  Adiabatic mixed quantum/classical molecular dynamics simulations were used to
generate snapshots of the hydrated electron (e-) in liquid water at 300 K.
Water cluster anions that include two complete solvation shells centered on the
e- were extracted from these simulations and embedded in a matrix of fractional
point charges designed to represent the rest of the solvent. Density functional
theory and single-excitation configuration interaction methods were then
applied to these embedded clusters. The salient feature of these hybrid
calculations is significant transfer (ca. 0.18) of the excess electron's charge
density into the O 2p orbitals in OH groups forming the solvation cavity. We
used the results of these calculations to examine the structure of the
molecular orbitals, the density of states, the absorption spectra in the
visible and ultraviolet, the hyperfine coupling (hfc) tensors, and the IR and
Raman spectra of the e-. The calculated hfc tensors were used to compute the
EPR and ESEEM spectra for the e- that compared favorably to the experimental
spectra of trapped e- in alkaline ice. The calculated vibrational spectra of
the e- are consistent with the red-shifted bending and stretching frequencies
observed in resonance Raman experiments. The model also accounts for the VIS
and 190-nm absorption bands of the e-. Thus, our study suggests that to explain
several important experimentally observed properties of the e-, many-electron
effects must be accounted for.
