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

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 coarsegrained model compatible with monatomic water. Despite the presence of SAMs, we show that nucleation occurs through a homogeneous mechanism in OHSAM and CH(3)SAM 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 CH(3)SAM 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 CH(3)SAM systems. Despite significant aggregation of guest molecules near CH(3)SAM, no nucleation is observed near the surface. The formation of guest contact pairs, facilitated by the presence of CH(3)SAM, 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. (C) 2017 Elsevier Ltd.