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Journal of Chemical Physics / Volume 119 / Issue 1 / ARTICLES / Condensed Phase Dynamics, Structure, and Thermodynamics: Spectroscopy, Reactions, and Relaxation

J. Chem. Phys. 119, 464 (2003); http://dx.doi.org/10.1063/1.1578056 (14 pages)

The effects of anion and cation substitution on the ultrafast solvent dynamics of ionic liquids: A time-resolved optical Kerr-effect spectroscopic study

Gerard Giraud1, Charles M. Gordon2, Ian R. Dunkin2, and Klaas Wynne1

1Department of Physics, University of Strathclyde, Glasgow G4 0NG, Scotland, United Kingdom
2Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow G1 1XL, United Kingdom

(Received 30 January 2003; accepted 4 April 2003)

Ultrafast solvent dynamics of room-temperature ionic liquids have been investigated by optical heterodyne-detected Raman-induced Kerr-effect spectroscopy (OHD-RIKES) by studying the effects of cation and anion substitution on the low frequency librational modes. The spectra of two series of imidazolium salts are presented. The first series is based on the 1-butyl-3-methylimidazolium salts [bmim]+ containing the anions trifluoromethanesulfate [TfO]−, bis(trifluoromethanesulfonyl)imide [Tf2N]−, and hexafluorophosphate [PF6]−. The second series is based on [Tf2N]− salts containing the three cations 1-butyl-2,3-dimethylimidazolium [bmmim]+, 1-methyl-3-octylimidazolium [omim]+, and [bmim]+. It is found in all five samples that the signal is due to libration of the imidazolium ring at three frequencies around 30, 65, and 100 cm−1 corresponding to three local configurations of the anion with respect to the cation. © 2003 American Institute of Physics.

© 2003 American Institute of Physics

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KEYWORDS and PACS

Keywords

negative ions, positive ions, solvent effects, optical Kerr effect, time resolved spectra, Raman spectra, librational states, molecular configurations

PACS

  • 31.70.Dk

    Environmental and solvent effects

  • 07.57.-c

    Infrared, submillimeter wave, microwave and radiowave instruments and equipment

  • 07.60.-j

    Optical instruments and equipment

  • 42.65.Jx

    Beam trapping, self-focusing and defocusing; self-phase modulation

  • 33.70.Jg

    Line and band widths, shapes, and shifts

  • 33.20.Fb

    Raman and Rayleigh spectra (including optical scattering)

  • 33.15.Mt

    Rotation, vibration, and vibration-rotation constants

  • 33.20.Tp

    Vibrational analysis

  • 33.15.Bh

    General molecular conformation and symmetry; stereochemistry

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.1578056

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

For access to fully linked references, you need to log in.
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