Combined Spectroscopic, Thermodynamic, and Theoretical Approach for Detecting and Quantifying Hydrogen Bonding and Dispersion Interaction in Ionic Liquids.

ConspectusIonic liquids (ILs) are attracting increasing interest in science and engineering due to their unique properties that can be tailored for specific applications. Clearly, a better understanding of their behavior on the microscopic scale will help to elucidate macroscopic fluid phenomena and thereby promote potential applications. The advantageous properties of these innovative fluids arise from the delicate balance of Coulomb interactions, hydrogen bonding, and dispersion forces. The development of these properties requires a fundamental understanding of the strength, location, and direction of the different types of interactions and their contribution to the overall phase behavior. Contrary to expectations, hydrogen bonding and dispersion interactions have a significant influence on the structure, dynamics, and phase behavior of ILs.The synergy between experimental and theoretical methods has now advanced to a stage where hydrogen bonds and dispersion effects as well as the competition between the two can be studied in detail. In this account, we demonstrate that a suitable combination of spectroscopic, thermodynamic, and theoretical methods enables the detection, dissection, and quantification of noncovalent interactions, even in complex systems such as ionic liquids. This approach encompasses far-infrared vibrational spectroscopy (FIR), various thermodynamic methods for determining enthalpies of vaporization, and quantum chemical techniques that allow us to switch dispersion contributions on or off when calculating the energies and spectroscopic properties of clusters.We briefly discuss these experimental and theoretical methods, before providing various examples illustrating how the mélange of Coulomb interaction, hydrogen bonds, and dispersion forces can be analyzed, and their individual contributions quantified. First, we demonstrated that both hydrogen bonding and dispersion interactions are manifested in the FIR spectra and can be quantified by observed shifts of characteristic spectral signatures. Through the selection of suitable protic ionic liquids (PILs) featuring anions with varying interaction strengths and alkyl chain lengths, we were able to demonstrate that dispersion interactions can compete with hydrogen bonding. The resultant transition enthalpy serves as a measure of the dispersion interaction. Contrary to expectations, PILs possess lower enthalpies of vaporization compared with aprotic ILs (AILs). The reason for this is simple: In protic ILs, ion pairs carry both the hydrogen bond and attractive dispersion between the cation and anion into the gas phase. By utilizing a well-curated set of protic ILs and molecular analogues, we successfully disentangled Coulomb interaction, hydrogen bonding, and dispersion interaction through purely thermodynamic methods.