Vertical ionization energies and electron affinities of ions in solution from outer-sphere charge transfer transition energies

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.