Precise Simulation of Near-critical Fluid Coexistence

Abstract

We present a novel method to derive liquid-gas coexisting densities, ${\rho }^{\pm }(T)$, from grand canonical simulations (without knowledge of $\Tc$ or criticality class). The minima of $Q_L\equiv <m^2{>}_L^2/<m^4{>}_L$ in an $L$$\times$$L\times$$L$ box with $m=\rho -<\rho {>}_L$ are used to generate recursively an unbiased universal finite-size scaling function. Monte Carlo data for a hard-core square-well fluid and for the restricted primitive model electrolyte yield ${\rho }^{\pm }$ to $\pm 1$-2% of $\rhoc$ down to 1 part in $10^4$-$10^3$ of $\Tc$ (and confirm well Ising character). Pressure mixing in the scaling fields is unequivocally revealed and indicates Yang-Yang ratios $R_{\mu }=-0.04_4$ and $0.2_6$ for the two models, respectively.

accepted for publication in Phys. Rev. Lett

References in corpus (1)

• Asymmetric Fluid Criticality I: Scaling with Pressure Mixing

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