Precise simulation of criticality in asymmetric fluids.

Abstract

Extensive grand canonical Monte Carlo simulations have been performed for the hard-core square-well fluid with interaction range b=1.5 sigma. The critical exponent for the correlation length has been estimated in an unbiased fashion as nu=0.63+/-0.03 via finite-size extrapolations of the extrema of properties measured along specially constructed, asymptotically critical loci that represent pseudosymmetry axes. The subsequent location of the critical point achieves a precision of five parts in 10(4) for Tc and about 0.3% for the critical density rhoc. The effective exponents gamma+(eff) and beta(eff) indicate Ising-type critical-point values to within 2% and 5.6%, respectively, convincingly distinguishing the universality class from the "nearby" XY and n=0 (self-avoiding walk) classes. Simulations of the heat capacity CV(T,rho) and d2psigma/dT2, where psigma is the vapor pressure below Tc, suggest a negative but small Yang-Yang anomaly, i.e., a specific-heat-like divergence in the corresponding chemical potential derivative (d2 musigma/dT2) that requires a revision of the standard asymptotic scaling description of asymmetric fluids.