Potential to stabilize 16-vertex tetrahedral coinage-metal cluster architectures related to Au ₂₀

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.