Polyelectrolyte chains in poor solvent. A variational description of necklace formation

We study the properties of polyelectrolyte chains under different solvent conditions, using a variational technique. The free energy and the conformational properties of a polyelectrolyte chain are studied minimizing the free energy $F_N$, depending on $N(N-1)/2$ trial probabilities that characterize the conformation of the chain. The Gaussian approximation is considered for a ring of length $2^4<N<2^{16}$ and for an open chain of length $2^4<N<2^9$ in poor and theta solvent conditions, including a Coulomb repulsion between the monomers. In theta solvent conditions the blob size is measured and found in agreement with scaling theory, including charge depletion effects, expected for the case of an open chain. In poor solvent conditions, a globule instability, driven by electrostatic repulsion, is observed. We notice also inhomogeneous behavior of the monomer--monomer correlation function, reminiscence of necklace formation in poor solvent polyelectrolyte solutions. A global phase diagram in terms of solvent quality and inverse Bjerrum length is presented.