Charge distribution analysis in Ag(n)(m⁺) clusters: molecular modeling and DFT calculations.

Neutral and charged silver clusters Ag₆₃(m⁺) and Ag₁₁₃(m⁺) (m=0,…,20) are investigated by simulated annealing molecular dynamics simulations. With increasing charge to size ratio the clusters undergo deformation to better accommodate surface charges. The latter are heterogeneously distributed and reflect the interplay of overall electrostatic repulsion and different degrees of local under-coordination of surface atoms. By comparison with atomic charges from natural population analysis based on density-functional calculations we demonstrate the suitability of the embedded-atom force-field in combination with the charge equilibrium approach.