Abstract
We present here a detailed analysis of the electric double layer at the gold electrode/[BMIM][BF4] interface using a polarizable model for the electrode, based on our recent approach to include image charges [Geada et al. Nat. Commun. 2018, 9, 716]. A double bell (camel) shape is obtained for the differential capacitance, where the inclusion of metal polarization allows for a higher density of ions in the double layer, particularly around the maxima, thereby increasing the capacitance. The charging mechanism differs for the positive and negative electrodes, with counterion adsorption prevailing at the anode and co-ion desorption prevailing at the cathode. The charging mechanism is predominantly governed by the BF4 anions, serving as counterions and co-ions at the anode and cathode, respectively. Within the considered range of potentials, only minor changes are observed in the dynamical properties, specifically in the diffusion coefficients. Notably, it is interesting to observe that bulk properties are restored at a shorter distance from the gold surface in the case of the anode compared to the cathode.
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