The transformation mechanisms among cuboctahedra, Ino's decahedra and icosahedra structures of magic-size gold nanoclusters

Abstract

Gold nanoclusters possess multiple competing structural motifs with small energy differences, enabling structural coexistence and interconversion. Using a high-accuracy machine learned potential trained on some 20 000 density functional theory reference data points, we investigate transformation pathways connecting both high-symmetry and distorted cuboctahedra, Ino's decahedra and icosahedra for Au₅₅, Au₁₄₇, Au₃₀₉ and Au₅₆₁ nanoclusters. Our saddle point searches reveal that high-symmetry transformations from cuboctahedra and Ino's decahedra to icosahedra proceed through a single barrier and represent soft-mode-driven jitterbug-type and slip-dislocation motions. In addition, we identify lower-barrier asymmetric transformation pathways that drive the system into disordered, Jahn–Teller–stabilized distorted icosahedra. Minima Hopping sampling further uncovers, in this context, many such low-symmetry minima. Some of the newly identified global minima for Au₃₀₉ and Au₅₆₁ have energies that are up to 2.8 eV lower than the previously reported global minima. Hence, both the shapes and the transformation pathways studied in previous investigations are not the physically relevant ones. In contrast to the previously studied pathways, our transformation pathways give reasonable transformation times that are in rough agreement with experiments.