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Linking Diffusion–Viscosity Decoupling and Jump Dynamics in a Hydroxyl‐Functionalized Ionic Liquid: Realization of Microheterogeneous Nature of the Medium
Author(s) -
Das Sudhir Kumar,
Majhi Debashis,
Sahu Prabhat Kumar,
Sarkar Moloy
Publication year - 2017
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201600983
Subject(s) - ionic liquid , decoupling (probability) , viscosity , realization (probability) , jump , chemistry , diffusion , chemical physics , ionic bonding , chemical engineering , thermodynamics , organic chemistry , ion , physics , catalysis , quantum mechanics , control engineering , engineering , statistics , mathematics
Analysis of time‐resolved fluorescence anisotropy data in light of the Stokes–Einstein–Debye hydrodynamic description reveals significant decoupling of rotational motion of the solute and the viscosity of the medium for a hydroxyl‐functionalized ionic liquid (IL). This behavior and NMR experiments indicate that the hydroxyl‐functionalized IL is more heterogeneous than other structurally similar ILs. Considering that recent theoretical investigations have demonstrated that the jump dynamics and hydrogen‐bond fluctuations are closely related in viscous media, in such a case the hydrodynamic description can provide inconsistent results, and the present inapplicability of the hydrodynamics description in explaining solute rotation in a viscous hydroxyl‐functionalized IL perhaps provides experimental support to the role of orientational jumps and hydrogen bond formation in that event.