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

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. copyright 1998 The American Physical Society