Probing surface tension additivity on chemically heterogeneous surfaces by a molecular approach

Surface free energy of a chemically heterogeneous surface is often treated as an approximately additive quantity through the Cassie equation [Cassie ABD (1948) Discuss Faraday Soc 3:11-16]. However, deviations from additivity are common, and molecular interpretations are still lacking. We use molecular simulations to measure the microscopic analogue of contact angle, theta(c), of aqueous nanodrops on heterogeneous synthetic and natural surfaces as a function of surface composition. The synthetic surfaces are layers of graphene functionalized with prototypical nonpolar and polar head group: methyl, amino, and nitrile. We demonstrate positive as well as negative deviations from the linear additivity. We show the deviations reflect the uneven exposure of mixture components to the solvent and the linear relation is recovered if fractions of solvent-accessible surface are used as the measure of composition. As the spatial variations in polarity become of larger amplitude, the linear relation can no longer be obtained. Protein surfaces represent such natural patterned surfaces, also characterized by larger patches and roughness. Our calculations reveal strong deviations from linear additivity on a prototypical surface comprising surface fragments of melittin dimer. The deviations reflect the disproportionately strong influence of isolated polar patches, preferential wetting, and changes in the position of the liquid interface above hydrophobic patches. Because solvent-induced contribution to the free energy of surface association grows as cos theta(c), deviations of cos theta(c) from the linear relation directly reflect nonadditive adhesive energies of biosurfaces.