Chemical Physics Letters, Vol.508, No.4-6, 306-313, 2011
How many molecules are required to measure a cyclic voltammogram?
The stochastic limit at which fully-reversible cyclic voltammetry can accurately be measured is investigated. Specifically, Monte Carlo GPU simulation is used to study low concentration cyclic voltammetry at a microdisk electrode over a range of scan rates and concentrations, and the results compared to the statistical limit as predicted by finite difference simulation based on Fick's Laws of Diffusion. Both Butler-Volmer and Marcus-Hush electrode kinetics are considered, simulated via random-walk methods, and shown to give identical results in the fast kinetic limit. (C) 2011 Elsevier B. V. All rights reserved.