Non-equilibrium molecular dynamics and continuum modelling of transient freezing of atomistic solids

In this work we investigate the transient solidification of a Lennard-Jones liquid using non-equilibrium molecular dynamics simulations and continuum heat transfer theory. The simulations are performed in slab-shaped boxes, where a cold thermostat placed at the centre of the box drives the solidification of the liquid. Two well-defined solid fronts propagate outwards from the centre towards the ends of the box until solidification is completed. A continuum phase change model that accounts for the difference between the solid and the liquid densities is formulated to describe the evolution of the temperature and the position of the solidification front. Simulation results for a small and a large nanoscale system, of sizes 30.27 nm and 60.54 nm, are compared with the predictions of the theoretical model. Following a transient period of similar to 20-40 ps and a displacement of the solidification front of 1-2.5 nm we find that the simulations and the continuum theory show good agreement. We use this fact to combine the simulation and theoretical approaches to design a simple procedure to calculate the latent heat associated to the liquid-solid phase transition. We also perform simulations of the homogeneous freezing process, i.e. in the absence of a temperature gradient and at constant temperature, by quenching the liquid at supercooled temperatures. We demonstrate that, for comparable temperature conditions, the solidification rate of homogenous freezing is much faster than the one obtained under a thermal gradient. Our study and conclusions should be of general interest to a wide range of atomistic solids. (C) 2020 Elsevier Ltd. All rights reserved.