Thermodynamics and structure of the primitive model near its gas–liquid transition

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Abstract
The hypernetted-chain/mean spherical approximation (HNC/MSA) is employed to calculate the thermodynamic properties of the restricted primitive model (symmetric binary mixture of charged hard spheres) in the low density–high coupling region, where the gas–liquid phase transition is located. The spinodal curve is calculated from the virial and the compressibility equations. The HNC/MSA total correlation function does not show long-range behavior as the spinodal curve is approached. This is due to the hybrid nature of this approximation. However, a consistent HNC/MSA total correlation function is defined which does show the expected long-range behavior. This long-range behavior is found to be related to the phenomenon of ionic clustering, in accordance with previous studies.