Anomalous Reorganization Free Energies in Optical Electron Transfer in Solution.

摘要

Autoionization bands are observed in the photoelectron emission spectroscopy of aqueous solutions of cyanometalate complexes (Mn, Fe, W, Mo), anions (NO(-)3, ClO(-)4) and cations (Ag(+), Tl(+)). Reorganization free energies for autoionization bands are anomalously low in absolute value (by ca. 1 eV) in comparison with direct transitions to the continuum. Interpretation is based on potential energy profiles and model calculations for the reorganization free energy.