The cages, dynamics, and structuring of incipient methane clathrate hydrates

Abstract

Interest in describing clathrate hydrate formation mechanisms spans multiple fields of science and technical applications. Here, we report findings from multiple molecular dynamics simulations of spontaneous methane clathrate hydrate nucleation and growth from fully demixed and disordered two-phase fluid systems of methane and water. Across a range of thermodynamic conditions and simulation geometries and sizes, a set of seven cage types comprises approximately 95% of all cages formed in the nucleated solids. This set includes the ubiquitous 5¹² cage, the 5¹²6ⁿ subset (where n ranges from 2–4), and the 4¹5¹⁰6ⁿ subset (where n also ranges from 2–4). Transformations among these cages occur viawater pair insertions/removals and rotations, and may elucidate the mechanisms of solid–solid structural rearrangements observed experimentally. Some consistency is observed in the relative abundance of cages among all nucleation trajectories. 5¹² cages are always among the two most abundant cage types in the nucleated solids and are usually the most abundant cage type. In all simulations, the 5¹²6ⁿ cages outnumber their 4¹5¹⁰6ⁿ counterparts with the same number of water molecules. Within these consistent features, some stochasticity is observed in certain cage ratios and in the long-range ordering of the nucleated solids. Even when comparing simulations performed at the same conditions, some trajectories yield swaths of multiple adjacent sI unit cells and long-range order over 5 nm, while others yield only isolated sI unit cells and little long-range order. The nucleated solids containing long-range order have higher 5¹²6²/5¹² and 5¹²6³/4¹5¹⁰6² cage ratios when compared to systems that nucleate with little long-range order. The formation of multiple adjacent unit cells of sI hydrate at high driving forces suggests an alternative or addition to the prevailing hydrate nucleation hypotheses which involve formation through amorphous intermediates.