Temperature Dependence of Volumetric and Dynamic Properties of Imidazolium-Based Ionic Liquids.

Abstract

Atomistically detailed molecular dynamics simulations were used to investigate the temperature dependence of the specific volume, dynamic properties, and viscosity of linear alkyl chain ([CnC1Im][NTf2], n = 3-7) and branched alkyl chain ([(n - 2)mCn-1C1Im][NTf2]) ionic liquids (ILs). The trend of the glass transition temperature (Tg) values obtained in the simulations as a function of the alkyl chain length of cations was similar to the trend seen in experiments. In addition, the system relaxation behavior as determined from the temperature dependence of the diffusion coefficient, rotational relaxation time, and viscosity close to Tg was observed to follow the Vogel-Fulcher-Tammann expression. Furthermore, the reciprocal of the diffusion coefficient of the anion and cation in both linear and branched IL systems showed a linear correlation with viscosity, thus confirming the validity of the Stokes-Einstein relationship for these systems. Similarly, the average rotational relaxation time of the ions was also found to correlate linearly with the viscosity of the ILs over a wide range of temperatures, thereby validating the Debye-Stokes-Einstein relationship for the ILs. These simulation findings suggest that the temperature dependence of the relaxation time of ILs is very similar to that of other glass-forming liquids.