Influences of 1-Propanol and Methanol Additives on Crystallization of Thin Amorphous Solid Water Films

In general, randomly oriented ice crystallites are formed by heating amorphous solid water (ASW) films at similar to 160 K via homogeneous nucleation. Here, we demonstrate that monolayers of methanol and 1-propanol additives incorporated in the multilayer ASW film lead to heterogeneous nucleation at the substrate interface of Pt(111), as evidenced by the occurrence of epitaxial ice growth. The mobility of water in direct contact with the Pt(111) substrate is decreased relative to that in the bulk, but it can be increased via interactions with hydrophobic moieties of alcohols that are segregated to the interfacial region. As a result, heterogeneous nucleation occurs at ca. 160 K along with homogeneous nucleation in the film interior. However, the template effect is quenched when the alcohols are in direct contact with the substrate. The methanol adspecies deposited onto the ASW film surface induces heterogeneous nucleation at a temperature as low as 145 K, but the 1-propanol adspecies has no such an effect. Their different ability of heterogeneous nucleation at the free ASW film surface, as well as their uptake behaviors in the near surface region, is associated with the hydrophobic hydration of the alcohols resulting from different lengths of the aliphatic moiety.

Automated summary

This study demonstrates that the addition of methanol and 1-propanol to ASW films can induce heterogeneous nucleation and epitaxial ice growth. Methanol enhances the interaction with the Pt substrate, resulting in heterogeneous nucleation at a lower temperature, while 1-propanol does not have such an effect. This phenomenon is related to the hydrophobic hydration of the alcohols and their adsorption behavior at the surface region.