Kinetics of Hydrogen Bonding between Ions with Opposite and Like Charges in Hydroxyl-Functionalized Ionic Liquids.

Hydrogen-bonded structures and their lifetimes in ionic liquids (ILs) are governed by the subtle balance between Coulomb interactions, hydrogen bonding, and dispersion forces. Despite the dominant Coulomb interaction, local and directional hydrogen bonds (HBs) can play an important role in the behavior of ILs. Compared to water, the archetype of hydrogen-bonded liquids, ILs have larger constituents and higher viscosities but are typically lacking a three-dimensional HB network. Hydroxyl-functionalized ionic liquids are even more special: regular HBs between cations and anions (ca) are accompanied by HBs between pairs of cations (cc). Recently, infrared (IR) measurements have suggested that the (cc) HBs are even stronger than their (ca) counterparts and their strength can be controlled via the hydroxyalkyl chain length. In this paper, we show by means of molecular dynamics (MD) simulations that the presence of HBs has a profound effect on the molecular mobility of the ions. We investigate the kinetic mechanism of hydrogen bonding in ILs and show that the lifetimes and hence the stability of (cc) HBs increase with the chain length, making them more stable than the respective (ca) HBs. The observed HB equilibrium can explain the peculiar chain length dependence of the relative molecular mobilities of the ions by a direct comparison between hydroxyl-functionalized ILs with their nonfunctionalized counterparts.