Crystal-liquid interfacial free energy of hard spheres via a novel thermodynamic integration scheme

Abstract

The hard sphere crystal-liquid interfacial free energy, ($\gamma_{\rm cl}$), is determined from molecular dynamics simulations using a novel thermodynamic integration (TI) scheme. The advantage of this TI scheme compared to previous methods is to successfully circumvent hysteresis effects due to the movement of the crystal-liquid interface. This is accomplished by the use of extremely short-ranged and impenetrable Gaussian flat walls which prevent the drift of the interface while imposing a negligible free-energy penalty. We find that it is crucial to analyze finite-size effects in order to obtain reliable estimates of $\gamma_{\rm cl}$ in the thermodynamic limit.