Adsorption of polyvinylpyrrolidone on Ag surfaces: insight into a structure-directing agent.

We use density functional theory to resolve the role of polyvinylpyrrolidone (PVP) in the shape-selective synthesis of Ag nanostructures. At the segment level, PVP binds more strongly to Ag(100) than Ag(111) because of a surface-sensitive balance between direct binding and van der Waals attraction. At the chain level, correlated segment binding leads to a strong preference for PVP bind to Ag(100). Our study underscores differences between small-molecule and polymeric structure-directing agents.