Water Orientation at the Anatase TiO(2) Nanoparticle Interface: A Probe of Surface pK(a) Values

[Image: see text] The acid–base properties of surfaces significantly influence catalytic and (photo)electrochemical processes. Estimation of acid dissociation constants (pK(a) values) for colloids is commonly performed through electroanalytical techniques or spectroscopic methods employing label molecules. Here, we show that polarimetric angle-resolved second harmonic scattering (AR-SHS) can be used as an all-optical, label-free probe of colloid surface pK(a) values. We apply AR-SHS to dispersions of 100 nm anatase TiO(2) particles to extract surface potential and surface susceptibility, a measure of interfacial water orientation, as a function of pH. The surface potential follows changes in surface charge density, while the interfacial water orientation inverts at pH ∼4.8, ∼6, and ∼7.6. As the variation in bulk pH modifies the populations of Ti–OH(2)(+), Ti–OH, and Ti–O(–) interfacial groups, a change in water orientation reports on the ratio of protonated/deprotonated species. Such observation allows for pK(a) evaluation from plots of surface susceptibility versus pH. A Nerstian trend in the surface potential is additionally demonstrated.