Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

6-20-2006

Journal or Book Title

Journal of Physical Chemistry A

Volume

110

Issue

28

First Page

8623

Last Page

8626

DOI

10.1021/jp062936l

Abstract

An analysis is provided of the subnanosecond dynamic solvation of ionic liquids in particular and ionic solutions in general. It is our hypothesis that solvation relaxation in ionic fluids, in the nonglassy and nonsupercooled regimes, can be understood rather simply in terms of the dielectric spectra of the solvent. This idea is suggested by the comparison of imidazolium ionic liquids with their pure organic counterpart, butylimidazole (J. Phys. Chem. B 2004, 108, 10245−10255). It is borne out by a calculation of the solvation correlation time from frequency dependent dielectric data for the ionic liquid, ethylammonium nitrate, and for the electrolyte solution of methanol and sodium perchlorate. Very good agreement is obtained between these theoretically calculated solvation relaxation functions and those obtained from fluorescence upconversion spectroscopy. Our comparisons suggest that translational motion of ions may not be the predominant factor in short-time solvation of ionic fluids and that many tools and ideas about solvation dynamics in polar solvents can be adapted to ionic fluids.

Comments

Reprinted (adapted) with permission from Journal of Physical Chemistry A 110 (2006): 8623, doi: 10.1021/jp062936l. Copyright 2006 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

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