EXCITED-STATES OF A HYDRATED ELECTRON AND AQUEOUS CHLORIDE BY COMPUTER-SIMULATION

Results of adiabatic molecular dynamics simulations for a hydrated electron and the aqueous chloride anion are reported. A novel technical feature is the efficient representation of solute electronic wavefunctions in terms of floating spherical Gaussian orbitals. The simulations account for the coupling of the excess electron to the solvent electronic polarization in an explicit and self-consistent fashion. The computed electronic ground state absorption spectrum for e-/H2O and the charge-transfer-to-solvent spectra for Cl-/H2O are analyzed. The energetic aspects of the models and the short time solute electronic dynamics are discussed.