Theoretical Study of Structures and Spectral Properties of <scp>ScSn</scp><i>_n</i>^0/−/2− (<i>n</i> = 4–17) Nanoalloy Clusters

ABSTRACT The ground‐state structures of neutral, monovalent, and divalent anion ScSn n 0/−/2− ( n = 4–17) clusters were calculated by using a global search technique combined with density functional theory, and their spectral properties, electronic configurations, and relative stability were also studied. It is found that the ground‐state structures for monovalent anion ScSn n − ( n = 4–17) clusters are similar to those of divalent anions, and the ground‐state structures for ScSn n −/2− are all adsorption structures obtained by adsorbing one Sn atom on the structures of ScSn n −1 −/2− . The growth mode of ScSn n 0/−/2− ( n = 4–17) clusters can be divided into three different types of adsorption modes ( n = 4–5, n = 6–10 and n = 11–17): ScSn 4 0/−/2− triangular bipyramid structures, ScSn 6 0/−/2− pentagonal bipyramid structures, and ScSn 11 0/−/2− single capped anti‐pentagonal prism structures are used as base units to adsorb 1–6 Sn atoms, forming adsorption structures. When n = 11, it is the smallest cage structure size. The simulated photoelectron spectra of ScSn n − clusters are in good agreement with the existing experimental spectra. The infrared, Raman, and ultraviolet spectral properties of ScSn n 0/−/2− ( n = 4–17) clusters were analyzed, and their natural population analysis, dissociation energy, second‐order energy difference, and HOMO‐LUMO energy gap were also discussed. The results show that the FK‐structure ScSn 16 − cluster not only has good thermodynamic stability and chemical stability, but also exhibits ideal optical properties, which can be used as a potential nano‐optical material building block.