A THEORETICAL SCHEME TO OBTAIN THE INNER-SPHERE REORGANIZATION ENERGIES FOR HA-EXCHANGE REACTIONS VIA IONIZATION-POTENTIALS AND ELECTRON-AFFINITIES(HA(+) (A=BE, B, C, N, O AND F) SELF)

This paper reports for the first time an accurate theoretical scheme f or obtaining directly the inner-sphere reorganization energies for the electron self-exchange reactions from ionization potentials and elect ron affinities. The total innersphere reorganization energy consists o f two contributions: the reorganization energy of the oxidized species and that of the reduced species. The former corresponds to the releva nt ionization potentials of the reduced species, and the latter to the relevant electron affinities of the oxidized species. The ionization potentials and electron affinities may be obtained from their photoele ctron spectra or alternatively from the vibration-rotation spectroscop ic data via accurate potential functions for the second row diatomic h ydrides (redox pairs) when the relevant ionization or excited energies of the dissociated products (atoms) of these redox species are availa ble. The inner-sphere reorganization energy values are calculated for the electron self-exchange reactions HA + HA(+) (A = Be, B, C, N, O an d F) and compared with those from other classical calculation methods.