TY - JOUR
T1 - Molecular theory of bending elasticity and branching of cylindrical micelles
AU - May, Sylvio
AU - Bohbot, Yardena
AU - Ben-Shaul, Avinoam
PY - 1997/10/23
Y1 - 1997/10/23
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=0031248719&partnerID=8YFLogxK
U2 - 10.1021/jp971328q
DO - 10.1021/jp971328q
M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???
AN - SCOPUS:0031248719
SN - 1520-6106
VL - 101
SP - 8648
EP - 8657
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 43
ER -