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Low-Frequency Spectra of 1‑Methyl-3-octylimidazolium Tetrafluoroborate Mixtures with Methanol, Acetonitrile, and Dimethyl Sulfoxide: A Combined Study of Femtosecond Raman-Induced Kerr Effect Spectroscopy and Molecular Dynamics Simulations

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journal contribution
posted on 27.08.2020 by Masatoshi Ando, Masahiro Kawano, Atsuya Tashiro, Toshiyuki Takamuku, Hideaki Shirota
In this study, we examined the low-frequency spectra of 1-methyl-3-octylimidazolium tetrafluoroborate ([MOIm]­[BF4]) mixtures with methanol (MeOH), acetonitrile (MeCN), and dimethyl sulfoxide (DMSO), which were obtained by femtosecond Raman-induced Kerr effect spectroscopy (fs-RIKES) and molecular dynamics (MD) simulations. In addition, we estimated the liquid properties of the mixtures, such as density ρ, surface tension γ, viscosity η, and electrical conductivity σ. The line shapes of the low-frequency Kerr spectra of the three [MOIm]­[BF4] mixture systems strongly depend on the mole fraction of the molecular liquid, XML. The spectral intensity increases with increasing XML of the [MOIm]­[BF4]/MeCN system but decreases for the [MOIm]­[BF4]/MeOH and [MOIm]­[BF4]/DMSO systems. These behaviors of the spectral intensities reasonably agree with the vibrational density-of-states spectra when the polarizability anisotropies of MeOH, MeCN, DMSO, and ion species are considered. The characteristic frequencies (first moments, M1) of the low-frequency spectra of the three mixture systems are almost insensitive at XML = 0–0.6. However, the frequencies vary mildly at XML = 0.6–0.9 and dramatically at XML = 0.9–1. The XML-dependent M1 in the Kerr spectra are well reproduced by the MD simulations. Plots of M1 versus bulk parameter, (γ/ρ)1/2, for the three mixture systems show that the mixtures at XML = 0–0.6 behave like aromatic cation-based ionic liquids (ILs), those at XML = 0.9–1 are molecular liquids (MLs), and those at XML = 0.6–0.9 are transitioning between aromatic cation-based ILs and MLs. MD simulations show that the solvent molecules localized at the interface between the ionic and the alkyl group regions without forming large solvent networks at XML = 0–0.6. However, solvent networks or regions develop largely at XML = 0.6–0.9 and the constituent ions of the IL disperse in the MLs at XML = 0.9–1. The MD simulations corroborate the results obtained by fs-RIKES.