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Issue 44, 2011
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The cages, dynamics, and structuring of incipient methane clathrate hydrates

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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.

Graphical abstract: The cages, dynamics, and structuring of incipient methane clathrate hydrates

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Publication details

The article was received on 10 Jun 2011, accepted on 14 Sep 2011 and first published on 14 Oct 2011

Article type: Paper
DOI: 10.1039/C1CP21899A
Citation: Phys. Chem. Chem. Phys., 2011,13, 19951-19959
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    The cages, dynamics, and structuring of incipient methane clathrate hydrates

    M. R. Walsh, J. D. Rainey, P. G. Lafond, D. Park, G. T. Beckham, M. D. Jones, K. Lee, C. A. Koh, E. D. Sloan, D. T. Wu and A. K. Sum, Phys. Chem. Chem. Phys., 2011, 13, 19951
    DOI: 10.1039/C1CP21899A

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