Protic Ionic Liquids Can Be Both Free Proton Conductors and Benign Superacids.

Superacids have been the source of much spectacular chemistry but very little interesting physics despite the fact that the states of cations formed by transfer of the superacid proton to molecular bases can approach that of the cations in free space. Indeed, some of the very strongest acids, such as HPF6 and HAlCl4, have no independent existence due to lack of screening of the bare proton self-energy: their acidities can only be assessed by study of the conjugate bases. Here we show that, by allowing the protons of transient HAlCl4 and HAlBr4 to relocate on pentafluoropyridine, PFP (a very weak base that is stable to superacids), we can create glass forming protic ionic liquids (PILs) that are themselves superacids but, being free of superacid vapors, are of benign character. At Tg, conductivities exceed "good" ionic liquid values by 9 decades, so must be superprotonic. Anomalous Walden plots confirm superprotonicity.

In situ AFM visualization of Li-O2 battery discharge products during redox cycling in an atmospherically controlled sample cell.

The in situ observation of electrochemical reactions is challenging due to a constantly changing electrode surface under highly sensitive conditions. This study reports the development of an in situ atomic force microscopy (AFM) technique for electrochemical systems, including the design, fabrication, and successful performance of a sealed AFM cell operating in a controlled atmosphere. Documentation of reversible physical processes on the cathode surface was performed on the example of a highly reactive lithium-oxygen battery system at different water concentrations in the solvent. The AFM data collected during the discharge-recharge cycles correlated well with the simultaneously recorded electrochemical data. We were able to capture the formation of discharge products from correlated electrical and topographical channels and measure the impact of the presence of water. The cell design permitted acquisition of electrochemical impedance spectroscopy, contributing information about electrical double layers under the system's controlled environment. This characterization method can be applied to a wide range of reactive surfaces undergoing transformations under carefully controlled conditions.

Studies of structural, dynamical, and interfacial properties of 1-alkyl-3-methylimidazolium iodide ionic liquids by molecular dynamics simulation.

Bulk and surface properties of the ionic liquids 1-alkyl-3-methyl-imidazolium iodides ([C(n)mim]I) were simulated by classical molecular dynamics using all atom non-polarizable force field (n = 4, butyl; 6, hexyl; 8, octyl). The structure of ionic liquids were initially optimized by density functional theory and atomic charges obtained by CHELPG method. Reduction of partial atomic charges (by 20% for simulation of density and surface tension, and by 10% for viscosity) found to improve the accuracy, while a non-polarizable force field was applied. Additionally, the simulation ensembles approach the equilibrium faster when the charge reduction is applied. By these refined force field parameters, simulated surface tensions in the range of 323-393 k are quite in agreement with the experiments. Simulation of temperature dependent surface tension of [C(4)mim]I well beyond room temperature (up to 700 K) permits prediction of the critical temperature in agreement with that predicted from experimental surface tension data. Simulated densities in the range of 298-450 K for the three ionic liquids are within 0.8% of the experimental data. Structural properties for [C(4)mim]I were found to be in agreement with the results of Car-Parrinello molecular dynamics simulation we performed, which indicates a rather well-structured cation-anion interaction and occurs essentially through the imidazolium ring cation. Diffusion coefficient changes with alkyl chain length in the order of [C(8)mim]I > [C(6)mim]I > [C(4)mim]I for the cation and the anion. Formation of a dense domain in subsurface region is quite evident, and progressively becomes denser as the alkyl chain length increases. Bivariate orientational analysis was used to determine the average orientation of molecule in ionic liquids surface, subsurface, and bulk regions. Dynamic bisector-wise and side-wise movement of the imodazolium ring cation in the surface region can be deduced from the bivariate maps. Atom-atom density profile and bivariate analysis indicate that the imidazolium cation takes a spoon like configuration in the surface region and the tilt of alkyl group is a function length of alkyl chain exposing as linear as possible to the vapor phase.

Ionic liquids: past, present and future.

An overview of the field of low-melting ionic liquids is given from its inception in 1886 through to the present time. The subject is divided into an introductory section that summarizes the early history of the field, and differentiates its subsections, before addressing matters judged of some interest in "pre-surge" and "post-surge" stages of its development, focusing on physicochemical as opposed to the prolific synthetic and industrial aspects in which the author has no competence. We give a final section specifically to protic ionic liquids, which we consider to have particular scientific potential.

Ab initio molecular dynamics simulation of ionic liquids.

Ab initio Car-Parinnello molecular dynamics is used to simulate the structure and the dynamics of 1-butyl-3-methylimidazolium iodide ([bmim]I) ionic liquid at 300 K. Site-site pair correlation functions reveal that the anion has a strong interaction with any three C-H's of the imidazolium ring. The ring bends over and wraps around the anion such that the two nitrogen atoms take a distance to the anion. Electron donating butyl group contributes the electronic polarization in addition to geometrical (out-of-plane) polarization of the ring due to the liquid environment. This facilitates bending of the ring along the axis passing through nitrogen atoms. The average bending angle depends largely on the alkyl chain length and slightly on the anion type. Redistribution of electron density over the ring caused by the electron donating alkyl group provides additional independent evidence to the instability of lattice structure, hence the low melting point of the ionic liquid. Simulated viscosity and diffusion coefficients of [bmim]I are in quite agreement with the experiments.