The origin of the core-level binding energy shifts in nanoclusters

Abstract

We investigate the shifts of the core-level binding energies in small gold nanoclusters by using {\it ab initio} density functional theory calculations. The shift of the 4$f$ states is calculated for magic number nanoclusters in a wide range of sizes and morphologies. We find a non-monotonous behavior of the core-level shift in nanoclusters depending on the size. We demonstrate that there are three main contributions to the Au 4$f$ shifts, which depend sensitively on the interatomic distances, coordination and quantum confinement. They are identified and explained by the change of the on-site electrostatic potential.