Understanding the Structure of the Hydrogen Bond Network and Its Influence on Vibrational Spectra in a Prototypical Aprotic Ionic Liquid.

Analysis of the hydrogen bond network in aprotic ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM-TFSI) has been performed based on structures obtained from ab initio or classical molecular dynamics simulations. Statistics of different donor and acceptor atoms and the amount of chelating or bifurcated bonds has been presented. Most of the hydrogen bonds in EMIM-TFSI are formed with oxygen atoms as hydrogen acceptors; and the most probable bifurcated bonds are those with a mixed pair of oxygen and nitrogen acceptors. Spectral graph analysis has shown that the cations may form hydrogen bonds with up to five different anions and the connectivity of the whole hydrogen bond network is supported mainly by H-O bonds. In the structures of the liquid simulated via force field-based dynamics, the number of hydrogen bonds is smaller and fluorine atoms are the most favored hydrogen acceptors. One-dimensional potential energy profiles for hydrogen atom displacements and corresponding vibrational frequencies have been calculated for selected C-H bonds. Individual C-H stretching frequencies vary by 200-300 cm-1, indicating differences in local environment of hydrogen atoms forming C-H···O hydrogen bonds.