Soluble Model Fluids with Complete Scaling and Yang-Yang Features.

Abstract

Yang-Yang (YY) and singular diameter critical anomalies arise in exactly soluble compressible cell gas (CCG) models that obey complete scaling with pressure mixing. Thus, on the critical isochore ρ=ρ(c), C(μ)≔-Td(2)μ/dT(2) diverges as |t|^(-α) when t∝T-T(c)→0^(-) while ρ(d)-ρ(c)∼|t|^(2β) where ρ(d)(T)=1/2[ρ(liq)+ρ(gas)]. When the discrete local CCG cell volumes fluctuate freely, the YY ratio R(μ)=C(μ)/C(V) may take any value -∞<R(μ)<1/2 but "anticorrelated" free volumes are needed for R(μ)>0. More general decorated CCGs, including "hydrogen bonding" water models, illuminate energy-volume coupling as relevant to R(μ).