Spontaneous electron emission vs dissociation in internally hot silver dimer anions

Referring to a recent experiment, we theoretically study the process of a two-channel decay of the diatomic silver anion (Ag2−), namely, the spontaneous electron ejection giving Ag2 + e− and the dissociation leading to Ag− + Ag. The ground state potential energy curves of the silver molecules of diatomic neutral and negative ions were calculated using proper pseudo-potentials and atomic basis sets. We also estimated the non-adiabatic electronic coupling between the ground state of Ag2− and the ground state of Ag2 + e−, which, in turn, allowed us to estimate the minimal and mean values of the electron autodetachment lifetimes. The relative energies of the rovibrational levels allow the description of the spontaneous electron emission process, while the description of the rotational dissociation is treated with the quantum dynamics method as well as time-independent methods. The results of our calculations are verified by comparison with the experimental data.