Marcus Theory - Experimental Results

Experimental Results

Marcus has published his theory in 1956. For long years there was an intensive search for the inverted region which would be a proof of the theory. But all experiments with series of reactions of more and more negative G0 revealed only an increase of the reaction rate up to the diffusion limit, i.e. to a value indicating that every encounter lead to electron transfer, and that limit held also for very negative G0 values (Rehm-Weller behaviour). It took about 30 years until the inverted region was unequivocally substantiated by Miller, Calcaterra and Closs for an intermolecular electron transfer in a molecule where donor and acceptor are kept at a constant distance by means of a stiff spacer (Fig.4).

A posteriori one may presume that in the systems where the reaction partners may diffuse freely the optimum distance for the electron jump may be sought, i.e. the distance for which G‡ = 0 and G0 = - _o. For _o is dependent on R, _o increases for larger R and the opening of the parabola smaller. It is formally always possible to close the parabola in Fig. 2 to such an extent, that the f-parabola intersects the i-parabola in the apex. Then always G‡ = 0 and the rate k reaches the maximum diffusional value for all very negative G0. There are, however, other concepts for the phenomenon, e.g. the participation of excited states or that the decrease of the rate constants would be so far in the inverted region that it escapes measurement.

R.A. Marcus and his coworkers have further developed the theory outlined here in several aspects. They have included inter alia statistical aspects and quantum effects, they have applied the theory to chemiluminescence and electrode reactions. R.A Marcus received the Nobel Prize in Chemistry in 1992, his Nobel Lecture gives an extensive view of his work.