Fluid Coexistence close to Criticality: Scaling Algorithms for Precise Simulation

Physics – Condensed Matter – Statistical Mechanics

Scientific paper

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Scientific paper

10.1016/j.cpc.2005.03.066

A novel algorithm is presented that yields precise estimates of coexisting liquid and gas densities, $\rho^{\pm}(T)$, from grand canonical Monte Carlo simulations of model fluids near criticality. The algorithm utilizes data for the isothermal minima of the moment ratio $Q_{L}(T;<\rho>_{L})$ $\equiv< m^{2}>_{L}^{2}/< m^{4}>_{L}$ in $L$$ \times$$ ...$$ \times$$ L$ boxes, where $m=\rho-<\rho>_{L}$. When $L$$ \to$$ \infty$ the minima, $Q_{\scriptsize m}^{\pm}(T;L)$, tend to zero while their locations, $\rho_{\scriptsize m}^{\pm}(T;L)$, approach $\rho^{+}(T)$ and $\rho^{-}(T)$. Finite-size scaling relates the ratio {\boldmath $\mathcal Y$}$ = $$(\rho_{\scriptsize m}^{+}-\rho_{\scriptsize m}^{-})/\Delta\rho_{\infty}(T)$ {\em universally} to ${1/2}(Q_{\scriptsize m}^{+}+Q_{\scriptsize m}^{-})$, where $\Delta\rho_{\infty}$$ = $$\rho^{+}(T)-\rho^{-}(T)$ is the desired width of the coexistence curve. Utilizing the exact limiting $(L$$ \to $$\infty)$ form, the corresponding scaling function can be generated in recursive steps by fitting overlapping data for three or more box sizes, $L_{1}$, $L_{2}$, $...$, $L_{n}$. Starting at a $T_{0}$ sufficiently far below $T_{\scriptsize c}$ and suitably choosing intervals $\Delta T_{j}$$ = $$T_{j+1}-T_{j}$$ > $0 yields $\Delta\rho_{\infty}(T_{j})$ and precisely locates $T_{\scriptsize c}$.

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