CO₂ hydration at the air-water interface: A surface-mediated "in-and-out" mechanism

An understanding of the CO₂ + H₂O hydration reaction is crucial for modeling the effects of ocean acidification, for enabling novel carbon storage solutions, and as a model process in the geosciences. While the mechanism of this reaction has been investigated extensively in the condensed phase, its mechanism at the air-water interface remains elusive, leaving uncertain the contribution that surface-adsorbed CO₂ makes to the overall acidification reaction. In this study, we employ machine-learned potentials trained to various levels of theory to provide a molecular-level understanding of CO₂ hydration at the air-water interface. We show that reaction at the interface follows a surface-mediated "in-and-out" mechanism: CO₂ diffuses into the aqueous surface layer, reacts to form carbonic acid, and is subsequently expelled from solution. We show that this surface layer provides a bulk-like solvation environment, engendering similar modes of reactivity and near-identical free energy profiles for the bulk and interfacial processes. Our study unveils an unconventional reaction mechanism that underscores the dynamic nature of the molecular reaction site at the air-water interface. The similarity between bulk and interfacial profiles shows that CO₂ hydration is equally as feasible under these two solvation environments and that acidification rates are likely enhanced by this additional surface contribution.