Statistical Mechanics Approaches for Studying Temperature and Rate Effects in Multistable Systems

Abstract

Systems with a multistable energy landscape are widespread in physics, biophysics, technology, and materials science. They are strongly influenced by thermal fluctuations and external mechanical actions that can be applied at different rates, moving the system from equilibrium to non-equilibrium regimes. In this paper, we focus on a simple system involving a single breaking phenomenon to describe the various theoretical approaches used to study these problems. To begin with, we propose the exact solution at thermodynamic equilibrium based on the calculation of the partition function without approximations. We then introduce the technique of spin variables, which is able to simplify the treatment even for systems with a large number of coordinates. We then analyze the energy balance of the system to better understand its underlying physics. Finally, we introduce a technique based on transition state theory useful for studying the non-equilibrium dynamical regimes of these systems. This method is appropriate for the evaluation of rate effects and hysteresis loops. These approaches are developed for both the Helmholtz ensemble (prescribed extension) and the Gibbs ensemble (applied force) of statistical mechanics. The symmetry and duality of these two ensembles is discussed in depth. While these techniques are used here for a simple system with theoretical purposes, they can be applied to complex systems of interest for several physical, biophysical, and technological applications.