A new secondary relaxation in the rigid and planar 1-methylindole: Evidence from binary mixture studies

作者：Wang, Meng; Li, Xiangqian; Guo, Yuxing; Wu, Tao; Liu, Ying Dan; Ngai, K. L.; Wang, Li-Min^*

来源：Journal of Chemical Physics, 2016, 145(21): 214501.

DOI：10.1063/1.4968564

• GLASS-FORMING SYSTEMS
• BAND DIELECTRIC-SPECTROSCOPY
• SUPERCOOLED LIQUIDS
• VISCOUS-LIQUIDS
• DYNAMICS
• TRANSITION
• TEMPERATURE
• FORMERS
• THERMODYNAMICS
• DEPENDENCE

Found in our recent dielectric study of a planar and rigid glass-former, 1-methylindole (1MID), is an unusual secondary relaxation unrelated in its dynamic properties to the structural alpha-relaxation. We speculated that it originates from the in-plane motion of the molecules, and the supposedly universal Johari-Goldstein (JG) beta-relaxation with strong connection to the structural alpha-relaxation in rigid glass-formers is not resolved [X. Q. Li et al. J. Chem. Phys. 143, 104505 (2015)]. In this work, dielectric measurements are performed in binary mixtures of 1MID with two aromatics of weak polarity, ethylbenzene (EB) and triphenylethylene (TPE), in the highly viscous regimes near glass transition. EB and TPE have smaller and larger molecular sizes and glass transition temperatures T-g than 1MID, respectively. Strikingly, the results show that the resolved secondary relaxations of 1MID in the two mixtures share the same relaxation time and their temperature dependence as pure 1MID, independent of the mode and degree of dilution. The results indicate that the unusual secondary relaxation is not directly coupled with the alpha-relaxation, and support the in-plane-rotation interpretation of its origin. On the other hand, the supposedly universal and intermolecular JG beta-relax.ation coming from the out-of-plane motion of the planar molecule has weaker dielectric strength, and it cannot be resolved from the more intense in-plane-rotation secondary relaxation because the dipole moment of 1MID lies on the plane. Published by AIP Publishing.

• 出版日期2016-12-21
• 单位燕山大学