Hydrogen bonding in ionic liquids probed by linear and nonlinear vibrational spectroscopy

Three imidazolium-based ionic liquids of the type [Cnmim][NTf2] with different alkyl chain lengths (n?=?1, 2 and 8) at the first position of the imidazolium ring were studied applying infrared, linear Raman and multiplex coherent anti-Stokes Raman scattering spectroscopy. The focus has been on the CH-stretching region of the imidazolium ring, which is supposed to carry information about a possible hydrogen bonding network in the ionic liquid. The measurements are compared with calculations of the corresponding anharmonic vibrational spectra for a cluster of [C2mim][NTf2] consisting of four ion pairs. The results support the hypothesis of weak hydrogen bonding involving the C(4)?H and C(5)?H groups and somewhat stronger hydrogen bonds of the C(2)?H groups.