The Seven Deadly Sins: when computing crystal nucleation rates, the devil is in the details

TL;DR

This paper reviews recent advances in calculating crystal nucleation rates, emphasizing subtle details like finite size effects and slow dynamics that significantly impact the accuracy and reproducibility of simulation results.

Contribution

It highlights overlooked factors affecting nucleation rate calculations, promoting more robust and reliable simulation practices in crystallization studies.

Findings

Finite size effects can bias nucleation rate estimates.

Slow dynamics introduce non-negligible uncertainties.

Addressing these details improves agreement between simulations and experiments.

Abstract

The formation of crystals has proven to be one of the most challenging phase transformations to quantitatively model - let alone to actually understand - be it by means of the latest experimental technique or the full arsenal of enhanced sampling approaches at our disposal. One of the most crucial quantities involved with the crystallization process is the nucleation rate, a single, elusive number that is supposed to quantify the average probability for a nucleus of critical size to occur within a certain volume and time span. A substantial amount of effort has been devoted to attempt a connection between the crystal nucleation rates computed by means of atomistic simulations and their experimentally measured counterparts. Sadly, this endeavour almost invariably fails to some extent, with the venerable classical nucleation theory typically blamed as the main culprit. Here, we review some of the recent advances in the field, focusing on a number of perhaps more subtle details that are sometimes overlooked when computing nucleation rates. We believe it is important for the community to be aware of the full impact of aspects such as finite size effects and slow dynamics, that often introduce inconspicuous and yet non-negligible sources of uncertainty into our simulations. In fact, it is key to obtain robust and reproducible trends to be leveraged so as to shed new light on the kinetics of a process, that of crystal nucleation, which is involved into countless practical applications, from the formulation of pharmaceutical drugs to the manufacturing of nano-electronic devices.