1 Centre for Research in Molecular Modeling, Department of Chemistry & Biochemistry, Concordia University, 1455 de Maisonneuve Boulevard West, Montréal, Québec, Canada H3G 1M8.

First-principles molecular dynamics simulations of the excited-state dynamics of I-(H2O)3 have been performed to gain some insight into the general features of the relaxation process of photoexcited I-(H2O)n clusters. The relaxation of excited I-(H2O)3 is characterized by rapid motion of water molecules and slow recoil motion of the iodine atom. Both solvent reorganization and iodine atom motion appear to be important for interpreting the existing femtosecond photoelectron spectroscopy...