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Dynamic solvation in imidazolium-based ionic liquids on short time scales
Lindsay Sanders Headley1, Prasun Mukherjee, Jared L Anderson
1Department of Chemistry, Iowa State University, Ames, IA 50011, USA.
The Journal of Physical Chemistry. A
|August 4, 2006
Summary
Initial solvation of coumarin 153 by ionic liquids is rapid, dominated by the organic part. A method to estimate missed initial solvation is also discussed.
Area of Science:
- Physical Chemistry
- Photochemistry
- Materials Science
Background:
- Ionic liquids (ILs) are versatile solvents with unique properties.
- Understanding solvation dynamics in ILs is crucial for their applications.
- Coumarin 153 is a common fluorescent probe for solvation studies.
Purpose of the Study:
- To investigate the initial solvation dynamics of coumarin 153 in various ionic liquids.
- To validate previous findings on the role of the organic moiety in IL solvation.
- To present a method for estimating the intramolecular contribution to reorganization energy.
Main Methods:
- Steady-state and time-resolved Stokes shift spectroscopy.
- Utilizing coumarin 153 as a fluorescent probe.
- Analysis of solvation dynamics in imidazoles and imidazolium-based ionic liquids.
Main Results:
- Initial solvation in imidazole-based liquids and imidazolium ILs is very rapid, often complete within 100 ps.
- Solvation is primarily governed by the organic component of the ionic liquid.
- A method for estimating the intramolecular reorganization energy was developed and yielded 2068 cm(-1).
Conclusions:
- The organic moiety of ionic liquids plays a dominant role in initial solvation.
- Rapid initial solvation dynamics are characteristic of imidazole and imidazolium-based ILs.
- The proposed method aids in quantifying solvation processes missed in time-resolved experiments.
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