Spontaneous Electron Emission Versus Dissociation in Internally Hot Silver Dimer Anions

TL;DR

This paper theoretically investigates the decay processes of silver dimer anions, focusing on spontaneous electron emission and dissociation, by calculating potential energy curves, electronic couplings, and lifetimes, and comparing results with experiments.

Contribution

It provides a detailed theoretical analysis of decay channels in Ag$_2^-$, including potential energy calculations and lifetime estimations, which are validated against experimental data.

Findings

Calculated potential energy curves match experimental data.

Estimated electron autodetachment lifetimes.

Described dissociation dynamics using quantum methods.

Abstract

Referring to a recent experiment, we theoretically study the process of a two-channel decay of the diatomic silver anion (Ag$_2^-$), namely the spontaneous electron ejection giving Ag$_2$ + e$^-$ and the dissociation leading to Ag$^-$ + Ag. The ground state potential energy curves of the silver molecules of diatomic neutral and negative ion were calculated using proper pseudo-potentials and atomic basis sets. We also estimated the non-adiabatic electronic coupling between the ground state of Ag$_2^-$ and the ground state of Ag$_2$ + 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 experimental data.