Sensitivity of Nucleation Thermodynamics and Kinetics to the Treatment of Long-Range Interactions

Abstract

Nucleation rates are exponentially sensitive to the thermodynamic driving force and can therefore depend strongly on the treatment of long-range intermolecular interactions. Here, using the Lennard--Jones (LJ) system as a benchmark, we combine molecular dynamics (MD) simulations, jumpy forward-flux sampling (jFFS), and free-energy calculations to quantify the effect of potential truncation on melting thermodynamics, homogeneous crystal nucleation kinetics, and computational cost. Within the cutoff-radius range $2.5σ\le r_c\le 6σ$, the melting temperature at zero pressure varies by approximately 11%, while the nucleation rate changes by approximately ten orders of magnitude. By invoking classical nucleation theory (CNT), we show that this pronounced kinetic sensitivity originates primarily from cutoff-induced changes in the chemical potential difference between the liquid and crystalline phases. Building on this observation, we develop a CNT-based framework for extrapolating finite-cutoff rates to the full-potential limit and for estimating the expected rate deviations at other cutoff radii and temperatures. These findings also provide a systematic basis for cutoff selection: the optimal cutoff should minimize computational cost while keeping the deviation from the full-potential rate within acceptable bounds. At $kT/ε=0.5$, $r_c=4σ$ provides a reasonable compromise according to these criteria. We further demonstrate that conventional homogeneous tail corrections do not offer a reliable alternative, as they cannot consistently account for the liquid, crystalline, and interfacial environments present during nucleation. Our findings highlight the need to specify and validate the truncation scheme as an integral component of force-field development in simulations of nucleation and other interfacial phase transitions within inhomogeneous environments.