Premicellar aggregation of amphiphilic molecules

Radina Hadgiivanova, Haim Diamant*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


We revisit the problem of amphiphilic aggregation using a simple two-state (monomer-aggregate) thermodynamic model, which allows the study of metastable aggregates of variable size. A sequence of well separated concentrations emerge: c1, where a metastable aggregated state appears; c2, above which an appreciable amount of metastable aggregates forms; and c 3, where the aggregated state becomes stable. Of these, c3 is shown to correspond to the critical micelle concentration (cmc) as commonly measured in macroscopic experiments. Thus, appreciable premicellar aggregation is predicted in the concentration range between c2 and c3. We show that, so long as the micelles are not too large, the extent of premicellar aggregation is much larger than that expected from mere finite-size effects. It stems from the variability of the micelle size and the small free energy difference between the metastable state, containing monomers and aggregates, and the pure monomeric one. The aggregate size is found to weakly change with concentration below and above the cmc. The existence of premicellar aggregates and their concentration-insensitive size are in agreement with a recent experiment.

Original languageEnglish
Pages (from-to)8854-8859
Number of pages6
JournalJournal of Physical Chemistry B
Issue number30
StatePublished - 2 Aug 2007


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