Fig. 5: ^*COOH splitting and CO desorption processes.

a One-dimensional FES of ^*COOH splitting along the distance between the C atom and the O atom of the hydroxyl/hydroxide group, with three stages identified: bond cleavage (Stage 1), first proton transfer of OH⁻ (Stage 2), and OH⁻ diffusion (Stage 3). b Representative snapshots illustrating three stages of the ^*COOH splitting process, captured from the biased trajectory at CP condition. The colors in the snapshots represent Ag in light gray, C in dark gray, O in red, and H in white. The green transparent ball illustrates the location of OH⁻. Only the water molecules involved in the reaction are shown in ball-stick style, while others are depicted in transparent stick style for clear illustration. c One-dimensional FES of the CO desorption process along the vertical distance of CO from the surface. The reference minima of the free energy profiles are aligned to the initial states in both FES plots for better comparison of the free energy difference at PZC and CP conditions. In the inset, the Ag slab is shown in light gray, C in dark gray, O in red, and H in white.