Gas hydrates consist of hydrogen-bonded water frameworks enclosing guest gas molecules and have been the focus of intense research for almost 40 y, both for their fundamental role in the understanding of hydrophobic interactions and for gas storage and energy-related applications. The stable structure of methane hydrate above 2 GPa, where CH4 molecules are located within H2O or D2O channels, is referred to as methane hydrate III (MH-III). The stability limit of MH-III and the existence of a new high-pressure phase above 40 to 50 GPa, although recently conjectured, remain unsolved to date. We report evidence for a further high-pressure, room-temperature phase of the CH4–D2O hydrate, based on Raman spectroscopy in diamond anvil cell and ab initio molecular dynamics simulations including nuclear quantum effects. Our results reveal that a methane hydrate IV (MH-IV) structure, where the D2O network is isomorphic with ice Ih, forms at ∼40 GPa and remains stable up to 150 GPa at least. Our proposed MH-IV structure is fully consistent with previous unresolved X-ray diffraction patterns at 55 GPa [T. Tanaka et al., J. Chem. Phys. 139, 104701 (2013)]. The MH-III → MH-IV transition mechanism, as suggested by the simulations, is complex. The MH-IV structure, where methane molecules intercalate the tetrahedral network of hexagonal ice, represents the highest-pressure gas hydrate known up to now. Repulsive interactions between methane and water dominate at the very high pressure probed here and the tetrahedral topology outperforms other possible arrangements in terms of space filling.

Methane hydrates naturally form on Earth and in the interiors of some icy bodies of the Universe, and are also expected to play a paramount role in future energy and environmental technologies. Here we report experimental observation of an extremely fast methane diffusion at the interface of the two most common clathrate hydrate structures, namely clathrate structures I and II. Methane translational diffusion—measured by quasielastic neutron scattering at 0.8 GPa—is faster than that expected in pure supercritical methane at comparable pressure and temperature. This phenomenon could be an effect of strong confinement or of methane aggregation in the form of micro-nanobubbles at the interface of the two structures. Our results could have implications for understanding the replacement kinetics during sI–sII conversion in gas exchange experiments and for establishing the methane mobility in methane hydrates embedded in the cryosphere of large icy bodies in the Universe.

We investigate the effects of high pressure on the reorientational and vibrational dynamics of methane molecules embedded in MH-III hydrate -the stable form of methane for pressures above 2 GPa at room temperature -by combining high-pressure Raman spectroscopy with ab-initio simulations including nuclear quantum effects. We observe a clear evolution of the system from a gas-filled ice structure, where methane molecules occupy the channels of the ice skeleton and rotate almost freely, to a CH 4 :D 2 O compound where methane rotations are hindered, and methane and water dynamics are tightly coupled. The gradual orientational ordering of the guest molecules results in a complete locking-in at approximately 20GPa. This happens along with a progesssive distortion of the guest molecules. Finally, as pressure increases beyond 20 GPa the system enters a strong mode coupling regime where methane guests and water hosts dynamics are intimately paired.