A variational approach to necklaces formation in polyelectrolytes

By means of a variational approach we study the conditions under which a polyelectrolyte in a bad solvent will undergo a transition from a rod-like structure to a ``necklace'' structure in which the chain collapses into a series of globules joined by stretched chain segments.Comment: 6 pages, 4 figures (unfortunately big). Requires revtex, eps

Collapse of Flexible Polyelectrolytes in Multivalent Salt Solutions

The collapse of flexible polyelectrolytes in a solution of multivalent counterions is studied by means of a two state model. The states correspond to rod-like and spherically collapsed conformations respectively. We focus on the very dilute monomer concentration regime where the collapse transition is found to occur when the charge of the multivalent salt is comparable (but smaller) to that of the monomers. The main contribution to the free energy of the collapsed conformation is linear in the number of monomers $N$, since the internal state of the collapsed polymer approaches that of an amorphous ionic solid. The free energy of the rod-like state grows as $N\ln N$, due to the electrostatic energy associated with that shape. We show that practically all multivalent counterions added to the system are condensed into the polymer chain, even before the collapse.Comment: LaTeX-revtex, psfig file, 4 figure

Surface-induced layer formation in polyelectrolytes

We analyze, by means of an RPA calculation, the conditions under which a mixture of oppositely charged polyelectrolytes can micro-segregate in the neighborhood of a charged surface creating a layered structure. A number of stable layers can be formed if the surface is sufficiently strongly charged even at temperatures at which the bulk of the mixture is homogeneous.Comment: 6 pages, 3 figures, revtex, epsf, psfi

Competing Interactions among Supramolecular Structures on Surfaces

A simple model was constructed to describe the polar ordering of non-centrosymmetric supramolecular aggregates formed by self assembling triblock rodcoil polymers. The aggregates are modeled as dipoles in a lattice with an Ising-like penalty associated with reversing the orientation of nearest neighbor dipoles. The choice of the potentials is based on experimental results and structural features of the supramolecular objects. For films of finite thickness, we find a periodic structure along an arbitrary direction perpendicular to the substrate normal, where the repeat unit is composed of two equal width domains with dipole up and dipole down configuration. When a short range interaction between the surface and the dipoles is included the balance between the up and down dipole domains is broken. Our results suggest that due to surface effects, films of finite thickness have a none zero macroscopic polarization, and that the polarization per unit volume appears to be a function of film thickness.Comment: 3 pages, 3 eps figure