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Title: Investigation of Dynamics in BMIM TFSA Ionic Liquid through Variable Temperature and Pressure NMR Relaxometry and Diffusometry

Abstract

A comprehensive variable temperature, pressure and frequency multinuclear (1H, 2H, and 19F) magnetic resonance study was undertaken on selectively deuterated 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (BMIM TFSA) ionic liquid isotopologues. This study builds on our earlier investigation of the effects of increasing alkyl chain length on diffusion and dynamics in imidazolium-based TFSA ionic liquids. Fast field cycling 1H T1 data revealed multiple modes of motion. Through calculation of diffusion coefficient (D) values and activation energies, the low- and high-field regimes were assigned to the translational and reorientation dynamics respectively. Variable-pressure 2H T1 measurements reveal site-dependent interactions in the cation with strengths in the order MD3 > CD3 > CD2, indicating dissimilarities in the electric field gradients along the alkyl chain, with the CD2 sites having the largest gradient. Additionally, the α saturation effect in T1 vs. P was observed for all three sites, suggesting significant reduction of the short-range rapid reorientational dynamics. This reduction was also deduced from the variable pressure 1H T1 data, which showed an approach to saturation for both the methyl and butyl group terminal methyl sites. Pressure-dependent D measurements show independent motions for both cations and anions, with the cations having greater D values over the entire pressure range.

Authors:
 [1];  [2];  [3];  [4];  [1];  [5];  [6];  [7];  [1]
  1. Hunter College, New York, NY (United States). Dept. of Physics; CUNY Graduate School, New York, NY (United States)
  2. Hunter College, New York, NY (United States). Dept. of Physics; CUNY Graduate School, New York, NY (United States); Univ. of Puerto Rico, Mayaguez, PR (United States). Dept. of Physics
  3. CUNY Graduate School, New York, NY (United States); Brooklyn College, Brooklyn, NY (United States). Physics Dept.
  4. Hunter College, New York, NY (United States). Dept. of Physics
  5. Univ. of Kelaniya (Sri Lanka). Dept. of Physics
  6. CUNY Graduate School, New York, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
  7. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Brooklyn College, Brooklyn, NY (United States); Hunter College, New York, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Professional Staff Congress City Univ. of New York (PSC CUNY) (United States); Office of Naval Research (ONR) (United States)
Contributing Org.:
CUNY Graduate School, New York, NY (United States); Univ. of Puerto Rico, Mayaguez, PR (United States); Univ. of Kelaniya (Sri Lanka)
OSTI Identifier:
1358032
Report Number(s):
BNL-113880-2017-JA
Journal ID: ISSN 0013-4651; R&D Project: CO-004; KC0301010
Grant/Contract Number:  
AC02-98CH10886; SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 164; Journal Issue: 8; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; BMIM TFSA; FFC NMR; PGSE; NMR; variable pressure; ionic liquid

Citation Formats

Pilar, Kartik, Rua, Armando, Suarez, Sophia N., Mallia, Christopher, Lai, Shen, Jayakody, J. R. P., Hatcher, Jasmine L., Wishart, James F., and Greenbaum, Steve. Investigation of Dynamics in BMIM TFSA Ionic Liquid through Variable Temperature and Pressure NMR Relaxometry and Diffusometry. United States: N. p., 2017. Web. https://doi.org/10.1149/2.0301708jes.
Pilar, Kartik, Rua, Armando, Suarez, Sophia N., Mallia, Christopher, Lai, Shen, Jayakody, J. R. P., Hatcher, Jasmine L., Wishart, James F., & Greenbaum, Steve. Investigation of Dynamics in BMIM TFSA Ionic Liquid through Variable Temperature and Pressure NMR Relaxometry and Diffusometry. United States. https://doi.org/10.1149/2.0301708jes
Pilar, Kartik, Rua, Armando, Suarez, Sophia N., Mallia, Christopher, Lai, Shen, Jayakody, J. R. P., Hatcher, Jasmine L., Wishart, James F., and Greenbaum, Steve. Thu . "Investigation of Dynamics in BMIM TFSA Ionic Liquid through Variable Temperature and Pressure NMR Relaxometry and Diffusometry". United States. https://doi.org/10.1149/2.0301708jes. https://www.osti.gov/servlets/purl/1358032.
@article{osti_1358032,
title = {Investigation of Dynamics in BMIM TFSA Ionic Liquid through Variable Temperature and Pressure NMR Relaxometry and Diffusometry},
author = {Pilar, Kartik and Rua, Armando and Suarez, Sophia N. and Mallia, Christopher and Lai, Shen and Jayakody, J. R. P. and Hatcher, Jasmine L. and Wishart, James F. and Greenbaum, Steve},
abstractNote = {A comprehensive variable temperature, pressure and frequency multinuclear (1H, 2H, and 19F) magnetic resonance study was undertaken on selectively deuterated 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (BMIM TFSA) ionic liquid isotopologues. This study builds on our earlier investigation of the effects of increasing alkyl chain length on diffusion and dynamics in imidazolium-based TFSA ionic liquids. Fast field cycling 1H T1 data revealed multiple modes of motion. Through calculation of diffusion coefficient (D) values and activation energies, the low- and high-field regimes were assigned to the translational and reorientation dynamics respectively. Variable-pressure 2H T1 measurements reveal site-dependent interactions in the cation with strengths in the order MD3 > CD3 > CD2, indicating dissimilarities in the electric field gradients along the alkyl chain, with the CD2 sites having the largest gradient. Additionally, the α saturation effect in T1 vs. P was observed for all three sites, suggesting significant reduction of the short-range rapid reorientational dynamics. This reduction was also deduced from the variable pressure 1H T1 data, which showed an approach to saturation for both the methyl and butyl group terminal methyl sites. Pressure-dependent D measurements show independent motions for both cations and anions, with the cations having greater D values over the entire pressure range.},
doi = {10.1149/2.0301708jes},
journal = {Journal of the Electrochemical Society},
number = 8,
volume = 164,
place = {United States},
year = {2017},
month = {5}
}

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