In theoretical chemistry, Marcus theory is a theory originally developed by Rudolph A. Marcus, starting in 1956, to explain the rates of electron transfer reactions – the rate at which an electron can move or jump from one chemical species (called the electron donor) to another (called the electron acceptor).[1] It was originally formulated to address outer sphere electron transfer reactions, in which the two chemical species only change in their charge with an electron jumping (e.g. the oxidation of an ion like Fe2+/Fe3+), but do not undergo large structural changes. It was extended to include inner sphere electron transfer contributions, in which a change of distances or geometry in the solvation or coordination shells of the two chemical species is taken into account (the Fe-O distances in Fe(H2O)2+ and Fe(H2O)3+ are different).[2][3]
For electron transfer reactions without making or breaking bonds Marcus theory takes the place of Eyring's transition state theory[4][5] which has been derived for reactions with structural changes. Both theories lead to rate equations of the same exponential form. However, whereas in Eyring theory the reaction partners become strongly coupled in the course of the reaction to form a structurally defined activated complex, in Marcus theory they are weakly coupled and retain their individuality. It is the thermally induced reorganization of the surroundings, the solvent (outer sphere) and the solvent sheath or the ligands (inner sphere) which create the geometrically favourable situation prior to and independent of the electron jump.
The original classical Marcus theory for outer sphere electron transfer reactions demonstrates the importance of the solvent and leads the way to the calculation of the Gibbs free energy of activation, using the polarization properties of the solvent, the size of the reactants, the transfer distance and the Gibbs free energy of the redox reaction. The most startling result of Marcus' theory was the "inverted region": whereas the reaction rates usually become higher with increasing exergonicity of the reaction, electron transfer should, according to Marcus theory, become slower in the very negative domain. Scientists searched the inverted region for proof of a slower electron transfer rate for 30 years until it was unequivocally verified experimentally in 1984.[6]
R. A. Marcus received the Nobel Prize in Chemistry in 1992 for this theory. Marcus theory is used to describe a number of important processes in chemistry and biology, including photosynthesis, corrosion, certain types of chemiluminescence, charge separation in some types of solar cells and more. Besides the inner and outer sphere applications, Marcus theory has been extended to address heterogeneous electron transfer.
- ^ "Electron Transfer Reactions in Chemistry: Theory and Experiment". Nobelstiftung. 8 December 1992. Retrieved 2 April 2007.
- ^ Contrary to Marcus' approach the inner sphere electron transfer theory of Noel S. Hush refers to a continuous change of the electron density during transfer along a geometrical coordinate (adiabatic case), and takes also into account the solvent influence as did Marcus. Hush's formulation is known as Marcus–Hush theory.
- ^ Hush, N.S. Trans. Faraday Soc. 1961, 57,557
- ^ P. W. Atkins: Physical Chemistry, 6. Ed., Oxford University Press, Oxford 1998 p.830
- ^ R.S. Berry, S. A. Rice, J. Ross: Physical Chemistry, Wiley, New York 1980, S. 1147 ff,
- ^ Miller J.R., Calcaterra L.T., Closs G.L.: "Intramolecular long-distance electron transfer in radical anions. The effects of free energy and solvent on the reaction rates", J.Am.Chem.Soc. 1984, 106, 3047, doi:10.1021/ja00322a058