Molecular theory of bending elasticity and branching of cylindrical micelles

Sylvio May, Yardena Bohbot, Avinoam Ben-Shaul*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

79 Scopus citations

Abstract

Two structural - thermodynamic characteristics of cylindrical, wormlike micelles in dilute solution are studied using a molecular-level model: (a) the bending elasticity of the micelles and (b) their tendency to form intermicellar junctions (branches). The internal (free) energy of the micelles, before and after a bending deformation and junction formation, are calculated using mean field theories for the free energies of the molecules constituting these structures. The molecular free energies, which depend on the local packing geometries, include the contributions of head group repulsion forces, the hydrocarbon - water interfacial energy, and the chain conformational free energy. We find that when only the head group and surface contributions to the packing energy are taken into account, the one-dimensional bending constant of the micelles is negligibly small. When the chain contribution is included, and when reasonable molecular packing parameters are used, we find that the persistence length, which is proportional to the bending rigidity, is typically a few tens of nanometers. The free energy change associated with the formation of a trijoint intermicellar junction upon the "fusion" of one micellar end cap with the cylindrical body of another micelle is found to be small but positive; about 10 kBT at room temperature. This conclusion does not refute the possibility that intermicellar junctions are metastable transients or that their formation may be favored entropically, due either to conformational degeneracy or excluded volume interactions between micelles. Our conclusions apply to aqueous solutions containing one, single-tail, surfactant species.

Original languageEnglish
Pages (from-to)8648-8657
Number of pages10
JournalJournal of Physical Chemistry B
Volume101
Issue number43
DOIs
StatePublished - 23 Oct 1997

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