Steady-state molecular dynamics simulation of vapour to liquid nucleation with McDonald's daemon

Physics – Atmospheric and Oceanic Physics

Scientific paper

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Journal of Physical Studies (L'viv), in press (2010)

Scientific paper

The most interesting step of condensation is the cluster formation up to the critical size. In a closed system, this is an instationary process, as the vapour is depleted by the emerging liquid phase. This imposes a limitation on direct molecular dynamics (MD) simulation of nucleation by affecting the properties of the vapour to a significant extent so that the nucleation rate varies over simulation time. Grand canonical MD with McDonald's daemon is discussed in the present contribution and applied for sampling both nucleation kinetics and steady-state properties of a supersaturated vapour. The idea behind that approach is to simulate the production of clusters up to a given size for a specified supersaturation. In that way, nucleation is studied by a steady-state simulation. A series of simulations is conducted for the truncated and shifted Lennard-Jones fluid which accurately describes the fluid phase coexistence of noble gases and methane. The classical nucleation theory is found to overestimate the free energy of cluster formation and to deviate by two orders of magnitude from the nucleation rate below the triple point at high supersaturations.

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