Disappearance of the gas-liquid phase transition for highly charged colloids.
We calculate the full phase diagram of spherical charged colloidal particles using Monte Carlo free energy calculations. The system is described using the primitive model, consisting of explicit hard-sphere colloids and point counterions in a uniform dielectric continuum. We show that the gas-liquid critical point becomes metastable with respect to a gas-solid phase separation at colloid charges Q > or =20 times the counterion charge. Approximate free energy calculations with only one and four particles in the fluid and solid phases, respectively, are used to determine the critical line for highly charged colloids up to Q=2000. We propose the scaling law T*(c) approximately Q(1/2) for this critical temperature.
Department of Chemical Engineering, Princeton University, Princeton, NJ 08544, USA.
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Hynninen
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Panagiotopoulos