Photon-induced electron transfer transitions of the solvated electrons

Abstract

The role of electron transfer transitions in the absorption spectrum of the solvated electron in liquid water is studied in terms of the generalized line shape function. When the density of trapping sites is greater than one third of the density of solvent molecules, the transition-dipole moment for photon-induced electron transfers was found to be greater than that of the single-site 1s→2p transition. The solvated electron is assumed to be coupled with low-frequency solvent modes and a high-frequency molecular mode. The latter mode is responsible for a small isotope shift in the peak energy. The spectrum consists of contributions from short-distance transfers (’’bound–bound’’) and long-distance (’’bound–free’’) transfers, the latter being the minor component of the total spectrum.