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The main theory describing the rates of outer sphere electron transfer was developed by Rudolph A. Marcus in the 1950s, for which he was awarded the Nobel Prize in Chemistry in 1992. [2] 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 ...
The ligand shells around A and D are retained. This process is called outer sphere electron transfer. Outer sphere ET is the main focus of traditional Marcus Theory. The other kind or redox reactions is inner sphere where A and D are covalently linked by a bridging ligand. Rates for such ET reactions depend on ligand exchange rates.
The first generally accepted theory of ET was developed by Rudolph A. Marcus (Nobel Prize in Chemistry in 1992) [8] to address outer-sphere electron transfer and was based on a transition-state theory approach. The Marcus theory of electron transfer was then extended to include inner-sphere electron transfer by Noel Hush and Marcus.
Electron transfer is one of the simplest forms of a chemical reaction. It consists of one outer-sphere electron transfer between substances of the same atomic structure likewise to Marcus’s studies between divalent and trivalent iron ions. Electron transfer may be one of the most basic forms of chemical reaction but without it life cannot exist.
Marcus' theory of outer sphere electron transfer predicts that such a tunneling process will occur most quickly in systems where the electron transfer is thermodynamically favorable (i.e. between strong reductants and oxidants) and where the electron transfer has a low intrinsic barrier.
Marcus Theory explains the rates of electron transfer reactions—the rate at which an electron can move from one chemical species to another. It was originally formulated to address outer sphere electron transfer reactions, in which two chemical species change only in their charge, with an electron jumping.
In most cases electron transfer can be assumed to be much faster than the chemical reactions. Unlike stoichiometric reactions where the steps between the starting materials and the rate limiting step dominate, in catalysis the observed reaction order is usually dominated by the steps between the catalytic resting state and the rate limiting step.
The Rice–Ramsperger–Kassel–Marcus (RRKM) theory is a theory of chemical reactivity. [1] [2] [3] It was developed by Rice and Ramsperger in 1927 [4] and Kassel in 1928 [5] (RRK theory [6]) and generalized (into the RRKM theory) in 1952 by Marcus [7] who took the transition state theory developed by Eyring in 1935 into account.