Local structure formation in alkyl-imidazolium-based ionic liquids as revealed by linear and nonlinear Raman spectroscopy.

We show several pieces of Raman spectroscopic evidence that are indicative of local structure formation in imidazolium-based ionic liquids. Low-frequency Raman spectra of C n mimX, where C n mim stands for 1-alkyl(C n H 2 n+1 )-3-methylimidazolium cation and X represents the anion, exhibit broad bands assignable to collective modes of local structures. Spatial distributions of coherent anti-Stokes Raman scattering (CARS) signals from C n mim[PF 6] are consistent with local structures whose size increases with increasing n. Picosecond Raman spectra of S 1 trans-stilbene as a "picosecond Raman thermometer" show microscopic thermal inhomogeneity ascribable to local structure formation in C 2mimTf 2N and C 4mimTf 2N. We also describe two novel phenomena that we believe are relevant to extraordinary nanoenvironments generated by local structures in a magnetic ionic liquid C 4mim[FeCl 4].