Nonequilibrium theory of polymer stretching based on the master equation.

We present a model for fast polymer-stretching experiments. We use the master equation and argue that the end-to-end extension of a polymer molecule can be used as a stochastic variable after appropriate coarse graining. The main effect of increasing pulling speed or force loading rate is a marked hysteresis in the force-extension curve as well as an overall shift of the curve to higher forces when compared to the equilibrium curve. This can be understood in terms of the moments of the transition probability in the master equation. An analysis of the fluctuations and relaxation times is also given in the framework of our theory.