A program has been funded by the Theoretical and Computational Chemistry Program of the Chemistry Division to support a theoretical study by Simons in the area of negative-ion chemistry. The research will investigate a variety of novel molecular anions of immediate experimental interest or whose study presents new experimental challenges. Goals include quantitative information (e.g., vibrational frequencies, dissociation energies, electron binding energies) needed by experimental groups as well as conceptual information (e.g., rates of vibration-to-electronic energy flow and bonding in small main group clusters) of interest to theorists. Double-Rydberg anions will continue to be studied, but the new work will also extend into investigation of main-group clusters of polyvalent electron deficient species, ion-molecule reaction energetics, and comparison of anion, neutral and cation reactive potential energy surfaces.%%% The chemistry of negative ions has been a difficult frontier in theoretical chemistry, presenting many methodological challenges to the investigator. Nevertheless, it is currently an active experimental field in physical chemistry and the work done with support from this grant will enable the predictive and interpretive assistance which theory has given to experimenters in the chemistry of neutral species to be extended to those working with negative ions.
