Photochemistry of AgCl-water clusters:: Comparison with Cl--water clusters

The electronic structure of AgCl-W-n (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 [p(r)] reorganization of the aggregates upon photoexcitation that is characterized by charge migration from the Ag d orbitals and delocalization of p(r) around the cation. This is in contrast with NaCl-w(n) 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. (c) 2005 Elsevier B.V. All rights reserved.