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

A comparative analysis of bond lengths (r(e)), vertical detachment energies (VDE), excitation energies of neutral clusters with geometry of anions (T-e) and vertical ionization potentials of neutral clusters (IPv) calculated within density functional theory (DFT) using different functionals with both effective core potential (ECP) and all-electron basis sets for silver clusters Ag-n, n less than or equal to 6, 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 Ag-2(-10)-, the difference between calculations with this functional and experimental values of VDE and T-e 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 Ag-7(-), Ag-9(-) and Ag-10(-) has been made. The electronic structure and geometrical characteristics of the low-lying isomers has been studied. (C) 2003 Elsevier B.V. All rights reserved.