Iterative Cup Overlapping: An Efficient Identification Algorithm for Cage Structures of Amorphous Phase Hydrates

YC Hao and Z Xu and S Du and XF Yang and TJ Ding and BW Wang and JF Xu and J Zhang and HQ Yin, JOURNAL OF PHYSICAL CHEMISTRY B, 125, 1282-1292 (2021).

DOI: 10.1021/acs.jpcb.0c08964

Molecular dynamics studies have revealed that the nucleation pathway of clathrate hydrates involves the evolution from amorphous to crystalline hydrates. In this study, complete cages are further classified into the standard edge-saturated cages (SECs) and nonstandard edge-saturated cages (non-SECs). Centered on studying the structure and evolution of non-SECs and SECs, we propose a novel and efficient algorithm, iterative cup overlapping (ICO), to monitor hydrate nucleation and growth in molecular simulations by identifying SECs and discuss possible causes of the instability of non-SECs. Manipulation of topological information makes it possible for ICO to avoid the repeated searches for identified cages and deduce all SECs with low time costs, improving the efficiency of identification significantly. The accuracy and efficiency of ICO were verified by comparing the identification results with other well-proven algorithms. Furthermore, it was found that non-SECs have short lifetimes and eventually decompose or reorganize into more stable structures. Some evidence suggests that the instability of non-SECs is closely related to the hydrogen-bonding configuration of water-ring aggregations that they contain. The spontaneous evolution of the hydrogen-bonding network into the tetrahedral network may be the main factor that causes the conversion of QWRAs and the evolution of non-SECs.

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