In this paper Monte Carlo simulations of a dissociative electron transfer reaction in solution have been performed in order to test to what extent the deviation of Marcus' relationship for this kind of reactions can be attributed to the features of the solute internal potential energy. It is shown that Marcus' equation does not apply to this kind of dissociative electron transfer processes if the ab initio solute internal potential energies are used. Conversely, if a Morse curve and its repulsive part are employed to describe the solute internal potential energies, Marcus' relationship is recovered. Then, the problem is reduced to what extent the ab initio solute internal potential energies can be represented by Morse curves. © 1994.