Sensitivity of solid phase stability to the interparticle potential range: studies of a new Lennard-Jones like model

Abstract

In a recent article, Wang et al. (Phys. Chem. Chem. Phys., 2020, 22, 10624) introduced a new class of interparticle potential for molecular simulations. The potential is defined by a single range parameter, eliminating the need to decide how to truncate truly long-range interactions like the Lennard-Jones (LJ) potential. The authors explored the phase diagram for a particular value of the range parameter for which their potential is similar in shape to the LJ 12-6 potential. We have reevaluated the solid phase behaviour of this model using both Lattice Switch Monte Carlo and thermodynamic integration. In addition to finding that the boundary between hexagonal close packed (hcp) and face centred cubic (fcc) phases presented by Wang et al. was calculated incorrectly, we show that owing to its finite range, the new potential exhibits several reentrant transitions between hcp and fcc phases. These phases, which do not occur in the full (untruncated) LJ system, are also found for typically adopted forms of the truncated and shifted LJ potential. However, whilst in the latter case one can systematically investigate and correct for the effects of the finite range on the calculated phase behaviour (a correction beyond the standard long-range mean field tail correction being required), this is not possible for the new potential because the choice of range parameter affects the entire potential shape. Our results highlight that potentials with finite range may fail to represent the crystalline phase behavior of systems with long-range dispersion interactions, even qualitatively.