Triple point of Lennard-Jones fluid in slit nanopore: Solidification of critical condensate

We report the results of a molecular dynamics simulation that looked for the triple point of Lennard-Jones fluid in slit-shaped nanopores. The simulation method employed for this purpose is able to maintain vapor-liquid coexistence in a nanopore at a specific equilibrium bulk-phase pressure. The triple point is the freezing point of the critical condensate. The triple-point temperature could be higher or lower than the bulk triple point, depending on the pore size. This is thought to be due to two opposing factors: the elevating effect of the pore-wall potential energy, and the depressing effect of the capillary condensate's tensile condition. Because of the cancellation, the deviation of the triple-point temperature from the bulk triple-point temperature was not considered significant. The pressure of the triple point, however, was significantly different from that of the bulk triple point. A simple model to describe the triple point is developed and shown to agree well with the results of the simulation. The importance of the two factors in nanoscale pores, which cannot be described by the classic Gibbs-Thomson equation, is emphasized.