Structure of the aqueous solvated electron from resonance Raman spectroscopy: lessons from isotopic mixtures

The structure and thermodynamics of the hydrated electron are probed with resonance Raman spectroscopy of isotopic mixtures of H(2)O and D(2)O. The strongly enhanced intramolecular bends of e(-)(H(2)O) and e(-)(D(2)O) produce single downshifted bands, whereas the e(-)(HOD) bend consists of two components: one slightly upshifted from the 1,446 cm(-1) bulk frequency to 1,457 cm(-1) and the other strongly downshifted to approximately 1,396 cm(-1). This 60 cm(-1) split and the 200 (120) cm(-1) downshifts of the OH (OD) stretch frequencies relative to bulk water reveal that the water molecules that are Franck-Condon coupled to the electron are in an asymmetric environment, with one proton forming a strong hydrogen bond to the electron. The downshifted bend and librational frequencies also indicate significantly weakened torsional restoring forces on the water molecules of e(-)(aq), which suggests that the outlying proton is a poor hydrogen bond donor to the surrounding solvent. A 1.6-fold thermodynamic preference of the electron for H(2)O is observed based on the relative intensities of the e(-)(H(2)O) and e(-)(D(2)O) bands in a 50:50 isotopic mixture. This equilibrium isotope effect is consistent with the downshifted vibrational frequencies and a relative reduction of the zero-point energy of H(2)O bound to the electron. Our results enhance the cavity model of the solvated electron and support only those models that contain water monomers as opposed to other molecular species.