RT Journal Article
T1 Mixtures of protic ionic liquids and molecular cosolvents: A molecular dynamics simulation
A1 Docampo Álvarez, Borja
A1 Gómez González, Víctor
A1 Méndez-Morales, Trinidad
A1 Carrete Montaña, Jesús
A1 Rodríguez, Julio R.
A1 Cabeza Gras, Oscar
A1 Gallego del Hoyo, Luis Javier
A1 Varela Cabo, Luis Miguel
K1 Polarizable force fields
K1 Molecular dynamics
K1 Probability theory
K1 Numerical integration
K1 Cage effect
K1 Ionic liquids
K1 Solvents
K1 Chemical bonding
K1 Solvation
K1 Fluid mixing
AB In this work, the effect of molecular cosolvents (water, ethanol, and methanol) on the structure of mixtures of these compounds with a protic ionic liquid (ethylammonium nitrate) is analyzed by means of classical molecular dynamics simulations. Included are as-yet-unreported measurements of the densities of these mixtures, used to test our parameterized potential. The evolution of the structure of the mixtures throughout the concentration range is reported by means of the calculation of coordination numbers and the fraction of hydrogen bonds in the system, together with radial and spatial distribution functions for the various molecular species and molecular ions in the mixture. The overall picture indicates a homogeneous mixing process of added cosolvent molecules, which progressively accommodate themselves in the network of hydrogen bonds of the protic ionic liquid, contrarily to what has been reported for their aprotic counterparts. Moreover, no water clustering similar to that in aprotic mixtures is detected in protic aqueous mixtures, but a somehow abrupt replacing of [NO3]− anions in the first hydration shell of the polar heads of the ionic liquid cations is registered around 60% water molar concentration. The spatial distribution functions of water and alcohols differ in the coordination type, since water coordinates with [NO3]− in a bidentate fashion in the equatorial plane of the anion, while alcohols do it in a monodentate fashion, competing for the oxygen atoms of the anion. Finally, the collision times of the different cosolvent molecules are also reported by calculating their velocity autocorrelation functions, and a caging effect is observed for water molecules but not in alcohol mixtures
PB AIP Publishing
SN 0021-9606
YR 2014
FD 2014-06-02
LK https://hdl.handle.net/10347/46180
UL https://hdl.handle.net/10347/46180
LA eng
NO J. Chem. Phys. 140 (2014)  214502
NO This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in J. Chem. Phys. 140 (2014)  214502 and may be found at https://pubs.aip.org/aip/jcp/article-abstract/140/21/214502/566707/Mixtures-of-protic-ionic-liquids-and-molecular?redirectedFrom=fulltext.
NO The authors wish to thank the financial support of Xunta de Galicia through the research projects of references 10- PXIB-103-294 PR, 10-PXIB-206-294 PR and GPC2013-043. Moreover, this work was funded by the Spanish Ministry of Science and Innovation (Grant No. FIS2012-33126). All these research projects are partially supported by FEDER. T. Méndez-Morales thanks the Spanish ministry of Education for her FPU grant. Facilities provided by the Galician Supercomputing Centre (CESGA) are also acknowledged
DS Minerva
RD 24 may 2026