The magnetic binary lithium clusters W 2 Li n ( n = 15‐19): A theoretical prediction of “di‐superatomic molecules”

Based on the super valence bond (SVB) model, a motif of face‐sharing bi‐tetrahexahedral superatomic molecules M 1 M 2 @Li 20 (M 1 /M 2 = Ti and W) was recently constructed by fusion of two tetrahexahedral superatoms Ti@Li 14 and W@Li 14 . Here, as an extension of the formation of molecules from superatoms, binary lithium clusters W 2 Li n ( n = 14‐19) are studied in conjunction with particle swarm optimization algorithm search and density functional theory calculations. The lowest‐lying isomers of W 2 Li n ( n = 15‐19) with the magnetic moments of 0 to 3 μ B are identified as superatomic molecules by analysis of their molecular orbitals and chemical bonding patterns, whereas the global minimum isomer of W 2 Li 14 does not possess the geometric structure of monomer. Via a lithium atom sequentially removed, a series of superatomic bond orders of 3, 3.5, 4, and 4.5 are exposed, reminiscent of classical chemical bonds. Meanwhile, many isosupermolecules are found in the low‐energy structures, predicting the diversity assembly of superatom materials. Our results highlight the tremendous opportunities for molecules assembled by superatoms, which may be in favor of the designs of nanoparticles or functional materials in future according to the SVB model.