To explore additional potential sub-structures within the ion-rich domain of a NaOTF WiS electrolyte, we extend our analysis to the adsorption of Na2OTF and Na(OTF)2 aggregates on the examined surfaces. While the resulting adsorption complexes closely resemble the structural properties of the adsorbed NaOTF ion pair in terms of the anion orientation relative to the surface (see Fig. , panels a and c, and Fig. ), both the distance of the ions from the surface and the cation-anion coordination configuration exhibit dependency on the adsorbate structure. In particular, the cation in the adsorbed Na(OTF)2 demonstrates a notably greater distance from the surface compared to that in the NaOTF and Na2OTF adsorbates. Additionally, unlike other adsorption structures where the adsorbed cation is bidentately coordinated to the anion(s), the adsorbed Na2OTF on the sodium surface exhibits two monodentate cation-anion configurations. Comparing the adsorption energies for the examined structures, the Na(OTF)2