Identification of a mechanism of transformation of clathrate hydrate structures I to II or H.

Binary mixed-gas hydrates including methane and other guest gases demonstrate a structural transition between the sI and sII phases. Under increasing pressure pure methane hydrate exhibits a phase transition first from sI to sII and then to sH. But the mechanism of the transformation from sI to sII or sH has not yet been identified. Recently, molecular dynamics simulations of methane hydrates suggest there may exist uncommon 15-hedral cages (5¹²6³), linking the sI and sII cages. In addition, xenon hydrate involving 15-hedral cages has been synthesized and named an hsI hydrate. Based on the hsI cages, we propose a mechanism for the transition of sI to sII or sH at atomic level resolution. The sI hydrate is first transformed to hsI, and hsI is further transformed to sII. Upon compression, hsI is transformed to sH owing to depletion of atomic layers. The mechanism of transformation speculated here calls for experimental verification.