Ionic Atmosphere Effects on the Energetics of Thermal and Optical Electron-Exchange Reactions: Application to Ferrocenium-Ferrocene Self Exchange
PURDUE UNIV LAFAYETTE IN DEPT OF CHEMISTRY
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A treatment of ionic-atmosphere effects upon symmetrical electron- transfer reactions resulting from added electrolyte is outlined. Relationships are derived on the basis of the extended Debye-Huckel model for the increase in the activation free energy, associated with reorganization of the ionic atmosphere for homogeneous-phase reactions involving a pair of spherical reactants with varying internuclear distance R. Similar relationships apply to the energetics of symmetrical optical electron transfer, since the increase in the optical transition energy, should equal the corresponding ionic atmosphere reorganization energy, under the anticipated linear response conditions. Keywords Electron-transfer reactions, Ionic atmosphere reorganization, Electrolyte effects upon rate constants for ferrocenium-ferrocene self exchange.
- Atmospheric Physics