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Title: Dynamical inversion of the energy landscape promotes non-equilibrium self-assembly of binary mixtures

Abstract

When driven out of equilibrium, many diverse systems can form complex spatial and dynamical patterns, even in the absence of attractive interactions. Using kinetic Monte Carlo simulations, we investigate the phase behavior of a binary system of particles of dissimilar size confined between semiflexible planar surfaces, in which the nanoconfinement introduces a non-local coupling between particles, which we model as an activation energy barrier to diffusion that decreases with the local fraction of the larger particle. The system autonomously reaches a cyclical non-equilibrium state characterized by the formation and dissolution of metastable micelle-like clusters with the small particles in the core and the large ones in the surrounding corona. The power spectrum of the fluctuations in the aggregation number exhibits 1/f noise reminiscent of self-organized critical systems. Finally, we suggest that the dynamical metastability of the micellar structures arises from an inversion of the energy landscape, in which the relaxation dynamics of one of the species induces a metastable phase for the other species.

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [4]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth and Environmental Science Area; Univ. of California, Berkeley, CA (United States). Dept. of Environmental Science, Policy, and Management
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Univ. of California, Berkeley, CA (United States). Dept. of Bioengineering; Dept. of Chemistry; Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1416403
Alternate Identifier(s):
OSTI ID: 1434007
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 9; Journal Issue: 6; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Pestana, Luis Ruiz, Minnetian, Natalie, Lammers, Laura Nielsen, and Head-Gordon, Teresa. Dynamical inversion of the energy landscape promotes non-equilibrium self-assembly of binary mixtures. United States: N. p., 2018. Web. doi:10.1039/c7sc03524a.
Pestana, Luis Ruiz, Minnetian, Natalie, Lammers, Laura Nielsen, & Head-Gordon, Teresa. Dynamical inversion of the energy landscape promotes non-equilibrium self-assembly of binary mixtures. United States. doi:10.1039/c7sc03524a.
Pestana, Luis Ruiz, Minnetian, Natalie, Lammers, Laura Nielsen, and Head-Gordon, Teresa. Tue . "Dynamical inversion of the energy landscape promotes non-equilibrium self-assembly of binary mixtures". United States. doi:10.1039/c7sc03524a.
@article{osti_1416403,
title = {Dynamical inversion of the energy landscape promotes non-equilibrium self-assembly of binary mixtures},
author = {Pestana, Luis Ruiz and Minnetian, Natalie and Lammers, Laura Nielsen and Head-Gordon, Teresa},
abstractNote = {When driven out of equilibrium, many diverse systems can form complex spatial and dynamical patterns, even in the absence of attractive interactions. Using kinetic Monte Carlo simulations, we investigate the phase behavior of a binary system of particles of dissimilar size confined between semiflexible planar surfaces, in which the nanoconfinement introduces a non-local coupling between particles, which we model as an activation energy barrier to diffusion that decreases with the local fraction of the larger particle. The system autonomously reaches a cyclical non-equilibrium state characterized by the formation and dissolution of metastable micelle-like clusters with the small particles in the core and the large ones in the surrounding corona. The power spectrum of the fluctuations in the aggregation number exhibits 1/f noise reminiscent of self-organized critical systems. Finally, we suggest that the dynamical metastability of the micellar structures arises from an inversion of the energy landscape, in which the relaxation dynamics of one of the species induces a metastable phase for the other species.},
doi = {10.1039/c7sc03524a},
journal = {Chemical Science},
issn = {2041-6520},
number = 6,
volume = 9,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1039/c7sc03524a

Figures / Tables:

Fig. 1 Fig. 1: Summary of the binary mixture model that exhibits non-equilibrium phase behavior. (a) Schematic representation of the system under study: a binary mixture of particles of dissimilar size under semiflexible planar confinement. The larger Cs particles expand the interlayer locally, which reduces the activation energy barrier of neighboring particles.more » (b) Activation energy barriers to diffusion, Ea, of each particle type as a function of the fraction of Cs in the local neighborhood, f$loc\atop{Cs}$ . The critical parameters are: (i) the difference between the Ea for the two species, which is ΔA for the same local environment, (ii) the strength of the dependence of Ea on the local environment, given by B, and (iii) the characteristic length scale of the local neighborhood in units of lattice sites, rloc. The geometric representation of the adimensional parameter ΔA/B is also presented.« less

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.