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:
-
- Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry and Chemical Theory Center
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Physical and Life Sciences Directorate
- Khalifa Univ. of Science and Technology, Abu Dhabi (United Arab Emirates). Petroleum Inst., Dept. of Chemical Engineering
- 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 Laboratory (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. https://doi.org/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. https://doi.org/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 = {Thu Dec 07 00:00:00 EST 2017},
month = {Thu Dec 07 00:00:00 EST 2017}
}
Web of Science
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