Dynamics of Solvated Electrons in Clusters

Solvated electrons are a fundamental species to many areas of physical science. In addition to playing a key role in aqueous phase chemistry, they have been implicated in a wide variety of phenomena including aerosol nucleation in the upper atmosphere, the Birch reduction reaction in organic chemistry, and a secondary role in the low-energy radiation damage to DNA. Infrared spectroscopy can be applied to determine the vibrational and electronic structure of the clusters, while photoelectron spectroscopy can access the relative energies of the cluster states and their ionized or detached products to understand the size-dependent energetics of electron solvation. A more fundamental question in cluster studies of electron solvation is exactly how to extrapolate cluster measurements into meaningful comparisons to measured or calculated values in bulk matter. Classical electrostatic models of continuous dielectric media offer a guide to understanding the material and size-specific properties of solvent clusters but are often not effective a priori.