Heterogeneous Slow Dynamics of Imidazolium-Based Ionic Liquids Studied by Neutron Spin Echo

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• 作者：Maiko Kofu ; Michihiro Nagao ; Takeshi Ueki ; Yuzo Kitazawa ; Yutaro Nakamura ; Syota Sawamura ; Masayoshi Watanabe ; Osamu Yamamuro
• 刊名：The Journal of Physical Chemistry B
• 出版年：2013
• 出版时间：March 7, 2013
• 年：2013
• 卷：117
• 期：9
• 页码：2773-2781
• 全文大小：575K
• 年卷期：v.117,no.9(March 7, 2013)
• ISSN：1520-5207

文摘

We have investigated structure and relaxation phenomena for ionic liquids 1-octyl-3-methylimidazolium hexafluorophosphate (C8mimPF₆) and bis(trifluoromethylsulfonyl)imide (C8mimTFSI) by means of neutron diffraction and neutron spin echo (NSE) techniques. The diffraction patterns show two distinct peaks appeared at scattering vectors Q of 0.3 and 1.0 脜^鈥?. The former originates from the nanoscale structure characteristic to ionic liquids and the latter due to the interionic correlations. Interestingly, the intensity of the low-Q peak drastically grows upon cooling and keeps growing even below the glass transition temperature. The NSE measurements have been performed at these two Q positions, to explore the time evolution of each correlation. The relaxation related to the ionic correlation (ionic diffusion) is of Arrhenius-type and exhibits nonexponential behavior. The activation energy (E_a) of the ionic diffusion, which is linked to viscosity, depends on the type of anion; the larger is the anion size, the smaller E_a becomes for most of anions. On the other hand, two kinds of relaxation processes, slower and faster ones, are found at the low-Q peak position. The most significant finding is that the fraction of the slower relaxation increases and that of the faster one decreases upon cooling. Combining the NSE data with the diffraction data, we conclude that there exist two parts in ILs: one with the ordered nanostructure exhibiting the slow relaxation, and the other with disordered structure showing faster relaxation. The structure and dynamics of ILs are heterogeneous in nature, and the fraction of each part changes with temperature.