The statistical mechanics and the thermodynamics of small systems are characterized by the non-equivalence of the statistical ensembles. When concerning a polymer chain or an arbitrary chain of independent units, this concept leads to different force-extension responses for the isotensional (Gibbs) and the isometric (Helmholtz) thermodynamic ensembles for a limited number of units (far from the thermodynamic limit). While the average force-extension response has been largely investigated in both Gibbs and Helmholtz ensembles, the full statistical characterization of this thermo-mechanical behavior has not been approached by evaluating the corresponding probability densities. Therefore, we elaborate in this paper a technique for obtaining the probability density of the extension when force is applied (Gibbs ensemble) and the probability density of the force when the extension is prescribed (Helmholtz ensemble). This methodology, here developed at thermodynamic equilibrium, is applied to a specific chain composed of units characterized by a bistable potential energy, which is able to mimic the folding and unfolding of several macromolecules of biological origin.
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