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outer sphere electron transfer
Outer sphere refers to an electron transfer (ET) event that occurs between chemical species that remain separate and intact before, during, and after the ET event.〔(Article: outer-sphere electron transfer ), from the IUPAC Gold book]〕 In contrast, for inner sphere electron transfer the participating redox sites undergoing ET become connected by a chemical bridge. Because the ET in outer sphere electron transfer occurs between two non-connected species, the electron is forced to move through space from one redox center to the other.
==Marcus Theory==
The main theory that describes the rates of outer-sphere electron transfer was developed by Rudolph A. Marcus in the 1950s. A major aspect of Marcus theory is the dependence of the electron transfer rate on the thermodynamic driving force (difference in the redox potentials of the electron-exchanging sites). For most reactions, the rates increase with increased driving force. A second aspect is that the rate of outer-sphere electron-transfer depends inversely on the "reorganizational energy." Reorganization energy describes the changes in bond lengths and angles that are required for the oxidant and reductant to switch their oxidation states. This energy is assessed by measurements of the self-exchange rates (see below). Outer sphere electron transfer is the most common type of electron transfer, especially in biochemistry, where redox centers are separated by several (up to about 11) angstroms by intervening protein. In biochemistry, there are two main types of outer sphere ET: ET between two biological molecules or fixed distance electron transfer, in which the electron transfers within a ''single'' biomolecule (e.g., intraprotein).〔S. J. Lippard, J. M. Berg “Principles of Bioinorganic Chemistry” University Science Books: Mill Valley, CA; 1994. ISBN 0-935702-73-3.〕
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