Brute-force nucleation rates of hard spheres compared with rare-event methods and classical nucleation theory

TL;DR

This study uses brute-force molecular dynamics to accurately measure nucleation rates of hard spheres, providing a benchmark to validate rare-event methods and classical nucleation theory with excellent agreement.

Contribution

It offers the first direct brute-force nucleation rate measurements for hard spheres, testing and confirming the accuracy of existing theoretical and simulation approaches.

Findings

Brute-force rates agree with umbrella sampling results.

Brute-force rates agree with seeding simulation results.

Nucleation barriers up to 28 k_B T successfully overcome.

Abstract

We determine the nucleation rates of hard spheres using brute-force molecular dynamics simulations. We overcome nucleation barriers of up to $28 k_B T$, leading to a rigorous test of nucleation rates obtained from rare-event methods and classical nucleation theory. Our brute-force nucleation rates show excellent agreement with umbrella sampling simulations by Filion et al. [J. Chem. Phys. 133, 244115 (2010)] and seeding simulations by Espinosa et al. [J. Chem. Phys. 144, 034501 (2016)].