Role of Ions on the Surface-Bound Water Structure at the Silica/Water Interface: Identifying the Spectral Signature of Stability.

Isolating the hydrogen-bonding structure of water immediately at the surface is challenging, even with surface-specific techniques like sum-frequency generation (SFG), because of the presence of aligned water further away in the diffuse layer. Here, we combine zeta potential and SFG intensity measurements with the maximum entropy method referenced to reported phase-sensitive SFG and second-harmonic generation results to deconvolute the SFG spectral contributions of the surface waters from those in the diffuse layer. Deconvolution reveals that at very low ionic strength, the surface water structure is similar to that of a neutral silica surface near the point-of-zero-charge with waters in different hydrogen-bonding environments oriented in opposite directions. This similarity suggests that the known metastability of silica colloids against aggregation under both conditions could arise from this distinct surface water structure. Upon the addition of salt, significant restructuring of water is observed, leading to a net decrease in order at the surface.