Interfacial Electric Fields in Water Nanodroplets are Weakly Dependent on Curvature and pH

The origin of enhanced reactivity in aqueous microdroplets remains debated, with interfacial electric fields (IEFs) often invoked as catalytic drivers. Here, we provide a quantum-mechanical, spatially resolved characterization of the electric field at air-water interfaces by combining deep-learning molecular dynamics with \emph{ab initio} re-sampling. Across planar interfaces and nanodroplets of varying curvature and charge state, we find an outward-oriented field of $\sim 1.0$--$1.2$ V/{\AA} along the intrinsic surface normal. Crucially, its magnitude scales linearly with the average number of hydrogen bonds per interfacial molecule, directly tying the field to the local hydrogen-bond network. Despite its large magnitude and contrary to common expectations, we find that curvature and pH exert only a minor influence on the IEF, becoming negligible at experimentally relevant droplet sizes and pH. Consequently, the reactivity differences observed in $\mu$m-sized droplets cannot be ascribed to variations in the IEF, which changes by a factor of only $\sim10^{-5}$ between $3$ and $40\mu$m-sized droplets. Moreover, the IEF is localized inside the interfacial region and rapidly vanishes within a few {\AA}. This strong spatial confinement renders the IEF strongly tied to the local electronic structure, identifying it as a local property of the air-water boundary rather than an independent physical driver of ``on-water'' catalysis.