Percolation transitions and fluid state boundaries

Woodcock, Leslie

http://hdl.handle.net/10400.1/15013

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Authors

Woodcock, Leslie

Abstract(s)

Percolation transitions define gas- and liquid-state limits of existence. For simple model fluids percolation phenomena vary fundamentally with dimensionality (d).In 3d the accessible volume (VA) and excluded volume(VE =V−VA) percolation transitions occur at different densities, whereas in 2d they coincide. The region of overlap for 3d fluids can be identified as the origin of a supercritical mesophase. This difference between 2d and 3d systems vitiates the hypothetical concept of “universality” in the description of critical phenomena. Thermodynamic states at which VA and VE , for a spher- ical molecule diameter σ, percolates the whole volume of an ideal gas, together with MD computations of percolation loci for the penetrable cohesive sphere (PCS) model of gas-liquid equilibria, show a connection between the intersection of percolation loci, and the 1st-order phase-separation transition. The results accord with previous findings for square-well and Lennard-Jones model critical and supercritical fluid equilibria. Percolation loci for real liquids, e.g. CO2 and argon, can be determined from literature thermodynamic equation-of-state data, and exhibit similar supercritical gas- and liquid-state bounds. For these real fluids the mesophase bounds extend to low density and pressures and appear to converge onto the Boyle temperature (TB ) in the low-density limit.