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Title: Effect of an external electric field on the dynamics and intramolecular structures of ions in an ionic liquid

Abstract

Simulations of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide in an external electric field have been performed using a Drude particle polarizable force field. The structure of the ions has been analyzed, with close attention paid to the configurations of the ions. The “charge arm” concept is used to explain certain changes of these configurations that would be difficult to rationalize otherwise, e.g., trans → cis isomerization of the bis(trifluoromethylsulfonyl)imide anion and extension of the alkyl chain of the cation. It has also been shown that the ions orient themselves so that their charge arms align with and stretch out along the field, and these effects occur at lower external electric field strengths than cause a change in the inherent diffusion of the ions. Here, the dynamics of the system parallel and perpendicular to the field were analyzed, and it was found that the applied field affected the diffusion normal to the field. This is explained as a secondary effect of a change in the ion cage formed by the surrounding counterions of a given ion in the ionic liquid. The breakdown of the ion cages was rationalized by correlating changes to the inherent diffusion of the ions with other changes tomore » the diffusion and bulk structure of the liquid, as well as considering the average forces on the ions compared to the force the ions would be expected to experience in an electric field. Parallel to the field, a drift was observed at every electric field studied. In electric fields with no changes to the ion cage structure, the relationship between the drift and electric field was found to be linear, becoming nonlinear as the ion cage structure breaks down.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Imperial College, London (United Kingdom)
  2. Univ. of Bonn (Germany)
  3. Virginia Commonwealth Univ., Richmond, VA (United States)
Publication Date:
Research Org.:
Virginia Commonwealth Univ., Richmond, VA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1638250
Alternate Identifier(s):
OSTI ID: 1571837
Grant/Contract Number:  
SC0004406
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 16; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electrostatics; isomerization; ionic liquids; polarizable force fields; Brownian motion; physical quantities; Drude oscillator

Citation Formats

Clark, Ryan, von Domaros, Michael, McIntosh, Alastair J. S., Luzar, Alenka, Kirchner, Barbara, and Welton, Tom. Effect of an external electric field on the dynamics and intramolecular structures of ions in an ionic liquid. United States: N. p., 2019. Web. doi:10.1063/1.5129367.
Clark, Ryan, von Domaros, Michael, McIntosh, Alastair J. S., Luzar, Alenka, Kirchner, Barbara, & Welton, Tom. Effect of an external electric field on the dynamics and intramolecular structures of ions in an ionic liquid. United States. https://doi.org/10.1063/1.5129367
Clark, Ryan, von Domaros, Michael, McIntosh, Alastair J. S., Luzar, Alenka, Kirchner, Barbara, and Welton, Tom. Fri . "Effect of an external electric field on the dynamics and intramolecular structures of ions in an ionic liquid". United States. https://doi.org/10.1063/1.5129367. https://www.osti.gov/servlets/purl/1638250.
@article{osti_1638250,
title = {Effect of an external electric field on the dynamics and intramolecular structures of ions in an ionic liquid},
author = {Clark, Ryan and von Domaros, Michael and McIntosh, Alastair J. S. and Luzar, Alenka and Kirchner, Barbara and Welton, Tom},
abstractNote = {Simulations of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide in an external electric field have been performed using a Drude particle polarizable force field. The structure of the ions has been analyzed, with close attention paid to the configurations of the ions. The “charge arm” concept is used to explain certain changes of these configurations that would be difficult to rationalize otherwise, e.g., trans → cis isomerization of the bis(trifluoromethylsulfonyl)imide anion and extension of the alkyl chain of the cation. It has also been shown that the ions orient themselves so that their charge arms align with and stretch out along the field, and these effects occur at lower external electric field strengths than cause a change in the inherent diffusion of the ions. Here, the dynamics of the system parallel and perpendicular to the field were analyzed, and it was found that the applied field affected the diffusion normal to the field. This is explained as a secondary effect of a change in the ion cage formed by the surrounding counterions of a given ion in the ionic liquid. The breakdown of the ion cages was rationalized by correlating changes to the inherent diffusion of the ions with other changes to the diffusion and bulk structure of the liquid, as well as considering the average forces on the ions compared to the force the ions would be expected to experience in an electric field. Parallel to the field, a drift was observed at every electric field studied. In electric fields with no changes to the ion cage structure, the relationship between the drift and electric field was found to be linear, becoming nonlinear as the ion cage structure breaks down.},
doi = {10.1063/1.5129367},
journal = {Journal of Chemical Physics},
number = 16,
volume = 151,
place = {United States},
year = {2019},
month = {10}
}

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Figures / Tables:

TABLE I TABLE I: Diffusion coefficients ($D$) and effective diffusion coefficients ($D$eff) of the cation and anion in the $z$ direction.

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Works referenced in this record:

Disordering and Reordering of Ionic Liquids under an External Electric Field
journal, August 2009

  • Wang, Yanting
  • The Journal of Physical Chemistry B, Vol. 113, Issue 32
  • DOI: 10.1021/jp906228d

Reversible tuning of the hydrophobic–hydrophilic transition of hydrophobic ionic liquids by means of an electric field
journal, January 2011

  • Sha, Maolin; Niu, Dongxiao; Dou, Qiang
  • Soft Matter, Vol. 7, Issue 9
  • DOI: 10.1039/c1sm05027c

Electromagnetic field effects on binary dimethylimidazolium-based ionic liquid/water solutions
journal, January 2009

  • English, Niall J.; Mooney, Damian A.
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 41
  • DOI: 10.1039/b910462c

Ion-Cage Interpretation for the Structural and Dynamic Changes of Ionic Liquids under an External Electric Field
journal, April 2013

  • Shi, Rui; Wang, Yanting
  • The Journal of Physical Chemistry B, Vol. 117, Issue 17
  • DOI: 10.1021/jp311017r

Structure of ionic liquids under external electric field: a molecular dynamics simulation
journal, March 2012


Long range electrostatic forces in ionic liquids
journal, January 2017

  • Gebbie, Matthew A.; Smith, Alexander M.; Dobbs, Howard A.
  • Chemical Communications, Vol. 53, Issue 7
  • DOI: 10.1039/c6cc08820a

Behavior of Deep Eutectic Solvents under External Electric Fields: A Molecular Dynamics Approach
journal, December 2016

  • Atilhan, Mert; Aparicio, Santiago
  • The Journal of Physical Chemistry B, Vol. 121, Issue 1
  • DOI: 10.1021/acs.jpcb.6b09714

Thermalized Drude Oscillators with the LAMMPS Molecular Dynamics Simulator
journal, December 2015

  • Dequidt, Alain; Devémy, Julien; Pádua, Agílio A. H.
  • Journal of Chemical Information and Modeling, Vol. 56, Issue 1
  • DOI: 10.1021/acs.jcim.5b00612

Application of ionic liquids in electrochemical sensing systems
journal, January 2011


Ionic velocities in an ionic liquid under high electric fields using all-atom and coarse-grained force field molecular dynamics
journal, January 2009

  • Daily, John W.; Micci, Michael M.
  • The Journal of Chemical Physics, Vol. 131, Issue 9
  • DOI: 10.1063/1.3197850

Solute Diffusion in Ionic Liquids, NMR Measurements and Comparisons to Conventional Solvents
journal, September 2013

  • Kaintz, Anne; Baker, Gary; Benesi, Alan
  • The Journal of Physical Chemistry B, Vol. 117, Issue 39
  • DOI: 10.1021/jp405393d

Double Layer Structure of Ionic Liquids at the Au(111) Electrode Interface: An Atomic Force Microscopy Investigation
journal, March 2011

  • Hayes, Robert; Borisenko, Natalia; Tam, Matthew K.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 14, p. 6855-6863
  • DOI: 10.1021/jp200544b

Diffuse-charge dynamics of ionic liquids in electrochemical systems
journal, November 2011


Free and Bound States of Ions in Ionic Liquids, Conductivity, and Underscreening Paradox
journal, May 2019


Self-assembly in the electrical double layer of ionic liquids
journal, January 2011

  • Perkin, Susan; Crowhurst, Lorna; Niedermeyer, Heiko
  • Chemical Communications, Vol. 47, Issue 23
  • DOI: 10.1039/c1cc11322d

Surface forces generated by the action of electric fields across liquid films
journal, January 2019

  • Perez-Martinez, Carla Sofia; Perkin, Susan
  • Soft Matter, Vol. 15, Issue 21
  • DOI: 10.1039/c9sm00143c

Ionic Liquids at Electrified Interfaces
journal, March 2014

  • Fedorov, Maxim V.; Kornyshev, Alexei A.
  • Chemical Reviews, Vol. 114, Issue 5
  • DOI: 10.1021/cr400374x

Conductivity of molten sodium chloride in an arbitrarily weak dc electric field
journal, September 2005

  • Delhommelle, Jerome; Cummings, Peter T.; Petravic, Janka
  • The Journal of Chemical Physics, Vol. 123, Issue 11
  • DOI: 10.1063/1.2035085

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


Structure in Confined Room-Temperature Ionic Liquids
journal, April 2007

  • Atkin, Rob; Warr, Gregory G.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 13
  • DOI: 10.1021/jp067420g

Conductivity of molten sodium chloride and its supercritical vapor in strong dc electric fields
journal, January 2003

  • Petravic, Janka; Delhommelle, Jérôme
  • The Journal of Chemical Physics, Vol. 118, Issue 16
  • DOI: 10.1063/1.1562612

Very Different Responses to Electromagnetic Fields in Binary Ionic Liquid-Water Solutions
journal, July 2009

  • English, Niall J.; Mooney, Damian A.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 30
  • DOI: 10.1021/jp902500m

Interfacial ionic ‘liquids’: connecting static and dynamic structures
journal, December 2014


The relationship between ionic structure and viscosity in room-temperature ionic liquids
journal, September 2008

  • Li, Hualin; Ibrahim, Murvat; Agberemi, Ismail
  • The Journal of Chemical Physics, Vol. 129, Issue 12
  • DOI: 10.1063/1.2978378

Time-dependent density functional theory for the charging kinetics of electric double layer containing room-temperature ionic liquids
journal, November 2016

  • Lian, Cheng; Zhao, Shuangliang; Liu, Honglai
  • The Journal of Chemical Physics, Vol. 145, Issue 20
  • DOI: 10.1063/1.4968037

PACKMOL: A package for building initial configurations for molecular dynamics simulations
journal, October 2009

  • Martínez, L.; Andrade, R.; Birgin, E. G.
  • Journal of Computational Chemistry, Vol. 30, Issue 13
  • DOI: 10.1002/jcc.21224

Modern Room Temperature Ionic Liquids, a Simple Guide to Understanding Their Structure and How It May Relate to Dynamics
journal, August 2015

  • Araque, Juan C.; Hettige, Jeevapani J.; Margulis, Claudio J.
  • The Journal of Physical Chemistry B, Vol. 119, Issue 40
  • DOI: 10.1021/acs.jpcb.5b05506

Ionic liquids: a brief history
journal, April 2018


Redox potentials and screening in ionic liquids: Effects of sizes and shapes of solute ions
journal, November 2008

  • Lynden-Bell, R. M.
  • The Journal of Chemical Physics, Vol. 129, Issue 20
  • DOI: 10.1063/1.3020439

Perspectives on external electric fields in molecular simulation: progress, prospects and challenges
journal, January 2015

  • English, Niall J.; Waldron, Conor J.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 19
  • DOI: 10.1039/c5cp00629e

Ionic liquids as electrolytes
journal, August 2006


Ionic Liquids in Electrochemical Devices and Processes: Managing Interfacial Electrochemistry
journal, November 2007

  • MacFarlane, Douglas R.; Forsyth, Maria; Howlett, Patrick C.
  • Accounts of Chemical Research, Vol. 40, Issue 11
  • DOI: 10.1021/ar7000952

Ion Association in [bmim][PF 6 ]/Naphthalene Mixtures: An Experimental and Computational Study
journal, June 2008

  • Del Pópolo, M. G.; Mullan, C. L.; Holbrey, J. D.
  • Journal of the American Chemical Society, Vol. 130, Issue 22
  • DOI: 10.1021/ja710841n

Ionic liquids in confined geometries
journal, January 2012

  • Perkin, Susan
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 15
  • DOI: 10.1039/c2cp23814d

Molecular Dynamics Simulations of Ionic Liquids and Electrolytes Using Polarizable Force Fields
journal, May 2019


Structure and Nanostructure in Ionic Liquids
journal, June 2015

  • Hayes, Robert; Warr, Gregory G.; Atkin, Rob
  • Chemical Reviews, Vol. 115, Issue 13
  • DOI: 10.1021/cr500411q

Dilute or Concentrated Electrolyte Solutions? Insight from Ionic Liquid/Water Electrolytes
journal, August 2015


Ionic liquids in external electric and electromagnetic fields: a molecular dynamics study
journal, February 2011


Molecular Force Field for Ionic Liquids Composed of Triflate or Bistriflylimide Anions
journal, October 2004

  • Canongia Lopes, José N.; Pádua, Agílio A. H.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 43
  • DOI: 10.1021/jp0476545

VMD: Visual molecular dynamics
journal, February 1996


Salts dissolved in salts: ionic liquid mixtures
journal, January 2011

  • Lui, Matthew Y.; Crowhurst, Lorna; Hallett, Jason P.
  • Chemical Science, Vol. 2, Issue 8
  • DOI: 10.1039/c1sc00227a

Interfacial Ionic Liquids: Connecting Static and Dynamic Structures
text, January 2014