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Reentrant phase behaviour for systems with competition between phase separation and self-assemblyAleks Reinhardt, Alexander J. Williamson, Jonathan P.K. Doye, Jesus Carrete, Luis M. Varela and Ard A. LouisJ. Chem. Phys. 134, 104905 (2011)AbstractIn patchy particle systems where there is competition between the self-assembly of finite clusters and liquid-vapour phase separation, reentrant phase behaviour is observed, with the system passing from a monomeric vapour phase to a region of liquid-vapour phase coexistence and then to a vapour phase of clusters as the temperature is decreased at constant density. Here, we present a classical statistical mechanical approach to the determination of the complete phase diagram of such a system. We model the system as a van der Waals fluid, but one where the monomers can assemble into monodisperse clusters that have no attractive interactions with any of the other species. The resulting phase diagrams show a clear region of reentrance. However, for the most physically reasonable parameter values of the model, this behaviour is restricted to a certain range of density, with phase separation still persisting at high densities.The full paper is available from The Journal of Chemical Physics and arXiv.org. |