<i>A priori</i>calculation of the optical absorption spectrum of the hydrated electron

Abstract

The optical-absorption spectrum of an excess electron solvated in a molecular sample of liquid water at 300 K has been calculated with use of solvent configurations generated via path-integral simulation and subsequent solution of the excess-electronic eigenvalue problem. Electronic transitions from an s-like ground state to three bound-localized, p-like excited states dominate the broad asymmetric spectrum with excitations into an apparent continuum following at higher energy. Asymmetric distortions and radial fluctuations of the solvent cavities contribute comparably to the spectral broadening.