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Communication: theoretical prediction of free-energy landscapes for complex self-assembly.


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Authors

Jacobs, William M 
Reinhardt, Aleks 

Abstract

We present a technique for calculating free-energy profiles for the nucleation of multicomponent structures that contain as many species as building blocks. We find that a key factor is the topology of the graph describing the connectivity of the target assembly. By considering the designed interactions separately from weaker, incidental interactions, our approach yields predictions for the equilibrium yield and nucleation barriers. These predictions are in good agreement with corresponding Monte Carlo simulations. We show that a few fundamental properties of the connectivity graph determine the most prominent features of the assembly thermodynamics. Surprisingly, we find that polydispersity in the strengths of the designed interactions stabilizes intermediate structures and can be used to sculpt the free-energy landscape for self-assembly. Finally, we demonstrate that weak incidental interactions can preclude assembly at equilibrium due to the combinatorial possibilities for incorrect association.

Description

Keywords

cond-mat.soft, cond-mat.soft, cond-mat.stat-mech

Journal Title

J Chem Phys

Conference Name

Journal ISSN

0021-9606
1089-7690

Volume Title

142

Publisher

AIP Publishing
Sponsorship
Engineering and Physical Sciences Research Council (EP/I001352/1)
Engineering and Physical Sciences Research Council (EP/I000844/1)
The Royal Society (wm072834)
European Research Council (227758)
W.M.J. acknowledges support from the Gates Cambridge Trust and the National Science Foundation Graduate Research Fellowship under Grant No. DGE-1143678. D.F. acknowledges European Research Council Advanced Grant No. 227758 and Engineering and Physical Sciences Research Council Programme Grant No. EP/I001352/1. Research carried out in part at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886.