Among the anions, the strongest interaction with the surface is observed for halides, which are followed by OH -and HCOO -. The weakest interaction with the (111) Au surface is observed for the nitrate ion, followed by TfO -and MeSO 3 -. The anions form a characteristic volcano-shaped E ads (ε HOMO ) dependence (Figure ) with a maximum at ε HOMO ~ -0.25 a.u., while no correlation is found for E ads (ε LUMO ) (Figure Some degradation of the correlations on the metal and deviation of a number of cations (on average, cations have stronger binding to Au (111) than anions) can be caused by the increased complexity of the adsorption process of bulk systems on the metal. In addition to a bigger population of electronic states in the metal and, consequently, a bigger number of electrode wave functions involved in the adsorption, there are also local perturbations of the electron density in the vicinity of the ions. In particular, we can talk about image charges, which can make a significant contribution to the adsorption energy when the adsorbent approaches the metal electrode at a sufficiently close distance. Unlike the previous model electrodes, on Au (111) the E ads (z 0 ) dependence is observed for both the cations (an exponential one, Figure .13 E, except for PyMe + , EMPyr + and H 3 O + ) and the anions (a linear one, Figure .13 F).