Accession Number : ADA139722

Title :   Inner-Sphere Reorganization in Optical Electron Transfer.

Descriptive Note : Technical rept.,

Corporate Author : NEW YORK UNIV NY DEPT OF CHEMISTRY

Personal Author(s) : Delahay,P ; Dziedzic,A

PDF Url : ADA139722

Report Date : Mar 1984

Pagination or Media Count : 30

Abstract : Free energies for photoelectron emission by aqueous solutions of hexaquocations (V2+, Cr2+, Fe2+) - metal complexes (Fe(CN)6 4-, Co (NH3)6 2+) and inorganic anions (OH, C1-, Br-, I-) are calculated from theory and compared with experimental threshold energies. Good agreement is obtained within the estimated error (+ or - 0.2 eV) on emission free energies. The free energy for outer-sphere reorganization is calculated from a continuous medium model. The inner-sphere reorganization energy is obtained from a bond-stretching model for hexaquo cations and metal complexes. A new method is developed for the calculation of the inner-sphere reorganization energies of univalent anions from their free energies of hydration, Reorganization free energies for electron transfer reactions (V(2+)/(3+), Cr(2+)/(3+), Mn(2+)/(3+), Fe(2+)/(3+), Fe(CN)6 (4-)/(3-) calculated from experimental threshold energies and computed outersphere reorganization free energies yield activation free energies in agreement with the values obtained from kinetic measurements. Improvements are discussed for the determination of threshold energies by extrapolation. (Author)

Descriptors :   *Photoelectrons, *Electron transfer, Emission, Anions, Free energy, Solutions(Mixtures), Liquids, Cations, Metal complexes, Threshold effects, Spheres, Models, Computations, Hydration, Activation energy, Kinetics, Extrapolation

Subject Categories : Nuclear Physics & Elementary Particle Physics

Distribution Statement : APPROVED FOR PUBLIC RELEASE