ABSTRACT

Among the various options as to aggregate size and shape that are open to a certain surfactant system, those aggregates that have the lowest free energy ∆Ωmic of the respective equilibrium aggregate, and, additionally, the shallowest minimum allowing a multitude of aggregates, but slightly differing in size and shape, will predominate as a result of equilibrium fluctuations. Generally, we can write for the volume fraction of a micellar species:

(206)

where the size fluctuations give rise to the preexponential factor* and the integral in the exponent extends over the dividing surface defining the size

and shape of the fully equilibrated surfactant aggregate (for which the OuYang-Helfrich shape equation is satisfied). The fluctuation factor Sfluct is rather small for ordinary spherical micelles (≈25), but increases rapidly with size and becomes large for rodshaped and disc-shaped micelles.