Tuning Interfacial Concentration Enhancement through Dispersion Interactions to Facilitate Heterogeneous Nucleation

D McKechnie and PA Mulheran and J Sefcik and K Johnston, JOURNAL OF PHYSICAL CHEMISTRY C (2022).

DOI: 10.1021/acs.jpcc.2c04410

Classical molecular dynamics simulations were used to investigate how dispersion (van der Waals) interactions between non-polar, hydrophobic surfaces and aqueous glycine solutions affect the solution composition, molecular orientation, and dynamics at the interface. Simulations revealed that dispersion interactions lead to a major increase in the concentration of glycine at the interface in comparison with the bulk solution, resulting from a competition between solute and solvent molecules to be or not to be near the interface. This can then lead to kinetic and/or structural effects facilitating heterogeneous nudeation of glycine at non-polar surfaces, in agreement with recent observations for tridecane, graphene, and polytetrafluoroethylene. A novel parameterization process was developed to map a model surface with tunable dispersion interactions to heptane, tridecane, and graphite materials. The model surface was capable of reproducing the solution structure observed in fully atomistic simulations with excellent agreement and also provided good agreement for dynamic properties, at a significantly reduced computational cost. This approach can be used as an effective tool for screening materials for heterogeneous nucleation enhancement or suppression, based on nonspecific dispersion interactions based on bulk material molecular properties, rather than interfacial functional groups, templating or confinement effects.

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