The cyclic voltammetry simulation of a competition between stepwise and concerted dissociative electron transfer, the modeling of alpha apparent variability, the relationship between apparent and elementary kinetic parameters

Abstract

A comparison of elementary (input) and apparent (output) values of the transfer coefficient was carried out for simulated kinetic cyclic voltammetry spectrum from stepwise to concerted mechanism. The resulting patterns of α_app versus E_p plots do not provide sufficient information to discriminate between the two mechanisms. It has been demonstrated that non-linear α_app patterns are characteristic for the pure stepwise mechanism obeying the Butler–Volmer kinetics. The change in α_app is not a sufficient condition for the transition from stepwise to concerted mechanism. This paper contains visualizations of the relationship between the apparent and elementary transfer coefficient. The difference between the potential variabilities of α_app and α_elem (a frequent source of confusion) is also discussed.