Screening in Ionic Systems: Simulations for the Lebowitz Length

TL;DR

This paper reports simulations of the Lebowitz length in ionic systems, analyzing finite-size effects and comparing results with theoretical predictions across various densities and temperatures.

Contribution

It provides the first detailed simulation-based analysis of the Lebowitz length in ionic fluids, highlighting deviations from low-density expansions and the applicability of generalized Debye-Hückel theory.

Findings

Lebowitz length exceeds Debye length at higher densities.

Low-density expansions fail beyond 0.1 times critical density.

Lebowitz length remains finite near criticality, with a weak singularity.

Abstract

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.