2003/06/12 by Young C. Kim, Michael E. Fisher · 3 citations
Materials Science · Physics and Astronomy · #Material Dynamics and Properties #Spectroscopy and Quantum Chemical Studies #Theoretical and Computational Physics #cond-mat.stat-mech
paper · pdf · doi:10.1103/physreve.68.041506
published as Phys. Rev. E 68, 041506 (2003) · 23 pages in the two-column format (including 13 figures) This is Part II of the previous paper [arXiv:cond-mat/0212145]
arxiv created 2003/06/12 · openalex publication_date 2003/10/29 · arxiv updated 2009/11/30 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
The vapor-liquid critical behavior of intrinsically asymmetric fluids is studied in finite systems of linear dimensions L focusing on periodic boundary conditions, as appropriate for simulations. The recently propounded ``complete'' thermodynamic (\stackrel\ensuremath→L\ensuremath∞) scaling theory incorporating pressure mixing in the scaling fields as well as corrections to scaling [Phys. Rev. E 67, 061506 (2003)] is extended to finite L, initially in a grand canonical representation. The theory allows for a Yang-Yang anomaly in which, when \stackrel\ensuremath→L\ensuremath∞, the second temperature derivative (d2\ensuremathμ_\ensuremathσ/dT2) of the chemical potential along the phase boundary \ensuremathμ_\ensuremathσ(T) diverges when \stackrel\ensuremath→TTc\ensuremath-. The finite-size behavior of various special critical loci in the temperature-density or (T,\ensuremathρ) plane, in particular, the k-inflection susceptibility loci and the Q-maximal loci --- derived from QL(T,〈\ensuremathρ〉L)\ensuremath≡〈m2〉L2/〈m4〉L where m\ensuremath≡\ensuremathρ\ensuremath-〈\ensuremathρ〉L --- is carefully elucidated and shown to be of value in estimating Tc and \ensuremathρc. Concrete illustrations are presented for the hard-core square-well fluid and for the restricted primitive model electrolyte including an estimate of the correlation exponent \ensuremathν that confirms Ising-type character. The treatment is extended to the canonical representation where further complications appear.