We reconsider the applicability of classical nucleation theory (CNT) to the calculation of the free energy of solid cluster formation in a liquid and its use to the evaluation of interface free energies from nucleation barriers. Using two different freezing transitions (hard spheres and NaCl) as test cases, we first observe that the interface-free-energy estimates based on CNT are generally in error. As successive refinements of nucleation-barrier theory, we consider corrections due to a nonsharp solid-liquid interface and to a nonspherical cluster shape. Extensive calculations for the Ising model show that corrections due to a nonsharp and thermally fluctuating interface account for the barrier shape with excellent accuracy. The experimental solid nucleation rates that are measured in colloids are better accounted for by these non-CNT terms, whose effect appears to be crucial in the interpretation of data and in the extraction of the interface tension from them.

Systematic improvement of classical nucleation theory / Prestipino, S; Laio, Alessandro; Tosatti, E.. - In: PHYSICAL REVIEW LETTERS. - ISSN 0031-9007. - 108:22(2012), pp. 1-5. [10.1103/PhysRevLett.108.225701]

Systematic improvement of classical nucleation theory

Laio, Alessandro;Tosatti E.
2012-01-01

Abstract

We reconsider the applicability of classical nucleation theory (CNT) to the calculation of the free energy of solid cluster formation in a liquid and its use to the evaluation of interface free energies from nucleation barriers. Using two different freezing transitions (hard spheres and NaCl) as test cases, we first observe that the interface-free-energy estimates based on CNT are generally in error. As successive refinements of nucleation-barrier theory, we consider corrections due to a nonsharp solid-liquid interface and to a nonspherical cluster shape. Extensive calculations for the Ising model show that corrections due to a nonsharp and thermally fluctuating interface account for the barrier shape with excellent accuracy. The experimental solid nucleation rates that are measured in colloids are better accounted for by these non-CNT terms, whose effect appears to be crucial in the interpretation of data and in the extraction of the interface tension from them.
2012
108
22
1
5
225701
https://arxiv.org/abs/1206.3849
Prestipino, S; Laio, Alessandro; Tosatti, E.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/20.500.11767/12488
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