Decay channels and appearance sizes of doubly anionic gold and silver clusters

Second electron affinities of Au-N and Ag-N clusters and the dissociation energies for fission of the Au-N(2-) and Ag-N(2-) dianions are calculated using the finite-temperature shell-correction method and allowing for triaxial deformations. Dianionic clusters with N>2 are found to be energetically stable against fission, leaving electron autodetachment as the dominant decay process. The second electron affinities exhibit pronounced shell effects in excellent agreement with measured abundance spectra for Au-N(2-) (N<30), with appearance sizes n(a)(2-)(Au) = 12 and n(a)(2-)(Ag) = 24.