The benzene radical anion is a molecular ion pertinent to several organic reactions, including the Birch reduction of benzene in
liquid ammonia. The species exhibits a dynamic Jahn–Teller effect due to its open-shell nature and
undergoes pseudorotation of its geometry. Here we characterize the complex electronic structure
of this condensed-phase system based on ab initio molecular dynamics simulations and GW calculations of the benzene radical anion solvated in
liquid ammonia. Our findings provide important insights into the electronic stability of the species,
revealing that it is indeed a bound state in the condensed phase, and offer electronic densities of states that aid
in the interpretation of experimental photoelectron spectra. Further, we find that the spatial character of the
excess electron of the solvated radical anion follows the underlying Jahn–Teller distortions of the molecular
structure and the time evolution of its symmetries.