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Impact of confinement and polarizability on dynamics of ionic liquids


Gäding, Johannes; Tocci, Gabriele; Busch, Mark; Huber, Patrick; Meißner, Robert H (2022). Impact of confinement and polarizability on dynamics of ionic liquids. Journal of Chemical Physics, 156(6):064703.

Abstract

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.

Abstract

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.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > General Physics and Astronomy
Physical Sciences > Physical and Theoretical Chemistry
Uncontrolled Keywords:Physical and Theoretical Chemistry, General Physics and Astronomy
Language:English
Date:14 February 2022
Deposited On:31 Jan 2023 18:32
Last Modified:28 Jun 2024 01:38
Publisher:American Institute of Physics
ISSN:0021-9606
OA Status:Hybrid
Publisher DOI:https://doi.org/10.1063/5.0077408
PubMed ID:35168338
Project Information:
  • : FunderDeutsche Forschungsgemeinschaft
  • : Grant ID390794421
  • : Project Title
  • : FunderDeutsche Forschungsgemeinschaft
  • : Grant ID192346071
  • : Project Title
  • : FunderDeutsche Forschungsgemeinschaft
  • : Grant IDSFB 986
  • : Project Title
  • Content: Published Version
  • Language: English
  • Licence: Creative Commons: Attribution 4.0 International (CC BY 4.0)
  • Content: Accepted Version
  • Language: English