Abstract
Polyelectrolytes with strong counterion couplings are compact at low electric fields but switch to elongated forms at high ones. As yet, little is known from both nano- manipulation experiments and theory about the transition mechanisms between the compact and extended states. Here, we systematically address this out-of-equilibrium conversion using molecular dynamics simulations of coarse-grained polyelectrolyte chains of 1, 000 and 1, 500 monomers in a salt buffer of about 20,000 and 80,000 charged par- ticles, respectively. We find that compact-to-elongated transitions are smooth and fast in only half of the trajectories. In the other half, the elongation is jammed halfway by the formation of backfolded, needle-like states. These states, which have not been envisioned before, have lifetimes that are orders of magnitude larger than the chain’s relaxation time and ought to be detectable with current single-molecule experimental setups.