Self-assembly of multicomponent structures in and out of equilibrium.
Theories of phase change and self-assembly often invoke the idea of a "quasiequilibrium," a regime in which the nonequilibrium association of building blocks results nonetheless in a structure whose properties are determined solely by an underlying free energy landscape. Here we study a prototypical example of multicomponent self-assembly, a one-dimensional fiber grown from red and blue blocks. We find that if the equilibrium structure possesses compositional correlations different from those characteristic of random mixing, then it cannot be generated without error at any finite growth rate: there is no quasiequilibrium regime. However, by exploiting dynamic scaling, structures characteristic of equilibrium at one point in phase space can be generated, without error, arbitrarily far from equilibrium. Our results, supported by mean-field theory in higher dimensions, thus suggest a "nonperturbative" strategy for multicomponent self-assembly in which the target structure is, by design, not the equilibrium one.
Molecular Foundry, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, USA. swhitelam@lbl.gov
Stephen
S
Whitelam
Rebecca
R
Schulman
Lester
L
Hedges