Universality of Ionic Criticality: Size- and Charge-Asymmetric Electrolytes

Grand canonical simulations designed to resolve critical universality classes are reported for $z$:1 hard-core electrolyte models with diameter ratios $\lambda {=} a_+/a_- {\lesssim} 6$. For $z {=} 1$ Ising-type behavior prevails. Unbiased estimates of $T_c(\lambda)$ are within 1% of previous (biased) estimates but the critical densities are $\sim$5 % lower. Ising character is also established for the 2:1 and 3:1 equisized models, along with critical amplitudes and improved $T_c$ estimates. For $z {=} 3$, however, strong finite-size effects reduce the confidence level although classical and O$(n {\geq} 3)$ criticality are excluded.Comment: 4 pages, 3 figure

Lattice Models of Ionic Systems

A theoretical analysis of Coulomb systems on lattices in general dimensions is presented. The thermodynamics is developed using Debye-Huckel theory with ion-pairing and dipole-ion solvation, specific calculations being performed for 3D lattices. As for continuum electrolytes, low-density results for sc, bcc and fcc lattices indicate the existence of gas-liquid phase separation. The predicted critical densities have values comparable to those of continuum ionic systems, while the critical temperatures are 60-70% higher. However, when the possibility of sublattice ordering as well as Debye screening is taken into account systematically, order-disorder transitions and a tricritical point are found on sc and bcc lattices, and gas-liquid coexistence is suppressed. Our results agree with recent Monte Carlo simulations of lattice electrolytes.Comment: 25 pages, 3 figures, ReVTeX 4, Submitted to J. Chem. Phy

Screening in Ionic Systems: Simulations for the Lebowitz Length

Simulations of the Lebowitz length, $\xi_{\text{L}}(T,\rho)$, are reported for t he restricted primitive model hard-core (diameter $a$) 1:1 electrolyte for densi ties $\rho\lesssim 4\rho_c$ and $T_c \lesssim T \lesssim 40T_c$. Finite-size eff ects are elucidated for the charge fluctuations in various subdomains that serve to evaluate $\xi_{\text{L}}$. On extrapolation to the bulk limit for $T\gtrsim 10T_c$ the low-density expansions (Bekiranov and Fisher, 1998) are seen to fail badly when $\rho > {1/10}\rho_c$ (with $\rho_c a^3 \simeq 0.08$). At highe r densities $\xi_{\text{L}}$ rises above the Debye length, \xi_{\text{D}} \prop to \sqrt{T/\rho}, by 10-30% (upto $\rho\simeq 1.3\rho_c$); the variation is portrayed fairly well by generalized Debye-H\"{u}ckel theory (Lee and Fisher, 19 96). On approaching criticality at fixed $\rho$ or fixed $T$, $\xi_{\text{L}}(T, \rho)$ remains finite with $\xi_{\text{L}}^c \simeq 0.30 a \simeq 1.3 \xi_{\text {D}}^c$ but displays a weak entropy-like singularity.Comment: 4 pages 5 figure

How Multivalency controls Ionic Criticality

To understand how multivalency influences the reduced critical temperatures, Tce (z), and densities, roce (z), of z : 1 ionic fluids, we study equisized hard-sphere models with z = 1-3. Following Debye, Hueckel and Bjerrum, association into ion clusters is treated with, also, ionic solvation and excluded volume. In good accord with simulations but contradicting integral-equation and field theories, Tce falls when z increases while roce rises steeply: that 80-90% of the ions are bound in clusters near T_c serves to explain these trends. For z \neq 1 interphase Galvani potentials arise and are evaluated.Comment: 4 pages, 4 figure

Ionic fluids: charge and density correlations near gas-liquid criticality

The correlation functions of an ionic fluid with charge and size asymmetry are studied within the framework of the random phase approximation. The results obtained for the charge-charge correlation function demonstrate that the second-moment Stillinger-Lovett (SL) rule is satisfied away from the gas-liquid critical point (CP) but not, in general, at the CP. However in the special case of a model without size assymetry the SL rules are satisfied even at the CP. The expressions for the density-density and charge-density correlation functions valid far and close to the CP are obtained explicitely

Lattice Models of Ionic Systems with Charge Asymmetry

The thermodynamics of a charge-asymmetric lattice gas of positive ions carrying charge $q$ and negative ions with charge $-zq$ is investigated using Debye-H\"uckel theory. Explicit analytic and numerical calculations, which take into account the formation of neutral and charged clusters and cluster solvation by the residual ions, are performed for $z=2$, 3 and 4. As charge asymmetry increases, the predicted critical point shifts to lower temperatures and higher densities. This trend agrees well with the results from recent Monte Carlo simulations for continuum charge-asymmetric hard-sphere ionic fluids and with the corresponding predictions from continuum Debye-H\"uckel theory.Comment: submitted to J.Chem.Phy

Discretization Dependence of Criticality in Model Fluids: a Hard-core Electrolyte

Grand canonical simulations at various levels, $\zeta=5$-20, of fine- lattice discretization are reported for the near-critical 1:1 hard-core electrolyte or RPM. With the aid of finite-size scaling analyses it is shown convincingly that, contrary to recent suggestions, the universal critical behavior is independent of $\zeta$ (\grtsim 4); thus the continuum $(\zeta\to\infty)$ RPM exhibits Ising-type (as against classical, SAW, XY, etc.) criticality. A general consideration of lattice discretization provides effective extrapolation of the {\em intrinsically} erratic $\zeta$-dependence, yielding (\Tc^ {\ast},\rhoc^{\ast})\simeq (0.0493_{3},0.075) for the $\zeta=\infty$ RPM.Comment: 4 pages including 4 figure