Stability of hydrocarbons at deep Earth pressures and temperatures

Determining the thermochemical properties of hydrocarbons (HCs) at high pressure and temperature is a key step toward understanding carbon reservoirs and fluxes in the deep Earth. The stability of carbon-hydrogen systems at depths greater than a few thousand meters is poorly understood and the extent of abiogenic HCs in the Earth mantle remains controversial. We report ab initio molecular dynamics simulations and free energy calculations aimed at investigating the formation of higher HCs from dissociation of pure methane, and in the presence of carbon surfaces and transition metals, for pressures of 2 to 30 GPa and temperatures of 800 to 4,000 K. We show that for T >= 2,000 K and P >= 4 GPa HCs higher than methane are energetically favored. Our results indicate that higher HCs become more stable between 1,000 and 2,000 K and P >= 4 GPa. The interaction of methane with a transition metal facilitates the formation of these HCs in a range of temperature where otherwise pure methane would be metastable. Our results provide a unified interpretation of several recent experiments and a detailed microscopic model of methane dissociation and polymerization at high pressure and temperature.