First-fracture kinetics in periodic chains: from free-energy landscapes and dynamical recrossing to absolute rates

Abstract

The nearly collinear configuration of highly stretched polymer chains before fracture motivates one-dimensional models. At fixed extension, stretching one bond redistributes length among the others, coupling rupture to the whole chain. In this work, I develop a framework for fracture-healing rates in periodic Morse chains, combining deterministic theories, equilibrium simulations and a quasi-deterministic approach using equilibrium fluxes and barrier-top trajectories. Constrained-partition calculations closely reproduce simulated populations and intact-state tensions. An intact-reservoir potential of mean force (PMF) supplies the first-fracture surface probability, while recrossing corrects the attempt flux without a rate-fitted prefactor. Independent rate tests identify an operational chain-length boundary for accurate two-state kinetics; failed-return durations decrease relative to population relaxation as chains grow. Kramers-Grote-Hynes (KGH), nonlinear reactive-flux and equilibrium rates show excellent agreement in this regime. KGH predicts rates away from coexistence and a chain-dependent local activation length dominated by the barrier response. Rates decrease approximately exponentially before declining more gently for longer chains: barrier growth dominates, additional fracture sites partly compensate, and transmission varies more weakly. Beyond coexistence, long chains can fracture practically irreversibly because healing becomes too rare to observe. Projected committor crossings, where the configuration-averaged probability of reaching the fractured core first is one half, lie near site-PMF maxima, although configurations at equal bond length retain different fracture probabilities. Multiple fractures remain negligible near coexistence through at least $N=50$. The framework could supply state-dependent rates to mesoscopic fracture models of polymer networks.