Structure of small silver clusters and static response to an external electric field

Abstract

The static response properties and the structural stability of silver clusters in the size range $1\ensuremath{\le}n\ensuremath{\le}23$ have been studied using a linear combination of atomic Gaussian-type orbitals within the density functional theory in the finite field approach. The Kohn-Sham equations have been solved in conjunction with a generalized gradient approximation (GGA) exchange-correlation functional. A proof that the finite basis set GGA calculation satisfies the Hellmann-Feynman theorem is also included in the Appendix. The calculated polarizabilities of silver clusters are compared with the experimental measurements and the jellium model in the spillout approximation. Despite the fact that the calculated polarizabilities are in good agreement with both of them, we have found that the polarizability appears to be strongly correlated to the cluster shape and the highest occupied--lowest unoccupied molecular-orbital gap.