Experimental and Theoretical Investigations of Solvation Dynamics of Ionic Fluids:  Appropriateness of Dielectric Theory and the Role of DC Conductivity

Experimental and Theoretical Investigations of Solvation Dynamics of Ionic Fluids:  Appropriateness of Dielectric Theory and the Role of DC Conductivity

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 spectr...

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Veröffentlicht in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2006-07, Vol.110 (28), p.8623-8626
Hauptverfasser: Halder, M, Headley, L. Sanders, Mukherjee, P, Song, X, Petrich, J. W
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container_issue 28
container_start_page 8623
container_title The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory
container_volume 110
creator Halder, M
Headley, L. Sanders
Mukherjee, P
Song, X
Petrich, J. W
description 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.
doi_str_mv 10.1021/jp062936l
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