Droplet crystallisation in large scale direct molecular dynamics simulations of homogeneous vapor-to-liquid nucleation

Abstract:

We use large scale direct (NVE and NVT) molecular dynamics simulations to study phase transitions. Typical runs contain one billion atoms and run for up to 100 million time-steps. This corresponds to scales of micrometers and microseconds and allows us to resolve similar nucleation rates as probed in some laboratory experiments. In homogeneous vapor-to-liquid nucleation simulations using Lennard-Jones atoms (Diemand et al. JCP 2013) and various water models (ongoing work) we observe a second phase transition form liquid-to-solid in some of the lower temperature runs (see Tanaka et al. JCP 2011 for one such case).

Here we will describe the crystallisation of these supercooled liquid-like nano-clusters in detail. We will present crystal structure, nucleation and growth rates for a range of temperatures, droplet sizes and interaction potentials and compare with model predictions. Since our liquid nano-droplets are condensing naturally out of the vapour phase, as in clouds and some experiments and industrial processes, we can address some specific questions relevant in these contexts: How does the droplet size, structure and especially its surface affect the freezing process? To what extend does the latent heat from the ongoing condensation onto the droplets surface delay and alter crystallisation? Can frozen nano-clusters grow by direct de-sublimation from the vapour, or is there always a liquid-like surface? And can they form directly without going through a liquid-like proto-cluster stage?