Theoretical prediction of free-energy landscapes for complex self-assembly
Jacobs, William M
Journal of Chemical Physics
MetadataShow full item record
Jacobs, W. M., Reinhardt, A., & Frenkel, D. (2015). Theoretical prediction of free-energy landscapes for complex self-assembly. Journal of Chemical Physics, 142 (021101)https://doi.org/10.1063/1.4905670
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.
Polymers, Free energy, Self assembly, Monte Carlo methods, Crystal structure
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.
Royal Society (wm072834)
European Research Council (227758)
External DOI: https://doi.org/10.1063/1.4905670
This record's URL: https://www.repository.cam.ac.uk/handle/1810/247255