Communication: Stiff and soft nano-environments and the “Octopus Effect” are the crux of ionic liquid structural and dynamicalheterogeneity

In a recent set of articles [J. C. Araque et al., J. Phys.Chem. B 119(23), 7015–7029 (2015) and J. C. Araque etal., J. Chem. Phys. 144, 204504 (2016)], we proposed the idea thatfor small neutral and charged solutes dissolved in ionic liquids, deviation from simplehydrodynamic predictions in translat...

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Bibliographic Details
Published in:The Journal of chemical physics 2017-08, Vol.147 (6)
Main Authors: Daly, Ryan P, Araque, Juan C, Margulis, Claudio J
Format: Article
Language:English
Subjects:
Charge density
Domains
Electrostriction
Ionic liquids
Ions
Physics
Species diffusion
Time dependence
Wireless networks
Online Access:Get full text
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Summary:In a recent set of articles [J. C. Araque et al., J. Phys.Chem. B 119(23), 7015–7029 (2015) and J. C. Araque etal., J. Chem. Phys. 144, 204504 (2016)], we proposed the idea thatfor small neutral and charged solutes dissolved in ionic liquids, deviation from simplehydrodynamic predictions in translational and rotational dynamics can be explained interms of diffusion through nano-environments that are stiff (high electrostriction, chargedensity, and number density) and others that are soft (charge depleted). The currentarticle takes a purely solvent-centric approach in trying to provide molecular detail andintuitive visual understanding of time-dependent local mobility focusing on the mostcommon case of an ionic liquid with well defined polar and apolar nano-domains. We findthat at intermediate time scales, apolar regions are fluid, whereas the charge network ismuch less mobile. Because apolar domains and cationic heads must diffuse as singlespecies, at long time the difference in mobility also necessarily dissipates.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4990666