Encapsulation kinetics and dynamics of carbon monoxide in clathrate hydrate

JL Zhu and SY Du and XH Yu and JZ Zhang and HW Xu and SC Vogel and TC Germann and JS Francisco and F Izumi and K Momma and Y Kawamura and CQ Jin and YS Zhao, NATURE COMMUNICATIONS, 5, 4128 (2014).

DOI: 10.1038/ncomms5128

Carbon monoxide clathrate hydrate is a potentially important constituent in the solar system. In contrast to the well-established relation between the size of gaseous molecule and hydrate structure, previous work showed that carbon monoxide molecules preferentially form structure-I rather than structure-II gas hydrate. Resolving this discrepancy is fundamentally important to understanding clathrate formation, structure stabilization and the role the dipole moment/molecular polarizability plays in these processes. Here we report the synthesis of structure-II carbon monoxide hydrate under moderate high-pressure/low-temperature conditions. We demonstrate that the relative stability between structure-I and structure-II hydrates is primarily determined by kinetically controlled cage filling and associated binding energies. Within hexakaidecahedral cage, molecular dynamic simulations of density distributions reveal eight low-energy wells forming a cubic geometry in favour of the occupancy of carbon monoxide molecules, suggesting that the carbon monoxide-water and carbon monoxide-carbon monoxide interactions with adjacent cages provide a significant source of stability for the structure-II clathrate framework.

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