Homogeneous SPC/E water nucleation in large molecular dynamics simulations

TL;DR

This study uses large-scale molecular dynamics simulations to accurately measure water nucleation rates, cluster properties, and compares results with classical and semi-phenomenological models, revealing significant discrepancies and new insights.

Contribution

It introduces a new functional form for nucleation rate measurement and provides detailed comparisons between simulation data and nucleation theories for water.

Findings

Classical nucleation theory overestimates rates by orders of magnitude.

Semi-phenomenological model under-predicts rates by up to a factor of 24.

Post-critical clusters have temperatures and densities close to bulk liquid.

Abstract

We perform direct large molecular dynamics simulations of homogeneous SPC/E water nucleation, using up to $\sim 4\cdot 10^6$ molecules. Our large system sizes allow us to measure extremely low and accurate nucleation rates, down to $\sim 10^{19}\,\textrm{cm}^{-3}\textrm{s}^{-1}$, helping close the gap between experimentally measured rates $\sim 10^{17}\,\textrm{cm}^{-3}\textrm{s}^{-1}$. We are also able to precisely measure size distributions, sticking efficiencies, cluster temperatures, and cluster internal densities. We introduce a new functional form to implement the Yasuoka-Matsumoto nucleation rate measurement technique (threshold method). Comparison to nucleation models shows that classical nucleation theory over-estimates nucleation rates by a few orders of magnitude. The semi-phenomenological nucleation model does better, under-predicting rates by at worst, a factor of 24. Unlike what has been observed in Lennard-Jones simulations, post-critical clusters have temperatures consistent with the run average temperature. Also, we observe that post-critical clusters have densities very slightly higher, $\sim 5\%$, than bulk liquid. We re-calibrate a Hale-type $J$ vs. $S$ scaling relation using both experimental and simulation data, finding remarkable consistency in over $30$ orders of magnitude in the nucleation rate range, and $180\,$K in the temperature range.