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Size-Dependent Surface Free Energy and Tolman-Corrected Droplet Nucleation of TIP4P/2005 Water

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journal contribution
posted on 17.12.2015, 00:06 by Mark N. Joswiak, Nathan Duff, Michael F. Doherty, Baron Peters
Classical nucleation theory is notoriously inaccurate when using the macroscopic surface free energy for a planar interface. We examine the size dependence of the surface free energy for TIP4P/2005 water nanodroplets (radii ranging from 0.7 to 1.6 nm) at 300 K with the mitosis method, that is, by reversibly splitting the droplets into two subclusters. We calculate the Tolman length to be −0.56 ± 0.09 Å, which indicates that the surface free energy of water droplets that we investigated is 5–11 mJ/m2 greater than the planar surface free energy. We incorporate the computed Tolman length into a modified classical nucleation theory (δ-CNT) and obtain modified expressions for the critical nucleus size and barrier height. δ-CNT leads to excellent agreement with independently measured nucleation kinetics.