Statistical mechanics of fluids under internal constraints: Rigorous results for the one-dimensional hard rod fluid

David S. Corti, Pablo G. Debenedetti

Research output: Contribution to journalArticle

29 Scopus citations

Abstract

The rigorous statistical mechanics of metastability requires the imposition of internal constraints that prevent access to regions of phase space corresponding to inhomogeneous states. We derive exactly the Helmholtz energy and equation of state of the one-dimensional hard rod fluid under the influence of an internal constraint that places an upper bound on the distance between nearest-neighbor rods. This type of constraint is relevant to the suppression of boiling in a superheated liquid. We determine the effects of this constraint upon the thermophysical properties and internal structure of the hard rod fluid. By adding an infinitely weak and infinitely long-ranged attractive potential to the hard core, the fluid exhibits a first-order vapor-liquid transition. We determine exactly the equation of state of the one-dimensional superheated liquid and show that it exhibits metastable phase equilibrium. We also derive statistical mechanical relations for the equation of state of a fluid under the action of arbitrary constraints, and show the connection between the statistical mechanics of constrained and unconstrained ensembles.

Original languageEnglish (US)
Pages (from-to)4211-4226
Number of pages16
JournalPhysical Review E - Statistical Physics, Plasmas, Fluids, and Related Interdisciplinary Topics
Volume57
Issue number4
DOIs
StatePublished - Jan 1 1998

All Science Journal Classification (ASJC) codes

  • Statistical and Nonlinear Physics
  • Statistics and Probability
  • Condensed Matter Physics

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