Molecular Simulation-Guided Spectroscopy of Imidazolium-Based Ionic Liquids and Effects of Methylation on Ion-Cage...

Classical molecular dynamics simulations were performed to assess an atomistic interpretation of the ion-probe structural interactions in two typical ionic liquids (ILs), 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [BMIm][NTf₂] and 1-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide [BDimIm][NTf₂] through computational ultrafast spectroscopy. The nitrile stretching vibrations of the thiocyanate anion, [SCN]^-, serve as the local mode of the ultrafast system dynamics within the imidazolium-based ionic liquid environment. The wavelet transform of classical trajectories determines the time-varying fluctuating frequencies and the stretch spectral signatures of SCN^- in the normalized distribution. However, computational modeling of the two-dimensional (2D) spectra from the wavelet-derived vibrational frequencies yields time evolution of the local molecular structure along with the varied time-dependent dynamics of the spectral diffusion process. We calculated the frequency-frequency correlation functions (FFCFs), time correlations associated with the ion-pair and -cage dynamics, and mean square displacements as a function of time, depicting diffusive dynamics. The calculated results based on the pair correlation functions and the distribution of atomic density suggest that the hydrogen and methylated carbon at the two-position of the imidazolium ring of [BMIm] and [BDimIm] cations, respectively, strongly interact with the probe through the N of the thiocyanate anion rather than the S atom. The center-of-mass center-of-mass (COM-COM) cation-probe radial distribution functions (RDFs) in conjunction with the site-specific structural analysis further reveal well-structured interactions of the thiocyanate ion and [BMIm]⁺ cation rather than the [BDimIm] cation. In contrast, the anion-probe COM-COM RDFs depict weak interactive associations within the vibrational probe [SCN]^- and [NTf₂]^- ions. Methylation at the two-position of the imidazolium ring predicts slower structural reorganization and breaking and reformation dynamics of the ion pairs and cages within the ionic liquid framework.