Nucleation rates from small scale atomistic simulations and transition state theory

Abstract

The evaluation of nucleation rates from molecular dynamics trajectories is hampered by the slow nucleation time scale and impact of finite size effects. Here, we show that accurate nucleation rates can be obtained in a very general fashion relying only on the free energy barrier, transition state theory (TST), and a simple dynamical correction for diffusive recrossing. In this setup, the time scale problem is overcome by using enhanced sampling methods, in casu metadynamics, whereas the impact of finite size effects can be naturally circumvented by reconstructing the free energy surface from an appropriate ensemble. Approximations from classical nucleation theory are avoided. We demonstrate the accuracy of the approach by calculating macroscopic rates of droplet nucleation from argon vapor, spanning sixteen orders of magnitude and in excellent agreement with literature results, all from simulations of very small (512 atom) systems.

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Cited by in corpus (5)

• The Seven Deadly Sins: when computing crystal nucleation rates, the devil is in the details
• Driving and characterizing nucleation of urea and glycine polymorphs in water
• Nucleation rates from small scale atomistic simulations and transition state theory
• Extending and validating bubble nucleation rate predictions in a Lennard-Jones fluid with enhanced sampling methods and transition state theory
• Reweighted Jarzynski sampling: Acceleration of rare events and free energy calculation with a bias potential learned from nonequilibrium work