From Kinetic Gateways to Thermodynamic Locking: Unveiling the Dynamic Adsorption Landscape of CO on Pt(111)

sites nearly vanish, creating a highly fluid phase that facilitates complex changes of adlayer structure. In contrast, at the saturation limit, the CO adlayer becomes thermodynamically locked into deep potential wells with high diffusion barriers, indicative of a rigid "catalyst poisoning" state. These findings bridge the gap between zero-temperature static models and finite-temperature experimental realities, offering a unified theoretical framework for understanding the dynamic interplay between thermodynamic site competition and kinetic accessibility.