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

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

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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. 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.

Original languageEnglish (US)
Pages (from-to)1245-1254
Number of pages10
JournalJournal of Physical Chemistry B
Issue number3
StatePublished - Jan 25 2018

Bibliographical note

Funding Information:
Financial support for this collaborative project from the Abu Dhabi Petroleum Institute Research Center (Project Code LTR14009) and through a grant from the National Science Foundation (CHE-1265849) is gratefully acknowledged. E.O.F. also acknowledges support from the University of Minnesota through a Graduate School Doctoral Dissertation Fellowship. Part of this work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory (LLNL) under Contract DE-AC52-07NA27344 with computing support from the Institutional Computing Grand Challenge program. Additional computer resources were provided by the Minnesota Supercomputing Institute at the University of Minnesota.

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