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121 - J.-M. Caillol , D. Levesque 2014
We present a Monte-Carlo study of the liquid-vapor transition and the critical behavior of a model of polyelectrolytes with soft gaussian charge distributions introduced recently by Coslovich, Hansen, and Kahl [J. Chem. Phys. textbf{134}, 244514 (201 1)]. A finite size study involving four different volumes in the grand canonical ensemble yields a precise determination of the critical temperature, chemical potential, and density of the model. Attempts to determine the nature of the criticality and to obtain reliable values for the critical exponents are not conclusive.
According to extensive experimental findings, the Ginzburg temperature $t_{G}$ for ionic fluids differs substantially from that of nonionic fluids [Schroer W., Weig{a}rtner H. 2004 {it Pure Appl. Chem.} {bf 76} 19]. A theoretical investigation of thi s outcome is proposed here by a mean field analysis of the interplay of short and long range interactions on the value of $t_{G}$. We consider a quite general continuous charge-asymmetric model made of charged hard spheres with additional short-range interactions (without electrostatic interactions the model belongs to the same universality class as the 3D Ising model). The effective Landau-Ginzburg Hamiltonian of the full system near its gas-liquid critical point is derived from which the Ginzburg temperature is calculated as a function of the ionicity. The results obtained in this way for $t_{G}$ are in good qualitative and sufficient quantitative agreement with available experimental data.
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