Statistical Aspects of Autoionization Lifetimes

Abstract
Long‐lived, parent‐molecule negative ions can serve as convenient prototypes for the autoionizing species frequently postulated in radiation chemistry. Recent measurements of the rates of formation and autoionization of a number of such ions are discussed. The assumptions involved in the derivation of electron affinities from the measurements are found to be identical with those inherent in unimolecular decomposition theory. Implications for photo‐ and radiation chemistry are noted.