Helmholtz plane by electrochemical means), i.e., immediately close to the contact line, to the interface of the diffuse layer and the bulk. As previously mentioned, the role of the electrode/solution interactions in the vicinity of the contact line and their influence on the free energy of the system has been studied by Taherian et al. , where the authors highlighted the much stronger influence of water molecular orientation on contact angle over that of relatively low charge densities (less than 2 μC cm -2 ). Here, the dominant role of at higher charge densities is demonstrated. In fact, despite focusing our discussion on the integral value of (see equation 3), variations in with surface charge density and electrolyte concentration are detected already from the first molecular layer close to the electrode (Figure ).