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

作者：Joswiak Mark N; Duff Nathan; Doherty Michael F; Peters Baron^*

来源：Journal of Physical Chemistry Letters, 2013, 4(24): 4267-4272.

DOI：10.1021/jz402226p

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 angstrom, 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 (delta-CNT), and obtain modified expressions for the critical nucleus size and barrier height. delta-CNT leads to excellent agreement with independently measured nucleation kinetics.

• 出版日期2013-12-19