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Abstract The properties of binary liquid mixtures of 1-butyl-3-methylimidazolium [BF 4 ]/[PF 6 ] with diethylene glycol methyl ether or diethylene glycol dimethyl ether were studied in the full composition range as a function of temperature. Excess and mixing properties were obtained from experimental density and viscosity data and analysed in terms of intermolecular forces and non-ideal mixing behaviour. The microscopic features were analysed with molecular dynamics simulations, which allowed characterizing intermolecular forces, hydrogen bonding, and liquid structuring as a function of the involved molecules and ions together with the effect of mixtures mole fraction. The joint experimental and computational study enables both microscopic and macroscopic characterization of the studied mixed fluids, thus this work contributes to the knowledge of the effect of molecular solvents for tuning ionic liquid properties in terms of the involved intermolecular forces and microscopic features. Highlights • Ionic liquids mixtures • Ether solvents • Thermophysics and excess properties • Molecular dynamics • Intermolecular forces in ionic liquid mixtures [ABSTRACT FROM AUTHOR]

[Display omitted] • Intermolecular forces in liquid mixtures. • Thermophysics and molecular modelling. • Competing intermolecular hydrogen bonding effects. • Homoassociation vs heteroassociations on liquid mixtures structuring. • Disruption of alkanol hydrogen bonding. The properties, structuring and intermolecular forces of diglyme + alkanol mixtures are studied using a combined experimental and theoretical approach. The thermophysical properties as well as the molecular simulation results provide detailed characterization of the mixtures in terms of composition, type of 1-alkanol and temperature. The possibility of development of heteroassociations by glyme - alkanol hydrogen bonding as well as their effect on the weakening and breaking on alkanols self-association show a pivotal role on the mixtures structure as well as the glyme self-association. The reported mixtures show complex structural effects varying with mixtures composition which may be considered as model of ether – hydroxyl interaction and their effects on the mixture's properties and nature. [ABSTRACT FROM AUTHOR]

The properties of binary liquid mixtures formed by lactams (2-pyrrolidone or N -methyl-2-pyrrolidone) with 1,2-alkanediols were studied as a function of mixtures composition using a combined experimental and theoretical approach. The experimental properties were analysed in terms of excess and mixing properties, thus inferring deviations from ideality and their relationships with types and extension of hydrogen bonding. The theoretical study using both quantum chemistry and classical molecular dynamics simulations provided a nanoscopic characterization of the mixed fluids and for the intermolecular forces in terms of homo and heteroassociations. The reported results allowed to characterize lactam–containing liquid mixtures in multiscale approach, thus inferring the properties of these systems and their relationships with their solvency capacity. • Mixtures of lactams and 1,2-alkanediols • Intermolecular forced as a function of temperature and composition • Ideality deviations from experiments • Molecular simulation with quantum chemistry and molecular dynamics • Hydrogen bonding in complex liquid mixtures [ABSTRACT FROM AUTHOR]

The properties of ionic liquid plus acetone or acetonitrile mixtures were studied from the macro and microscopic levels by the measurement of relevant thermophysical properties and through molecular modelling studies. The liquid mixtures were considered in the whole composition range and analysed in terms of possible hydrogen bonding between the ions and ions with the molecular solvents. The reported results show how the large non-ideality of these systems stands on the high affinity of acetone and acetonitrile for the imidazolium hydrogen bond donor sites, which allow competition with the corresponding anions for these sites specially but not limited to molecular solvent rich mixtures. The reported results allow to quantify the relevance of hydrogen bonding for the properties of ionic liquid – molecular solvent mixtures, which can be fine-tuned through the amounts of cosolvent present in the mixture as a mechanism to control mixed fluids organization. • Ionic liquid mixtures with molecular solvents • Intermolecular forces in terms of ideality deviations • Molecular modelling of hydrogen bonding • Dynamic of hydrogen bonding in ionic liquid mixtures [ABSTRACT FROM AUTHOR]