Docampo Álvarez, BorjaGómez González, VíctorMéndez-Morales, TrinidadCarrete Montaña, JesúsRodríguez, Julio R.Cabeza Gras, OscarGallego del Hoyo, Luis JavierVarela Cabo, Luis Miguel2026-02-282026-02-282014-06-02J. Chem. Phys. 140 (2014) 2145020021-9606https://hdl.handle.net/10347/46180This 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.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 mixtureseng© 2014 AIP Publishing LLC.Polarizable force fieldsMolecular dynamicsProbability theoryNumerical integrationCage effectIonic liquidsSolventsChemical bondingSolvationFluid mixing22 Físicajournal article10.1063/1.48796601089-7690open access