Charge and Density Fluctuations Lock Horns : Ionic Criticality with Power-Law Forces

TL;DR

This paper investigates how charge and density fluctuations interact in ionic fluids near criticality, incorporating long-range power-law forces, and reveals how these interactions influence critical behavior and screening properties.

Contribution

It introduces exactly solvable models with power-law interactions to analyze ionic criticality, highlighting the effects of charge-density mixing and the failure of the Stillinger-Lovett sum rule at criticality.

Findings

Critical universality class remains unchanged by Coulomb interactions for certain conditions.

Screening becomes algebraic and weaker at criticality with power-law forces.

The Stillinger-Lovett sum rule fails at criticality when the critical exponent η equals zero.

Abstract

How do charge and density fluctuations compete in ionic fluids near gas-liquid criticality when quantum mechanical effects play a role ? To gain some insight, long-range $\Phi^{{\mathcal{L}}}_{\pm \pm} / r^{d+\sigma}$ interactions (with $\sigma>0$), that encompass van der Waals forces (when $\sigma = d = 3$), have been incorporated in exactly soluble, $d$-dimensional 1:1 ionic spherical models with charges $\pm q_0$ and hard-core repulsions. In accord with previous work, when $d>\min \{\sigma, 2\}$ (and $q_0$ is not too large), the Coulomb interactions do not alter the ($q_0 = 0$) critical universality class that is characterized by density correlations at criticality decaying as $1/r^{d-2+\eta}$ with $\eta = \max \{0, 2-\sigma\}$. But screening is now algebraic, the charge-charge correlations decaying, in general, only as $1/r^{d+\sigma+4}$; thus $\sigma = 3$ faithfully mimics known \textit{non}critical $d=3$ quantal effects. But in the \textit{absence} of full ($+, -$) ion symmetry, density and charge fluctuations mix via a transparent mechanism: then the screening \textit{at criticality} is \textit{weaker} by a factor $r^{4-2\eta}$. Furthermore, the otherwise valid Stillinger-Lovett sum rule fails \textit{at} criticality whenever $\eta =0$ (as, e.g., when $\sigma>2$) although it remains valid if $\eta >0$ (as for $\sigma<2$ or in real $d \leq 3$ Ising-type systems).