Spin variable approach for the statistical mechanics of folding and unfolding chains

The force-extension response of chains composed of bistable (or multistable) units strongly depends on the applied boundary conditions. As a matter of fact, isotensional conditions (soft devices) lead to a plateau-like response, whereas isometric conditions (hard devices) lead to a sawtooth-like pattern. We develop an equilibrium statistical mechanics methodology, based on the introduction of a set of discrete or spin variables, which is able to describe the thermal and mechanical properties of a folding and unfolding chain under arbitrary external conditions. In particular, we will work within the Gibbs and Helmholtz ensembles, which correspond to soft and hard devices, respectively. We introduce a one-dimensional system composed of multistable units and a bistable freely jointed chain. For both systems we obtain explicit expressions for the force-extension relation and we study the spinoidal behavior induced by the isometric conditions.