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

J. Chem. Phys. 119, 464 (2003); doi:10.1063/1.1578056

Issue Date: 1 July 2003

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Gerard Giraud
Department of Physics, University of Strathclyde, Glasgow G4 0NG, Scotland, United Kingdom

Charles M. Gordon and Ian R. Dunkin
Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow G1 1XL, United Kingdom

Klaas Wynne
Department of Physics, University of Strathclyde, Glasgow G4 0NG, Scotland, United Kingdom
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.
History: Received 30 January 2003; accepted 4 April 2003
Permalink: http://link.aip.org/link/?JCPSA6/119/464/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.70.Dk
    Environmental and solvent effects on electronic structure of atoms and molecules
  • 39.30.+w
    Spectroscopic techniques for atomic and molecular physics
  • 42.65.Hw
    Optical phase conjugation; photorefractive and Kerr effects
  • 33.70.Jg
    Molecular line and band widths, shapes, and shifts
  • 33.20.Fb
    Raman and Rayleigh molecular spectra including optical scattering
  • 33.15.Mt
    Molecular rotation, vibration, and vibration-rotation constants
  • 33.20.Tp
    Vibrational analysis (molecular spectra)
  • 33.15.Bh
    General molecular conformation and symmetry; stereochemistry
  • YEAR: 2003

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PUBLICATION DATA

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