Electron Transfer Reaction Through an Adsorbed Layer

We consider electron transfer from a redox to an electrode through and adsorbed intermediate. The formalism is developed to cover all regimes of coverage factor, from lone adsorbate to monolayer regime. The randomness in the distribution of adsorbates is handled using coherent potential approximation. We give current-overpotential profile for all coverage regimes. We explictly analyse the low and high coverage regimes by supplementing with DOS profile for adsorbate in both weakly coupled and strongly coupled sector. The prominence of bonding and anti-bonding states in the strongly coupled adsorbates at low coverage gives rise to saddle point behaviour in current-overpotential profile. We were able to recover the marcus inverted region at low coverage and the traditional direct electron transfer behaviour at high coverage.