Freezing phenomena of lennard-jones fluid confined in jungle-gym nanospace: a monte carlo study

We performed grand canonical Monte Carlo simulations for a Lennard-Jones fluid confined in a jungle-gym (JG) nanospace of cubic structure modeled on a specific type of metal organic frameworks (MOFs) to investigate freezing phenomena. Our simulations clarified that the JG nanospace with the pore sizes from 5sigma to 11sigma strongly depresses freezing due to a geometrical hindrance effect, resulting in far lower freezing temperature than the bulk freezing point. The fluid-rod interaction is found to give little effect on the freezing temperature in the larger pore sizes. For smaller pores from 2sigma to 3sigma, on the other hand, a dominant factor is a template effect to enhance the localization of molecules into a specific configuration that matches the locations of potential minima, leading to a variety of molecular configurations. In this range of smaller pore sizes, the solidification temperatures are higher than those of the larger pores mainly due to strong influence of the fluid-rod interaction but are still lower than the bulk freezing temperature. In addition, a unique solid-to-solid transition is observed in a specific size of pore of 2.73sigma, which is caused by structural correlation between adjacent cells. On the basis of these results, a phase diagram in the JG nanospace is drawn.