Test of classical nucleation theory on deeply supercooled high-pressure simulated silica

TL;DR

This study tests classical nucleation theory on supercooled high-pressure silica simulations, finding reasonable agreement in nucleation rates and free energy predictions, despite challenges at very small embryo sizes.

Contribution

It provides a detailed validation of classical nucleation theory for supercooled silica, including direct rate calculations and modifications for small embryo sizes.

Findings

CNT reasonably predicts free energy barriers at various temperatures.

Critical nucleus size decreases with temperature, reaching about 3 silicon atoms at 3000 K.

Nucleation rates from direct simulation and CNT estimates agree within an order of magnitude.

Abstract

We test classical nucleation theory (CNT) in the case of simulations of deeply supercooled, high density liquid silica, as modelled by the BKS potential. We find that at density $\rho=4.38$~g/cm$^3$, spontaneous nucleation of crystalline stishovite occurs in conventional molecular dynamics simulations at temperature T=3000 K, and we evaluate the nucleation rate J directly at this T via "brute force" sampling of nucleation events. We then use parallel, constrained Monte Carlo simulations to evaluate $\Delta G(n)$, the free energy to form a crystalline embryo containing n silicon atoms, at T=3000, 3100, 3200 and 3300 K. We find that the prediction of CNT for the n-dependence of $\Delta G(n)$ fits reasonably well to the data at all T studied, and at 3300 K yields a chemical potential difference between liquid and stishovite that matches independent calculation. We find that $n^*$, the size of the critical nucleus, is approximately 10 silicon atoms at T=3300 K. At 3000 K, $n^*$ decreases to approximately 3, and at such small sizes methodological challenges arise in the evaluation of $\Delta G(n)$ when using standard techniques; indeed even the thermodynamic stability of the supercooled liquid comes into question under these conditions. We therefore present a modified approach that permits an estimation of $\Delta G(n)$ at 3000 K. Finally, we directly evaluate at T=3000 K the kinetic prefactors in the CNT expression for J, and find physically reasonable values; e.g. the diffusion length that Si atoms must travel in order to move from the liquid to the crystal embryo is approximately 0.2 nm. We are thereby able to compare the results for J at 3000 K obtained both directly and based on CNT, and find that they agree within an order of magnitude.