Marcus theory multidimensional

Rates of addition to carbonyls (or expulsion to regenerate a carbonyl) can be estimated by appropriate forms of Marcus Theory. " These reactions are often subject to general acid/base catalysis, so that it is commonly necessary to use Multidimensional Marcus Theory (MMT) - to allow for the variable importance of different proton transfer modes. This approach treats a concerted reaction as the result of several orthogonal processes, each of which has its own reaction coordinate and its own intrinsic barrier independent of the other coordinates. If an intrinsic barrier for the simple addition process is available then this is a satisfactory procedure. Intrinsic barriers are generally insensitive to the reactivity of the species, although for very reactive carbonyl compounds one finds that the intrinsic barrier becomes variable. ... 

J. P. Guthrie, Multidimensional Marcus Theory an Analysis of Concerted Reactions, J. Am. Chem. Soc. 1996,118,12878. 

As a first step toward reducing the amount of empirical information needed to go from equilibrium to rate constant, we developed multidimensional Marcus theory (MMT)8 as a way of treating concerted reactions that could... 

For multidimensional problems, the generalization of WKB theory to the description of scattering problems is often called Miller-Marcus or classical -matrix theory [51]. The reader is referred to review articles for a more complete description of this theory [52]. 

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