Catalytic and Magnetic Behaviors of Excessively Charged Silver, Copper, Platinum, and Rhodium Atomic Clusters

Abstract

Spin-resolved density functional theory examination revealed that 0, ±1e, and ±2e additional surface charge has impact to the bond-electron-energy relaxation, and the associated catalystic and magnetic properties of MN atomic clusters (M = Ag, Cu, Pt, and Rh; N = 13–147 atoms). Trends consistency between calculations and experimental observations confirmed our predictions [Chem. Rev. 2015, 115, 6746] that the shorter-and-stronger bonds between undercoordinated atoms induce the local densification and quantum entrapment of the core electrons, which in turn polarize the valence electrons dominating the catalytic and magnetic performance of the clusters. The excessive charge states has an important impact to the magnetization of MN. Specifically, even excessive charge states addition induces magnetization of all the MN clusters while odd excessive charge addition affects only Pt and Rh clusters. Observations provide insight on the relationship between excessive charge and the intrinsic effect of the atomic u...