The coordination number of the cations changed within 0.2 after 12 ps (Figure ), hence the coordination analysis at different z-distances (Figure ) was done using the final 3 ps of the trajectories. The larger standard deviations on K + and Cs + as compared to Li + can be related to their loose first coordination shell merging with the second shell (Figure ). The standard deviations are directly proportional to the ability of the cation to desolvate and change its water coordinations, which is the easiest for Cs + followed by K + and Li + (energetics in Figure ). To assess whether varying cation concentrations affect the coordination shifts, we performed additional AIMD simulations for K + by decreasing the cation coverage to 1/27 ML. Further, to check if a cation forming a solvent-separated ion pair with CO 2 -influences the coordination shifts, we performed AIMD simulations by placing K + at-least 5 Å away from CO 2 -. In both cases, the coordination shift, as the K + moves from the OHP towards the surface remained around 1 (Figure ) and the desolvation energies remain within 0.06 eV, which is within the error bars reported in Figure . This observation highlights that the coordination shift is primarily influenced by the cation's distance from the surface, rather than its proximity to the adsorbed species. Therefore, our approach of treating the cation desolvation as an independent step in the microkinetic model is justified. The barriers for the ratedetermining CO 2 to COOH PCET for Ag(111)-M + (H 2 O) 72 were calculated using the thermodynamic integration method (Table ) and verified to be within 0.1 eV of the Ag(111)-M + (H 2 O) 3 .