Theoretical Study on the Structures and Properties of Transition Metal‐Doped Copper Clusters M@Cu ₁₂ (M = 3d–5d)

The structures of copper clusters doped with transition metal M@Cu 12 (M = 3d–5d) clusters are obtained by genetic algorithm and density functional theory. There are five types of the global minimum structures of M@Cu 12 clusters, which are: (1) A perfect icosahedron cage (I h ) with 20 congruent triangular faces (Cr, Mo, W), and icosahedron cages clusters in C 2 , C 2h , C s , D 2h and D 4h symmetry (Co, Nb, Tc, Ta, Hf); (2) Half cage structures in C s symmetry (Sc, Mn, Ti, Zr, Hf, La, Y); (3) Half cage structures in C s symmetry with one Cu 4 tetrahedron extending outside the structures (Fe, Ru, O s ); (4) Double layered structures with C s and C 1 symmetry (Rh, Pd, Ag, Cd, Pt, Au, Hg, Cu); (5) Self‐contained structures (Zn, Ni). The coordination number of M, CHELPG charges on M atoms, HOMO‐LUMO gaps, average M‐Cu and Cu‐ Cu bond lengths of M@Cu 12 clusters have been studied. Binding energies and chemical hardness analysis are performed. The stabilities of Hf@Cu 12 , Cr@Cu 12 , Mo@Cu 12 and W@Cu 12 clusters are stronger than other clusters. Reduced density gradient analysis on Hf@Cu 12 , Cr@Cu 12 , Mo@Cu 12 and W@Cu 12 clusters reveals that noncovalent interactions exist in the clusters and it plays an important role in stabilizing these clusters.