Using Purely Sinusoidal Voltammetry for Rapid Inference of Surface-Confined Electrochemical Reaction Parameters

Alternating current (AC) voltammetric techniques are experimentally powerful as they enable Faradaic to be isolated from non-Faradaic contributions. Finding the best global fit between experimental data and simulations based on reaction models requires searching a substantial parameter space at high resolution. In this paper, we estimate parameters purely sinusoidal voltammetry (PSV) experiments, investigating redox reactions of surface-confined ferrocene derivative. The advantage PSV is that complete experiment can simulated relatively rapidly, compared other AC techniques. one example involving thermodynamic dispersion, inference effort requiring 7,500,000 was completed in 7 h, whereas same process for our previously used technique, ramped Fourier transform (ramped FTACV), would have taken 4 days. Using both synthetic with surface confined diazonium substituted derivative, it shown technique recover key chemical physical parameters. By applying Bayesian Markov chain Monte Carlo methods, confidence, distribution, degree correlation recovered visualized quantified.