Figure shows that the orientation of the anion in the adsorption complex is notably sensitive to the electrode material. On graphite, the S-C bond of the triflate anion tends to orient nearly perpendicular to the electrode surface (Fig. ), suggesting the potential formation of a strongly ordered brush-like interfacial layer in direct contact with the surface. In contrast, the adsorbed anion adopts a tilted orientation on the sodium surface (Fig. , panels b and c). Furthermore, surface characteristics exhibit the potential to alter the anion-cation coordination configuration in the adsorption complex. Fig. demonstrates a monodentate ion pair configuration on the hcp (0001) sodium surface, where the cation interacts with only one triflate oxygen. However, the coordination configuration shifts to a bidentate arrangement in the presence of both graphite and the bcc (100) sodium surface (Fig. , panels a and c), with the cation coordinating with two triflate oxygens. Considering the prevalent occurrence of monodentate configurations in bulk NaOTF WiS electrolyte (see Ref. ), this observation suggests that ion pairs involved in the aggregates may require less rearrangement to achieve their most stable configuration when adsorbed on the hcp (0001) sodium surface. However, we note that the resulting adsorption configuration may still be less stable than achievable on a bcc (100) sodium surface (see the adsorption energies presented in Fig. , panels b and c).