Study the structures and electronic properties of CsSin− (n = 5–16) clusters by ab initio global search

Herein, we investigated the structural evolution and electronic properties of CsSi n − ( n = 5–16) clusters at density functional theory (DFT) level. Low-lying isomers of these clusters have been globally searched by using a homemade genetic algorithm coupled with the ORCA 5.0.3 program. The ground-state structures of these clusters have been confirmed by comparing the calculated and measured photoelectron spectra (PES). Cs atoms prefer to adsorb on the surface of the silicon frames without causing serious reorganization of the frame. Cs atoms always act as electron donors in all these CsSi n − ( n = 5–16) clusters. The impurity Cs atom can reduce the thermodynamic stabilities of corresponding Si n − cluster, but increase their chemical stabilities.