Resonance Raman spectra and vibronic analysis of the aqueous solvated electron

Resonance Raman spectra of the aqueous solvated electron reveal enhancements of the water inter- and intramolecular vibrations demonstrating that electronic excitation is significantly coupled to these modes. The Raman cross-sections and absorption spectra are quantitatively modeled, yielding an optimized Gaussian homogeneous broadening of 4660 cm−1 (FWHM), inhomogeneous broadening of 2700 cm−1, and Franck–Condon displacements (Δ) of ∼1 for each of the three librations, 0.4 for the water bend, and 0.2 for the stretch. Frequency downshifts of the resonantly enhanced H2O bend to 1615 cm−1, and of the stretch to 3100 cm−1 are best explained by charge donation into solvent frontier orbitals.