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

Fetisov, Evgenii O.; Harwood, David B.; Kuo, I-Feng William; Warrag, Samah E.  E.; Kroon, Maaike C.; Peters, Cor J.; Siepmann, J. Ilja

doi:10.1021/acs.jpcb.7b10422

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

Journal Article · Thu Dec 07 00:00:00 EST 2017 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI:https://doi.org/10.1021/acs.jpcb.7b10422· OSTI ID:1455411

Fetisov, Evgenii O. ^[1]; Harwood, David B. ^[1]; Kuo, I-Feng William ^[2];

^[3];

^[3]; Peters, Cor J. ^[3];

^[4]

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

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.

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Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF)

Grant/Contract Number:: AC52-07NA27344; CHE-1265849

OSTI ID:: 1455411

Report Number(s):: LLNL-JRNL-739501; 893168; TRN: US1901235

Journal Information:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Vol. 122, Issue 3; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 118 works

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