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Title: Design principles from multiscale simulations to predict nanostructure in self-assembling ionic liquids

Abstract

Molecular dynamics simulations (up to the nanoscale) were performed on the 3-methyl-1-pentylimidazolium ionic liquid cation paired with three anions; chloride, nitrate, and thiocyanate as aqueous mixtures, using the effective fragment potential (EFP) method, a computationally inexpensive way of modeling intermolecular interactions. The simulations provided insight (preferred geometries, radial distribution functions and theoretical proton NMR resonances) into the interactions within the ionic domain and are validated against 1H NMR spectroscopy and small- and wide-angle X-ray scattering experiments on 1-decyl-3-methylimidazolium. Ionic liquids containing thiocyanate typically resist gelation and form poorly ordered lamellar structures upon mixing with water. Conversely, chloride, a strongly coordinating anion, normally forms strong physical gels and produces well-ordered nanostructures adopting a variety of structural motifs over a very wide range of water compositions. Nitrate is intermediate in character, whereby upon dispersal in water it displays a range of viscosities and self-assembles into nanostructures with considerable variability in the fidelity of ordering and symmetry, as a function of water content in the binary mixtures. The observed changes in the macro and nanoscale characteristics were directly correlated to ionic domain structures and intermolecular interactions as theoretically predicted by the analysis of MD trajectories and calculated RDFs. Specifically, both chloride and nitratemore » are positioned in the plane of the cation. Anion to cation proximity is dependent on water content. Thiocyanate is more susceptible to water insertion into the second solvent shell. Experimental 1H NMR chemical shifts monitor the site-specific competition dependence with water content in the binary mixtures. As a result, thiocyanate preferentially sits above and below the aromatic ring plane, a state disallowing interaction with the protons on the imidazolium ring.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA), Office of Nonproliferation and Verification Research and Development (NA-22)
OSTI Identifier:
1415417
Alternate Identifier(s):
OSTI ID: 1420071
Report Number(s):
LA-UR-17-26026
Journal ID: ISSN 1359-6640; FDISE6; TRN: US1800811
Grant/Contract Number:  
AC52-06NA25396; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Faraday Discussions
Additional Journal Information:
Journal Volume: 206; Conference: Faraday Discussions, Cambridge (United Kingdom), 11 Sep 2017; Journal ID: ISSN 1359-6640
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Nebgen, Benjamin Tyler, Magurudeniya, Harsha D., Kwock, Kevin Wen Chi, Ringstrand, Bryan Scott, Ahmed, Towfiq, Seifert, Sonke, Zhu, Jian -Xin, Tretiak, Sergei, and Firestone, Millicent Anne. Design principles from multiscale simulations to predict nanostructure in self-assembling ionic liquids. United States: N. p., 2017. Web. doi:10.1039/C7FD00154A.
Nebgen, Benjamin Tyler, Magurudeniya, Harsha D., Kwock, Kevin Wen Chi, Ringstrand, Bryan Scott, Ahmed, Towfiq, Seifert, Sonke, Zhu, Jian -Xin, Tretiak, Sergei, & Firestone, Millicent Anne. Design principles from multiscale simulations to predict nanostructure in self-assembling ionic liquids. United States. doi:10.1039/C7FD00154A.
Nebgen, Benjamin Tyler, Magurudeniya, Harsha D., Kwock, Kevin Wen Chi, Ringstrand, Bryan Scott, Ahmed, Towfiq, Seifert, Sonke, Zhu, Jian -Xin, Tretiak, Sergei, and Firestone, Millicent Anne. Tue . "Design principles from multiscale simulations to predict nanostructure in self-assembling ionic liquids". United States. doi:10.1039/C7FD00154A. https://www.osti.gov/servlets/purl/1415417.
@article{osti_1415417,
title = {Design principles from multiscale simulations to predict nanostructure in self-assembling ionic liquids},
author = {Nebgen, Benjamin Tyler and Magurudeniya, Harsha D. and Kwock, Kevin Wen Chi and Ringstrand, Bryan Scott and Ahmed, Towfiq and Seifert, Sonke and Zhu, Jian -Xin and Tretiak, Sergei and Firestone, Millicent Anne},
abstractNote = {Molecular dynamics simulations (up to the nanoscale) were performed on the 3-methyl-1-pentylimidazolium ionic liquid cation paired with three anions; chloride, nitrate, and thiocyanate as aqueous mixtures, using the effective fragment potential (EFP) method, a computationally inexpensive way of modeling intermolecular interactions. The simulations provided insight (preferred geometries, radial distribution functions and theoretical proton NMR resonances) into the interactions within the ionic domain and are validated against 1H NMR spectroscopy and small- and wide-angle X-ray scattering experiments on 1-decyl-3-methylimidazolium. Ionic liquids containing thiocyanate typically resist gelation and form poorly ordered lamellar structures upon mixing with water. Conversely, chloride, a strongly coordinating anion, normally forms strong physical gels and produces well-ordered nanostructures adopting a variety of structural motifs over a very wide range of water compositions. Nitrate is intermediate in character, whereby upon dispersal in water it displays a range of viscosities and self-assembles into nanostructures with considerable variability in the fidelity of ordering and symmetry, as a function of water content in the binary mixtures. The observed changes in the macro and nanoscale characteristics were directly correlated to ionic domain structures and intermolecular interactions as theoretically predicted by the analysis of MD trajectories and calculated RDFs. Specifically, both chloride and nitrate are positioned in the plane of the cation. Anion to cation proximity is dependent on water content. Thiocyanate is more susceptible to water insertion into the second solvent shell. Experimental 1H NMR chemical shifts monitor the site-specific competition dependence with water content in the binary mixtures. As a result, thiocyanate preferentially sits above and below the aromatic ring plane, a state disallowing interaction with the protons on the imidazolium ring.},
doi = {10.1039/C7FD00154A},
journal = {Faraday Discussions},
number = ,
volume = 206,
place = {United States},
year = {2017},
month = {7}
}

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