A theoretical scheme to obtain the inner-sphere reorganization energies for HA + HA + (A = Be, B, C, N, O and F) self-exchange reactions via ionization potentials and electron affinities

Abstract

This paper reports for the first time an accurate theoretical scheme for obtaining directly the inner-sphere reorganization energies for the electron self-exchange reactions from ionization potentials and electron affinities. The total innersphere reorganization energy consists of two contributions: the reorganization energy of the oxidized species and that of the reduced species. The former corresponds to the relevant 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 photoelectron spectra or alternatively from the vibration-rotation spectroscopic data via accurate potential functions for the second row diatomic hydrides (redox pairs) when the relevant ionization or excited energies of the dissociated products (atoms) of these redox species are available. The inner-sphere reorganization energy values are calculated for the electron self-exchange reactions HA + HA + (A = Be, B, C, N, O and F) and compared with those from other classical calculation methods.