DFT study of electronic structure and geometry of anionic silver clusters Agn- (n = 11, 12, 17)

Based on both total energy calculations and comparison of experimental and calculated characteristics of photoelectron spectra (PHES), the structural assignment of clusters Ag11- and Ag12- has been made using DFT model with recently developed S2LYP functional. The calculated characteristics of PHES for the assigned structures are in excellent agreement with the experimental ones. The electronic structure, geometry and energetic characteristics of low-lying isomers have also been studied. The calculated geometrical parameters of Ag11- and Ag12- clusters as well as the geometries of earlier established clusters Ag4-10- have been compared with the geometrical characteristics of anionic sodium clusters. The structures of anionic silver and sodium clusters have been found to be very similar. The difference has been observed only for Me4,10,12-. Based on similarity of the geometries of silver and sodium clusters as well as on the comparison of calculated and experimental characteristics of PHES, the geometry of Ag17- cluster has been assigned.