How to Quantify and Avoid Finite Size Effects in Computational Studies of Crystal Nucleation: The Case of Heterogeneous Ice Nucleation

Abstract

Computational studies of crystal nucleation can be impacted by finite size effects, primarily due to unphysical interactions between crystalline nuclei and their periodic images. It is, however, not always feasible to systematically investigate the sensitivity of nucleation kinetics and mechanism to system size due to large computational costs of nucleation studies. Here, we use jumpy forward flux sampling to accurately compute the rates of heterogeneous ice nucleation in the vicinity of square-shaped model structureless ice nucleating particles (INPs) of different sizes, and identify three distinct regimes for the dependence of rate on the INP dimension, $L$. For small INPs, the rate is a strong function of $L$ due to artificial spanning of critical nuclei across the periodic boundary. Intermediate-sized INPs, however, give rise to the emergence of non-spanning 'proximal` nuclei that are close enough to their periodic images to fully structure the intermediary liquid. While such proximity can facilitate nucleation, its effect is offset by the higher density of the intermediary liquid, leading to artificially small nucleation rates overall. The critical nuclei formed at large INPs are neither spanning nor proximal. Yet, the rate is a weak function of $L$, with its logarithm scaling linearly with $1/L$. The key heuristic emerging from these observations is that finite size effects will be minimal if critical nuclei are neither spanning nor proximal, and if the intermediary liquid has a region that is structurally indistinguishable from the supercooled liquid under the same conditions.

arXiv comment21 pages, 9 figures, 1 main table, 17 supplementary tables

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• The Impact of Hydration Shell Inclusion and Chain Exclusion in the Efficacy of Reaction Coordinates for Homogeneous and Heterogeneous Ice Nucleation
• Robustness of classical nucleation theory to chemical heterogeneity of crystal nucleating substrates