DFT calculations were carried out on a series of tetrahedral 16-atom superatomic clusters having 20 or 18 jellium electrons (je) and structurally related to Au 20 , namely, [M 16 ] 4-/2- (M = Cu, Ag, and Au) and [M 4 ′M 12 ′′] 0/2+ (M′ = Zn, Cd, Hg; M′′ = Cu, Ag, Au). While the bare homonuclear 20-je species required further stabilization to be isolated, their 18-je counterparts exhibited better stability. Lowering the electron count led to structural modification from a compact structure (20-je) to a hollow sphere (18-je). Such a change could be potentially controlled by tuning redox properties. Among the 20-je heteronuclear [M 4 ′M 12 ′′] neutral series, [Zn 4 Au 12 ] appeared to meet the best stability criteria, but their 18-je relatives [M 4 ′M 12 ′′] + , in particular [Zn 4 Cu 12 ] 2+ and [Cd 4 Au 12 ] 2+ , offered better opportunities for obtaining stable species. Such species exhibit the smallest models for the M(111) surface of fcc metals, which expose designing rules towards novel high-dopant-ratio clusters as building blocks of nanostructured materials.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry