Simulation of the resonance Raman spectrum of the hydrated electron in the hydrated-hydronium cluster model

Abstract

Vibrational frequencies and resonance Raman (RR) intensities associated with the s → p transition of the unpaired electron in H₃O and H₃O(H₂O)_3m clusters have been calculated using ab initio electronic-structure methods and density functional theory. It is found that the simulated spectra converge with increasing cluster size towards the RR spectrum of the solvated electron in water measured recently by Mizuno and Tahara [M. Mizuno and T. Tahara, J. Phys. Chem. A, 2001, 105, 8823] and Tauber and Mathies [M. Tauber and R. Mathies, J. Phys. Chem. A, 2001, 105, 10952]. The results suggest that hydronium–water clusters are useful finite-size model systems for the rationalization of the spectroscopic properties of the solvated electron in liquid water.