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The cyclic voltammetry of the reaction of a solution-phase species at a macroelectrode under semi-infinite diffusion is simulated assuming irreversible electrode kinetics within the Marcus–Hush–Chidsey model. The resulting peak currents are shown to deviate from the square root dependence on voltage scan rate predicted by the Randles–Ševčík equation. Simulated voltammetry of a surface-bound redox...
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