Structural Relaxation in Charged Metal Surfaces and Cluster Ions

Abstract Space‐charge layers can noticeably affect the properties of metal electrode surfaces, for instance by modifying the surface dielectric response or indirectly via the induced atomic relaxations. While there are efforts to exploit this concept for designing novel functional nanomaterials, the underlying microscopic processes are poorly understood. Here, we report on a density functional theory (DFT) study of atomic relaxation in Au cluster ions comprising up to 309 atoms. Suitable averages over atomic displacements respond to charging consistent with experimental observation on macroscopic Au single‐crystal surfaces. Moreover, the overall DFT response is also consistent with predictions of a simple phenomenological model. Motivated by our observations, we propose a scenario in which the surface relaxation (“stretch”) results from out‐of‐plane Hellman–Feynman forces exerted on the surface atoms by the excess charge, and where the in‐plane surface stress represents essentially an elastic transverse contraction tendency of the surface layer in response to stretch.