Intra-cage structure, vibrations and tetrahedral-site hopping of H2 and D2 in doubly-occupied 51264 cages in sII clathrate hydrates from path-integral and classical molecular dynamics

Abstract

The intra-cage behaviour of guest H2 and D2 molecules in doubly occupied 512 64 cages in structure-II (Sii) clathrate hydrates were investigated using classical and path-integral molecular dynamics at 100 K. We probed the structure of tetrahedral sites, proton vibrations, localised molecular rattling timescales at sites, and the jump-diffusion travel of H2 and D2 molecules between sites. The site-diffusion model was correlated with experimental neutron scattering data, and the cage occupancies were then discussed in light of recent state-of-the-art experimental and theoretical findings in the literature.