Irreducible finite-size effects in the surface free energy of NaCl crystals from crystal-nucleation data.
In this Letter we report a simulation study in which we compare the solid-liquid interfacial free energy of NaCl at coexistence, gamma_{LS}, with the value that follows from the height of the homogeneous nucleation barrier. The two estimates differ by more than 100%. Smaller discrepancies are found for gamma_{LS} of hard-sphere and of Lennard-Jones particles. We consider a variety of possible causes for this discrepancy and conclude that it is due to a finite-size effect that cannot be corrected for by any simple thermodynamic procedure. By taking into account the finite-size effects of gamma_{LS} obtained in real nucleation experiments, we obtain quantitative agreement between gamma_{LS} estimated in the simulations and derived from the experiments. Our finding suggests that most published solid-liquid surface free energies derived from nucleation experiments will have to be revised.
Zykova-Timan
T
T
Department of Chemistry and Applied Biosciences, ETHZ, 6900 Lugano, Switzerland.
Valeriani
C
C
Sanz
E
E
Frenkel
D
D
Tosatti
E
E