rich atmospheres, to explain aspects of the sub-Neptune population, including the radius valley. Interactions between the H₂-rich envelope and a potential magma ocean may lead to observable atmospheric signatures. We report a coupled interior-atmosphere modeling framework for gas dwarfs to investigate the plausibility of magma oceans on such planets and their observable diagnostics. We find that the surface–atmosphere interactions and atmospheric composition are sensitive to a wide range of parameters, including the atmospheric and internal structure, mineral composition, volatile solubility and atmospheric chemistry. While magma oceans are typically associated with high-temperature rocky planets, we assess if such conditions may be admissible and observable for temperate sub-Neptunes. We find that a holistic modeling approach is required for this purpose and to avoid unphysical model solutions. Using our model framework, we consider the habitable-zone sub-Neptune K2-18 b as a case study and find that its observed atmospheric composition is incompatible with a magma ocean scenario. We identify key atmospheric molecular and elemental diagnostics, including the abundances of CO₂, CO, NH₃, and, potentially, S-bearing species. Our study also underscores the need for fundamental material properties for accurate modeling of such planets.

Finite element analysis (FEA) is a powerful tool for numerically solving partial differential equations over complex geometries and is thus useful for analyzing heat transport in laser-heated diamond anvil cell (LHDAC) experiments. Our models expand on previously published simulations by calculating the volume-averaged temperatures of both the sample and insulation/pressure media under steady-state heating to determine the thermal pressure of the hot sample. Our goal is to produce an accurate relationship between the measured surface temperature of the absorbing sample and the temperature of the transparent insulating media, which is used to determine thermal pressure but susceptible to steep temperature gradients. We find that in doing so, our FEA models of temperature within the pressure/insulation media can differ from simplified estimates of temperature gradients by more than a factor of 2. We also explore temperature-dependent and temperature-independent thermal conductivity models and find that the volume-averaged temperatures differ by up to a factor of 1.3, forcing the predicted thermal pressures determined to also differ by up to a factor of 1.5 at a temperature of 2000 K at 50 GPa for neon. Higher temperatures exacerbate this difference. We also find that unintentional asymmetric sample insertion and sample heating, which are common in LHDAC experiments, do not have a first-order effect on volume-averaged temperatures. The FEA models, available in both Python and FlexPDE, are versatile across different sample geometries, materials, and heat source laser shapes.

Astronomical surveys have discovered thousands of transiting exoplanets, revealing that rocky planets are common in the galaxy. A planet's interior chemistry is frequently inferred by average density, described by mass‐radius (M‐R) relationships. However, M‐R relationships give rise to non‐unique interpretations of a planet's interior composition, an issue that limits our ability to characterize far‐away worlds. We present experimental and density functional theoretical results addressing the influence of an ultra‐reducing (oxygen‐poor) interior chemistry on rocky mantle phases and discuss the possible implications for atmospheric observables. We show that silicon carbide (SiC) and molecular nitrogen (N ₂ ) react to form solid silicon nitride (γ‐Si ₃ N ₄ ) at high pressures and high temperatures in a laser‐heated diamond‐anvil cell, consistent with ab initio computations. Si ₃ N ₄ remains stable under extreme conditions and when quenched to ambient conditions. As SiC is a common compound found under very reducing conditions, these results indicate that nitrogen may form solid phases in an oxygen‐poor rocky planet. If, by sequestering nitrogen in a planet's mantle, the distribution of nitrogen between a planet's interior and atmosphere is altered (i.e., a nitrogen‐rich mantle and nitrogen‐poor atmosphere), these results indicate that there may be atmospheric observables connected to the mantle‐redox state of a rocky planet besides the oxygen‐containing phases ubiquitous in exoplanet literature.

The amount of ferric iron Fe³⁺ in the lower mantle is largely unknown and may be influenced by the disproportionation reaction of ferrous iron Fe²⁺ into metallic Fe and Fe³⁺ triggered by the formation of bridgmanite. Recent work has shown that Fe³⁺ has a strong effect on the density and seismic wave speeds of bridgmanite and the incorporation of impurities such as aluminum. In order to further investigate the effects of ferric iron on mineral behavior at lower mantle conditions, we conducted laser‐heated diamond‐anvil cell (LHDAC) experiments on two sets of samples nearly identical in composition (an aluminum‐rich pyroxenite glass) except for the Fe³⁺ content; with one sample with more Fe³⁺ (“oxidized”: Fe³⁺/ΣFe ~ 55%) and the other with less Fe³⁺ (“reduced”: Fe³⁺/ΣFe ~ 11%). We heated the samples to lower mantle conditions, and the resulting assemblages were drastically different between the two sets of samples. For the reduced composition, we observed a multiphase assemblage dominated by bridgmanite and calcium perovskite. In contrast, the oxidized material yielded a single phase of Ca‐bearing bridgmanite. These Al‐rich pyroxenite samples show a difference in density and seismic velocities for these two redox states, where the reduced assemblage is denser than the oxidized assemblage by ~1.5% at the bottom of the lower mantle and slower (bulk sound speed) by ~2%. Thus, heterogeneities of Fe³⁺ content may lead to density and seismic wave speed heterogeneities in Earth's lower mantle.

Magma oceans were once ubiquitous in the early solar system, setting up the initial conditions for different evolutionary paths of planetary bodies. In particular, the redox conditions of magma oceans may have profound influence on the redox state of subsequently formed mantles and the overlying atmospheres. The relevant redox buffering reactions, however, remain poorly constrained. Using first-principles simulations combined with thermodynamic modeling, we show that magma oceans of Earth, Mars, and the Moon are likely characterized with a vertical gradient in oxygen fugacity with deeper magma oceans invoking more oxidizing surface conditions. This redox zonation may be the major cause for the Earth’s upper mantle being more oxidized than Mars’ and the Moon’s. These contrasting redox profiles also suggest that Earth’s early atmosphere was dominated by CO₂ and H₂O, in contrast to those enriched in H₂O and H₂ for Mars, and H₂ and CO for the Moon.

Significance: Carbon is critical to life on Earth, climate regulation, and many geological processes. Despite its importance, the amount of carbon in the planet has been poorly understood due to uncertainty in the composition of Earth’s core, likely the largest reservoir of carbon. Here, we demonstrate that carbon becomes increasingly compatible in silicate compared to metal at the high pressures and temperatures at which Earth’s core formed. Therefore, carbon can only be present in the core in low abundances, although the core still likely holds the vast majority of the planet’s carbon.

We present results from high‐pressure and high‐temperature experiments on mixtures of SiC and SiO₂ to explore the stability of SiC in the presence of oxygen‐rich silicates at planetary mantle conditions. We observe no evidence of the ambient pressure predicted oxidation products, CO or SiO, resulting from oxidation reactions between SiC and SiO₂ at pressures up to ~40 GPa and temperatures up to ~2500 K. We observe the decomposition of SiC through releasing C, resulting in vacancies in the SiC lattice and consequently the contracted SiC ambient volume V₀ observed in the heated regions of sample. The decomposition is further supported by the observations of diamond formation and the expanded SiO₂ V₀ in the heated regions of samples indicating the incorporation of C into SiO₂ stishovite. We provide a new interpretation of SiC decomposition on laboratory timescales, in which kinetics prevent the reaction from reaching equilibrium. We consider how the equilibrium decomposition reaction of SiC will influence the differentiation of a SiC‐containing body on planetary timescales and find that the decomposition products may become isolated during early planetary differentiation. The resulting presence of elemental Si and C within a planetary body may have important consequences for the compositions of the mantles and atmospheres of such planets.

Density of silicate melt dictates melt migration and establishes the gross structure of Earth's interior. However, due to technical challenges, the melt density of relevant compositions is poorly known at deep mantle conditions. Particularly, water may be dissolved in such melts in large amounts and can potentially affect their density at extreme pressure and temperature conditions. Here we perform first‐principles molecular dynamics simulations to evaluate the density of Fe‐rich, eutectic‐like silicate melt (E melt) with varying water content up to about 12 wt %. Our results show that water mixes nearly ideally with the nonvolatile component in silicate melt and can decrease the melt density significantly. They also suggest that hydrous melts can be gravitationally stable in the lowermost mantle given its likely high iron content, providing a mechanism to explain seismically slow and dense layers near the core‐mantle boundary.