SupMat_EPSR_Solution_Partials_SQ.dat from Molecular interactions in short-chain perfluoroalkyl carboxylic acids and aqueous solutions

The presence of short-chain per- and polyfluoroalkyl substances in water poses a major health and environmental challenge. Here, we have performed high-energy small- and wide-angle X-ray scattering measurements on CF₃[CF₂]<i>_n</i>COOH (where <i>n</i> = 1, 2, 3 represents the chain length) and their aqueous solutions at 10% mole concentrations to characterize their molecular interactions at the atomic and nanometer length scales. The experimental wide-angle structure factors have been modelled using Empirical Potential Structural Refinement. The oxygen–oxygen partial X-ray pair distribution functions show that the coordination number between the hydroxyl oxygen on the acid and surrounding oxygen water molecules increases significantly with acid chain length, rising from 3.2 for <i>n</i> = 1 to 4.1 for <i>n</i> = 3. The small-angle scattering is dominated by a sharp, high-intensity peak at <i>Q</i>₁∼0.2 Å⁻¹ and a smaller peak at <i>Q</i>₂= 1.2 Å⁻¹ for <i>n</i> = 3, both of which decrease with decreasing chain length. The <i>Q</i>₂ peak is attributed to groups of adjacent non-bonded acid molecules, and <i>Q</i>₁ has contributions both from correlations between acid molecules and water–water interactions. In all cases, the models show nanoscale aggregation occurs in the form of denser channels of winding hydrogen-bonded chains, approximately 20 water molecules in length, surrounding clusters of acid molecules.This article is part of the theme issue 'XXXX'.