title: Size-Dependent Surface Free Energy and Tolman-Corrected Droplet Nucleation of TIP4P/2005 Water.
abstract: 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/m(2) 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.
authors: †Department of Chemical Engineering and ‡Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, United States.
authors: Mark N
authors: MN
authors: Joswiak
authors: †Department of Chemical Engineering and ‡Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, United States.
authors: Nathan
authors: N
authors: Duff
authors: †Department of Chemical Engineering and ‡Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, United States.
authors: Michael F
authors: MF
authors: Doherty
authors: †Department of Chemical Engineering and ‡Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, United States.
authors: Baron
authors: B
authors: Peters
keywords: classical nucleation theory; curvature; hybrid Monte Carlo; mitosis method; surface tension