Ionic liquids—Conventional solvent mixtures, structurally different but dynamically similar

Araque, Juan C.; Hettige, Jeevapani J.; Margulis, Claudio J.

doi:10.1063/1.4932331

Title: Ionic liquids—Conventional solvent mixtures, structurally different but dynamically similar

Journal Article · Tue Oct 06 00:00:00 EDT 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4932331· OSTI ID:1469475

^[1]; Hettige, Jeevapani J. ^[1]; Margulis, Claudio J. ^[1]

Univ. of Iowa, Iowa City, IA (United States). Dept. of Chemistry

In more ways than one, pure ionic liquids (ILs) can be seen as mixtures. By definition they are comprised of cationic and anionic components and they also possess dual charge and apolar characteristics. We recently uncovered interesting dynamical behavior [Araque et al., J. Phys. Chem. B 119(23), 7015 (2015)] that can be ascribed to this duality. For small neutral solutes local friction can be high in certain regions and much lower in others. It is only reasonable to ask whether this interesting behavior is unique to ILs or is also common in certain conventional solvent mixtures such as dimethylsufoxide/glycerol for which the viscosity can be tuned to be similar. We make the case that the latter scenario is correct and that whereas viscous conventional solvent mixtures are structurally very different from ILs, dynamically they are not. From the perspective of a solute that is small, both ILs and viscous conventional solvent mixtures display frictionally stiff and soft regions associated with cage and jump diffusive regimes. In the case of ILs these are associated with charge-enhanced and charge-depleted liquid regions, whereas in the case of the conventional solvents by the distinct frictional properties of the two components.

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Research Organization:: Univ. of Iowa, Iowa City, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: SC0008644

OSTI ID:: 1469475

Alternate ID(s):: OSTI ID: 1223040

Journal Information:: Journal of Chemical Physics, Vol. 143, Issue 13; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 35 works

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Heterogeneity in the microstructure and dynamics of tetraalkylammonium hydroxide ionic liquids: insight from classical molecular dynamics simulations and Voronoi tessellation analysis Reddy, Th. Dhileep N.; Mallik, Bhabani S. Physical Chemistry Chemical Physics, Vol. 22, Issue 6 https://doi.org/10.1039/c9cp06796e	journal	January 2020
Communication: Nanoscale structure of tetradecyltrihexylphosphonium based ionic liquids Hettige, Jeevapani J.; Araque, Juan C.; Kashyap, Hemant K. The Journal of Chemical Physics, Vol. 144, Issue 12 https://doi.org/10.1063/1.4944678	journal	March 2016
In an ionic liquid, high local friction is determined by the proximity to the charge network Araque, Juan C.; Margulis, Claudio J. The Journal of Chemical Physics, Vol. 149, Issue 14 https://doi.org/10.1063/1.5045675	journal	October 2018

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Title: Ionic liquids—Conventional solvent mixtures, structurally different but dynamically similar

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