Universal sequence of ordered structures obtained from mesoscopic description of self-assembly.
Mesoscopic theory for soft-matter systems that combines density functional and statistical field theory is derived by a systematic coarse-graining procedure. For particles interacting with spherically symmetric potentials of arbitrary form, the grand-thermodynamic potential consists of two terms. The first term is associated with microscopic length-scale fluctuations, and has the form of the standard density functional. The second term is associated with mesoscopic length-scale fluctuations, and has the form known from the statistical field theory. For the correlation function between density fluctuations in mesoscopic regions, a pair of equations similar to the Ornstein-Zernicke equation with a new closure is obtained. In the special case of weak ordering on the mesoscopic length scale, the theory takes a form similar to either the Landau-Ginzburg-Wilson (LGW) or the Landau-Brazovskii (LB) field theory, depending on the form of the interaction potential. Microscopic expressions for the phenomenological parameters that appear in the Landau-type theories are obtained. Within the framework of this theory, we obtain a universal sequence of phases: disordered, bcc, hexagonal, lamellar, inverted hexagonal, inverted bcc, disordered, for increasing density well below the close-packing density. The sequence of phases agrees with experimental observations and with simulations of many self-assembling systems. In addition to the above phases, more complex phases may appear depending on the interaction potentials. For a particular form of the short-range attraction long-range repulsion potential, we find the bicontinuous gyroid phase ( Ia3d symmetry) that may be related to a network-forming cluster of colloids in a mixture of colloids and nonadsorbing polymers.
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Institute of Physical Chemistry, Polish Academy of Sciences, 01-224 Warszawa, Poland.