The partial molar volumes of alcohols in water exhibit a non-monotonic dependence on concentration at room temperature, initially decreasing with increasing concentration before passing through a minimum and rising to the pure liquid plateau. This anomalous behavior is associated with hydrophobic interactions. We report molecular simulations of short chain alcohols and alkanes in water to examine the volumetric properties of these mixtures at infinite dilution over a range of temperatures. Our simulations find this anomaly disappears at a crossover temperature, above which the solute volume only varies monotonically with concentration. A Voronoi volume analysis of solution configurations finds that solutes in clusters take up less space than individual solutes at low temperature and more space at elevated temperatures. These changes in cluster volumes are subsequently shown to correlate with the derivative of the solute partial molar volume with respect to solute concentration. The changes in solute volume upon nonpolar solute association impact the response of molecular-scale hydrophobic interactions for assembly with increasing pressure.
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