Molecular Dynamic Simulations of Ionic Liquids: A Reliable Description of Structure, Thermodynamics and Dynamics

The parameterization of a new force‐field and its validation for the liquid description of five imidazolium‐based ionic liquids [Cnmim][NTf2] (n=1,2,4,6,8) are described. The proposed force‐field is derived to reproduce densities, self‐diffusion coefficients for cations and ions as well as NMR rotat...

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Bibliographic Details
Published in:Chemphyschem 2007-12, Vol.8 (17), p.2464-2470
Main Authors: Köddermann, Thorsten, Paschek, Dietmar, Ludwig, Ralf
Format: Article
Language:English
Subjects:
Chemistry
Computer Simulation
Exact sciences and technology
force-field calculations
General and physical chemistry
ionic liquids
Ionic Liquids - chemistry
molecular dynamics
Molecular Structure
Solutions
Solvation. Solvent properties
Thermodynamics
Time Factors
Viscosity
Volatilization
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Summary:The parameterization of a new force‐field and its validation for the liquid description of five imidazolium‐based ionic liquids [Cnmim][NTf2] (n=1,2,4,6,8) are described. The proposed force‐field is derived to reproduce densities, self‐diffusion coefficients for cations and ions as well as NMR rotational correlation times for cations and water molecules in [C2mim][NTf2]. The temperature dependence and the cation chain‐length dependence of these properties is described well. Very good agreement between simulated and experimental values for the heats of vaporization, shear viscosities and NMR rotational correlation times is also achieved. All properties are crucial for understanding the nature and interaction of ionic liquids. The good performance of the new force‐field suggests that the Lennard–Jones interactions previously were strongly overestimated. The given force‐field now allows us to investigate other important properties of this class of ionic liquids such as the micro segregation of ionic liquids, ion pair formation, lifetimes of ion pairs and the solvent dependency of these properties. Move with the force: A new force field for simulating imidazolium‐based ionic liquids [Cnmim][NTf2] (see figure) reproduces with good agreement the experimental values for the heats of vaporization, shear viscosities and NMR rotational correlation times. The results suggest that the inaccuracies arising from previous methods are due to the overestimation of the Lennard–Jones interactions.
ISSN:1439-4235
1439-7641
DOI:10.1002/cphc.200700552