Exploring the structural evolution of clusters with similar sizes and atom numbers induced by the removal or addition of a few atoms contributes to a deep understanding of structure-property relationships....

A Cu-rich alloy nanocluster [Ag13Cu10(SAdm)12]X3 is reported, and its geometric and electronic structures are further determined via theoretical calculations.

The bonding character within metal nanoclusters represents an intriguing topic, shedding light on the inherent driving force for the packing preference in nanomaterials. Herein, density functional theory (DFT) calculations were conducted to investigate the correlation of the series of isomeric [Au 13 Ag 12 (PR 3 ) 10 X 8 ] + (X=Cl/Br) clusters, which are mainly differentiated by the coordination mode of the equatorial halides (μ 2 -, μ 3 -and μ 4 -) in the rod-like, bi-icosahedral framework. The theoretical simulation corroborates the variety in the configuration of the Au 13 Ag 12 clusters and elucidates the fast isomerization kinetics among the different configurations. The easy tautomerization and the variety in chloride binding modes correspond to a fluxionality character of the equatorial halides and are verified by the potential energy curve analysis. The structural flexibility of the central Au 3 Ag 10 block is the main driving force, while the relatively stronger AgÀ X bonding interaction (compared to that of AuÀ X), and a sufficient number of halides are also requisite for the associating AgÀ X tautomerizations.

Oxidation-induced conversion of gold nanoclusters is an important strategy for preparing novel atomically precise clusters and elucidating the kinetic correlations of different clusters. Herein, the oxidation-induced growth from [Au 6 (dppp) 4 ] 2+ to [Au 8 (dppp) 4 Cl 2 ] 2+ (reported by Konishi and co-workers) has been studied by density functional theory calculations. A successive oxidation → Cl − coordination → oxidation → Cl − coordination sequence occurs first to activate the Au 6 structure, resulting in the high Au(core)−Au(corner) bond cleavage activity and the subsequent formation of [Au 2 (dppp) 2 Cl] + and [Au 4 (dppp) 2 Cl] + fragments. Then, the dimerization of two Au 4 fragments and the rearrangement of the diphosphine coordination occur to generate the thermodynamically stable [Au 8 (dppp) 4 Cl 2 ] 2+ products. The proposed mechanism agrees with the experimental outcome for the fast reaction rate and the residual of the Au 2 components. Specifically, a multivariate linear regression analysis indicates the strong correlation of the oxidation potential of Au 6 , Au 8 , Au 23 , and Au 25 clusters with the HOMO energy, the number of Au atoms, and cluster charge state. The main conclusions [e.g., oxidationinduced Au(corner)−Au(core) bond activation, easy 1,2-P transfer steps, etc.] of this study might be widely applicable in improving our understanding of the mechanism of other cluster-conversion reactions.

Herein, density functional theory (DFT) calculations were performed to elucidate the mechanism of the reversible single atom size conversion between [Au10(DMPP)4(C6H11C≡C)]3+ and [Au9(DMPP)4]3+ (DMPP is 2,2’-bis-(dimethylphosphino)-1,1’-biphenyl, the simplified, theoretical model...