TY - JOUR
T1 - Stripping voltammetry and chronoamperometry of an adsorbed species with repulsive lateral interactions
AU - Koper, M.T.M.
PY - 2003
Y1 - 2003
N2 - In this paper a simple model is considered for the stripping voltammetry and chronoamperometry of an adsorbed species with repulsive lateral interactions. In the limit of
strongly repulsive lateral interactions, the chronoamperometric transient is predicted to
be hyperbolic, i.e. to have a t-1 dependence. This dependence is confirmed by both
the numerical simulation of the mean-field equations and by the Dynamic Monte Carlo
simulations. However, in the analysis of the Dynamic Monte Carlo simulations, inflexion
points are found in a log-log plot of the data, corresponding to the formation of ordered
configurations on the surface. The stripping voltammetry exhibits broader stripping peaks
with increasingly repulsive lateral interactions. An analysis of the peak potential versus
the logarithm of the scan rate yields the Tafel slope, irrespective of the strength of the
lateral interactions. In the Dynamic Monte Carlo simulations, strong repulsive interactions
lead to multiple stripping peaks, the peaks becoming more pronounced with a faster
surface diffusion of the adsorbed species. These peaks are related to the existence of
ordered configurations on the electrode, whose long-range order is enhanced at faster
diffusion rates.
AB - In this paper a simple model is considered for the stripping voltammetry and chronoamperometry of an adsorbed species with repulsive lateral interactions. In the limit of
strongly repulsive lateral interactions, the chronoamperometric transient is predicted to
be hyperbolic, i.e. to have a t-1 dependence. This dependence is confirmed by both
the numerical simulation of the mean-field equations and by the Dynamic Monte Carlo
simulations. However, in the analysis of the Dynamic Monte Carlo simulations, inflexion
points are found in a log-log plot of the data, corresponding to the formation of ordered
configurations on the surface. The stripping voltammetry exhibits broader stripping peaks
with increasingly repulsive lateral interactions. An analysis of the peak potential versus
the logarithm of the scan rate yields the Tafel slope, irrespective of the strength of the
lateral interactions. In the Dynamic Monte Carlo simulations, strong repulsive interactions
lead to multiple stripping peaks, the peaks becoming more pronounced with a faster
surface diffusion of the adsorbed species. These peaks are related to the existence of
ordered configurations on the electrode, whose long-range order is enhanced at faster
diffusion rates.
U2 - 10.1524/zpch.217.5.547.20461
DO - 10.1524/zpch.217.5.547.20461
M3 - Article
SN - 0942-9352
VL - 217
SP - 547
EP - 556
JO - Zeitschrift für Physikalische Chemie
JF - Zeitschrift für Physikalische Chemie
ER -