Magnus Ullner, Bo Jönsson, Carsten Peterson, Ola Sommelius and Bo Söderberg
The Electrostatic Persistence Length calculated from Monte Carlo, Variational and Perturbation Methods
Journal of Chemical Physics 107, 1279-1287 (1997)
Monte Carlo simulations and variational calculations using a Gaussian ansatz are applied to a model consisting of a flexible linear polyelectrolyte chain as well as to an intrinsically stiff chain with up to 1000 charged monomers. Addition of salt is treated implicitly through a screened Coulomb potential for the electrostatic interactions. For the flexible model the electrostatic persistence length shows roughly three regimes in its dependence on the Debye-Hückel screening length, kappa-1. As long as the salt content is low and kappa-1 is longer than the end-to-end distance, the electrostatic persistence length varies only slowly with kappa-1. Decreasing the screening length, a controversial region is entered. We find that the electrostatic persistence length scales as (xip)1/2/kappa, in agreement with experiment on flexible polyelectrolytes, where xip is a strength parameter measuring the electrostatic interactions within the polyelectrolyte. For screening lengths much shorter than the bond length, the kappa-1 dependence becomes quadratic in the variational calculation. The simulations suffer from numerical problems in this regime, but seem to give a relationship half-way between linear and quadratic. A low temperature expansion only reproduces the first regime and a high temperature expansion, which treats the electrostatic interactions as a perturbation to a Gaussian chain, gives a quadratic dependence on the Debye length. For a sufficiently stiff chain, the persistence length varies quadratically with kappa-1 in agreement with earlier theories.
LU TP 96-30