Photochemistry of AgCl–water clusters: Comparison with Cl−–water clusters

The electronic structure of AgCl–wn (w ≡ H2O and n = 1–6, 8) clusters is investigated by ab initio and time dependent density functional theory calculations with emphasis on the electronic density [ρ(r)] reorganization of the aggregates upon photoexcitation that is characterized by charge migration from the Ag d orbitals and delocalization of ρ(r) around the cation. This is in contrast with NaCl–wn aggregates, where charge migration from Cl− to the water molecules takes place when n ⩾ 5. The results for AgCl–water clusters are also compared with those for photoexcited Cl−–water clusters, which provide a classical illustration of CTTS precursor states.