DFT study of electronic structure and geometry of neutral and anionic silver clusters

A comparative analysis of bond lengths <f>(re),</f> vertical detachment energies (VDE), excitation energies of neutral clusters with geometry of anions <f>(Te)</f> and vertical ionization potentials of neutral clusters <f>(IPv)</f> calculated within density functional theory (DFT) using different functionals with both effective core potential (ECP) and all-electron basis sets for silver clusters Agn, <f>n≤6,</f> have been carried out. DFT methods provide a good agreement between calculated and experimental data of some characteristics. The accurate prediction of all characteristics simultaneously can be achieved with all-electron DZVP basis set only. A new functional has been developed. It provides results close to experimental data using the moderate basis set. For anionic clusters Ag2–10−, the difference between calculations with this functional and experimental values of VDE and <f>Te</f> for the most stable isomers does not exceed 0.1 eV. Based on both total energy calculations and comparison of experimental and calculated photoelectron spectra, the structural assignment of clusters Ag7−, Ag9− and Ag10− has been made. The electronic structure and geometrical characteristics of the low-lying isomers has been studied. [Copyright &y& Elsevier]