Deducing solid–liquid interfacial energy from superheating or supercooling: application to H2O at high pressures

Abstract

We present a general method to determine the solid–liquid interfacial energy (γsl) from the maximum supercooling (or superheating), and apply it to the water–ice system. For solid–liquid phase transitions, the nucleation-theory-based systematics of maximum superheating and supercooling relate a dimensionless nucleation barrier to the superheating (supercooling) and heating (cooling) rates. Given superheating (or supercooling) values from either experiments or simulations, γsl can then be deduced from the dimensionless nucleation barrier, equilibrium melting temperature and enthalpy of fusion. We demonstrate the accuracy of this approach using molecular dynamics (MD) simulations of the Lennard–Jones system: our predictions of γsl at various pressures are in excellent agreement with independent, direct MD simulations. With this approach, we predict γsl for the water–ice (Ih and III) system using experimental supercooling values in the pressure range of 0–0.3 GPa. The predicted value (28 ± 0.8 mJ m−2) agrees with measurements on H2O–Ih at ambient pressure.