Inorganic Chemistry, Vol.37, No.18, 4584-4588, 1998
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.
Keywords:PHOTOELECTRON EMISSION-SPECTROSCOPY;MIXED-VALENCE COMPOUNDS;INTERVALENCE TRANSFER;CRYSTAL-STRUCTURE;AQUEOUS-SOLUTION;COMPLEXES;POTENTIALS;PAIRS;ANIONS;WATER