title: A molecular dynamics investigation of the structural and dynamic properties of the ionic liquid 1-n-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide.
abstract: Molecular dynamics simulations have been performed to investigate the structure and dynamics of the ionic liquid, 1-n-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C(4)mim][Tf(2)N]) in the temperature range of 283-460 K. Extensive analysis was carried out to characterize a number of structural and dynamic features. Transport properties were computed using a variety of equilibrium methods that employed the Green-Kubo and Einstein formulations. Nonequilibrium techniques were also used. In general, different methods mostly yielded consistent results, although some differences were observed. Computed self-diffusivities and ionic conductivities tended to be slightly lower than experimental values, while computed viscosities were significantly higher than experiment. Computed thermal conductivities agreed reasonably well with experimental data. Despite these discrepancies, the simulations capture the experimental temperature-dependent trends for all these transport properties. Single ion dynamics were studied by examining diffusional anisotropy, the self-part of the van Hove function, non-Gaussian parameters, and incoherent intermediate scattering functions. It is found that cations diffuse faster than anions and are more dynamically heterogeneous. A clear anisotropy is revealed in cation displacement, with the motion normal to the imidazolium ring plane being the most hindered and the motion along the alkyl chain in the plane of the ring being the most facile. Cations structurally relax faster than anions but they rotationally relax slower than anions. There is a pronounced temperature dependence to the rotational anisotropy of the cations, but only a weak temperature dependence for the anions. The ionic conductivity deviates from the Nernst-Einstein relation due to the correlated motion of cations and anions. The results suggest that the dynamical behavior of this and related ionic liquids is extremely complex and consists of many different modes with widely varying timescales, making the prediction of dynamical trends extremely difficult.
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame, Indiana 46556, USA. hliu4@nd.edu
authors.forename: Hongjun
authors.initials: H
authors.lastname: Liu
authors.forename: Edward
authors.initials: E
authors.lastname: Maginn
mesh_terms: D007093:Imidazoles / Q000737:chemistry*; D007094:Imides / Q000737:chemistry*; D052578:Ionic Liquids / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D013816:Thermodynamics
chemical_list: C569906:1-n-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide; D007093:Imidazoles; D007094:Imides; D052578:Ionic Liquids