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Title: Dynamical properties of a room temperature ionic liquid: Using molecular dynamics simulations to implement a dynamic ion cage model [plus supplemental information]

Abstract

The transport behavior of ionic liquids (ILs) is pivotal for a variety of applications, especially when ILs are used as electrolytes. Many aspects of the transport dynamics of ILs remain to be understood. Here, a common ionic liquid, 1-butyl-3- methylimidazolium bis(trifluoromethylsulfonyl)imide (BmimNTf2), was studied with molecular dynamics simulations. The results show that BmimNTf2 displays typical structural relaxation, sub-diffusive behavior, and a breakdown of the Stokes-Einstein diffusion relation as in glass-forming liquids. In addition, the simulations show that the translational dynamics, reorientation dynamics, and structural relaxation dynamics are well described by the Vogel-Fulcher-Tammann equation like fragile glass forming liquids. Building on previous work that employed ion cage models, it was found that the diffusion dynamics of the cations and anions were well described by a hopping process random walk where the step time is the ion cage lifetime obtained from the cage correlation function. Detailed analysis of the ion cage structures indicated that the electrostatic potential energy of the ion cage dominates the diffusion dynamics of the caged ion. The ion orientational relaxation dynamics showed that ion reorientation is a necessary step for ion cage restructuring. The dynamic ion cage model description of ion diffusion presented here may have implications formore » designing ILs to control their transport behavior.« less

Authors:
 [1];  [2];  [2];  [2];  [3]; ORCiD logo [4]
+ Show Author Affiliations
  1. Hefei Normal University, Hefei (China); Stanford Univ., CA (United States)
  2. Hefei Normal University, Hefei (China)
  3. Anhui Normal University, Wuhu (China). Institute of Atomic and Molecular Physics
  4. Stanford Univ., CA (United States)
Publication Date:
Research Org.:
Stanford Univ., CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Anhui Higher Education Top-notch Talent of China; Anhui Provincial Natural Science Foundation; Natural Science Foundation of the Anhui Higher Education Institutions of China; Hefei Normal University
OSTI Identifier:
1781695
Alternate Identifier(s):
OSTI ID: 1570870; OSTI ID: 1781696
Grant/Contract Number:  
FG02-84ER13251; FG03-84ER13251; gxgwfx2018066; 1808085QE127; 2017QN16; 1808085QE154; KJ2017A930
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 15; Related Information: Dynamical Properties of a Room Temperature Ionic Liquid: Using Molecular Dynamics Simulations to Implement a Dynamic Ion Cage Model; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ionic liquids; Transport dynamics; Glass-forming liquids; Ion cage; Random walk

Citation Formats

Sha, Maolin, Ma, Xiaohang, Li, Na, Luo, Fabao, Zhu, Guanglai, and Fayer, Michael D. Dynamical properties of a room temperature ionic liquid: Using molecular dynamics simulations to implement a dynamic ion cage model [plus supplemental information]. United States: N. p., 2019. Web. doi:10.1063/1.5126231.
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Sha, Maolin, Ma, Xiaohang, Li, Na, Luo, Fabao, Zhu, Guanglai, & Fayer, Michael D. Dynamical properties of a room temperature ionic liquid: Using molecular dynamics simulations to implement a dynamic ion cage model [plus supplemental information]. United States. https://doi.org/10.1063/1.5126231
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Sha, Maolin, Ma, Xiaohang, Li, Na, Luo, Fabao, Zhu, Guanglai, and Fayer, Michael D. Mon . "Dynamical properties of a room temperature ionic liquid: Using molecular dynamics simulations to implement a dynamic ion cage model [plus supplemental information]". United States. https://doi.org/10.1063/1.5126231. https://www.osti.gov/servlets/purl/1781695.
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@article{osti_1781695,
title = {Dynamical properties of a room temperature ionic liquid: Using molecular dynamics simulations to implement a dynamic ion cage model [plus supplemental information]},
author = {Sha, Maolin and Ma, Xiaohang and Li, Na and Luo, Fabao and Zhu, Guanglai and Fayer, Michael D.},
abstractNote = {The transport behavior of ionic liquids (ILs) is pivotal for a variety of applications, especially when ILs are used as electrolytes. Many aspects of the transport dynamics of ILs remain to be understood. Here, a common ionic liquid, 1-butyl-3- methylimidazolium bis(trifluoromethylsulfonyl)imide (BmimNTf2), was studied with molecular dynamics simulations. The results show that BmimNTf2 displays typical structural relaxation, sub-diffusive behavior, and a breakdown of the Stokes-Einstein diffusion relation as in glass-forming liquids. In addition, the simulations show that the translational dynamics, reorientation dynamics, and structural relaxation dynamics are well described by the Vogel-Fulcher-Tammann equation like fragile glass forming liquids. Building on previous work that employed ion cage models, it was found that the diffusion dynamics of the cations and anions were well described by a hopping process random walk where the step time is the ion cage lifetime obtained from the cage correlation function. Detailed analysis of the ion cage structures indicated that the electrostatic potential energy of the ion cage dominates the diffusion dynamics of the caged ion. The ion orientational relaxation dynamics showed that ion reorientation is a necessary step for ion cage restructuring. The dynamic ion cage model description of ion diffusion presented here may have implications for designing ILs to control their transport behavior.},
doi = {10.1063/1.5126231},
journal = {Journal of Chemical Physics},
number = 15,
volume = 151,
place = {United States},
year = {Mon Oct 21 00:00:00 EDT 2019},
month = {Mon Oct 21 00:00:00 EDT 2019}
}
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