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

Santos, Cherry S.; Annapureddy, Harsha V. R.; Murthy, N. Sanjeeva; Kashyap, Hemant K.; Castner, Edward W.; Margulis, Claudio J.

doi:10.1063/1.3526958

Cited by 155 publications

(226 citation statements)

References 55 publications

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“…As expected from previous results on NTf 2 -anion ILs, 56 the part of S(q) for q > 2.0 Å −1 results from intramolecular contributions, while intermolecular interactions contribute to S(q) for q < 2.0 Å −1 . As noted above, unlike the S(q) functions for ILs with alkyl chains of n ≥ 6, no pre-peak is observed in the range of 0.25 < q < 0.50 Å −1 in the X-ray experimental data for the oligoethers.…”

Section: Molecular Dynamics Simulations-assupporting

confidence: 64%

“…As we have shown previously, 2,49,53,[56][57][58] understanding the intermediate-range order contributions to the IL structure can best be understood by partitioning the S(q) obtained from molecular simulations. Figure 7 shows the ionic partitioning, where the total S(q) is considered as the sum of structural correlations between ions as follows: 53,56 …”

Section: Molecular Dynamics Simulations-asmentioning

confidence: 99%

“…Figure 7 shows the ionic partitioning, where the total S(q) is considered as the sum of structural correlations between ions as follows: 53,56 …”

Section: Molecular Dynamics Simulations-asmentioning

confidence: 99%

“…The CL&P transferable force field for ILs, in itself a generalization of Jorgensen's OPLS-AA force field, has provided very good predictive capability for IL structures. 2,49,53,[56][57][58] The radial pair distribution functions g(r) between all atom pairs are obtained from the trajectory of the production run. The structure functions are calculated using Equation 1:…”

mentioning

confidence: 99%

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Connecting Structural and Transport Properties of Ionic Liquids with Cationic Oligoether Chains

Lall-Ramnarine

Zhao

Rodriguez

et al. 2017

J. Electrochem. Soc.

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X-ray diffraction and molecular dynamics simulations were used to probe the structures of two families of ionic liquids containing oligoether tails on the cations. Imidazolium and pyrrolidinium bis(trifluoromethylsulfonyl)amide ILs with side chains ranging from 4 to 10 atoms in length, including both linear alkyl and oligo-ethylene oxide tails, were prepared. Their physical properties, such as viscosity, conductivity and thermal profile, were measured and compared for systematic trends. Consistent with earlier literature, a single ether substituent substantially decreases the viscosity of pyrrolidinium and imidazolium ILs compared to their alkyl congeners. Remarkably, as the number of ether units in the pyrrolidinium ILs increases there is hardly any increase in the viscosity, in contrast to alkylpyrrolidinium ILs where the viscosity increases steadily with chain length. Viscosities of imidazolium ether ILs increase with chain length but always remain well below their alkyl congeners. To complement the experimentally determined properties, molecular dynamics simulations were run on the two ILs with the longest ether chains. The results point to specific aspects that could be useful for researchers designing ILs for specific applications. The focus of the ionic liquid (IL) community is shifting beyond the mere measurement of physical properties and identification of trends arising from particular structural moieties. Researchers are delving deeper into the nanostructural interactions between the ions to determine the topographical landscape of the ions within the liquids that influence IL properties.1-3 Such information is valuable when tuning the properties of ILs for particular applications. The ability to tune the properties of ionic liquids for specific applications is a major factor in their allure as remarkable solvents that make it possible to do extreme chemistry without extreme conditions. It has been acknowledged that although ionic liquids have a combination of physical properties that make them attractive alternatives to traditional solvents, they have relatively high viscosities that hamper their practical application in large-scale processes. For example, in the area of electrochemical energy storage devices there is still an urgent need for improved electrolytes exhibiting properties of combustion resistance, high conductivity, and wide electrochemical windows. ILs with improved transport properties (viscosity, conductivity and diffusivity) would be perfect candidates to address this need. Structural modification of the IL cation and anion is a proven tool to dramatically alter IL properties. In particular, substituting ether functionalities for alkyl functionalities on IL cations has been shown to reduce the viscosity of ionic liquids significantly.2,4-6 In this work we examine the effect of incorporating oligoether side chains of varying lengths (1-3 repeating ethoxy units, Figure 1) on the physical properties and structural characteristics of imidazolium and pyrrolidinium NTf 2 ionic liquids in ...

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Section: Molecular Dynamics Simulations-assupporting

confidence: 64%

Section: Molecular Dynamics Simulations-asmentioning

confidence: 99%

“…Figure 7 shows the ionic partitioning, where the total S(q) is considered as the sum of structural correlations between ions as follows: 53,56 …”

Section: Molecular Dynamics Simulations-asmentioning

confidence: 99%

mentioning

confidence: 99%

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Connecting Structural and Transport Properties of Ionic Liquids with Cationic Oligoether Chains

Lall-Ramnarine

Zhao

Rodriguez

et al. 2017

J. Electrochem. Soc.

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“…Instead, it means that a complete analysis of the experimental data necessitates computational work in order to fully dissect the different ionic and sub-ionic contributions to S(q). 40,41 The purpose of this Communication is to give physical interpretation to the anomalous behavior observed experimentally and computationally at the smallest scattering vectors corresponding to the prepeak region in the case of popular tetradecyltrihexylphosphonium based ionic liquids. As far as we are aware, in most ILs for which temperature dependent X-ray scattering studies have been performed, the prepeak indicative of polar-apolar alternation decreases in intensity as temperature is increased in the liquid phase.…”

mentioning

confidence: 99%

Communication: Anomalous temperature dependence of the intermediate range order in phosphonium ionic liquids

Hettige

Kashyap

Margulis

2014

The Journal of Chemical Physics

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In a recent article by the Castner and Margulis groups [Faraday Discuss. 154, 133 (2012)], we described in detail the structure of the tetradecyltrihexylphosphonium bis(trifluoromethylsulfonyl)-amide ionic liquid as a function of temperature using X-ray scattering, and theoretical partitions of the computationally derived structure function. Interestingly, and as opposed to the case in most other ionic-liquids, the first sharp diffraction peak or prepeak appears to increase in intensity as temperature is increased. This phenomenon is counter intuitive as one would expect that intermediate range order fades as temperature increases. This Communication shows that a loss of hydrophobic tail organization at higher temperatures is counterbalanced by better organization of polar components giving rise to the increase in intensity of the prepeak.

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Nanoconfined Ionic Liquids

Marcinkowski

Kloskowski

Namieśnik

2019

Handbook of Smart Materials in Analytical Chemistry

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

Cited by 155 publications

References 55 publications

Connecting Structural and Transport Properties of Ionic Liquids with Cationic Oligoether Chains

Connecting Structural and Transport Properties of Ionic Liquids with Cationic Oligoether Chains

Communication: Anomalous temperature dependence of the intermediate range order in phosphonium ionic liquids

Nanoconfined Ionic Liquids

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