Phase Diagram of Methane Hydrates and Discovery of MH-VI Hydrate.

Methane hydrate is not only the predominant natural deposits of permafrost and continental margins of Earth but also the dominant methane-containing phase in the nebula and major moons of gas giants. Depending on the surrounding environment (mainly pressure), seven methane hydrate phases have been discovered by experiment or predicted by computer simulation, such as clathrate methane hydrates I, II, H, and K, and filled-ice methane hydrates III, IV, and V. Using extensive Monte Carlo packing algorithm and density functional theory optimization, here we predict a partial clathrate methane hydrate VI built by basic units of 46 water bowl encapsulating a methane molecule, which is dynamically stable from the computed phonon dispersion. Its density and structural characteristics are comparable to that of filled-ice methane hydrate III. By calculating the formation enthalpies of a variety of candidate phases at different pressures, a phase diagram of methane hydrates is constructed. As pressure rises, phase transitions occur  among the methane hydrates along with decreasing water/methane molecular ratios. The newly predicted methane hydrate VI emerges as the most stable phase in the region between clathrate phase II and filled-ice phase III, suggesting that methane hydrate VI might be synthesized in a laboratory under accessible conditions.