Structure Evolution of Transition Metal-doped Gold Clusters M@Au12 (M = 3d–5d): Across the Periodic Table

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The comprehensive genetic algorithm (CGA) incorporated with density functional theory (DFT) calculations were used for a global search of the potential energy surfaces of M@Au 12 (M = 3d–5d) clusters. The feasibility of the revTPSS functional was confirmed by comparison between experimental and calculated data such as bond lengths and vibrational frequencies of transition metal dimers. We found the ground state structures of Mo/W@Au 12 clusters to be the perfect icosahedron cage. The V/Nb/Ta/Tc/Re@Au 12 clusters were found to have the distorted icosahedron cages owing to Jahn–Teller effects. The lowest energy structures of Sc/Ti/Cr/Mn/Fe/Co/Ru/Rh/Ir@Au 12 have the perfect or distorted magnetic cuboctahedron cages, which can be explained by a 14-electron rule in a cuboctahedral ligand field (M 2+ @Au 12 2– ). Y/Zr/La/Hf@Au 12 clusters have the half-cage ground states, while Ni/Cu/Zn/Pt/Ag/Cd/Pd/Au/HgAu 12 clusters have oblate ground states. The scalar relativistic X2C method combined with revTPSS/TZP were used to calculate the energy difference between the magnetic cuboctahedron ground state and the icosahedron isomers of Cr@Au 12 using energy decomposition analysis-natural orbitals for chemical valence. The magnetic M 2+ @Au 12 2– model was found to significantly enhance the d orbital interactions of transition metal atoms and reduce Pauli repulsion, resulting in magnetic cuboctahedra as the more stable structures.