In the presence of the sodium surface, our DFT calculations yield positive adsorption energies for contact and solvent-separated ion pair structures (Fig. , panels e and g), suggesting their minimal presence in close proximity to the surface. Although partial desolvation enhances the stability of the adsorbed structures, as reflected in ∆𝐸 ",% < 0 (Fig. , panels f and h), the positive adsorption energies obtained for the fully solvated structures still act as a barrier against their approach to the surface and subsequent desolvation. Consequently, ions are anticipated to form the vast majority of adsorbed species on the sodium surface, with water rarely present within the interfacial region. The absence of water in this region could significantly contribute to expanding the electrochemical stability window by inhibiting watersurface interactions, thus preventing water reduction on the electrode surface. Eq. 1, and for the partly desolvated adsorbates, the panels show the desolvation energies, ∆𝐸 ,-< , approximated from Eq. 3.