Separating the pH-Dependent Behavior of Water in the Stern and Diffuse Layers with Varying Salt Concentration

Vibrational sum frequency generation (SFG) spectroscopy was utilized to distinguish different populations of water molecules within the electric double layer (EDL) at the silica/water interface. By systematically varying the electrolyte concentration, surface deprotonation, and SFG polarization combinations, we provide evidence of two regions of water molecules that have distinct pH-dependent behavior when the Stern layer is present (with onset between 10 and 100 mM NaCl). For example, water molecules near the surface in the Stern layer can be probed by the pss polarization combination, while other polarization combinations (ssp and ppp) predominantly probe water molecules further from the surface in the diffuse part of the electrical double layer. For the water molecules adjacent to the surface within the Stern layer,…