On the occurrence of clathrate hydrates in extreme conditions: Dissociation pressures and occupancies at cryogenic temperatures with application to planetary systems

We investigate the thermodynamic stability of clathrate hydrates at cryogenic temperatures from the 0 K limit to 200 K in a wide range of pressures, covering the thermodynamic conditions of interstellar space and the surface of the hydrosphere in satellites. Our evaluation of the phase behaviors is performed by setting up quantum partition functions with variable pressures on the basis of a rigorous statistical mechanics theory that requires only the intermolecular interactions as input. Noble gases, hydrocarbons, nitrogen, and oxygen are chosen as the guest species, which are key components of the volatiles in such satellites. We explore the hydrate/water two-phase boundary of those clathrate hydrates in water-rich conditions and the hydrate/guest two-phase boundary in guestrich conditions, either of which occurs on the surface or subsurface of icy satellites. The obtained phase diagrams indicate that clathrate hydrates can be in equilibrium with either water or the guest species over a wide range far distant from the three-phase coexistence condition and that the stable pressure zone of each clathrate hydrate expands significantly on intense cooling. The implication of our findings for the stable form of water in Titan is that water on the surface exists only as clathrate hydrate with the atmosphere down to a shallow region of the crust, but clathrate hydrate in the remaining part of the crust can coexist with water ice. This is in sharp contrast to the surfaces of Europa and Ganymede, where the thin oxygen air coexists exclusively with pure ice.