Vibrational Signatures of Cation–Anion Hydrogen Bonding in Ionic Liquids: A Periodic Density Functional Theory and Molecular Dynamics Study

Abstract

Hydrogen bonding in alkylammonium based protic ionic liquids was studied using density functional theory (DFT) and ab-initio molecular dynamics (AIMD) simulations. Normal-mode analysis within the harmonic approximation and power spectra of velocity autocorrelation functions were used as tools to obtain the vibrational spectra in both the gas phase as well as in the crystalline phases of these protic ionic liquids. The hydrogen bond vibrational modes were identified in the 150-240 cm(-1) region of the far infrared spectra. A blue shift in the far-IR mode was observed with increasing number of hydrogen bonding sites on the cation; the exact peak position is modulated by the cation-anion hydrogen bond strength. Sub-100 cm(-1) bands in the FIR spectrum is assigned to the rattling motion of the anions. Calculated NMR chemical shifts of the acidic protons in the crystalline phase of these salts also exhibit signature of cation-anion hydrogen bonding.