Solvation of Al cations in bulk and confined protic ionic liquids: a computational study.

Despite the growing interest in the potential electrochemical applications of both aluminium and ionic liquids in batteries, the microstructure of mixtures of trivalent salts and these dense ionic environments is completely unknown. In this work, the solvation of Al3+ cations in highly dense ionic solvents is investigated. For this purpose, molecular dynamics simulations of mixtures of a protic ionic liquid, ethylammonium nitrate (EAN), with aluminium nitrate (Al(NO3)3), both in bulk and confined between graphene walls, are performed.

Molecular dynamics simulations of the structure of mixtures of protic ionic liquids and monovalent and divalent salts at the electrochemical interface.

We perform molecular dynamics simulations of mixtures of a prototypical protic ionic liquid, ethylammonium nitrate, with lithium or magnesium nitrate (LiNO3/Mg(NO3)2) confined between two graphene walls. The structure of the system is analyzed by means of ionic density profiles, angular orientations of ethylammonium cations close to the wall and the lateral structure of the first layer close to the graphene wall. All these results are compared to those of the corresponding aprotic ionic liquid systems, analyzing the influence of the graphene wall charge in the structure of the protic and aprotic mixtures.

The effect of alkyl chain length on the structure and thermodynamics of protic-aprotic ionic liquid mixtures: a molecular dynamics study.

Mixtures of alkylammonium based protic ionic liquids and alkylmethylimidazolium based aprotic ionic liquids were studied by means of molecular dynamics simulations. Close to ideal mixing is observed in most studied magnitudes; however, the effect of increasing alkyl chain length in each of the cations is markedly different, with longer protic cations showing larger deviations, especially with regards to mixing enthalpy, which exhibits a strong compound forming tendency. The compound forming nature of these protic ionic liquids is shown to induce sharp changes in their local environment upon mixing.

Molecular dynamics simulation of the structure and interfacial free energy barriers of mixtures of ionic liquids and divalent salts near a graphene wall.

A molecular dynamics study of mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF]) with magnesium tetrafluoroborate (Mg[BF]) confined between two parallel graphene walls is reported. The structure of the system is analyzed by means of ionic density profiles, lateral structure of the first layer close to the graphene surface and angular orientations of imidazolium cations. Free energy profiles for divalent magnesium cations are calculated using two different methods in order to evaluate the height of the potential barriers near the walls, and the results are compared with those of mixtures of the same ionic liquid and a lithium salt (Li[BF]).

Molecular dynamics simulations of mixtures of protic and aprotic ionic liquids.

Molecular dynamics simulations of mixtures of the protic ionic liquid ethylammonium nitrate (EAN) and the aprotic 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]) are reported and the results are compared with experimental density and electrical conductivity measurements. Essentially ideal mixing of the ionic liquids is seen to take place by means of experimental and simulated excess molar volumes, whose very low values suggest a gradual transition between the structures of the two end constituents of the mixture. A weak dominance of the structure of the protic ionic liquid is nevertheless registered, due to a slight preferential formation of the network of hydrogen bonds, as reflected in the coordination number and the number of hydrogen bonds in the mixture.

Structural origin of proton mobility in a protic ionic liquid/imidazole mixture: insights from computational and experimental results.

The structure, dynamics, and phase behavior of a binary mixture based on the protic ionic liquid 1-ethylimidazolium bis(trifluoromethanesulfonyl)imide (C2HImTFSI) and imidazole are investigated by (1)H NMR spectroscopy, vibrational spectroscopy, diffusion NMR, calorimetric measurements, and molecular dynamics simulations. Particular attention is given to the nature of the H-bonds established and the consequent occurrence of the Grotthuss mechanism of proton transfer. We find that due to their structural similarity, the imidazolium cation and the imidazole molecule behave as interchangeable and competing sites of interaction for the TFSI anion.

Molecular dynamics simulations of the structure and single-particle dynamics of mixtures of divalent salts and ionic liquids.

We report a molecular dynamics study of the structure and single-particle dynamics of mixtures of a protic (ethylammonium nitrate) and an aprotic (1-butyl-3-methylimidazolium hexaflurophosphate [BMIM][PF6]) room-temperature ionic liquids doped with magnesium and calcium salts with a common anion at 298.15 K and 1 atm. The solvation of these divalent cations in dense ionic environments is analyzed by means of apparent molar volumes of the mixtures, radial distribution functions, and coordination numbers.

Mixtures of protic ionic liquids and molecular cosolvents: a molecular dynamics simulation.

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.