Thermodynamics and simulation of 3D crystals and phase transitions under external fields

Abstract

A field-supported multiphase kinetic Monte Carlo method previously applied to self-assembled trimesic acid molecular layers [Ustinov et al., Phys. Chem. Chem. Phys. 24, 26111 (2022)] was generalized to three-dimensional gas–liquid and gas–solid systems. This method allows us to calculate the thermodynamic potentials of the liquid and solid phases and then determine the parameters of the liquid–solid phase transition. In this study, the requirement that the gas phase be ideal was introduced as an additional condition. It was shown that in a two-phase system, the sum of the analytical expression for the chemical potential of an ideal gas and the external potential imposed on the gas phase exactly equals the chemical potential of the equilibrium crystal or liquid phase. For example, the coexistence of crystalline/liquid krypton and ideal gas has been considered. A comparison with previously published data has shown that the proposed approach provides the most accurate results for determining the parameters of phase transitions and fully satisfies the Gibbs–Duhem equation. This method does not impose any restrictions on the complexity or hardness of dense phases.