Both simulations in the bulk and at the interface were preliminarily equilibrated for at least 5 ps keeping the RC fixed whereas water molecules were allowed to relax. All AIMD+MetD simulations were conducted employing the dispersion-corrected BLYP-D3 exchange and correlation functional with DZVP-MOLOPT-SR-GTH basis set. The energy cutoff was set to 400 Ry. The self-consistent field cycle was converged using the orbital transformation method. The dynamics of the system was simulated classically within the NVT ensemble with a timestep of 1 fs. The average temperature was controlled at 300 K using a Nose-Hoover thermostat chain with a coupling time constant of 50 fs. The distances between two pairs of C-C atoms, i.e. C1-C4 and C2-C3 distances, were selected as the collective variables (CVs) for this study (Figure ). Additionally, block average analysis was performed on the calculated free-energy barriers and on the chosen CVs of the TSs for all the investigated systems to estimate the associated error bars. A more detailed description along with additional results of all the AIMD+MetD simulations can be found in the Supporting Information.