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Title: First-Principles Molecular Dynamics Study of a Deep Eutectic Solvent: Choline Chloride/Urea and Its Mixture with Water

Abstract

First-principles molecular dynamics simulations in the canonical ensemble at temperatures of 333 and 363 K and at the corresponding experimental densities are carried out to investigate the behavior of the 1:2 choline chloride/urea (reline) deep eutectic solvent and its equimolar mixture with water. Analysis of atom–atom radial and spatial distribution functions and of the H-bond network reveals the microheterogeneous structure of these complex liquid mixtures. In neat reline, the structure is governed by strong H-bonds of the trans- and cis-H atoms of urea to the chloride ion. In hydrous reline, water competes for the anions, and the H atoms of urea have similar propensities to bond to the chloride ions and the O atoms of urea and water. Finally, the vibrational spectra exhibit relatively broad peaks reflecting the heterogeneity of the environment. Although the 100 ps trajectories allow only for a qualitative assessment of transport properties, the simulations indicate that water is more mobile than the other species and its addition also fosters faster motion of urea.

Authors:
 [1];  [1];  [2]; ORCiD logo [3]; ORCiD logo [3];  [3]; ORCiD logo [4]
  1. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry and Chemical Theory Center
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Physical and Life Sciences Directorate
  3. Khalifa Univ. of Science and Technology, Abu Dhabi (United Arab Emirates). Petroleum Inst., Dept. of Chemical Engineering
  4. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry and Chemical Theory Center; Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemical Engineering and Materials Science
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF)
OSTI Identifier:
1455411
Report Number(s):
LLNL-JRNL-739501
Journal ID: ISSN 1520-6106; 893168; TRN: US1901235
Grant/Contract Number:  
AC52-07NA27344; CHE-1265849
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 122; Journal Issue: 3; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Fetisov, Evgenii O., Harwood, David B., Kuo, I-Feng William, Warrag, Samah E. E., Kroon, Maaike C., Peters, Cor J., and Siepmann, J. Ilja. First-Principles Molecular Dynamics Study of a Deep Eutectic Solvent: Choline Chloride/Urea and Its Mixture with Water. United States: N. p., 2017. Web. doi:10.1021/acs.jpcb.7b10422.
Fetisov, Evgenii O., Harwood, David B., Kuo, I-Feng William, Warrag, Samah E. E., Kroon, Maaike C., Peters, Cor J., & Siepmann, J. Ilja. First-Principles Molecular Dynamics Study of a Deep Eutectic Solvent: Choline Chloride/Urea and Its Mixture with Water. United States. doi:10.1021/acs.jpcb.7b10422.
Fetisov, Evgenii O., Harwood, David B., Kuo, I-Feng William, Warrag, Samah E. E., Kroon, Maaike C., Peters, Cor J., and Siepmann, J. Ilja. Thu . "First-Principles Molecular Dynamics Study of a Deep Eutectic Solvent: Choline Chloride/Urea and Its Mixture with Water". United States. doi:10.1021/acs.jpcb.7b10422. https://www.osti.gov/servlets/purl/1455411.
@article{osti_1455411,
title = {First-Principles Molecular Dynamics Study of a Deep Eutectic Solvent: Choline Chloride/Urea and Its Mixture with Water},
author = {Fetisov, Evgenii O. and Harwood, David B. and Kuo, I-Feng William and Warrag, Samah E. E. and Kroon, Maaike C. and Peters, Cor J. and Siepmann, J. Ilja},
abstractNote = {First-principles molecular dynamics simulations in the canonical ensemble at temperatures of 333 and 363 K and at the corresponding experimental densities are carried out to investigate the behavior of the 1:2 choline chloride/urea (reline) deep eutectic solvent and its equimolar mixture with water. Analysis of atom–atom radial and spatial distribution functions and of the H-bond network reveals the microheterogeneous structure of these complex liquid mixtures. In neat reline, the structure is governed by strong H-bonds of the trans- and cis-H atoms of urea to the chloride ion. In hydrous reline, water competes for the anions, and the H atoms of urea have similar propensities to bond to the chloride ions and the O atoms of urea and water. Finally, the vibrational spectra exhibit relatively broad peaks reflecting the heterogeneity of the environment. Although the 100 ps trajectories allow only for a qualitative assessment of transport properties, the simulations indicate that water is more mobile than the other species and its addition also fosters faster motion of urea.},
doi = {10.1021/acs.jpcb.7b10422},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 3,
volume = 122,
place = {United States},
year = {2017},
month = {12}
}

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