Gas-liquid critical parameters of asymmetric models of ionic fluids

The effects of size and charge asymmetry on the gas-liquid critical parameters of a primitive model (PM) of ionic fluids are studied within the framework of the statistical field theory based on the collective variables method. Recently, this approach has enabled us to obtain the correct trends of the both critical parameters of the equisize charge-asymmetric PM without assuming ionic association. In this paper we focus on the general case of an asymmetric PM characterized by the two parameters: hard-sphere diameter-, $\lambda=\sigma_{+}/\sigma_{-}$ and charge, $z=q_{+}/|q_{-}|$, ratios of the two ionic species. We derive an explicit expression for the chemical potential conjugate to the order parameter which includes the effects of correlations up to the third order. Based on this expression we consider the three versions of PM: a monovalent size-asymmetric PM ($\lambda\neq 1$, $z=1$), an equisize charge-asymmetric PM ($\lambda=1$, $z\neq 1$) and a size- and charge-asymmetric PM ($\lambda\neq 1$, $z=2$). Similar to simulations, our theory predicts that the critical temperature and the critical density decrease with the increase of size asymmetry. Regarding the effects of charge asymmetry, we obtain the correct trend of the critical temperature with $z$, while the trend of the critical density obtained in this approximation is inconsistent with simulations, as well as with our previous results found in the higher-order approximation. We expect that the consideration of the higher-order correlations will lead to the correct trend of the critical density with charge asymmetry.Comment: 23 pages, 6 figure

Gas-liquid critical point of the ultrasoft restricted primitive model from analytic theory

Gas-liquid criticality in the ultrasoft restricted primitive model (URPM) of polyelectrolytes is studied using the collective variables-based theory. For the model, an effective Hamiltonian is derived and explicit expressions for all the coefficients are found in a one-loop approximation. Based on this Hamiltonian, the phase and critical behaviour is analysed. Our results provide evidence that the nature of the gas-liquid criticality in the URPM is the same as in the restricted primitive model that includes a hard core.Comment: 6 pages, 2 figure

Gas-liquid phase equilibrium in ionic fluids: Coulomb versus non-Coulomb interactions

Using the collective variables theory, we study the effect of competition between Coulomb and dispersion forces on the gas-liquid phase behaviour of a model ionic fluid, i.e. a charge-asymmetric primitive model with additional short-range attractive interactions. Both the critical parameters and the coexistence envelope are calculated in a one-loop approximation as a function of the parameter $\alpha$ measuring the relative strength of the Coulomb to short-range interactions. We found the very narrow region of $\alpha$ bounded from the both sides by tricritical points which separates the models with "nonionic" and "Coulombic" phase behaviour. This is at variance with the result of available computer simulations where no tricritical point is found for the finely-discretized lattice version of the model.Comment: 10 pages, 8 figure

Spatial inhomogeneities in ionic liquids, charged proteins and charge stabilized colloids from collective variables theory

Effects of size and charge asymmetry between oppositely charged ions or particles on spatial inhomogeneities are studied for a large range of charge and size ratios. We perform a stability analysis of the primitive model (PM) of ionic systems with respect to periodic ordering using the collective variables based theory. We extend previous studies [A. Ciach et al., Phys. Rev.E \textbf{75}, 051505 (2007)] in several ways. First, we employ a non-local approximation for the reference hard-sphere fluid which leads to the Percus-Yevick pair direct correlation functions for the uniform case. Second, we use the Weeks-Chandler-Anderson regularization scheme for the Coulomb potential inside the hard core. We determine the relevant order parameter connected with the periodic ordering and analyze the character of the dominant fluctuations along the $\lambda$-lines. We show that the above-mentioned modifications produce large quantitative and partly qualitative changes in the phase diagrams obtained previously. We discuss possible scenarios of the periodic ordering for the whole range of size- and charge ratios of the two ionic species, covering electrolytes, ionic liquids, charged globular proteins or nanoparticles in aqueous solutions and charge-stabilized colloids

A mesoscopic field theory of ionic systems versus a collective variable approach

We establish a link between the two functional approaches: a mesoscopic field theory developed recently by A.Ciach and G.Stell [A. Ciach and G. Stell, J. Mol. Liq. 87 (2000) 253] for the study of ionic models and an exact statistical field theory based on the method of collective variables.Comment: 7 page

The method of collective variables: a link with the density functional theory

Recently, based on the method of collective variables the statistical field theory for multicomponent inhomogeneous systems was formulated [O. Patsahan, I. Mryglod, J.-M. Caillol, Journal of Physical Studies, 2007, 11, 133]. In this letter we establish a link between this approach and the classical density functional theory for inhomogeneous fluids.Comment: 6 page