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

Gerard Giraud, Charles M. Gordon, Ian R. Dunkin, Klaas Wynne

Research output: Contribution to journalArticle

216 Citations (Scopus)

Abstract

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#1 containing the anions trifluoromethanesulfate @TfO#2, bis~trifluoromethanesulfonyl!imide @Tf2N#2, and hexafluorophosphate @PF6#2. The second series is based on @Tf2N#2 salts containing the three cations 1-butyl-2,3-dimethylimidazolium @bmmim#1, 1-methyl-3-octylimidazolium @omim#1, and @bmim#1. 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 cm21 corresponding to three local configurations of the anion with respect to the cation.
Original languageEnglish
Pages (from-to)464-477
Number of pages13
JournalJournal of Chemical Physics
Volume119
Issue number1
DOIs
Publication statusPublished - 1 Jul 2003

Keywords

  • anion
  • cation
  • ionic liquids
  • Kerr-effect spectroscopy
  • nanoscience

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