Vertical Ionization Energies and Electron Affinities of Ions in Solution from Outer-Sphere Charge Transfer Transition Energies

Abstract

Outer-sphere charge transfer (OSCT) transitions are shown to correlate with previously published photoelectron emission threshold energies. From these data it is possible to generate a set of parameters, I(D) and I(A), which define these OSCT energies, where I(D) is identified as the solution phase vertical ionization potential, and I(A) is the solution phase vertical electron affinity. An easy procedure for deriving these data for a wide variety of cations and anions is presented. The application of these data leads to a powerful procedure for extracting reorganization and solvation energies of value in a variety of applications.