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

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Abstract:

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 by minimizing the free energy FN, 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 24 < N < 28 and for an open chain of length 50 < N < 200 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.

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Received 7 June 2001 and Received in final form 17 October 2001

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Migliorini, G., Lee, N., Rostiashvili, V. et al. Polyelectrolyte chains in poor solvent. A variational description of necklace formation. Eur. Phys. J. E 6, 259–270 (2001). https://doi.org/10.1007/s101890170009

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  • DOI: https://doi.org/10.1007/s101890170009

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