Đã lưu trong:
Chi tiết về thư mục
Những tác giả chính: Brookes, Samuel G. H., Kapil, Venkat, Michaelides, Angelos, Schran, Christoph
Định dạng: Preprint
Được phát hành: 2025
Những chủ đề:
Truy cập trực tuyến:https://arxiv.org/abs/2502.08348
Các nhãn: Thêm thẻ
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Mục lục:
  • An understanding of the CO$_2$ + H$_2$O 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 CO$_2$ 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 CO$_2$ hydration at the air-water interface. We show that reaction at the interface follows a surface-mediated `In and Out' mechanism: CO$_2$ 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 a new, 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 CO$_2$ hydration is equally as feasible under these two solvation environments and that acidification rates are likely enhanced by this additional surface contribution.