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Title: Temperature-dependent structure of methyltributylammonium bis(trifluoromethylsulfonyl)amide: X ray scattering and simulations

Authors:
; ; ; ; ;  [1];  [2]
  1. Rutgers
  2. (
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
National Science Foundation (NSF)
OSTI Identifier:
1223999
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 134; Journal Issue: 6
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Santos, Cherry S., Annapureddy, Harsha V.R., Murthy, N. Sanjeeva, Kashyap, Hemant K., Castner, Jr., Edward W., Margulis, Claudio J., and Iowa). Temperature-dependent structure of methyltributylammonium bis(trifluoromethylsulfonyl)amide: X ray scattering and simulations. United States: N. p., 2015. Web. doi:10.1063/1.3526958.
Santos, Cherry S., Annapureddy, Harsha V.R., Murthy, N. Sanjeeva, Kashyap, Hemant K., Castner, Jr., Edward W., Margulis, Claudio J., & Iowa). Temperature-dependent structure of methyltributylammonium bis(trifluoromethylsulfonyl)amide: X ray scattering and simulations. United States. doi:10.1063/1.3526958.
Santos, Cherry S., Annapureddy, Harsha V.R., Murthy, N. Sanjeeva, Kashyap, Hemant K., Castner, Jr., Edward W., Margulis, Claudio J., and Iowa). Thu . "Temperature-dependent structure of methyltributylammonium bis(trifluoromethylsulfonyl)amide: X ray scattering and simulations". United States. doi:10.1063/1.3526958.
@article{osti_1223999,
title = {Temperature-dependent structure of methyltributylammonium bis(trifluoromethylsulfonyl)amide: X ray scattering and simulations},
author = {Santos, Cherry S. and Annapureddy, Harsha V.R. and Murthy, N. Sanjeeva and Kashyap, Hemant K. and Castner, Jr., Edward W. and Margulis, Claudio J. and Iowa)},
abstractNote = {},
doi = {10.1063/1.3526958},
journal = {Journal of Chemical Physics},
number = 6,
volume = 134,
place = {United States},
year = {Thu Oct 15 00:00:00 EDT 2015},
month = {Thu Oct 15 00:00:00 EDT 2015}
}
  • In this article we determine the temperature-dependent structure of the tetradecyltrihexylphosphonium bis(trifluoromethylsulfonyl)amide ionic liquid using a combination of X-ray scattering and molecular dynamics simulations. As in many other room-temperature ionic liquids three characteristic intermolecular peaks can be detected in the structure function S(q). A prepeak or first sharp diffraction peak is observed at about q = 0.42 {angstrom}{sup -1}. Long range anion-anion correlations are the most important contributors to this peak. In all systems we have studied to date, this prepeak is a signature of solvation asymmetry. The peak in S(q) near q = 0.75 {angstrom}{sup -1} is the signaturemore » of ionic alternation and arises from the charge ordered separation of ions of the same charge. The most intense diffraction peak near q = 1.37 {angstrom}{sup -1} arises from short-range separation between ions of opposite charge combined with a significant contribution from cationic carbon-carbon interactions, indicating that cationic hydrophobic tails have significant contacts.« less
  • The reaction between the tantalum compound TaCl3[N(TMS)2]2 and the hydridic reducing agent sodium bis(2-methoxyethoxy)aluminum hydride (Vitride) has been investigated in toluene solution at room temperature and found to afford the dimeric aluminate complex [NaAl{N(TMS)2}(OCH2CH2OMe)3]2 as the sole isolable product. The molecular structure of the product establishes the existence of a four-coordinate aluminum atom and the formal transfer of the 2-methoxyethoxy and bis(trimethylsilyl)amide groups to the aluminate product. The aggregation of two NaAl{N(TMS)2}(OCH2CH2OMe)3 units serves to bind the two sodium cations in a crown-ether fashion through six ancillary oxygen atoms.
  • Two-dimensional NP{sub xy}T and isostress-osmotic (N{sub 2}P{sub xy}Tf{sub 1}) Monte Carlo simulations were used to compute the density and gas absorption properties of the ionic liquid (IL) 1-n-hexyl-3- methylimidazolium bis(Trifluoromethylsulfonyl)amide ([hmim][Tf{sub 2}N]) confined in silica slit pores (25-45 Å). Self-diffusivity values for both gas and IL were calculated from NVE molecular dynamics simulations using both smooth and atomistic potential models for the silica. Simulations show that the molar volume for [hmim][Tf{sub 2}N] confined in 25-45 Å silica slit pores are 12-31% larger than for the bulk IL at 313-573 K and 1 bar. The amounts of CO{sub 2}, H{sub 2},more » and N{sub 2} absorbed in the confined IL are typically 1.1-3 times larger than in the bulk IL due to larger molar volumes for the confined IL compared to the bulk IL. The CO{sub 2}, N{sub 2}, and H{sub 2} molecules are generally absorbed close to the silica wall where the IL density is very low. This arrangement causes the self-diffusivities for these gases in the confined IL to be 2 to 8 times larger than in the bulk IL at 298-573 K. The solubility for water in the confined and bulk ILs are similar, which is likely due to strong water interactions with [hmim][Tf{sub 2}N] through hydrogen-bonding resulting in the confined IL molar volume playing a less important role in determining H{sub 2}O solubility. Water molecules were largely absorbed in the IL-rich region rather than close to the silica wall. The self-diffusivities for water correlate with the confined IL. The confined IL exhibits self-diffusivities larger than the bulk IL at lower temperatures, but smaller than the bulk IL at higher temperatures. The findings from simulations are consistent with available experimental data for similar confined IL systems.« less