The infrared spectrum of the protic ionic liquid 1-methylimidazolium nitrate: An ab initio molecular dynamics simulation study

Complex features observed in the infrared (IR) spectrum of the protic ionic liquid 1-methylimidazolium nitrate, [C1im][NO3], are assigned using ab initio molecular dynamics (AIMD) simulation. AIMD is used at the same level of theory to simulate the known X-ray crystal structure of [C1im][NO3] and a cluster of ionic pairs representing the liquid phase. The calculation of several single particle and collective time correlation functions of velocity forms the basis for the AIMD simulation assignment of the infrared spectra. The AIMD simulation demonstrates that the lift of the degeneracy of the anion asymmetric stretching mode, νas(NO3), due to symmetry breaking and coupling to external modes result in multiple band splitting in the crystal spectrum in the region of the νas(NO3) mode. Owing of the intrinsic anharmonic characteristic of the AIMD simulation, the calculation accounts for the broad band in the high-frequency range of the IR spectrum caused by the cation ν(NH) stretching mode in strong cation–anion hydrogen bond. The AIMD simulation of the liquid captures spectral changes upon melting of [C1im][NO3] due to loosening of the NH···O hydrogen bond and changes in the [NO3]- interaction with other hydrogen atoms of the imidazolium ring. The AIMD simulation assigns the intermolecular stretching mode of the hydrogen bond, ν(NH…O), as the band at 183 cm−1 in the far infrared spectrum of the [C1im][NO3] crystal. © 2024 Elsevier B.V.