Neutron scattering studies on short- and long-range layer structures and related dynamics in imidazolium-based ionic...

Alkyl-methyl-imidazolium ionic liquids CnmimX (n: alkyl-carbon number, X: anion) have short-range layer structures consisting of ionic and neutral (alkylchain) domains. To investigate the temperature dependences of the interlayer, interionic group, and inter-alkylchain correlations, we have measured the neutron diffraction (ND) of C16mimPF₆, C9.5mimPF₆, and C8mimPF₆ in the temperature region from 4 K to 470 K. The quasielastic neutron scattering (QENS) of C16mimPF₆ was also measured to study the dynamics of each correlation. C16mimPF₆ shows a first-order transition between the liquid (L) and liquid crystalline (LC) phases at T_c = 394 K. C8mimPF₆ exhibits a glass transition at T_g = 200 K. C9.5mimPF₆, which is a 1:3 mixture between C8mimPF₆ and C10mimPF₆, has both transitions at T_c = 225 K and T_g = 203 K. In the ND experiments, all samples exhibit three peaks corresponding to the correlations mentioned above. The widths of the interlayer peak at ca. 0.2 Å^-1 changed drastically at the L-LC transitions, while the interionic peaks at ca. 1 Å^-1 exhibited a small jump at T_c. The peak position and area of the three peaks did not change much at the transition. The structural changes were minimal at T_g. The QENS experiments demonstrated that the relaxation time of the interlayer motion increased tenfold at T_c, while those of other motions were monotonous in the whole temperature region. The structural and dynamical changes mentioned above are characteristic of the L-LC transition in imidazolium-based ionic liquids.