Nucleation and droplet growth from supersaturated vapor at temperatures below the triple point temperature

In 1897 Ostwald formulated his step rule for formation of the most stable crystal state for a system with crystal polymorphism. The rule describes the irreversible way a system converts to the crystal with lowest free energy. But in fact the irreversible way a supercooled gas below the triple point temperature Ttr.p. crystallizes via a liquid droplet is an example of Ostwald's step rule. The homogeneous nucleation in the supersaturated gas is not to a crystal, but to a liquid-like critical nucleus. We have for the first time performed constant energy (NVE) Molecular Dynamics (MD) of homogeneous nucleation without the use of a thermostat. The simulations of homogeneous nucleation in a Lennard-Jones system from supersaturated vapor at temperatures below Ttr.p. reveal that the nucleation to a liquid-like critical nucleus is initiated by a small cold cluster [S. Toxvaerd, J. Chem. Phys. 143, 154705 (2015)]. The release of latent heat at the subsequent droplet growth increases the temperature in the liquid-like droplet, which for not deep supercooling and/or low supersaturation, can exceed Ttr.p.. The temperature of the liquid-like droplet increases less for a low supersaturation and remains below Ttr.p., but without a crystallization of the droplet for long times. The dissipation of the latent heat into the surrounding gas is affected by a traditional MD thermostat, with the consequence that droplet growth is different for (NVE) MD and constant temperature (NVT) MD.