Cascade of Transitions of Polyelectrolytes in Poor Solvents

We develop a scaling model for the dilute solution conformation of a uniformly charged polymer in a poor solvent. We find that there is a range of temperatures and charge densities for which the polymer has a necklace-like shape with compact beads joined by narrow strings. The free energy of a polye...

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Bibliographic Details
Published in:Macromolecules 1996-04, Vol.29 (8), p.2974-2979
Main Authors: Dobrynin, Andrey V, Rubinstein, Michael, Obukhov, Sergei P
Format: Article
Language:English
Subjects:
Applied sciences
Calculations
Computer simulation
Conformations
Exact sciences and technology
Free energy
Mathematical models
Monomers
Monte Carlo methods
Organic polymers
Physicochemistry of polymers
Polymerization
Properties and characterization
Solution and gel properties
Solvents
Surface tension
Temperature
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Summary:We develop a scaling model for the dilute solution conformation of a uniformly charged polymer in a poor solvent. We find that there is a range of temperatures and charge densities for which the polymer has a necklace-like shape with compact beads joined by narrow strings. The free energy of a polyelectrolyte in this conformation is lower than in a cylindrical globule because the length of the necklace is larger than that of a cylinder and is proportional to the total charge on the chain. With changing charge on the chain or temperature, the polyelectrolyte undergoes a cascade of abrupt transitions between necklaces with different numbers of beads.
ISSN:0024-9297
1520-5835
DOI:10.1021/ma9507958