CYCLIC VOLTAMMETRIC ANALYSIS OF FERROCENE ALKANETHIOL MONOLAYER ELECTRODE-KINETICS BASED ON MARCUS THEORY

Theory for electrode kinetics of surface-immobilized monolayers in cyclic voltammetry is developed based on the Marcus free energy-rate relation. Numerical calculations show that when the applied overpotential exceeds similar to 30% of the reorganizational energy of the electrode reaction, voltammetry predicted from Marcus theory differs from that based on classical Butler-Volmer kinetics with regard to wave shape, peak currents and their dependence on potential sweep rate, and variation of peak potential with potential sweep rate. Estimates of the standard rate constant, k(0), can be made from E(peak) data without exact knowledge of reorganizational energies. Examples are given of evaluating k(0) for monolayers of ferrocene alkanethiols chemisorbed on Au(111) electrodes, when the monolayers are highly ordered, and kinetically monodisperse, and when they are somewhat disordered, and kinetically disperse on bulk gold electrodes at room and 150 K temperatures.