Molecular dynamics simulations of room temperature molten salts (ionic liquids) containing imidazolium cations have been performed. Ten different systems were simulated at 323 K by using united atom force fields, in which the anion size (F-, Cl-, Br-, and PF6-) and the length of the alkyl chain of 1-alkyl-3-methylimidazolium cations (1-methyl-, 1-ethyl-, 1-butyl-, and 1-octyl-) were systematically varied. It is shown that the resulting equilibrium structures account for the observed features of experimental static structure factors when available. A detailed analysis of the simultaneous effect of changing the anion and the alkyl chain on the preferential location of nearest-neighbor anions around the cations is provided. It is shown that regions above and below the imidazolium ring are the preferential ones in case of large anions. By increasing the length of the alkyl chain, nearest-neighbor anions are pushed away from the volume occupied by the flexible alkyl chain. Partial structure factors of 1-butyl- and 1-octyl- derivatives display a peak at a wave vector smaller than the main peak, indicating the occurrence of an intermediate range order in these ionic liquids due to the presence of long alkyl chains.

Ionic dynamics in room temperature molten salts (ionic liquids) containing 1-alkyl-3-methylimidazolium cations is investigated by molecular-dynamics simulations. Calculations were performed with united atom models, which were used in a previous detailed study of the equilibrium structure of ionic liquids [S. M. Urahata and M. C. C. Ribeiro, J. Chem. Phys. 120, 1855 (2004)]. The models were used in a systematic study of the dependency of several single particle time correlation functions on anion size (F-, Cl-, Br-, and PF6-) and alkyl chain length (1-methyl-, 1-ethyl-, 1-butyl-, and 1-octyl-). Despite of large mass and size of imidazolium cations, they exhibit larger mean-square displacement than anions. A further detailed picture of ionic motions is obtained by using appropriate projections of displacements along the plane or perpendicular to the plane of the imidazolium ring. A clear anisotropy in ionic displacement is revealed, the motion on the ring plane and almost perpendicular to the 1-alkyl chain being the less hindered one. Similar projections were performed on velocity correlation functions, whose spectra were used to relate short time ionic rattling with the corresponding long time diffusive regime. Time correlation functions of cation reorientation and dihedral angles of the alkyl chains are discussed, the latter decaying much faster than the former. A comparative physical picture of time scales for distinct dynamical processes in ionic liquids is provided.

Given their relevant physicochemical properties, ionic liquids (ILs) are attracting great attention as electrolytes for use in different electrochemical devices, such as capacitors, sensors, and lithium ion batteries. In addition to the advantages of using ILs containing lithium cations as electrolytes in lithium ion batteries, the Li(+) transport in ILs containing the most common anion, bis(trifluoromethanesulfonyl) imide anion ([Tf2N]), is reportedly small; therefore, its contribution to the overall conductivity is also low. In this work, we describe the preparation and characterization of two new and one known IL containing the tetracyanoborate anion ([B(CN)4]) as the anionic species. These ILs have high thermal and chemical stabilities, with almost twice the ionic conductivity of the [Tf2N] ILs and, most importantly, provide a greater role for the Li(+) ion throughout the conductivity process. The experimental ionic conductivity and self-diffusion coefficient data show that the [B(CN)4]-based ILs and their Li(+) mixtures have a higher number of charge carriers. Molecular dynamics simulations showed a weaker interaction between Li(+) and [B(CN)4] than that with [Tf2N]. These results may stimulate new applications for ILs that have good Li(+) transport properties.

Collective dynamics in a representative model of ionic liquids, namely, 1-butyl-3-methylimidazolium chloride, have been revealed by molecular dynamics simulation. Dispersion of energy excitation, omega versus k, of longitudinal acoustic (LA) and transverse acoustic (TA) modes was obtained in the wave vector range 0.17 < k < 1.40 Angstroms(-1), which encompasses the main peak of the static structure factor S(k). Linear dispersion of acoustic modes is observed up to k approximately 0.7 Angstroms(-1). Due to mixing between LA and TA modes, LA spectra display transverselike component, and vice versa. Due to anisotropy in short-time ionic dynamics, acoustic modes achieve distinct limiting omega values at high k when the cation displacement is projected either along the plane or perpendicular to the plane of the imidazolium ring. In charge current spectra, branch with negative dispersion of omega versus k is a signature of optic modes in the simulated ionic liquid. Conductivity kappa estimated by using ionic diffusion coefficients in the Nernst-Einstein equation is higher than the actual kappa calculated by integrating the charge current correlation function. From TA spectra, a wave vector dependent viscosity eta(k) has been evaluated, whose low-k limit gives eta in reasonable agreement with experimental data.

The effect of water on the hydrophobic ionic liquid (IL) 1-n-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonylimide) and its Li(+) mixture was evaluated. The electrochemical stability, density, viscosity, and ionic conductivity were measured for both systems in different concentrations of water. The presence of Li(+) causes a large increase in the water absorption ability of the IL. The experimental results suggest a break of the interactions between Li(+) and Tf2N(-) anions in the strong aggregates formed in dried Li(+) mixtures, modifying the size and physicochemical nature of these aggregates. It is also observed that the size of the ions aggregates with formal charge increases at high temperature and decreases the mobility of the charge carrier, explaining the break in the Walden rules at high temperature. Raman spectroscopy and molecular dynamic simulations show the structural change of these systems. In neat ILs, the water molecules interact mainly among each other, while in the Li(+) mixtures, water interacts preferentially with the metallic cation, causing an important change in the aggregates present in this system.