The ab initio molecular dynamics (AIMD) simulations were done using the canonical NVT ensemble at 300 K using the Nosé-Hoover thermostat . To simulate the water density of 1000 kg/m 3 , a larger p(3 √ 3 x 3 √ 3) • Ag (111) unit cell of 4 layers was used with the Brillouin zone sampled at a Γ point. The solvent configurations were taken from our previous work on the Au surface and placed on top of the Ag (111) surface with the cation coverage set to 0.07 ML (2/27). The AIMD simulations were run for 10 ps as pre-equilibration for all the cases. The constrained molecular dynamics using the slow-growth approach were run with distance between cation and surface as the reaction coordinate. A set of 4 images were taken along this coordinate and run for additional 18 ps at the constrained reaction coordinate. The cation that forms the contact-ion pair with CO 2 -has been chosen for this analysis. Coordination analysis on each image was performed using the neighbor list function from the Atomic Simulation Environment (ASE) by using a cutoff distance of 1.1 times the covalent radii of the atoms.