期刊
JOURNAL OF PHYSICAL CHEMISTRY C
卷 125, 期 15, 页码 8430-8439出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.1c00987
关键词
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资金
- SFI-NSFC bilateral funding scheme [SFI/17/NSFC/5229]
- Irish Research Council by a Government-of-Ireland postdoctoral fellowship [GOIPD/2016/365]
The passage predicts the leakage of hydrogen and deuterium from sII clathrate hydrates through simulations, and analyzes the impact of different large-cage occupancies on the intercage hopping of hydrogen and deuterium.
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 exper-imentally. 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; her; not unexpectedly, double occupancies occurred more favorably in large cages and single occupancies dominated in small cages.
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