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Asymmetric Fluid Criticality I: Scaling with Pressure Mixing | | Young C. Kim
; Michael E. Fisher
; G. Orkoulas
; | | Date: |
6 Dec 2002 | | Journal: | Phys. Rev. E vol. 67, 061506 (2003) | | Subject: | Statistical Mechanics | cond-mat.stat-mech | | Affiliation: | University of Maryland at College Park RPI, NY | | Abstract: | The thermodynamic behavior of a fluid near a vapor-liquid and, hence, asymmetric critical point is discussed within a general ``complete’’ scaling theory incorporating pressure mixing in the nonlinear scaling fields as well as corrections to scaling. This theory allows for a Yang-Yang anomaly in which mu_{sigma}^{primeprime}(T), the second temperature derivative of the chemical potential along the phase boundary, diverges like the specific heat when T o T_{scriptsize c}; it also generates a leading singular term, |t|^{2eta}, in the coexistence curve diameter, where tequiv (T-T_{scriptsize c}) /T_{scriptsize c}. The behavior of various special loci, such as the critical isochore, the critical isotherm, the k-inflection loci, on which chi^{(k)}equiv chi(
ho,T)/
ho^{k} (with chi =
ho^{2} k_{scriptsize B}TK_{T}) and C_{V}^{(k)}equiv C_{V}(
ho,T)/
ho^{k} are maximal at fixed T, is carefully elucidated. These results are useful for analyzing simulations and experiments, since particular, nonuniversal values of k specify loci that approach the critical density most rapidly and reflect the pressure-mixing coefficient. Concrete illustrations are presented for the hard-core square-well fluid and for the restricted primitive model electrolyte. For comparison, a discussion of the classical (or Landau) theory is presented briefly and various interesting loci are determined explicitly and illustrated quantitatively for a van der Waals fluid. | | Source: | arXiv, cond-mat/0212145 | | Other source: | [GID 1126231] pmid16241232 | | Services: | Forum | Review | PDF | Favorites | |
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