Mail:
Dept. of Chemistry
Ohio State University
100 W. 18th Ave.
Columbus, OH 43210
Office:
412 CBEC
Email:
herbert@
chemistry.ohio-state.edu
The aqueous electron, e–(aq), and its finite analogues, the anionic water clusters (H2O)n–, have attracted significant attention from both theory and experiment over the past few decades. Nevertheless, some of the most basic structural aspects of these systems, as well as the interpretation of certain spectroscopic features, remain controversial or else have defied theoretical explanation altogether. Due to the solvent-supported nature of the ion, a large number of water molecules is required in order to obtain a realistic model of e–(aq), and a wide variety of structural morphologies are available in (H2O)n– clusters. These aspects severely limit the role of ab initio quantum chemistry in elucidating the properties of solvated-electron systems, but at the same time, the fundamentally quantum-mechanical nature of the ion must be taken into account. Most theoretical studies have therefore relied upon one-electron pseudopotential models and mixed quantum/classical molecular dynamics. In view of the highly diffuse, polarizable nature of the ion, however, it is surprising how little attention has been paid to the development of polarizable one-electron models. This article presents an overview of our efforts to develop such a model, as well as computational evidence to suggest that self-consistent, many-body electron–water polarization is qualitatively important in the description of both (H2O)n– clusters and e–(aq) in bulk water.