Modeling Zeta Potential for Nanoparticles in Solution: Water Flexibility Matters

[Image: see text] Nonequilibrium molecular dynamics simulations were performed to study the electrokinetic properties of five mainstream TIPxP water models (namely, TIP3P-FB, TIP3Pm, TIP4P-FB, TIP4P-Ew, and TIP4P/2005) in NaCl aqueous solutions in the presence of a negatively charged TiO(2) surface. The impact of solvent flexibility and system geometry on the electro-osmotic (EO) mobility and flow direction was systematically assessed and compared. We found that lack of water flexibility decelerates the forward EO flow of aqueous solutions at moderate (0.15 M) or high (0.30 M) NaCl concentrations, in some special cases to such an extent that EO flow reversal occurs. Zeta potential (ZP) values were then determined from the bulk EO mobilities using the Helmholtz–Smoluchowski formula. The straight comparison against available experimental data strongly suggests that water flexibility improves the ZP determination of NaCl solutions adjacent to a realistic TiO(2) surface under neutral pH conditions.