To overcome this limitation, various enhanced sampling methods have been developed to promote transitions across high-energy barriers separating metastable states. Those strategies involve increasing the system's temperature , or adding a bias potential to the global PES of the system , in order to boost the likelihood of barrier crossing. These approaches often employ multiple replicas, as in parallel tempering, or constrain molecules within a small fictitious volume 33 while applying elevated temperatures. While effective in facilitating exploration, these methods can also introduce artifacts, leading to the identification of high-energy pathways and reaction products that may not be experimentally relevant under realistic conditions.