Rotational dynamics in ionic liquids from NMR relaxation experiments and simulations: Benzene and 1-ethyl-3-methylimidazolium

Christopher A. Rumble, Anne Kaintz, Sharad K. Yadav, Brian Conway, Juan C. Araque, Gary A. Baker, Claudio Margulis, Mark Maroncelli

Research output: Contribution to journalArticlepeer-review

30 Scopus citations


Temperature-dependent 2H longitudinal spin relaxation times (T1) of dilute benzene-d6 in 1-butyl-3-methylimidazolium tetrafluoroborate ([Im41][BF4]) and two deuterated variants of the 1-ethyl-3-methylimidazolium cation (Im21+-d1 and Im21+-d6) in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Im21][Tf2N]), measured at multiple Larmor frequencies, were used to probe rotational dynamics in ionic liquids. Rotational correlation times significantly faster than predicted by slip hydrodynamic calculations were observed for both solutes. Molecular dynamics simulations of these systems enabled extraction of more information about the rotational dynamics from the NMR data than rotation times alone. The multifrequency 2H T1(T) data could be fit to within uncertainties over a broad region about the T1 minimum using models of the relevant rotational time correlation functions and their viscosity/temperature dependence derived from simulation. Such simulation-guided fitting provided confidence in the semiquantitative accuracy of the simulation models and enabled interpretation of NMR measurements to higher viscosities than previously possible. Simulations of the benzene system were therefore used to explore the nature of solute rotation in ionic liquids and how it might differ from rotation in conventional solvents. Whereas "spinning" about the C6 axis of benzene senses similarly weak solvent friction in both types of solvents, "tumbling" (rotations about in-plane axes) differs significantly in conventional solvents and ionic liquids. In the sluggish environment provided by ionic liquids, orientational caging and the presence of rare but influential large-amplitude (180°) jumps about in-plane axes lead to rotations being markedly nondiffusive, especially below room temperature.

Original languageEnglish (US)
Pages (from-to)9450-9467
Number of pages18
JournalJournal of Physical Chemistry B
Issue number35
StatePublished - Sep 8 2016

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry


Dive into the research topics of 'Rotational dynamics in ionic liquids from NMR relaxation experiments and simulations: Benzene and 1-ethyl-3-methylimidazolium'. Together they form a unique fingerprint.

Cite this