The van der Waals Interactions of n‐Alkanethiol‐Covered Surfaces: From Planar to Curved Surfaces

In this work, we report on the van der Waals (vdW) interactions of n-alkanethiols (ATs) adsorbed on planar Au (111) and Au (100) surfaces and curved Au nanoparticles of different diameters. By means of electrochemical measurements and molecular dynamic calculations, we show how the increase in the average geometrical curvature of the surface influences the global interactions; that is, decreasing vdW interactions between neighboring molecules. We found that small NPs do not present the same electrochemical behavior as planar surfaces. The transition between nanoparticle to flat surface electrochemical response is estimated to occur at a ~13-20 nm diameter range.