Spatially Heterogeneous Water Properties at Disordered Surfaces Decrease the Hydrophobicity of Nonpolar Self-Assembled Monolayers

Understanding the relationship between hydrophobicity and the properties of functionalized surfaces is vital to the design of materials that interact in aqueous environments. In this Letter, we use atomistic molecular dynamics simulations to investigate the effects of surface order on the hydrophobicity of self-assembled monolayers (SAMs) containing nonpolar ligands. We find that the interfacial hydrophobicity is highly correlated with SAM order and, strikingly, poorly correlated with the solvent-accessible surface area, which typically has been related to interfacial hydrophobicity. Analysis of spatial variations in both SAM and water properties reveals that the SAM-water interface is pinned near regions of disordered SAM surfaces with increased free volume, decreasing the overall interfacial hydrophobicity. Spatial variations in ligand end group positions at disordered SAM surfaces thus translate to spatial variations in hydrophobicity, yielding heterogeneous surface properties. These findings provide new insights into how surface order can alter the hydrophobicity of chemically uniform surfaces.