Impact of confinement and polarizability on dynamics of ionic liquids

Polarizability is a key factor when it comes to an accurate description of different ionic systems. The general importance of including polarizability into molecular dynamics simulations was shown in various recent studies for a wide range of materials, ranging from proteins to water to complex ionic liquids and for solid-liquid interfaces. While most previous studies focused on bulk properties or static structure factors, this study investigates in more detail the importance of polarizable surfaces on the dynamics of a confined ionic liquid in graphitic slit pores, as evident in modern electrochemical capacitors or in catalytic processes. A recently developed polarizable force field using Drude oscillators is modified in order to describe a particular room temperature ionic liquid accurately and in agreement with recently published experimental results. Using the modified parameters, various confinements are investigated and differences between non-polarizable and polarizable surfaces are discussed. Upon introduction of surface polarizability, changes in the dipole orientation and in the density distribution of the anions and cations at the interface are observed and are also accompanied with a dramatic increase in the molecular diffusivity in the contact layer. Our results thus clearly underline the importance of considering not only the polarizability of the ionic liquid but also that of the surface.

DDC Class

600: Technik

More Funding Information

This work was funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation)—Grant Nos. 390794421 and 192346071—GRK 2462 and SFB 986.

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https://creativecommons.org/licenses/by/4.0/

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Impact of confinement and polarizability on dynamics of ionic liquids