Local Order Disorder Transition Driving by Structural Heterogeneity in a Benzyl Functionalized Ionic Liquid
LFO Faria and VH Paschoal and TA Lima and FF Ferreira and RS Freitas and MCC Ribeiro, JOURNAL OF PHYSICAL CHEMISTRY B, 121, 9902-9909 (2017).
A local order disorder transition has been disclosed in the thermophysical behavior of the ionic liquid 1-benzyl-3-methylimidazolium dicyanamide, Bzmim N-(CN)(2), and its microscopic nature revealed by spectroscopic techniques. Differential scanning calorimetry and specific heat measurements show a thermal event of small enthalpy variation taking place in the range 250-260 K, which is not due to crystallization or melting. Molecular dynamic simulations and X-ray diffraction measurements have been used to discuss the segregation of domains in the liquid structure of BzmimN(CN)(2) Raman and NMR spectroscopy measurements as a function of temperature indicate that the microscopic origin of the event observed in the calorimetric measurements comes from structural rearrangement involving the benzyl group. The results indicate that the characteristic structural heterogeneity allow for rearrangements within local domains implying the good glass-forming ability for the low viscosity ionic liquid Bzmim N(CN)(2). This work sheds light on our understanding of the microscopic origin behind complex thermal behavior of ionic liquids.
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