Multistep Micellization of Standard Surfactants Evidenced by Second Harmonic Scattering

Processes involving in solution a reduced number of molecules are difficult to identify and characterize. Here, we show that micellization of standard surfactants, namely sodium dodecyl sulfate and trimethyl tetradecyl ammonium bromide, two nonefficient compounds for quadratic nonlinear optics, can be investigated by second harmonic scattering (SHS). In particular, the formation of aggregates at concentrations smaller than the critical micellar concentration is evidenced through a nonmonotonic behavior of the SHS intensity as a function of the surfactant concentration. A simple model based on chemical equilibria between monomers and micelles is proposed to account for the experimental observations. Signature of long-range molecular orientation correlation is revealed by polarization resolved experiments and is discussed regarding micellization and charge-induced effects.