Surface chemistry effects on heterogeneous clathrate hydrate nucleation: A molecular dynamics study

Ryan S. DeFever, Sapna Sarupria

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19 Scopus citations


We report results from a molecular dynamics study of clathrate hydrate nucleation near model hydrophilic and hydrophobic surfaces. –CH3 and –OH terminated self-assembled monolayers (SAMs) are used as model surfaces. We study the nucleation of a soluble, structure II forming guest molecule with a coarse-grained model compatible with monatomic water. Despite the presence of SAMs, we show that nucleation occurs through a homogeneous mechanism in OHSAM and CH3SAM systems. Formation of ice-like or intermediate water structure is not observed near either surface prior to nucleation. Nucleation occurs more quickly in OHSAM systems than CH3SAM systems. However, the faster nucleation is driven by a partitioning of guest molecules which results in higher bulk guest concentration in OHSAM systems compared with CH3SAM systems. Despite significant aggregation of guest molecules near CH3SAM, no nucleation is observed near the surface. The formation of guest contact pairs, facilitated by the presence of CH3SAM, may prevent nucleation in this region. Our results highlight the numerous routes by which surfaces can affect hydrate nucleation due to the multicomponent nature of the phenomena.

Original languageEnglish (US)
Pages (from-to)205-213
Number of pages9
JournalJournal of Chemical Thermodynamics
StatePublished - Feb 2018
Externally publishedYes

Bibliographical note

Funding Information:
The authors acknowledge Clemson University for generous allocation of compute time on the Palmetto Cluster. Acknowledgement is made to the Donors of the American Chemical Society Petroleum Research Fund for support of this research (ACS PRF DNI #54557-DNI6).

Publisher Copyright:
© 2017 Elsevier Ltd


  • Clathrate hydrates
  • Heterogeneous
  • Molecular dynamics
  • Nucleation
  • Simulations


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