Hydrogen and Deuterium Molecular Escape from Clathrate Hydrates: “Leaky” Microsecond-Molecular-Dynamics Predictions

[Image: see text] It is predicted herewith that the leakage of both hydrogen (H(2)) and deuterium (D(2)) from sII clathrate hydrates, borne of guest chemical-potential equalization driving enhanced nonequilibrium intercage hopping, should be observable experimentally. To this end, we have designed simulations to realize and study this process by microsecond molecular dynamics within the temperature range of 150–180 K—for which the hydrate lattice was found to be stable. In this pursuit, we considered initial large-cage (5(12)6(4)) guest occupancies of 1–4, with single occupation of 5(12) cavities. Examining transient, nonequilibrium intercage hopping, we present a lattice-escape activation energy for the four nominal large-cage occupancies (1–4), by fitting to the hydrate-leakage rate. The intercage hopping of H(2) and D(2) was studied using Markov-chain models and expressed at different temperatures and large-cage occupancies. The free energy of guest “binding” in the large and small cages was also computed for all of the occupancies. Toward equilibrium, following the majority of H(2)/D(2) escape via leakage, the percentage of occupancies was calculated for both H(2) and D(2) for all of the systems for all initial nominal large-cage occupancies; here, not unexpectedly, double occupancies occurred more favorably in large cages and single occupancies dominated in small cages.