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.
Irreducible finite-size effects in the surface free energy of NaCl crystals from crystal-nucleation data
Tosatti E
2008
Abstract
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.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
