Convergence of the Freely Rotating Chain to the Kratky-Porod Model of Semi-flexible Polymers

Abstract

The freely rotating chain is one of the classic discrete models of a polymer in dilute solution. It consists of a broken line of N straight segments of fixed length such that the angle between adjacent segments is constant and the $$N-1$$ torsional angles are independent, identically distributed, uniform random variables. We provide a rigorous proof of a folklore result in the chemical physics literature stating that under an appropriate scaling, as $$N\rightarrow \infty $$ , the freely rotating chain converges to a random curve defined by the property that its derivative with respect to arclength is a Brownian motion on the unit sphere. This is the Kratky-Porod model of semi-flexible polymers. We also investigate limits of the model when a stiffness parameter, called the persistence length, tends to zero or infinity. The main idea is to introduce orthogonal frames adapted to the polymer and to express conformational changes in the polymer in terms of stochastic equations for the rotation of these frames.