Abstract
Long-range order in solutions of reversibly self-assembling molecules results from interactions among the asymmetric aggregates. Even for electrically neutral species, repulsions between the aggregates become significant at high concentrations. At the very least, the excluded volume of asymmetric aggregates creates formidable packing constraints which are relieved by orientational and positional alignment. Aggregate growth thus promotes long-range order, and long-range order facilitates growth. Nematic phases occur if aggregate growth is strong enough to induce orientational ordering at concentrations lower than those that induce positional ordering. The symmetry of the positionally ordered phases reflects aggregate morphology: the polydispersity of aggregates that grow in one (two) dimension(s) to form rod-like (plate-like) particles suppresses the smectic (columnar) phase in favour of the columnar (smectic) phase. Because plate-like aggregates pack more easily than rod-like aggregates, increasing concentration induces a rearrangement from rod-like to plate-like aggregates, and a transition from columnar to smectic ordering, in solutions of molecules, such as surfactants, capable of forming both types of aggregates. In mixtures of aggregating and non-aggregating species, the difficulty of packing spherically shaped particles among elongated particles results in dramatic demixing such that a very concentrated solution of very large, highly aligned aggregates coexists with a relatively dilute solution depleted of the aggregating species.
Long-range order in solutions of reversibly self-assembling molecules results from interactions among the asymmetric aggregates. Even for electrically neutral species, repulsions between the aggregates become significant at high concentrations. At the very least, the excluded volume of asymmetric aggregates creates formidable packing constraints which are relieved by orientational and positional alignment. Aggregate growth thus promotes long-range order, and long-range order facilitates growth. Nematic phases occur if aggregate growth is strong enough to induce orientational ordering at concentrations lower than those that induce positional ordering. The symmetry of the positionally ordered phases reflects aggregate morphology: the polydispersity of aggregates that grow in one (two) dimension(s) to form rod-like (plate-like) particles suppresses the smectic (columnar) phase in favour of the columnar (smectic) phase. Because plate-like aggregates pack more easily than rod-like aggregates, increasing concentration induces a rearrangement from rod-like to plate-like aggregates, and a transition from columnar to smectic ordering, in solutions of molecules, such as surfactants, capable of forming both types of aggregates. In mixtures of aggregating and non-aggregating species, the difficulty of packing spherically shaped particles among elongated particles results in dramatic demixing such that a very concentrated solution of very large, highly aligned aggregates coexists with a relatively dilute solution depleted of the aggregating species.