skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Communication: Theoretical prediction of free-energy landscapes for complex self-assembly

Authors:
 [1];  [1];  [1]
  1. Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1228476
Grant/Contract Number:
AC02-98CH10886
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 142; Journal Issue: 2; Related Information: CHORUS Timestamp: 2018-02-14 22:34:23; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics
Country of Publication:
United States
Language:
English

Citation Formats

Jacobs, William M., Reinhardt, Aleks, and Frenkel, Daan. Communication: Theoretical prediction of free-energy landscapes for complex self-assembly. United States: N. p., 2015. Web. doi:10.1063/1.4905670.
Jacobs, William M., Reinhardt, Aleks, & Frenkel, Daan. Communication: Theoretical prediction of free-energy landscapes for complex self-assembly. United States. doi:10.1063/1.4905670.
Jacobs, William M., Reinhardt, Aleks, and Frenkel, Daan. Wed . "Communication: Theoretical prediction of free-energy landscapes for complex self-assembly". United States. doi:10.1063/1.4905670.
@article{osti_1228476,
title = {Communication: Theoretical prediction of free-energy landscapes for complex self-assembly},
author = {Jacobs, William M. and Reinhardt, Aleks and Frenkel, Daan},
abstractNote = {},
doi = {10.1063/1.4905670},
journal = {Journal of Chemical Physics},
number = 2,
volume = 142,
place = {United States},
year = {Wed Jan 14 00:00:00 EST 2015},
month = {Wed Jan 14 00:00:00 EST 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1063/1.4905670

Citation Metrics:
Cited by: 18works
Citation information provided by
Web of Science

Save / Share:
  • 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 themore » 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.« less
  • A Cu(II) malonate complex with formula [Cu(C{sub 3}H{sub 2}O{sub 4})(C{sub 6}H{sub 8}N{sub 2})(H{sub 2}O)]{sub 2}·4H{sub 2}O (1) [C{sub 6}H{sub 8}N{sub 2}=2-picolylamine, C{sub 3}H{sub 2}O{sub 4}{sup 2−}=malonate dianion] has been synthesized by mixing the reactants in their stoichiometric proportion and its crystal structure has been determined by single-crystal X-ray diffraction. In 1, monomeric neutral metal malonate units [Cu(C{sub 3}H{sub 2}O{sub 4})(C{sub 6}H{sub 8}N{sub 2})(H{sub 2}O)] are interlinked with each other through hydrogen bonds, weak lone pair⋯π and cuprophilic interactions to generate supramolecular dimers, which in turn further associated through hydrogen bonding to form infinite 1D chains. Water dimers, through series ofmore » hydrogen bonds and weak π–stacking forces are found to be responsible for interconnection of 1D chains, which resulted in a 3D network. A density functional (DFT) study of the energetic features of several noncovalent interactions observed in the solid state have been analyzed and characterized using Bader's theory of “atoms-in-molecules”. We also present here Hirshfeld surface analysis to investigate the close intermolecular contacts. - Graphical Abstract: Interplay of weak forces like hydrogen bonding, lone pair⋯π, Cu⋯Cu and π–stacking interactions leading to the formation of supramolecular network in [Cu(C{sub 3}H{sub 2}O{sub 4})(C{sub 6}H{sub 8}N{sub 2})(H{sub 2}O)]{sub 2}·4H{sub 2}O complex. - Highlights: • A complex of Cu(II) with malonate and 2-picolylamine is synthesized and X-ray characterized. • We report a density functional study of the energetic features of several noncovalent interactions • We perform Hirshfeld surface analysis to investigate the close intermolecular contacts.« less
  • No abstract prepared.