Electrochemistry within a limited number of molecules:: Delineating the fringe between stochastic and statistical behavior

The behavior of a limited number of molecules is expected to show a profound stochastic character and therefore to significantly differ from the usual chemical kinetic laws. This dichotomy is investigated theoretically within an electrochemical framework by considering the specific example of the oxidation of a PAMAM redox dendrimer caped by 64 ruthenium bis-terpyridine centers (see picture). Thus the maximum number of adsorbed molecules at which the observation of the intrinsic stochastic nature of the phenomenon should remain observable can be evaluated, either by itself, or when instrumental distortions are involved.