Molecular dynamics simulations of the Ag+ or Na+ cation with an excess electron in bulk water

The properties of an excess electron interacting with a monovalent cation in bulk water are studied by molecular dynamics simulations. Sodium and silver cations are chosen as prototypical cases because of their very different redox properties. In both cases, mixed quantum classical molecular dynamics simulations reproduce the experimental UV-Vis spectra. In the case of silver, we observe a highly polarized neutral atom, corresponding to a dipolar excitonic state. For sodium a contact cation/electron pair is observed. Free energy curves along the cation electron coordinate are calculated using quantum Umbrella Sampling technique. The relative stability of the different chemical species is discussed.