Crystal-liquid interfacial free energy via thermodynamic integration

A novel thermodynamic integration (TI) scheme is presented to compute the crystal-liquid interfacial free energy (gamma(cl)) from molecular dynamics simulation. The scheme is applied to a Lennard-Jones system. By using extremely short-ranged and impenetrable Gaussian flat walls to confine the liquid and crystal phases, we overcome hysteresis problems of previous TI schemes that stem from the translational movement of the crystal-liquid interface. Our technique is applied to compute gamma(cl) for the (100), (110), and (111) orientation of the crystalline phase at three temperatures under coexistence conditions. For one case, namely, the (100) interface at the temperature T = 1.0 (in reduced units), we demonstrate that finite-size scaling in the framework of capillary wave theory can be used to estimate. cl in the thermodynamic limit. Thereby, we show that our TI scheme is not associated with the suppression of capillary wave fluctuations. (C) 2014 AIP Publishing LLC.